MXPA99009399A - Effervescent compositions and dry effervescent granules - Google Patents

Abstract

The present invention discloses dry effervescent granules comprising an acid, carbonate source and optionally a binder, wherein said acid, carbonate source and optionally binder are in close physical proximity. The invention also discloses granular compositions, containing effervescence material comprising an acid and a carbonate source, which has an effervescence index (EI) of at least 50. The granular compositions may be obtainable by incorporating said pre-formed dry effervescent granules into said granular compositions, especially detergent compositions. Improved effervescence is obtained when diluting these granular detergent compositions with water to obtain a washing/soaking liquor, resulting thereby in improved dissolution/dispensing characteristics and improved stain removal performance on soiled fabrics.

Description

EFFERVESCENT COMPOSITIONS AND DRY EFFERVESCENT GRANULES TECHNICAL FIELD The present invention is applicable to compositions that require to be dissolved in an aqueous medium in an easy and fast manner. This technology can find application in various fields, for example, in detergent compositions such as laundry detergent compositions, soaking detergent compositions, dishwashing compositions or any other composition for domestic applications, in pharmaceutical preparations, dental preparations, food and the like . Very particularly, the present invention relates to granular detergent compositions designed for fabric cleaning.

BACKGROUND OF THE INVENTION A problem associated with conventional granular compositions that will be used by the consumer after they have been typically diluted with water is their tendency toward poor dissolution. This has been increased by the recent trend, for example, in the detergent industry, towards granular detergent compositions of higher overall density and towards granular detergent compositions having a higher content of active ingredients. The detergent compositions granules of high global densities ranging from 650 to 1100 kg / m3 are attractive to consumers but do not dissolve satisfactorily in an aqueous medium / Another difficulty with the detergent compositions is that they are not easily dispensed from the reservoir. supply of a washing machine. Similar problems are encountered when using granular detergent compositions in a dosing device in the tub of the washing machine. The use of citric acid and bicarbonate in powder compositions is known to promote the dissolution of, for example, pharmaceutical preparations. To ensure a uniform distribution of these effervescent materials in these preparations, it is essential to use sodium bicarbonate and citric acid in the form of a fine powder. It is also necessary to incorporate considerable proportions of these effervescent materials into the preparations to obtain the desired effect. In addition, a major aspect with said powder compositions is the poor stability under storage when exposed to moisture. Thus, an object of the present invention is to provide compositions with improved dissolution and / or supply characteristics after dilution in an aqueous medium. A further object of the present invention is that the effective dissolution characteristics of the compositions of the present invention are not reduced or lost during storage. It has now been found that these objectives can be met by providing a detergent composition comprising an effervescent material containing an acid and a carbonate source having a specific effervescence index. Preferably, the effervescent material, or at least part thereof, is comprised in a dry effervescent granule. In particular, it has been found that the objectives can be met in this manner by providing a granular composition obtainable by a process comprising the step of first forming a dry effervescent granule comprising an acid, carbonate and / or bicarbonate and optionally a binder. , wherein the acid, carbonate and / or bicarbonate and the binder are in close physical proximity, then incorporating this granule into the granulated composition. In fact, it has been found that for example the incorporation of said preformed dry effervescent granules which are typically obtained by compaction of dry powder or pressure agglomeration in the compositions according to the present invention, provides improved dissolution characteristics and / or supply to all the active ingredients present in the compositions, as well as an adequate stability under storage with respect to the dissolution potential. It has been found that the compositions according to the present invention provide improved effervescence, which results in an improved dissolution or supply of the compositions, when the compositions are contacted with water (i.e., under conditions of use), as compared to compositions having the same effervescent powders present at the same levels, wherein all the effervescent materials are uniformly distributed in the whole granulated compositions, that is, they are two separate granulated particles. Another problem associated with conventional detergents is their tendency to not always or satisfactorily satisfy the needs of the consumer with respect to the yield provided by the active ingredients present in said compositions. Further, when formulating bleach-containing detergent compositions comprising an oxygenated bleach, it is not only desirable to provide an effective stain removal performance (eg, in bleach stains), but importantly such compositions also need to be thermally stable for a period of time. Prolonged storage time before actual use. It has now been found that these problems are solved by means of the detergent compositions of the present invention, such as those described herein. Furthermore, it has been found that in a preferred embodiment of the present invention, the presence of preformed dry effervescent granules such as those described herein in a detergent composition comprising an active detergent ingredient, produces an improved effervescence after contact with water, which results in improved dissolution and / or supply of the composition, as well as improved stain removal performance observed on the treated fabrics, as compared to the stain removal performance provided under the same conditions with the compositions having the same ingredients, at the same levels, but which nevertheless comprise all the effervescent materials evenly distributed in the complete granular compositions, or with the same compositions but being free of any effervescent materials. In a very particular way, it has been found that the stain removal performance is further improved due to the presence of dry effervescent granules preformed in a detergent composition. This has also been found when the composition is used in short soaking operations, ie when the soiled fabrics are immersed in a soaking liquid comprising water and said composition, simultaneously or immediately after their preparation (for example, before 5 minutes). and most preferably within 1 minute after its preparation), typically for less than about 30 minutes, before being removed from the soaking liquid. Advantageously, the improvement in stain removal performance associated with the detergent compositions of the present invention is also even more remarkable at low temperatures of use, typically less than 30 °. Advantageously, the improved stain removal performance is observed on a wide variety of stains, including tough greasy stains type outer dirt (eg, spaghetti sauce, bacon grease), enzymatic stains (blood), bleach stains (grass) ) and / or particulate dirt (mud / clay). Another advantage of the present invention is that the stain removal performance when soaking / washing a fabric in the presence of a detergent composition as described herein, improves even in the presence of relatively high levels of hardness ions. It has now been found that the compositions of the invention and the preformed dry effervescent granules are compatible with bleach and are stable under storage.

BRIEF DESCRIPTION OF THE INVENTION The present invention provides a detergent composition comprising a source of effervescence, containing an acid and a carbonate source, wherein the effervescence index of the composition is at least 10, as described herein. The present invention also encompasses a dry effervescent granule comprising an acid, a carbonate source, preferably carbonate / bicarbonate and optionally a binder, wherein said acid, carbonate source and optionally the binder are in close physical proximity.

The present invention also encompasses a process for making dry effervescent granules such as those described herein, wherein said process comprises the steps of: first mixing the acid, the carbonate source and optionally the binder to obtain a mixture, then subjecting the mixing at a pressure agglomeration step, as defined herein, to obtain an agglomerated mixture, and finally subjecting the agglomerated mixture to a granulation step. The present invention also encompasses a composition obtainable by a process comprising the step of first forming a dry effervescent granule comprising an acid, a carbonate source, preferably carbonate and / or bicarbonate and optionally a binder, wherein the acid , the carbonate source and optionally the binder are in close physical proximity, then incorporating this granule in said composition. In a preferred embodiment the compositions are granular or solid detergent compositions comprising at least one active detergent ingredient, preferably at least one oxygenated bleach or a mixture thereof. The present invention also encompasses the use of a dry effervescent granule, as described herein, in a detergent composition, preferably solid or granular, comprising at least one active detergent ingredient, for improved stain removal performance. This may typically be when the fabrics are dipped, for an effective period of time, into a soaking liquid comprising water and an effective amount of said granulated detergent composition before removing said fabrics from said soaking liquid. The present invention further encompasses the use of a dry effervescent granule, as described herein, in a composition, preferably granulated or solid, comprising an oxygenated bleach, preferably percarbonate and / or perborate, for improved thermal stability of said composition under storage. . Finally, the present invention also encompasses a process of soaking fabrics, wherein said fabrics are immersed in a soaking liquid comprising water and an effective amount of a composition described herein, for an effective period of time, then remove from said soaking liquid; and also encompasses a fabric washing process in a domestic washing machine comprising, introducing into a delivery device that is placed in the tub of the washing machine, or entering into the supply tank d? a washing machine, an effective amount of a detergent composition as described herein.

DETAILED DESCRIPTION OF THE INVENTION The dry effervescent granule and the process for its manufacture The present invention encompasses a dry effervescent granule comprising an acid, carbonate source, preferably carbonate and / or bicarbonate, and optionally a binder, wherein the acid, the carbonate source and optionally the binder is in close physical proximity, and a process for making the same. By "dry" it should be understood that the granules are substantially free of water, ie, that no water has been added, or the water is present other than as the moisture of the raw material itself. Typically, the water level is less than 5% by weight of the total granule, preferably less than 3% and most preferably less than 1.5%. For the purpose of the present invention, the term close physical proximity means that the effervescent materials, ie, the acid and the carbonate source are intimately mixed in the effervescent granules and can not be separated by anything other than a binder, if the binder is present in the dry effervescent granule. Preferably, in accordance with the present invention, at least part of the acid and efcarbonate are not separate individual particles in the granulated compositions.

The dry effervescent granules according to the present invention comprising the effervescent materials, ie the acid and the carbonate source in close physical proximity, are preferably obtained by compacting dry powder or pressurized agglomeration. Although all bonding mechanisms can occur in pressure agglomeration, the adhesion forces between the solid particles, ie between the acid, the carbonate source and optionally the binder if present, play an especially important role. This is because pressure agglomeration, especially high pressure agglomeration, is an essentially dry process that forms novel entities (ie, dry effervescent granules) from solid particles (ie, acid, bicarbonate source or carbonate and optionally the binder) applying external forces to densify a more or less defined mass or global volume and create bonding mechanisms between the solid particles, providing resistance to the new entity, that is, the high applied external force joins the solid particles closely together. The dried effervescent particles result in a very rapid production of carbon dioxide and therefore a faster rate of dispersion and dissolution capacity of the granulated composition. The granular compositions of the present invention, such as those described herein, which comprise the dry effervescent granules, allow the dissolution and supply in water of the granulated compositions in a shorter period of time and at a lower total level of particles. effervescent materials, and ensure a faster and more effective supply of detergent ingredients in the wash. Suitable acids to be used herein include organic, mineral or solid inorganic acids, salts or derivatives thereof or a mixture thereof. It may be preferred that the acids are mono-, bi- or tri-protonic acids. Such acids include mono- or polycarboxylic acids, preferably citric acid, adipic acid, glutaric acid, 3-ketoglutaric acid, citramalic acid, tartaric acid, maleic acid, fumaric acid, malic acid, succinic acid and malonic acid. Such acids are preferably used in their acid forms, and the use of their anhydrous forms, or mixtures thereof, may be preferred. The derivatives also include esters of the acids. Surprisingly, it has now been found that by the use of tartaric acid, maleic acid and in particular malic acid as the acid in the dry effervescent granules, said granules provide improved physical and / or chemical stability after periods of prolonged storage. When citric acid is used it may be preferred that its level be kept below 20% in the dry effervescent granules according to the present invention, in particular to facilitate the processability and to allow adequate storage stability of the granules. The acid is preferably present in the dried effervescent granules according to the present invention at a level of from 0.1% to 99% by weight of the total granule, preferably from 3% to 75%, most preferably from 5% to 60% and more preferably from 15% to 50%. According to the present invention, 80% or more of the acid source preferably has a particle size in the range of about 150 microns to about 1200, or even 1000 or even 710 microns. Another essential feature of the present invention is a carbonate source, including carbonate, percarbonate and bicarbonate salts, in particular bicarbonate and / or carbonate. Suitable carbonates which will be used herein include carbonate and potassium hydrogen carbonate, lithium, sodium and the like, among which sodium and potassium carbonate are preferred. Suitable bicarbonates for use herein include any bicarbonate alkali metal salt such as lithium, sodium, potassium and the like, among which sodium bicarbonate and potassium are preferred. Bicarbonate may be preferred over carbonate, because its weight is more effective, that is, in a parity weight bicarbonate is a CO2"receptacle" larger than carbonate. However, the choice of bicarbonate or carbonate or mixtures thereof in the dried effervescent granules can be made depending on the desired pH in the aqueous medium in which the dried effervescent granules are dissolved. For example, when a relatively high pH is desired in the aqueous medium (for example, a pH of more than 9.5) it may be preferred to use carbonate alone, or to use a carbonate-bicarbonate combination in which the carbonate level is higher than the level of bicarbonate, typically in a carbonate to bicarbonate weight ratio of 0.1. to 10, most preferably 1 to 5 and more preferably 1 to 2. The carbonate source is preferably present in the dried effervescent granules according to the present invention at a level of 0.1% to 99% by weight of the total, preferably from 30% to 95%, most preferably from 45% to 85% and more preferably from 50% to 80%. According to the present invention, 80% or more of the carbonate source preferably has a particle size in the range of about 50 microns to about 1200, or even 150 microns. 1000 micras For optimal effervescence in aqueous medium, the weight ratio of acid to carbonate and / or bicarbonate in the dry effervescent granules is from 0.1 to 10, preferably from 0.5 to 2.5 and most preferably from 1 to 2. The diameter size of the Dry effervescent granules of the present invention is preferably 0.001 mm to 7 mm, most preferably less than 2 mm. The size of the diameter as defined herein may be determined by sieving a sample of the granules in a number of fractions (typically 5 fractions) over a series of sieves, with meshes of various diameters or aperture size. The average diameter size of the granules can be calculated by plotting the weight fractions, obtained by sieving, against the opening size of the sieves. The average particle size is taken as the size of the opening through which 50% by weight of the sample could pass. The overall density of the dry effervescent granules of the present invention is preferably from 500 g / l to 1200 g / l, most preferably from 700 g / l to 1100 g / l. The dry effervescent granules of the present invention may optionally comprise a binder or a mixture thereof.

Typically, dry effervescent granules comprise up to 50% by weight of the total granule, a binder or a mixture thereof, preferably up to 35% and most preferably up to 20%. Binders suitable for use herein are those known to those skilled in the art and include anionic surfactants such as alkyl or alkylarylsulfonates or C6-C20 sulfates, preferably C8-C20 alkylbenzenesulphonates, cellulose derivatives such as carboxymethylcellulose and polycarboxylic acid homo- or copolymer or its salts, nonionic surfactants, preferably C10-C20 ethoxylated alcohols containing 5-100 moles of ethylene oxide per mole of alcohol and most preferably C15-C20 primary ethoxylated alcohols containing -100 moles of ethylene oxide per mole of alcohol. Of these, ethoxylated tallow alcohol is preferred with 25 moles of ethylene oxide per mole of alcohol (TAE25) or 50 moles of ethylene oxide per mole of alcohol (TAE50). Other binders that are preferred include polymeric materials such as polyvinylpyrrodilones with an average molecular weight of 12,000 to 700,000 and polyethylene glycols with a molecular weight of 600 to 10. 000. Other examples of polymeric binders are copolymers of maleic anhydride with ethylene, methylvinyl ether, methacrylic acid or acrylic acid. Other binders also include mono- and diglycerol ethers of C10-C20, as well as the acid grades of C10-C20. In the embodiment of the present invention in which a binder is desired, C8-C20 alkylbenzene sulphonates are particularly preferred. In a preferred embodiment, the granules according to the present invention consist of an acid, a carbonate source and optionally a binder, wherein the acid, the carbonate source and optionally the binder are in close physical proximity. The present invention further encompasses a process for making the dry effervescent granules of the present invention comprising an acid, carbonate source and optionally a binder, wherein the acid, carbonate source and optionally the binder are in close physical proximity. This process preferably comprises the steps of: first mixing the acid, carbonate source and optionally the binder to form a mixture, then subjecting the mixture to an agglomeration step (preferably under pressure) to form an agglomerated mixture, and finally the granulation of the agglomerated mixture in a granulation step in such a way that said granules are obtained. According to this process, the effervescent raw material and optionally the binder if present are first mixed together without the addition of water and / or moisture other than that which comes from the raw material itself., so as to obtain a dry, free-flowing powder mixture. This dry, free-flowing powder mixture comprising the effervescent particles (ie, the acid and the carbonate source) and optionally the binder particles, if present, is subjected to a pressurized agglomeration step, i.e. dry processing step in which this free-flowing powder mix is subjected to high external forces that bind the particles tightly together, thus densifying the overall mass of said particles and creating bonding mechanisms between the solid effervescent particles and the binder if present. In fact, the pressure agglomeration results in an aggregation mechanism characterized by the presence of bonds between the primary solid effervescent particles and a structure in which these effervescent particles are still identifiable and retain many of their characteristics, for example, the ability to react together in the presence of water to provide carbon dioxide. The increase in density associated with the preparation of the dry effervescent granules of the present invention obtainable by pressure agglomeration is strongly related to the applied pressure.

Typically, the overall density will be increased to 200 g / l, preferably from 10 g / l to 150 g / l, starting from the density of the mixture comprising the effervescent feedstock, ie, acid and carbonate source, and optionally the binder, before being subjected to a pressurized agglomeration. The pressure agglomeration can be carried out using different procedures that can be classified by the level of applied forces. One method that is preferred to be used herein is roll compaction. In this process, the acid, bicarbonate and / or carbonate and optionally the binder after having been mixed, are forced between two compaction rollers which apply a pressure to said mixture in such a way that the rotation of the rollers transforms the mixture into a blade / compacted leaflet. This compacted sheet / flake is then granulated. Typical roller compactors for use herein are for example: Pharmapaktor L200 / 50P®, commercially available from Hosokawa Bepex GmbH. The processing variables during the pressure agglomeration step by means of roller compaction are the distance between the rollers, the feed speed, the compaction pressure and the roller speed. A typical feeding device is a feeding worm. The distance between the rolls is typically 0.5 to 10 cm, preferably 3 to 7 cm, most preferably 4 to 6 cm.

The pressing force is typically between 20 kN to 120 kN, preferably 30 kN to 100 kN, most preferably 40 kN to 80 kN.

Typically, the roll speed is between 1 rpm and 180 rpm, preferably 2 rpm at 50 rpm and most preferably 2 rpm at 35 rpm. Typically, the feed rate is from 1 rpm to 100 rpm, preferably from 5 rpm to 70 rpm, most preferably from 8 rpm to 50 rpm.

The temperature at which the compaction is carried out is not relevant, but typically varies from 0 ° C to 40 ° C. By "granulation step" is meant that the resulting mixture, after having been subjected to the pressure agglomeration step, is cut into granules of the required length and rounded to obtain round or spherical granules in accordance with the diameter size as defined above here. In the preferred embodiment, one way of carrying out the granulation step after the roll compaction step is to spray the compacted sheet / sheet. Spraying can typically be carried out with a Flake Crusher FC 200®, commercially available from Hosokawa Bepex GmbH. Depending on the desired final diameter size for the dried effervescent granules, the pulverized material can also be screened. Said sieving of the dried effervescent granules can for example be carried out with a commercially available Alpine Airjet Screen®.

DETERGENT COMPOSITIONS The present invention relates in an embodiment to a detergent composition comprising an effervescent material, which contains an acid and a carbonate source, wherein the acid and carbonate source are present in a granule together and / or the acid and the carbonate source are present separately in the composition, further characterized in that the effervescence index (El) is at least 10, or even at least 15, the effervescence index (El) being: El = (L x S x l OO) X (NCmter + NCn) M where L is the number of acid groups of the acid having a pKa of less than or equal to 6, S is 3V (solubility in water of the acid in g / liter at 25 ° C), M is the molecular weight of the acid, NC This is the density of the contact points between the carbonate source and the acid, which are present separately in the composition, per mm3, and NC1ntra (the weight fraction of the acid in said granule) x ( the weight fraction of the carbonate source in said granule) x 12. The NCintra and NCnter can be calculated according to the method established in: T Tanaka and N Ouchiyama, nd. Chem. Fundam., 1980. 19. 338-340.

It is believed that the CNT represents the density of the contact points between the acid and the carbonate source that are present in the same granule, per mm3. The compositions of the invention provide improved and efficient effervescence when the El is at least 0. The granular compositions of the present invention, such as those described herein, comprising the dried effervescent granules allow the supply and dissolution in water of the compositions granulated in a shorter period and at a lower total level of effervescent particles / materials, and ensure a faster and more effective supply of the detergent ingredients in the wash. The compositions are preferably granular detergent compositions. When used herein, the granular compositions include any composition that is in the form of granules, tablets, sticks, flakes, extruded materials, etc. The compositions of the invention preferably comprise a dry effervescent granule, as described herein, comprising the acid and the carbonate source or part thereof. It can be preferred that all the acid of the composition is comprised in the dry effervescent granule. Alternatively, it may be preferred that the composition comprises a dry effervescent granule and a dry-added acid, as well as a dry-added carbonate source, preferably less than 10% by weight of acid, most preferably less than 8% or even less of 5% by weight.

The composition may preferably be obtained by means of a process comprising the step of first forming a dry effervescent granule comprising an acid, carbonate source and optionally a binder, wherein the acid, carbonate source and binder are in physical proximity close, as described herein, and then the addition of this granule to the detergent ingredients of the composition as well. The granulated compositions of the present invention are. they can be prepared with different overall densities, preferably from 500 to 1200 g / l, most preferably from 750 to 1050 g / l, These compositions can be made by a variety of methods well known in the art, including dry blending, drying by sprinkling, agglomeration and granulation and combinations thereof. In a preferred embodiment, the compositions comprise from 0.1% to 99% by weight of the total composition of the dry effervescent granule, preferably from 2% to 50%, whereby the soaking compositions preferably comprise from 5% to 40% and very preferably 15% to 35% by weight, and the compositions for automatic dishwashing or laundry preferably from 3% to 25%, most preferably from 4% to 15% by weight.

Additional ingredients The compositions according to the present invention typically comprise at least one active ingredient on all the dry effervescent granules mentioned. In a preferred embodiment in which the granulated compositions according to the present invention are granular detergent compositions, they comprise at least one active detergent ingredient or a mixture thereof. Typically, the granular detergent compositions comprise from 0.1% to 99% by weight of the total composition of an active detergent ingredient or a mixture thereof, preferably from 1% to 80% and most preferably from 5% to 70%. By "active detergent ingredient" is meant any ingredient known to those skilled in the art to provide a cleaning and / or bleaching benefit, including, for example, surfactants, bleaches, enzymes, polymers, brighteners, detergency builders, activators of bleaching, surfactants, silicate alkali metal salt, chelating agents, fillers, soil suspending agents, dispersants, soil release agents, photoactivated whiteners such as Zn phthalocyanine sulfonate, colorants, dye transfer inhibitors, pigments, perfumes, suds suppressors, clay softening systems, cationic fabric softening agents and mixtures thereof. Depending on the desired end use, different mixtures of ingredients and levels can be used. In a preferred embodiment of the present invention, the granulated compositions comprise an oxygenated bleach or a mixture thereof. In fact, oxygenated bleaches provide a multitude of benefits such as bleaching of stains, deodorization, as well as disinfection. The oxygenated bleach in the granular compositions of the present invention can come from a variety of sources such as hydrogen peroxide or any of the hydrogen peroxide addition compounds, or organic peroxyacid, or mixtures thereof. By "hydrogen peroxide addition compounds" is meant compounds that are formed by the addition of hydrogen peroxide to a second chemical compound, which may be for example an inorganic salt, urea or organic carboxylate, to provide the addition compound.

Examples of the hydrogen peroxide addition compounds include inorganic perhydrate salts, the compounds that hydrogen peroxide forms with organic carboxylates and urea, and compounds in which hydrogen peroxide is cross-linked. Example of inorganic perhydrated salts include perborate, percarbonate, perphosphate, peroximonopersulfate and persilicate salts. Among the perhydrated inorganic salts are usually the alkali metal salts. The alkali metal salt of percarbonate, perborate or mixtures thereof, are the inorganic perhydrated salts that are preferred to be used herein. The preferred alkali metal salt of percarbonate is sodium percarbonate, which may be or be present also in the carbonate source. The preferred perborate is sodium perborate in monohydrated or tetrahydrated form, especially of the nominal formula NaB? 2H2? 2 and NaB? 2H2? 2.3H2 ?. Other suitable oxygenated bleaches include persulfates, particularly potassium persulfate K2S2? 8 and sodium persulfate Na2S208. Typically, the granulated compositions in the present invention comprise up to 90% by weight of the total composition of an oxygenated bleach or mixtures thereof, preferably from 2% to 45% and most preferably from 10% to 40%. It has now surprisingly been found that in the embodiment of the present invention in which the granular compositions comprise at least one oxygenated bleach as the active ingredient and the dried effervescent granules, the thermal stability of the granulated composition during prolonged storage is improved. Thus, in a broader aspect, the present invention also encompasses the use of said dry effervescent granule as defined hereinbefore, in a granular composition comprising an oxygenated bleach, preferably percarbonate and / or perborate, for improved thermal stability of said composition under storage.

Bleach activators Preferably, the granulated compositions herein further comprise a bleach activator or a mixture thereof up to 30% by weight of the total composition. Examples of suitable compounds of this type are described in GB 1 586 769 and GB 2 143 231. Preferred examples of said compounds are tetracetylethylenediamine (TAED), sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate, diperoxydodecanoic acid as described for example in US 4 818 425 and peroxyadipic acid nonyl amide as described for example in US 4 259 201 and n-nonanoyloxybenzenesulfonate (NOBS), and acetyltriethyl citrate (ATC such as that described in European patent application 91870207, acid 7-e-phthalimidoperoxyhexanoic acid (PAP), N-nonanoyl-6-aminocaproic acid phenolsulfonate ester, aliphatic diacyl peroxide (DAP) having the general formula RC (O) -OO- (O) C-R1, wherein R and R1 may be the same or different and are linear or branched aliphatic groups having from 6 to 20 carbon atoms. Also particularly preferred is N-acylcaprolactam selected from the group consisting of substituted or unsubstituted benzoylcaprolactam, octanoylcaprolactam, nonanoylcaprolactam, hexanoylcaprolactam, decanoylcaprolactam, undecenoylcaprolactam, formylcaprolactam, acetylcaprolactam, propanoylcaprolactam, butanoylcaprolactam and pentanoylcaprolactam. The granulated compositions herein may comprise blends of said bleach activators.

Precursors of alkylperoxyacid substituted with amide The precursors of alkylperoxyacid substituted with amide are suitable herein, including those of the following general formulas: R1- C- N- R2- C- L R1- N- C- R2- C- L II I? II O R5 O R5 O O wherein R1 is an alkyl group with 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 outgoing group. Amide-substituted bleach activating compounds of this type are described in EP-A-0170386. A highly preferred bleach activator is nonanamido-caproyloxybenzenesulfonate, preferably in the form of the sodium salt (NACA-OBS). Mixtures of bleach activators which are preferred herein comprise n-nonanoyloxybenzenesulfonate and / or nonanamido-caproyloxybenzenesulfonate together with a second bleach activator having a low general diacyl peroxide tendency, but mainly providing peracid. Said second bleach activators may include tetracetylethylenediamine (TAED), acetyltriethyl citrate (ATC), acetylcaprolactam, benzoylcaprolactam and the like, or mixtures thereof. In fact, it has been found that mixtures of bleach activators comprising n-nonanoyloxybenzenesulfonate and said second bleach activators contribute to further promote the removal performance of particulate soils, while exhibiting adequate performance over peroxide-sensitive soils. of diacyl (for example, beta-carotene) and in dirt sensitive to perishes (for example, body soiling). Accordingly, the granulated compositions herein may comprise from 0% to 15% by weight of the total composition of NOBS or NACA-OBS, preferably from 1% to 10% and most preferably from 3% to 7%, and from 0% to 15% by weight of the total composition of said second bleach activator, preferably from 1% to 10% and most preferably from 3% to 7%.

Surfactants The granulated compositions of the present invention may comprise a surfactant or a mixture thereof. Such surfactants may be desirable since they contribute to providing an effective performance of stain removal in various soils, including greasy stains, enzymatic stains, particulate soils and the like. Such surfactants may be present in the compositions according to the present invention in amounts of up to 50% by weight of the composition, preferably from 1 to 30% and more preferably from 5 to 20% by weight. The surfactants which will be used herein include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants and mixtures thereof.

Anionic Surfactants The ethoxylated alkyl sulfates as well as the propoxylated alkyl sulphates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl- and trimethylammonium cations and quaternary ammonium cations, such as tetramethylammonium, dimethylpiperidinium and cations derived from the alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like. Exemplary surfactants are polyethoxylated alkylsulfate of Ci2-C18 (1.0) Ci2-C? 8E (1.0) M, polyethoxylated alkyl sulfate of C? 2-C? 8 (2.25) C2-C? 8E (2.25) M, polyethoxylated alkyl sulfate of C12-C18 (3.0) Ci2-C18E (3.0) and polyethoxylated alkyl sulfate of C12-C? 8 (4.0) C12-C? 8E (4.0) M), wherein M is conveniently selected from sodium and potassium. Other anionic surfactants useful for detersive purposes may also be used herein. These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts, such as mono-, di- and triethanolamine salts) of soap, linear C9-C20 alkylbenzenesulfonates. C8-C4 olefinsulfonates, sulfonated polycarboxylic acids prepared by the sulfonation of the pyrolyzed product of alkaline earth metal citrates, for example, as described in the description of British Patent No. 1, 082,179, C8-C24 alkyl polyglycol ether sulphates (containing up to 10 moles of ethylene oxide); alkyl ether sulfonates such as C -C16 methyl ester sulfonates; acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, ethersulfates of alkyl phenolics of ethylene oxide, alkyl phosphates, isethionates such as acyl isethionates, N-acyltaurates, alkylsuccinamates and sulfosuccinates, disulfosuccinate monoesters (especially saturated and unsaturated C? 2-C? 8 monoesters), diesters of sulfosuccinate (especially saturated and unsaturated Cd-C diesters), acyl sarcosinates, alkylpolysaccharide sulfates such as the alkyl polyglycoside sulphates (the non-sulfated nonionic compounds described below), branched primary alkyl sulphates, alkylpolyethoxycarboxylates such as those of the formula RO (CH2CH2? ) kCH2COO-M + wherein R is a C8-C22 alkyl, k is an integer from 0 to 10 and M is a soluble salt-forming cation. The rosin acids and the hydrogenated rosin acids are also suitable, such as rosin, hydrogenated rosin and rosin and hydrogenated rosin acids present in or derived from tallow oils. Additional examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally described in the US patent. 3,929,678, issued December 30, 1975 to Laughlin, and others, in column 23, line 58 to column 29, line 23 (incorporated in the present reference manner).

Other suitable anionic surfactants for use herein may also include those in accordance with the formula R-SO3M, wherein R is a substituted or unsubstituted, saturated or unsaturated, straight or branched hydrocarbon chain having from 6 to 40 atoms of carbon and M is H or a cation. Preferably, R is a substituted or unsubstituted, saturated or unsaturated, linear or branched alkyl group having from 6 to 40 carbon atoms, preferably from 8 to 30, most preferably from 10 to and more preferably 12 to 18. Preferably, M is a cation which may be for example a metal cation (eg, sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted ammonium (eg, cations). of methyl-, dimethyl- and trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, as well as quaternary ammonium cations derived from alkylamine such as ethylamine, diethylamine, triethylamine and mixtures thereof and the like). Anionic sulfonates suitable for use herein are sodium paraffinsulfonate. They can be commercially available from Hoechst under the trade name Hostapur® or Hostatat®.

Nonionic Surfactants The nonionic surfactants suitable for use herein are typically the alkoxylated nonionic surfactants according to the formula RO- (A) nH, wherein R is a substituted or unsubstituted, saturated or substituted hydrocarbon chain. Nsaturated, linear or branched having from 6 to 40 carbon atoms, A is an alkoxy group having from 2 to 10 carbon atoms and wherein n is an integer from 9 to 100, or a mixture thereof. Preferably, R is an alkyl group or a substituted or unsubstituted, saturated or unsaturated, linear or branched aryl group having from 6 to 40 carbon atoms, preferably from 8 to 25, most preferably from 12 to 20. Typical aryl groups they include the alkylbenzene groups of Ci2C? 8. Preferably, n is an integer from 9 to 100, most preferably from 10 to 80 and more preferably from 10 to 30. A is preferably an alkoxy group having from 2 to 8 carbon atoms, preferably from 2 to 5 and most preferably is propoxy and / or ethoxy. Accordingly, the alkoxylated nonionic surfactants suitable for use herein are Dobanol® 91-10 (R is a mixture of alkyl chains of C9 to Cu, A is ethoxy, n is 10) Luthensol AT® or AO® surfactants (wherein R is a mixture of a linear or unbranched C16 to C18 alkyl chain of C13-C15, A is ethoxy and n may be 1 1, 18, 25, 50 or 80), or mixtures thereof. These Dobanol® surfactants are commercially available from SHELL, while the Luthensol® surfactants are available from BASF. Suitable chemical processes for preparing alkoxylated nonionic surfactants for use herein include the condensation of the corresponding alcohols with alkylene oxide, in the desired proportions. Such methods are well known to the person skilled in the art and have been extensively described therein. Such highly alkoxylated nonionic surfactants are particularly suitable for use herein, since they provide improved particulate removal performance. In fact, it is speculated that they act as a dirt suspending agent, that is, they allow the suspension of particle dirt and prevent / prevent the redeposition of said dirt. Other suitable surfactants to be used herein are the sorbitan esters according to the formula C6H9? 2 (C2H4?)? R R2R3, wherein x is an integer from 0 to 40, R ,, R2 are independently OH or ( CnH2n +?) COO and R3 is a group (CnH2n +?) COO, where n is an integer from 1 to 17. In the preferred compositions herein, x is 0 or 20, and the compositions that are most preferred in the present comprise polyethoxylated sorbitan tristerate (20), ie C6H9? 2 (C2H4O) 2o (C7H35COO) 3 or polyethoxylated sorbitan monostearate (20), ie C6H9O2 (C2H4?) 2o (OH) 2 (Ci7H35COO) or sorbitan monostearate, ie C6H9? 2 ( OH) 2 (C17H35COO) or sorbitan monopalmitate, ie C6H9? 2 (OH) 2 (Ci5H3iCOO) or mixtures thereof. All these materials are commercially available under various trade names such as Lonza Glycosperse TS 20 (polyethoxylated sorbitan tristerate), Lonza Glycosperse S 20 (polyethoxylated sorbitan monostearate), Finas Radiasurf 7145 (sorbitan monostearate), Radiasurf 7135 Fina (sorbitan monopalmitate), Armotan MP from Akzo (sorbitan monopalmitate). It has also been found that combining ethoxylated sorbitan esters with non-ethoxylated sorbitan esters provides better performance than with any type alone. A suitable example of an alkylamphodicarboxylic acid is Miranol (TM) C2M Conc. Manufactured by Miranol, Inc., Dayton, NJ. The polyhydroxy fatty acid amines suitable for use herein are those having the structural formula R2CONR1Z wherein: R1 is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy or a mixture thereof , preferably C 1 -C 4 alkyl, most preferably Ci or C 2 alkyl, more preferably Ci alkyl (ie, methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight chain C5-C19 alkyl or alkenyl, most preferably straight chain C9-C17 alkyl or alkenyl, more preferably straight chain C11-C17 alkyl or alkenyl, or a mixture 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. Z will preferably be derived from a reducing sugar in a reductive amination reaction; most preferably Z is a glucitol. Suitable fatty acid amide surfactants include those having the formula: R6CON (R7) 2 wherein R6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R7 is selected from the group which consists of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl and - (C2H4?) xH, wherein x is on the scale of 1 to 3. The alkylpolysaccharides suitable for use herein are described in the US Pat. USA 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 hydrophilic polyglucoside group containing from 1.3 to 10 saccharide units. Preferred alkyl polyglucosides have the formula: R2O (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 from 0 to 10, and x is from 1.3 to 8. The glucosyl is preferably derived from glucose. Suitable amine oxides include those compounds having the formula R3 (OR) xN ° (R5) 2 wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropyl and alkylphenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms or mixture 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, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Preference is given to the C 0 -C 18 alkyldimethylamine oxide and the C 10 -C 8 acylamido-alkyldimethylamine oxide.

Cationic surfactant A cationic surfactant may be comprised in the surfactant component of the composition of the invention, preferably present at a level of from 0.5% to 80% by weight of the component, most preferably from 1% to 60%, more preferably from 3 % to 50% by weight of the component. Preferably, the cationic surfactant is selected from the group consisting of cationic ester surfactants, cationic monoalkoxylated amine surfactants, cationic bisalkoxylated amine surfactants and mixtures thereof.

Cationic monoalkoxylated amine cationic surfactants The optional monoalkoxylated amine cationic surfactant for use herein has the general formula: X "wherein R1 is an alkyl or alkenyl portion containing from about 6 to about 18 atoms, preferably 6 to about 16 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; R4 is selected from hydrogen (preferred), methyl and ethyl, X- is an anion such as chloride, bromide, methylisulfate, sulfate or the like, to provide electrical neutrality; A is selected from C1-C4 alkoxy, especially ethoxy (i.e., -CH2CH2O-), propoxy, butoxy and mixtures thereof; and p is from 1 to about 30, preferably 1 to about 15, most preferably 1 to about 8. The highly preferred monoalkoxylated amine cationic surfactants for use herein have the formula: wherein R1 is a C6-C8 hydrocarbyl and mixtures thereof, preferably C6-Cu alkyl, especially C-Cn, preferably C8 and C-io alkyl, and X is any convenient anion to provide balance to the charge, preferably chloride or bromide.

As mentioned, compounds of the above type include those in which the ethoxy (CH2CH2O) (EO) units are replaced by butoxy, isopropoxy units [CH (CH3) CH2O] and [CH2CH (CH3O)] (i-Pr) or n-propoxy (Pr), or mixtures of EO and / or Pr and / or i-Pr units.

Cationic bis-alkoxylated amine cationic surfactant The cationic 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 6 to about 16 carbon atoms, most preferably 6 to about 11, more preferably about 8 to about 10 carbon atoms; R2 is an alkyl group containing one to three carbon atoms, preferably methyl; R3 and R4 can independently vary and are selected from hydrogen (preferred), methyl and ethyl, X "is an anion such as chloride, bromide, methisuclease, sulfate or the like, sufficient to provide electrical neutrality.A and A 'can vary independently and each is selected from C1-C4 alkoxy, especially ethoxy, (ie, -CH2CH2O-), propoxy, butoxy and mixtures thereof, p is from 1 to about 30, preferably 1 to about 4, and q is from 1 at about 30, preferably 1 to about 4, and more preferably both p and q are 1. The highly preferred bis-alkoxylated amine cationic surfactants for use herein have the formula: wherein R1 is C6-C-? 8 hydrocarbyl and mixtures thereof, preferably C6, C8, C-io, C12, and C14 alkyl and mixtures thereof. X is any convenient anion to provide charge balance, preferably chloride. With reference to the general structure of the bis-alkoxylated cationic amine mentioned above, since in a preferred compound R1 is derived from fatty acids (coconut) with C-12-C14 alkyl moiety, R2 is methyl and ApR3 and A 'qR4 are each monoethoxy. Other cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula: wherein R 1 is C 1 -C 8 hydrocarbyl, preferably C 6 -C 8 alkyl, p is independently 1 to about 3 and q is 1 to about 3, R2 is C 1 -C 3 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 by units (Bu) isopropoxy [CH (CH3) CH2O] and [CH2CH (CH3O] (i-Pr) or n-propoxy ( Pr) or mixtures of EO and / or Pr and / or i-Pr units. The surfactants may also include an ester cationic surfactant, ie, a water dispersible compound preferably having surfactant properties comprising at least an ester linkage (ie -COO-) and at least one cationically charged group Suitable ester cationic surfactants, including choline ester surfactants, have been described for example in US Pat Nos. 422,8042, 4239660 and 4260529 The preferred cationic ester surfactants are those having the formula: wherein R1 is a linear or branched C5-C31 alkyl, alkenyl or alkylaryl or M "» N + (R6R7R8) (CH2) S; X and Y, independently, are selected from the group consisting of COO, OCO, O, CO , OCOO, CONH, NHCO, OCONH and NHCOO wherein at least one of X or Y is a group COO, OCO, OCOO, OCONH or NHCOO; R2, R3, R4, Re, R7 and Rs are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl and alkaryl groups having from 1 to 4 carbon atoms and R5 is independently H or a C1-6 alkyl group C3; where the values of m, n, syt are independently on the scale from 0 to 8, the value of b is on the scale from 0 to 20 and the values of a, u and v independently are each 0 or 1, with the condition that at least one of uov must be 1, and where M is a counter anion. Preferably, R2, R3 and R4 are independently selected from CH3 and -CH2CH2OH. Preferably, M is selected from the group consisting of halide, methylisulfate, sulfate and nitrate, most preferably methylisulfate, chloride, bromide or iodide. Preferred cationic water dispersible ester surfactants are choline esters having the formula: wherein R-i is a linear or branched C11-C19 alkyl chain. Choline esters of this type that are particularly preferred include the quaternary methylammonium halides of stearoylcholine ester (R = C17 alkyl), quaternary methylammonium halides of palmitoylcholine ester (R1 = C15 alkyl), quaternary methylammonium halides of myristoylcholine ester (R1 = C13 alkyl), lauroylcholine ester methylammonium halides (R1 = Cu alkyl), cocoyl choline ester quaternary methylammonium halides (R1 = C11-C13 alkyl), quaternary methylammonium halides of seboylcholine ester (R1 = C15-17 alkyl) and mixtures thereof. Particularly preferred choline esters, mentioned above, can be prepared by direct esterification of a fatty acid of the desired chain length with dimethylammonioethanol, in the presence of an acid catalyst. The reaction product is then quaternized with a methyl halide, preferably in the presence of a solvent such as ethanol, propylene glycol or preferably an ethoxylated fatty alcohol such as an ethoxylated fatty alcohol of C-? 0-C? 8 having a degree of ethoxylation of 3 to 50 ethoxy groups per mole forming the desired cationic material. They can also be prepared by the direct esterification of a long chain fatty acid of the desired chain length together with 2-halogenoethanol, in the presence of an acid catalyst material. The reaction product is then quaternized with trimethylamine, forming the desired cationic material.

Other suitable cationic ester surfactants have the structural formulas below, wherein d can be from 0 to 20.

Amphoteric surfactant The amphoteric surfactants suitable for use herein include the amine oxide surfactants and the alkylamphocarboxylic acids. Suitable amine oxides include those compounds having the formula R3 (OR4) XN0 (R5) 2, wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkylphenyl group, or mixtures thereof, containing from 8 to 26 atoms of carbon; R 4 is an alkylene or hydroxyalkylene group containing 2 to 3 carbon atoms, or mixtures thereof, X is 0 to 5, preferably 0 to 3; and each R 5 is an alkyl or hydroxyalkyl group containing 1 to 3, or a polyethylene oxide group containing 1 to 3 ethylene oxide groups. Alkyl dimethylamine oxide of C? O-C? 8 and acylamidoalkyldimethylamine oxide of C-io-C-I8 are preferred. A suitable example of an alkylamphodicarboxylic acid is Mirano (TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.

Zwitterionic Surfactant Zwitterionic surfactants may also be comprised in the surfactant component of the composition of the invention or the compositions containing 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 quaternary sulfonium. The betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein. Suitable betaines are those compounds having the formula R (R ') 2N + R 2 -COO-, wherein R is a C 6 -C 8 hydrocarbyl group, each R 1 is typically C 1 -C 3 alkyl and R 2 is a group hydrocarbyl of C C5. Preferred betaines are C12-? S dimethylammonium hexanoate and C? O-? 8 acyl amidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.

Alkaline silicate metal salt The granular compositions herein may comprise a silicate alkali metal salt, or mixtures thereof, among the optional ingredients that are preferred. The alkali silicate metal salt that is preferred to be used herein is sodium silicate. In the preferred embodiment of the present invention, wherein the granular compositions comprise an oxygenated bleach and a soaking application is typically attempted., it has been found that the decomposition of the available oxygen produced in the soaking liquids after the dissolution of the granulated compositions is reduced by the presence of at least 40 parts per million of sodium silicate and said liquids in said soaking liquids. Any type of silicate alkali metal salt, including crystalline forms, as well as amorphous forms of said silicate alkali metal salt or mixtures thereof can be used herein. Suitable crystalline forms of sodium silicate to be used are the layered crystalline silicates of the general formula: NaMSixO2x-n and H2O wherein M is sodium or hydrogen, X is a number from 1.9 to 4 and (y) is number from 0 to 20 or mixtures thereof. Laminated crystalline sodium silicates of this type are described in EP-A-164 514 and methods for their preparation are described in DE-A-34 17 649 and DE-A-37 42 043. 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. Most preferably, M is sodium and (y) is 0, and preferred examples of this formula comprise the forms a, b, g and d of Na 2 S 2? 5. These materials are available from Hoechst AG FRG respectively as NaSKS-5, NaSKS-7, NaSKS-1 1 and NaSKS-6. The most preferred material is d-Na2Si2? 5, NaSKS-6. The layered crystalline silicates are incorporated into the soaking compositions herein, either as dry mixed solids or as solid components of agglomerates with other components. Suitable amorphous forms of sodium silicate to be used herein have the following general formula: NaMSix? 2X + -? wherein M is sodium or hydrogen and x is a number of 1.9 to 4, or mixtures thereof. It is preferred to use amorphous forms of YES2O5 Na2O in the present. Suitable zeolites for use herein are aluminosilicates which include those having the empirical formula: Mz (zAIO2.and SiO2) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2 y (and ) is 1; this material has a magnesium ion exchange capacity of at least about 50 milligrams equivalent of CaCO3 hardness per gram of anhydrous aluminosilicate. The zeolites that are preferred have the formula: Nazi (AIO2) z (SiO2) yu.xH2O where zy (y) are integers of at least 6, the molar ratio of zay is on the scale of 1.0 to about 0.5 and x is an integer of about 15 to about 264. Useful materials are commercially available. These aluminosilicates may be of crystalline or amorphous structure and may be natural aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is described in US Patent 3,985,669, Krummel et al., Issued October 12, 1976. Synthetic crystalline aluminosilicate ion exchange materials useful herein are available under US Pat. designations Zeolite A, Zeolite P (B), and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula: Na12i (AI02) 12 (siO2) 12u.xH2O wherein x is 20 at 30, especially around 27. This material is known as Zeolite A. Preferably, the aluminosilicate has a particle size of about 0.1 to 10 microns in diameter. Typically, the compositions herein comprise from 0.5% to 15% by weight of the total composition of an alkali metal salt of silicate or mixtures thereof, preferably from 1% to 10% and most preferably from 2% to 7% .

Detergency Enhancers The granular compositions herein may also comprise a builder or a mixture thereof. All builders known to those skilled in the art can be used here. Phosphate builders suitable for use herein include sodium potassium tripolyphosphate and pyrophosphate, polymeric metaphosphate having a degree of polymerization of about 6 to 21, and orthophosphate. Other phosphorus builder compounds are described in the U.S. Patents. Nos. 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148, incorporated herein by reference. Polycarboxylate detergent builders suitable for use herein include ether polycarboxylates, including oxydisuccinate, such as those described in Berg, U.S. 3,138,287, issued April 7, 1964, and Lamberti et al., US patent. 3,635,830, issued January 18, 1972. See also the "TMS / TDS" detergency builders of the U.S. patent. No. 4,663,071, issued to Bush et al., May 5, 1987. Suitable ether ether carboxylates also include cyclic compounds, particularly alicyclic compounds such as those described in US Patents. 3,923,679; 3,835,163; 4,120,874 and 4,102,903. Other useful builders include etherhydroxypolycarboxylates, 1,3-trihydroxybenzene-2,4,6-trisulfonic acid and carboxylmethyloxysuccinic acid, the different alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid. , as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1, 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and soluble salts thereof. Also suitable in the granulated compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hedioates and the related compounds described in the US patent. No. 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include alkyl and C5-C20 alkenyl succinic acids and salts thereof. A compound of this type that is particularly preferred is dodecenylsuccinic acid. Specific ples of succinate builders include: lauryl succinate, myristiisuccinate, palmitiisuccinate, 2-dodecenyl succinate (preferred), 2-pentadecenylsuccinate and the like. Lauryl succinates are the preferred detergency builders of this group and are described in European patent application 86200690.5 / 0,200,263, published November 5, 1986. Other suitable polycarboxylate builders are described in the U.S. patent. 4,144,226, Crutchfield et al., Issued March 13, 1979 and in the US patent. 3,308,067, issued March 7, 1967. See also Diehl, US patent. 3,723,322.

Other polycarboxylate builders suitable for use herein include builders according to formula I: R 1. -Yp- - (- CH2-CR3 -.} - - R I C02M n where Y is a comonomer or comonomer mixture; R1 and R2 are stable polymer end groups in bleach and alkali; R3 is H, OH or C- alkyl; M is H, an alkali metal, alkaline earth metal, ammonium or substituted ammonium; p is from 0 to 2; and n is at least 10 or mixtures thereof. The polymers that are preferred for use herein are in two categories. The first category belongs to the class of copolymeric polymers which are formed from an unsaturated polycarboxylic acid such as maleic acid, citraconic acid, itaconic acid, mesaconic acid and salts thereof as the first monomer and an unsaturated monocarboxylic acid such as acrylic acid or an alpha alkylacrylic acid of C- as the second monomer. With reference to formula I above, the polymers belonging to said first class are those in which p is not 0 and Y is selected from the acids listed hereinabove. The polymers of this class that are preferred are those according to formula I above, wherein Y is maleic acid. Similarly, in a preferred embodiment R3 and M are H, and n is such that the polymers have a molecular weight of 1000 to 400,000 atomic mass units. The second category of preferred polymers to be used belongs to the class of polymers in which, with reference to formula I above, p is 0 and R3 is H or C-? -4 alkyl. In a preferred embodiment n is such that the polymers have a molecular weight of 1000 to 400,000 units of atomic mass. In a highly preferred embodiment, R3 and M are H. The alkali stable polymer end groups R1 and R2 of formula I above suitably include alkyl groups, oxyalkyl groups and alkylcarboxylic acid groups and salts and esters thereof . In the above, n, the degree of polymerization of the polymer can be determined from the molecular weight of the average polymer by dividing the latter by the molecular weight of the average monomer. Thus, for an acrylic-maleic copolymer having an average molecular weight of 15,500 and comprising 30 mol% of units derived from maleic acid, n is 182 (ie 15,500 / (1 16 x 0.3 + 72 x 0.7)) . The temperature controlled columns at 40 ° C against sodium polystyrenesulfonate polymer parameters, available from Polymer Laboratories Ltd., Shropshire, UK, polymer standards being sodium dihydrogen phosphate at 0.15 M and tetramethylammonium hydroxide at 0.02 M at pH 7.0 in 80/20 water / acetonitrile.

Of the foregoing, the highly preferred polymers for use herein are those of the first category, wherein n averages 100 to 800, preferably 120 to 400. The detergency builders that are preferred to be used herein are polymers of maleic or acrylic acid, or copolymers of maleic acid and acrylic acid. Typically, the granulated compositions of the present invention comprise up to 50% by weight of the total composition of a builder or mixtures thereof, preferably from 0.1% to 20% and most preferably from 0.5% to 1%.

Guelatary Agents Preferably, the granulated compositions herein further comprise a chelating agent or mixtures thereof. Chelating agents are desired herein to help control the level of free heavy metal ions in the wash / soak liquids, thereby preventing the rapid decomposition of the oxygen released by the oxygenated bleach. Suitable aminocarboxylate chelating agents that can be used herein include diethylenetriaminepentaacetic acid, ethylenediaminetetraacetates (EDTA), N-hydroxyethylenediaminetriacetates, nitrilotriacetates, ethylenediaminetetrapropionates, triethylenetetraaminehexaacetates and ethanoldiglicines., alkali metal salts of ammonium and substituted ammonium thereof or mixtures thereof. Additional and suitable chelating agents include ethylenediamine-N, N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium or substituted ammonium salts thereof. Particularly suitable EDDS compounds are the free acid form and the sodium or magnesium salt, or complexes thereof. Other suitable chelating agents can also be the organic phosphonates, which include aminoalkylene poly (alkylene phosphonate), alkali metal ethane-1-hydroxydiphosphonates, nitrilotrimethylene phosphonates, ethylenediaminetetramethylphosphonates and diethylenetriaminepentamethylenephosphonates. The phosphonate compounds may be present in either their acid form or in the form of an alkali metal salt. Preferably, the organic phosphonate compounds when present are in the form of their magnesium salt. The granulated compositions of the present invention may accordingly comprise from 0 to 5% by weight of the total compositions of said chelating agents, preferably from 0% to 3%, most preferably from 0.05% to 2%.

Fillers The granular composns herein may further comprise an inorganic filler-type filler salt such as sulfates. Typically, the composns of the present invention comprise up to 50% by weight of the total composn of a filler or a mixture thereof, preferably from 0.1% to 20% and most preferably from 0. 5% to 10%.

Enzymes The granulated composns herein also typically comprise an enzyme or a mixture thereof. Preferably, the composns herein comprise a protease or mixtures thereof. Protease enzymes are normally present in the preferred embodiments of the invention at levels sufficient to provide 0.005 to 0.2 units (AU) of activity per gram of the composn. The proteolytic enzyme can be of animal, vegetable or preferably microorganism origin. The serine proteolytic enzyme of bacterial origin is more preferred. Purified and non-purified forms of enzyme can be used. Proteolytic enzymes produced by means of chemically or genetically modified mutants are included by definn, since they are variants of enzyme of close structure. Particularly preferred as a proteolytic enzyme is the bacterial serine proteolytic enzyme obtained from Bacillus, Bacillus subtilis and / or Bacillus licheniformis. Suitable commercial proteolytic enzymes include Alcalase®, Esperase®, Durazym®, Savinase®, Maxatase®, Maxacal® and Maxapem® 15 (designed Maxacal protein); Purafect® and subtilisin BPN and BPN * are also commercially available. Preferred proteolytic enzymes also encompass modified bacterial serine proteases such as those described in European Patent Application No. 87303761.8, filed on April 28, 1987 (particularly pages 17, 24 and 98), and which is called here "Protease B", and in the European patent application 199,404, Venegas, published on October 29, 1986, which refers to a bacterial serine proteolytic enzyme modified that is called "Protease A", in the present. More preferred is what is called here "Protease C", which is a triple variant of a Bacillus alkaline serine protease in which tyrosine replaces valine in posn 104, serine replaces asparagine in posn 123 and alanine replaces threonine at posn 274. Protease C is described in EP 90915958.4, which corresponds to WO 91/06637, published May 16, 1991 and which is incorporated herein by reference. Genetically modified variants, particularly C protease are also included here. Also suitable for use herein is a protease called "Protease D", which is a variant of carbonyl hydrolase having an amino acid sequence not found in nature and which is derived from a precursor carbonyl hydrolase by substituting a different amino acid. by a plurality of amino acid residues at a posn to said carbonyl hydrolase equivalent to the +76 posn in combination with one or more amino acid residue posns equivalent to those selected from the group consisting of +99, +101, +103, + 107 and +123 in Bacillus emyloliquefaciens as described in concurrently filed patent applications of A. Baeck, CK Ghosh, P.P. Greycar, R.R.

Bott and L.J. Wilson, titled "Protease-Containing Cleaning Composns" that has the serial number E.U. 08 / 136,797 (Case 5040 of P &G) and "Bleaching Composns Comprising Protease Enzymes "which has the serial number E.U. 08 / 136,626, which are incorporated herein by reference. Some preferred proteolytic enzymes are selected from the group consisting of Savinase®, Esperase®, Maxacal®, Purafect®, BPN \ Protease A and Protease B and mixtures thereof. Bacterial serine protease enzymes obtained from Bacillus subtilis and / or Bacillus licheniformis are preferred. Particularly preferred are Savinase®, Alcalase®, Protease A and Protease B. Typically, the granulated compositions herein also comprise an amylase or mixtures thereof. The manipulation of the enzymes is known for improved stability, for example, oxidative stability. See, for example J. Biological Chem., Vol. 260, No. 11, June 1985, pp 6518-6521. The term "reference amylase" hereinafter refers to an amylase outside the scope of the amylase component of this invention and against which the stability of any amylase within the invention can be measured. The present invention then makes use of amylases which have improved stability in detergents, especially improved oxidative stability. A convenient absolute stability reference point against which amylases used in the present invention represent a measurable improvement is the stability of TERMAMYL (R) in commercial use in 1993 and available from Novo Nordisk A / S. This TERMAMYL (R) amylase is a "Reference amylase". Amylases within the spirit and scope of the invention share the characteristic of being "improved stability" amylases, characterized, at a minimum by a measurable improvement in one or more of: oxidative stability, for example, to hydrogen peroxide / tetracetylethylenediamine in pH solution regulated at 9-10; thermal stability, for example, at common wash temperatures such as about 60 ° C; or alkaline stability, for example, at a pH of about 8 to about 1 1, all measured against the reference amylase mentioned above. The amylases that are preferred herein may demonstrate further improvement against reference amylases representing a greater challenge, these latter reference amylases being illustrated by any of the precursor amylases of which the amylases within the invention are variants. Said precursor amylases may in turn be natural or be the product of genetic manipulation. Stability can be measured using any of the technical tests described in the art. See the references described in WO 94/02597, and documents therein which are referenced and incorporated herein. In general, the improved stability amylases of the invention can be obtained from Novo Nordisk A / S or Genencor International. The amylases that are preferred here have the common ability to be derived using the site-directed mutagenesis of one or more of the Bacillus amylases, especially the Bacillus alpha amylases, regardless of whether one, two or more amylase strains are the precursors. immediate. As mentioned, it is preferred to use the amylases herein "of improved oxidative stability". Said amylases are illustrated in a non-limiting manner by the following: (a) An amylase according to the aforementioned WO / 94/02597, published on February 3, 1994, which is best illustrated by a mutant in which the substitution, using alanine or threonine (preferably threonine), of the methionine residue located at position 197 of Bacillus licheniformis alpha amylase, known as TERMAMYL (R), or the homologous position of a variation of a similar progenitor amylase such as Bacillus amyloliquefaciens, Bacillus subtilis, or Bacillus stearothermophilus; (b) amylases of improved stability such as those described by Genencor International in a document entitled "Oxidatively Reistant alfa-Amilases", presented at the 207 National Board of the American Chemical Society, March 13-17, 1994 by C. Mitchinson. It was noted that the bleaches in the automatic dishwashing detergents inactivate the alpha amylases but that amylases of improved oxidative stability have been achieved by Genencor from Bacillus licheniformis NCIB8061. Methionine (Met) was identified as the residue most likely to be modified. The Met was substituted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 348 leading to specific mutants, particularly important being M197L and M197T with the M97T being the most stable expressed variant. The stability was measured in CASCADE (R) and SUNLIGHT (R); said enzymes are commercially available from Genencor under the trade name Plurafact Oxam®. (c) Particularly preferred herein are the amylase variants which have a further modification in the immediate parent available from Novo Nordisk A / S. These amylases do not yet have a commercial name but are those called by the supplier QL37 + M197T. Said enzymes are commercially available under the trade name SP 703 from Novo. Any other amylases of improved oxidative stability can be used, for example, as derivatives by means of site-directed mutagenesis of chimeric, hybrid progenitor or single mutant forms of available amylases.

Soil suspension agents The granulated compositions herein may also comprise a soil suspending agent or a mixture thereof., typically at a level of up to 20% by weight, preferably from 0.1 to 10%, most preferably from 0.5% to 2%. Suitable soil suspending agents include ethoxylated diamines, ethoxylated polyamines, ethoxylated amine polymers such as those described in EP-A-1 12 593, incorporated herein by reference. The soil suspending agents that are preferred to be used herein include ethoxylated polyethylene diamine having a molecular weight of 140 to 310 before ethoxylation, ethoxylated tetraethylenepentamine 15-18, ethoxylated polyethyleneamine 15-18, ethoxylated ethylenediamine 15-18, ethoxylated polyethyimine. having a molecular weight of 600 to 1800 before ethoxylation, and mixtures thereof.

Foam suppression systems Detergent compositions, when formulated for use in machine wash compositions, preferably comprise a foam suppression system present at a level of from 0.01% to 15%, preferably from 0.05% to 10% and very preferably from 0.1% to 5% by weight of the composition. The foam suppression systems suitable for use in the present invention may comprise essentially any known antifoam compound, including, for example, silicone antifoam compounds and 2-alkyl alkanol antifoam compounds. By "antifoaming compound" is meant in the present invention any compound or mixture of compounds that acts in such a way as to reduce the foaming produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.

Particularly preferred anti-foam compounds for use in the present invention are the silicone antifoam compounds defined herein as any antifoam compound that includes a silicone component. Said antifoam silicone compounds also typically contain a silica component. The term "silicone", in the present invention, and in general in industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and a hydrocarbyl group of various types. Preferred silicone antifoam compounds are siloxanes, particularly polydimethylsiloxanes having trimethylsilyl end blocking units. Other suitable antifoam compounds include the monocarboxylic fatty acids and their soluble salts. These materials are described in the U.S. patent. No. 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids and their salts for use as suds suppressors typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as the sodium, potassium and lithium salt salts, and the ammonium and alkanolammonium salts. Other suitable antifoam compounds include, for example, high molecular weight fatty esters (eg, fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C18-C40 ketones (eg, stearone), N-alkylated aminotriazines such as tri- to hexa-alkylmelamines or di- to tetraalkyldiaminoclortriazines formed as cyanuric chloride products with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and di-alkali metal monostearyl phosphates (eg, sodium, potassium, lithium) and phosphate esters. A preferred foam suppressor system comprises: (a) an antifoam compound, preferably a silicon antifoam compound, most preferably a silicone antifoam compound comprising in combination: (i) polydimethylsiloxane, at a level of 50% to 99%, preferably from 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 dispersing compound, most preferably comprising a silicone glycol copolymer with comb structure with a polyoxyalkylene content between 72 and 78% and a ratio of ethylene oxide to propylene oxide of 1: 0.9 to 1: 1.1, at a level of 0.5% to 10%, preferably 1% to 10% by weight; A particularly preferred glycol silicone copolymer with comb structure of this type is DC0544, commercially available from DOW Corning under the tradename of DCO544; (c) an inert carrier fluid compound, more preferably comprising an ethoxylated C 16 -C 18 alcohol with a degree of ethoxylation of from 5 to 50, preferably from 8 to 15, at a level of 5% to 80%, preferably from 10% to 70% by weight. A much preferred highly particulate foam suppressor system is described 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, in the that 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 discloses other preferred particulate foam suppressor systems in which 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 45 ° C to 80 ° C.

Clay Softening Systems The detergent compositions of the present invention typically designed to wash fabrics in a domestic washing machine may contain a clay softening system comprising a clay mineral compound and optionally a clay flocculating agent.

The clay mineral compound is preferably a smectite clay compound. Smectite clays are described in the patents of E.U.A. Nos. 3,862,058, 3,948,790, 3,954,632 and 4,062,647. European patents Nos. EP-A-299,575 and EP-A-313,146 in the name of The Procter & Gamble Company describes suitable organic polymeric clay flocculating agents.

Polymeric Dye Transfer Inhibitory Agents The detergent compositions of the present invention typically designed to wash fabrics in a domestic washing machine may additionally comprise 0.01% to 10%, preferably 0.05% a 0. 5% by weight of polymeric agents inhibitors of dye transfer. 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. a) Polyamine N-oxide polymers Polyamine N-oxide polymers suitable for use in the present invention contain units having the following structural formula: (1) Ax R where P is a polymerizable unit, and O O O II II II A is NC, CO, C, -O-, -S-, -N-; x is 0 or 1; R are aliphatic, aliphatic, ethoxylated, aromatic, heterocyclic or alicyclic groups, or any combination thereof, to which the nitrogen of the N-O group may be attached or in which the nitrogen of the N-O group is part of these groups. The N-O group can be represented by the following general structures: - (R4) x • wherein R1, R2 and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups, or combinations thereof, xy / oyy / oz is 0 or 1 and wherein the nitrogen of the NO group can be fixed or wherein the nitrogen of the NO group forms part of these groups. The N-O group can be part of the polymerizable unit (P) or it can be attached to the polymeric base structure or to a combination of both.

Suitable polyamine N-oxides in which the N-O group forms part of the polymerizable unit comprise the polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. A class of N-oxides of said polyamine comprises the group of polyamine N-oxides in which the nitrogen of the group NO is part of the group R. The preferred N-oxides of polyamine are those in which R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine, and derivatives thereof. Other suitable polyamine N-oxides are the polyamine oxides to which the N-O group is attached to the polymerizable unit. A preferred class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I), wherein R is an aromatic, heterocyclic or alicyclic group, in which the nitrogen of the functional group is NOT part of said group R. Examples of these classes are polyamine oxides in which R is a heterocyclic compound such as pyrridine, pyrrole, imidazole, and derivatives thereof. The polyamine N-oxides can be obtained in almost any degree of polymerization. The degree of polymerization is not critical, as long as the material has the water solubility and the desired dye suspension power. Typically, the average molecular weight is within the range of 500 to 1,000,000. b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole The copolymers of N-vinylimidazole and N-vinylpyrrolidone suitable in the present invention have an average molecular weight scale of 5,000 to 50,000. Preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2. c) Polyvinylpyrrolidone The detergent compositions of the present invention may also use polyvinylpyrrolidone ("PVP") having an average molecular weight of 2,500 to 400,000. Suitable polyvinyl pyrrolidones are commercially available from ISP Corporation, New York, NY and Montreal, Canada, under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000) and PVP K-90 (average molecular weight of 360,000). PVP K-15 is also available from ISP Corporation. Other suitable polyvinyl pyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12. d) Polyvinyloxazolidone The detergent compositions of the present invention can also use polyvinyloxazolidones as a polymeric dye transfer inhibiting agent. Said polyvinyloxazolidones have an average molecular weight of 2,500 to 400,000. e) Polyvinylimidazole The detergent compositions herein can also use polyvinylimidazole as a polymeric dye transfer inhibiting agent. Said polyvinylimidazoles have an average molecular weight of 2,500 to 400,000.

Optical brighteners The detergent compositions of the present invention also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners. Hydrophilic optical brighteners useful in the present invention include those having the structural formula: wherein R-j is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R 2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphino, chloro and amino; and M is a salt-forming cation such as sodium or potassium. When in the previous formula R- | is aniline, R2 is N-2-bis-hydroxyethyl and M is a cation like sodium, the brightener is 4,4 ', - bis [(4-anilino-6- (N-2-bis-hydroxyethyl)] -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is marketed under the trade name Tinopal UNPA-GX by Ciba-Geigy Corporation. The Tinopal UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions of the present invention. When in the previous formula R- | it is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation like sodium, the brightener is the disodium salt of 4,4'-bis [(4-ani-amino-6- (N-2)] -hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] 2,2'-stilbenedisulfonic acid. This particular brightener species is marketed under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation. When in the previous formula Rj is anilino, R2 is morphino and M is a cation like sodium, the brightener is the sodium salt of 4,4'-bis [(4-ani-na-6-morphino-s -triazn-2-yl) amino] 2,2'-stilbenedisulfonic acid. This particular brightener species is marketed under the trade name Tinopal AMS-GX by Ciba-Geigy Corporation.

Fabric Softening Cationic Agents Fabric softening cationic agents can also be incorporated into the granulated compositions of the present invention. Suitable cationic fabric softening agents include water insoluble tertiary amines or doubly long chain amide materials such as those described in GB-A-1 514 276 and EP-B-0 01 1 340. Cationic fabric softening agents are typically incorporate at 0.5% total levels to % by weight, usually from 1% to 5% by weight.

The fabric soaking process The present invention encompasses processes for soaking fabrics. In fact, the present invention encompasses a process for soaking fabrics, wherein said fabrics are immersed in a soaking liquid comprising water and an effective amount of a granulated composition as described hereinabove, for an effective period of time, and then they are removed from said soaking liquid. As used in the present, the term "fabric soaking process" refers to the action of allowing the fabrics to soak in a soaking liquid comprising water and a composition as described above, for a period of time sufficient to clean said fabrics. In contrast to the typical washing operation used by a washing machine, the soaking procedure of the present allows a prolonged contact time between the fabrics and the soaking liquid, typically up to 24 hours. The soaking process can be carried out independently of any other process, such as a typical washing operation, or a first step before a typical second washing step, or a second step after a typical first washing operation. In the preferred soaking procedures of the invention, the fabrics are allowed to soak for a period ranging from 1 minute to 24 hours, preferably 10 minutes to 24 hours, most preferably 30 minutes to 18 hours, even most preferably 1 hour to 6 hours. After the fabrics have been immersed in said soaking liquid for a sufficient period, they can be removed and rinsed with water. The fabrics can also be washed in a normal washing operation after they have been soaked, with or without being rinsed between the soaking operation and the subsequent washing operation. In the soaking process of the present, a soaking composition described hereinabove is diluted in a suitable amount of water to produce a soaking liquid. Suitable doses may vary from 40 to 55 grams of soaking composition in 3.5 to 5 liters of water, up to 90 to 100 grams of soaking composition in 20 to 45 liters of water. Typically, a dose is 40-55 grams in 3.5 to 5 liters for a concentrated soak (bucket / cell). For soaking in a washing machine, the dose is 90-100 grams in approximately 20 (Europe) to 45 (E.U.) liters of water. The fabrics that will be soaked are then immersed in the washing liquid for a suitable period. There are factors that could influence the overall stain removal performance of the procedures in various soils / dirt. These factors include a prolonged soaking time. In fact, the longer the fabrics are soaked, the better the final results. In this way, the instructions in commercially available soaking compositions ideally recommend a nighttime soaking time, i.e. 8 hours up to 24 hours. An advantage of the present invention is that effective results are obtained even in short soaking operations, typically less than 30 minutes. Another factor is the initial warm or warm temperature. In fact, the higher initial temperatures of the soaking liquids ensure great performance benefits.

Another advantage of the present invention is that effective results are obtained even at a low soak temperature, typically less than 30 ° C or even less than 20 ° C. The method of the present is suitable for cleaning a variety of fabrics, but finds a preferred application in the soaking of socks, which are particularly exposed to the accumulation of sediment and clay.

The process of washing fabrics in a domestic washing machine The present invention encompasses methods for washing fabrics.

In fact, the present invention encompasses a process for washing fabrics in a domestic washing machine comprising introducing into a delivery device that is placed in the tub of the washing machine, or introducing into the supply tank of a washing machine, an effective amount of a granulated detergent composition comprising dry effervescent granules as described herein.

The laundry washing methods of the present invention typically comprise treating soiled laundry with an aqueous washing solution in a washing machine to which an effective amount of a laundry detergent composition has been delivered or dissolved in a washing machine in accordance with the invention. For an effective amount of the detergent composition is meant from 40 g to 300 g of product dissolved or dispersed in a washing solution with a volume of 5 to 65 liters, which are typical product doses and volumes of washing solution commonly used in conventional washing machine washing methods. In a preferred use aspect a dispensing device is employed in the washing method. The delivery device is charged with the detergent product, and is used to introduce the product directly into the tub of the washing machine before the start of the washing cycle. Its volume capacity must be such that it can contain sufficient detergent product that would normally be used in the washing method. Once the washing machine has been loaded with the laundry, the supply device containing the detergent product is placed inside the tub. At the beginning of the washing cycle of the washing machine, water is introduced into the tub and it rotates periodically. The design of the delivery device must be such as to allow the dry detergent product to be contained but then allow this product to be released during the wash cycle in response to its agitation while the tub is spinning, and also as a result of its contact with the wash water .

To allow the release of the detergent composition during washing, the device must possess a number of openings through which the product can pass. Alternatively, the device can be made of a material that is liquid permeable but impermeable to the solid product, which will allow the release of the dissolved product. Preferably, the detergent product will be released rapidly at the start of the wash cycle, thereby providing localized high concentrations of product in the washing tub at this stage of the wash cycle. Preferred delivery devices are reusable and are designed in such a way that the integrity of the container is maintained both in the dry state and during the wash cycle. Especially preferred delivery devices for use with the composition of the invention have been described in the following patents: GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP- A-0288345 and EP-A-0288346. An article by J. Bland, published in Manufacturing Chemist, November 1989, p. 41-46 also discloses especially preferred delivery devices for use with granular laundry products that are of the type commonly known as "granulette". Another delivery device that is preferred for use with the compositions of this invention is disclosed in PCT Patent Application No. WO94 / 11562. Especially preferred delivery devices are described in European Patent Applications Publication Nos. 0343069 and 0343070. This latter application describes a device comprising a flexible cover in the form of a bag extending from a support ring defining an orifice, the orifice being adapted to allow entry to the product bag sufficient for a washing cycle in a washing process. A portion of the washing medium flows through the hole into the bag, dissolves the product and the solution then passes out through the hole into the washing medium. The support ring is provided with a masking arrangement to prevent the release of wet and undissolved product, this arrangement typically comprising walls extending radially from a central protrusion in a gearwheel configuration or a similar structure in which the walls have a helicoid shape. Alternatively, the delivery device may be a flexible container such as a bag or bag. The bag may have a fibrous structure coated with a waterproof protective material in a manner that retains the contents as described in published European patent application No. 0018678. Alternatively, it may be formed from a synthetic polymeric material insoluble in water. water provided with a sealing or sealing edge designed to break in the aqueous medium, such as that described in published European patent applications Nos. 001 1500, 0011501, 001 1502, and 001 1968. A convenient form of frangible water closure comprises a water soluble adhesive disposed along and sealing an edge of a bag formed of a waterproof polymeric film such as polyethylene or polypropylene.

Pile for the granulated compositions The commercially sold embodiments of the granulated compositions can be packaged in any suitable container including those constructed of paper, cardboard, plastic materials and any suitable laminates.

Form of cleaning compositions Granulated compositions can be made by a variety of methods, including dry blending, extrusion, compression and agglomeration of the different components comprised in the detergent composition. The dry effervescent granule of the invention may be present in the cleaning compositions as a separate component of the composition, or may be part of or be added to the other components or compounds of the compositions. Cleaning compositions can have a variety of physical forms, including granular, flake, extruded, tablet or stick. Cleaning compositions are particularly so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of a supply device placed in the tub of the lamellar machine with the load of laundry. The average particle size of the base composition of the granular cleaning compositions containing the foam-forming composition according to the invention may be from 0.1 mm to 5.0 mm, but preferably it should be such that no more than 5% of the particles measuring more than 2.5 mm in diameter, or even 1.7 mm, and not more than 5% of the particles are less than 0.15 mm in diameter. The term average particle size as defined herein is calculated by sifting a sample of the composition in a number of fractions (typically 5 fractions) in a series of Tyler sieves. The fractions of weight obtained in this way are plotted against the opening size of the sieves. The average particle size is then taken as the size of the opening through which 50% of the sample would pass. The overall density of the granular detergent or cleaning compositions containing the particulate composition according to the present invention is typically an overall density of at least 300 g / liter, most preferably 500 g / liter or even 650 g / liter. liter at 1200 g / liter, more preferably at 850 g / liter.

The Stain Removal Performance Test Method The stain removal performance of a certain composition on a soiled fabric, for example under soaking conditions, can be evaluated by the following test method. Liquids are formed for soaking by diluting, for example, 45 g of the soaking compositions of the present in 3.78 liters of water or 90 g of the soaking composition in 45 liters of water. The fabrics are then immersed in the resulting soaking liquid for a time ranging from 1 minute to typically 18 hours.

Finally, the fabrics are removed from the soaking liquids, rinsed with water and washed in a regular washing procedure, by hand washing or washing, with a regular detergent, with or without reusing the soaking liquid, and then Fabrics are allowed to dry. For example, typical dirty fabrics that will be used in this stain removal performance test are commercially available from EMC (Empirical Manufacturing Company) Cincinnati, Ohio, USA; such as clay stains, grass, spaghetti sauce, dirty engine oil, meat sauce and blood on different substrates: cotton (CW 120) and polycotton (PCW28). The stain removal performance can be evaluated by comparing side by side the soiled fabrics treated with the composition according to the present invention with those treated with the reference, for example, the same composition without said dry effervescent granules according to the present invention. . A visual grading scale can be used to assign differences in panel scoring units on a scale of 0 to 4.

The thermal stability test method To evaluate the stability of a certain composition, a sample of the same can be placed in an oven whose temperature is set at 60 ° C.

When the sample reaches the temperature of the oven (60 ° C), it is isolated with an adiabatic campaign and its temperature is monitored for two hours. The self-heating speed is determined (SHR, average increase in temperature during the first two hours). The lower the SHR, the more stable the composition.

The effervescence test method The effervescence of a certain granular composition can be measured by visual grading. A composition in accordance with the present invention and a reference composition without the dried effervescent granules, or a reference composition in which the effervescent materials are uniformly and separately distributed in the complete granular composition, are each individually diluted in 5 liters of water at 35 ° C and the resulting carbon dioxide generation is evaluated by visual grading.

The dissolution test method The dissolution characteristics of a certain granulated composition can be measured by visual grading. A composition in accordance with the present invention and a reference composition without the dried effervescent granules, or a reference composition in which the effervescent materials are evenly and separately distributed in the complete granular composition, are each individually diluted in two liters of water at 5 ° C. Then the water is evaporated with a normal evaporator with a black cloth instead of a filter paper. A visual grading scale can be used to assign the differences in the panel determination units (psu), on a scale of 0 to 4.

The supply test method The supply can be evaluated by means of a standard test using a washing machine and by introducing a certain amount of composition into the dispenser and flowing water for a certain period of time. Then dry weight is measured of the laundry detergent composition remaining in the dispenser, in grams, and the percentage by weight of the composition not supplied in the washing machine is calculated.

Global density test method The overall density of the granular composition and / or dry effervescent granules of the present invention can be measured by means of a simple funnel-cup device consisting of a conical funnel rigidly molded on a base and provided with a butterfly valve at its lower end to allow the contents of the funnel to be emptied into an axially aligned cylindrical cup disposed below the funnel. The funnel measures 130 mm high and has internal diameters of 130 mm and 40 mm in its respective upper and lower extremities. It is mounted in such a way that the lower extremity is 140 mm above the upper surface of the base. The cup has a total height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml. To carry out a measurement, the funnel is filled with powder by hand, the butterfly valve opens and the powder is allowed to overfill the cup. The full cup is removed from the frame and excess powder is removed from the cup by basing a straight edge implement, eg, a knife, across its edge. higher. The filled cup is then weighed and the value obtained for the weight of the powder is doubled to provide a global density in g / liter. Equal measurements are made as required. The following examples will further illustrate the present invention.

EXAMPLES l) Soaking compositions The following soaking compositions were prepared by mixing the ingredients listed in the listed proportions. Inquirements 1 2 3 (% P / P) (% p / p) (% P / P) Sodium percarbonate 22 22 22 Ethoxylated alcohol EO 25 2 - - Ethoxylated alcohol EO 1 1 - 2 - Ethoxylated alcohol EO 50 - - 2 Anionic (LAS / AS / AES) 8 8 8 DTPA 0.2 0.2 0.2 TAED 8.3 5 5 Effervescent granule 20 10 10 dry Sodium bicarbonate (40%) Sodium carbonate (16%) Malic acid (44%) C. Minor and inert to 100 to 100 to 100 Inquirements 4 5 6 (% P / P) (% P / P) (% p / p) 2.5 - Sorbitan monostearate (SMS) - 3.0 - Eosin - 20 - sorbitan monostearate (SMS EO 20) - Sorbitan tristearate EO 0.5 - 3.0 (STS EO 20) Citric acid 10 10 10 Polyacrylate (Acusol 445 1 1 1 1 1 1 ND®) Silicate (amorphous; 1.6r) 0.4 0.4 0.4 Sodium percarbonate 31 31 31 NOBS 6 6 6 TAED 5 5 5 Anionic (LAS / AS / AES) 7 7 7 Alcohol EO 25 2 2 2 Effervescent granule 20 20 20 dry Sodium bicarbonate (40%) Sodium carbonate (16%) Malic acid (40%) Citric acid (4%) Others, c. minors and up to 100 up to 100 inerts Ingredients 10 11 12 (% v / v) (% v / v) (% v / v) Sodium percarbonate 45 40 35 Anionic (LAS / AS / AES) 8 8 8 DTPA 0.2 0.2 0.2 TAED 8.3 8.3 8.3 Brightener 0.15 0.15 0.15 Phthalocyanine sulphate of Zn 0.06 0.06 0.06 Enzymes (amylase, lipase, 1.9 1.9 1.9 protease) Dry effervescent granule 20 15 10 Sodium bicarbonate (40%) Sodium carbonate (16%) Malic acid (44%) C. Minor and inert to 100 to 100 to 10 ( TAED is tetraacetylethylene. NOBS is n-nonanoyloxybenzenesulfonate. NaPS is sodium paraffinsulfonate. DTPA is diethylenetriaminepentaacetic acid. LAS is C12 alkylbenzene sulfonate. Liquids are formed for soaking by diluting each time 45 g of the above compositions in between 3.5 lit. to 5.0 lit. of water. Then 0.5 to 2 kg of fabrics are dipped each time in said soaking liquid. The soaking periods for the soaking liquids comprising any of the soaking compositions 1 to 12 are typically from 1 minute to 24 hours. Finally, the fabrics are removed from the soaking liquids, rinsed with water and washed with a regular washing procedure, washed by hand or washed in a washing machine, with a regular detergent, with or without reusing the soaking liquid, and then said fabrics are allowed to dry. Excellent stain removal performance is obtained with these compositions on various stains including greasy stains and / or enzymatic stains and / or bleach stains and the like.

EXAMPLE OF THE METHOD FOR MANUFACTURING THE DRY FERTILE GRANULES IN ACCORDANCE WITH THE PRESENT INVENTION The following procedure can be carried out to form a dry effervescent granule consisting of 40% by weight of the total bicarbonate granule, 40% by weight of malic acid, 16% by weight of carbonate and 4% by weight of citric acid. In a first step, the respective ingredients are mixed together at respective levels. The mixture obtained is then incorporated into a Pharmapaktor L200 / 50P® commercially available from Hosokawa Bepex GmbH. The distance between the rollers is about 5 cm, the pressing force applied during the compacting step is about 60 kN, the speed of the roller is about 15 rpm and that of the feeding worm is about 14 rpm. In the Pharmapaktor L200 / 501® the mixture is forced between the compaction rollers in such a way as to form a compacted leaf / sheet. This flake / compacted sheet is then ground with a Flake Crusher FC 200® with a mesh size of 1.2 mm. A rod head is installed on the Flake Crusher FC 200®. The processing temperature is approximately 25 ° C. The resulting granules are then incorporated into a granular composition according to the present invention (for example, compositions 4 to 6 above).

II) Detergent compositions for laundry in washing machine In the detergent compositions, the abbreviated component identifications have the following meanings: LAS: Sodium linear alkyl C-2 alkyl acid benzenes: sodium tallow alkyl sulfate C45AS: Sodium linear alkylsulphate of C- j4-C-? 5 MONTH: C-t8 fatty acid a-sulfomethyl ester CxyEzS: C- | xC? branched sodium alkyl sulfate and condensed with z moles of ethylene oxide MBASx and: Sodium alkyl ethoxylated on the medium chain that has an average of x carbon atoms, of which an average of and carbons are included in the branching units (a) C48SAS: SodExS secondary C -C 8 sodium alcohoolsulfate: C14-C22 sodium alkyldisulfate of formula 2- (R). C4 H7 - 1, 4- (S? 4-) 2 where R = C? 00Cl8, condensed with z moles of ethylene oxide CxyEz: A branched primary alcohol of ClX -? And condensed with z moles of ethylene oxide QAS I : R2.N + (CH3) 2 (C2H4? H) with R2 = 50% -60% Cg; 40% - 50% C- | -i QAS II: R .N + (CH3) (C2H4? H) 2 with R = C12-C14 Soap: Linear sodium alkylcarboxylate derived from an 80/20 mixture of tallow and coconut oils TFAA I: alkyl N-methylglucamide C12-C14 TFAA II: C16-C18 alkyl N-methylglucamide TPKFA: Whole cut fatty acids of C-12-C 4 STPP: Anhydrous sodium tripolyphosphate Zeolite A Hydrated sodium aluminosilicate of the formula Na- | 2 (A102Si? 2) i2- 27H2O, which has a primary particle size on the scale of 0.1 to 10 microns. Zeolite A ll: Zeolite A I overdrawn NaSKS-6: Crystalline layered silicate of the formula d-Na 2 Si 2? Citric acid I: Citric acid anhydrous Citric acid II: Citric acid monohydrate Malic acid: Malic acid anhydrous Maleic acid: Maleic acid anhydrous Tartaric acid: Aspartic acid anhydrous Carbonate I: Anhydrous sodium carbonate with an average particle size of 200μm and 900μm Carbonate II: Anhydrous sodium carbonate with an average particle size of 100μm and 200μm Bicarbonate: Anhydrous sodium bicarbonate with a particle size distribution between 400μm and 1200μm Silicate: Amorphous sodium silicate (ratio 2.0; Si? 2: Na2? ) Sodium sulphate: Anhydrous sodium sulfate Citrate: Trisodium citrate dihydrate with 86.4% activity with a particle size distribution of between 425μm and 850μm MA / AA: Copolymer of 1: 4 maleic acid / acrylic acid with a molecular weight average of approximately 70,000 CMC: Sodium carboxymethylcellulose Protease: 4KNPU / g activity proteolytic enzyme marketed by Novo Industries A / S under the trade name of Savinase Alcalasa: 3AU / g activity proteolytic enzyme marketed by Novo Industries A / S Cellulase: Activity cellolytic enzyme 1000CEVU / g marketed by Novo Industries A / S under the trade name of Carezyme Amylase: Amylolytic enzyme activity 60KNU / g marketed by Novo Industries A / S under the trade name of Termamyl 60T Lipase: Lipolytic activity enzyme 100kLU / g marketed by Novo Industries A / S under the trade name of Lipolase Endolase: Enzyme endoglucanase activity 3000CEVU / g marketed by Novo Industries A / S PB4: Anhydrous sodium perborate tetrahydrate of nominal formula NaBO2.3H2O.H2O2 PB1: Anhydrous sodium perborate bleach monohydrate of nominal formula NaB? 2-H2? 2 Percarbonate: Sodium percarbonate of nominal formula 2Na2CO3.3H2? 2 NAC-OBS: (Nonamido caproyl) oxybenzenesulfonate in the form of sodium salt NOBS: Nonanoyloxybenzenesulfonate in the form of sodium salt DPDA: Diperoxydodecanoic acid PAP: N-phthaloylamidoperoxycaproic acid NAPAA: Nonanoylamidoperoxoadipic acid NACA: 6-Nonylamino-6-oxo-caproic acid TAED: Tetraacetylethylenediamine DTPMP: Diethylenetriaminepenta (methylenephosphonate) marketed by Monsanto under the trade name Dequest 2060.

Photoactivated bleach: Sulfonated zinc phthalocyanine encapsulated in soluble polymer in dextrin bleach Brightening 1: 4,4, -bis (2-sulphotryryl) biphenyl disodium Brightening 2: 4,4'-bis (4-anilino-6-morpholine-1.3) .5-triazin-2-yl) amino) ester-2: 2'-disulfonate HEDP: 1, 1-hydroxyethoxyphosphonic acid PVNO: N-oxide of polyvinylpyridine PVPVI: Copolymer of polyvinylpyrrolidone and vinylimidazole QEA: bs ((C2H5O) (C2H4O) n) (CH3) -N + -C6H12-N + - (CH3)) bis ((C2H5O) -C2H40) n). where n = from 20 to 30 SRP 1: Esters of blocked ends with structure of base of oxyethyleneoxy and terephthaloyl SRP2: Polymer of short block of poly (1,2-propylene terephthalate) diethoxylated Antifoam of Silicon: Controller of polydimethylsiloxane foam with a siloxane-oxyalkylene copolymer as a dispersing agent with a ratio of said foam controller to said dispersing agent from 10: 1 to 100: 1. In the following examples, all levels are cited in% by weight of the composition: The following granular detergent compositions for high density laundry A to F of particular utility were prepared under European washing conditions according to the invention: The following granular laundry detergent compositions according to the invention G a I were prepared, of particular utility under European washing conditions: The following are formulations for high density detergents and containing bleach in accordance with the present invention: The following are formulations for detergents in accordance with the present invention: The following are formulations for high density detergents in accordance with the present invention:

Claims (21)

NOVELTY OF THE INVENTION CLAIMS

1. - A dry effervescent granule comprising an acid, a carbonate source, preferably carbonate and / or bicarbonate, and optionally a binder, wherein said acid, carbon source and optionally binder are in close physical proximity.

2. A granule according to claim 1, which has a diameter size of 0.001 to 7 mm, preferably less than 2 mm.

3. A granule according to any of the preceding claims, having an overall density of 500 g / l at 1200 g / l, preferably from 700 g / l to 1 100 g / l.

4. A granule according to any of the preceding claims, which comprises from 0.1% to 99% by weight of the total granule, of the acid or a mixture thereof, preferably from 3% to 75%, very preferably from 5% to 75% by weight. % to 60% and more preferably from 15% to 50%, with the proviso that when the citric acid is present its level is preferably less than 20% by weight of the total granule.

5. A granule according to any of the preceding claims, further characterized in that the acid is a mono- or polycarboxylic acid or a mixture thereof, preferably citric acid, adipic acid, glutaric acid, 3-ketoglutaric acid, citralic acid, tartaric acid, maleic acid, fumaric acid, malic acid, succinic acid and / or malonic acid in its acid form, its salt forms (mono-, di- and tri- salts), in its anhydrous and / or hydrated forms.

6. A granule according to any of the preceding claims, which comprises from 0.1% to 99% by weight of the total granule, carbonate and / or bicarbonate, preferably from 30% to 95%, most preferably 45% by weight. 85% and more preferably 50% to 80%.

7. A granule according to any of the preceding claims, which comprises up to 50% by weight of the total granule, of a binder or a mixture thereof, preferably up to 35% and more preferably up to 20%.

8. A granule according to any of the preceding claims, further characterized in that the binder is selected from the group consisting of cellulose derivatives, carboxymethylcellulose and homo- and copolymeric polycarboxylic acid and its salts, alkyl- and alkylarylsulfonates and sulfates of C6 -C20, C10-C20 ethoxylated alcohols containing 5-100 moles of ethylene oxide per mole of alcohol, polyvinylpyrrolidones with an average molecular weight of 12,000 to 700,000, polyethylene glycols with an average weight of 600 to 10,000, copolymers of maleic anhydride with ethylene, methylvinyl ether, methacrylic acid or acrylic acid, C10-C20 mono- and diglycerol ethers, C10-C20 fatty acids and mixtures thereof, and preferably is C8-C20 alkylbenzenesulfonates.

9. - A process for manufacturing a dry effervescent granule according to any of claims 1 to 8, characterized in that said method comprises the steps of: - first mixing the acid, the carbon source and optionally the binder to form a mixture; - subjecting the mixture to an agglomeration step, preferably a pressure agglomeration step to form an agglomerated mixture, and finally the granulation of the agglomerated mixture in a granulation step.

10. A process according to claim 9, further characterized in that the overall density of the dry effervescent granule which has been subjected to said pressure agglomeration step is increased to 200 g / l, preferably from 10 g / l to 150 g / l. l, compared to the overall density of the resulting mixture comprising the acid and bicarbonate and / or carbonate, and optionally the binder, before being subjected to said pressure agglomeration step. 1.

A method according to claim 9 or 10, further characterized in that said pressure agglomeration step is a roller compaction step in which the resulting mixture is passed between compaction rollers under pressure., after which the compacted mixture (sheet / flake) obtained in this way is granulated to form dry effervescent granules and optionally screened.

12. A granulated composition comprising an effervescent material containing an acid and a carbonate source, whereby the acid and the carbonate source are present in a granule, and / or the acid and carbonate source are present by separated in the composition, characterized in that the effervescence index (El) is at least 10, the effervescence index (El) being El = (L x S x lOO) x (NC¡nt8r + NCin) M where L is the number of acidic acid groups having a pKa of less than or equal to 6, S is 3V (solubility in water of the acid in g / liter, at 25 ° C), M is the molecular weight of the acid, NCnter is the density of the contact points between the carbonate source and the acid, which are present separately in the composition, per mm3, and NC1ntra is (the weight fraction of the acid in said granule) x (the weight fraction of the carbon source in said granule) x 12.

13. A granular composition in accordance with n claim 12, further characterized in that the granule comprises a dry effervescent granule according to any of claims 1 to 8.

14. A granulated composition according to claim 12 or 13, comprising a dry effervescent granule and detergent ingredients. additional that can be obtained by means of a process comprising the step of first forming a dry effervescent granule according to any of claims 1 to 8, and then adding the granule to the additional detergent ingredients.

15. - A granulated composition according to any of claims 12 to 14, which comprises from 0.1% to 99% by weight of the total composition of the dry effervescent granule, preferably 2% by weight. 50%, most preferably from 3% to 25% and more preferably from 4% to 15%.

16. A granulated composition according to any of claims 12 to 15, which comprises an oxygenated bleach, preferably an alkali metal salt of precarbonate and / or perborate, up to a level of 80% by weight of the total composition, preferably from 2% to 45% and most preferably from 10% to 40% and preferably a bleach activator up to a level of 30% by weight of the total composition.

17. A granulated composition according to any of claims 12 to 16, which comprises at least one surfactant or a mixture thereof up to a level of 50% by weight of the total composition, preferably from 1% to 30%. % and most preferably from 5% to 20%, preferably comprising a nonionic surfactant.

18. A granulated composition according to any of claims 12 to 18, comprising the dry effervescent particle and a dry-added acid, preferably citric acid or malic acid, and / or a dry-added carbonate source.

19. A granulated composition according to any of claims 12 to 19, in the form of an extruded material or a tablet.

20. - A process of soaking fabrics, wherein said fabrics are submerged for an effective period of time in a soaking liquid comprising water and an effective amount of a detergent composition - N granules according to any of claims 12 to 19 above, and then removed from said soaking liquid.

21. The use of a dry effervescent granule according to any of claims 1 to 8 above, in a granular composition comprising an oxygenated bleach, preferably percarbonate and / or perborate, for improved thermal stability of said 10 composition under storage.