MXPA01005770A - Effervescence components - Google Patents

Abstract

The present invention provides an effervescence composition comprisingan acid source and a carbon dioxide source, wherein at least 85%of said acid source has a particle size from 0.1 to 150 microns, preferably from 0.5 to 100 microns. The carbon dioxide source is preferably also of a small particle size. The effervescence composition is in particular useful in solid detergent compositions. The effervescence component is preferably in the form of a granule comprising at least part of the acid source and the at least part of the carbon dioxide source. The effervescence component can also be coated by a coating comprising an alkoxylated alcohol having an alkoxylation degree of at least 20.

Description

EFFERVESCENCE COMPONENTS TECHNICAL FIELD The present invention is applicable to compositions that need 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 and any other compositions for home applications, in pharmaceutical preparations, dental preparations, food and similar. More 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 are to be used by the consumer after being typically diluted with water is their tendency to poor dissolution or poor assortment. This tendency has been exacerbated by the recent trend in for example the detergent industry towards granular compositions of higher volumetric density and towards granular detergent compositions having a higher content of active ingredients. Granular detergent compositions of high bulk densities in the range of 650 to 1100 kg / m3 are attractive to consumers but do not dissolve satisfactorily in the aqueous medium. Another difficulty with detergent compositions is that they do not flow easily from the drawer spout of a washing machine. Similar problems are encountered when granular detergent compositions are used in a dosing device in the washing drum. It is known to use citric acid and carbonate in powder compositions to promote the dissolution of for example pharmaceutical preparations and detergents by effervescence. A problem with such compositions containing particulate acid and carbonate may be poor storage stability when exposed to moisture, which leads to reduced effervescence. Therefore, it is suggested for example, EP 534525-A, to use citric acid of large particle size, which is said to be stable when exposed to moisture. However, the inventors have now surprisingly discovered that very small particle size acid materials provide improved effervescence. Surprisingly, they discovered that the small particle size acid can be used in compositions without incurring stability problems of the effervescence system, in contrast to the prior art teachings, while still providing effervescence more efficiently and rapidly. They have discovered that the incorporation of acid sources of very small particle size results not only in an improved assortment / dissolution compared to larger particle size acids, but also in improved, faster foam formation, which can be highly advantageous in certain applications. An improved effervescence performance and more efficient assortment and / or dissolution and / or foam formation is achieved when the carbon dioxide source is also of a small particle size. It can be highly preferred that the acid and carbon dioxide source be in intimate admixture, preferably in the form of a dry effervescence granule. This not only further improves the stability of the effervescence system, but also increases effervescence efficiency, thereby resulting in smaller amounts of acid source necessary for the desired effervescence, assortment / dissolution and / or foaming . Additionally, the inventors have discovered that it may be advantageous if the effervescence granule is of a large particle size, to obtain a more stable, better effervescent granule. The inventors have discovered surprisingly that when using small particle size acid sources, you can have a stronger and more homogeneous particle, thus improving effervescence performance. Additionally, when a compact effervescence granule is required, the compacting pressure can be reduced when using the small particle size acid source and optionally the carbon dioxide source of small particle size. Said granule dissolves more quickly and therefore provides an improved effervescence. Additionally, or alternatively, when the granule is made by agglomeration, it has been found to be beneficial to use the small granule size acids. In particular, it has been found that when a binder is used to form the agglomerates, the performance characteristics of the effervescence agglomerate are less affected by the binder when small acid material is incorporated than when using larger granule size material. Additionally, the inventors have discovered that when a coating comprising a specific alkoxylated alcohol is present on the effervescence component, or one or more ingredients thereof, this not only increases the stability of the effervescence component when exposed to moisture, but also Surprisingly it improves the production of foam of longer duration of high volume. The improved production of high volume long lasting foam by the coated effervescence component also has the additional benefit of giving a clear signal to the user that the detergent composition comprising the coated effervescence component has been dissolved and is now, or is ready to start, to clean dirty items. This is especially applicable in hand washing applications when the introduction of soiled articles in the wash cycle may not be optimal until the detergent composition has dissolved.

In addition, the selected alkoxylated alcohol mentioned above can act as a foam suppressant during the latter stages of the wash cycle, such as during rinsing, and therefore has a dual role in the wash cycle. The specific alkoxylated alcohol, by acting in this double manner, has a good impact on the formulation space, allowing more space for other optional detergent components, because it helps to deny the need for two constituents of separate detergent composition for production and suppression of foams.

BRIEF DESCRIPTION OF THE INVENTION The present invention provides an effervescence component comprising an acid source and a carbon dioxide source, wherein at least 75% of said acid source has a particle size of 0.1 to 150 microns, more preferably 0.5 to 100 microns. 100 micras In one embodiment, it is highly preferred that the carbon dioxide source have a volume average particle size of 5 to 375 microns, wherein preferably at least 60% has a particle size of 1 to 425 microns, or even preferably a mean particle size in volume of 10 to 250 microns, in which preferably at least 60% has a particle size of 1 to 375 microns. In a preferred embodiment the carbon dioxide source has a particle size similar to the acid source, preferably such that at least 60% or even 75% of the carbon dioxide source has a particle size of 1 to 150. microns, more preferably from 1 to 100 microns. In a highly preferred embodiment, the source of acid and the source of carbon dioxide are present in an intimate mixture with one another, preferably in a granule. The invention also provides a method for manufacturing said granule comprising the steps of: mixing the source of acid and the source of carbon dioxide and optionally a binder to form a mixture, then subjecting the mixture to a granulation step, which preferably comprises a compaction and / or agglomeration step to form a compacted and / or agglomerated mixture. Preferably the acid source is a particulate material that is first ground to obtain the acid source of the invention, before mixing with the carbon dioxide source. The source of carbon dioxide can also be obtained by grinding larger particle size material. The present invention also encompasses compositions that contain the effervescence component. In a preferred embodiment, the compositions are solid or non-aqueous detergent compositions, including laundry, pretreatment and dishwashing compositions, preferably solid compositions in the form of granules, tablet or stick. Additionally, the present invention also encompasses detergent compositions comprising a coated effervescence component, wherein the coating comprises an alkoxylated alcohol having a degree of alkoxylation of at least 20.

DETAILED DESCRIPTION OF THE INVENTION Source of acid Suitable acid sources herein are capable of providing solid, mineral or inorganic organic acids, and the sources are therefore preferably in the form of acids, salts or derivatives thereof or a mixture thereof. The derivatives include, in particular, ester of the acids. In particular, organic acids are preferred. It may be preferred that the acids are mono-, bi or tri-protonic acids. Such preferred 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, malonic acid. Such acids are preferably used in their acid forms, and it may be preferred that their anhydrous forms are used, or mixtures thereof. Preferred acid sources are maleic acid anhydrate and malic acid anhydrate. Other preferred acids include sulfonic acids such as toluene sulfonic acid. In a surprising way, it has now been discovered that using citric acid, tartaric acid, maleic acid and / or malic acid, improved physical and / or chemical stability is achieved with prolonged storage periods. Additionally, it has been found that these materials, in particular tartaric acid, have an improved dissolution, resulting in improved effervescence performance. The acid source and preferably the acid itself is a particulate compound of which at least 75%, preferably at least 85% or even at least 90% or even at least 95% or even at least 99% by volume, has a particle size from 0.1 to 150 microns and more preferably from 0.5 to 100 microns and it may even be preferred that at least 65% or even at least 75% or even at least 85% have a particle size of 1.0 to 75 microns or even from 1.0 to 55 microns or even from 1.0 to 25 microns. The particle size of the acid source and the present carbon dioxide source can then be determined by any method known in the art, in particular by laser light scattering or defraction technique, such as with equipment (or defractometer) of laser light scattering Malvem 2600 or Sympatec Helos.

At present it may be preferred that the acid source have a mean particle size by volume of between 1 to 120 microns or even between 5 to 75 microns or even between 5 to 55 microns or 5 to 30 microns. The average particle size by volume of the acid source and the carbon dioxide source can be determined by any method known in the art, in particular hereby using the laser light scattering equipment mentioned herein. , which is programmed to provide the average particle size in volume. The acid source herein is preferably obtained by grinding or milling raw acid source material, which has a larger particle size than the acid source herein, just prior to incorporation into the effervescence component. That is, it has been discovered that the handling of fine particle size acid sources in the present after storage can run into problems, and therefore it may be advantageous to store the acid source in a coarser form and crush this material before using it Carbon dioxide source Another essential feature of the present invention is a source of carbon dioxide. When used herein, the source of carbon dioxide includes any material that can provide carbon dioxide when reacted with an acid source upon contact with water.

This particular source includes carbonate, bicarbonate and percarbonate salts or mixtures thereof, in particular bicarbonate and / or carbonate. Carbonates suitable for use 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 alkali metal salt of bicarbonate such as lithium, sodium, potassium and the like, among which sodium bicarbonate and potassium are preferred. The bicarbonate may be preferred to be used in combination with or alternately carbonate, because it is more effective in weight. However, the selection of carbonate or bicarbonate or mixtures thereof in dry effervescent granules can be made depending on the desired pH in the aqueous medium in which the dry effervescent granules are dissolved. For example where a relatively high pH is desired in the aqueous medium (for example above pH 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 weight ratio of carbonate to bicarbonate of 0.1 to 10, more preferably 1 to 5 and more preferably 2. The source of carbon dioxide preferably has a mean particle size by volume of 5 to 375. microns, in which preferably at least 60%, preferably at least 70% or even at least 80% or even at least 90% by volume has a particle size of 1 to 425 microns. More preferably, the source of carbon dioxide has a volume average particle size of 10 to 250, preferably at least 60%, or even at least 70% or even at least 80% or even at least 90% in volume, has a particle size of 1 to 375 microns; or even preferably a volume average particle size of 10 to 200 microns, in which preferably at least 60%, preferably at least 70% or even at least 80% or even at least 90% by volume has a particle size of 1 to 250 microns. In a preferred embodiment the carbon dioxide source has a particle size similar to the acid source, preferably such that at least 60% or even 75% of the carbon dioxide source has a particle size of 1 to 150. microns, in which preferably the source has a mean particle size in volume of between 1 to 120 microns, but more preferably at least 60% or even 75% of the source having a particle size of 1 to 100 microns, has a mean particle size in volume of 5 to 75, or even preferably at least 60% or even 75% of the source has a particle size of 1.0 to 75 microns or even 1.0 to 55 microns or even 1.0 to 25 microwaves It may be preferred that the carbon dioxide source of the required particle size is obtained by grinding a material of larger particle size, optionally followed by selection of the material with the required particle size by any suitable method.

Intimate Mixture of effervescence / effervescent granule and process for its manufacture The source of acid and the source of carbon dioxide, or at least part thereof, are preferably present in an intimate mixture with one another, which means for purposes of the invention that the source of acid and the source of carbon dioxide are mixed in a homogeneous manner. Thus, in a highly preferred embodiment, at least part of the acid source and at least part of the carbon dioxide source are not discrete and separate particles. It is highly preferred that the source of acid and the source of carbon dioxide be present in an effervescent granule, preferably being a dry effervescence granule. The acid is preferably present in the intimate mixture or the effervescent granules at a level of 0.1 to 99% by weight of the total granule, preferably 3%, 75% more preferably 5% to 60% and more preferably 15% by weight. fifty%. The source of carbon dioxide is preferably present in the intimate mixture or the effervescent granules at a level of 0.1 to 99% by weight of the total, preferably 30% to 95%, more preferably 45% to 85% and more preferably 50%. % to 80%. By "dry" it is to be understood that the granule is substantially free of water, ie, that no water has been added or is present except for the moisture of the raw materials themselves. Typically, the water level is below 5% by weight of the total intimate mixture or granule, preferably below 3% and more preferably below 1.5%. It may be preferred that a desiccant be present in the intimate mixture or the effervescence granule, such as overorganic organic or inorganic salts, anhydrous salts, in particular silicates and overdosed aluminosilicates, anhydrous silicates and / or sulfate salts. For optimum effervescence in the aqueous medium the weight ratio of acid source to carbon dioxide source in the intimate mixture or the effervescent granule is preferably from 0.1 to 10, preferably from 0.5 to 2.5 and more preferably from 1 to 2. Effervescent granules are preferably obtainable by a process comprising a granulation step, preferably comprising the step of compaction of dry powder or agglomeration by pressure. Although all binding mechanisms can occur in pressure agglomeration, the adhesion forces between the solid particles, ie, between the acid, the carbon dioxide 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 new entities (ie, dry effervescent granules) from solid particles (ie, acid, bicarbonate, carbonate source and optionally the binder) applying external forces to densify a mass or volume more or less defined volume and create bonding mechanisms between the solid particles that provide resistance to the new entity, ie the high external force applied attracts close together the particles solid. The inventors have surprisingly discovered that in the present invention the reduced pressure may be sufficient to form a stable granule incorporating the small particle size acid source, preferably the carbon dioxide source of small particle size as defined above. The effervescent granules can have any particle size, the preferred particle size depends on the application and the granule component. In a preferred embodiment, the effervescence granule has a weight average particle size of 500 microns to 1500 microns in which preferably at least 70% or even at least 80% by weight of said granule has a particle size of 350 to 2000 microns, or even has a weight average particle size of 650 microns at 1180 microns in which preferably at least 70% or even 80% by weight of said granule has a particle size of 500 to 1500 microns, or even having a weight average particle size of 710 microns at 1000 microns in which preferably at least 70% or even 80% by weight of said granule has a particle size of 600 to 1180 microns. It has been found that the effervescence particles of those particle size parameters, comprising the acid source as defined herein, can not only provide improved assortment / dissolution but can also provide improved foam formation, including formation of faster foam, and / or improved foam. In another preferred embodiment, the effervescence granule preferably has a weight average particle size of 200 microns at 500 microns in which preferably at least 70% of said granule has a particle size of 100 to 710 microns, or even has a weight average particle size of 250 microns to 450 microns in which preferably at least 70% of said granule has a particle size of 150 to 650 microns. It has been found that the effervescence particles of those particle size parameters, comprising the acid source as defined herein, can provide better assortment and / or dissolution of the detergent composition than the larger effervescence particles, mentioned previously. The average weight particle size of the effervescence granule herein and the detergent granules herein can be determined by any method known in the art, in particular by screening a sample of the relevant particulate acid material in the present through a series of screens, typically 5, with grids of various diameters or opening sizes, obtaining a fraction number (thus having a particle size of up, down or between the grid sizes of the sizes of sieves used), which determines the weight (fractions by weight). The average particle size per fraction and then the average particle size in weight of the material can be calculated, taking into account the percentage by weight per fraction (for example, plotting the fractions by weight against the opening size of the sieves). The intimate mixture or the effervescent granules may optionally comprise a binder or a mixture of binders. Any binder material known in the art can be used. For example, highly suitable materials having a melting point above 40 ° C, but preferably below 200 ° C or 100 ° C. In general, the binders suitable for use herein are those known to those skilled in the art and may include anionic surfactants such as C6-C20 alkyl or alkylaryl sulfonates or sulfates, preferably C8-C20 alkyl benzene sulphonates, fatty acids, cellulose derivatives such as carboxymethylceulose and homo- or co-polymeric polycarboxylic acid or its salts, nonionic surfactants, preferably ethoxylates of C10-C20 alcohol containing from 5 to 100 moles of ethylene oxide per mole of alcohol and more preferably alcohols Primary ethoxylates of C15-C20 containing 20-100 moles of ethylene oxide per mole of alcohol. Of these, tallow alcohol ethoxylated with 25 moles of ethylene oxide per mole of alcohol (TAE25) or 50 moles of ethylene oxide per mole of alcohol (TAE50) are preferred. Other preferred binders include polymeric materials such as polyvinylpyrrolidones with an average molecular weight of 12,000 to 700,000 and polyethylene glycols with an average weight of 600 to 10,000. Copolymers of maleic anhydride with ethylene, methyl vinyl ether, methacrylic acid or acrylic acid are other examples of polymeric binders. Other additional binders include C10-C20 mono- and diglycerol ethers as well as C10-C20 fatty acids. It may be preferred that the effervescence granule comprises a coating agent, which may be selected from any coating agent known in the art. Preferred coating agents are materials that can be applied to the granule in the form of a casting, which is solid under ambient conditions, such as polymeric materials, nonionic surfactants. These materials can also be used as binding agents, which are described herein. Coating agents that can be applied to the granule in the form of an aqueous solution or a solution in an organic solvent, including organic or inorganic acids or salts, may also be preferred. Additionally, the granules can also be coated by powder with a particulate material on the granule, for example desiccants as described herein. It may be preferred that the intimate mixture or granule comprises other ingredients, such as detergent actives when used in detergent compositions. Surfactants (which may act as a binder and / or coating agents), bleaching components in particular bleach activators or precursors, catalysts or perhydrogen salts, perfumes, brighteners, builders, enzymes are preferred.

Typically, they comprise up to 70% by weight of the granule or total blend of one or more binders and / or other active ingredients, preferably up to 50% and more preferably up to 35%. • The present invention further encompasses a process for making the effervescent granules of the present invention comprising an acid, a source of carbon dioxide and optionally a binder, in which the acid, the source of carbon dioxide and optionally the binder They are in an intimate mix. This process preferably comprises the steps of: • 10 - first obtaining the acid source of the particle size defined herein, preferably by grinding larger particle size acid source material as commercially available, - mixing the source of acid obtained in this manner with the carbon dioxide source, preferably by grinding larger particle size acid source material as is commercially available, and optionally mixing a binder and / or other ingredients, to form a mixture, then subjecting the mixture to a granulation step, which preferably comprises the extrusion step, spheroidization, more preferably compaction or agglomeration.

Optionally, other ingredients can be added to the obtained granule, such as coating agents, which will be discussed in more detail later. By "granulation step" it means that the resulting mixture is made into granules of the required size as defined herein above. A preferred process to be used herein is roll compaction. In this process the sources of acid and carbon dioxide and optionally the binder and other ingredients, after mixing together, are forced between two compaction rollers which applies a pressure to said mixture so that the rotation of the rollers transforms the mixture in a compact sheet / flake.

This compact sheet / flake is then grainy. One way to accomplish this is to grind the compact flake / sheet or granulate the agglomerated mixture by conventional means. Grinding can typically be carried out with a Flake Crusher Fc 200® commercially available from Hosokawa Bepex GmbH. Depending on the final particle size desired for the effervescent granules, the ground material can be further screened. Said sieving of the dried effervescent granules can be carried out for example with a commercially available Alpine Airjet Screen® apparatus. According to this process the effervescent raw materials and optionally the binder if present are preferably mixed together without the addition of water and / or moisture other than that which comes from the raw materials themselves so as to obtain a powder mixture of dry free flow. Then this dry free-flowing powder mixture comprising the effervescent particles (ie the source of acid and carbon dioxide), and optionally the binder particles if present, undergo a granulation step, which preferably includes a step pressure agglomeration, ie a dry process step in which this mixture of free flowing powder suffers high external forces that attract the particles together closely thereby densifying the volumetric mass of said particles and creating bonding mechanisms between the solid effervescent particles and the binder if present. Typical roll compactors for use herein are for example Pharmapaktor L200 / 50P® commercially available from Hosokawa Bepex GmbH. The process variables during the pressure agglomeration step by means of roller compaction are the distance between the rollers, the feed rate, the compaction pressure and the roll speed. The typical feeding device is a feed screw. The distance between the screws is typically from 0.5 cm to 10 cm, preferably 3 to 7 cm, more preferably 4 to 6 cm. The pressing force is typically between 20 kN and 120 kN, preferably 30 kN to 100 kN, more preferably 40 kN to 80 kN, although lower pressures are possible and may be preferred in the present invention using fine particle size. Typically, the roll speed is between 1 rpm and 180 rpm, preferably 2 rpm at 50 rpm and more preferably 2 rpm at 35 rpm. Typically, the feed rate is between 1 rpm and 100 rpm, preferably 5 rpm at 70 rpm, more preferably 8 rpm at 50 rpm.

• The temperature at which the compaction is carried out is not relevant, 5 typically varying from 0 ° C to 40 ° C. It may be preferred that the granules are made under air drying, which have a humidity below 30%.

Coating of the Effervescence Component • It may be preferred that the effervescence component be coated by any coating agent known in the art or a mixture thereof. Preferably the coating comprises a surfactant and any other optional detergent ingredient. Normally, the surfactant forms at least 20% by weight of the coating, preferably > 75%, more preferably > 95% and even more preferably 100%. The surfactant may be any surface-active agent known in the art, preferably an alkoxylated alcohol, more preferably an alkoxylated alcohol with an average degree of alkoxylation of at least 20, more preferably at least 40, even more preferably from 50 to 80. Alcohoxy alcohol typically has a melting point of at least 40 ° C, preferably at least 50 ° C, more preferably 60 ° C to 70 ° C. Preferably, the alkoxy groups are ethoxy groups. The alkoxylated alcohol is derived from an alcohoxylated alcohol comprising a hydrocarbon group preferably comprising from 12 to 18 carbon atoms, preferably comprising a hydrocarbon chain of a length of 12 to 18 carbon atoms. The hydrocarbon chain may be linear or branched and includes all derivative forms obtainable by 12 to 18 carbon atoms in any configuration. ^ F 10 The coating is applied to the effervescence component by any method known in the art, preferably by spraying a molten form of the coating comprising the alkoxylated alcohol on the effervescence component. This involves melting the coating comprising the alkoxylated alcohol normally to a temperature of at least 40 ° C, preferably 50 ° C, more preferably from 60 ° C to 70 ° C. The spraying process can be any one known in the art, preferably by a hot melt spray gun spraying the coating in a rotating mixer containing the core, or by fluidized bed counterflow spray or a countercurrent forming type former, both of which spray the coating in a fluidized bed containing the effervescence component.

The effervescence component obtainable by the above process comprises coating on the surface, preferably such that the coating encloses the effervescence component, although the coating may also partially enclose the effervescence component. The coating may also enclose totally or partially any ingredient of the effervescence component, i.e. the source of acid and / or the source of carbon dioxide. Preferably, the coating is contacted with the effervescence component by any method known in the art. Usually to form an intimate mixture, preferably such that the coating partially or completely encloses the effervescence component. The coating is from 0.5% to 25% by total weight of the effervescence component, preferably from 2% to 10%. The coated effervescence component can be obtained by any process that involves the mixing of the ingredients, which can be part of a compression or tabletting process, extrusion process and agglomeration process. Preferably, the coated effervescence component is prepared by a process in which a melting of an ingredient is mixed with another ingredient whereby solid particles are formed simultaneously or subsequently., preferably by subsequently solidifying the melt, preferably by reducing the process temperature. When more than one ingredient is to be incorporated in the coated effervescence component the melt is preferably mixed with a premix of ingredients, which are premixed prior to mixing with the function, to obtain an intimate mixture of the ingredients prior to the addition of the foundry The ingredients mentioned above are a specific alkoxylated alcohol, a source of acid, a source of carbon dioxide, any other optional detergent ingredient, or any combination thereof. The effervescence component together with any other optional detergent ingredients can be part of a detergent composition for the application of hand washing and / or automated applications. In particular, the coated effervescence component comprising the specific alkoxylated alcohol can act to cause foaming during the washing cycle assortment stage and can also act as a foam suppressant during the later stages of the washing cycle. The final stages of the washing cycle being at least 5 minutes after the assortment stage.

DETERGENT COMPOSITIONS In a preferred embodiment the effervescence component or effervescence granules herein are comprised in a composition that requires assortment and dissolution in water, in particular in a shorter period of time and / or in cold water and / or at a lowest total effervescent / material particles. The effervescence component is preferably present at a level such that the acid source is present at a level of 0.5% to 40% by weight of the detergent component, more preferably 1% to 30% or even 2% to 25%, or even from 4% to 20% by weight; and so that the source of carbon dioxide is preferably present at a level of 1% to 60% by weight of the detergent composition, more preferably 2% to 50% or even 4% to 35% or even 6% to 30% by weight. In particular the effervescence components herein are incorporated into cleaning compositions such as laundry detergent compositions, pre-treatment compositions, hard surface cleaning compositions and dishwashing detergent compositions. In particular, non-aqueous liquid compositions and solid compositions, in particular granular compositions, tablets, extruded materials and bars are contemplated herein. The composition may comprise the acid source and the carbon dioxide source as separate particulate components. The compositions preferably comprise the effervescence component in the form of an effervescence granule. It may be preferred that all the acid of the composition be comprised in the dry effervescence granule. Alternatively, it may be preferred that the composition comprises an effervescence granule and a dry added acid and / or a dry added carbon dioxide source. In a preferred embodiment, the solid detergent composition herein comprises detergent-based granules, in which at least one comprises at least one effervescence component, preferably in granular form. Then, the detergent-based granules preferably have a weight average particle size of 350 microns to 4 mm, more preferably 500 microns to 2.5 mm or even 710 microns to 2 mm. Preferably, the effervescence component of the invention is present in a detergent granule comprising ingredients that may incur assortment or dissolution problems or which require more rapid dissolution, such as surfactants, in particular nonionic surfactants and / or anionic surfactants, and detergent actives such as bleach activators and mixtures of surfactants and builders, in particular aluminosilicate builder and anionic surfactants. This detergent-based granule can be made by any process and can comprise any detergent ingredient. It is preferred that the detergent base granule be made in a process in which the different detergent granules comprising different mixtures of detergent ingredients, preferably granulated by agglomeration, spray drying or extrusion, are mixed and compacted subsequently, agglomerated , spheronizer or marumerisen or are extruded, optionally with the addition of a binder. In this way, it may be preferred that the effervescence granule of the present and other granular detergent components be mixed with a binder and subsequently subjected to a granulation step, such as agglomeration, spheronization, or marumerization. It has been found that when the effervescence component of the invention is present in a granule of a large particle size, improved foam formation of the detergent composition is obtained. In this manner, the present invention provides a method for providing improved foaming of a detergent composition by incorporating an effervescence component of the invention into a detergent granule (including the effervescence component in granular form)., which is described herein) having a weight average particle size of 500 microns to 1500 microns in which preferably at least 70% of said granule has a particle size of 350 to 2000 microns, or even has a size of a weight average particle of 650 microns at 1180 microns in which preferably at least 70% of said granule has a particle size of 500 to 1500 microns. Furthermore, it has been found that when the effervescence component of the invention is present in a granule of a small particle size, a more efficient assortment and / or dissolution of the detergent composition is obtained. Thus, the present invention provides a method for providing improved assortment and / or dissolution of a detergent composition by incorporating an effervescence component according to any of claims 1 to 13 in a granule. • detergent having a weight average particle size of 200 microns 5 to 500 microns in which preferably at least 70% of said granule has a particle size of 100 to 710 microns, or even has an average particle size of 250 microns at 450 microns in which preferably at least 70% of said granule has a particle size of 150 to 650 microns. The granular compositions of the present invention can be prepared with different volumetric densities, preferably being from 300 to 1200 g / l, preferably from 500 to 1100 g / l. These compositions can be made by a variety of methods well known in the art, including dry blending, spray drying, Agglomeration and granulation and combinations thereof. In a preferred embodiment, the composition comprises from 0.1% to 99% by weight of the total composition of the effervescence or granule component, preferably from 2% to 50%, or even from 3% to 25% by weight. In a preferred embodiment, the composition comprises Preferably granules in which at least 60%, more preferably at least 80% by weight have an average particle size, by weight, from 600 microns to 1400 microns, preferably from 700 microns to 1100 microns or even from 750 to 1000 microns . It may be preferred that the compositions comprise less than 20% or even less than 10% or even less than 5% by weight of particulate components of a particle size of less than 300 microns, or even less than 425 microns or even less. 600 microns; it may also be preferred that the composition comprises less than 20% or even less than 10% or even less than 5% by weight of the composition, of particulate components of a particle size of more than 1700 microns, or even more than 1400 microns or even more than 1180 microns. The composition can be made by any method known in the art, including by agglomeration and / or spray drying, whereby certain ingredients can be mixed or sprayed as described herein. It may be preferred that the composition be made by mixing all or part of the granules, including those made by agglomeration or spray drying and even including the effervescence composition herein, and subsequently adding a binder and mixing or agglomerating the granules and binder to form the preferably agglomerated detergent granules. These can be of the required particle size or can be sifted to obtain particles of the required size. The compositions according to the invention may also contain additional detergent components. The precise nature of these additional components, and the levels of addition thereof will depend on the physical form of the composition or component, and the precise nature of the washing operation for which they are to be used.

When present in the detergent compositions, it may also be preferred that only less than 25% by weight of the detergent composition of hydratable inorganic salts be present. • mixed, being therefore present as separate particles, or even less than 25% by weight of the detergent composition of hydratable inorganic salts in the total composition. It may be preferred that an inorganic peroxygen bleach be present, whereby it is preferred that a percarbonate salt be present. In one embodiment of the invention, it may be preferred that the The detergent composition herein comprises one or more anionic surfactants and an aluminosilicate builder, whereby it is preferred that only small amounts of the aluminosilicate builder and the anionic surfactant are intimately mixed, i.e. less of 50% or even less than 30% of the The total amount of the anionic surfactant and less than 50% or even less than 30% of the total amount of aluminosilicate; it may even be preferred that the substantially non-anionic surfactant and the aluminosilicate builder be in an intimate mixture. Therefore, it may be preferred that the composition comprises at least two particles per comprising anionic surfactant or aluminosilicate. "Intimate mixture" means for purposes of the invention that the two or more ingredients of the component are substantially homogeneously divided into the component or particle. That is, it has been found that the solubility and / or the assortment of the composition is improved in this way. In another embodiment of the invention, it may be preferred that the # composition only comprises low levels of aluminosilicate builder 5, for example, less than 10% or even less than 5% by weight of the composition, whereby it is preferred that the composition comprises highly soluble builders, for example sodium citrate or citric acid, carbonate, and / or stratified crystalline silicate. It may also be preferred that the composition comprises a The builder system or as part of the builder system, an agglomerate comprising from 0.5% to 80% by weight of a layered crystalline silicate, preferably NaSKS-6, and from 10% to 70% by weight of a surfactant. , preferably an anionic surfactant, with which it may be preferred that less than 10% by weight of the agglomerate of free moisture, more preferably from 30% to 60% by weight of a layered crystalline silicate and from 20% to 50% by weight of an anionic surfactant. The effervescence component of the invention may contain one or more additional detergent components as described in The present invention and the detergent compositions herein preferably comprise one or more other ingredients selected from the following: Surfactant The components according to the invention and the compositions herein preferably contain one or more surfactants selected from anionic, nonionic, cationic, ampholytic, amphoteric and switerionic surfactants and mixtures thereof. A special list of anionic, non-ionic, ampholytic, and switerionic classes and species of these surfactants is given in the U.S. patent. 3,929,678 issued to Laughiin and Heuring on December 30, 1975. Additional examples are given in "Surface Active Agents and Detergents" (vol.1 and II by Schwatz, Perry and Berch). A list of suitable cationic surfactants is given in the U.S.A. 4,259,217 issued to Murphy on March 31, 1981. When present, the ampholytic, amphoteric and suteryionic surfactants are generally used in combination with one or more anionic and / or nonionic surfactants.

Anionic Surfactant The components according to the present invention and / or the detergent compositions herein preferably comprise an additional surfactant. Essentially any anionic surfactants useful for detersive purposes may be comprised in the detergent composition. These may include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di-, and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate, and sarcosinate surfactants. Anionic sulfate and sulfonate surfactants are preferred. The anionic surfactant is preferably present at a level of 0.1% to 60%, more preferably 1 to 40%, more preferably 5% to 30% by weight. Most preferred are surfactant systems comprising a sulfonate and sulfate surfactant, preferably a linear or branched alkylbenzene sulfonate and alkyl ethoxy sulfates, as described herein, preferably combined with cationic surfactants as described herein. Other anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, methyl tauride fatty acid amides, alkyl succinates and sulfosuccinates, sulfosuccinate monoesters (especially saturated and unsaturated C? 2-C? And monoesters), sulfosuccinate diesters (especially saturated and unsaturated C6-C? 4 diesters) and N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and hydrogenated resin acids and resin acids present in, or derived from, tallow oil.

Sulphonic Anion Surfactant Anionic sulfate surfactants suitable for use herein include primary and secondary, linear and branched alkyl sulphates, alkyl ethoxy sulphates, oleoyl glycerol fatty sulfates, alkylphenol ethylene oxide sulphates, acyl-N- ( C 1 -C 4 alkyl) of C 5 -C 17 and -N- (C 2 -hydroxyalkyl) glucamine sulphates, and alkyl polysaccharide sulfates, such as the alkyl polyglucoside sulphates (the non-sulphonated nonionic compounds described herein) Alkyl sulfate surfactants are preferably selected from the linear and branched C10-C18 primary alkyl sulfates, more preferably the C11-C15 branched chain alkyl sulphates, and the C ?2-C straight chain alkyl sulfates? . The alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of the C 1 or C 8 alkylsulphates > which have been ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkylethylsulfate surfactant is a C 11 -C 18 alkyl sulfate, more preferably C 11 -C 15, which has been ethoxylated with 0.5 to 7, preferably 1 to 5, moles of ethylene oxide per molecule. A particularly preferred aspect of the invention uses mixtures of the preferred alkyl sulfate and / or sulphonate and alkyl ethoxysulfate surfactants. Such mixtures have been described in PCT patent application No. WO 93/18124.

Sulfonate Anionic Surfactant Anionic sulphonate surfactants suitable for use herein include salts of C5-C20 linear alkylbenzene sulphonates, alkyl ester sulfonates, C6-C22 primary or secondary alkanesulfonates, C6-C2 olefinsulfonates, sulfonated polycarboxylic acids , acylglycerol fatty sulfonates, oleylglycerol fatty sulfonates, and any mixtures thereof.

Carboxylate Anionic Surfactant Suitable carboxylate anionic surfactants include alkyl ethoxy carboxylates, alkyl polyethoxy polycarboxylate surfactants and soaps ("alkylcarboxyls"), especially certain secondary soaps, as described herein. Suitable alkyl ethoxy carboxylates include those having the formula RO (CH2CH20) xCH2C00-M +, in which R is an alkyl group of C6 a of, x ranges from 0 to 10, and the distribution of ethoxylate is such that, on a base in weight, the amount of material where x is 0, is less than 20%, and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO- (CHR -.- CHR2-O) -R3, wherein R is an alkyl group of Ce to C-.8, x is from 1 to 25, Ri and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon it has between 1 and 8 carbon atoms, and mixtures thereof. Suitable soap surfactants include secondary soap surfactants that contain a carboxyl unit attached to a secondary carbon. Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps can also be included as suds suppressors.

Alkali metal sarcosinate surfactant agent Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON (R) CH2COOM, wherein R is a linear or branched C5-C17 alkyl or alkenyl group, R1 is an alkyl group of C? -C4, and M is an alkali metal ion. Preferred examples are myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.

Non-ionic alkoxylated surfactants Essentially any alkoxylated nonionic surfactants are suitable herein. Ethoxylated and propoxylated nonionic surfactants are preferred.

The preferred alkoxylated surfactants can be selected from the condensate classes of nonionic alkylphenols, nonionic ethoxylated alcohols, ethoxylated / propoxylated non-ionic fatty alcohols, ethoxylated / propoxylated non-ionic condensates with propylene glycol, and the ethoxylate condensation products. Non-ionic with propylene oxide / ethylene diamine adducts.

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

Non-ionic surfactant of polyhydroxy fatty acid amide The polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R2-CONR1Z wherein: R1 is H, hydrocarbyl of C -? -, 2-hydroxyethyl; 2-hydroxypropyl; ethoxy, propoxy, or a mixture thereof, preferably C1-C4 alkyl, more preferably C1 or C2 alkyl, most preferably C- alkyl. (ie, methyl); and R2 is a C5-C31 hydrocarbyl, preferably C5-C19 alkyl or alkenyl, more preferably straight-chain C9-C7 alkyl or alkenyl, most preferably straight-chain C11-C17 alkyl or alkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly attached to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Preferably, Z will be derived from a reducing sugar in a reductive amination reaction; more preferably, Z is a glycityl.

Non-ionic surfactant of fatty acid amide The 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 consisting of hydrogen, C1-C4, hydroxyalkyl of C -? - C4 and - (C2H40) xH, where x is on the scale of 1 to 3.

Alkylpolysaccharide Nonionic Surfactant The alkyl polysaccharides suitable for use herein are described in US Pat. 4,565,647, Filling, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms, and a polysaccharide, for example a polyglucoside, hydrophilic group containing from 1.3 to 10 units of saccharide. Preferred alkyl polyglycosides have the formula: R20 (CnH2nO) t (glucosyl) x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is 0 to , and x is from 1.3 to 8. The glucosyl is preferably derived from glucose.

Amphoteric Surfactant Amphoteric surfactants suitable for use herein include amine oxide surfactants and alkylamphocarboxylic acids. Suitable amine oxides include those compounds having the formula R3 (OR4) 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 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R 5 is an alkyl or hydroxyalkyl group containing from 1 to 3 carbon atoms, or a group of polyethylene oxide containing from 1 to 3 ethylene oxide groups. The alkyl dimethylamine oxide of C < α-C- | 8 and e 'acylamidoalkyldimethylamine oxide of CI Q-C-IS- A suitable example of an alkylalanodicarboxylic acid is Miranol (TM) C2M Conc., manufactured by Miranol, Inc., Dayton, NJ.

Zwitterionic Surfactant Zwitterionic surfactants may also be incorporated in the detergent compositions according to the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. The surfactants of sultaine and betaine are examples of zwitterionic surfactants that can be used herein. Suitable betaines are those compounds having the formula: R (R ') 2N + R2COO- in which R is a hydrocarbyl group of CQ-C < \ Q, each R1 is typically C-1-C3 alkyl, and R2 is a C-1-C5 hydrocarbyl group. Preferred betaines are the betaines of C12-C18 dimethyl ammonium hexanoate and the acylamidopropane (or ethane) dimethyl (or diethyl) betaines of C-io-C-jd. Also suitable for use in the present invention are complex betaine surfactants.

Cationic Surfactants Cationic surfactants suitable for use in the detergent compositions of the present invention include the quaternary ammonium surfactants. Preferably, the quaternary ammonium surfactant is a mono-based surfactant N-alkyl or alkenylammonium of C6-C16, preferably CQ-C < Q, in which the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. Also preferred are monoalkoxylated or bisalkoxylated amine surfactants. Another suitable group of cationic surfactants which can be used in the detergent compositions or components thereof in the present invention are cationic ester surfactants.The cationic ester surfactant is a compound, preferably dispersible in water , which has surfactant properties comprising at least one ester linkage (ie, -COO-) and at least one cationically charged group The appropriate cationic ester surfactants, including choline ester surfactants, have been described for example in US patents Nos. 42228042, 4239660 and 4260529. In a preferred aspect the ester linkage and the cationically charged group are separated from each other in the surfactant molecule by a spacer group consisting of a chain containing at least 3 atoms (ie, chain length of 3 atoms), preferably from 3 to 8 atoms, more preferred from 3 to 5 atoms, and most preferred still 3 atoms. The atoms forming the chain of the spacer group are selected from the group consisting of carbon, nitrogen and oxygen atoms and mixtures thereof, with the proviso that any nitrogen or oxygen atom in said chain is connected only with carbon atoms. In the chain. Therefore, spacer groups having, for example, -OO- (ie peroxide), -NN-, and -NO- bonds are excluded, while spacer groups having, for example, -CH2-O- bonds are included. CH2- and -CH2-NH-CH2-. In a preferred aspect the chain of the spacer group contains only carbon atoms, preferably the chain is a hydrocarbyl chain.

Cationic surfactants based on monoalkoxylated amine In the present invention, the cationic surfactants based on monoalkoxylated amine preferably of the general formula I are highly preferred: wherein R1 is an alkyl or alkenyl portion containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, more preferred from about 6 to about 14 carbon atoms; R2 and R3 are each independently alkyl groups containing from 1 to about 3 carbon atoms, preferably methyl, more preferably both R2 and R3 are methyl groups; R 4 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 an alkoxy group, especially an ethoxy, propoxy or butoxy group, and p is from 0 to about 30, preferably 2 to about 15. , more preferred 2 to about 8. Preferably the group ApR4 in formula I has p = 1 and is a hydroxyalkyl group, having no more than 6 carbon atoms in which the -OH group is separated from the ammonium nitrogen atom quaternary by not more than 3 carbon atoms Particularly preferred groups ApR4 are -CH2CH2OH, -CH2CH2CH2OH, -CH2CH (CH3) OH and -CH (CH3) CH2OH, with -CH2CH2OH being particularly preferred.The preferred R1 groups are linear alkyl groups Linear R1 groups having from 8 to 14 carbon atoms are preferred.More other preferred monoalkoxylated amine cationic surfactants for use in the present invention are of the formula ula wherein R1 is Cio-C-iß hydrocarbyl and mixtures thereof, especially C- o or -14 alkyl, preferably C10 alkyl and C? 2 alkyl, and X is any convenient anion to provide balance of charges, preferably chloride or bromide. As indicated, compounds of the above type include those in which the ethoxy (CH2CH2O) (EO) units are replaced with butoxy, isopropoxy [CH (CH3) CH20] and units (i-Pr) [CH2CH (CH30)] or n-propoxy units (Pr), or mixtures of units EO and / or Pr and / or i-Pr. The levels of the monoalkoxylated amine-based cationic surfactants used in the detergent compositions of the invention preferably range from 0.1% to 20%, more preferred from 0.2% to 7%, more preferred still from 0.3% to 3.0% by weight .

Cationic surfactant based on bis-alkoxylated amine The cationic surfactant based on bis-alkoxylated amine preferably has the general formula II: wherein R1 is an alkyl or alkenyl portion containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, more preferred from about 10 to about 14 carbon atoms; R2 is an alkyl group containing from 1 to 3 carbon atoms, preferably methyl; R3 and R4 can vary independently and are selected from hydrogen (preferred), methyl and ethyl; X "is an anion such as chloride, bromide, methylisulfate, sulfate or the like, sufficient to provide electrical neutrality.A and A 'can vary independently and each is selected from CrC4 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 to about 30, preferably 1 to about 4, and most preferred still both p and q are 1. The agents highly preferred bis-alkoxylated amine based cationic surfactants for use in the present invention are of the formula wherein R1 is C10-C? -hydrocarbyl and mixtures thereof, preferably C0, C2, C2 alkyl? and mixtures thereof. X is any convenient anion to supply charge balance, preferably chloride. With reference to the general cationic structure of bis-alkoxylated amine indicated above, since in a preferred compound R1 is obtained from the alkyl fractions of C ?2-Cu (coconut) fatty acids, R2 is methyl and ApR3 and A'qR4 they are each monoethoxy. Other cationic bis-alkoxylated amine based cationic surfactants useful in the present invention include compounds of the formula: wherein R1 is hydrocarbyl of C-.0-C-.8. preferably C 10 -C 14 alkyl, independently p is 1 to about 3 and q is 1 to about 3, R 2 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 (CH2CH0) (EO) units are replaced with butoxy (Bu) isopropoxy [CH (CH3) CH2O] units and units (i-Pr) [CH2CH (CH30)] or n-propoxy units (Pr), or mixtures of units EO and / or Pr and / or i-Pr.

BLENDING ACTIVATOR The components according to the present invention and / or the detergent compositions herein preferably comprise a bleach activator, preferably comprising a bleach precursor based on organic peroxyacid. It is preferable that the composition comprises at least two peroxyacid bleach precursors, preferably at least one hydrophobic peroxyacid based bleach precursor and at least one hydrophilic peroxy acid bleach precursor, as defined in US Pat. I presented. The production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. The bleach activator alternatively, or in addition, may comprise a preformed peroxy acid-based bleach. It is preferred that the bleach activator be present in a particulate component in the component or compositions herein. It is preferable that it be present as a mixed particle, separated. Alternatively, the bleach activator or part of it may be present in a detergent base particle. Preferably, at least one of the bleach activators, preferably a peroxy acid-based bleach precursor is present in a particulate component having an average particle size, by weight, of 600 microns at 1,400 microns, preferably 700 microns. microns to 1, 100 microns. Most preferably, all activators are present in one or more particulate components having the specified average weight particle size. Therefore, it is preferable that at least 80%, preferably at least 90% or even at least 95% or substantially 100% of the component or components comprising the bleach activator have a particle size of 300 microns at 1, 700 microns, preferably from 425 microns to 1, 400 microns. The precursor of bleaching based on peroxyacid hydrophobic preferably comprises a compound having an oxy-benzene sulfonate group, preferably NOBS, DOBS, LOBS and / or NACA-OBS, as described in the present.

The hydrophilic peroxy acid-based bleach precursor preferably comprises TAED, as described herein.

Peroxyacid-based blanket precursor Peroxyacid-based bleach precursors are compounds that can react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Peroxyacid precursors can generally be represented as: ° X-C-L wherein L is a leaving group and X is essentially any functionality, such that in perhydrolysis, the structure of the peroxyacid produced is: O II X-C-OOH For purposes of the invention, the hydrophobic peroxy acid-based bleach precursors produce a peroxy acid of the above formula wherein X is a group comprising at least 6 carbon atoms and a hydroxylic peroxy acid-based bleach precursor produces a bleach of peroxyacid of the above formula in which X is a group • comprising from 1 to 5 carbon atoms. The peroxy acid-based bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, most preferably from 1% to 15% by weight, most preferably from 1.5% to 10% by weight of the compositions . The ratio of hydrophilic to hydrophobic base precursors, when present, is preferably 10: 1 to • 10 1: 10, most preferably from 5: 1 to 1: 5 or even from 3: 1 to 1: 3. Suitable peroxyacid bleach precursor compounds typically contain one or more N-acyl or O-acyl groups, whose precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are described in GB-A-1586789. The esters • suitable are described in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

Outgoing groups The leaving group, hereinafter group L, must be sufficiently reactive so that the perhydrolysis reaction occurs within the optimum time frame (eg, a wash cycle). However, if L is very reactive, this activator will be difficult to stabilize to be used in a bleaching composition.

The preferred L groups are selected from the group consisting of: R3 and I I - O- CH = C- CH = CH ^ - O- CH = C- CH = CH- R3 OR Y - O - C: = CHR4. V - N-S-CH-R4 3 II ^ O and mixtures thereof, in which R1 is an alkyl, aryl or alkaryl group containing 1 to 14 carbon atoms, R3 is an alkyl chain that contains 1 to 8 carbon atoms, R4 is H or R3, and Y is H or a group solubilizer. Any of R1, R3 and R4 can be essentially substituted by any functional group including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkylammonium groups. The preferred solubilizing groups are -S? 3"M +, -C? 2" M +, - S? 4"M +, -N + (R3) 4X" and 0 < -N (R3) and most preferably -S? 3"M + and -C? 2_ +, wherein R3 is an alkyl chain containing 1 to 4 carbon atoms, M is a cation that provides solubility to the bleach activator and X is an anion that provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with more sodium and potassium being preferred, and X is a halide, hydroxide, methylisulfate or acetate anion.

Bleeding precursors based on alkenecarboxylic acid Bleach precursors based on alkylpercarboxylic acid form percarboxylic acids in perhydrolysis. Preferred precursors of this type provide peracetic acid in the perhydrolysis. Preferred alkylcarbaryl bleach precursors of the amide type include the N-, NN, N-tetraacetylated alkylene diamines in which the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group It contains 1, 2 and 6 carbon atoms. Particular preference is given to tetraacetylethylenediamine (TAED) as a hydrophilic peroxy acid-based bleach precursor.

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

Precursors of allylperoxy-substituted amide The amide substituted alkylperoxy acid precursor compounds are suitable herein, including those having the following general formulas: R1- C-N-R2- C- L R1- N-C-R2- C- L II II I- II II OR R5 O or R5 0 O wherein R1 is a haloaryl or alkaryl group having from 1 to 14 carbon atoms carbon, R2 is an alkylene, arylene and alkarylene group containing from 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl or alkaryl group containing 1 to 10 carbon atoms and L may be essentially any leaving group. R1 preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. R1 can be a straight or branched chain alkyl, aryl or substituted alkylaryl which contains branching, substitution or both and can be obtained from synthetic or natural sources including for example bait fat. Analogous structural variations are permissible for R2. R 2 may include alkyl, aryl, wherein R 2 may also contain halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R5 is preferably H or methyl. R and R5 must not contain more than 18 carbon atoms in total. Amide-substituted bleach activating compounds of this type are described in EP-A-0170386. It may be preferable that R1 and R5 together with the nitrogen and carbon atoms form a ring structure. Preferred examples of bleach precursors of this type include amide-substituted peroxyacid-based precursor compounds selected from (6-octanamido-caproyl) oxybenzene sulphonate, (6-decanamido-caproyl) oxybenzene sulfonate, and the most preferred sulfonate of ( 6-nonanamidocaproyl) oxybenzene and mixtures thereof as described in EP-A-0170386.

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

Precursors based on cationic peroxyacid Precursor compounds based on cationic peroxyacid produce cationic peroxyacids in perhydrolysis. Typically, cationic peroxyacid based precursors are formed by substituting the peroxyacid part of a suitable peroxyacid based precursor compound with a positively charged functional group, such as an ammonium or alkylammonium group, preferably an ethyl or methylammonium group. Cationic peroxyacid based precursors are typically present in solid detergent compositions as a salt with a suitable anion, such as a halide ion. The peroxyacid precursor compound to be cationically substituted can be a perbenzoic acid precursor compound or its substituted derivative as described herein. Alternatively, the peroxyacid-based precursor compound may be a precursor compound based on alkylpercarboxylic acid or a precursor based on alkyl peroxyacid substituted with amide as described herein. Precursors based on cationic peroxyacid are described in the patents of E.U.A. 4,904,406; 4,751, 015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; R.U. 1, 382.5694; EP 475,512, 458,396 and 284,292; and in JP 87-318,332. Examples of precursors based on cationic peroxyacid are described in UK patent application No. 9407944.9 and patent application of E.U.A. Nos. 08/298903, 08/298650, 08/298904 and 08/298906.

Suitable cationic peroxyacid-based precursors include any of the ammonium or alkylammonium sulfonates substituted by alkyl or benzoyl oxybenzene, N-acylated caprolactams, and benzoyl peroxides of monobenzoyltetraacetylglucose. Preferred cationic peroxyacid-based precursors of the N-acylated caprolactam class include trialkylammonium methylenebenzoylcaprolactam and trialkylammonium methylenealkylcaprolactam.

Precursors based on benzoxaxine organic peroxyacid The benzoxaxin type precursor compounds are also suitable, as shown for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula. wherein R-i is H, alkyl, alkaryl, aryl or arylalkyl.

Preformed organic peroxyacid The detergent composition may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid, typically at a level of from 1% to 15% by weight, most preferably from 1% to 10% by weight of the composition.

A preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulas: R1- C-N-R2-C-OOH R1- N-C-R2-C-OOH II I? II I tIII II O R5 O or F O O wherein R ^ is an alkyl, aryl or alkaryl group having from 1 to 14 carbon atoms, R2 is an alkylene, arylene and alkarylene group that it contains from 1 to 14 carbon atoms, and R is H or an alkyl, aryl or alkaryl group containing 1 to 10 carbon atoms. Amide-substituted organic peroxyacid compounds of this type are described in EP-A-0170386. Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanoic acid, diperoxytetradecanedioic acid and diperoxyhexadecandioic acid. Also suitable in the present invention are mono- and diperazelaic acid, mono- and diperbrasyl acid and N-phthaloylaminoperoxycaproic acid Peroxide source Inorganic perhydrate salts are preferred as a source of peroxide. Preferably these salts are present at a level of 0.01% to 50% by weight, most preferably from 0.5% to 30% by weight of the composition or component. Examples of inorganic perhidate salts include perborate, percarbonate, perfosphate, persulfate, and persilicate salts. The inorganic perhydrate salts are usually the alkali metal salts. The inorganic perhydrate salt can be included as the crystalline solid without additional protection. However, for certain perhydrate salts, the preferred embodiments of said granular compositions use a coated form of the material that provides better storage stability to the perhydrate salt in the granular product. Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as waxes, oils or fatty soaps. Sodium perborate is a preferred perhydrate salt and may be in the form of the monohydrate of the nominal formula NaB02H202 or the tetrahydrate NaBO2H2O2.3H20. The alkali metal percarbonates, particularly sodium percarbonate, are preferred perhydrates herein. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2CO3.3H202, and is commercially available as a crystalline solid. Potassium peroximonopersulfate is another inorganic perhydrate salt for use in the detergent compositions herein.

Dyes A preferred ingredient of the compositions herein are colorants and colored particles or specks, which may be sensitive to bleach. The colorant as used herein may be a coloring material or an aqueous or non-aqueous solution of a coloring material. It is preferable that the dye be an aqueous solution comprising coloring material, at any level to obtain the appropriate coloration of the detergent particles or specks, preferably so that the coloring solution levels are obtained up to 2% by weight of the coloring particle, or very. preferably up to 0.5% by weight, as described above. The colorant may also be mixed with a non-aqueous carrier material, such as non-aqueous liquid materials including nonionic surfactants. Optionally, the colorant also comprises other ingredients as organic binder materials, which can also be a non-aqueous liquid. The coloring material can be any suitable coloring material. Specific examples of suitable coloring matters include edible yellow E104 13 (yellow quinoline), edible yellow E110 3 (sunset yellow FCF), edible blue E131 5 (patent blue V), ultramarine blue (trade name), edible blue E133 2 (bright blue) FCF), E140- natural green 3 (chlorophyll and chlorophyllin), E141 and green pigment 7 (chlorinated Cu phthalocyanine). The preferred coloring matters can be blue paste Monastral BV (trade name) and / or green pigmasol (trade name). The detergent coloring particles or effervescence components preferably comprise up to 10% or more preferably up to 2% or up to 1% by weight of the colored particle or component.

Perfumes Another preferred ingredient of the component of the invention or of the compositions herein is a perfume or perfume composition. Any perfume composition can be used herein. Perfumes can also be encapsulated. Preferred perfumes are those which contain at least one component with a volatile low molecular weight component, for example having a molecular weight of 150 to 450 or preferably 350. Preferably, the perfume component comprises an oxygen-containing functional group, Preferred functional groups are functional groups of aldehyde, ketone, alcohol or ether or mixtures thereof.

Heavy metal ion sequestrant Heavy metal ion sequestrants are also useful additional ingredients in the present invention. By heavy metal ion sequestrant herein it means components that act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelating ability, but preferably show selectivity for binding heavy metal ions such as iron, manganese and copper. The sequestrants are not considered as detergency builders for the purposes of the invention. Heavy metal ion sequestrants are generally present at a level from 0.005% to 10%, preferably from 0.1% to 5%, more preferably from 0.25% to 7.5% and more preferably from 0.3% to 2% by weight of the compositions . Heavy metal ion sequestrants suitable for use herein include organic phosphonates, such as the aminoalkylene poly (alkylene phosphonates), alkali metal ethan-1-hydroxy diphosphonates, and nitrilotrimethylene phosphonates. Preferred among the above species are diethylenetriaminpenta (methylene phosphonate), ethylene diamine (methylene phosphonate), hexamethylenediamintetra (methylene phosphonate) and hydroxyethylene 1,1-diphosphonate, acid, 1-hydroxyethoediphosphonic acid and 1,1-hydroxynediimethylene phosphonic acid. Another heavy metal ion sequestrant suitable for use herein includes nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenediamine disuccinic acid, ethylene diamine diglutaric acid, 2-hydroxypropylenediamine diuccinic acid or any salt thereof.

Other heavy metal ion sequestrants suitable for use herein are the iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid-N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein. Sequestrants of β-alanine-N, N'-diacetic acid, aspartic acid-N, N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid described in EP-A-509,382 are also suitable. EP-A-476,257 describes suitable amino-based sequestrants, EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Also suitable are dipicolinic acid and 2-phosphonobutan-1, 2,4-tricarboxylic acid. Glycinamide-N-N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutharic acid (EDDG) and 2-hydroxypropylendiamin-N-N'-duccinic acid (HPDDS) are also suitable. Especially preferred are diethylenetriaminepentaacetic acid, ethylenediamine-N, N'-disuccinic acid (EDDS), 1,1-hydroxytenediphosphonic acid, and 1,1-hydroxygenatedimethylenephosphonic acid or the alkali metal, alkaline earth metal, ammonium or ammonium salts. substituted thereof, or mixtures thereof.

In particular, chelating agents comprising an amino or amine group can be sensitive to the bleach and are suitable for the compositions of the invention.

Enzymes Another preferred ingredient useful in detergent compositions is one or more additional enzymes. Additional preferred enzyme materials include commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases incorporated in conventional manner in detergent compositions. Suitable enzymes are discussed in U.S. Patent Nos. 3,519,570 and 3,533,139. Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinasa, Primasa, Durazim, and Esperasa by Novo Industries A / S (Denmark), those sold under the trade names of Maxatasa, Maxacal, and Maxapen by Gist- Brocades, those sold by Genecor International, and those sold under the trade name Opticlean and Optimase by Solvay Enzimes. The protease enzyme can be incorporated into the compositions according to the invention at a level from 0.0001% to 4% active enzyme by weight of the composition. Preferred amylases include, for example, α-amylases obtained from a special strain of S licheniformis described in more detail in GB-1, 269,839 (Novo). Preferred commercially available amylases include, for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl, Duramyl and BAN by Novo Industries A / S. The highly preferred amylase enzymes can be those described in PCT / US9703635, and in W095 / 26397 and W096 / 23873. The amylase enzyme can be incorporated into the composition according to the invention at a level from 0.0001% to 2% active enzyme by weight. The lipolytic enzyme may be present at active lipolytic enzyme levels from 0.0001 to 2% by weight preferably from 0.001% to 1% by weight, most preferably from 0.001% to 0.5% by weight. The lipase can be fungal or bacterial in origin obtained, for example, from a lipase-producing strain of the Humicola, Thermomyces or Pseudomonas species, including pseudomonas pseudoalcaligenes or Pseudomonas fluorescens. Also mutant or genetically modified lipases are useful herein. modified from these strains. A preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in the European patent granted, EP-B-0218272. Another preferred lipase herein is obtained by cloning the Humicola lanuginosa gene and expressing the gene in Aspergillus orvza, as a host as described in European patent application EP-A-0258 068, which is commercially available from Novo Industri A / S, Bagsvaerd, Denmark under the trade name lipolasa. This lipase is also described in the patent of E.U.A. 4,810,414, Huge-Jensen et al, issued March 7, 1989.

Optical brightener The detergent compositions herein also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners. The hydrophilic optical brighteners useful in the present • Invention include those that have the structural formula: • in which R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphino, chloro and amino; and M is a salt-forming cation such as sodium or potassium. When in the above formula Ri is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4'-bis ^ -anilino-e-ÍN ^ -bis-hydroxieti- s-triazin ^ -i aminoj ^^ '- stilbendisulfonic and disodium salt. This particular kind of brightener is marketed under the trade name Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions of the present invention. When in the above formula R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is the disodium salt of 4,4'-bis [(4-anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2 'acid -stilbendisulfonic. This particular kind of brightener is marketed under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation. When in the above formula Rj is anilino, R2 is morphino and M is a cation such as sodium, the brightener is the sodium salt of 4,4'-bis [(4-anilino-6-morphino-s-triazin -2-yl) amino] 2,2'-stilbenesulfonyl. This particular kind of brightener is marketed under the trade name Tinopal AMS-GX by Ciba-Geigy Corporation.

Photobleaching agent Photobleaching agents are preferred ingredients of the compositions or components herein. The preferred photobleaching agent herein comprises a compound having a porphyrin or porphyrin structure. Porphyrin and porphyrin, in the literature, are used as synonyms, but porphyrin conventionally represents the simplest porphyrin without any substituent; Porphyrin is a subclass of porphine. References to the porphine in this application will include porphyrin. The porphine structures preferably comprise a metal element or cation, preferably Ca, Mg, P, Ti, Cr, Zr, In, Sn or Hf, most preferably Ge, Si or Ga or most preferably Al, with Zn being most preferred. It may be preferable that the photobleaching compound or component is substituted with substituents selected from alkyl groups such as methyl, ethyl, propyl, t-butyl and aromatic ring systems as ^^^ 10 portions of pyridyl, pyridyl N-oxide, phenyl, naphthyl and anthracyl. The photobleaching compound or component may have solubilizing groups as substituents. Alternatively, or in addition to this the photobleaching agent may comprise a polymeric component capable of solubilizing the photobleaching compound, for example PVP, PVNP, PVI or its copolymers or their mixtures. Highly preferred photobleaching compounds are compounds having a phthalocyanine structure, which preferably has metal elements or cations described above. The metal phthalocyanines and their derivatives have the structure indicated in Figure 1 and / or Figure 2, wherein the atom positions of the phthalocyanine structure are conventionally listed.

The phthalocyanines can be substituted, for example, the phthalocyanine structures which are substituted at one or more of the positions of atoms 1-4, 6, 8-11, 13, 15-18, 20, 22-25, 27.

Water-soluble detergency builder composition The composition or compositions of the present invention preferably contain a water-soluble builder compound, typically present in detergent compositions at a level of 1% a 80% by weight, preferably from 10% to 60% is weight and most preferably from 15% to 40% by weight. The detergent compositions of the invention may comprise a phosphate-containing builder material. Present preferably at a level of 0.5% to 60%, or from 5% to 50%, or even from 8% to 40% by weight. The phosphate-containing builder material preferably comprises tetrasodium pyrophosphate, or more preferably anhydrous sodium tripolyphosphate. Suitable water-soluble builder compounds include the water-soluble monomeric polycarboxylates, or their acid forms, homopolymeric or copolymeric polycarboxylic acids or their salts wherein the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more than two. carbon atoms and mixtures of any of the foregoing.

The carboxylate or polycarboxylate builder may be of the monomeric or oligomeric type, although monomeric polycarboxylates are generally preferred for reasons of cost and performance. Suitable carboxylates containing a carboxy group include the water soluble salts of lactic acid, glycolic acid, and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid, malic acid and fumaric acid, as well as ether carboxylates and the sulfinylcarboxylates. Polycarboxylates or their acids containing three carboxy groups include, in particular, citrates, aconitrates and water-soluble citraconates, as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1, 379,241, lactoxysuccinates described in British Patent No. 1, 389,732, and aminosuccinates described in the Netherlands application 7205873, and oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in the patent British No. 1, 387,447. The most preferred polycarboxylic acid containing three carboxy groups is citric acid, preferably present at a level of 0.1% to 15%, most preferably 0.5% to 8% by weight. Polycarboxylates containing four carboxy groups include the oxydisuccinates described in British Patent No. 1, 261, 829, 1, 1, 2,2-ethane tetracarboxylates, 1, 1, 3,3-propane tetracarboxylates and 1, 2, 3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives described in British Patent Nos. 1, 398,421 and 1, 398,422 and in the US patent. No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1, 439,000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates. The mother acids of the monomeric or oligomeric polycarboxylate chelating agents or their mixtures with their salts, for example, citric acid or citric acid / citrate mixtures are also considered to be useful as builders components. Borate builder builders, as well as builders that contain borate-forming materials that can produce borate under detergent storage or detergent wash conditions, are water soluble builders useful herein. Suitable examples of water-soluble phosphate builders are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, potassium and sodium orthophosphate, sodium polymetaphosphate in which the degree of polymerization varies from 6 to 21, and salts of pítico acid.

Partially soluble or insoluble detergency metering compositions The component according to the present invention or the compositions herein may contain a partially soluble or insoluble builder compound, typically present in detergent compositions at a level of 0.5% to 60% by weight , preferably from 5% to 50% by weight, most preferably from 8% to 40% by weight. Examples of detergents mainly water-insoluble builders include sodium aluminosilicates. Suitable aluminosilicate zeolites have the unit cell formula Naz [(AIO) z (SiO2) y], xH2O, wherein z and y are at least 6; the molar ratio of z: y is from 1.0 to 0.5, and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material is in hydrated form, and is preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% of water in bound form. The aluminosilicate zeolites can be naturally occurring materials, but preferably are derived synthetically. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations zeolite A, zeolite B, zeolite P, zeolite X, zeolite HS, and mixtures thereof. Zeolite A has the formula: Na12 [AIO2) 12 (SiO2) 2]. XH2O wherein x is from 20 to 30, especially 27. The zeolite of X has the formula Na86 [(AIO2) 86 (SiO2) i06]. 276 H20 Another preferred aluminosilicate zeolite is the zeolite MAP builder. The zeolite MAP can be present at a level of 1% to 80%, most preferably from 15% to 40% by weight. Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon: aluminum ratio not greater than 1.33, preferably within the range of 0.9 to 1.33, and more preferably within the range of 0.9 to 1.2. Of particular interest is zeolite MAP which has a silicon: aluminum ratio not greater than 1.15 and, more particularly, not greater than 1.07. In a preferred aspect, the zeolite MAP builder has a particle size, expressed as a dso value of 1.0 to 10.0 microns, more preferably 2.0 to 7.0 microns, most preferably 2.5 to 5.0 microns. The value d5o indicates that 50% by weight of the particles have a smaller diameter than that figure. The particle size can be determined, in particular, by conventional analytical techniques such as micopic determination using a scanning electron micope or by a laser granulometer. Other methods for establishing the d50 values are described in EP 384070A.

Organic polymeric compound Organic polymeric compounds are preferred additional components of detergent compositions, and are preferably present as components of any particulate components, where they can act such as to bind the particulate component together. By "organic polymeric compound" is meant essentially any polymeric organic compound that are commonly used as dispersants and anti-redeposition agents and suspension of soils in detergent compositions, including any of the high molecular weight organic polymer compounds described as flocculating agents of clay in the present, including quaternized ethoxylated (poly) amine agent of dirt removal / anti-redeposition clay according to the invention. The organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1% to 30%, preferably from 0.1% to 15%, more preferably from 0.5% to 10% by weight of the compositions. Examples of organic polymeric compounds include organic homo- or copolymeric water-soluble polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from one another by not more than two carbon atoms. The polymers of the latter type are described as G B-A- 1596,756. Examples of such salts are polyacrylates of MW 1000-5000 and their copolymers with maleic anhydride, said copolymers have a molecular weight of 2000 to 100,000, especially 40,000 to 80,000. Polyamino compounds are useful herein, including those derived from aspartic acid such as those described in EP-A-305282, EP-A-305283 and EP-A-351629. Also suitable herein are terpolymers containing selected monomeric units of maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of 5,000 to 10,000. Other organic polymeric compounds suitable for incorporation into the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose. Additional useful organic polymeric compounds are the polyethylene glycols, particularly those with a molecular weight of 1000-10000, more particularly 2000 to 8000 and more preferably around 4000. The highly preferred polymeric components herein are cotton soil release polymers and do not cotton according to U.S. Patent No. 4,968,451, Scheibel et al, and the patent of U.S.A. No. 5,415,807, Gosselink et al, and in particular in accordance with the application of E.U.A. No. 60/051517.

Another organic compound, which is a preferred dispersing / anti-redeposition clay agent for use herein, may be the ethoxylated cationic diamines and monoamines of the fla: Wherein X is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or alkyl groups, and mixtures thereof, a is 0 to 20, pref 0 to 4 (e.g. ethylene, propylene, hexamethylene), b is 1 or 0; for cationic monoamines (b = 0), n is at least 16, with a typical scale of 20 to 35; for cationic diamines (b = 1), n is at least about 12 with a typical scale of about 12 to about 42. Other dispersing / anti-rejection agents to be used herein are described in EP-B-011965 and E.U.A 4,659,802 and E.U.A. 4,664,848.

Foam suppression system The detergent compositions of the invention, when flated for use in machine wash compositions, may comprise a foam suppression system present at a level of 0. 01% to 15%, preferably from 0.02% to 10%, more preferably from 0. 05% to 3% by weight of the composition.

The foam suppression systems suitable for use herein may comprise essentially any known antifoam compound, including, for example, silicone anti-foam compounds and 2-alkyl alkanol antifoaming compounds.

By "antifoam compound" is meant herein any compound or mixtures of compounds which act to depress the foaming or foaming produced by a solution of a detergent composition, particularly in the presence of the agitation of that solution. Particularly preferred antifoam compounds for use herein are the silicone anti-foam compounds defined herein as any antifoaming compound that includes a silicone component. Said silicone anti-foam compounds also typically contain a silica component. The term "silicone", as used herein and generally in the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl groups of various types. Preferred antifoam silicone compounds are siloxanes, particularly polydimethylsiloxanes having trimethylsilyl end blocking units. Other suitable antifoam compounds include the monocarboxylic fatty acids and the soluble salts thereof. 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 salts thereof, for use as foam 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 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), amino triazines N -alkylated such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiaminclortriazines fd as cyanuric chloride products with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, amide of acid bis stearic and the di-alkali metal monostearyl phosphates (eg, sodium, potassium, lithium) and phosphate esters. A preferred foam suppressor system comprises: (a) an antifoam compound, preferably a silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination: (i) polydimethylsiloxane, at a level of 50% to 99%, preferably 75% to 95% by weight of 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 anti-foam compound is incorporated at a level of 5% to 50%, preferably 10% to 40% by weight; (b) a dispersing compound, most preferably comprising a glycol silicone hardener copolymer having a polyoxyalkylene content of 72-78% and a ratio of ethylene oxide to propylene oxide of from 1: 0.9 to 1: 1.1, level from 0.5% to 10%, preferably 1% a 10% by weight; a particularly preferred glycol silicone hardener copolymer of this type is DC0544, commercially available from DOW Corning under the tradename DC0544; (c) an inert carrier fluid compound, most preferably comprising a C < 6-C- | 8 ethoxylated with a degree of ethoxylation from 5 to 50, preferably 8 to 15, at a level of 5% to 80%, preferably 10% to 70% by weight; A highly preferred particulate suppressant system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a point of Fusion on the scale of 50 ° C to 85 ° C, in which 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.

Other highly preferred foam suppression systems 5 comprise polydimethylsiloxane or mixtures of silicone, such as polydimethylsiloxane, aluminosilicate and carboxylic polymers, such as copolymers of laic acid and acrylic acid.

Polymeric Dye Transfer Inhibition Agents The component and / or compositions herein may also contain from 0.01% to 10%, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibition agents. The polymeric dye transfer inhibiting agents are preferably selected from N-oxide polymers of Polyamine, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof, in which these polymers can be interlaced polymers.

Polymeric agent that releases dirt 20 Polymeric agents that release dirt, from now on "SRA", may be optionally employed in the components or compositions herein. If used, the SRA's will generally comprise from about 0.01% to 10.0%, typically from about 0.1% to 5%, preferably from 0.2% to 3.0% by weight. Preferred SRA's typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit on and remain adhered to through hydrophobic fibers through the term of the wash and rinse cycles, thus serving as an anchor for the hydrophilic segments. This can make it possible for stains that occur after treatment with the SRA to be cleansed more easily in subsequent washing procedures. Preferred SRAs include oligomeric terephthalate esters, typically prepared by methods that include at least one transesterification / oligomerization, commonly with a metal catalyst such as a titanium (IV) alkoxide. Said esters can be manufactured using additional monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely intertwined overall structure. Suitable SRA's include a sulphonated product of a substantially linear ester oligomer formed from an oligomeric ester base structure of terephthaloyl and oxyalkylenoxy repeating units and sulfonated terminal portions derived from allyl covalently bonded to the base structure, for example, as described in the US patent 4,968,451, November 6, 1990 by J. J. Scheibel and E.P. Gosselink. Said ester oligomers can be prepared: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG") in a two step transesterification / oligomerization process; and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRA's include the 1,2-propylene / polyoxyethylene terephthalate polyesters of non-ionic blocked ends of the U.S. patent. No. 4,711, 730, of December 8, 1987 to Gosselink and others, for example those produced by the • 10 transesterification / oligomerization of polyethylene glycol methyl ether, DMT, PG and polyethylene glycol ("PEG"). Other examples of SRA's include: the oligomeric esters of anionic blocked ends partially and completely of the U.S. patent. No. 4,721, 580, from January 26, 1988 to Gosselink, such as oligomers of ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-hydroxyoctansulfonate; the non-ionic blocked block polyester oligomeric compounds of the U.S.A. 4J02.85J, • from October 27, 1987 to Gosselink, for example produced from DMT, PEG and EG and / or PG (Me) -blocked methyl or a combination of DMT, EG and / or PG, Me-blocked PEG and Na -dimethyl-5-sulfoisophthalate; and the 20 blocked terephthalate esters of the anionic ends, especially of sulfoaroyl of the U.S. patent. No. 4,877,896 of October 31, 1989 to Maldonado, Gosselink and others, the latter being typical of SRA's useful in both fabric conditioning and laundry products, one example being an ester composition made from the monosodium salt of the acid m-sulfobenzoic, PG and DMT, optionally but preferably further comprising added PEG, eg, PEG 3400. SRA's also include: simple copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide terephthalate or polypropylene oxide, see the EU patent No. 3,959,230 to Hays of May 25, 1976 and the patent of E.U. No. 3,893,929 to Basadur, July 8, 1975, cellulose derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; C1-C4 alkylcelluloses and C4 hydroxyalkylcellulas, see E.U.A. Do not. 4,000,093, from December 28, 1976 to Nicol, et al., And the methyl cellulosic esters having an average degree of substitution (methyl) per anhydroglucose unit of about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoises measured at 20 ° C as a 2% aqueous solution. Such materials are available as METOLOSE SM100 and METOLOSE SM200, which are the commercial brands of the methylcellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK. Additional classes of SRA's include: (I) non-ionic terephthalates using diisocyanate coupling agents to link the polymeric ester structures, see E.U. 4,201, 824, Violland et al. And E.U. 4,240,918 Lagasse et al., And (II) SRA's with carboxylate end groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. With the proper selection of the catalyst, the trimellitic anhydride forms bonds to the polymer terminals through a carboxylic acid ester isolated from the trimellitic anhydride instead of opening the anhydride linkage. Both non-ionic or anionic SRAs can be used as starting materials, as long as they have hydroxyl end groups that can be esterified. See E.U. No. 4,525,524 Tung and others. Other classes include (lll) anionic terephthalate-based SRAs of the urethane-linked variety, see E.U. 4,201, 824, Violland et al .; Other Optional Ingredients Other optional ingredients suitable for inclusion in the compositions of the invention include colors and filler salts, with sodium sulfate being a preferred filler salt. Extremely preferred compositions include from about 2% to about 10% by weight of an organic acid, preferably citric acid. Lesser amounts (for example, less than about 20% by weight), preferably combined with a carbonate salt, neutralizing agents, pH regulating agents, phase regulators, hydrotropes, enzyme stabilizing agents, polyacids, may also be present. foam-forming, opaque, anti-oxidant, bactericide and dye regulators, such as those described in U.S. Patent No. 4,285,841 to Barrat et al, August 25, 1981 (incorporated herein by reference).

Chlorine-based bleacher The detergent compositions may include as an additional component a chlorine-based bleacher. However, because the detergent compositions of the invention are solid, most of the liquefied chlorine-based bleaches will not be suitable for these detergent compositions and only granular or granular chlorine bleaches will be suitable. Alternatively, the detergent compositions can be formulated in a manner that is compatible with chlorine-based bleach, thereby ensuring that the user can add a chlorine-based bleach to the detergent composition at the start or during the washing process. The chlorine-based bleach is such that a kind of hypochlorite is formed in aqueous solution. The hypochlorite ion is represented chemically by the formula OCT. Bleaching agents that produce a kind of hypochlorite in aqueous solution include alkali metal and alkaline earth metal hypochlorites, hypochlorite addition products, chloramines, chlorimines, chloramides, and chlorimides. Specific examples of compounds of this type include sodium hypochlorite, potassium hypochlorite, calcium monobasic hypochlorite, dibasic magnesium hypochlorite, chlorinated trisodium phosphate dodecahydrate, potassium dichloroisocyanurate, sodium dichloroisocyanurate, sodium dichloroisocyanurate dihydrate, trichlorocyanuric acid, 1, 3. Dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, Chloramine T, Dicloramine T, chloramine B and Dicloramine B. A preferred bleaching agent for use in the compositions of the present invention is sodium hypochlorite, potassium hypochlorite, or a mixture of them. A preferred chlorine-based bleach may be Triclosan (tradename). Most of the bleaching agents that produce hypochlorites described above are available in solid or concentrated form and are dissolved in water during the preparation of the compositions of the present invention. Some of the above materials are available as aqueous solutions.

Laundry Method The laundry washing methods herein typically comprise treating soiled laundry with an aqueous washing solution in a washing machine having dissolved or dispensed therein an effective amount of a washing detergent composition. clothes in machine according to the invention. By an effective amount of the detergent composition is meant 10g to 300g of product dissolved or dispersed in a volume wash solution of 5 to 65 liters, as are the product dosages and typical wash solution volumes commonly employed in methods for Washing clothes in conventional machines. The preferred washing machines can be so-called low filling machines. In a preferred use aspect the composition is formulated in such a way that it is suitable for hard surface cleaning or hand washing. In another preferred aspect the detergent composition is a pretreatment or soaking composition, which is to be used to pretreat or soak dirty and soiled fabrics.

Abbreviations used in the examples of effervescence component and detergent composition LAS: Linear sodium alkylbenzene sulfonate of Cn-3 LAS (I): linear or branched potassium alkylbenzenesulfonate of Cp-? 3. TAS: Sodium alkyl sulphate CxyAS: Sodium alkylsulfate of C-fX-C- | and C46SAS: (2,3) secondary sodium alkyl sulfate of Cu-C-iß CxyEzS: Sodium alkyl sulfate of C- | x-C? and condensed with z moles of ethylene oxide CxyEz: Primary alcohol of C- | xC- | and predominantly linear condensed with an average of z moles of ethylene oxide QAS: R2.N + (CH3) 2 (C2H4OH) with R2 = C12 -C14 QAS 1: R2.N + (CH3) 2 (C2H4OH) with R2 = C8-Cn APA: Amidopropyldimethylamine of Cß-io Soap: Linear sodium alkylcarboxylate derived from an 80/20 mixture of coconut and tallow fatty acids STS: Sodium toluene sulfonate CFAA: (coco) (C12-C14) alkyl N-methyl glucamide TFAA: N-methyl alkyl glucamide of Ci6- - | 8 TPKFA: Whole cut fatty acids of C12-14 STPP: Anhydrous sodium tripolyphosphate TSPP: Tetrasodium pyrophosphate Zeolite A: Hydrated sodium aluminosilicate of the formula Na-12 (Al? 2Si? 2) i2 27H2O, which has a primary particle size in the range of 0.1 to 10 micrometers (weight expressed on an anhydrous basis) NaSKS-6: Crystalline layered silicate of formula d-Na2Si20s Citric acid I: Anhydrous citric acid, 80% having a particle size of 40 microns at 70 microns, and having a mean particle size in volume of 55 microns Citric acid II: Anhydrous citric acid or monohydrate, 80% having a size of particle from 15 microns to 40 microns, having an average particle size in volume of 25 microns Malic acid: anhydrous malic acid, 80% having a particle size of 50 microns at 100 microns, having a mean particle size in volume of 75 microns Maleic acid: Anhydrous maleic acid, 80% having a particle size of 5 microns at 30 microns, having a mean particle size in volume of 15 microns Tartaric acid: Anhydrous tartaric acid, 80% having a particle size of 25 microns at 75 microns, having a mean particle size in volume of 50 microns Carbonate I: Anhydrous sodium carbonate having 80% by volume of particles with a particle size of 50 miera sa 150 microns with a mean particle size in volume of 100 microns Carbonate II: Anhydrous sodium carbonate having 80% by volume of particles with a particle size of 35 microns to 75 microns, having a mean particle size by volume of 55 bromars Bicarbonate II: Anhydrous sodium bicarbonate having 80% by volume of particles with a particle size of 100 microns at 200 microns with a mean particle size in volume of 150 microns Bicarbonate Anhydrous sodium bicarbonate having 80% by volume of particles with a particle size of 15 microns at 40 microns, having a mean particle size in volume of 25 microns Silicate: Amorphous sodium silicate (Si? 2.'Na2? = 2.0: 1) Sulfate: Anhydrous sodium sulfate Mg sulfate: Anhydrous magnesium sulfate Citrate: Trisodium citrate dihydrate of 86.4% activity with a particle size distribution of between 425 μm and 850 μm MA / AA: Copolymer of maleic / acrylic acid 1: 4, average molecular weight of approximately 70,000 MA / AA (1): Copolymer of maleic / acrylic acid 4: 6, average molecular weight of approximately 10,000 AA: Sodium polyacrylate polymer of average molecular weight of 4,500 CMC: Sodium carboxymethylcellulose Cellulose ether: Cellulose methyl ether with a degree of polymerization of 650 available from Shin Etsu Chemicals Protease: Proteolytic enzyme, which has 3.3% by weight of active enzyme, sold by NOVO Industries A / S under the trade name Savinase Protease Proteolytic Enzyme, which has 4% by weight of active enzyme, as described in WO95 / 10591, sold by Genencor Int. Inc.

Alcalase: Proteolytic enzyme, which has 5.3% by weight of active enzyme, sold by NOVO Industries A / S Cellulase: Cellulite enzyme, which has 0.23% by weight of active enzyme, sold by NOVO Industries A / S under the trade name Carezyme Amylase : Amylolytic enzyme, having 1.6% by weight of active enzyme, sold by NOVO Industries A / S under the trade name Termamyl 120T Lipase: En2: lipolytic acid, having 2.0% by weight of active enzyme, sold by NOVO Industries A / S under the trade name Lipolase Lipase (1): Lipolytic enzyme, which has 2.0% by weight of active enzyme, sold by NOVO Industries A / S under the trade name Lipolase Ultra. Endolase: Enzyme endoglucanase, which has 1.5% by weight of active enzyme, sold by NOVO Industries A S PB4: Sodium perborate tetrahydrate of nominal formula NaB? 2-3H2? containing particles, the particles having a weight average particle size of 950 microns, 85% of the particles having a particle size of 850 microns to 950 microns PB1: Anhydrous sodium perborate bleach with nominal formula NaB 2-H2 2 containing particles, the particles having a weight average particle size of 800 microns, 85% of the particles having a particle size of 750 microns to 950 microns Percarbonate: Sodium percarbonate of nominal formula 2Na2C? 3.3H2? 2 containing particles, the particles having a weight average particle size of 850 microns , 5% or less having a particle size less than 600 microns and 2% or less having a size of more than 1180 microns NOBS: Nonanoyloxybenzenesulfonate in the form of a sodium salt comprising particles, the particles having an average particle size by weight from 750 microns to 900 microns NAC-OBS: (6-nonamidocaproyl) oxybenzenesulfonate comprising particles, the particles having a weight average particle size of 825 microns to 875 microns TAED Tetraacetiletilenediamine containing particles, the particles having a weight average particle size of 700 microns 1000 microns TAED I: Tetraacetylethylenediamine of a particle size of 150 microns to 600 microns DTPA: Diethylenetriaminpentaacetic acid DTPMP: Diethylenetriaminpenta (methylenephosphonate), marketed by Monsanto under the trade name Dequest 2060 Photoactivated bleach: Sulfonated sulfonated zinc phthalocyanine encapsulated in a bleach-dextrin-soluble polymer (l) Photoactivated bleach: Sulfonated alumina phthalocyanine encapsulated in a bleach-dextrin-soluble polymer (2) 1: 4,4'-bis Brightener (2) 2-sulphotyryl) biphenyl disodium brightener 2: 4,4'-bis (disodium 4-anyl-6-morpholino-1, 3,5-triazin-2-yl) stilben-2,2'-disulfonate EDDS : Ethylenediamine-N, N'-disuccinic acid, isomer (S, S) in the form of its sodium salt HEDP: 1, 1-hydroxydandiphosphonic acid PEGx: Polyethylene glycol with a molecular weight of x (typically 4,000) PEO: Polyethylene oxide , with an average molecular weight of 50,000 TEPAE: Tetraethylenepentamine-ethoxylate PVI: Polyvinylimidazole, with an average molecular weight of 20,000 PVP: Polyvinylpyrrolidone polymer, with an average molecular weight of 60,000 PVNO: Polyvinylpyridine N-oxide polymer, with a weight average molecular weight of 50,000 PV P VI: Copolymer of polyvinylpyrrolidone and vinylimidazole, with an average molecular weight of 20,000 QEA: bis ((C2H5?) (C2H4?) N) (CH3) -N + -C6H12-N + - (CH3) "10 bis ((C2H5?) - (C2H4? N)), where n = from 20 to 30 SRP 1: Anionically blocked poly esters at the ends SRP 2: Poly (1, 2 propylene terephthalate) short block polymer diethylated PEI: Polyethyleneimine with an average molecular weight of 1800 and an average degree of ethoxylation of 7 ethyleneoxy residues per nitrogen Silicone Antifoam: Foam controller based on polydimethylsiloxane with siloxane-oxyalkylene copolymer as an agent of Dispersion with a ratio of said foam controller to said dispersing agent from 10: 1 to 100: 1 Oparant: Mixture of water-based monostyrene-latex, sold by BASF Aktiengesellschaft under the trade name Lytron 621 Wax: Granule paraffin wax of effervescence Any of the effervescence granules I to XII The following effervescence granules I to XII are according to the invention (ingredients in% by weight of effervescence granule). The granules can be prepared by mixing the ingredients and agglomerating the ingredients or compacting the mixed ingredients, the second being the preferred procedure for preparing the particles I, IV and VIII. # excess dried or anhydrous salts / zeolite or zeolite dried in excess * non-ionic ethoxylated alcohol surfactant which has a degree of • average ethoxylation from 3 to 9, having an alkyl alcohol chain of 12 to 18 carbon atoms.

EXAMPLE 1 • 10 In the following examples all levels are expressed as% by weight of the composition: • TABLE I The following compositions are according to the invention. • 15 20 • • TABLE II The following compositions are according to the invention.

TABLE III The following are high density detergent formulations and contain bleacher according to the present invention: EXAMPLE 2 Coating of the effervescence component Condensate of tallow alcohol ethylene oxide (TAE) of tallow alcohol type condensed with 50 to 80 moles of ethylene oxide (TAE 50/80) is melted at 70 ° C. 4,750 kg of effervescence component (64% citric acid with 36% compacted sodium carbonate) are placed in a rotating drum mixer (Eirich) and the mixer is turned on but not adjusted for turn. This is to favor a gentle mixing of the "effervescent particles". 250g of melted TAE 50/80 is placed in a heated container (external water cover ~ 80 ° C) attached to a Devilbliss spray gun with atomization air at 80 ° C. This is to give 5% of APR 50/80 of the total weight. The drum mixer is turned on to spin and the molten TAE 50/80 is sprayed on the moving effervescence components in such a way that it adheres to the surface of the effervescence components, effectively coating the effervescence components. Once all the melted TAE 50/80 has been sprayed on the effervescence components, the drum mixer is allowed to spin until the TAE 50/80 has hardened on the surface of the effervescence components (i.e. that has solidified). The effervescence components coated with TAE 50/80 are sieved at 1180 microns to remove any agglomerated particles. This is particle XIII with respect to the examples.

Claims (20)

NOVELTY OF THE INVENTION CLAIMS

1. - An effervescence component comprising an acid source and a carbon dioxide source, wherein at least 75% of said acid source has a particle size of 0.1 to 150 microns, preferably 0.5 to 100 microns.

2. The effervescence component according to claim 1, further characterized in that the source of carbon dioxide has a mean particle size in volume of 5 to 375 microns, wherein preferably at least 60% has a particle size. from 1 to 425 microns, or even preferably a mean particle size in volume of 10 to 250 microns, wherein preferably at least 60% has a particle size of 1 to 375 microns, or even a mean particle size by volume from 1 to 120 microns, wherein preferably at least 60% has a particle size of 1 to 150 microns.

3. The component according to any preceding claim, further characterized in that the acid source comprises a sulfonic acid or mono or polycarboxylic acid or a mixture thereof, preferably citric acid, adipic acid, glutaric acid, ketoglutaric acid, citramalic acid, tartaric acid, maleic acid, fumaric acid, malic acid, succinic acid and / or malonic acid and / or toluenesulfonic acid in their anhydrous forms and / or in their hydrated forms, preferably citric acid, malic acid, maleic acid or tartaric acid or mixtures thereof. A.

The component according to claim 1, further characterized in that the effervescence component, or one or more of the source of carbon dioxide acid or source, is coated by a coating comprising an alkoxylated alcohol having a degree of of average alkoxylation of at least 20.

5. The component according to any preceding claim, further characterized in that the source of carbon dioxide comprises carbonate of. sodium or sodium bicarbonate or mixtures thereof.

6. The effervescence component according to any preceding claim, further characterized in that the source of acid and the source of carbon dioxide are in an intimate mixture with one another.

7. The effervescence component according to claim 6, further characterized in that the source of acid and the source of carbon dioxide are present in a granule, preferably having a weight average particle size of 500 microns to 1500 microns , wherein preferably at least 70% of said granule has a particle size of 350 to 2000 microns, or even having a weight average particle size of 650 microns to 1180 microns, wherein preferably at least 70% of said Granule has a particle size of 500 to 1500 microns.

8. The effervescence granule according to claim 6, further characterized in that the source of acid and the source of carbon dioxide are present in a granule having a weight average particle size of 200 microns at 500 microns, wherein preferably at least 70% of said granule has a particle size of 100 to 710 microns, or even having a weight average particle size of 250 microns to 450 microns, wherein preferably at least 70% of said granule has a particle size of 150 to 650 microns.

9. The granule according to any of claims 7 or 8, comprising from 30% to 95% by weight of the total carbon dioxide source granule, preferably 45% to 85% and most preferably 50% to 80% and from 3% to 75% by weight of acid source, preferably from 5% to 60%, or most preferably from 15% to 50%.

10. The granule according to any of claims 7 to 9 comprising up to 50% by weight of the total granule of one or more binders, detergent actives, preferably surfactants and / or bleaching agents, or mixtures thereof .

11. The granule according to claim 10, further characterized in that the binder is selected from the group comprising cellulose derivatives, carboxymethyl cellulose and homo- and copolymeric polycarboxylic acid and its salts, C6-C20 alkyl and alkylarylsulfonates and sulfates, C10-C20 alcohol ethoxylates containing -100 moles of ethylene oxide per mole of alcohol, fatty acids, 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 acid acrylic, mono and diglycerol ethers of C10-C20, C10-C20 fatty acids and mixtures thereof and preferably C8-C20 alkylbenzenesulfonates.

12. A process for manufacturing a granule according to any of claims 7 to 11 characterized in that said method comprises the steps of: grinding a source of crude acid to obtain an acid source wherein at least 75% has a size of particle from 0.1 to 150 microns, preferably from 0.5 to 100 microns; mixing said source of ground acid and the source of carbon dioxide and optionally the binder and / or other active ingredients to form a mixture; then subjecting the mixture to a granulation step, preferably comprising a compaction step and / or an agglomeration step.

13. The process according to claim 11 or 12, further characterized in that said step of granulation comprises a step of compaction by roller where the resulting mixture is forced between rollers of compaction under pressure, after which the mixture compacted obtained It is granulated in effervescent granules and is sieved optionally.

14. - A detergent composition comprising an efen / essence component characterized in that the effervescence component is coated by a coating comprising an alkoxylated alcohol having an average degree of alkoxylation of at least 20.

15. The detergent composition according to claim 14, comprising a coated effervescence component that can be obtained by a process comprising the following steps: (a) formation of a molten alkoxylated alcohol; (b) contacting the molten alkoxylated alcohol with an effervescence component.

16. The detergent composition according to claim 14 or 15, further characterized in that the coating is present at a level of 0.5% to 25% by weight of the effervescence component.

17. A detergent composition, preferably in the form of a liquid, non-aqueous, granular, tablet or stick composition, comprising the effervescence component according to any preceding claim, preferably at a level of 2% to 50% by weight of the detergent composition, most preferably from 3% to 25% and most preferably from 4% to fifteen%.

18. The granular detergent composition according to claim 17, further characterized in that at least one effervescence component, preferably in granular form, comprises at least one detergent-based granule, the base granule preferably having a size of weight average particle from 350 microns to 4 mm, most preferably from 500 microns to 2.5 mm or even from 710 microns to 2 mm.

19. A method for providing improved foaming of a detergent composition by incorporating an effervescence component according to any of claims 1 to 12 into a detergent granule having a weight average particle size of 500 microns at 1500 microns. , wherein preferably at least 70% of said granule has a particle size of 350 to 2000 microns, or even having a weight average particle size of 650 microns to 1180 microns, wherein preferably at least 70% of said Granule has a particle size of 500 to 1500 microns.

20. A method for providing improved assortment and / or dissolution of a detergent composition by incorporating an effervescence component according to any of claims 1 to 11 into a detergent granule having a weight average particle size of 200 microns. at 500 microns, wherein preferably at least 70% of said granule has a particle size of 100 to 710 microns, or even having a weight average particle size of 250 microns at 450 microns, preferably at least 70 % of said granule has a particle size of 150 to 650 microns.