MXPA02002396A - Bleaching detergent compositions. - Google Patents

Abstract

The invention relates to compositions comprising a peroxyacid bleach precursor, a peroxide source, at least 15 % by weight of a carbonate source, which may comprise the hydrogen peroxide source or part thereof, and at least 7 % by weight of an organic carboxylic acid whereby a 1 % solution of the composition in demineralised water provides a pH from 8.8 to 9.9. The compositions are useful to provide sanitisation of fabrics, in particular to reduce the activity of certain bacteria groups.

Description

COMPOSITIONS BLEACHING DETERGENTS TECHNICAL FIELD This invention provides specific sanitizing compositions and methods for improved fabric sanitization.

BACKGROUND OF THE INVENTION Traditionally, hard surface cleaners contain bleach as a cleaning agent and disinfectant. Generally, they contain high levels of chlorine bleach to achieve the required cleaning disinfection properties. Research has shown that hydrogen peroxide bleach in laundry detergents and dishwashing also has a disinfecting action and, very recently, detergent manufacturers have been interested in the disinfecting properties of these detergents. The precursors of the peroxyacid bleach are also known to provide antimicrobial action. However, not all bleaching systems that have sufficient disinfection properties are suitable for detergents: the bleach is not always compatible with other detergent ingredients, such as enzymes or in addition the levels of bleach required to obtain disinfection are too high and can damage the fabrics. The inventors found that the peroxyacid bleach precursors can be preferred bleaching species to provide sanitization of fabrics during washing. However, they have found that a problem with these bleach precursors is that they form the peroxyacid bleach at a high alkaline pH, but that at said high alkaline pH the peroxyacid which is found to be the active species that gives the benefits of sanitization is dissociates the inactive form, thus resulting in reduced sanitization. Also, a preferred bleach ingredient in detergents is a percarbonate salt. The percarbonate makes the solution very alkaline, which is, as stated above, not convenient when it is intended to maintain high levels of active species, ie, the peroxyacid itself, and therefore the antimicrobial performance thereof. Also many builders provide an alkaline pH in the wash, which is not convenient when looking for efficient sanitization. In addition, many detergent ingredients also require high alkaline pH conditions in the wash, which is not compatible with the preferred pH of the wash required to have a high peroxy acid level. Therefore, it is difficult to formulate detergents in such a way that preferably small amounts of peroxyacid bleach precursors provide efficient sanitization at the same time that excellent cleaning is achieved.

The inventors have also found a way to provide efficient antimicrobial performance or efficient sanitization while achieving good cleaning of bleachable and non-bleachable boats. They also found that when the pH of the detergent in the wash water is controlled, namely 8.8 and 9.9, preferably 9.0 to or even 9.85 or even 9.8, in particular it is achieved by using specific levels of acidic and alkaline ingredients and optionally regulators of pH, good sanitization and cleaning is obtained, while only limited amounts of precursor are required, making the compositions more stable to storage and safe to use. They found that these detergent compositions can even contain percarbonate bleach. The specific compositions of the invention are preferably used to effectively provide fabric sanitization or effectively inactivate microorganisms, in particular bacteria that are difficult to inactivate, such as in particular E. hirae, but also S. aureus, E. coli and P. aeruginosa.

BRIEF DESCRIPTION OF THE INVENTION The invention relates to a detergent composition for laundry or dishwashing comprising at least 15% by weight of a carbonate source and a bleaching system containing at least 2.5% by weight of a peroxyacid bleach precursor and a source of hydrogen peroxide, which may include a salt of a percarbonate and therefore may be part of the carbonate source, and at least 7% by weight of an acid, most preferably including an organic carboxylic acid, characterized in that a mixture of 1% Weight of the composition in demineralized water of a temperature of 20 ° C obtained after 10 minutes with stirring at a speed of 200 rpm, provides a pH of 8.8. to 9.9. The invention also relates to a method for providing sanitization during washing by the use of a composition of the invention and a method for inactivating E. hirae, S. aureus, E. coli and P. aeruginosa. The inventors have also found that when the laundry and dishwashing compositions of the invention are to be used in automatic laundry methods, the improved antimicrobial performance or sanitization of the fabrics is achieved when the composition is delivered directly into the laundry tub. the machine of the washing machine, for example during the use of an assortment device. One embodiment of the invention therefore relates to a washing method for washing fabrics by means of which the composition is introduced into the tub of a washing machine by placing an assortment device comprising the composition in the tub before the washing. introduction of washing water.

DETAILED DESCRIPTION OF THE INVENTION The composition of the invention is preferably such that a mixture of 1% of the composition in demineralized water, at a íAt-A k iti.Stitail, *. . * Me? ** & . «... ... .. i. _ «, -i *» ~ X * ^ »« «* ^ .i. «Fc tj.» 4 < Temperature of 20 ° C, obtained after 10 minutes of agitation at a speed of 200 rpm provides a pH of 9.0 to 8.85 or even 9.2 to 9.85 or even to 9.8, or even from 9.4 to 9.8. The pH is measured after stirring the mixture for 10 minutes at a constant temperature, by means of a conventional pH measurement method. By the term "1% mixture" is meant any mixture, expression or solution of a unit weight of the composition in 99 weight units of demineralized water, and therefore it should be understood that if the composition does not completely dissolve after 10 minutes, the pH is measured from said mixture or dispersion. When used herein, "reduction of microorganism activity" includes a reduction in activity as defined in the prEN 1276 method of CEN, (Européen Committee for Standardization) and the prEN 1650 method of CEN. The reduction in it is preferably represented as a reduction of the specific microorganism or bacterium by at least 105, most preferably at least 2 x 105, or most preferably at least 3 x 105. The reduction of the activity of the microorganisms when used herein includes the reduction of any of the procedures conducted by the microorganisms, including the secretion of products but preferably the growth of microorganisms. The invention also provides a method for reducing the activity of microorganisms, or preferably specific bacteria, comprising the steps of contacting the microorganism with an aqueous solution comprising the composition of the invention such that the peroxyacid a level of at least 100 ppm in the solution, per 106 microorganisms. Preferably, the composition is such that at least the activity of E. hirae, but most preferably also of S. aureus, E. coli and P. aeruginosa is reduced by at least 105, preferably at least 2 x 105 even 3. x 105 by the previous CEN method. In particular, the reduction of activity is done during a laundry procedure. Therefore, the position of the invention can be brought into contact with a specific microorganism in the form of a solid, but preferably, the bleaching agent is present in a solution in contact with the microorganisms. The specific microorganisms, preferably the specific bacteria, can be present on the surfaces to be cleaned and sanitized, for example on the fabrics to be cleaned in a laundry process. The bacteria may also be present in the solution used for the cleaning or sanitizing process or in the equipment used in the process, such as the washing machine or assortment device. The composition of the invention is particularly useful for activating microorganisms having cell walls comprising relatively high actual peptidoglycan microorganisms, in particular gram-positive bacteria which may be present in soils or spots on fabrics or surfaces, in particular in body soils. The amount of composition required to obtain an effective reduction of the activity of the specific microorganisms depends on several factors, such as the amount of microorganisms present, the conditions of the sanitization or cleaning process, including the other compounds present and the temperature of the process of cleaning. In the method of the invention, the solution used preferably comprises at least 100 ppm of peroxyacid per 106 microorganisms, most preferably at least 200 ppm, or even 250 ppm. The reduction of the activity of specific microorganisms that have cell walls containing peptidoglycan can be determined by the method of Petrocci and Clarke, as described in JOAC 1981, but is preferably determined for the purpose of this invention by the prEN1276,1993 method for bacteria and the prEN1650 method for yeasts. Said method of CEN involves, for example, the preparation of inoculum of gram-positive bacteria according to the method of CEN, pages 7 and later, preparation of a solution comprising the hydrophobic bleaching agent at a level of approximately 250 ppm, conducting the test by The CEN method, incubation TSA plates for 24 hours at 36 ° C; and subsequently counting bacterial colonies on the plates. This is compared to the results of the reference and the reduction in bacterial growth is calculated for the defined contact time. i? ,. .. á *.? M..i .. ^ - & a. Acids The composition comprises at least 7% by weight of one or more acids, preferably an organic acid, preferably including at least one organic carboxylic acid.The exact levels will depend on the others ingredients of the detergent composition and the alkalinity thereof, whereby the level of the acid is adjusted to provide the desired pH Preferably, the acid is present at a level of at least 8% by weight of the composition or even by at least 9% or even at least 10% by weight of the composition, as upper limit with a level of preferably 30% or even 20% by weight of the composition.Acts suitable for use include materials that not only help provide the required pH of the formulation, but also have a secondary function in the composition, such as acting as a chelating agent, builder and / or source of effervescence.The useful inorganic acids include boric acid, bisulfite salts, preferably sodium salts thereof. Preferably, the acid comprises at least one organic carboxylic acid. Said 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, but also polymeric polycarboxylic acids or oligomers, such as polymers of acrylic acid or polymers of maleic acid, or copolymers of maleic acid and acrylic acid.

Most preferably, the organic carboxylic acid herein comprises at least 7% by weight of the composition of maleic acid, malic acid or citric acid or mixtures thereof. It may be preferred that mixtures of organic carboxylic acids and inorganic acids are used, for example in a ratio of 1: 1 to 10: 1 or even 2: 1 to 5: 1. The acid may be present as separate components or in solid compositions of the invention, the acid may be incorporated into a granule together with other detergent ingredients. In the latter case, it may be preferred that the acid be a particulate material, whereby at least 75%, preferably at least 85% or even at least 90% or even at least 95% or even at least less 99% by volume, has a particle size of from 1 to 500 microns and most preferably from 1 to 350 microns and can even be preferred than at least 65%, or even at least 75%, or even at least 85% % have a particle size of 1.0 to 250 microns or even 1.0 to 150 microns. These particle sizes can be determined by any method known in the art in particular by laser light scattering or diffraction technique, such as Malvem 2600 or Sympatec Helos (or diffractometer) laser light scattering equipment. When the acid is present as a separate particle in the solid composition in the present invention, the average particle size distribution is preferably similar to the particle size distribution and average of the other components of the composition, as described further ahead. Salts of inorganic acids and / or salts or esters of organic carboxylic acids may also be present as additional components, in particular because it may be beneficial to regulate the pH of the composition at the required pH. For example, it may be preferred that the composition comprises a salt of citric acid, acid, maleic acid, malic acid, glutaric acid or tartaric acid or borate salt, or mixtures thereof.

Carbonate source The compositions of the present invention comprise at least 15% by weight of a carbonate source. The carbonate sources preferably contain carbonate, bicarbonate and percarbonate salts and preferably the carbonate source comprises a mixture of three salts. It should be understood that the carbonate salt when, is present, forms part of both the carbonate source and the hydrogen peroxide source as defined herein. Thus, in a preferred embodiment of the invention, the composition comprises a percarbonate salt to provide hydrogen peroxide and carbonate. For example, when the composition comprises at least 10% by weight of a percarbonate salt, as a source of hydrogen peroxide and a carbonate source, the composition also comprises at least 5% by weight of another carbonate source. t The level of carbonate source will depend on the nature of the detergent. Also, the percarbonate salt is used as a source of hydrogen peroxide, the reduced levels of other carbonate sources may only be necessary. Preferably, the composition comprises a mixture of carbonate sources, preferably including a carbonate salt, bicarbonate salt and percarbonate salt. In this way, the composition preferably comprises at least 5% by weight of a carbonate salt, at least 2% by weight of a bicarbonate salt and at least 8% by weight of a percarbonate salt, most preferably at least 7% by weight of a carbonate salt, at least 4% by weight of a bicarbonate salt and at least 15% by weight of a percarbonate salt. Suitable carbonate sources for use herein include carbonate, and alkali earth or alkali metal acid or bicarbonate carbonate and sodium and potassium salts. The inventors found that it may be particularly useful to include a bicarbonate salt in the compositions, since it has been found that the bicarbonate salt provides a regulated pH at about the value necessary to form the peroxyacids from the precursors, for example from TAED as described later. In the preferred embodiment of the invention, the composition comprises at least 1%, preferably at least 2% or even at least 4% by weight of the composition of an alkaline or alkaline earth salt of bicarbonate, preferably sodium bicarbonate. This salt may be present up to any level, preferably up to 20% by weight of the composition, most preferably up to 15% by weight or even up to 10% by weight of the composition. The carbonate, bicarbonate and percarbonate salts of the present invention may be present as separate particulate components or may be incorporated in detergent granules together with other detergent ingredients. The carbonate and bicarbonate material, when present in other detergent granules, can preferably have an average particle size of volume of 1 to 500 microns, preferably at least 60%, preferably at least 70% or even at least 80% or even at least 90% by volume, have a particle size of 0.5 to 1180 microns. Most preferably, the carbonate and bicarbonate salts have a volume average particle size of from 10 to 375, preferably at least 60% or even at least 70% or even at least 80% or even at least 90% by weight, has a particle size of 1 to 850 microns; or even preferably a volume average particle size of 10 to 250 microns, so preferably at least 60%, preferably at least 70% or even at least 80% or even at least 90% by volume has a particle size from 5 to 425 microns. It may be preferred that the required particle size of the carbonate and / or bicarbonate salt is obtained by grinding a material of larger particle size, optionally followed by the selection of the material with the required particle size by any suitable method.

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Preferably, the carbonate source is incorporated into the composition in a manner such that it is capable of reacting with the acid to provide effervescence upon contact with water.

Source of hydrogen peroxide The compositions of the invention comprise a source of hydrogen peroxide. Preferably, this is a persalt such as percarbonate, perbonate, perphosphate, peroximonopersulfate and persilicate salts. The inorganic perhydrate salts naturally are the alkali metal salts. The alkali metal salts of percarbonate, perborate or mixture thereof, are preferred inorganic perhydrate salts for use herein. The preferred perborate is sodium perborate in the form of monohydrate or tetrahydrate, respectively since the nominal formula NaBO2H2O2 and NaB02H202.3H20. Other suitable oxygen bleaches include persulfates, particularly potassium persulfate K2S2Os and sodium persulfate Na2S2O8. Highly preferred is the alkali metal salt of percarbonate, preferably sodium percarbonate, which then also forms part of the carbonate source, described above. Typically, the compositions in the present invention comprise from 5% to 50% by weight of the total composition of a source of hydrogen peroxide, preferably from 10% to 45% and most preferably from 15% to 35% by weight or even 17% or even 19% to 30% or even up to 25% by weight of the composition. The persalts can be coated by any coating material, preferably comprising a persulfate salt, such as magnesium persulfate or preferably a sulfate, carbonate or sodium bicarbonate salt or mixtures thereof. Preferred persalts and methods for making them are described, for example, in W097 / 35951, WO96 / 14388, WO97 / 19890, WO94 / 02568, EP891417-A, EP681557A.

Bleach precursors The granulated compositions herein comprise a peroxyacid bleach precursor. Preferably, the peroxyacid bleach precursor is present at a level of 3% to 10% or even 3.5% to 8% or even 4% to 6% by weight of the composition. Peroxyacid bleach precursors are compounds that react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally, peroxyacid bleach precursors may be represented as O II X-C-L where L is a residual group and X is essentially any functionality, such that during perhydrolysis the structure of the produced peroxyacid is O X-C-OOH Peroxyacid bleach precursor compounds typically they contain one or more N- or O- groups, said precursors can be selected from a broad spectrum 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. Suitable esters are described in GB-A-836988, 864798, 1147871, 2143231, and EP-A-0170386. The residual group, hereinafter group L, must be sufficiently reactive, so that the perhydrolysis reaction occurs within the optimum time frame (for example, a wash cycle). However, if L is too reactive, this activator will be difficult to establish for use in a bleaching composition. The preferred L groups are selected from the group consisting of: _N_¿_R1 -N? N -N-C-CH-R R3 Y _0_CH = C-CH = CH2 -O-CH = C-CH = CH2 And mixtures thereof, wherein R 1 is an alkyl, aryl or alkaryl group containing 1 to 14 carbon atoms, R 3 is an alkyl chain containing 1 to 8 carbon atoms, R 4 is H or R 3 , and Y is H or a solubilizing group. Any of R1, R3 and R4 can be substituted essentially by any functional group including, for example, alkyl, hydroxy, alkoxy, 15 halogen, amine, nitrosyl, amide and ammonium or alkylammonium. The preferred solubilizable groups are -SO3"M \ -CO2" M +, SO4"M \ - N + (R3) 4X" and 0 <l. -N (R3) 3 and most preferably -S03"M + and -C02" M + where R3 is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation that provides solubility to the bleach activator and X is an anion that provides 20 solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being more preferred, and X being a halide, hydroxide, methylisulfate or acetate anion. ____ __á _________ Í * a a. . «N ~ m ^ k. j? ^. i .. -. ace. .. «... *. ..., jt.! . -ni .. ^^ t .. .

Preferred examples of said compounds are tetraacetylethylene diamine (TAED), sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate, peroxyadipic acid nonylamide and n-nonanoyloxybenzene sulfonate (NOBS), decanoyloyloxybenzenesulfonate, dodecanoyloxybenzenesulfonate and acetyltriethyl citrate (ATC), N-nonanoyl phenolsulfonate ester -6-aminocaproic, diacyl-aliphatic peroxide (DAP) having the general formula RC (O) -OO- (O) C-R1, wherein R and R1 may be the same or different and are linear or branched aliphatic groups having 6 to 20 carbon atoms. Also particularly preferred are N-acylcaprolactam selected from the group consisting of benzoylcaprolactam, octanilcaprolactam, nonanoylcaprolactam, hexanoylcaprolactam, decanoylcaprolactam, undecenoylcaprolactam, formylcaprolactam, acetylcaprolactam, propanoylcaprolactam, substituted or unsubstituted butanoylcaprolactam pentanoylcaprolactam. Examples of other suitable compounds are described in British patent GB 1 586 769, GB 2 143 231, E.U.A. 4 818 425 and E.U.A. 4 259 201. The amido substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulas: R1 __c_-N -R2-C-L R1 -N-C-R2-C-L wherein R1 is an alkyl group with 1 to 14 carbon atoms, R2 is an alkylene group containing 1 to 14 carbon atoms and R5 is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any residual group, preferably an oxybenzenesulfonate. Amide-substituted bleach activator compounds of this type are described in EP-A-0170386. The nonamidocaproyloxybenzenesulfonate, preferably in the form of the sodium salt, NACA-OBS, is a preferred precursor of this type. A highly preferred bleach precursor here is TAED, NACA-OBS, DOBS and / or NOBS. The compositions herein may comprise blends of said bleach activators, since it has been found that this may result in improved sanitization. Highly preferred is a TAED mixture and a precursor selected from NOBS, DOBS or NACA-OBS. It has been found that additional improved sanitization is achieved when using such mixed precursor systems, particularly when the ratio of TAED to NOBS, DOBS or NACA-OBS is from 1: 2 to 2: 1. The precursor should be in the form of a separate detergent granule, which can be coated, or in the form of a detergent granule which also comprises other detergent actives. Preferably, it is present in the form of a particulate component having a particle size distribution similar in average particle size, like the other detergent particles. The inventors also found that it can be beneficial when the precursor and the source of hydrogen peroxide are present ^^^^^ s ^ N ^ gj ^^^^^^^^^^^ intimately mixed with each other, for example in a granule. This mixture or granule is preferably substantially free of organic acids. It should be understood that for the purpose of the invention, the peroxyacid formed from the precursor is not part of the acid component of the composition of the invention.

Laundry and dishwashing method The machine washing methods of the present invention only consist of treating soiled clothes or dishes with an aqueous washing solution and in a washing machine having dissolved or dispersed the same effective amount of a detergent according to the invention. In particular, the laundry washing methods are contemplated here. For example, an effective amount of the laundry detergent composition for laundry laundry is usually understood to be 10 g to 300 g of product dissolved or dispersed in a volume wash solution of 5 to 65 liters, since these are the doses of typical product and the volumes of washing solution commonly employed in conventional machine washing method. The dose depends on particular conditions such as hardness of the water and degree of soiling of the laundry. The reduction of the activity of the microorganisms present in the washing and in the dirty fabrics preferably takes place during a washing method, preferably an automatic or manual washing, at low temperatures up to 60 ° C or even up to 45 ° C or even about 30 ° C.

The detergent composition may be dispensed, for example, from the drawer spout of a washing machine or it may be sprayed onto the laundry placed on the machine. In a highly preferred aspect, an assortment device is used in the washing method to introduce the composition of the invention directly into the washing tub. It has been found that in this way improved sanitization is achieved. Any assortment device may be used, including preferred assortment devices for use with the composition of the invention that have been described in the following patents; GB-B-2,157 717, GB-B-2, 157, 718 EP-A-0201376, EP-A-0288345 and EP-A-0288346, W094 / 11562.

DETERGENT COMPOSITIONS The compositions of the present invention can be prepared with different bulk densities preferably from 300 to 1200 g / l, preferably from 500 to 1100 g / l or even from 550 g / l to 900 g / l. These compositions are preferably solid compositions, preferably solid laundry detergents, which can be made by a variety of methods well known in the art, including dry blending, extrusion drying, roll compaction, agglomeration and combinations thereof. The solid compositions may have any form, preferably granulated or in the form of a tablet or stick. t? : 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 subsequently adding a binder and mixing or agglomerating the granules and the binder to mix the preferably agglomerated detergent granules. This may be the required particle size or it may be sifted to obtain particles of the required size. In the highly preferred embodiment, the acid or part thereof, and the carbonate source or part thereof, are present in an intimate mixture with one another, preferably in a granule, which means for the purpose of the invention that the The acid and the carbonate source are preferably mixed uniformly. For optimum effervescence in the aqueous medium, the weight ratio of acid to carbonate source in the intimate mixture or the effervescent granule is preferably from 0.1 to 10, preferably from 0.5 to 2.5 and most preferably from 1 to 2. The acid is preferably present in said granule at a level of 5% to 85% by weight of the total granule, preferably from 10% to 75%, most preferably from 15% to 60% and most preferably still from 10% to 50%. The carbonate source is preferably present in said granule at a level of 5% to 90% by weight of the total, preferably from 10% to 80%, most preferably from 20% to 75% and most preferably still from 30% to 65% . The granule is preferably substantially free of water, i.e. no water has been added nor is another present other than the moisture of the fctj-fll ¡J ^ .A .-? - ^ s - ^ - -fc starting materials themselves. Typically, the water level is below 5% by weight of the intimate mixture or granule, preferably below 3% and most preferably below 1.5%. It may be preferred that the desiccant be present in the intimate mixture or the granule, such as excessively dried inorganic and organic salts, anhydrous salts, in particular excessively dried silicates and aluminosilicates, anhydrous silicates and / or sulfate salts. The granules can preferably be obtained by a process consisting of a granulation step, preferably comprising the step of compaction of dry powder or agglomeration under pressure. Although all the agglutination mechanisms can occur in the presence of agglomeration, the adhesion forces between the solid particles, that is, between the acid, carbonate source and optionally in binders 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) by applying external forces to densify a less densified mass or volume and create bonding mechanisms between the solid particles providing resistance to the new entity, i.e., the high external force applied leads the solid particles to be closely joined.

The effervescent granules optionally comprise a binder or mixture thereof. Typically, the granules comprise up to 50% by weight of the total granule of a binder or a mixture thereof, preferably up to 35% and most preferably up to 20%. Suitable binders for use herein are those known to those skilled in the art and include anionic surfactants such as alkyl or alkylaryl sulfonates or C6-C2o sulfates, preferably C8-C2o alkylbenzenesulfonate, cellulose derivatives such as carboxymethylcellulose and homopolymeric or copolymeric polycarboxylic acids or its salts, nonionic surfactants, preferably C? or C Co-ethoxylated alcohols containing from 5 to 100 moles of ethylene oxide per mole of alcohol and preferably the primary alcohols of C?-C2o ethoxylates containing from 20 to 100 moles of ethylene oxide per mole of alcohol. Of these tallow alcohol ethoxylated with 25 moles of ethylene oxide per mole of alcohol (TAE 25) or 50 moles of ethylene oxide per mole of alcohol (TAE 50) are preferred. Other preferred binders include polymeric materials or polyvinylpyrrolidones with a 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 monoglycerol and diglycerol ethers of C? 0-C20, as well as C? 0-C20 fatty acids. ÍU *. * * ?. Í ~? +? * ¿* ^ .... ^ .. "....,. -. . . > .__ ,, ... ... ^. . »_ .. ,; t -? to? ri? t Effervescent granules can have any particle size, the preferred particle size depending on the application and the granule component. The inventors have found that it may be beneficial for the sanitizing and cleaning performance that the acid of the present invention is separated from the precursor and preferably any other bleaching components present including any source of hydrogen peroxide including percarbonate salt if present. In this way, the effervescence granules described above; they preferably do not comprise percarbonate salt as a carbonate source, but preferably comprise carbonate salts and / or bicarbonate salts. In the preferred embodiment, the composition preferably comprises granules wherein at least 60%, most preferably 80% by weight have an average particle size, by weight, from 400 microns to 1400 microns, preferably from 500 microns to 1100 microns or even 750 to 1000 microns. It may be preferred that the compositions comprise less than 20% 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 of 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, the particle components of particle size of more than 1700 microns, or even more than 1400 microns or even more than 1180 microns.

In this way, the compositions may comprise different granular components, each having the above particle size requirements, and therefore have a particle size distribution similar to a similar average particle size. The inventors found that improved sanitization is achieved when the composition contains perfumes or perfume components with a high cloth substantivity. It is believed that this is due to the perfume oils that remain on the surface of the washed fabric and that therefore can provide sanitization during subsequent use of the fabric. Said preferred perfume granules of encapsulated perfume oils are described in European patent application 98870137.1. Preferred levels of perfume granules will depend on the level of perfume oils therein, but generally the level is around 0.05 to 8% or even 0.5% to 5% or even 0.8% to 3% by weight of the composition. In addition, preferably the composition also comprises perfume components that are not in the form of encapsulated perfume oil granules, but preferably are in the form of perfume components sprayed onto the detergent granules of the composition. The compositions herein preferably contain one or more additional detergent components selected from surfactants, bleach catalysts, soil suspending and anti-redeposition agents, soil release agents, brighteners, photobleaching agents and additional corrosion inhibitors. .t ^ .A ... Í ... .. ... you .. ^^. It should be understood that the levels of detergent ingredients will be chosen such that the pH of 1% by weight of the composition in demineralized water is as defined above. For example, it may be preferred that when crystalline layered silicates or amorphous silicates are used, the level thereof is up to 12% by weight or up to 10% by weight.

Surfactant The detergent compositions herein preferably contain one or more surfactants. The surfactant may comprise any surfactant known in the art selected from anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof. It should be understood that for the purpose of the invention the detergent composition may comprise surfactant which is not present in the intimate mixture with the crystalline layered silicate but which is present in the other detergent components.

Anionic Surfactant The compositions according to the present invention preferably comprise an anionic surfactant. Essentially any anionic surfactants useful for detersive purposes can be contained 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. Highly preferred are the surfactant systems comprising a sulphonate 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. Highly preferred herein are anionic sulfonate surfactants. Particularly suitable for use herein include salts of linear or branched C5-C2al alkylbenzene sulphonates, but also alkylesters sulfonates, primary or secondary C6-C22 alkanesulfonates, Cs-C24 olefinsulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, acyl glycerol sulfonates. fatty acids, fatty oleylglycerolsulphonates and mixtures thereof. Very preferred are linear alkylbenzene sulphonates of Cg-C-? . The anionic sulfate surfactants to be used herein include the straight and branched chain primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleoyl glycerol sulfates, ethylene oxide alkylphenol ether sulfates, the C-C acyl-N- (CrC4 alkyl) glucamin sulphates. ? and -N- (CrC2 hydroxyalkyl) glucamin sulfates, and sulfates or alkylpolysaccharides such as alkylpolysaccharide sulfates such as alkyl polyglucoside sulfates (the non-sulfated nonionic compounds being described herein). i «itt.¿fa¿..i -,? JJ fl.t» -S, ?? *? -. í *. . *** ~ Aa *? »... ..... * ~. . . t. -. . - -. ..- > ".. ... ..«. «I-. -i > . & * i i? The alkyl sulfate surfactants are preferably selected from straight-chain or branched-chain primary alkyl do-C-iß sulfates, most preferably the branched chain alkyl sulfates of C11-C15 and straight chain alkyl sulfates of C? 2-C? . The alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of C10-C18 alkyl sulphates which have been ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. Most preferably, the ethoxysulfate surfactant is a Cn-C18 alkyl sulfate, most preferably C1-C15 alkyl which has been ethoxylated with 0.5 to 7, preferably 1 to 5 moles of ethylene oxide per molecule. A particularly preferred aspect of the invention employs mixtures of the alkyl sulfate and / or sulfonate and alkyethoxysulfate surfactants. Such mixtures have been described in PCT patent application No. WO 93/18124. Highly preferred here, in particular to provide an improved surfactant performance, are the alkyl chain, branched, chain-middle surfactant compounds of the formula R R1 2 I I I CH3CH2 (CH2) wCH (CH2)? CH (CH2) and CH (CH2) r wherein the total number of carbon atoms in the primary alkyl portion of this formula (including the R, R1 and R2 branching) is from 13 to 19; R, R1 and R2 are each selected from hydrogen and C3 alkyl (preferably methyl), provided that R, R1 and R2 are not all hydrogen and, when z is 0, at least R or R1 is not hydrogen; w is an integer from 0 to 13; x is an integer from 0 to 13; and is an integer from 0 to 13; z is an integer from 0 to 13; and w + x + y + z is from 7 to 13. The most preferred half-chain branched surfactant compounds for use in the detergent compositions of the present invention are the primary alkyl sulfonate surfactants., and even more preferably sulfate, branched to the middle of the chain. It should be understood that for the purpose of the invention, it is preferred that the surfactant system comprises a mixture of two or more primary alkylsulfate or sulfonate surfactants branched to the middle of the chain. The preferred branched chain alkyl primary alkylsulfate surfactants are of the formula R R 1 f C Hicn 2 (Cu 2): H (C n 2 n (CH 2.) Y (CR 2 H Pso M 15 Surfactants have a chain base structure of linear primary alkyl sulphate (i.e., the longest linear carbon chain including the sulfated carbon atom) preferably comprising from 12 to 19 carbon atoms and its branched primary alkyl portions preferably comprise a total of at least 14 and preferably not more than 20 carbon atoms In the surfactant system comprising more than one of these sulfate surfactants, the average total number of carbon atoms of the primary alkyl portions Branched is preferably within the range of more than 14.5 to about 17.5. Therefore, the surfactant system preferably comprises at least one primary branched alkyl sulfate surfactant compound having a longer linear carbon chain of not less than 12 carbon atoms or not more than 19 carbon atoms, and the total number of carbon atoms, including the branch, must be at least 14, and further, the average total number of carbon atoms for the branched primary alkyl portion is within the range of more than 14.5 to about 17.5. R, R1 and R2 are each independently selected from hydrogen and an alkyl group of C3 C3 (preferably hydrogen or C2 + C2 alkyl, most preferably hydrogen or methyl, and most preferably methyl), provided that R, R1 and R2 Do not be all hydrogen. Also, when z is 1, at least R or R1 is not hydrogen. Preferred preferred monomethyl branched alkyl sulphates are selected from the group consisting of: 3-methylpentadecanolsulfate, 4-methylpentadecanolsulfate, 5-methylpentadecanolsulfate, 6-methylpentadecanol-sulfate, 7-methylpentadecanolsulfate, 8-methylpentadecanolsulfate, 9-methylpentadecanolsulfate, 10-methylpentadecanolsulfate , 11 -methylpentadecanolsulfate, 12-methylpentadecanolsulfate, 13-methylpentadecanolsulfate, 3-methylhexadecanol-sulfate, 4-methylhexadecanolsulfate, 5-methylhexadecanolsulfate, 6-methylhexa-decanolsulfate, 7-methylhexadecanolsulfate, 8-methylhexadecanolsulfate, 9-methylhexadecanolsulfate, 10-methylhexadecanolsulfate, 11 -methylhexadecanol sulfate, 12-methylhexadecanolsulfate, 13-methylhexadecanolsulfate, 14-methylhexadecanolsulfate, and mixtures thereof. The preferred dimethyl branched alkyl sulfates are selected from the group consisting of: 2,3-methyltetradecanolsulfate, 2,4-methyltetradecanolsulfate, 2,5-methyltetradecanolsulfate, 2,6-methyltetradecanol sulfate, 2,7-methyltetradecanolsulfate, 2,8 -methyltetradecanolsulfate, 2,9-methyltetradecanolsulfate, 2,10-methyltetradecanolsulfate, 2,11 -methyltetradecanolsulfate, 2,12-methyltetradecanolsulfate, 2,3-methylpentadecanolsulfate, 2,4-methylpentadecanolsulfate, 2,5-methylpentadecanolsulfate, 2,6-methylpentadecanol sulfate, 2J-methylpentadecanolsulfate, 2,8-methylpentadecanolsulfate, 2,9-methylpentadecanolsulfate, 2,10-methylpentadecanolsulfate, 2,11-methylpentadecanolsulfate, 2,12-methylpentadecanolsulfate, 2,13-methylpentadecanolsulfate, and mixtures thereof.

Non-ionic alkoxylated surfactant Essentially any alkoxylated nonionic surfactants are suitable herein. Ethoxylated and propoxylated nonionic surfactants are preferred. The preferred alkoxylated surfactants can be selected from the classes of nonionic condensates of alkylphenols, nonionic ethoxylated alcohols, nonionic ethoxylated / propoxylated fatty alcohols, nonionic ethoxylate / propoxylate condensates with propylene glycol, and nonionic ethoxylate condensation products with Adducts of propylene / ethylenediamine oxides. Nonionic surfactants may be present in the detergent compositions. It may be preferred that the level of nonionic surfactants ethoxylated in the intimate mixture be below 10% by weight of the mixture, preferably even 5% by weight. The condensation products of aliphatic alcohols with an amount of 1 to 25 moles of alkylene oxide, particularly ethylene oxide and / or propylene oxide, are suitable for use herein. The alkyl chain of the aliphatic alcohol may be either straight or branched, primary or secondary and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with an amount of 2 to 20 moles of ethylene oxide per mole of alcohol.

Cationic Surfactants Cationic surfactants suitable for use herein include quaternary ammonium surfactants. Preferably, the quaternary ammonium surfactant is a C6-C16, preferably C8-Cu mono-N-alkyl or alkenyl ammonium surfactant wherein the remaining N portions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. Also preferred are mono-alkoxylated and bis-alkoxylated amine surfactants. 1 ??? ¿Jí > -, t feAfcM, * > ^ ** ~ ^. . .,. i fiyaadiAa * Another suitable group of cationic surfactants that can be used in the detergent compositions or components thereof herein are cationic ester surfactants. The cationic ester surfactant is a compound, preferably dispersible in water, which has surfactant properties comprising at least one ester (ie -COO-) and at least one cationically charged group. Suitable ester cationic surfactants, including choline ester surfactants, have been described, for example, in U.S. Patents. Nos. 422,8042, 4239660 and 4260529.

Bleach Catalyst The composition of the present invention may contain a bleach catalyst containing transition metal. A suitable type of bleach catalyst is described in the U.S.A. 4,430,243. Other types of bleach catalysts include the manganese-based complexes described in the U.S.A. 5,246,621 and the patent of E.U.A. 5,244,594. Preferred examples of these catalysts include Mn? V2 (u-0) 3 (1,4J-trimethyl-1,4,7-triazacyclononane) 2- (PF6) 2, Mnlll2 (uO)? (U-OAc) 2 - ( 1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2- (CI04) 2, Mn? V4 (u-0) 6 (1, 4,7-triazacyclo-nonane) 4- (CI04) 2, MnmMnlv4 (uO)? (U-OAc) 2- (1, 4,7-trimethyl-1, 4,7-triazacyclo-nonane) 2- (CIO) 3, and mixtures thereof. Others are described in European Patent Application Publication No. 549,272. Other ligands suitable for use herein include 1, 5,9-trimethyl-1, 5,9-triazacyclododecane, 2-methyl-1,4-triazacyclononane, 2-methyl-1, 4-7-triazacyclononane, 1, 2.4J -tetramethyl-1, 4,7-triazacyclononane, and mixtures thereof. Bleach catalysts useful herein may also be selected as appropriate for the present invention. For examples of suitable bleach catalysts see U.S. Pat. 4,246,612 and US patent. 5,227,084. See also the patent of E.U.A. 5,194,416 which teaches mononuclear manganese (IV) complexes such as Mn (1, 4,7-trimethyl-1, 4,7-triazacyclononane) (OCH 3) 3- (PF 6). Another type of bleach catalyst, as described in the patent of E.U.A. 5,114,606, is a water-soluble complex of manganese (III) and / or (IV) with a ligand that is a polyhydroxy compound containing no carboxylate having at least three consecutive C-OH groups. Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylitol, arabitol, adonitol, mesoerythritol, mesoinositol, lactose, and mixtures thereof. The patent of E.U.A. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with a non-macro (cyclic) cyclic ligand. These ligands have the formula: R¿R R1-N = C-B-C = N-R4 ¿T, í * i. wherein R1, R2, R3 and R4 may each be selected from H, alkyl and substituted aryl groups such that each R1-N = C-R2 and R3-C = N-R4 forms a five or six membered ring. Said ring can also be substituted. B is a bridge-forming group selected from O, S. CR5R6, NR7 and C = 0, wherein R5, R6 and R7 may each be H, alkyl or aryl groups including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole and triazole rings. Optionally, said rings can be substituted with substituents such as alkyl, aryl, alkoxy, halide and nitro. Particularly preferred is the 2,2'-bispyridylamine ligand. Preferred bleach catalysts include the complexes of Co, Cu, Mn, Fe.-bispyridylmethane and -bispyridylamine. Highly preferred catalysts include Co (2,2'-bispyridylamine) CI2, Di (isothiocyanato) bispyridylamine-cobalt (ll), trisdipyridylamine-cobalt perchlorate (ll), Co (2,2-bispyridylamine) 202C04, Bis perchlorate, Bis - (2,2'-bispyridylamine) copper (ll), tris (di-2-pyridylamine) iron perchlorate (II) and mixtures thereof. Other examples include binuclear Mn in complex with ligands of N-dentate and bi-N-dentate including N4MNMI (u-0) 2MNlvN4) + and [Bipy2Mn '"(u-0) 2MNlvbipy2] - (CI04) 3. bleach are described, for example, in the European patent application, publication No. 408,131 (cobalt complex catalysts), European patent applications, publication No. 384,503, and 306,089 (metallo-porphyrin catalysts), E.U.A. 4,728,455 (manganese ligand / multidentate catalyst), E.U.A. 4,711, 748 and patent application , .m < a «tJi» ,, J- »* • &- - -" J *. * JBl.fa l.,. .. ,,,, - afc y +, .. i. - - * • ' European thesis, publication No. 224,952, (manganese catalyst absorbed on aluminosilicate), USA 4,601, 845 (aluminosilicate support with manganese and zinc or magnesium salt), USA 4,6262,373 (manganese / ligand catalyst) , US 4,119,557 (ferric complex catalyst), German patent specification 2,054,019 (cobalt chelator catalyst), Canadian patent 866,191 (transition metal containing salts), US 4,430,243 (chelators with manganese cations and non-catalytic metal cations) and US 4,728,455 (manganese gluconate catalysts).

Detergency builder material In addition to organic carboxylic acids, which may act as builders, and carbonate salts, which may act as builders, the detergent compositions of the invention generally comprise a water soluble builder material and / or insoluble in additional water. Silicates, aluminosilicates, crystalline layered silicates and phosphate salts are preferred. The compositions may comprise, for example, phosphate-containing builder material, preferably comprise tretrasodium pyrophosphate or very preferably anhydrous sodium tripolyphosphate, present at a level of 0.5% to 60%, most preferably from 5% to 50%, very preferably still from 8% to 40%. Suitable water-soluble builder compounds include the water-soluble polycarboxylate salts and borates. 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. It is preferred that the carboxylates and / or the polymeric or oligomeric polycarboxylates are present at levels less than 5%, preferably less than 3% or even less than 2% or even 0% by weight of the compositions. Examples of water insoluble builders include sodium aluminosilicates. Suitable aluminosilicate zeolites are in the form of a unit cell Naz [AI02] z (SiO2) y. XH2O where z and y are at least 6; the molar ratio of zay is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, most preferably from 10 to 264. The aluminosilicate material is in hydrated form and is preferably crystalline, containing from 10% to 28% , most preferably from 18% to 22% water in bound form. The aluminosilicate zeolites may be materials that occur naturally, but preferably are synthetic derivatives. 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: Na 2 [AI02)? 2 (Si02) 12] .xH20 where x is from 20 to 30, especially 27. Zeolite X has the formula Na86 [(AIO2) 86 (SiO2) 106J. 276 H2O).

Another preferred aluminosilicate zeolite is the MPA builder. Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal aluminosilicate of zeolite P type having a silicon to aluminum ratio not greater than 1.33, preferably in the range of 0.9 to 1.33 and most preferably within the range of 0.9 to 1.2. The compositions herein may also comprise additional silicate material, including amorphous silicate material, meta-silicates, preferably at least layered silicate material such as that sold under the tradename SKS-6. The silicate material is preferably present at a level of less than 20% in the compositions, preferably less than 15% by weight or even less than 10% by weight.

Heavy Metal Ion Sequester Heavy metal ion sequestrants are also useful ingredients here. By heavy metal ion sequestrant is meant herein components that act to sequester (chelate) heavy metal ions. These components also have the ability to chelate calcium and magnesium but preferably show selectivity for binding heavy metal ions such as iron., manganese and copper. Heavy metal ion sequestrants are generally present at a level of 0.1% to 5%, most preferably 0.25% to 7.5% and most preferably preferably still 0.3% to 2% by weight of the compositions.

The heavy metal ion sequestrants to be used 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 diethylenetriamine penta (methylenephosphonate), ethylenediamine tri (methylenephosphonate) hexamethylenediamine tetra (methylenephosphonate) and hydroxyethylene 1,1-diphosphonate, 1,1-hydroxyethane diphosphonic acid and 1,1-hydroxyethanedimethylene phosphonic acid. Other heavy metal ion sequestrants suitable for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenediamine disuccinic acid, ethylenediaminediglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof. Other heavy metal ion sequestrants suitable for use herein are iminodiacetic acid derivatives such as 2-h idroxyethyl acetic acid or glycerylimino diacetic acid, described in EP-A-317,542 and EP-A-399, 133. The sequestrants of iminodiacetic acid-N-2-hydroxypropylsulfonic acid and aspartic acid-N-carboxymethyl-N-2-hydroxypropyl-3-sulfonic acid described in EP-A-516,102 are also suitable in the present invention. The ablators of ß-alanine-N, N'-diacetic acid, aspartic acid-N, N'-diacetic acid, aspartic acid-N-monoacetic acid and imido-disuccinic acid described in EP-A-509,382 are also suitable.

EP-A-476,257 describes suitable amino-based scavengers. EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A-528,859 discloses a suitable alkyliminodiacetic acid sequestrant. Also suitable are dipicolinic acid and 2-phosphonobutane-1, 2,4-tricarboxylic acid. Also suitable are glycinamide-N-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (DEG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS). Especially preferred are diethylenetriaminepentaacetic acid, ethylenediamine-N, N'-disuccinic acid (EDDS) and hydroxyandiphosphonic acid 1, 1-h or the alkali metal, alkaline earth metal, ammonium or substituted ammonium salts thereof, or mixtures thereof. the same.

Enzymes Another preferred ingredient useful in the present invention is one or more additional enzymes. Additional preferred enzyme materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endulases, esterases, pectinases, lactases and peroxidases which conventionally incorporate detergent compositions. Suitable enzymes are described in the U.S. patent. 3,519,570 and 3,533,139. Preferred commercially available protease enzymes include those sold under the trade names Alcalase, Savinase, t. - *. »" * A "» »¿A. . . i.,.

Primase, Durazym, and Esperase by Novo Industries A S (Denmark), those sold under the trade names Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the trade names Opticlean and Optimase by Solvay Enzymes. The protease enzymes can be incorporated in the compositions according to the invention at a level of 0.0001% to 4% active enzyme by weight of the composition.

Additional Organic Polymeric Compound Additional organic polymeric compounds, without being carboxylic acids herein, are preferred additional components of the compositions herein or the agglomerates herein, where they can act to bind the agglomerate components together. By "organic polymeric compound" is meant essentially any polymeric organic compound commonly used as binder, dispersants and anti-redeposition and soil suspension agents in detergent compositions, including any high molecular weight organic polymer compounds described as clay flocculating agents herein, including quaternized ethoxylated polyamine clay dirt removal / antiredeposition agent according to the invention. The organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.01% to 30%, preferably from 0.1% to 15%, most preferably from 0.5% to 10% by weight of the compositions. Suitable polymeric compounds for incorporation into the detergent compositions herein include cellulose derivatives such as methylcellulose, sodium carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose. Also highly preferred is amide-modified carboxymethyl cellulose and / or amide-modified celluloses or derivatives thereof. Additional useful organic polymeric compounds are polyethylene glycols, particularly those of molecular weight of 1000-10000, very particularly of 2000 to 8000 and most preferably of about 4000.

Foaming Suppressor System The detergent compositions of the invention, when formulated for use in machine wash compositions, may comprise a foam suppressor system present at a level of from 0.01% to 15%, preferably from 0.02% to 10%, very preferably from 0.05% to 3% by weight of the compositions. The suds suppressor systems suitable for use herein may comprise essentially any known foam antifoam compound, including for example silicone foam antiforming compounds and 2-alkylalcanol foam antiforming compounds. t .t.A -? ? , í. .. - - l ... i - ~ ^ ....... _ ^ ^. "«. . - "- - - - ^ ____ __. tv *. tITMM Clay softening agents The present composition can be a detergent that provides softening during washing.It is preferred that the composition comprises a clay softening agent and preferably an agent Specific examples of suitable smectite clay include those selected from the classes of montmorillonites, hectorites, volchonoskoites, nontronites, saponites and suconites, particularly those having an alkali metal or alkaline earth metal ion within the crystalline lattice structure. or calcium is particularly preferred Bentonite clays are preferred, preferred as clay flocculating agents herein are organic polymeric materials having a weight average of 100,000 to 10,000,000, preferably 150,000 to 5,000,000, most preferably 200,000 to 2,000,000 Suitable organic polymeric materials comprise homopoly grouts or copolymers containing monomer units selected from alkylene oxide, particularly ethylene oxide, acrylamide, acrylic acid, vinyl alcohol, vinyl pyrrolidone and ethylene imide. Homopolymers, in particular, of ethylene oxide, but also acrylamide and acrylic acid are preferred. European patents No. EP-A-299,575 and EP-A-313,146 in the name of Procter and Gamble Company disclose preferred organic polymeric clay flocculating agents for use herein.

Other Optional Agents Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes, such as encapsulated perfumes described above, brighteners, specks, including colors or dyes, filler salts, with the sodium sulfate filler salt being preferred. Minor amounts (for example, less than about 20% by weight) of neutralizing agents, additional pH regulating agents, phase regulators, hydrotropes, enzyme stabilizing agents, polyacids, foam regulators, opacifiers, antioxidants, bactericides and dyes, such as those described in the US patent 4,285,841, Barrat et al., Issued August 25, 1981 (incorporated herein by reference).

Abbreviations used in the examples: LAS: Sodium linear alkynebenzenesulfonate of C11 .- 3 TAS Sodium tallow alkyl sulfate CxyAS: Sodium alkylsulfate of C? X-C? And C45SAS: Sodium secondary alkyl sulfate (2,3) of C? -C-.6 CxyEzS: Sodium alkylsulfate of C? X-C? And condensed with z moles of ethylene oxide CxyEz: A predominantly linear primary alcohol of C1x-C1 and condensed with an average of z moles of ethylene oxide t A i A. QAS: R2.N + (CH3) 2 (C2H40H) with R2 = C12-C14 QAS: R2.N + (CH3) 2 (C2H4OH) with R2 = C8-C11 Soap: Sodium linear alkylcarboxylate derived from a 80/20 mixture of tallow and coconut fatty acids STS: Sodium toluene sulfonate STPP: Anhydrous sodium tripolyphosphate Zeolite A: Hydrated sodium aluminosilicate of the formula Na12 (AI02SiO2) 12. 27H2O, which has a primary particle size in the range of 0.1 to 10 microns (weight expressed on an anhydrous basis) NaSKS-6: Crystalline layered silicate of the formula d-Na2Si2O5 particle size of 25 microns Carbonate: Anhydrous sodium carbonate Bicarbonate: Anhydrous sodium bicarbonate Silicate: Amorphous sodium silicate (Si? 2: Na2 ?; 2.0: 1) Sulfate Anhydrous sodium sulfate Mg sulfate: Magnesium sulfate anhydrous Citrate: Trisodium citrate dihydrate MA / AA: Copolymer of 1 4: maleic acid / acrylic acid with an average molecular weight of about 70,000 AA 4,500 CMC molecular weight sodium polyacrylate polymer: Sodium carboxymethylcellulose Cellulose ether Methylcellulose ether with a polymerization degree of 650, available from Shin Etsu Chemicals Protease: Proteolytic activity enzyme, which has 3.3 wt.% Enzyme active, sold by NOVO Industries AS under the trade name Savinase or proteolytic enzyme, which has 4% by weight of active enzyme, as described in WO 95/10591, sold by Genecor Int.lnc. Amylase: Amylolytic enzyme, which has 1.6% by weight of active enzyme, sold by NOVO Industries A / S under the trade name Termamyl 120T Lipase: Lipolytic enzyme, which has 2.0 wt. Of active enzyme, sold by NOVO Industries A / S under the trade name Lipolase or lipolytic enzyme, which has 2.0% by weight of active enzyme, sold by NOVO Industries A / S under the trade name Lipolase Ultra PB4: Particle containing sodium perborate tetrahydrate of nominal formula NaB02.3H20.H202, particles having a weight average particle size of 950 microns, 85% of particles having a particle size of 850 microns to 950 microns PB1: Particle containing anhydrous sodium perborate bleach of nominal formula NaB02.H202, the particles having a average particle size by weight of 800 microns, 85% of particles having a particle size of 750 microns to 950 microns Percarbonate: sodium percarbonate Nominal formula 2Na2C03.3H202, the particles having a weight average particle size of 550 to 850 microns, 5% or less having a particle size of less than 300 microns and 7% or less having a particle size of more than 1180 NOBS microns: Particles containing nonanoyloxybenzenesulfonate in the sodium salt form, the particles having a weight average particle size of 550 to 900 microns NAC-OBS Particle comprising (6-nonamidocaproyl) oxybenzenesulfonate, the particles having a size particle weight average 550 to 900 microns TAED I: Particle containing tetraacetylethylene diamine, the particles having a weight average particle size of 550 to 900 microns DTPA Diethylenetriaminepentaacetic acid DTPMP: Diethylenetriaminpenta (methylenephosphonate), marketed by Monsanto under the trade name Dequest 2060 Photoactivated bleach 1: Sulfonated zinc phthalocyanine encapsulated in soluble polymer in dextrin > «» * It ^ ...,., ,,., ,,,, Photoactivated bleach 2: Sulfonated aluminum phthalocyanine encapsulated in dextrin-soluble polymer Brightener: disodium 4,4'-bis (2-sulphotrisyl) biphenyl or , 4'-bis (4-anilino-6-morpholino-1,3,5-triazin-2-yl) amino) stilbene-2: 2'-disulfonate, disodium EDDS: Ethylenediamine-N, disuccinic acid, isomer (S, S) in the form of its sodium salt HEDP: 1, 1-hydroxyethyl-diphosphonic 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 Ethoxylated tetraethylene-propane PV1: Polyvinylimidosol , with an average molecular weight of 20,000 PVP: Polyvinylpyrrolidone polymer, with an average molecular weight of 60,000 PVNO: Polyvinylpyridine N-oxide polymer, with an average molecular weight of 50,000 PVPVI: Copolymer of polyvinylpyrrolidone and vinylimidazole, with a molecular weight average of 20,000 QEA: bis ((C2H50) (C2H40) n) (CH3) -N + -C6H12-N + - (CH3) bis ((C2H50) (C2H40) n), n = ded 20 to 30 Í? »- ^» fal.

SRP: Anionically blocked polyesters at the ends Antifoam: Polydimethylsiloxane foam controller with silicone or oxyalkylene siloxane copolymer as a dispersant suppressant agent with a ratio of said foaming agent controller to said dispersing agent from 10: 1 to 100: 1 In the following examples, all levels are quantified as% by weight of the composition.

.?. (. », * ^ .A,.». I ^ ....-.- aa ».., ...., aiMlfairlf-." ^. "." ^ ¿, -É j, * A. I TABLE 1 The following compositions are according to the invention and have a pH in the wash, as measured by the method defined herein, from about 9.4 to 9.85. iM.?-A?****.kJJA +L «*« *, * i?. »*:. *? 4 - l 'a. Ti l

Claims (14)

t. NOVELTY OF THE INVENTION CLAIMS

1. A detergent composition for laundry or dishwashing comprising a bleaching system containing a source of hydrogen peroxide and at least 2.5% by weight of a peroxyacid bleach precursor, at least 15% by weight of a source of carbonate, which may include the source of hydrogen peroxide, at least 7% by weight of an acid, preferably an organic acid, whereby a mixture of 1% by weight of the composition in demineralized water provides a pH of 8.8. . to 9.9.

2. The composition according to claim 1, further characterized in that it comprises at least 7% by weight of an acid selected from carboxylic acids, preferably citric acid, maleic acid, malic acid or mixtures thereof and therefore the carbonate source comprises at least 5% by weight of the composition of an alkali metal or alkaline earth metal carbonate salt, at least 8% by weight of the composition of an alkali metal or alkaline earth metal percarbonate salt and at least 2% by weight of the composition of an alkali metal or alkaline earth metal bicarbonate salt.

3. The composition according to claim 1, further characterized in that the peroxyacid bleach precursor is present at a level of 3% to 10% by weight of the composition, or even 4% to 6% by weight, and because the composition comprises from 10% to 45% by weight, most preferably from 15% to 35% by weight of the source of hydrogen peroxide, preferably a percarbonate salt which, when present, forms part of the carbonate source.

4. The composition according to claim 1, further characterized in that the pH is from 9.2 to 9.85, or even from 9.4 to 9.8.

5. The composition according to claim 4, further characterized in that it comprises at least two precursors of peroxyacid bleach, preferably TAED and a precursor selected from NOBS, DOBS or NACA_OBS.

6. The composition according to claim 1, further characterized in that it comprises a granule comprising said precursor or part thereof and a carbonate salt, percarbonate salt and / or bicarbonate salt, preferably in the form of a homogeneous mixture. intimate with each other, the granule being substantially free of the acid.

7. The composition according to claim 1, further characterized in that it comprises a granule containing the acid or part thereof and the carbonate and / or bicarbonate salt present in the source of carbonate, acid and carbonate and / or bicarbonate preferably being present in the form of a homogeneous mixture intimate with each other.

8. The composition according to claim 1, further characterized in that it comprises a perfume component that contains a mixture of perfume oils encapsulated by an agent of - -n _i > ..1. ít.a. , encapsulation, preferably the agent comprises a starch or starch derivative.

9. The use of a composition according to claim 1, further characterized by sanitization of fabrics or dirty surfaces.

10. The use of a composition as claimed in claim 1 to reduce the activity of microorganisms, in particular bacteria, preferably E. Coli, E. Hirae, S Aureus and Ps Aeruginosa.

11. The use as claimed in claim 10, wherein the activity of at least one, preferably all of the bacteria selected from the group comprising E Colli, E Hirae, S Aureus and Ps Aeruginosa is reduced pro at least 105 or even 3x105, as measured by the CEN method.

12. The use as claimed in claim 10, wherein it comprises the steps of causing the contact of the bacteria with an aqueous solution comprising an amount of the composition, so that the peroxyacid bleaching is present at a level of at least 100 ppm in the solution, per 106 microorganisms.

13. The use of a pH regulator system comprising at least one acid and a carbonate source, in a cleaning composition comprising a peroxyacid bleach precursor, wherein the pH regulator system has the ability to provide the pH of a 1% mixture of the composition in demineralized water is 8.8 to 9.9, preferably 9.2 to 9.8.

14. - A washing method for washing textiles in a washing machine, characterized in that a composition according to any of claims 1 to 8 is introduced in a device that is then introduced into the tub of the machine before introducing the washing water. í í í _,