MXPA01009180A - Detergent compositions - Google Patents

Abstract

Detergent compositions especially suitable for laundry applications are disclosed, which contain low absorbency zeolite with a dibutyl phthalae (DBP) absorption value greater than or equal to 68g/100g, a particle size of 15 microns or below and a particle size distribution where no more thant 0.09%by weight has a particle size greater than 45 microns.

Description

DETERGENT COMPOSITIONS FIELD OF THE TECHNIQUE This invention relates to detergents, in particular to laundry detergents. Very particularly, this invention relates to solid detergents, for example in the form of granules or tablets.

BACKGROUND OF THE INVENTION Detergent compositions, particularly those which are used as laundry detergents are well known. A problem related to detergent products, particularly solid detergent products, is their incomplete dissolution or gelling which can form detergent residues in the dispensing compartment or during the washing process which can cause the undissolved product to become trapped in the fabrics. This is not convenient since these residues are visible on the fabrics even after drying. This problem increases with the recent trend in the detergent industry towards higher bulk density granular compositions having a higher content of active ingredients, for example granular detergent compositions having a bulk density of 50 g / l or even 600g / the most.

It is well known that water hardness ions are detrimental to the effectiveness of surfactant cleaning systems, for example by the interaction with certain dirt components and the detergent cleaning system. Detergent formulators attack this problem by incorporating a builder system in detergent compositions that sequesters water hardness ions, thus ensuring maximum cleaning performance of the surfactant system. Phosphate builder systems are highly effective, however in view of the environmental problems related to their use, alternative detergency builders such as zeolites have become well known and widely used. Zeolites have effective builder properties and have been successfully incorporated into detergent compositions since the 1970s. However, zeolite builders are very insoluble in water and the nature of the zeolite, as it is processed, interacts with other detersive components such as surfactants, carbonates and silicates and the like, may increase the problem of waste deposition of detergent composition in the fabrics. There are many descriptions of the use of zeolite builders in detergents. For example, patent of E.U.A. 4000094, E.U.A. 4264464, Japanese Patent 08/283799, WO 96/21717 all disclose said detergent compositions, specifying the preferred average particle sizes of the zeolite. WO 97/34980 relates to providing zeolite particles which produce a reduced amount of waste in the fabrics and have an increased liquid transport capacity. For this purpose, this patent application describes the modified zeolite powder in which alkali metal silicate is deposited in zeolite P having a weight average particle size (50% by weight of the zeolite has a particle size) of 1 to 10 μm. The patent of E.U.A. No. 4457854 teaches that basic spray-dried pearl particles, made by spray-drying an aqueous suspension of zeolite and carbonate and then dried with a water-soluble silicate powder and non-ionic detergent in liquid form, produce a flow detergent. free. The residues in the fabrics are reduced by the subsequent adhesion of the hydroalkali metal silicate instead of the incorporation of the silicate in the support mixture with the zeolite and the carbonate. The patent also shows the preferred "average maximum zeolite particle sizes" of less than 15 μm. In practice, although they may have the average particle sizes indicated in the references discussed above, commercially available zeolites have a wider particle size distribution and contain larger zeolite particles. This may be the case in particular, for highly absorbent zeolites due to the processing conditions of said zeolites. The highly absorbent crystalline zeolite is suitable for use in detergent compositions since it allows the loading of high levels of surfactant while maintaining a good flowability of the detergent. This can be done by a method in which the zeolite crystals are formed in the forming process and adhere to each other to form a particle comprising a multitude of crystals having good absorbency. This method of preparation is relatively difficult to control so that the particles of the zeolite produced tend to be very irregular in shape and with a very wide particle size distribution. The inventors of the present have observed that the choice of a specific fraction of absorbent crystalline zeolite gives a surprisingly improved fabric waste performance when used in a detergent composition that even uses said irregularly shaped zeolite crystals. The inventors have observed with surprise that the selection of the zeolite based only on the average particle size does not offer this benefit, but that in addition, the presence of larger particles is critical, so that a considerable reduction in waste is achieved in the fabric when a specific fraction of zeolite is selected.

BRIEF DESCRIPTION OF THE INVENTION According to the present invention there is provided a detergent composition comprising zeolite which is characterized in that the zeolite has an absorption value of dibutyl phthalate (DBP) of at least 68 grams / 100 grams (as defined herein) and a particle size so that at least 99% by weight of the zeolite has a particle size of 15 μm or less as measured by laser diffraction as defined below and no more than 0.09% by weight of the zeolite has a particle size 45 μm as defined by the wet sieve test. In preferred detergent compositions, the zeolite has a particle size in which not more than 0.05% by weight, and most preferably not more than 0.01% by weight of the zeolite has a particle size of 45 μm or more. Also, preferably the particle size of at least 99% by weight of the zeolite is 0.05 μm or more, most preferably 0.01 μm or more. While not wishing to be bound by any theory, the inventors believe that the waste in the fabrics is reduced by using zeolite in which at least 99% by weight has a particle size of 0.05μm, preferably over 0.1μm or more and that a smaller particle size of the zeolite tends to be trapped by the fibrils on the surfaces of the fabrics in the washing process and then can form lumps to form larger particles that produce trapped cloth trapped on the surfaces of the fabrics. According to the invention, the use of a zeolite having a DBP absorption value of at least 68g / 100g as defined herein and a particle size of at least 99% by weight is also provided. of the zeolite has a particle size of 15 μm or less as measured by laser diffraction as defined below and that no more than 0.09% by weight of the zeolite has a particle size greater than 45 μm as measured by wet sieve test, in a detergent composition to reduce fabric waste.

DETAILED DESCRIPTION OF THE INVENTION Zeolite The measurement of particle size to determine the proportion of the zeolite having a particle size greater than 45 μm was performed using a wet sieve test. According to the wet sieve test, for a batch of zeolite to be tested, the following test is performed twice on each zeolite sample to find the proportion of the zeolite having a particle size greater than 45 μm and the average value of the two samples is calculated. The average value provides the required proportion of particle size. If the two values differ by more than 10% of the largest value, the results are discarded and the procedure is repeated. A sample of 100g zeolite (+/- 0.1g) is placed in a 1000ml beaker with 500 ml of distilled water. The liquid in the beaker is stirred until no residue remains in the bottom of the beaker. The contents of the beaker are emptied into a sieve of 45 micron openings (standard brass or stainless steel sieve of 200 mm diameter). The liquid is not retained. Then, more distilled water is poured into the glass to mix with any residue that remains and the enamel water is poured into the sieve. Then a sieve tongue step is performed: a base tray for the sieve is filled with distilled water and the sieve is placed on top of the base tray. Extra distilled water is added until the water level is approximately 5 to 10 mm above the level of the maya. The residue is washed with a gentle vortex movement for 2 to 3 minutes. The sieve is removed and the water is examined in the base tray. If any turbidity remains, the water is discarded and the screening step is repeated. If the water is clear, the water is placed in a preheated oven at 10 +/- 2 ° C for one hour. The sieve is then removed from the oven and allowed to cool for 10 minutes +/- 1 minute. The residue is shaken using a brass wire brush and gathers in a previously heavy petri dish. The weight of the waste is determined as soon as possible (in 2 to 3 minutes) by weighing on a scale with an accuracy of at least 2 decimals. The weight of the residue (g) is the percentage weight of zeolite having a particle size greater than 45 microns. Since the wet sieve test measures fractions of specific particle size it is not adequate to measure the particle size distribution of the zeolite to determine whether 99% by weight of the zeolite has a particle size of 15 microns or less. Thus, for this calculation, a laser diffraction measurement method is used. In this test, a Sympatec laser difractor is used, comprising a HELOS / KA central unit with a software system (computer program) Paradox, a liquid dispersion system QUIXEL and a 2 mm CUV. 500 ml of distilled water are placed in an ultrasonic bath and a sample of zeolite is added. The liquid is left in the ultrasonic bath operating at a frequency of 40KHz for 10 minutes during which time; the ultrasound ensures a substantially homogeneous dispersion of the individual zeolite particles. A sample is removed from the ultrasonic bath dispersion and slowly added to one liter of distilled water in a QUIXEL until the software indicates that an optimum concentration has been achieved to measure. A suitable concentration can be, for example, 0.5 g / l. A 2 mm CUVETTE is placed in the QUIXEL and the distribution of the aqueous suspension is measured in a 10 second lap using an 87.5 μm lens. This measurement method gives the percentage by weight of the sample having a particle size of 15 μm or less. In order to determine the absorption value of the DBP of the zeolite, di-n-butylphthalate (DBP) is automatically titrated on a previously weighed sample of zeolite in a mixing chamber. When the DBP is evaluated, the mix and agglomeration profile is recorded at the saturation point using a torque rheometer. More specifically, a sample of 25 g of zeolite is weighed to 2 decimals and then placed in a mixing chamber of a Brabender absorber with a substantially equal distribution. The DBP passes to the mixing chamber of a LEWA pump, pre-calibrated to deliver DBP at a speed of 2.4 ml / min (+/- 0.2 ml / min) with agitation of the absorptometer at a speed of 125 rpm and the torque of Twisting during mixing is recorded by the Brabender box record. The DBP is added until the maximum torque has been reached. After another 20 to 30 seconds to ensure that the saturation point has been exceeded, the Brabender frame registration is stopped. In order to calculate the value of the DBP, a horizontal line is drawn at half the value of the highest torque and the baseline. This horizontal line A, passes through the peak. The distance between the upper slope and the lower slope of the peak is measured along line A and a vertical line B is drawn equidistantly from the upper and lower slopes of the peak along line A. This line B is used to determine the DBP value according to the following formula: DBP absorption value (g / 100g) = [(D / R) X (V) X (100)] / M where D = distance from the beginning of the saturation test (mm) R = frame registration paper speed (mm / min) V = average DBP delivery speed per minute (mm / minute) ie [(g) DBP supplied in 5 minutes before the return + (g) delivered in 5 minutes after the return] / 10 M = mass of the sample used (g) The preferred DBP values they are at least 70g / 100g or even at least 75 or 80g / 100g. Preferred zeolites for use in the present invention have a particle size such that 99% of the zeolite has a particle size of 0.05 μm or more, most preferably 0.1 μm or more. In order to detect the proportion of particles of such a small particle size, these particles can be measured by scanning electron microscopy using the stereological interpretation of the data as discussed in Computer Assisted Microscopy-The Measurement and Analysis of Images by John C. Russ; Plenum Press, NY and London 1990, Chapter 8 pp.221-265. In order to obtain the zeolites as determined, commercially available materials can be classified in any conventional manner, for example using screens to obtain the appropriate zeolite fraction. The inventors have observed that it is particularly useful to ensure that in a sample of one tonne of zeolite, the particle size requirements of the claims are met. Such a large sample of zeolites is particularly useful since it is large enough that its value is not affected by the variability of the plant. Zeolites are crystalline aluminosilicates. Suitable aluminosilicate zeolites have the unit cell formula Naz [(Al? 2) z (Si? 2) y] xH2? in which z and y are integers of 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, more 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 naturally occuring materials, but are preferably derived in synthetic form. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula: Na < | 2 [(Al? 2) i2 (Si? 2) i2] -xH2 ?, in which x is from 20 to 30, especially 27.

Zeolite X has the formula: Na86 [(Al? 2) 86 (SiO2) l06] -276H2 ° - Another suitable aluminosilicate zeolite for the foregoing invention is the zeolite MAP builder. Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminum ratio of not more 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 to aluminum ratio no greater than 1.15, more particularly not greater than 1.07. The zeolite may be present in the detergent compositions of the invention or its components in amounts as low as 1% by weight and as high as 99% by weight.

Generally, the zeolite levels in a detergent composition of the invention are at least 2% by weight or at least 5% by weight or even at least 10 to 20% by weight. Generally in the detergent composition, the zeolite as determined is present in amounts not greater than 80% by weight, or no greater than 50% by weight, or even in amounts not greater than 40% by weight. The zeolite as determined can be incorporated in the detergent composition as a dry aggregate particle material either directly in the specific particle size or as a larger particle eg 100 to 1500 microns, formed from the particle size zeolite determined and binder. Suitable binders include other detergent and binder ingredients conventional in the field of detergents as polymeric materials for example based on maleic acid monomers and / or acrylic acid, polyalkylene glycols such as PEG, or hydratable salts or acids of said salts, such as citric acid or alkali metal silicates or alkali metal carbonates. In said particle the zeolite will comprise up to 99% by weight of the particle, generally at least 90% by weight of the dry aggregate particle. The granules based on zeolite of larger particle size will generally contain at least 60% by weight of zeolite. Alternatively, the determined particle size zeolite goes through a detergent processing step with one or more additional detergent ingredients, such as other builder components and / or surfactants to form a particulate detergent. In this case, the particulate detergent component containing the specific zeolite generally contains up to 80% by weight, or very generally up to 70% by weight or even up to 60% by weight of the particulate detergent component. In a preferred feature of the invention, the zeolite is present as a particulate detergent composition comprising cationic surfactant. In another preferred embodiment of the invention, the zeolite is present as a particulate detergent composition comprising anionic surfactant or anionic and cationic surfactant. Suitable anionic surfactants are described below in the section entitled "Surfactants" and include alkylbenzene sulphonates. Particularly preferred anionic surfactants are those having a Kraft temperature of 45 ° C or less or 40 ° C or less. According to one embodiment of the invention, the zeolite is incorporated into the detergent composition by a dry spray particle. These particles preferably contain at least 15% by weight of surfactant, or at least 20% by weight or even more than 25% by weight of surfactant. The surfactant may be anionic, cationic, nonionic, amphoteric or zwitterionic or mixtures thereof as will be described below. In view of the reduction in the waste provided by the present invention, the spray dried particles can also contain alkali metal silicates so that the zeolite and the alkali metal silicate are added to the support mixture and spray-dried together . Therefore, according to a process of the present invention, the zeolite of specific particle size and absorbency are mixed with additional detergent ingredients to form a suspending suspension that is spray dried, the spray dried powder is mixed with ingredients additional detergents to form a granular detergent which is optionally compressed into a tablet. Additional binders can be included at any stage of the process. According to another embodiment of the invention, the specific zeolite is incorporated into the detergent composition by means of an agglomerate. The zeolite can be agglomerated with other detergent ingredients in conventional forms, retaining its high-absorbency characteristics and also producing products with superior fabric waste performance. The agglomeration processes can be as described in any of the following patent applications: EP-A-367 339, EP-A-420 317 and EP-A-506 184. Again, the particulate detergent components produced can be mixed with Additional detergent ingredients and optionally compressed into tablets. Optional binders can be included at any stage of the process. According to another aspect of the invention, the zeolite can be incorporated into the detergent compositions of the invention by an extrudate. Thus in a preferred process of the present invention the specific zeolite is mixed with other detergent ingredients to form a coarse paste which is extruded to form extruded lengths of detergent composition. These lengths are cut into short portions and optionally molded to produce detergent granules. The detergent particles produced can be mixed with additional detergent ingredients and optionally compressed into tablets. The use of zeolites as determined can be particularly beneficial in said extrusion processes. Due to the highly absorbent nature of the zeolite, high proportions of organic detergent components can be incorporated as surfactants into the detergent paste while still producing an easily extruded non-tacky paste. A typical extrusion process is described in DE-A-195 24 287. Since the zeolites have good absorbency characteristics, the liquid detergent ingredients can be post-dosed to the detergent compositions containing zeolite or its components before adding other ingredients detergents In particular, the anionic and / or nonionic and / or cationic surfactants in liquid form can be added to the preformed detergent ingredients, optionally with dissolution aids such as fatty acids and their derivatives and / or esterified polyols such as glycerides and / or soaps. In the detergent compositions of the invention, another benefit may be observed in detergent compositions which also contain percarbonate bleaching agents. Percarbonates are particularly vulnerable to loss of activity during storage due to moisture pickup and specific zeolites have a large surface area and good moisture pick-up so that they can act as an improved moisture trap during storage, protecting the percarbonate of moisture and loss of subsequent activity. When present in detergent compositions, it may also be preferred that only less than 25% by weight of the detergent composition of mixed hydratable inorganic salts are present, thus being 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 present detergent composition comprises one or more anionic surfactants and a zeolite (aluminosilicate) builder, whereby it is preferred that only small amounts of the aluminosilicate builder and the anionic surfactant are in an intimate mixture, ie less than 50% or even less than 30% of the total amount of the anionic surfactant and less than 50% or even less than 30% of the total amount of aluminosilicate; it may also be preferred that substantially no anionic surfactant and aluminosilicate builder be in an intimate mixture. In this way, it may be preferred that the composition comprises at least two separate particles comprising either the anionic surfactant or aluminosilicate. "Intimate mixture" means for the purpose 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 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, for example less than 10% or even less than 5% by weight of the composition, whereby it is preferred that the composition comprise highly soluble detergency builders, for example sodium citrate or citric acid, carbonate, and / or layered crystalline silicate. It is also preferred that the composition comprises as a 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 10% by weight. 70% by weight of a surfactant, preferably an anionic surfactant, in which it may be preferred that less than 10% by weight of the agglomerate is free of moisture, more preferably 30% to 60% by weight of a layered crystalline silicate and 20% to 50% of an anionic surfactant.

Other detergency ingredients The compositions according to the invention may also contain other additional detergent ingredients. The precise nature of these additional components, and levels of incorporation will depend on the physical form of the composition or component, and the precise nature of the washing operation for which it is to be used.

Surface Active The detergent compositions according to the invention preferably contain one or more surfactants selected from anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants, and mixtures thereof. A typical list of anionic, nonionic, ampholytic and zwitterionic classes, and species of these surfactants, is given in the U.S. patent. No. 3,929,678, issued to Laughiin and Heuring on December 30, 1975. Additional examples are given in "Surface Active Agents and Detergents" (Vols. I and II, by Schwartz, Perry and Berch). A listing of suitable cationic surfactants is given in the U.S.A. No. 4,259,217, issued to Murphy on March 31, 1981. When present, ampholytic, amphoteric and zwitterionic surfactants are generally used in combination with one or more anionic and / or nonionic surfactants.

Anionic Surfactant The compositions according to the present invention preferably comprise an additional anionic surfactant. Essentially any surfactant 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 surfactants are preferably present at a level of from 0.1% to 60%, very preferably from 1 to 40%, most preferably from 5% to # 0% by weight. Highly preferred surfactant systems are those comprising a sulfonate and sulfate surfactant, preferably a linear or branched alkylbenzene sulphonate and alkyl ethoxy sulfates, as described herein, preferably combined with cationic surfactants as described herein. Other anionic surfactants include isethionates such as acyl isethionates, N-acyltaurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, sulfosuccinate monoesters (especially saturated and unsaturated C12-C18 monoesters), sulfosuccinate diesters (especially C6-diesters) C14 saturated and unsaturated), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin and resin acids, as well as hydrogenated resin acids present in tallow oil or derivatives thereof.

Sulfate anionic surfactant The sulfate anionic surfactants suitable for use herein include the alkyl ethoxy sulfates, oleyl glycerol sulfates, ethylene oxide ether sulfates of alkylphenol, the acyl glucamin sulfates of C5-C < 7-N- (C 1 -C 4 alkyl) and -N- (C 1 -C 2 hydroxyalkyl), and alkylpolysaccharide sulfates such as alkylpolyglucoside sulfates (non-sulphonated nonionic compounds are described herein). The alkyl sulfate surfactants are preferably selected from the group consisting of the linear and branched primary C 10 -C 18 alkyl sulfates, more preferably the branched chain C 11 -C 15 alkyl sulfates and the straight chain C 12 -CH alkyl sulfates. The alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of the C 10 -C 18 alkyl sulphates which have been ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkylethylsulfate surfactant is a C- alkyl sulfate. ? -C- | 8. most preferably C11-C15, which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5 moles of ethylene oxide per molecule.

A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxylate surfactants. Such mixtures have been described in PCT application No. WO 93/18124.

Anionic Sulfonate Surfactant Anionic sulphonate surfactants suitable for use herein include linear C5-C20 alkylbenzene sulphonate salts. alkyl esters sulfonates, primary or secondary C6-C22 alkan sulfonates, C6-C24 olefinsulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates and any mixtures thereof.

Carboxylate anionic surfactant Suitable carboxylate anionic surfactants include alkylethoxycarboxylates, alkylpolyethoxy polycarboxylate surfactants and soaps ("alkylcarboxyls"), especially certain secondary soaps as described herein. Suitable alkylethoxycarboxylates include those with the formula RO (CH2CH20) xCH2C00-M + wherein R is an alkyl group of Ce to C- | 8- x ranges from 0 to 10, and the ethoxylate distribution is such that, on a base of weight, the amount of material in which x is 0 is less than 20% and M is a cation. Suitable alkylpolyethoxypolycarboxylate surfactants include those having the formula RO- (CHR? -CHR2-O) -R3 wherein R is an alkyl group of CQ to C- | 8. x is from 1 to 25, Rj and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof. Suitable soap surfactants include secondary soap surfactants that contain a carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are the water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, -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 the formula R-CON (RI) CH2COOM, in which R is a linear or branched C5-C17 alkyl or alkenyl group, R1 is a C1-C4 alkyl group and M is an alkali metal group. Preferred examples are myristyl or oleoyl methylsarcosinates in the form of their sodium salts.

Alkoxylated nonionic surfactant Essentially any alkoxylated nonionic surfactants are suitable herein. Ethoxylated and propoxylated nonionic surfactants are preferred. Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkylphenols, nonionic ethoxylated alcohols, ethoxylated / propoxylated nonionic fatty alcohols, ethoxylated / propoxylated non-ionic condensates with propylene glycol and the non-ionic ethoxylated condensation products with adducts of propylene oxide / ethylenediamine.

A non-ionic alkoxylated alcohol surfactant The condensation products of aliphatic alcohols with from 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 from 2 to 10 moles of ethylene oxide per mole of alcohol.

A non-ionic surfactant of polyhydroxy fatty acid amide The polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R ^ CONR ^ Z, wherein: R1 is H, C1-C4 hydrocarbyl, -hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy, or a mixture thereof, preferably C 1 -C 4 alkyl, most preferably C 1 alkyl; or C2, more preferably C1 alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C5-C1Q alkyl or alkenyl, most preferably straight-chain C9-C17 alkyl or alkenyl, more preferably C-n-C- alkyl or alkenyl; 7 straight chain or a mixture thereof, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z will preferably be derived from a reducing sugar in a reductive amination reaction; most preferably Z is a glycityl.

Nonionic Fatty Acid Amide Surfactant 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 atoms of carbon and each R7 is selected from the group consisting of hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, and - (C 2 H 4) x H, wherein x is on the scale of 1 to 3.

Alkylpolysaccharide nonionic surfactant The suitable alkylpolysaccharides which are used herein are described in US Pat. No. 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 polyglycoside, a hydrophilic group containing from 1.3 to 10 units of saccharide. Preferred alkyl polyglycosides have the formula R2? (CnH2nO) t (glycosyl) x in which R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glucosyl is preferably derived from glucose.

Amphoteric surfactant The amphoteric surfactants suitable for use herein include the amine oxide surfactants and the alkylamphocarboxylic acids. Suitable amine oxides include those compounds having the formula R3 (OR4) xN ° (R5) 2, wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropyl and alkylphenyl group or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R 5 is an alkyl or hydroxyalkyl group containing from 1 to 3 carbon atoms, or a group of polyethylene oxide containing from 1 to 3 ethylene oxide groups. Preferred are C 10 -C 18 alkyldimethylamine oxide and acylamidoalkyldimethylamine oxide from C < o-Ci8- A suitable example of an alkylamphodicarboxylic acid is Miranol (MR) C2M Conc., manufactured by Miranol, Inc., Dayton, NJ.

Zwitterionic Surfactant Zwitterionic surfactants can also be incorporated into 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 CQ-C ^ Q hydrocarbyl group, each R1 is typically C1-C3 alkyl, and R2 is a group C1-C5 hydrocarbyl. Preferred betaines are the betaines of C12-C18 dimethylammonium hexanoate and the acylamidopropane (or ethane) dimethyl (or diethyl) betaines of C-J O-C-IS- Also the complex betaine surfactants are suitable for use herein.

Cationic Surfactants Cationic surfactants suitable for use in the detergent herein include the quaternary ammonium surfactants. Preferably the quaternary ammonium surfactant is a mono-N-C6-C16 alkyl, preferably N-alkyl or C6-C10 alkenyl ammonium surfactant in which the remaining N-positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. The mono-alkoxylated and bis-alkoxylated amine surfactants are also preferred. Another suitable group of cationic surfactants that can be used in the detergent compositions or components thereof herein are the cationic ester surfactants. The cationic ester surfactant is a compound preferably dispersible in water, having surfactant properties and comprising at least one ester linkage (ie, -COO-) and at least one cationically charged group.

Suitable cationic ester surfactants, including choline ester surfactants, have been described, for example, in U.S. Patents. Nos. 422,8042, 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 comprising at least three atoms (ie said chain length of three atoms), preferably three to eight atoms, most preferably three to five atoms, more preferably three atoms. The atoms forming the chain of the spacer group are selected from the group consisting of carbon, nitrogen and oxygen atoms, and any mixtures thereof, with the proviso that no nitrogen or oxygen atom in said chain connects only with the atoms of carbon in the chain. In this way, groups which have, for example, -OO- (ie, peroxide), -NN- and -NO- bonds are excluded, but include the spacer groups having, for example, -CH2-O bonds -CH2- and -CH2-NH-CH2. In a preferred aspect, the chain of the spacer group only comprises carbon atoms, most preferably the chain is a hydrocarbyl chain.

Mono-alkoxylated cationic amine surfactants Mono-alkoxylated amine cationic surfactants are highly preferred herein, preferably of the general formula: Wherein R1 is an alkyl or alkenyl portion containing 6 to 18 carbon atoms, preferably 6 to 16 carbon atoms, more preferably 6 to 14 carbon atoms; R2 and R3 are each independently alkyl groups containing from one to three 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 chlorine, bromine, 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 30, preferably from 2 to 15, more preferably from 2 to 8. Preferably ApR4 is a hydroxyalkyl group, having no more than 6 carbon atoms in which the -OH group is separated from the quaternary ammonium nitrogen atom by not more than 3 carbon atoms. Particularly preferred ApR4 groups are -CH2CH2OH, -CH2CH2CH2OH, -CH2CH (CH3) OH and -CH (CH3) CH2OH, with -CH2CH2OH being particularly preferred.The preferred R1 groups are linear alkyl groups.The linear R groups having from 8 to 14 carbon atoms are preferred.

Other highly preferred cationic mono-alkoxylated amine surfactants for use herein are of the formula: Wherein R1 is C10-C18 hydrocarbyl and mixtures thereof, especially C10-C14 alkyl, preferably C10 and C12 alkyl, and X is any convenient anion to provide charge balance, preferably chlorine or bromine. As noted, compounds of the type mentioned above include those in which the (CH2CH2O) ethoxy units (EO) are replaced by butoxy, isopropoxy [CH (CH3) CH20] and units [CH2CH (CH30] (i-Pr) or n-propoxy (Pr) units, or mixtures of EO and / or Pr and / or i-Pr units. The levels of mono-alkoxylated amine cationic surfactants used in the compositions Detergents of the invention are preferably from 0.1% to 20%, more preferably from 0.2% to 7%, more preferably from 0.3% to 3.0% by weight of the composition.

Cationic bis-alkoxylated amine cationic surfactant The cationic bis-alkoxylated amine surfactant preferably has the general formula II: Wherein R1 is an alkyl or alkenyl portion containing from 8 to 18 carbon atoms, preferably from 10 to 16 carbon atoms, more preferably from 10 to 14 carbon atoms; R2 is an alkyl group containing one to three 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 chlorine, bromine, methylisulfate, sulfate, or the like, sufficient to provide electrical neutrality, A and A 'can vary independently and each is selected from C? -C alkoxy, especially ethoxy, (i.e. -CH2CH2O-), propoxy, butoxy and mixtures thereof, p is from 1 to 30, preferably from 1 to 4 and q is from 1 to 30, preferably from 1 to 4, and more preferably p and q are 1. Cationic surfactants highly preferred bis-alkoxylated amine for use herein are of the formula: Wherein R1 is C10-C18 hydrocarbyl and mixtures thereof, preferably C12 alkyl, C12, Cu and mixtures thereof. X is any convenient anion to provide charge balance, preferably chlorine. With reference to the general structure of the bis-alkoxylated cationic amine noted above, because in a preferred compound R1 is derived from fractions (coco) Ci2-Cu alkyl of fatty acids, R2 is methyl and ApR3 and A'qR4 are each monoethoxy. Other cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula: Wherein R1 is C10-C18 hydrocarbyl, preferably C10-C14 alkyl, independently p is 1 to 3 and q is 1 to 3, R2 is C?-C3 alkyl, preferably methyl, and X is an anion, especially chlorine or bromine. Other compounds of the above type include those in which the (CH2CH20) ethoxy (EO) units are replaced by butoxy (Bu), isopropoxy [CH (CH3) CH20] and units [CH2CH (CH30] (i-Pr) or n units -propoxy (Pr), or mixtures of units EO and / or Pr and / or i-Pr.

Bleach activator The ingredients according to the present invention and / or the detergent compositions herein preferably comprise a bleach activator, preferably comprising an organic peroxyacid bleach precursors. It may be preferred that the composition comprises at least two peroxyacid bleach precursors, preferably at least one hydrophobic peroxyacid bleach precursor and at least one hydrophilic peroxy acid bleach precursor, as defined herein. The production of the organic peroxyacid then occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. The bleach activator may comprise, alternatively or in addition to, a preformed peroxy acid bleach. It is preferred that the bleach activator be present in a particulate component in the compositions herein. It may be preferred that it be present as a separately mixed particle. Alternatively, the bleach activator or part thereof may be present in the basic detergent particle. Preferably, at least one of the bleach activators, preferably a peroxyacid bleach precursor, is present in a particulate component having an average particle size, by weight, from 600 microns to 1400 microns, preferably from 700 microns to 1100 microns. More preferably, all of the activator is present in one or more particulate components that are the size of average particle in determined weight. In the present, it may be preferred 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 to 1700 microns, preferably from 425 microns to 1400 microns. The hydrophobic peroxy acid bleach precursor preferably comprises a compound having an oxo-benzenesulfonate group, preferably NOBS, DOBS, LOBS and / or NACA-OBS, as described herein. The hydrophilic peroxy acid bleach precursor preferably comprises TAED, as described herein.

Peroxyacid bleach precursor Peroxyacid bleach precursors are compounds that react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Peroxyacid bleach precursors can generally be represented as: OR II X-C-L where L is a residual group and X is essentially any functionality, such that in perhydrolysis, the structure of the peroxyacid produced is: O II X-C-OOH For the purpose of the invention, the hydrophobic peroxyacid bleach precursors produce a peroxy acid of the above formula in which X is a group comprising at least 6 carbon atoms and a hydrophilic peroxy acid bleach precursor yields a bleach precursor of the above formula wherein X is a group comprising from 1 to 5 carbon atoms. The peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 30% by weight, most preferably from 1% to 15% by weight, more preferably from 1.5% to 10% by weight of the detergent compositions. The ratio of hydrophilic to hydrophobic peroxy acid bleach precursors, when present, is preferably from 10: 1 to 1:10, more 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- or O-acyl groups, whose precursors may be selected from a wide variety 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.

Outgoing groups The leaving group, hereinafter group L, must be sufficiently reactive so that the perhydrolysis reaction occurs within the optimum time frame (for example, a wash cycle). However, if L is very reactive, this activator will be difficult to stabilize for use in a bleaching composition. The preferred L groups are selected from the group consisting of: 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 And it is H or a solubilizing group. Any of R 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" M +, 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.

Alkylpercarboxylic acid bleach precursors The alkylpercarboxylic acid bleach precursors form percarboxylic acids in the perhydrolysis. Preferred precursors of this type provide peracetic acid in the perhydrolysis. Preferred alkylpercarboxylic type precursor compounds include the N-, NN ^ N- ^ tetraacetylated alkylenediamines in which the alkylene group contains 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1 to 2 carbon atoms. and 6 carbon atoms. Particularly preferred is tetraacetylethylenediamine (TAED) as precursors of hydroxylic peroxy acid bleach. Other preferred alkylpercarboxylic acid precursors include sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (iso-NOBS), sodium nonanoyloxybenzenesulfonate (NOBS), sodium acetoxybenzenesulfonate (ABS) and pentaacetylglucose.

Precursors of alkylperoxyacid substituted with amide Preferred peroxyacid precursors are the amide-substituted alkylperoxy acid precursor compounds, including those having the following general formulas: R1- C-N-R2- C-L R1- N-C-R2- C- L II II O R5 OR R5 O O wherein R1 is an aryl or alkaryl group with from 1 to about 14 carbon atoms, R2 is an alkylene, arylene and alkarylene group that it contains from about 1 to 14 carbon atoms, and R ^ is H or an alkyl, aryl or alkaryl group containing 1 to 10 carbon atoms and L may be essentially any residual group. R preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. R1 may be straight or branched chain alkyl, aryl or substituted alkylaryl which contains branching, substitution or both and may originate from synthetic sources or natural sources including for example bait grease. Structural variations for R2 are permissible. R 2 may include alkyl, aryl, wherein R 2 may also contain halogen, nitrogen, sulfur or other typical substituent groups or organic compounds. R5 is preferably H or methyl. R1 and R2 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 preferred that R1 and R5 form a ring structure together with the nitrogen and carbon atom. Preferred examples of bleach precursors of this type include amide-substituted peroxyacid precursor compounds selected from (6-octamido-caproyl) oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzenesulfonate, and the most highly preferred (6-nonamido-caproyl) oxybenzenesulfonate , 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 midazole and N-benzoyl benzimidazole. Other perbenzoic acid precursors containing a useful N-acyl group include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Cationic peroxyacid precursors Cationic peroxyacid precursor compounds produce cationic peroxyacids in perhydrolysis. Typically, cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkylammonium group, preferably an ethyl or methylammonium group. Cationic peroxyacid precursors are typically present in solid detergent compositions as a salt with a suitable anion, such as a halide ion. The peroxyacid precursor compound which will be so cationically substituted may be a perbenzoic acid precursor compound or a substituted derivative thereof as described hereinabove. Alternatively, the peroxyacid precursor compound may be a precursor alkylcarboxylic acid compound or a precursor of alkylperoxyacid substituted with amide as described hereinafter. Cationic peroxyacid precursors are described in the U.S. Patents. Nos. 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, 382.594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332. Examples of preferred cationic peroxyacid precursors are described in United Kingdom patent application No. 9407944.9 and in the patent applications of E.U.A. Nos. 08/298903, 08/298650, 08/298904 and 08/298906. Suitable cationic peroxyacid precursors include any of the substituted ammonium or alkylammonium alkyl or benzoyloxybenzenesulfonates, the N-acylated caprolactams and the benzoylperoxides of monobenzoyltetraacetyl glucose. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include trialkylammonium methylenebenzoylcaprolactams and trialkylammonium methylenealkylcaprolactams.

Benzoxazine organic peroxyacid precursors Also suitable are the benzoxazine type precursor compounds such as those described for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula: where R- | is H, alkyl, alkyl.

Preformed organic peroxyacid The organic peroxyacid bleach system 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, very preferably from 1% to 10% by weight of the composition. A preferred class of organic peroxyacid compounds are the amine substituted compounds of the following general formulas: R1- C-N-R2-C-OOH R1- N-C-R2-C-OOH N II O R5 OR R5 O O wherein R 1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R 2 is an alkylene, arylene and alkarylene group containing 1 to 14 carbon atoms, and R 2 is H or an alkyl group, aryl or alkaryl containing 1 to 10 carbon atoms. Amide-substituted organic peroxyacid compounds of this type are described in EP-A-0170386. Other organic peroxyacids include the diacyl and tetraacylperoxides, especially diperoxydodecanoic acid, diperoxytetradecanedioic acid and diperoxyhexadecanedioic acid. Also suitable here are mono- and diperazelaic acid, mono- and diperbrasyl acid and N-phthaloylaminoperoxycaproic acid.

Peroxide source Inorganic perhydrate salts are a preferred 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 perhydrate salts include perborate, percarbonate, perfosphate, persulfate and persilicate salts. The inorganic perhydrate salts are usually 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 stability and storage for the perhydrate salt in the granular product. Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, organic materials such as waxes, oils or fatty soaps. Sodium perborate is a preferred salt of perhydrate and may be in the form of the monohydrate of the nominal formula NaB2H202 or the tetrahydrate NaB02H2? 2-3H2 ?. The alkali metal percarbonates, particularly sodium percarbonate, are preferred perhydrates herein. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C03-3H2? 2, and is commercially available as a crystalline solid. Potassium peroximonopersulfate is another salt of inorganic perhydrate for use in the detergent compositions herein.

Colorant A preferred ingredient of the compositions of the invention are dyes and particles of dyes or dots, which may be sensitive to bleach. The colorant as used herein may be a dye material or an aqueous or non-aqueous solution of a dye material. It may also be preferred that the colorant be an aqueous solution comprising a coloring material, at any level to obtain suitable coloration of the detergent particles or spots, preferably so that the levels of the coloring solution are obtained up to 2% by weight of the dye particle, or more 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 may also comprise other ingredients such as organic binder materials, which may also be a non-aqueous liquid. The coloring material can be any suitable coloring material. Specific examples of suitable coloring materials include E104- yellow food 13 (yellow quinoline), E110- yellow food 3 (yellow sunset FCF), E131- blue food 5 (blue V patent), ultramarine blue (trade name), E133- blue food 2 (bright blue FCF), E140- natural green 3 (chlorophyll and chlorophyllins), E141 and green pigment 7 (chlorinated Cu phthalocyanine). The preferred coloring materials can be Monastral Blue BV (trade name) and / or Pigmasol Green (trade name). The colored detergent particles or effervescent components preferably comprise up to 10% or more preferably up to 2% or even up to 1% by weight of the particle or colored component.

Perfumes Another preferred ingredient of the component of the invention or the compositions herein is a perfume or perfume composition. Any perfume composition can be used herein. Perfumes can also be encapsulated. Preferred perfumes 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 aldehyde, ketone, alcohol or ether functional groups or mixtures thereof.

Heavy Metal Sequestrant The components according to the present invention and / or the detergent compositions herein preferably contain as an optional component a heavy metal ion sequestrant or chelator or chelating agent. By heavy metal ion sequestrant means in the present components that act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelating ability, but preferably show selectivity to bind heavy metal ions such as iron, manganese and copper. Heavy metal ion sequestrants are generally present at a level from 0.005% to 10%, preferably from 0.1% to 5%, more preferably from 0.25% to 7.5% and more preferably from 0.3% to 2% by weight of the compositions or component. Heavy metal ion sequestrants suitable for use herein include organic phosphonates, such as the aminoalkylene poly (alkylene phosphonates), alkali metal ethane-1-hydroxy diphosphonates, and nitrilotrimethylene phosphonates. Preferred among the above species are diethylenetriaminepenta (methylene phosphonate), ethylenediaminetri- (methylene phosphonate), hexamethylenediaminetetra (methylene phosphonate) and hydroxyethylene 1,1-diphosphonate, 1,1-hydroxyethoediphosphonic acid and 1,1-hydroxyethanedimethylenephosphonic 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 salts thereof. Other heavy metal ion sequestrants suitable for use herein are the iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glycerylimino diacetic acid, which are 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 acid, 2,4-tricarboxylic. Glycinamide-N-N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable. Especially preferred are diethylenetriaminepentaacetic acid, ethylenediamine-N.N'-disuccinic acid (EDDS), and 1,1-hydroxyethanediphosphonic acid, or the alkali metal, alkaline earth, ammonium or substituted ammonium salts of the same, or mixtures thereof. In particular chelating agents comprising an amino or amine group can be sensitive to bleach and are suitable in the compositions of the invention.

Enzymes Another highly preferred ingredient useful in the components or compositions herein 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 conventionally incorporated in detergent compositions. Suitable enzymes are discussed in the patents of E.U.A.

Nos. 3,519,570 and 3,533,139. Preferred commercially available protease enzymes include those sold under the trademarks Alcalase, Savinase, 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 enzyme may be incorporated in the compositions according to the invention at a level of 0.0001% to 4% active enzyme by weight of the composition. Preferred amylases include, for example, α-amylases obtained from a special strain of B. licheniformis, described in more detail in GB-1, 269,839 (Novo). Preferred commercially available amylases include, for example, those sold under the trade name Rapidase by Gist-Brocades, and those sold under the trade name Termamyl, Duramyl and BAN by Novo Industries A / S. Highly preferred amylase enzymes may be those described in PCT / US 970365, and in W095 / 26397 and W096 / 23873. The amylase enzyme may be incorporated in the composition according to the invention at a level of 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, more preferably from 0.001% to 0.5% by weight. The lipase can be fungal or bacterial in origin, being obtained, for example, from a strain producing lipase Humicola sp., Thermomvces sp. or Pseudomonas sp., including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipases from mutants chemically or genetically modified from those strains are also useful herein. 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 gene from Humicola lanuqinosa and expressing the gene in Asperqillus oryza, as a host, as described in the European patent application EP-A-0258 068, which is commercially available from Novo Industri A / S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent No. 4,810,414, Huge-Jensen et al, issued March 7, 1989.

Optical brightener The component or compositions herein also preferably contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners, as mentioned above. The hydrophilic optical brighteners useful herein include those having the structural formula: wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R 2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphino, chloro and amino; and M is a salt-forming cation such as sodium or potassium. When in the above formula R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is acid 4,4'-b1s [(4-anilino-6- (N- 2-b.s-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-styldisulfonic acid and the disodium salt. This particular brightener species is marketed under the trade name Tinopal UNPA-GX by Ciba-Geigy Corporation. The Tinopal CBS-X and Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.

When in the above formula Ri 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 acid 4,4, -bis [(4-anilino -6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid. This particular brightener species is marketed under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation. When in the above formula Ri is anilino, R2 is morphino and M is a cation like sodium, the brightener is the sodium salt of 4,4'-bis [(4-anilino-6-morphino-s-triazin-2) -yl) amino] 2,2'-stilbenedisulfonic acid. This particular kind of brightener is sold commercially under the trade name Tinopal DMS-X and Tinopal AMS-GX by Ciba-Geigy Corporation.

Photo-bleaching agent Photo-bleaching agents are preferred ingredients of the compositions or components herein. The preferred photo-bleaching agent herein comprises a compound having a porphyrin or porphyrin structure. Porphyrin and porphyrin, in the literature, are used as synonyms, but conventionally porffin represents the simplest form of porphyrin without any substituent; in which porphyrin is a sub-class of porphine. References to porfin 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, more preferably Ge, Si or Ga, or more preferably Al, more preferably Zn. It may be preferred that the photobleaching compound or component be substituted with substituents selected from alkyl groups such as methyl, ethyl, propyl, t-butyl group and aromatic ring systems such as pyridyl, pyridyl N-oxide, phenyl, naphthyl moieties. and anthracil. The photobleaching compound or component may have solubilizing groups as substituents. Alternatively, or in addition to, the photobleaching agent may comprise a polymeric component capable of solubilizing the photobleaching compound, for example, PVP, PVNP, PVI or co-polymers thereof or mixtures thereof. Highly preferred photobleaching compounds are compounds having a phthalocyanine structure, which preferably has the metal elements or cations described above. The metal phthalocyanines and their derivatives have the structure indicated in formula I and / or formula II, in which the atom positions of the phthalocyanine structure are numbered in a conventional manner. Phthalocyanines can be substituted, for example, phthalocyanine structures which are substituted at one or more of the atom positions 1-4, 6, 8-11, 13, 15-18, 20, 22-25, 27.

Water soluble detergent meiorator compound The component or compositions herein preferably contain a water soluble builder compound, typically present in detergent compositions at a level of 1% to 80% by weight, preferably 10% to 60% by weight, more preferably from % to 40% by weight. The detergent compositions of the invention may comprise phosphate-containing builder material in addition to the specified zeolite builder. When present the phosphate is generally present at a level of 0.5% to 60%, more preferably from 5% to 50%, more preferably from 8% to 40% by weight of the composition. The phosphate-containing builder preferably comprises tetrasodium pyrophosphate or even more preferably anhydrous sodium tripolyphosphate. Suitable water-soluble builder compounds include water-soluble monomeric polycarboxylates, or their acid forms, homo- or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from one another by no more than two carbon atoms, borates, 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 and fumaric acid, as well as ether carboxylates and sulfinyl carboxylates . Polycarboxylates or their acids containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates, as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1, 379,241, the lactoxysuccinates described in the patent. British No. 1, 389,732 and the aminosuccinates described in Dutch application 7205873 and oxypolycarboxylate materials such as 2-oxa-1,1,1-propanedicarboxylates described in British Patent 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%, more 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-etantetracarboxylates, 1, 1, 3,3-propanetracarboxylates and 1, 1, 2,3 -propanetracarboxylates. 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 hydrocarboxylates containing up to three carboxy groups per molecule, most particularly citrates. The origin acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, for example, citric acid or citrate / citric acid mixtures are also contemplated as useful builders components. Borate builders, as well as detergency builders containing borate-forming materials that can produce borate under detergent storage conditions or under washing conditions are water soluble builders useful herein. Suitable examples of water-soluble phosphate builders are metalalkaline tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium pyrophosphate and ammonium, sodium and potassium orthophosphate, and polymeta / sodium phosphate, in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.

Organic polymeric compound Organic polymeric compounds are preferred additional components herein 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 herein essentially any polymeric organic compound that is 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 herein, including quaternized ethoxylated (poly) amine dirt removal / antiredeposition clay according to the invention. The organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of 0.01% to 30%, preferably from 0.1% to 15%, more preferably from 0.5% to 10% by weight of the compositions or component. 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. Polymers of the latter type are described GB-A-1, 596,756. Examples of such salts are polyacrylates of PMp 1000-5000 and their copolymers with maleic anhydride, said copolymers have a molecular weight of from 2,000 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 polyethylene glycols, particularly those of molecular weight of 1000-10000, more particularly 2000 to 8000 and more preferably about 4000. The highly preferred polymeric components herein are cotton soil release polymers and do not Cotton according to the US patent No. 4,968,451, Scheibel et al, and the patent of E.U.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 clay dispersing / anti-redeposition agent for use herein, may be the ethoxylated cationic diamines and monoamines of the formula: Wherein X is a nonionic group selected from the group consisting of H, alkyl or hydroxyalkyl ester or alkyl groups of C? -C, and mixtures thereof, a is from 0 to 20, preferably from 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 for use herein are described in EP-B-011965 and E.U.A. 4,659,802 and E.U.A. 4,664,848.

Disintegrating Agents Disintegrating agents such as effervescent particles comprising acid and alkali components with optional binders can be incorporated into the detergent compositions of the invention. Polymeric disintegrating agents such as those formed from absorbent, swellable polymeric materials can also be incorporated. Suitable material is described, for example, in WO98 / 40463 (Henkel) and WO98 / 40462 (Rettenmaier).

Foam suppression system The detergent components and compositions herein, when formulated for use in compositions for machine washing, may comprise a foam suppression system present at a level of 0.01% to 15%, preferably 0.02% to 10%, more preferably from 0.05% to 3% by weight of the composition or component. The foam suppression systems suitable for use herein may comprise essentially any known antifoam compound, including, for example, silicone antifoam compounds and 2-alkyl alkanol antifoam compounds. By "antifoam compound" is meant herein any compound or mixtures of compounds which act as to decrease 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 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 with trimethylsilyl end blocking units. Other suitable antifoam compounds include the monocarboxylic fatty acids and the soluble salts thereof. These materials are described in the patent of E.U.A. No. 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids and the 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 metalalkaline 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 (for example, fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C deß-C or (eg stearone) amino ketones. N-alkylated triazines such as tri- or hexa-alkylmelamines or di- to tetra-alkyldiaminclortriazines formed as cyanuric chloride products with two or three moles of a primary or secondary amine containing from 1 to 24 carbon atoms, propylene oxide, amide of bis stearic acid and 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 from 75% to 95% by weight of the silicone antifoam compound; and (i) silica, at a level of 1% to 50%, preferably 5% to 25% by weight of the silicone / silica antifoam compound; wherein said silica / silicone antifoam compound is incorporated at a level of 5% to 50%, preferably 10% to 40% by weight; (b) a dispersing compound, most preferably comprising a copolymer of silicone glycol drag with a polyoxyalkylene content of 72-78% and a ratio of ethylene oxide to propylene oxide of 1: 0.9 to 1: 1.1, at a 0.5% to 10% level, preferably 1% to 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 an ethoxylated C-ethanol alcohol with an ethoxylation degree of 5 to 50, preferably 8 to 15, at a level of 5% to 80%, preferably 10 % to 70% by weight; A highly preferred particulate foam suppression system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range of 50 ° C to 85 ° C, wherein The organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate foam suppressor systems in which the organic carrier material is an acid or fatty alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof. same, with a melting point of 45 ° C to 80 ° C. Other highly preferred foam suppression systems comprise polydimethylsiloxane or silicone blends, such as polydimethylsiloxane, aluminosilicate and carboxylic polymers, such as copolymers of secular and acrylic acid.

Polymeric Dye Transfer Inhibition Agents The component and / or the detergent 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 polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof, whereby these polymers can be entangled polymers.

Polymeric agent for releasing dirt Polymeric agents for dirt release, hereinafter "SRA", may optionally be employed in the components or compositions herein. If used, the SRA's will generally comprise from 0.01% to 10.0%, typically from about 0.1% to 5%, preferably from about 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 the hydrophobic fibers through the completion of the wash and rinse cycles, thus serving as an anchor for the hydrophilic segments. This can make it possible for spots that occur after treatment with the SRA to be cleaned 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 made using additional monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely intertwined overall structure. Suitable SRA's include a sulphonated product of a substantially linear ester oligomer composed of an oligomeric ester base structure of terephthaloyl and oxyalkylenoxy repeating units and sulfonated terminal portions derived from allyl covalently linked to the base structure, eg, as is described in the US patent 4,968,451, November 6, 1990 to J. J. Scheibel and E.P. Gosselink. Said ester oligomers can be prepared by: (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 polyesters of 1, 2-propylene / polyoxyethylene terephthalate of non-ionic blocked ends of the U.S. patent. No. 4,711, 730, of December 8, 1987 to Gosselink and others, for example those produced by the transesterification / oligomerization of methyl ether of poly (ethylene glycol), DMT, PG and poly (ethylene glycol) ("PEG"). Other examples of SRA's include: the oligomeric esters of partially blocked and fully anionic ends 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 nonionic blocked block polyester oligomeric compounds of the document E.U.A. 4,702,857, 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, PEG Me-blocked and Na-dimethyl-5-sulfoisophthalate; and the blocked esters of terephthalate of the ends, anionic, especially of sulfoaroyl of the patent of E.U.A. No. 4,877,896 of October 31, 1989 to Maldonado, Gosselink and others, the latter being a typical SRA's useful in both packaging and packaging products. laundry fabrics, an example being an ester composition made from the monosodium salt of m-sulfobenzoic acid, PG and DMT, optionally but preferably further comprising added PEG, eg, PEG 3400. SRA's also include: copolymer blocks simple of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see US Patent No. 3,959,230 to Hays, dated May 25, 1976 and the US patent. 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 hydroxyalkylcellulas of C, see the patent of E.U.A. No. 4,000,093, of December 28, 1976 to Nicol, et al; and 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 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.A. 4,201, 824, Violland et al, and E.U.A. 4,240,918 Lagasse et al; and (II) SRA's with carboxylate end groups made by adding trimethyl anhydride to known SRA's for converting 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 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. Consult E.U.A. No. 4,525,524 Tung et al. Other classes include (lll) anionic terephthalate-based SRA's of the variety bound to urethane, see E.U.A. 4,201, 824, Violland et al.

Other Optional Ingredients Other optional ingredients suitable for inclusion in the compositions of the invention include colors and filler salts, with sodium sulfate being a preferred filler salt. Highly preferred compositions contain from 2% to about 10% by weight of an organic acid, preferably citric acid. In addition, preferably combined with a carbonate salt, minor amounts (for example less than 20% by weight) of neutralizing agents, pH regulating agents, phase regulators, hydrotropes, enzyme stabilizing agents, polyacids, foaming regulators may be present. , opacifiers, anti- oxidant.es, bactericides and colorants, such as those described in US Patent No. 4,285,841 to Barral et al, issued August 25, 1981 (incorporated herein by reference).

Chlorine-based bleach The detergent compositions may include as an additional component a chlorine-based bleach. However, because the detergent compositions of the invention are solid, most chlorine-based liquid bleaches will not be suitable for these detergent compositions and only chlorine-based or granular bleach based products will be suitable. Alternatively, the detergent compositions can be formulated in such a manner as to be compatible with chlorine-based bleach, thereby ensuring that a chlorine-based bleach can be added to the detergent composition by the user at the start or during the washing process. . The bleach based on chlorine is such that a hypochlorite species is formed in aqueous solution. The hypochlorite ion is represented chemically by the formula OCI. "These bleaching agents that yield a hypochlorite species in aqueous solution include metalalkaline and metalalcalin ferric 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 dichloramine B. A preferred bleaching agent for use in the compositions of the instant invention is sodium hypochlorite, potassium hypochlorite or a mixture of them. A preferred chlorine-based bleach may be Triclosan (tradename). The majority of the hypochlorite-yielding bleaching agents described above are available in solid or concentrated form and are dissolved in water during the preparation of the instant compositions of the invention. Some of the above materials are available as aqueous solutions.

Laundry Method The laundry washing methods hereby typically comprise treating laundry with an aqueous wash solution in a washing machine having an effective amount of a laundry detergent composition dissolved or dispensed therein. by machine according to the invention. For an effective amount of the detergent composition means from 10 g to 300 g of product dissolved or dispersed in a volume wash solution of 5 to 65 liters, as are the typical product dosages and volumes of wash solution commonly used in methods of conventional machine laundry. Preferably the 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 pre-treatment or rinse composition, to be used to pre-treat or rinse soiled and soiled fabrics. The detergent compositions of the invention may be in the form of a liquid, gel, powder or tablet.

EXAMPLES Abbreviations used in the examples of detergent composition and effervescence component LAS: Linear sodium alkylbenzene sulfonate of C11 -13. LAS (I): Linear or branched potassium alkylbenzenesulfonate of C11-13. TAS: Sodium alkyl sulfate CxyAS: Sodium alkylsulfate of C1x-C1y C46SAS: Sodium alkylsulphate secondary (2,3) of C14-C16. CxyEzS: Sodium alkylsulfate of C1 x-C1 and condensed with z moles of ethylene oxide CxyEz: Linear primary alcohol predominantly of C1x-C1 and condensed with an average of z moles of ethylene oxide QAS: R2.N + (CH3) 2 ( C2H4? H) with R2 = C? 2-C14 QAS 1: R2.N + (CH3) 2 (C2H4OH) with R2 = C8-C11 APA: amidopropyl dimethylamine from Cs-Cio Soap: Linear sodium alkylcarboxylate derived from an 80/20 mixture of tallow and coconut fatty acids STS: Sodium toluenesulfonate. CFAA: N-methylglucamide of (coconut) C12-C14 alkyl TFAA: C16-C18 alkyl N-methylglucamide TPKFA: C12-C14 whole cut fatty acids STPP: Anhydrous sodium tripolyphosphate TSPP: Tetrasodium pyrophosphate Zeolite A: Hydrated sodium aluminosilicate of formula Na12 (A102Si02) 12.27H20, which has an absorbency of 70g / 100g and a particle size such that 99% by weight is below 15 microns and 0.04% in weight is above 45 micras. NaSKS-6: Crystalline stratified silicate of the formula d-Na2Si2? 5 Citric acid Anhydrous citric acid, 80% has a particle size of 40 to 70 microns, and has a mean particle size in volume of 55 microns. Citric acid II: Anhydrous citric acid or monohydrate, 80% has a particle size of 15 to 40 microns, and has an average particle size in volume of 25 microns. Malic acid: Anhydrous malic acid, 80% has a particle size of 50 microns to 100 microns, and has a mean particle size in volume of 75 microns. Maleic acid: Anhydrous maleic acid, 80% has a particle size of 5 microns at 30 microns, and has a mean particle size in volume of 15 microns. Tartaric acid: Anhydrous tartaric acid, 80% has a particle size of 25 microns to 75 microns, and has a mean particle size in volume of 50 microns. Carbonate Anhydrous sodium carbonate having 80% by volume of particles with a particle size of 50 microns at 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, has a mean particle size in volume of 55 microns.

Bicarbonate Anhydrous sodium bicarbonate that has 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 I: Bicarbonate of anhydrous sodium having 80% by volume of particles with a particle size of 15 microns at 40 microns with 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 1: 4 maleic acid / acrylic acid, average molecular weight of about 70,000 MA / AA (1): Copolymer of maleic acid / acrylic acid 4: 6, average molecular weight of about 10,000 AA: Sodium polyacrylate polymer with average molecular weight of 4,500 CMC: Sodium carboxymethylcellulose Cellulose ether: Methylcellulose ether with a degree of polymerization of 650 available from Shin Etsu Chemicals Protease: Proteolytic enzyme, having 3.3% by weight of active enzyme, sold by Novo Industries A / S under the trade name Savinase Protease 1: Enzyme proteolytic, having 4% by weight of active enzyme, as described in WO 95/10591, sold by Genencor Int. Inc. Alcalase: Proteolytic enzyme having 5.3% by weight of active enzyme, sold by Novo Industries A / S Cellulase : Cellulite enzyme having 0.23% by weight of active enzyme sold by Novo Industries A / S under the trade name Carezyme Amylase: Amiolitic enzyme having 1.6% by weight of active enzyme sold by Novo Industries A / S under the trade name Termamyl 120T Lipase: Lipolytic enzyme having 2.0% by weight of active enzyme sold by Novo Industries A / S under the trade name Lipolasa Lipase (1): Lipolytic enzyme having 2.0% by weight Active enzyme weight sold by Novo Industries A / S under the trade name Lipolasa Ultra Endolase: Enzyme endoglunase, which has 1.5% by weight of active enzyme sold by Novo Industries A / S PB4: Sodium perborate tetrahydrate of nominal formula NaB02.3H20 , the particles have a weight average particle size of 950 microns, 85% of the particles have a particle size of 850 microns to 950 microns. PB1: Particle containing anhydrous sodium perborate bleach of nominal formula NaB? 2-H2? 2 The particles have a weight average particle size of 800 microns, 85% of the particles have a particle size of 750 microns to 950 mieras Percarbonate: Sodium percarbonate containing particles of nominal formula 2Na2C? 3.3H2? 2 | as particles have a weight average particle size of 850 microns, 5% or less have a particle size of less than 600 microns and 2% or less have a particle size of more than 1180 microns. NOBS / LOBS / DOBA: Particle comprising Nonanoyloxybenzenesulfonate / lauryloxybenzenesulfonate in the form of sodium salt or decaniloxybenzoic acid, the particles have a weight average particle size of 750 microns at 900 microns.

NAC-OBS: Particle comprising (6- nonamidocaproyl) oxybenzenesulfonate, the particles have a weight average particle size of 825 microns at 875 microns. TAED I: Particle containing Tetraacetylethylenediamine, the particles have a weight average particle size of 700 microns at 1000 microns. TAED II: Tetraacetylethylenediamine, with a particle size of 150 microns at 600 microns. DTPA: Diethylenetriaminepentaacetic acid DTPMP: Dethylenetriaminpenta (methylenephosphonate), marketed by Monsanto under the trade name Dequest 2060. Photoactivated: Sulfonated zinc phthalocyanine encapsulated in bleach polymer (1) soluble in dextrin Photoactivated: Aluminum-sulfonated phthalocyanine encapsulated in bleaching polymer (2) soluble in dextrin Brightening 1: 4,4'-bis (2-sulfoestyryl) b-phenyl disodium Brightening 2: 4,4'-bis (4-antylan-6-morpholino-1,3,5-triazin 2-yl) amino) stilbene-2: 2'-disulfonate. EDDS: Isomer (S, S) of ethylenediamine-N, N'-disuccinic acid 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 pentaamine PVI: Polyvinylimidazole, with an average molecular weight of 20,000 PVP: Polyvinylpyrrolidone polymer with an average molecular weight of 60,000 PVNO: Polyvinylpyridine N-oxide polymer, with an average molecular weight of 50,000 PVPVI: Polyvinylpyrrolidone copolymer and vinylimidazole, with an average molecular weight of 20,000 QEA: bis ((C2H50) ( C2H40) n) (CH3) -N + -C6Hi2-N + - (CH3) b1s ((C2H50) - (C2H40)) n, in which n = from 20 to 30 SRP 1: Ammonically blocked end polishers SRP 2: Poly (1, 2-propylene terephthalate) dietoxylated short block polymer PEI: Polyethylenimine with an average molecular weight of 1800 and an average degree of ethoxylation of 7 ethyleneoxy residues per nitrogen. Silicone antifoams: Polydimethylsiloxane foam controller with a siloxane-oxyalkylene copolymer as a dispersing agent with a ratio of said foam controller to said dispersing agent from 10: 1 to 100: 1. Opacifier: Mixture of water-based monostyrene latex, sold by BASF Aktiengesellshaft under the trade name Lytron 621 Wax: Paraffin wax Effervescence granule: 60% by weight citric acid; 40% by weight co-compacted sodium carbonate or malic acid / sodium carbonate / sodium bicarbonate in weight ratio of 40:20:40.

In the following examples of the invention all levels are cited as% by weight of the composition. The detergents illustrated are granular detergents, however, in order to form tablets, the illustrated granular detergents may undergo a tabletting step by conventional compression and optionally they may be coated.

TABLE 1 The following compositions are according to the invention TABLE II The following compositions are according to the invention TABLE The following are high density detergent formulations containing bleach according to the present invention: B Powder blown Zeolite A 15.0 Sodium sulphate 0.0 5.0 0.0 LAS 3.0 3.0

Claims (14)

NOVELTY OF THE INVENTION CLAIMS

1. - A detergent composition comprising zeolite characterized in that the zeolite has an absorption value of dibutyl phthalate (DBP) of at least 68g / 100g as defined herein, at least 99% by weight of the zeolite has a particle size of 15 microns or lower (measured as defined herein) and no more than 0.09% has a larger particle size of 45 microns (measured as defined herein).

2. The detergent composition according to claim 1, further characterized in that not more than 0.05% by weight of the zeolite has a particle size larger than 45μm.

3. The detergent composition according to claim 2, further characterized in that not more than 0.01% by weight of the zeolite has a particle size larger than 45 μm.

4. The detergent composition according to any of the preceding claims, further characterized in that the zeolite has a particle size such that 99% by weight of the zeolite has a particle size of 0.1 μm or higher.

5. The detergent composition according to any of the preceding claims, further characterized in that the zeolite is mixed with a preformed detergent composition or component thereof.

6. The detergent composition according to any preceding claim, further characterized in that it further comprises a percarbonate compound.

7. The detergent composition according to any preceding claim, further characterized in that it additionally comprises a fabric softening clay.

8. The detergent composition according to any preceding claim, further characterized in that the zeolite is present as part of a preformed particle, the preformed particle further comprises at least 5% by weight of an anionic surfactant.

9. The detergent composition according to claim 8, further characterized in that the surfactant has a Kraft point below 40 ° C.

10. The detergent composition according to any of the preceding claims, further characterized in that the zeolite is zeolite A or zeolite X.

11. The detergent composition according to any preceding claim, further characterized in that the zeolite is zeolite A.

12. - A process for manufacturing a detergent composition in which zeolite having a DBP value of at least 68g / 100g and a particle size distribution such that at least 99% by weight has a particle size of 15 microns or less , and less than 1% by weight of the zeolite has a particle size larger than 45 microns, it is mixed with additional detergent ingredient to form an agglomerate or extruded material.

13. A process for manufacturing a detergent composition in which zeolite having a DBP value of at least 68g / 100g and a particle size distribution such that at least 99% by weight of the zeolite has a particle size of 15 μm or lower, is sorted by passing through a sorting screen to remove substantially all of the zeolite particles having a particle size above 45 μm, the remaining zeolite being mixed with additional detergent ingredients in a second step .

14. The use of a zeolite having a particle size distribution such that at least 99% by weight has a particle size of 15 μm or less, and less than 1% by weight of the zeolite has a size of particles larger than 45 μm and a DBP absorption value of at least 68 in a detergent composition to reduce fabric debris.