MXPA01009092A - Detergent compositions. - Google Patents

Abstract

Detergent compositions espectially suitable for laundry applications are disclosed, which contain low absorbency zeolite with a dibutyl phthalate (DBP) absorption value less than 68g/100g, a particle size of 15 microns or below and a particle size distribution where no more thant 0.009 % by weight has a particle size greater than 45 microns.

Description

DETERGENT COMPOSITIONS TECHNICAL FIELD The invention relates to detergents, in particular laundry detergents. More particularly, this invention relates to solid detergents, for example in a granulated or tablet form.

BACKGROUND OF THE INVENTION Detergent compositions, particularly those for use as laundry detergents, are well known. A problem associated with detergent products, particularly solid detergent products is their incomplete dissolving or gelling which can lead to residues of detergents in a dispenser drawer or during the washing process which can lead to trapping the undissolved product in the fabrics. It is not desired that said residues be visible on the fabrics even after drying. This problem is exacerbated by the recent trend in the detergent industry towards granular compositions of higher volume density having a higher content of active ingredients, for example, granular detergent compositions having a bulk density of 550 g / L or even 600 g. /the most.

It is well known that the water hardness values are detrimental to the effectiveness of surfactant cleaning systems, for example, by the interaction with certain components of the dirt and the cleaning system of the detergent. Detergent formulators address this problem by incorporating a detergency builder system in detergent compositions that sequesters the hardness of water, thus ensuring maximum cleaning performance of the surfactant system. The phosphate builder systems are highly effective, however, in view of the environmental concerns associated with their use, alternative detergency builders, such as zeolites, are now well known and widely used. Zeolites have effective builder properties and have been successfully incorporated into detergent compositions since 1970. However, zeolite builders are largely insoluble in water and the nature of the zeolite, in the way it is processed , interacts with other detersive components, such as surfactants, carbonates and silicates and they can exacerbate the problem of depositing residues of detergent compositions on fabrics. There are many descriptions of the use of zeolite builders in detergents. For example, US 4000094, US 4264464, JP 08/283799, WO 96/21717, all describe said detergent compositions, specifying the preferred average particle sizes for the zeolite. WO 97/34980 refers to the provision of zeolite particles that give reduced fabric waste and have an increasing liquid carrying capacity. For this purpose, this patent application describes modified zeolite powder in which alkali metal silicate is deposited on Zeolite P having a weight average particle size (50% by weight of the zeolite has a particle size) of 1. -1 Oμm. US 4457854 teaches that the spray-dried base beads particles, formed by spray-drying an aqueous slurry of zeolite and carbonate and then mixed with a water-soluble silicate powder and the non-ionic detergent in a liquid form, produce a free-flowing detergent. . The fabric residues are those that will be reduced by the subsequent addition of the alkali metal silicate anhydride instead of by the incorporation of the silicate in the grinding mixture with zeolite and carbonate. The patent also discloses preferred final average zeolite particle sizes below 15 μm In practice, although they may have the average particle sizes underlined in the references discussed above, the commercially available zeolites have a broad particle size distribution. and they contain larger particles of zeolite.This may be the case in particular, for highly absorbent zeolites due to the processing conditions for said zeolites. The highly absorbent crystalline zeolite can be made by a method in which the zeolite crystallites are formed and in the formation process they are joined to form a particle comprising a crystallite herd having good absorbency. Said method of preparation is relatively difficult to control since the zeolite particles produced tend to have a highly irregular shape and with a wide particle size distribution. The method used to form zeolite with low absorbency requires longer crystallization times for the formation of longer, more regular crystals, the individual crystals that are produced generally provide the white particle size to be used. The inventors of the present have now found that the choice of a specific fraction of crystalline zeolite gives a surprisingly improved fabric residue performance when used in a detergent composition. The inventors have surprisingly found that the selection of the zeolite based on the average particle size not only causes this benefit, but also that the presence of larger particles is critical, so that a significant reduction in fabric residues results when the select a specific fraction of zeolite. Therefore, compared to the very small crystallite herds formed in the production of absorbent zeolite, it can be expected that the increased regularity of the zeolite with low absorbency will solve the problems of the prior art and produce a good residue profile. However, the inventors have found that in the process to form low absorbency zeolite, in fact, the relatively large crystals produced (size of average individual crystals up to 10 or even up to 20 μm) to join in final stages of the process or when stored before use, to form herds of 2 or 3 or more crystals. Since individual crystals are relatively large, this small amount of herd formation can quickly lead to a poor residue profile even when good results can be expected. Therefore, it is even more critical that not only is the selected average particle size, but also that the larger sized particles are removed before incorporation into a detergent composition.

BRIEF DESCRIPTION OF THE INVENTION According to the present invention, there is provided a detergent composition comprising zeolite characterized in that the zeolite has a dibutyl phthalate (DBP) with an absorption value of less than 68g / 100g (as defined herein) and a particle size of 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 of 45μm or higher 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 more preferably not more than 0.01% by weight of the zeolite has a particle size greater than 45μm. Also, preferably the particle size of at least 99% by weight of the zeolite is 0.05 μm or greater, more preferably 0.1 μm or greater. While not wishing to be bound by a theory, the inventors think that fabric waste is minimized by using zeolite in which at least 99% by weight has a particle size of O.O.sub.m, preferably above 0.1 .mu.m or more. because the zeolite of smaller particle size tends to be trapped by fibrils on the surface of the fabrics in the washing process and then accumulate together to form larger particles which leads to the residue of the fabric being trapped in the surface of the fabric. According to the invention, there is also provided the use of a zeolite having a DBP absorption value below 68g / 100g as defined herein and a particle size such that at least 99% by weight of the zeolite has a particle size of 15μm 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 greater than 45μm as measured by the Wet Sieve Test , in a detergent composition to reduce fabric residues.

DETAILED DESCRIPTION OF THE INVENTION Zeolite The measurement of the particle size to determine the proportion of zeolite having a particle size greater than 45 μm is carried out using a Wet Sieve Test. According to the wet screen test, of a batch of zeolite to be tested, the following test is carried out 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. In the Wet Sieve Test, 100 g (+/- 0.1 g) of zeolite sample is placed in a 1000 ml shaker with 500 ml of distilled water. The liquid in the agitator is stirred until no residue remains on the bottom of the agitator. The contents of the agitator are emptied into a sieve with an opening of 45 microns (copper sieve or standard stainless steel of 200 mm diameter). The liquid is not retained. Additional distilled water is then poured into the agitator to mix with the remaining residues and the rinse water is poured into the sieve. Then a rinse step is carried out for the sieve: a base tray for the sieve is filled with distilled water and the sieve is placed on top of the base pan. Extra distilled water is added until the water level is approximately 5-10 mm above the mesh level. The residue is washed with a gentle rotating action for 2-3 minutes. The sieve is then removed and the water is examined in the base pan. If there is any cloudiness, the water is discarded and the sieving step is repeated. If the water is clear, the sieve is placed in a preheated oven at 105 +/- 2 degrees C for 1 hour. The sieve is then removed from the oven and let it cool for 10 minutes +/- 1 minute. The residue is then shaken using a copper wire brush and collected in a pre-weighed heavy box. The weight of the residue is determined as soon as possible (within 2-3 minutes) by weighing on a precision scale to at least 2 places of decimals. The weight of the residue (g) is the percentage of zeolite having a particle size greater than 45 microns. The fractions of measurements of the Wet Sieve Test of specific particle size are not suitable for measuring 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 determination, a Laser Diffraction measurement method is used. In this test, a Simpatetic Laser Diffractor is used, comprising a Helos / KA central unit with the Parados software system, a QUIXEL liquid dispersion system and a 2 mm CUVETTE. 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 at a frequency of 40 KHz for 10 minutes, during which time the ultrasound ensures that a substantially homogeneous dispersion of individual zeolite particles is obtained. A sample of the dispersion is removed from the ultrasonic bath and added slowly in 1 liter of distilled water in a WUIXEL until the software indicates that an optimum concentration for measurement has been reached. A suitable concentration can be, for example, 0.5 g / l. A 2 mm CUVETTE is placed in the QUIXEL and a particle size distribution measurement is performed for the aqueous suspension taken for 10 seconds using an 87.5 μm lens. This measurement method gives the percentage by weight of the sample giving the particle size of 15 μm or less. In order to determine the DBP absorption value of the zeolite, it is automatically titrated the di-n-butyl phthalate (DBP) in a preweighed sample of zeolite in a mixing chamber. As the DBP is titrated, the mixing and agglomeration profile is recorded at the saturation point using a torque rheometer. More specifically, a 25 g sample of zeolite is weighed at two places of decimals and then placed in a mixing chamber of a Brabender absorber with substantially the same distribution. DBP is supplied in the mixing chamber from an LESNA pump, pre-calibrated to give DBP at an average of 2.4 ml / min (+/- 0.2 ml / min) with agitation from the absorber at an average of 125 rpm and the torque of Twisting during mixing is recorded by a Brabender plotter. DBP is added until the maximum torque is reached. After an additional 20-30 seconds to ensure that the saturation point has been exceeded, the Brabender graphics registration stops. In order to calculate the DBP value, a horizontal line is drawn halfway between the highest torque value and the baseline. The horizontal line A passes through the peak. The distance between the upward slope and the downward sloping of the peak is measured along line A and a vertical line B is drawn equidistantly from the upward and downward slopes of the peak along line A. This line B is used to determine the DBP value according to the following formula: absorption value of DBP 0 (g / 100 g) = [(D / R) X (V) X (100) / M where D = distance from the start of the test to saturation (mm) R = speed of the graph paper (mm / min) V = average DBP supply average per minute (ml / min) ie [(g) DBP supplied 5 min before the operation + (g) supplied 5 min after the operation] / 10 M = sample mass used (g) The value of CBP can be below 65 g / 100 g or even below 60 or 55 g / 100 g. Preferred zeolites for use in the present invention have a particle size such that 99% by weight of the zeolite has a particle size of 0.05 μm or more, more preferably 0.1 μm or more. In order to detect the proportion of particles of said low particle size, these particles can be measured by Scanning by Electron Microscopy using stereological interpretation of data as discussed in Computer Assisted Microscopy - The Measurement and Analyzes of Images by John C. Russ; Plenum Press, NY and London 1900, Chapter 8 p. 221-265. In order to obtain zeolites as specified, commercially available materials can be classified in a conventional manner, for example, using screens to obtain the appropriate zeolite fraction. The inventors have found that it can be particularly useful to ensure that in a sample of one tonne of zeolite, the particle size requirements of the claims are met. Said large sample of zeolite is particularly useful because it is sufficiently large so that its value is not adversely affected by plant variability. Zeolites are crystalline aluminosilicates. Suitable aluminosilicate zeolites have the unit cell formula Na2 [(AIO2) z (SiO2) and]. XH2O wherein "z" and "y" are at least 6; the molar ratio of "z" to "y" is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material is in hydrated form and preferably is crystalline, containing from 10% to 28%, more preferably from 18% to 22% of water in bound form. The aluminosilicate zeolites may be materials present in nature, but are preferably synthetically derived. The synthetic crystalline aluminosilicate ion exchange materials are available as Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A and X are preferred. Zeolite A, which is particularly preferred, has the formula Na? 2 [AI02) .2 (SiO2) i2.xH2 ?, wherein x is from 20 to 30, especially 27. Zelite X has the formula Na86 [(L? 2) 86 (SiO2)? o6] -276H2O. The Zeolite MAP builder is also suitable for use in the present invention. Zeolite MAP was described in EP 384070a (Unilever). It was defined as an alkali metal aluminosilicate of P-type zeolite having a silicon to aluminum ratio not greater than 1.33, preferably within the range of 0.9 to 1.33 and more preferably within the range of 0.9 to 1.2. Of particular interest is zeOlite MAP which has a silicon to aluminum ratio not greater than 1.15 and more particularly, not greater than 1.07.

The zeolite may be present in the detergent compositions of the invention or components thereof in amounts as low as 1% by weight to as high as 99% by weight. Generally, the zeolite levels in the detergent compositions of the invention are at least 2% by weight or at least 5% by weight or even at least 10 or 20% by weight. Generally, in the detergent composition, the zeolite as specified, is present in amounts not greater than 80% by weight or not greater than 50% by weight or even in amounts not greater than 40% by weight. The specified zeolite can be incorporated into the detergent composition as a dry particulate material added either directly to the specific particle size or as a larger particle, eg, 100 to 1500 microns, formed from the specific particle size zeolite and binder. Suitable binders include other detergent ingredients and binders conventional in the detergent field such as polymeric materials, for example, based on maleic acid and / or acrylic acid monomers, 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. Said zeolite-based granules with a larger particle size generally contain at least 60% by weight of zeolite.

Alternatively, the specific particle size zeolite is subjected to a detergent processing step with one or more additional detergent ingredients, so that other detergency builders and / or surfactants form a particulate detergent. In this case, the particulate detergent component containing the specific zeolite, generally contains up to 80% by weight, or more, usually up to 70% by weight or even up to 60% by weight of the particulate detergent component. In a preferred aspect of the invention, the zeolite is present as a particulate detergent composition comprising cationic surfactant. In a further 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, the 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 via a spray-dried particle. Said particles preferably contain at least 15% by weight of surfactant or at least 20% by weight or even greater than 25% by weight of surfactant. The surfactant may be anionic, cationic, nonionic, amphoteric or zwitterionic and their mixtures. In view of the reduction in waste provided by the present invention, the spray-dried particles can also contain alkali metal silicate so that both the zeolite and the alkali metal silicate are added in the grinder mixture and spray-dried together. Therefore, according to a process of the present invention, the zeolite of the specific particle size and absorbency is mixed with additional detergent ingredients to form a grinding slurry that is spray dried, the spray-dried powder is then mixed with ingredients of additional detergent to form a granular detergent which optionally is compressed into a tablet. Optional binders can be included at any stage of the process. According to a further embodiment of the invention, the specific zeolite is incorporated into the detergent composition via an agglomerate. The zeolite can agglomerate with other detergent ingredients in conventional ways, retaining its high absorbency properties 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 components of particulate detergents produced are they can be mixed with additional detergent ingredients and optionally compressed into tablets. Optional binders can be included at any stage in the process. According to a further aspect of the invention, the zeolite can be incorporated into the detergent compositions of the invention via an extrudate. Therefore, in a preferred process of the present invention, the specific zeolite is mixed with other detergent ingredients to form a thick paste which is extruded to form extruded lengths of detergent composition. These lengths are cut into short portions and optionally configured to produce detergent granules. Again, the produced detergent particle materials can be mixed with additional detergent ingredients and optionally compressed into tablets. The use of the zeolites as specified, particularly may be beneficial in said extrusion processes. Due to the highly absorbent nature of the zeolite, high proportions of organic detergent components can be incorporated so that the surfactants can be incorporated into the detergent paste while still producing an easily extruded non-tacky paste. A normal extrusion process is described in DE-A-195 24 287. Since zeolites have good absorbency properties, the liquid detergent ingredients can be further dosed to the detergent compositions containing zeolite or components thereof, before the addition of additional detergent ingredients. In particular, the anionic and / or nonionic and / or cationic surfactants, in liquid form, can be added to preformed detergent ingredients, optionally with dissolution aids such as fatty acids and their derivatives and / or esterified polyols such as glycerides and / or soap.

In the detergent compositions of the invention, an additional benefit can be observed in detergent compositions which also contain percarbonate bleaching agents. Percarbonates are particularly vulnerable to losing storage activity due to moisture absorption and the specified zeolites have a high surface area and good moisture absorption so that they can act as a moisture dump during storage, protecting the percarbonate from 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 is 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 the inorganic peroxygen bleach be present, so it is preferred that a percarbonate salt be present. In one embodiment of the invention, it may be preferred that the present detergent composition comprise one or more anionic surfactants and a zeolite (aluminosilicate) builder, so it is preferred that only small amounts of the aluminosilicate builder and the anionic surfactant is in an intimate mixture, that is, 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 be preferred that substantially none of the anionic surfactant and aluminosilicate builder be in an intimate mixture. Therefore, it may be preferred that the composition comprises at least two separate particles comprising anionic surfactant or aluminosilicate. 'Intimate mixture' means, for the purpose of the invention, that two or more ingredients of the component are substantially homogeneously divided into the component or particle. Namely, it has been found that the solubility and / or dispensing of the composition is thus improved. 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, so it is preferred that the composition comprise highly soluble detergency builders, for example, sodium citrate or citric acid, carbonate and / or silicate in crystalline layers. It may also be 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 crystalline layered silicate, preferably NaSKS-6, and 10% by weight. to 70% by weight of a surface-active agent, preferably an anionic surfactant, by which less than 10% by weight of the free moisture agglomerate may be preferred, more preferably 305 to 60% by weight of a crystalline layered silicate. % to 50% by weight of an anionic surfactant.

Other detergent ingredients The compositions according to the invention will also contain additional detergent components. The precise nature of these additional components and levels of incorporation thereof 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.

Surfactant The components according to the invention and the present compositions 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. 3,929,678 issued to Laughiin and Heuring on December 30, 1975. Additional examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz Perry and Berch). A list of suitable cationic surfactants is given in the U.S.A. 4,259,217 issued to Murphy on March 31, 1981.

When present, ampholytic, amphoteric and zwitterionic surfactants are generally used in combination with one or more anionic and / or nonionic surfactants.

Anionic surfactant The components according to the present invention and / or the detergent compositions herein, preferably comprise an additional anionic surfactant. Essentially any anionic surfactants useful for detersive purposes may be comprised of 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 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%, more preferably from 1 to 40%, even more preferably from 5% to 30% by weight. Highly preferred are surfactant systems comprising a sulphonate and a sulfate surfactant, preferably a linear or branched alkylbenzene sulfonate and alkyl ethoxysulfates, such as those described herein, preferably combined with cationic surfactants as described in US Pat. the present.

Other anionic surfactants include isethionates such as acyl isethionates, N-acyl taurates, methyl tauride fatty acid amides, alkyl succinates and sulfosuccinates, sulfosuccinate monesters (especially saturated and unsaturated C 12 -C 18 monoesters), diesters of sulfosuccinate (especially saturated and unsaturated C6-C14 diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin and hydrogenated resin acids and resin acids present in, or derived from tallow oil.

Surfactant anionic surfactant Suitable anionic sulfate surfactants for use herein include linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, oleoyl glycerol fatty sulfates, alkyl phenol ethylene ether sulfates, C5 acyl sulfates -C? 7-N (C? -C4 alkyl) and N- (C2-C2 hydroxyalkyl) glucamine and alkylpolysaccharide sulfates such as alkylpolyglucoside sulfates (the nonionic nonionic compounds being described herein). The alkyl sulfate agents are preferably selected from primary branched C-? Or C? 8 alkyl sulfates, more preferably the branched chain Cn-C-15 alkyl sulfates and the C? 2-Cu chain alkyl sulfates linear.

The alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C 10 -C 8 alkyl sulfates which have been ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the ethoxysulfate surfactant is a C 11 -C 18 alkyl sulfate, more preferably C 11 -C 15, which has been ethoxylated with 0.5 to 7, preferably 1 to 5, moles of ethylene oxide per molecule. A particularly preferred aspect of the invention employs mixtures of preferred alkyl sulfate and / or sulfonate and alkyl ethoxysulfate surfactants. Such mixtures have been described in PCT patent application No. WO 93/18124.

Anionic sulfonate surfactant Suitable anionic sulfonate surfactants for use herein include the salts of C5-C20 linear alkyl benzene sulphonates, alkyl esters sulfonates, primary or secondary C6-C22 alkane sulphonates, C6-C24 olefin sulphonates, polycarboxylic acids sulphonates, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, oleoyl glycerol sulfonates and mixtures thereof.

Anionic carboxylate surfactant Suitable anionic carboxylate surfactants include alkyl ethoxycarboxylates, alkyl polyethoxy polycarboxylate surfactants and soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein. Suitable alkyl ethoxy carboxylates include those with the formula RO (CH2CH2O)? CH2COO "M + wherein R is an alkyl group from Ce to C? 8, x ranges from 0 to 10, and the ethoxylate distribution is such that, on a base in weight, the amount of material wherein x is 0 is less than 20% and M is a cation The polyethoxy polycarboxylate alkyl surface active agents include those having the formula RO- (CHR-r CHR2-O) - R3 wherein R is an alkyl group of Ce to Cie, x is from 1 to 25, Ri and R2 are selected from the group consisting of hydrogen, radial of methyl acid, radical of succinic acid, radial hydroxysuccinic acid and mixtures of the 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 containing a carboxyl unit connected to a sec coal The preferred secondary soap agents for use herein are water-soluble members selected from the group consisting of water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1 -nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps can also be included as foam suppressors.

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

Non-ionic alkoxylated surfactant Any non-ionic alkoxylated surfactants are suitable herein. Ethoxylated and propoxylated nonionic surfactants are preferred. Preferred alkoxylated surfactants can be selected from the limes of nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated / propoxylated non-ionic fatty alcohols of ethoxylate / propoxylate with propylene glycol, and the ethoxylate condensation products. nonionic with the propylene oxide / ethylene diamine adducts.

Non-ionic alkoxylated alcohol surfactant The condensation products of aliphatic alcohols with 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 can be straight or branched, primary or secondary and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms from 2 to 10 moles of ethylene oxide per mole of alcohol.

Non-ionic polyhydroxyl fatty acid amide surfactants The polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R2CONR1Z wherein: R1 is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy, or a mixture thereof. same, preferably C 1 -C alkyl, more preferably C 1 or C 2 alkyl, even more preferably C 1 alkyl (ie, methyl); and R2 is a C5-C31 hydrocarbyl. preferably straight chain C5-C19 alkyl or alkenyl, more preferably straight chain Cg-Ci7 alkyl or alkenyl, even more preferably straight chain C11-C17 alkyl or alkenyl or 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; more preferably Z is a glycityl.

Non-ionic 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 carbon atoms and each R7 is selected from the group which consists 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.

Non-ionic algayl polysaccharide surfactant Alkyl polysaccharides suitable for use herein are described in the U.S.A. 4,565,647, Filling, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing 1. 3 to 10 units of saccharide.

The alkyl polyglycosides have the formula: R2O (CnH2nO) t (glycosyl) x wherein 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; t is from 1.3 to 8. The glycosyl is preferably derived from glucose.

Amphoteric surfactant Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids. Suitable amine oxides include those compounds having the formula R3 (OR4) xN ° (R5) 2 wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoxy and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R 4 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 1 to 3, or a polyethylene oxide group containing 1 to 3 ethylene oxide groups. Preference is given to C-γ-CC-8-dimethylamine oxide and C-io-is-acylamido-alkyl-dimethylamine oxide. A suitable example of an alkyl dicarboxylic acid is Miranol (TM) X2M Conc. Manufactured by Miranol, Inc. , Cayton, 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 and tertiary sulfonium compounds. The betaine and sultaine surfactants are illustrative zwitterionic surfactants for use herein. Suitable betaines are those compounds having the formula R (R ') 2N + R2COO "wherein R is a hydrocarbyl group of C6-C? 8, each R1 is usually C1-C3 alkyl and R2 is a hydrocarbyl group of C1 The preferred betaines are C12-18 dimethylammonium hexanoate and C10-18 acylamidopropane dimethyl (or diethyl) betaines (or ethane).) Complex betaine surfactants are also suitable for use herein.

Cationic surfactants Suitable cationic surfactants that will be used herein include the quaternary ammonium surfactants.

Preferably, the quaternary ammonium surfactant is an N-alkyl or alkylenyl ammonium surfactant of C6-C16 mono, preferably Ce-C-io wherein 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 cationic ester surfactants. The cationic ester surfactant is a compound preferably dispersible in water, which has surfactant properties comprising at least one ester linkage (i.e., -COO-) and at least one cationically charged group. Suitable cationic ester surfactants include choline ester surfactants, for example, have been described in US patents. A. Nos. 422,8042, 4239660 and 4260529. In a preferred aspect, the ester ligature and the cationically charged group are separated from each other in the surfactant molecule by a separation group consisting of a chain comprising at least three atoms (ie, chain length of three atoms), preferably three to eight atoms, more preferably three to five atoms, still more preferably three atoms. The atoms forming the chain of the separation group are selected from the group consisting of carbon, nitrogen and oxygen atoms and mixtures thereof, provided that no nitrogen or oxygen atom in the chain is connected only with the carbon atoms In the chain. Therefore, the spacer groups having, for example, ligatures of -OO- (ie, peroxide), -NN- and -NO-, are excluded while including the separation groups they have, for example ligatures of - CH2-O-CH2- and -CH2-NH-CH2-. In a preferred aspect, the chain of the separation group comprises only carbon atoms, even more preferably the chain is a hydrocarbyl chain.

Cationic monoalkoxylated amine surfactants Herein, mono-alkoxylated amine surfactants preferably of the general formula I are highly preferred: wherein R1 is an alkyl or alkenyl portion containing from about 6 to about 18 carbon atoms, preferably from 6 to about 16 carbon atoms, still more preferably from about 6 to about 14 carbon atoms; R2 and R3 are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl, even more preferably R2 and R3 are methyl groups; R 4 is selected from hydrogen (preferred), methyl and ethyl; X "is an anion such as chlorine, bromine, methylsulfate, sulfate or the like, to provide electrical neutrality, A is an alkoxy group, especially an ethoxy, propoxy or butoxy group, and p is from 0 to about 30, preferably from 2 to about 15, even more preferably from 2 to about 8. Preferably the group ApR4 in formula I has p = 1 and is a hydroxyalkyl group, which has no more than 6 carbon atoms so that the -OH group was separated of the nitrogen atom and quaternary ammonium for not more than 3 carbon atoms Particularly, the preferred ApR4 groups are -CH2CH2OH, -CH2CH2CH2OH, -CH2CH (CH3) OH and -CH (CH3) CH2OH, with -CH2CH2OH being particularly preferred. Preferred R groups are linear alkyl groups R1 linear groups having from 8 to 14 carbon atoms are preferred Other highly preferred cationic monoalkoxylated amine agents for use herein have the formula wherein R1 is C10-C18 hydrocarbyl and mixtures thereof, especially Cio-Cu 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 above type include those in which the ethoxy (EO) (CH2CH20) units are replaced by units of butoxy, isopropoxy [CH (CH3) CH2O] and [CH2CH (CH3O] (i-Pr) or n-propoxy units (Pr), or mixtures of EO and / or Pr and / or i-Pr units.

The levels of the cationic monoalkoxylated amine surfactants are preferably from 0.1% to 20%, more preferably from 0.2% to 7%, even more preferably from 0.3% to 3.0% by weight.

Surfactant of cationic bis-alkoxylated amine The cationic bis-alkoxylated amine surfactant preferably has the general formula II: wherein R1 is an alkyl or alkenyl portion containing from about 8 to about 18 carbon atoms, preferably from 10 to about 16 carbon atoms, still more preferably from about 10 to about 14 carbon atoms; R2 is an alkyl group containing from one to three carbon atoms, preferably methyl; R3 and R4 may independently vary and are selected from hydrogen (preferred), methyl and ethyl, X "is an anion such as chlorine, bromine, methyl sulfate, sulfate or the like, sufficient to provide electrical neutrality.A and A 'may vary independently and each is selected from C1-C4 alkoxy, especially ethoxy, (i.e., -CH2CH2O-), propoxy, butoxy and mixtures thereof, p is from 1 to about 30, preferably from 1 to about 4 and q is from 1 to about 30, preferably from 1 to about 4, and even more preferably both p and q are 1. The highly preferred cationic bis-ethoxylated amine surfactants for use herein have the formula wherein R1 is C10-C8 hydrocarbyl and mixtures thereof, preferably C, C, C, C alkyl, and mixtures thereof. X is any convenient anion to provide charge balance, preferably chloride. With reference to the general cationic bis-alkoxylated amine structure observed above, since in a preferred R1 compound is derived from fatty acids of (coconut) C? 2-Cu alkyl, R2 is methyl and ApR3 and A'qR4 they are each monoethoxy. Other cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula: and? where R is C 0 -C 18 hydrocarbyl, preferably C 0 0 Cu alkyl, independently p is from 1 to about 3 and q is from 1 to about 3, R 2 is C 1 -C 3 alkyl, preferably methyl and X is an anion, especially chloride or bromide.

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

Bleach activator The components according to the present invention and / or the detergent compositions herein preferably comprise a bleach activator, preferably comprising an organic peroxyacid bleach precursor. 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 peroxyacid bleach precursor, as defined herein. The production of the organic peroxyacid is then presented by an in situ reaction of the precursor with a source of hydrogen peroxide. The bleach activator alternatively, or in addition, may comprise a preformed peroxy acid bleach. It is preferred that the bleach activator be present in a particulate component in the component or compositions herein. It may be preferred that it be present as a separate mixed particle. Alternatively, the bleach activator or part thereof may be present in the base 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, of 600 microns at 1400 microns, preferably 700 microns. 1100 mieras More preferably, all of the activator are present in one or more components in particles having the specific weight average particle size. Therefore, it may be preferred that at least 80%, preferably at least 90% or even at least 95% or even substantially 100% of the component or components comprising the bleach activator have a particle size of 300 microns a 1700 microns, preferably from 425 microns to 1400 microns. The hydrophobic peroxyacid bleach precursor preferably comprises a compound having an oxybenzene sulfonate group, preferably NOBS, DOBS, LOBS and / or NACA-OBS, as described herein. The hydrophilic peroxyacid bleach precursor preferably comprises TAED, as described herein.

Precursor of Peroxyacid Bleaching Peroxyacid bleach precursors are compounds that react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally, bleach precursors can be represented as OR II X-C-L wherein L is a leaving group and X is essential and functionally, such that in perhydrolysis the structure of the produced peroxyacid is OR II X-C-OOH For the purpose of the invention, the hydrophobic peroxyacid bleach precursors produce a peroxy acid of the above formula wherein X is a group comprising at least 6 carbon atoms and a hydrophilic peroxy acid bleach precursor yields a peroxy acid bleach of the above formula wherein X is a group comprising from 1 to 5 carbon atoms. Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 30% by weight, more preferably from 1% to 15% by weight, more preferably from 1.5% to 10% by weight. The ratio of hydrophilic to hydrophobic 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 usually contain one or more N- or O-acyl groups, said precursors may be selected from a broad class range. 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 (e.g., 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: R3 and I - O- CH = C- -CH = CH2 - O- CH = C- CH = CH2 and mixtures thereof, wherein R1 is an alkyl, aryl or alkaryl group containing 1 to 14 carbon atoms, R3 is an alkyl chain containing 1 to 8 carbon atoms, R4 is H or R3 and Y is H or a solubilization group. Any of R1, R3 and R4 can be substituted essentially by any functional group including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkylammonium groups.

The preferred solubilization groups are -SO 3"M +, -C 2" M +, -SO 4"M +, -N + (R 3) 4X- and O <-N (R 3) 3 and more preferably -SO 3" M +, -CO 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 sodium and potassium being more preferred, and X being a halide, hydroxide, methyl sulfate or acetate anion.

Precursors of algayl percarboxylic acid bleacher The percarboxylic acid bleach precursors form percarboxylic acids in perhydrolysis. Preferred precursors of this type provide peracetic acid in perhydrolysis. Preferred alkyl percarboxylic precursor compounds of the imide type include tetra acetylated N, N, N 1 N 1 alkylene diamines in which the alkylene group contains 1, 2 and 6 carbon atoms. Particular preference is given to tetra-acetyl ethylenediamine (TAED) as precursors of hydroxylic peroxy acid bleach. Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzenesulfonate (ABS) and pentaacetyl glucose.

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

Precursor of perbenzoic acid The perbenzoic acid precursor compounds provide perbenzoic acid in perhirolisis. Suitable O-acylated perbenzyl acid precursor compounds include the unsubstituted benzoyl oxybenzene sulfates and the benzoylation products of sorbitol, glucose and all saccharides with benzoylating agents, and those of the metric type including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas. Suitable perbenzoic acid precursors of the imidazole type include N-benzoyl midazole and N-benzoyl benzimidazole. Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Precursors of cationic peroxyacid The cationic peroxyacid precursor compounds produce cationic peroxyacids in perhydrolysis. Typically, the 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 alkylammonium group, preferably an ethyl or methyl ammonium group. Cationic peroxyacid precursors are normally present in the solid detergent compositions as a salt with a suitable anion such as a halide ion. The peroxyacid precursor compound to be cationically substituted may be a perbenzoic acid, or substituted derivative thereof, the parent compound as described above. Alternatively, the peroxyacid precursor compound may be a precursor of alkyl percarboxylic acid or an alkyl peroxyacid precursor substituted by amide as described below. Peroxyacid cationium precursors are described in U.S. Patents. 4,904,406; 4,751, 015; 4,988,451; 4,397,757; 5,269,962, 5,127,8532; 5,093,022; 5,106,258; R. U. 1, 382.594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.

Examples of cationic peroxyacid precursors are described in United Kingdom Patent Application No. 9407944.9 and patent applications of E.U.A. Nos. 08/298903, 08/298650, 08/298904 and 08/298906. Suitable cationic peroxyacid precursors include any of the alkyl or benzoyl oxybenzene sulfonates substituted by ammonium or alkyl ammonium, N-acylated caprolactams and monobenzoyltetracetyl-glucose-benzoyl peroxides. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkylammonium-methylene-benzoyl caprolactams and the methylenealkyl trialkyl ammonium caprolactams.

Precursors of benzoxazine organic peroxyacid Precursor compounds of the benzoxazine type are also suitable, as described for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula: wherein Ri is H, alkyl, alkaryl, aryl or arylalkyl.

Preformed organic peroxyacid The components according to the present invention and / or the detergent compositions herein may contain, other than, or as an alternative to, a precursor organic peroxyacid bleach compound, a preformed organic peroxyacid, typically at a level of 1% to 15% by weight, more preferably from 1% to 10% by weight. A preferred class of organic peroxyacid compounds are compounds substituted by amide of the following general formulas: R1- C- N- R2-C-OOH R1-N-C-R2-C-OOH I or R5 O O wherein R1 is an alkyl, aryl or alkaryl group having 1 to 14 carbon atoms, R2 is an alkylene, arylene and alkarylene group containing 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl or alkaryl group containing 1 to 10 carbon atoms. Organic substituted peroxyacid compounds by amide of this type are described in EP-A-0170386. Other organic peroxyacids include diacyl and tetraacyl peroxides, especially diperoxydecanedioic acid, diperoxytetradecanedioic acid and diperoxyhexanedioic acid. Also present in the present invention 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 from 0.01% to 50% by weight, more preferably from 0.5% to 30% by weight of the composition or component. Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are usually the alkali metal salts. The inorganic perhydrate salt can be included as the talline solid without additional protection. However, for certain perhydrate salts, the preferred embodiments of said granulated compositions utilize a coated form of the material that provides better storage stability 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, or organic materials such as waxes, oils or fatty soaps. Sodium perborate is a preferred perhydrate salt and may be in the form of the monohydrate of the nominal formula NaBO2H2 2 2 or the tetrahydrate NaBO2H2 2.3 2.3H2O. The alkali metal percarbonates, particularly sodium percarbonate, are preferred perhydrates herein. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C? 3.3H2? 2 and is commercially available as a talline solid. Potassium peroximonopersulfate is another inorganic perhydrate salt for use in the detergent compositions herein.

Colorant A preferred ingredient of the present compositions are dyes and particles or sparks of dyes, which may be sensitive to the bleach. The colorant as used herein may be a dye material or an aqueous or non-aqueous solution of a dye material. It may be preferred that the colorant be an aqueous solution comprising a coloring material, at any level to obtain adequate coloration of the detergent particles or sparks, preferably such that dye solution levels up to 2% by weight of the colorant are obtained. stained particle or more preferably up to 0.5% by weight, as described above. The colorant can also be mixed with a non-aqueous carrier material, such as non-aqueous liquid materials including nonionic surfactants. Optionally, the colorant also comprises other ingredients 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 yellow 13 for food E104 (quinoline yellow), yellow 3 for food E110 (tropical yellow FCF), blue 5 for food E131 (blue patent V), blue Ultra Marine (trade name), blue 2 for food E133 (bright blue FCF), green 3 natural E140 (chlorophyll and chlorophyllin), green 7 pigment E141 (chlorinated Cu phthalocyanine). The preferred dye materials can be Monastral Blue BV (trade name) and / or Green Pigmasol (trade name) paste. The dyed detergent particles or effervescence components preferably comprise up to 10% or more preferably up to 2% or even up to 1% by weight of the particle or dyed component.

Perfumes Another preferred ingredient of the component of the invention or the present compositions is a perfume or perfume composition. Any perfume composition can be used herein. Perfumes can also be encapsulated. Preferred perfumes contain at least one volatile low molecular weight component, e.g., 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 ion sequestrator The components according to the present invention and / or detergent compositions herein preferably contain as an optional component a heavy metal chelator ion sequestrant or chelating agent. Here we mean components that act to sequester (chelate) heavy metal ions. These components may also have chelating capacity of calcium and magnesium, but preferably show selectivity for binding heavy metal ions such as iron, manganese and copper. Heavy metal ion sequestrants are generally present at a level from 0.005% to 10%, preferably from 0.1% to 5%, more preferably from 0.25% to 7.5% and even more preferably from 0.3% to 2% by weight of the compositions or components. Heavy metal ion sequestrants suitable for use herein include organic phosphonates, such as amino alkylene poly (alkylene phosphonates), alkyl-methyl ethane-1-hydroxy diphosphonates, and nitrile trimethylene phosphonates. Among the above species are the penta (methylenephosphonate) of diethylene triamine, tri (methylenephosphonate) of ethylenediamine, tetra (methylenephosphonate) of hexamethylenediamine and hydroxyethylene 1,1-diphosphonate, 1,1-hydroxydanediphosphonic 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 disuccinic acid or any salts thereof. Other heavy metal ion sequestrants suitable for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyldiacetic acid or glyceryl methanediacetic acid, described in EP-A-317,133. 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. Sequents of β-alanine-N, N'-diacetic acid, aspartic acid-N, N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants 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-describes suitable sequestrants derived from collagen, keratin or casein. EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Also suitable are dipicolinic acid and 2-phosphonobutan-1, 2,4-tricarboxylic acid. Also suitable are glycinamide-N, N'-disuccinic acid (GADS), ethylenediamine-N, N'-diglutaric acid (DEG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS). Especially preferred are diethylenetriaminpentaacetic acid, ethylenediamine-N'-disuccinic acid (EDDS) and 1,1-hydroxyethanediphosphonic acid or the alkali metal, alkaline earth metal, ammonium or substituted ammonium salts thereof, or mixtures thereof. the same. In particular, chelating agents comprising an amino or amine group can be sensitive to bleaching and are suitable in the compositions of the invention.

Enzyme Another highly preferred ingredient useful in the components or compositions present is one or more additional enzymes. Preferred additional enzyme materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases incorporated in detergent compositions. Suitable enzymes are discussed in the U.S. Patents. 3,519,570 and 3,533,139. Preferred commercially available protease enzymes include those sold under the trademarks Alcalase, Savinase, Primase, Durazym and Esoperase by Novo Industries A / S (Denmark), those sold under the trade name Maxase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International and those sold under the trade name Opticlean and Optimase by Solvay Enzymes. The protease enzyme can be incorporated in the compositions according to the invention at a level of 0.0001% to 4% of active enzyme per 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). Commercially preferred amylases include, for example, those sold under the tradename 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 9703635 and in WO95 / 26397 and WO96 / 23873. The amylase enzyme can be incorporated in the composition according to the invention at a level of 0.0001% to 2% by weight of active enzyme. 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 of fungal or bacterial origin, being obtained, for example, from a lipase-producing strain of Humicola sp., Thermomvces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomonas fluorescens. The lipase of chemically or genetically mutated mutants of these 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 Humicula lanuqinosa and expressing the gene in Aspergillus orvza, as host, as described in European patent application EP-A-0258 068, which is commercially available from Novo Industri A / S, Bagsvaerd, Cenmak, under the trade name Lipolase. This lipase was also described in the patent of E.U.A. 4,810,414, Huge-Jensen et al., Issued March 7, 1989.

Optical brighteners The component or compositions herein also preferably contain from 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 formation cation such as sodium or potassium. When in the above formula, R is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4'-bis [(4-aniol-6-) acid. (N-2-bis-hydroxyethyl) -s-triazin-2-yl) amino [-2,2'-styldisulfonic acid and disodium salt. These particular brightener species are marketed under the trade name Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-CBS-X 2 and Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions present. 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 disodium salt of acid 4,4, -bis [(4- anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazine-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, R1 is anilino, R2 is morpholino and M is a cation such as sodium, the brightener is sodium salt of 4,4'-bis [(4-aniolin-6-morpholino- s-triazine-2-yl) amino] 2,2'-styldisulfonyl. These particular brightener species are marketed under the trade name Tinopal-DMS-X and Tinopal A; S-GX by Ciba-Geigy Corporation.

Photo-blangueo agent Photobleaching agents are preferred ingredients of the compositions or components herein. The preferred photobleaching agent of the present invention comprises a compound having a porphyrin or porphyrin structure. In the literature, porphyrin and porphyrin are used as synonyms, but porphine conventionally represents the simplest porphyrin without any substituent; where porphyrin is a sub-class of porphine. The porfin reference in that 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 A1, even 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 and anthracyl. The photobleaching compound or component may have solubilization groups as substituents. Alternatively, or in addition, the photobleaching agent may comprise a polymeric component capable of solubilizing the photobleaching compound, for example, PVP, PVNP, PVI or copolymers thereof or mixtures thereof. Highly preferred photobleaching compounds are compounds having a phthalocyanine structure, which preferably have the metal elements or cations described above. The metal phthalocyanines and their derivatives have the structure indicated in Figure 1 and / or Figure 2, wherein the atom positions of the phthalocyanine structure are conventionally numbered. Phthalocyanines can be substituted, for example, phthalocyanine structures which are substituted at one or more of the positions of atoms 1 -4, 6, 8-11, 13, 15-18, 20, 22-25, 27.

Water soluble detergent meiorator compound The present component or compositions preferably contain a water-soluble builder compound, usually present in detergent compositions at a level of 1% to 80% by weight, preferably 10% to 60% by weight, more preferably 15% by weight. 40% by weight. The detergent compositions of the invention may comprise phosphate-containing builder material, in addition to the specific zeolite builder. When present, the phosphate is generally present at a level of from 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 material preferably comprises tetrasodium pyrophosphate or even more preferably sodium tripolyphosphate anhydride. Suitable water-soluble builder compounds include the 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, borate, 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, glycic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) acetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as ether carboxylates and carboxylates of sulfinyl. Polycarboxylates or their acids containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as carboxymethyloxysuccinates described in British Patent No. 1, 379,241, Lactoxysuccinates described in British Patent No. 1, 389,732 and aminosuccinates written in the Netherlands application 7205873, and oxypolycarboxylate materials such as 2-oxa-1,1,3-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 oxydisuccinates described in British Patent No. 1, 261, 829, 1, 1, 2,2-ethane-tetracarboxylates, 1, 1, 3,3-propane-tetracarboxylates and 1, 21, 2,3-propan tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives described in British Patent Nos. 1, 398,421 and 1, 398,422 and in the US patent. No. 3,936,448, and the sulfonated pyrolyzed citrates described in British Patent No. 1, 439,000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates. The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, eg, mixtures of citric acid or citrate / citric acid are also contemplated as useful builders components. Borate builders, as well as builders that contain borate-forming materials that can produce borate under detergent storage or washing conditions, are water soluble builders useful herein. Suitable examples of water-soluble phosphate builders are the tripolyphosphates of alkali metals, sodium pyrophosphate, potassium and mono, sodium and potassium pyrophosphate and ammonium, sodium and potassium orthophosphate, sodium polymetaphosphate in which the degree of polymerization ranges from about 6 to 21 and salts of phytic acid.

Organic polymeric compound The organic polymeric compounds are additional preferred herein and are preferably present as components of any particulate components where they can act as such to bind the particulate component. By "organic polymeric compound" is meant herein, essentially any polymeric organic compound commonly used as dispersing agents and against redeposition and suspension of dirt in detergent compositions, including any of the high molecular weight organic polymer compounds described as clay flocculating agents in the present, including removal agent / against the clay-dirt redeposition of quaternized ethoxylated (poly) amine according to the invention. The organic polymeric compound is usually incorporated in the detergent compositions of the invention at a level of from 0.01% to 30%, preferably from 0.1% to 15%, even more preferably from 0.5% to 10% by weight of the compositions or component. Examples of organic polymeric compounds include water-soluble organic or homo-copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. The last type of polymers is described in GB-A-1, 596,756. Examples of such salts are polyacrylates of molecular weight 1000-5000 and their copolymers with maleic anhydride, said copolymers having a molecular weight of 2000 to * _ 100,000, especially 40,000 to 80,000. The polyamino compounds are useful herein including those aspartic acid derivatives such as those described in EP-A-3052282, EP-A-305283 and EP-A-351629. Terpolymers containing selected monomer units of maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of 5,000 to 10,000, are also suitable herein. 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 with molecular weight 1000-10000, more particularly 2000 to 8000 and even more preferably about 4000. The highly preferred polymer components herein are soil release polymer that are not of cotton according to the US patent 4,968,451, Scheibel et al., And patent of E.U.A. 5,415,807, Gosselink et al., And in particular, according to the application of E.U.A. No. 60/051517. Another organic compound, which is a preferred clay dispersant / anti-redeposition agent, for use herein, may be ethoxylated cationic monoamines and diamines of the formula: wherein X is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof, a is 0 to 20, preferably 0 to 4 (v .gr., ethylene, propylene, hexamethylene) b is 1 or 0; for cationic monoamines (b = 0), n is at least 16, with a normal scale of 20 to 35; for cationic diamines (b = 1), n is at least about 12 with a normal scale of about 12 to about 42. Other dispersant / anti-redeposition agents to be used herein are described in EP-B-011965 and US Pat. 4,659,802 and US 4,664,848.

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

Suds suppressor system The detergent components and compositions herein, when formulated for use in washing machine compositions, may comprise a suds suppressor system present at a level of 0.01% to 15%, preferably 0.02% to 10%, more preferably 0.05% to 3% by weight of the composition or composition. The suds suppressor systems suitable for use herein may comprise essentially any foam anti-foaming composition, including, for example, silicone foam anti-foaming compounds and 2-alkyl alkanol foam anti-foaming compounds. The term "foam antifoaming compound" is understood as meaning any compound or mixtures of compounds which act in such a way as to suppress the formation of suds or foam produced by a solution of a detergent composition, particularly in the presence of agitation of that solution. Particularly preferred foam anti-foaming compounds for use herein are silicone foam antifoaming compounds defined herein as any foam anti-foaming compound that includes a silicone component. Said foam antifoaming compounds also typically contain a silica component. The term "silicone", as used herein, and in general in industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types. Preferred silicone foam antifoaming compounds are siloxanes, particularly polydimethylsiloxanes with final trimethylsilyl blocking units. Other suitable foam anti-foaming compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in the patent of E.U.A. 2,954,347, issued September 27, 1960, from Wayne St. John. The monocaroxy fatty acids and salts thereof, for use as a suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium and lithium salts, and ammonium and alkanolammonium salts. Other suitable foam anti-foaming compounds include, for example, fatty acid esters of high molecular weight (eg, fatty acid triglycerides), fatty acid esters of monovalent alcohols, N-alkylated aminotriazines of aliphatic ketones of Ci8-C 0 (e.g., stearone) such as tri- or hexa-alkylmelamine or di- or tetra-alkyldiamine chlortriazines formed as cyanuric chloride products with two or three moles of a primary or secondary amine containing from 1 to 24 carbon atoms. carbon, propylene oxide, stearic acid bis amide, and alkali metal di-metal monostearyl phosphates (e.g., sodium, potassium, lithium) and phosphate esters. A preferred suds suppressor system comprises: (a) foam antifoam compound, preferably silicone foam antiforming compound, more preferably a silicone foam antiforming compound comprising in combination (i) polydimethylsiloxane, at a level of 50% to 99 %, preferably from 75% to 95% by weight of the silicone foam antiforming compound; and (ii) silica, at a level of 1% to 50%, preferably 5% to 25% by weight of the silicone / silica foam antiforming compound; wherein said silica / silicone foam antiforming compound is incorporated at a level of 5% to 50%, preferably 1% to 40% by weight; (b) a dispersant compound, more preferably comprising a silicone glycol compilation copolymer with a polyoxylalkylene content of 72-78% and a ratio of ethylene oxide to propylene oxide from 1: 0.9 to 1: 1.1 at a level from 0.5% to 10%, preferably from 1% to 10% by weight; a particularly preferred silicone glycol compilation copolymer of this type is DCO544, commercially available from DOW Corning under the trade name DCO544; (c) an inert carrier fluid compound, more preferably comprising an ethoxylated alcohol of Cie-Cía with an ethoxylation degree of from 5 to 50, preferably from 8 to 15, at a level of 5% to 80%, preferably of 10% a 70% by weight. A highly preferred particulate suds suppressor system was described in EP-A-0210731 and comprises a silicone foam antiforming compound and an organic carrier material having a melting point in the range of 50 ° C to 85 ° C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms. EP-A-0210721 describes other preferred particulate foam suppressor systems wherein 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, with a melting point of 45CC at 80 ° C. Other highly preferred suds suppressor systems comprise polydimethylsiloxane or mixtures of silicone, such as polydimethylsiloxane, aluminosilicate and polycarboxylic polymers, such as copolymers of selic acid and acrylic.

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

Polymeric dirt release agent Polymeric dirt release agents, hereinafter "SRA", can optionally be used in the components or compositions present. If used, SRAs will generally comprise from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight. Normally the preferred SRAs have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to be deposited on hydrophobic fibers and remain adhered to them until completing the washing and rinsing cycles, thus serving as an anchor for the hydrophilic segments. This may allow stains that occur after treatment with the SRA to be more easily cleaned in subsequent washing procedures. Preferred SRAs include oligomeric terephthalate esters, usually prepared by processes involving at least one transesterification / oligomerization, often with a metal catalyst such as titanium (IV) alkoxide. Such esters can be made using additional monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, of course, without forming a densely intertwined overall structure. Suitable SRAs include a sulphonated product of a substantially linear ester oligomer comprised of a structure of the oligomeric ester base of repeating units of terephthaloyl and oxyalkylenenoxy and sulfonated terminal portions derived with allyl covalently attached to the structure of the base, for example , as described in the US patent 4,968,451, on November 6, 1990 to JJ. Scheibel and E.P. Gosselink. Said ester oligomers can be prepared by: (a) allyl alcohol of ethoxylation; (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG") in a two step transesterification / oligomerization process; and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRAs include non-ionic endcapped 1,2-propylene / polyoxyethylene terephthalate polyesters of the U.S.A. 4,711, 730, of December 8, 1987, Gosselink et al., For example, those produced by transesterification / oligomerization of methyl ether of poly (ethylene glycol), DMT, PG and poly (ethylene glycol) ("PEG"). Other examples of SRA include: partially and fully anionic oligomeric stresses crowned at one end of the U.S. patent. 4,721, 580, from January 26, 1988 by Gosselink, such as ethylene glycol oligomers ("EG"), PG, DMT and Na-3,6-dioxa-8-hydroxyoctane sulfonate; the nonionic crowned block polyester oligomeric compounds of the U.S.A. 4,702,857, of October 27, 1987, by Gosselink, for example, produced from DMT, EF and / or PG, PEG crowned with Me and 5-sulfoisophthalate of Na-dimethyl; and the anionic end-capped esters of terephthalate, especially sulfoaroyl of the U.S. patent. 4,877,896, of October 31, 1989 by Maldonado, Gosselink and others, the latter being typical of SRA useful in both laundry and fabric conditioning products, an example being an ester composition made of monosodium salt of m-sulfobenzoic acid , PG and DMT, optionally but preferably further comprising added PEG, e.g., PEG 3400.

SRA also includes: simple copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide terephthalate or polypropylene oxide, see U.S. Pat. 3,959,230 to Hays, May 25, 1976 and patent of E.U.A. 3,983,929 of Basadur, July 8, 1975; cellulose derivatives such as hydroxyether cellulosic polymers available as METHOCEL from Dow; C1-C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S. Pat. 4,000,093, December 28, 1976 to Nicol, et al .; and the methyl cellulose ethers 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 centipose measured at 20 ° C as an aqueous solution to 2%. Such materials are available as METOLOSE SM100 and METOLOSE SM200, which are the commercial names of methyl cellulose ether manufactured by Shin-etsu Kagaku Kogyo KK. Additional classes of SRAs include: (1) non-ionic terephthalates using diisocyanate coupling agents to bind polymeric ester structures, see U.S. Pat. 4,201, 824, Violland et al. And US patent. 4,240,918 to Lagasse et al .; and (II) SRA with carboxylate end groups made by the addition of trimellitic anhydride for known SRAs in order to convert the terminal hydroxyl groups to trimellitate esters. With the appropriate selection of catalysts, the trimellitic anhydride forms are linked to the polymer terminals through a carboxylic acid ester isolated from trimellitic anhydride instead of opening the anhydride bond. The nonionic or anionic SRAs can be used as starting materials as long as they have hydroxyl end groups that can be esterified. See patent of E.U.A. 4,525,524 of Tung and others. Other classes include: (III) SRA based on anionic terephthalate of the variety bound with urethane, see patent of E.U.A. 4,201, 824, Violland et al. Other optional ingredients The detergent compositions may include as an additional component a bleach-based bleach. However, since the detergent compositions of the invention are solid, most chlorine-based liquid bleaches will not be suitable for these detergent compositions and only granular or powder chlorine bleaches will be suitable. Alternatively, the detergent compositions can be formulated so that they are compatible with the chlorine-based bleach, thereby ensuring that a chlorine-based bleach can be added to the detergent composition by the user at the beginning or during the washing process. The bleach based on chlorine is such that a kind of hypochlorite is formed in aqueous solution. Hypochlorite is represented chemically by the formula OCI. "Bleaching agents that give a kind of hypochlorite in aqueous solution include alkali metal and alkaline earth metal hypochlorites, hypochlorite addition products, chloramines, chlorimines, chloramides and chlorimides. compounds of this type include sodium hypochlorite, potassium hypochlorite, monobasic calcium hypochlorite, dibasic magnesium hypochlorite, chlorinated trisodium phosphate dodecahydrate, potassium dichloroisocyanurate, sodium dichloroisocyanurate, sodium dichloroisocyanurate dihydrate, trichlorocyanuric acid, 1,3 -dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, Chloramine T, Dicloramine T, chloramine B and Dicloramine B. A preferred bleaching agent for use in the compositions of the present invention is sodium hypochlorite, potassium hypochlorite or a mixture A preferred bleach-based bleach can be Triclosan (tradename). Most of the hypochlorite bleaching agents described above are available in solid or concentrated form and are dissolved in water during the preparation of the compositions of the present invention. Some of the above materials are available as aqueous solutions.

Method for laundry The laundry methods herein usually comprise treating laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a washing detergent composition according to the invention. By an effective amount of the detergent composition is meant 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 doses and volumes of wash solution commonly used in conventional laundry methods. The preferred washing machines can be the so-called low filling machines. In a preferred aspect, the composition is formulated so that it is suitable for hard surface cleaning or hand washing. In another preferred aspect, the detergent composition is a pretreatment and soaking composition that will be used to pretreat or soak soiled and soiled fabric. The detergent compositions of the invention can take the form of a liquid, gel, powder or tablet.

EXAMPLES Abbreviations used in the examples of effervescent component and detergent composition LAS: linear C11-C13 alkyl sodium bencensulfonate LAS (I): C11-13 linear or branched potassium alkyl bencensulfonate TAS: CxyAS sodium and tallow alkyl sulfate CxyAS: C1 x-C1 alkyl and sodium C46SAS: secondary alkyl sulfate (2.3) of sodium C14.C16 CxyEzS: C1x-C1y alkylsulfate of sodium condensed with z moles of ethylene oxide CxyEz: Primary predominantly linear alcohol of C1x-C1 and condensed with an average of moles moles of ethylene oxide QAS R2.N + (CH3) 2 (C2H4OH) with R2 = C12-C14 QAS 1 R2.N + (CH3) 2 (C2H4OH) with R2 = C8-C11 APA amidopropyldimethylamine of C8-C10 Linear alkyl sodium carboxylate soap Derivative of a mixture of 80/20 tallow and coconut fatty acids STS Toluen sodium sulfonate CFAA N-methyl glucamide from (coconut) C12-C14 alkyl TFAA N-methyl alkyl glucamide from C16-C18 TPKFA Coronary whole cut fatty acids of C12-C14 STPP Sodium Tripolyphosphate Anhydride TSPP Tetrasodium Pyrophosphate Zeolite A Sodium aluminosilicate hydrate of the formula Na12 (A1O2S0O2) 12.27H2O having an absorbency of 70g / 100g and a particle size such that 99% by weight is below 15 microns and 0.04% by weight is above 45 micras. NaSKS-6: Crystal-layered silicate of the formula d-Na2Si2O5 Citrus acid I: Citric acid anhydride, 80% having a particle size of 40 micras at 70 microns, and having a mean particle size in volume of 55 microns. Citric acid II: Citric acid anhydride, 80% having a particle size of 15 microns at 40 microns, and having a mean particle size in volume of 25 microns. Malic acid: Malic acid anhydride, 80% having a particle size of 50 microns to 100 microns, and having a mean particle size in volume of 75 microns. Maleic acid Anhydrous maleic acid, 80% having a particle size of 5 microns at 30 microns, and having a mean particle size in volume of 15 microns. Tartaric acid: tartaric acid anhydride, 80% having a particle size of 25 microns to 75 microns, and having a mean particle size in volume of 50 microns. Carbonate I sodium carbonate anhydride 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 sodium carbonate anhydride having 80% by volume of particles with a particle size of 35 microns to 75 microns with a mean particle size in volume of 55 microns. Bicarbonate II: anhydrous sodium bicarbonate having 80% by volume of particles with a particle size of 100 microns at 200 microns with a mean particle size in volume of 150 microns. Bicarbonate I: anhydrous sodium bicarbonate 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 (SiO2: Na2O = 2.0: 1) Sulfate Sodium sulphate anhydride Mg sulfate: Magnesium sulfate anhydride Citrate: Activity trisodium citrate dihydrate 86.4% with particle size distribution between 425μm and 850μm MA / AA Maleic / acrylic acid copolymer 1: 4, molecular weight Average of approximately 70,000 MA AA (1): Maleic / acrylic acid copolymer 4: 6, molecular weight Average of approximately 10,000 AA: Weight sodium polyacrylate polymer average molecular weight of 4,500 CMC: Sodium carboxymethyl cellulose Cellulose ether: Methyl cellulose ether with a degree of polymerization of 650 available from Shin Etsu Chemicals Protease: Proteolytic enzyme, which has 3.3 wt.% active enzyme, sold by NOVO Industries A / S under the trade name Savinase Protease I: Proteolytic enzyme, which has 4% by weight of active enzyme, As described in WO 95/10591, sold by Genecor Int. Inc.

Alcalase Proteolytic enzyme, which has 5.3% by weight of active enzyme, sold by NOVO Industries A / S Cellulose Enzyme cellulite, which has 0.23% by weight of active enzyme, sold by NOVO Industries A / S under the trade name Carezyme Amylase Amylolytic enzyme , which has 1.6% by weight of active enzyme, sold by NOVO Industries A / S under the trade name Termamyl 120T Lipase Lipolytic Enzyme, which has 2.0% by weight of active enzyme, sold by NOVO Industries A / S under the trade name Lipolase Lipase (1) Lipolytic enzyme, which has 2.0% by weight of active enzyme, sold by NOVO Industries A / S under the trade name Lipolase Ultra Endolase Enzyme endoglucanase, which has 1.5% by weight of active enzyme, sold by NOVO Industries A / S PB4 Particle containing sodium perborate tetrahydrate of nominal formula NaBO2.3H2O, the particles having a weight average particle size of 950 microns, 85% of particles having a size or particle from 850 microns to 950 microns PB1 Particle containing anhydrous sodium perborate bleach of nominal formula NaB02.H2O2, the particles having a weight average particle size of 800 microns, 85% of particles having a size of particle from 750 microns to 950 microns Percarbonate: Particle containing sodium percarbonate tetrahydrate of nominal formula 2Na2CO2.3H2O2, the particles having a weight average particle size of 850 microns, 5% or less having a particle size smaller than 600 microns and 2% or less that has a particle size of more than 1180 microns. NOBS / LOBS / DOBA: Particle comprising nonanoyloxybenzene sulphonate / lauryloxybenzene sulphonate in the form of sodium salt or decaniloxybenzoic acid, the particles having a particle size having a particle size of 750 microns to 900 microns NAC-OBS: Particle comprising (6-nonamidocaroyl) oxybenzene sulfonate, the particles having a weight average particle size of 825 microns to 875 microns TAED I: Particle containing tetracetylethylenediamine, the particles having a weight average particle size of 700 microns at 1000 microns TAED II: tetraethylethylenediamine, particle size from 150 microns to 600 microns DTPA: Diethylene thiamine pentaacetic acid DTPMP: Diethylenetriamine penta (methylene phosphonate), marketed by Monsanto under the trade name Dequest 2060 Photoactivated: sulfonated zinc phthalocyanine encapsulated in soluble polymer of dextrin bleach (1) Photoactivated: Phthalocyanine sulfonated aluminum encapsulated in soluble dextrin bleach polymer (2) Disodium 1: 4,4'-bis (2-sulphotryryl) biphenyl polisher 2: 4,4'-bis (4-anilino-6-morpholino-1.3. Disodium 5-triazin-2-yl) amino) stilbene-2,2'-disulfonate EDDS Ethylenediamine-N'-disuccinic acid, isomer (S, S) in the form of its sodium salt HEDP: Acid 1, 1-hydroxyethane diphosphonic PEGx: Polyethylene glycol, with a molecular weight of x (normally 4,000) PEO: Polyethylene oxide, with an average molecular weight of 50,000 TEPAE Tetraethylene pentanoline ethoxylate Polyvinylimidosol, with an average molecular weight of 20,000 PVP Polyvinylpyrrolidone polymer, with an average molecular weight of 60,000 PVNO Polyvinylpyridine N-oxide polymer, with an average molecular weight of 50,000 PVPVI Polyvinylpyrrolidone copolymer and vinylimidazole, with an average molecular weight of 20,000 QEA bis ((C2H5O) (C2H4O) n) ( CH3) -N + -C6H 12-N + - (CH3) bis ((C2H5O) - (C2H4O)) n, where n = from 20 to 30 SRP 1 Polyesters crowned at one end amonically SRP 2 Poly block short polymer ( 1, 2 propylene terephthalate) diethoxylated PEI Polyethyleneimine with an average molecular weight of 1800 and an average degree of ethoxylation of 7 ethyleneoxy residues per nitrogen Silicone Antifoaming: The polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as a dispersing agent with a ratio of said foam controller to the dispersing agent from 10: 1 to 100: 1 Opacrator: Mix of water-based monostyrene latex, sold by BASF Aktiengesellschaft under the trade name Lytron 621 Wax Wax of PA rafina Effervescence Granules: 60% by weight of citric acid; 40% by weight of carbonate Co-compacted sodium or malic acid / sodium carbonate / sodium bicarbonate in weight ratios 40:20:40.

In the following examples of the invention, all levels are cited as% by weight of the composition. The exemplified detergents are granular detergents, however, in order to form tablets, the exemplified granular detergents may be subjected to a conventional compression tablet forming step and optionally may be coated. TABLE I The following compositions are in accordance with the invention.

The following compositions are in accordance with the present invention.

PICTURE The following are high density detergent formulations and containing bleach according to the present invention:

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) below 68g / 100g as defined herein, at least 99% by weight of the zeolite has a particle size of 15 microns or less (measured as defined herein) and no more than 0.09% by weight has particle size greater than 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 greater 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 greater than 45μm.

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 greater.

5. The detergent composition according to any preceding claim, 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. 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 additionally comprises at least 5% by weight of an anionic surfactant. 9. The detergent composition according to claim 8, further characterized in that the anionic surfactant has a Kraft point below 40 ° C. 10. The detergent composition according to any preceding claim, further characterized in that the zeolite is Zeolite A or Zeolite X. 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 the zeolite has such a particle size distribution that at less 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 greater than 45 microns and a DBP value below 68g / 100g is mixed with an ingredient of additional detergent to form an agglomerate or extrudate. 13. A process for manufacturing a detergent composition, further characterized in that in a first step, the commercially available zeolite having a particle size such that 99% by weight is below 15μm, and a DBP value below 68g / 100g is passed through a sorting screen to remove substantially all of the zeolite particles having a particle size above 45μm, the remaining zeolite being combined with other 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 1% by weight of the zeolite has a size of particle greater than 45 μm and a DBP absorption value below 68g / 100g in a detergent composition to reduce fabric debris.