BUILDER COMPONENT

Abstract: The invention provides a builder component comprising a ground crystalline layered silicate which comprises at least 95 %, or even 98 % or even 100 % by weight of crystalline layered silicate having a particle size of less than 150 microns or even 102 microns, whilst having a weight average particle size of more than 15.0 microns, preferably from 16.0 to 48.8 microns. The builder component can be used in particular in solid detergent compositions.

Description: Builder component Technical field The invention relates to builder components which have an excellent building performance an improved dispensing and dissolution and which are in particular useful for detergent compositions. Background to the Invention In the past decades detergent manufacturers have been focused on the development of improved builders as alternatives to phosphate builders. On one hand, new builder materials have been developed and on the other hand existing builders or builder combinations have been improved, for example by optimizing the levels or ratios of the builder materials. In general, most detergents still employ polycarboxylate builders and silicate builders, such as aluminosilicates, amorphous and crystalline sodium silicates. It has been found that one of the main complaints of the users of detergent products is that the products do not always dispense satisfactory. This results in residues of the product in the dispensing drawer, for example in the form of a gel, in the washing machine and also on the fabrics after the wash. This can be in particular a problem with certain ingredients or with high density products, under cold water washing conditions or when limited amounts of water are used in the washing process, such as the case in the initial phase of the washing process when small amounts of water contact the product in the dispensing drawer or in the interior of the machine. A problem related to the gelling of the product is that the product is not delivered efficiently to the wash because not only the gelling ingredients do not dispense well, also the product trapped in the gel is not dispensed well, whereby these ingredients can not contribute to the cleaning performance. Furthermore, the incorporation in detergents of certain ingredients which have a tendency to gel or cake have a negative impact on the flowability of the product. Another problem associated with certain detergent ingredients is that they do not always dissolve satisfactory, for example aluminosilicates, amorphous silicates, coarse silicate materials. This may result in a reduced cleaning performance or deposition of product on the fabric or the washing machine. The inventors have now found that often those ingredients which dispense well, do not dissolve satisfactory and have a tendency to deposit and form residues on the fabrics in the wash. On the other hand, ingredients which dissolve well, have a tendency to gel upon initial contact with water. The inventors have now found that a builder component, containing a ground crystalline layered silicate material whereof the particles have a particle size of less than about 100 microns and having a weight average particle size of more than about 15 microns dissolves readily and provides excellent building. Preferably, the builder component is also such that 90% by weight of the particle has a particle size of from 17.3 to 88.2. They have found that detergent compositions comprising this builder component have an improved flowability, an improved dispensing, a reduced gelling and a less product residues in the dispensing device, in the washing machine and on the fabrics, compared to other silicate materials, such as materials of larger particle size, smaller particle size, aluminosilicates, amorphous materials, or non-layered materials. It is believed that that the layered structure is essential to reduce the formation of gels, whilst the particle size is essential to provide a product which both dispenses and dissolves whilst having a good flowability. Furthermore, it is believed that the ground material has a modified surface structure whereby improved building and dispensing are achieved. Furthermore, it has been found that the intimately mixing this crystalline layered silicate material with other detergent ingredients which have a tendency to form residues or gel, such as surfactants, in particularly anionic surfactant, reduces the formation of residues or the gelling of the ingredients and thus improves the dispensing and the efficiency cleaning performance of ingredients. Summary of the Invention The invention provides a builder component comprising a ground crystalline layered silicate which comprises at least 95% or even 98% or even 100% by weight crystalline layered silicate having a particle size of less than 150 microns or even 102 microns, whilst having a weight average particle size of more than 15.0 microns, preferably from 16.0 to 48.8 microns. The builder component is in particular useful in solid detergent compositions, in particular solid laundry and dish washing detergent compositions. The invention also relates to the use of a builder system comprising a ground crystalline layered silicate which comprises at least 95% or even 98% or even 100% by weight of crystalline layered silicate having a particle size of less than 150 microns or even 102 microns, whilst having a weight average particle size of more than 15.0 microns, preferably from 16.0 to 48.8 microns, in a detergent composition, comprising a surfactant and other detergent components, for improving the dispensing of the detergent component. Detailed Description of the Invention The builder component Crystalline layered silicate The ground crystalline layered silicate of the builder component of the invention comprises at least 95% or even 98% or even 100% by weight of the crystalline layered silicate has a particle size of less than 150 microns or even 102 microns or even less than 88.2 microns or even less than 65.6 microns, whilst having a weight average particle size of more than 15.0 microns, preferably from 16.0 to 48.8 microns or even from 17.3 to 42.1 microns, as measured with a Malvern Instruments SB.OC light scattering equipment, as descibed in the Malvern Instrument users manual. Preferably, when the weight average particle is from 16.0 to 48.8 microns, at least 90% by weight of the particle has a particle size of from 17.3 to 88.2 and when the weight average particle is from 17.3 to 42.1 microns, at least 90% by weight of the particle has a particle size of from 23.3 to 76.0, as measured with a Malvern Instruments SB.OC light scattering equipment. The ground material may be obtained by any method of grinding, preferably by grinding crystalline layered silicate material of a larger particle size than the material of the invention in an ceramic ball mill or an air jet mill. The preferred crystalline layered silicate herein have the general formula NaMSi x 0 2x +i .yH 2 0 wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043. For the purpose of the present invention, x in the general formula above has a value of 2, 3 or 4 and is preferably 2. M is preferably H, K or Na or mixtures thereof, preferably Na. The most preferred material is α-Na2Si2θ5 β. Na2Si205 or δ-Na2Si2θ5, or mixtures thereof, preferably being at least 75%) -Na2Si2θ5 for example available from Clariant as NaSKS-6. The crystalline layered silicate material, in particular of the formula Na2Si2θ5 may optionally comprise other elements such as B, P, S, for example obtained by processes as described in EP 578986-B. The component of the invention may comprise other detergent builders or other detergent ingredients, as described herein. Typically, the builder component may comprise up to 85% or preferably 75% or 50% of other ingredients. Hereby, it may be preferred that the builder component of the invention comprises an intimate mixture of the crystalline layered silicate with other ingredients. When used herein, 'intimately mixing/ mixed' or 'intimate mixture' means for the purpose of the invention that components of the particle are substantially homogeneously divided in the particle. The intimate mixture can be obtained by any process involving the mixing of the components, which can be part of spray-drying process, a tableting process, extrusion process and granulation processes including agglomeration processes. Hereby, preferably a first step comprises forming a mixture of the crystalline layered silicate and the other ingredients, including preferably surfactants and granulation of the mixture to form a particle. The intimately mixing step is preferably done by agglomerating the surfactant and the crystalline layered silicate. This may be done by any conventional agglomeration process. Thus, the builder component may preferably be in the form of an agglomerate. Preferred materials are organic acids or salts, including (poly) carboxylic acids and salts thereof, including polymeric compounds such as acrylic and/ or maleic acid polymers, polymeric compounds, inorganic acids or salts, including carbonates and sulphates, other silicate material, including amorphous silicate, meta silicates, other crystalline layered silicates and aluminosilicates, as described herein. Preferred may be that the builder component of the invention comprises at least a surfactant, preferably comprising at least an anionic surfactant, as described hereinafter. It may be preferred that the particle comprising of from 10% to 60% by weight, preferably from 20% to 50% or even 35% to 45% of other ingredients and from 35% to 90%, preferably form 40% to 80% or even 45% to 65% of the crystalline layered silicate. It may be preferred that the other ingredient comprises a surfactant. Preferably, the weight ratio of the crystalline layered silicate to the surfactant in the builder component is from 4:5 to 7:3, more preferably from 1 :1 to 2:1, most preferably from 5:4 to 3:2. It may be preferred that the builder component comprising less than 10% by weight, preferably less than 5% by weight of free moisture. The free moisture content as used herein, can be determined by placing 5 grams of the builder compoennt in a petri dish and placing this petri dish in a convection oven at 50°C for 2 hours, and subsequently measuring the weight loss, due to water evaporation. It may be preferred that the intimate mixture comprises polymeric binder material. Hereby, it is preferred to use as little binder material as possible. It may be preferred that the intimate mixture comprises less than 25%, preferably less than 10%, more preferably less than 5% by weight, most preferably 0% by weight of ethylene oxide polymers. It may be preferred that the builder component is present in a detergent compositions. Hereby, it may be preferred that the builder composition is present in the form of a separate particle, preferably an agglomerate, preferably having a weight average particle size of from 150 microns to 1700 microns, or more preferably 80% by weight of the particles has an particle size of more than 300 microns (80%) by weight on Tyler sieve mesh 48) and less than 10% by weight of the particles has a particle size of more than 1180 microns (on Tyler mesh sieve 14) or even 710 microns (on Tyler mesh sieve 24). The detergent composition may have any form, including aqueous and non-aqueous liquids, but preferably the composition is a solid composition in the form of bars, flakes, extrudates, but the composition is in the form of granules or tablets. When the composition comprises granules, the granules are preferably of a particle size of from 150 microns to 2500 microns, or even 1500 microns, or more preferably 80% by weight of the granules has an particle size of more than 300 microns (80% by weight on Tyler sieve mesh 48) and less than 10% by weight of the granules has a particle size of more than 1180 microns or even 710 microns (on Tyler mesh sieve24). Preferably the detergent composition has a density of from 300g/litre to 1500g/litre, or more preferably from 400g/litre or even 580g/litre to 1200g/litre or even 850g/litre. The detergent composition and the builder composition, as described above, may comprise additional ingredients, preferred ingredients are described hereinafter. It has been found that detergent composition comprising as builder system or part thereof the builder component of the invention, preferably intimately mixed with any of the ingredients described herein, have an improved dispensing. Thus, the invention also provides a method for improving the dispensing of a detergent composition or component thereof comprising a builder system, by providing a detergent composition comprising as builder system or part thereof a ground crystalline layered silicate whereof at least 90% or preferably at least 95%> by weight has a particle size of more than 20.2 microns and whereof at least 90% or preferably at least 95% by weight has a particle size of less than 100.2 microns. Hereby is meant that the dispensing of the detergent composition or component thereof in the wash water, including from a dispensing drawer of a washing machine or a dispensing device, is improved compared to detergent compositions which comprise do not comprise the builder component of the invention. When used herein, 'improving the dispensing' includes improving dissolution, reducing gelling and reducing residue formation. Additional ingredients The builder component or the compositions herein may contain additional detergent components. The precise nature of these additional components, and levels of incorporation thereof will depend on the physical form of the builder component and the compositions comprising the builder component and the precise nature of the washing operation for which it is to be used. The builder component and the compositions herein preferably contain one or more additional detergent components selected from surfactants, bleaches, bleach catalysts, alkalinity systems, additional builders, organic polymeric compounds, enzymes, suds suppressors, lime soap, dispersants, soil suspension and anti-redeposition agents soil releasing agents, perfumes, brightners, photobleaching agents and additional corrosion inhibitors. Surfactant The builder component of the invention or the detergent compositions herein preferably contain one or more surfactants. The surfactant may comprise any surfactant known in the art selected from anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof. It should be understood that for the purpose of the invention the detergent composition may comprise surfactant which is not present in the intimate mixture with the crystalline layered silicate, but present in the other detergent components. Anionic Surfactant The compositions and the builder component in accord with the present invention preferably comprise an anionic surfactant. Essentially any anionic surfactants useful for detersive purposes can be comprised in the detergent composition. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate and sulfonate surfactants are preferred. Highly preferred are surfactants systems comprising a sulfonate and a sulfate surfactant, preferably a linear or branched alkyl benzene sulfonate and alkyl ethoxylsulfates, as described herein, preferably combined with a cationic surfactants as described herein. Other anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C., ~-C, o monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C^-C, , diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil. Anionic Sulfonate Surfactant Highly preferred herein are anionic sulfonate surfactants. Particularly suitable for use herein include the salts of C5-C20 linear or branched alkylbenzene sulfonates, but also alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof. Most preferred are C 9 -C, 4 linear alkyl benzene sulfonates. Anionic Sulfate Surfactant Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N-(Cι -C4 alkyl) and -N-(Cι - C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein). Alkyl sulfate surfactants are preferably selected from the linear and branched primary l0" l8 alkyl sulfates, more preferably the Ci j-Ci 5 branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates. Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the Cl0" l8 alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a Ci j-Cjg, most preferably Ci 1-C15 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule. A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and/ or sulfonate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124. Anionic Carboxylate Surfactant Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein. Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH2θ) x CH2C00"M + wherein R is a Cg to Ci g alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHRι -CHR2-O)-R3 wherein R is a Cg to Ci g alkyl group, x is from 1 to 25, R\ and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof. Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water- soluble salts of 2-methyl-l-undecanoic acid, 2-ethyl-l-decanoic acid, 2-propyl-l- nonanoic acid, 2-butyl-l-octanoic acid and 2-pentyl-l-heptanoic acid. Certain soaps may also be included as suds suppressors. Alkali Metal Sarcosinate Surfactant Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON (R1) CH2 COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, R is a C1 -C4 alkyl group and M is an alkali metal ion. Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts. Mid-chain branched anionic surfactants Highly preferred herein, in particular for providing an improved surfactant performance, are alkyl chain, mid-chain branched surfactant compounds of the above formula wherein the A D moiety is a branched primary alkyl moiety having the formula: R Rl R2 I I I CH 3 CH 2 (CH 2 ) w CH(CH 2 )χCH(CH 2 )yCH(CH 2 ) z - wherein the total number of carbon atoms in the branched primary alkyl moiety of this formula (including the R, R , and R^ branching) is from 13 to 19; R, R*, and R^ are each independently selected from hydrogen and C1 -C3 alkyl (preferably methyl), provided R, Rl , and R^ are not all hydrogen and, when z is 0, at least R or R* is not hydrogen; w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z is an integer from 0 to 13; and w + x + y + z is from 7 to 13. In general, for the mid-chain branched surfactant compounds of the surfactant system, certain points of branching (e.g., the location along the chain of the R, R , and/or R^ moieties in the above formula) are preferred over other points of branching along the backbone of the surfactant. The formula below illustrates the mid-chain branching range (i.e., where points of branching occur), preferred mid-chain branching range, and more preferred mid-chain branching range for mono-methyl branched alkyl A D moieties useful according to the present invention. CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 (CH 2 ) 1 . 7 CH 2 CH 2 CH 2 CH 2 CH 2 - mid-chain branching range- It should be noted that for the mono-methyl substituted surfactants these ranges exclude the two terminal carbon atoms of the chain and the carbon atom immediately adjacent to the -X - B group. The formula below illustrates the mid-chain branching range, preferred mid-chain branching range, and more preferred mid-chain branching range for di-methyl substituted alkyl A D moieties useful according to the present invention. CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 (CH 2 )o. 6 CH 2 CH 2 CH 2 CH 2 CH 2 - more preferred range — preferred range mid-chain branching range Preferred are surfactant compounds wherein in the above formula the A D moiety does not have any quaternary substituted carbon atoms (i.e., 4 carbon atoms directly attached to one carbon atom). The most preferred mid-chain branched surfactants compounds for use in the detergent compositions herein are mid-chain branched primary alkyl sulfonate and, even more preferably, sulfate surfactants. It should be understood that for the purpose of the invention, it may be preferred that the surfactant system comprises a mixture of two or more mid-chain branched primary alkyl sulfate or sulphonate surfactants. Preferred mid-chain branched primary alkyl_sulfate surfactants are of the formula R Rl R2 I I I CH 3 CH 2 (CH 2 ) w CH(CH 2 ) x CH(CH 2 )yCH(CH 2 ) z OSO 3 M These surfactants have a linear primary alkyl sulfate chain backbone (i.e., the longest linear carbon chain which includes the sulfated carbon atom) which preferably comprises from 12 to 19 carbon atoms and their branched primary alkyl moieties comprise preferably a total of at least 14 and preferably no more than 20, carbon atoms. In the surfactant system comprising more than one of these sulfate surfactants, the average total number of carbon atoms for the branched primary alkyl moieties is preferably within the range of from greater than 14.5 to about 17.5. Thus, the surfactant system preferably comprises at least one branched primary alkyl sulfate surfactant compound having a longest linear carbon chain of not less than 12 carbon atoms or not more than 19 carbon atoms, and the total number of carbon atoms including branching must be at least 14, and further the average total number of carbon atoms for the branched primary alkyl moiety is within the range of greater than 14.5 to about 17.5. R, Rl, and R^ are each independently selected from hydrogen and C1 -C3 alkyl group (preferably hydrogen or C1 -C2 alkyl, more preferably hydrogen or methyl, and most preferably methyl), provided R, Rl, and R^ are not all hydrogen. Further, when z is 1, at least R or Rl is not hydrogen. M is hydrogen or a salt forming cation depending upon the method of synthesis. Examples of salt forming cations are lithium, sodium, potassium, calcium, magnesium, quaternary alkyl amines having the formula R3 R6— N-R4 wherein R^, R4, R5 and R are independently hydrogen, C1-C22 alkylene, C4-C22 branched alkylene, Ci -Cg alkanol, C1-C22 alkenylene, C4-C22 branched alkenylene, and mixtures thereof. Preferred cations are ammonium ( , R4, R5 and R^ equal hydrogen), sodium, potassium, mono-, di-, and trialkanol ammonium, and mixtures thereof. The monoalkanol ammonium compounds of the present invention have R equal to Cj-Cg alkanol, R4, R5 and R^ equal to hydrogen; dialkanol ammonium compounds of the present invention have R~> and R4 equal to C j -Cό alkanol, R^ and R6 equal to hydrogen; trialkanol ammonium compounds of the present invention have R->, R4 and R-> equal to C1 -C alkanol, R^ equal to hydrogen. Preferred alkanol ammonium salts of the present invention are the mono-, di- and tri- quaternary ammonium compounds having the formulas: H 3 N + CH2CH 2 OH, H 2 N + (CH2CH2OH) 2 , HN + (CH 2 CH 2 OH) 3 . Preferred M is sodium, potassium and the C2 alkanol ammonium salts listed above; most preferred is sodium. Further regarding the above formula, w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z is an integer of at least 1; and w + x + y + z is an integer from 8 to 14. A preferred mid-chain branched primary alkyl sulfate surfactant is, a C16 total carbon primary alkyl sulfate surfactant having 13 carbon atoms in the backbone and having 1, 2, or 3 branching units (i.e., R, R! and/or R^) of in total 3 carbon atoms, (whereby thus the total number of carbon atoms is at least 16). Preferred branching units can be one propyl branching unit or three methyl branching units. Another preferred surfactant system of the present invention have one or more branched primary alkyl sulfates having the formula Rl R2 I I CH 3 CH 2 (CH 2 ) x CH(CH 2 )yCH(CH 2 ) z pSO 3 M wherein the total number of carbon atoms, including branching, is from 15 to 18, and when more than one of these sulfates is present, the average total number of carbon atoms in the branched primary alkyl moieties having the above formula is within the range of greater than 14.5 to about 17.5; Rl and R2 are each independently hydrogen or C] -C3 alkyl; M is a water soluble cation; x is from 0 to 11 ; y is from 0 to 11 ; z is at least 2; and x + y + z is from 9 to 13; provided Rl and R^ are not both hydrogen. Preferably, the surfactant system comprises at least 20% by weight of the system, more preferably at least 60% by weight , even more preferably at least 90% by weight of the system, of a mid chain branched primary alkyl sulfates, preferably having Rl and R^ independently hydrogen or methyl, provided Rl and R2 are not both hydrogen; x + y is equal to 8, 9, or 10 and z is at least 2, whereby the average total number of carbon atoms in these sulfate surfactants is preferably from 15 to 17, more preferably from 16-17. Furthermore, preferred surfactant systems are those, which comprise at least about 20%, more preferably at least 60%, even more preferably at least 905 by weight of the system, of one or more mid-chain branched alkyl sulfates having the formula: CH 3 CH 3 (CH 2 CH (CH 2 CH 2 OSO 3 M (I) a D , or CH 3 CH 3 CH 3 (CH 2 ) d CH (CH 2 ) e CH CH 2 OSO 3 M or mixtures thereof; wherein M represents one or more cations; a, b, d, and e are integers, a+b is from 10 to 16, d+e is from 8 to 14 and wherein further when a + b = 10, a is an integer from 2 to 9 and b is an integer from 1 to 8; when a + b = 11 , a is an integer from 2 to 10 and b is an integer from 1 to 9; when a + b = 12, a is an integer from 2 to 11 and b is an integer from 1 to 10; when a + b = 13, a is an integer from 2 to 12 and b is an integer from 1 to 11 ; when a + b = 14, a is an integer from 2 to 13 and b is an integer from 1 to 12; when a + b = 15, a is an integer from 2 to 14 and b is an integer from 1 to 13; when a + b = 16, a is an integer from 2 to 15 and b is an integer from 1 to 14; when d + e = 8, d is an integer from 2 to 7 and e is an integer from 1 to 6; when d + e = 9, d is an integer from 2 to 8 and e is an integer from 1 to 7; when d + e = 10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d + e = l l, d is an integer from 2 to 10 and e is an integer from 1 to 9; when d + e = 12, d is an integer from 2 to 11 and e is an integer from 1 to 10; when d + e = 13, d is an integer from 2 to 12 and e is an integer from 1 to 11 ; when d + e = 14, d is an integer from 2 to 13 and e is an integer from 1 to 12; whereby, when more than one of these sulfate surfactants is present in the surfactant system, the average total number of carbon atoms in the branched primary alkyl moieties having the above formulas is within the range of greater than 14.5 to about 17.5. Preferred mono-methyl branched primary alkyl sulfates are selected from the group consisting of: 3 -methyl pentadecanol sulfate, 4-methyl pentadecanol sulfate, 5-methyl pentadecanol sulfate, 6-methyl pentadecanol sulfate, 7-methyl pentadecanol sulfate, 8- methyl pentadecanol sulfate, 9-methyl pentadecanol sulfate, 10-methyl pentadecanol sulfate, 11 -methyl pentadecanol sulfate, 12-methyl pentadecanol sulfate, 13 -methyl pentadecanol sulfate, 3-methyl hexadecanol sulfate, 4-methyl hexadecanol sulfate, 5- methyl hexadecanol sulfate, 6-methyl hexadecanol sulfate, 7-methyl hexadecanol sulfate, 8-methyl hexadecanol sulfate, 9-methyl hexadecanol sulfate, 10-methyl hexadecanol sulfate, 11 -methyl hexadecanol sulfate, 12-methyl hexadecanol sulfate, 13-methyl hexadecanol sulfate, 14-methyl hexadecanol sulfate, and mixtures thereof. Preferred di-methyl branched primary alkyl sulfates are selected from the group consisting of: 2,3-methyl tetradecanol sulfate, 2,4-methyl tetradecanol sulfate, 2,5- methyl tetradecanol sulfate, 2,6-methyl tetradecanol sulfate, 2,7-methyl tetradecanol sulfate, 2,8-methyl tetradecanol sulfate, 2,9-methyl tetradecanol sulfate, 2,10-methyl tetradecanol sulfate, 2,11 -methyl tetradecanol sulfate, 2, 12-methyl tetradecanol sulfate, 2,3-methyl pentadecanol sulfate, 2,4-methyl pentadecanol sulfate, 2,5-methyl pentadecanol sulfate, 2,6-methyl pentadecanol sulfate, 2,7-methyl pentadecanol sulfate, 2,8-methyl pentadecanol sulfate, 2,9-methyl pentadecanol sulfate, 2,10-methyl pentadecanol sulfate, 2,11 -methyl pentadecanol sulfate, 2, 12-methyl pentadecanol sulfate, 2,13-methyl pentadecanol sulfate, and mixtures thereof. The following branched primary alkyl sulfates comprising 16 carbon atoms and having one branching unit are examples of preferred branched surfactants useful in the present invention compositions: 5-methylpentadecylsulfate having the formula: 6-methylpentadecylsulfate having the formula 3 M 7-methylpentadecylsulfate having the formula ,O S0 3 M CH. 8-methylpentadecylsulfate having the formula 9-methylpentadecylsulfate having the formula l O-methylpentadecylsulfate having the formula wherein M is preferably sodium. The following branched primary alkyl sulfates comprising 17 carbon atoms and having two branching units are examples of preferred branched surfactants according to the present invention: 2,5-dimethylpentadecylsulfate having the formula: 2,6-dimethylpentadecylsulfate having the formula 2,7-dimethylpentadecylsulfate having the formula 2,8-dimethylpentadecylsulfate having the formula 2,9-dimethylpentadecylsulfate having the formula 2,10-dimethylpentadecylsulfate having the formula wherein M is preferably sodium. Alkoxylated Nonionic Surfactant Essentially any alkoxylated nonionic surfactants are suitable herein. The ethoxylated and propoxylated nonionic surfactants are preferred. Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts. Nonionic Alkoxylated Alcohol Surfactant Nonionic surfactant can be present in the detergent compositions. It may be preferred that the level of ethoxylated nonionic surfactants in the intimate mixture are below 10% by weight of the mixture, preferably even 5% by weight. The condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are suitable for use herein. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol. Nonionic Polyhydroxy Fatty Acid Amide Surfactant Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R CONR*Z wherein : Rl is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably Cj or C2 alkyl, most preferably Cj alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C5-C19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain Cι 1 -Cj 7 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 preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl. Nonionic Fatty Acid Amide Surfactant Suitable fatty acid amide surfactants include those having the formula: R"CON(R')2 wherein R° is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R is selected from the group consisting of hydrogen, C1 -C4 alkyl, C\- C4 hydroxyalkyl, and -(C2H4θ) x H, where x is in the range of from 1 to 3. Nonionic Alkylpolysaccharide Surfactant Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647, Llenado, 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 from 1.3 to 10 saccharide units. Preferred alkylpolyglycosides have the formula: R2θ(C n H 2n O)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 3; t is from 0 to 10, and x 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 wherein R J is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Preferred are Ci Q-Ci g alkyl dimethylamine oxide, and CiQ-lg acylamido alkyl dimethylamine oxide. A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ. Zwitterionic Surfactant Zwitterionic surfactants can also be incorporated into the detergent compositions or the builder components in accord with the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein. Suitable betaines are those compounds having the formula R(R')2N + R2cOO " wherein R is a Cg-Ci g hydrocarbyl group, each R^ is typically C1-C3 alkyl, and R2 is a C1 -C5 hydrocarbyl group. Preferred betaines are C \2- lg dimethyl-ammonio hexanoate and the ClO-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein. Cationic Surfactants Suitable cationic surfactants to be used herein include the quaternary ammonium surfactants. Preferably the quaternary ammonium surfactant is a mono Cg-Cjg, preferably Cg-Ci Q N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. Preferred are also the mono-alkoxylated and bis-alkoxylated amine surfactants. Another suitable group of cationic surfactants which can be used in the detergent compositions or components thereof herein are cationic ester surfactants. The cationic ester surfactant is a, preferably water dispersible, compound having surfactant properties comprising at least one ester (i.e. -COO-) linkage and at least one cationically charged group. Suitable cationic ester surfactants, including choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529. In one preferred aspect the ester linkage and cationically charged group are separated from each other in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms (i.e. of three atoms chain length), preferably from three to eight atoms, more preferably from three to five atoms, most preferably three atoms. The atoms forming the spacer group chain are selected from the group consisting of carbon, nitrogen and oxygen atoms and any mixtures thereof, with the proviso that any nitrogen or oxygen atom in said chain connects only with carbon atoms in the chain. Thus spacer groups having, for example, -O-O- (i.e. peroxide), -N-N-, and -N-O- linkages are excluded, whilst spacer groups having, for example -CH2-O- CH2- and -CH2-NH-CH2- linkages are included. In a preferred aspect the spacer group chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain. Cationic mono-alkoxylated amine surfactants Highly preferred herein are cationic mono-alkoxylated amine surfactant preferably of the general formula I: wherein R* is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to about 14 carbon atoms; R and R-5 are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl, most preferably both R and R- are methyl groups; R is selected from hydrogen (preferred), methyl and ethyl; X " is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality; A is a alkoxy group, especially a ethoxy, propoxy or butoxy group; and p is from 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8. Preferably the ApR4 group in formula I has p=l and is a hydroxyalkyl group, having no greater than 6 carbon atoms whereby the — OH group is separated from the quaternary ammonium nitrogen atom by no more than 3 carbon atoms. Particularly preferred ApR groups are — CH CH 2 OH, — CH2CH 2 CH OH, — CH 2 CH(CH 3 )OH and — CH(CH3)CH OH, with — CH2CH2OH being particularly preferred. Preferred R 1 groups are linear alkyl groups. Linear R groups having from 8 to 14 carbon atoms are preferred. Another highly preferred cationic mono-alkoxylated amine surfactants for use herein are of the formula wherein RI is CI Q-CI g hydrocarbyl and mixtures thereof, especially C\ 0-C14 alkyl, preferably C1 Q and C12 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide. As noted, compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy, isopropoxy [CH(CH3)CH2θ] and [CH2CH(CH3θ] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units. The levels of the cationic mono-alkoxylated amine surfactants used in detergent compositions of the invention is preferably from 0.1 % to 20%, more preferably from 0.2% to 7%, most preferably from 0.3% to 3.0% by weight of the composition. Cationic bis-alkoxylated amine surfactant The cationic bis-alkoxylated amine surfactant preferably has the general formula II: wherein R is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms; R2 is an alkyl group containing from one to three carbon atoms, preferably methyl; R^ and R can vary independently and are selected from hydrogen (preferred), methyl and ethyl, X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, sufficient to provide electrical neutrality. A and A' can vary independently and are each selected from C1 -C4 alkoxy, especially ethoxy, (i.e., - CH2CH2O-), propoxy, butoxy and mixtures thereof; p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30, preferably 1 to about 4, and most preferably both p and q are 1. Highly preferred cationic bis-alkoxylated amine surfactants for use herein are of the formula wherein R* is Cιø-Cι g hydrocarbyl and mixtures thereof, preferably C]o > 12, C14 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 noted above, since in a preferred compound R is derived from (coconut) C12- C14 alkyl fraction fatty acids, R is methyl and ApR^ and A'qR4 are each monoethoxy. Other cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula: wherein RI is CI Q-CI g hydrocarbyl, preferably C10-C14 alkyl, independently p is 1 to about 3 and q is 1 to about 3, R is Ci -C3 alkyl, preferably methyl, and X is an anion, especially chloride or bromide. Other compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy (Bu) isopropoxy [CH(CH3)CH2θ] and [CH2CH(CH3θ] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units. Perhydrate Bleaches A preferred additional components of the builder component but preferably the compositions herein is a perhydrate bleach, such as metal perborates, metal percarbonates, particularly the sodium salts. Perborate can be mono or tetra hydrated. Sodium percarbonate has the formula corresponding to 2Na2CO3.3H2O2, and is available commercially as a crystalline solid. Potassium peroxymonopersulfate, sodium per is another optional inorganic perhydrate salt of use in the detergent compositions herein. Organic Peroxyacid Bleaching System A preferred feature of the composition or agglomerstes herein is an organic peroxyacid bleaching system. In one preferred execution the bleaching system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound. The production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches, such as the perborate bleach of the claimed invention. In an alternative preferred execution a preformed organic peroxyacid is incorporated directly into the composition. Compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged. Peroxyacid Bleach Precursor Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as O X- C -L where L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is O X- C - OOH Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1%> to 15% by weight, most preferably from 1.5% to 10% by weight of the detergent compositions. Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O- acyl groups, which precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A- 1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386. Leaving Groups The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition. Preferred L groups are selected from the group consisting of: Y R 3 Y I I -O-CH=C-CH=CH 2 -O-CH=C-CH=CH 2 O O II Y v II O CH 2 -C > — C. . -O^-R ι C , - N NR4 o ii A o R 3 O Y i I' I -0-C=CHR 4 , and — N— S-CH— R 4 R 3 O and mixtures thereof, wherein R is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R 3 is an alkyl chain containing from 1 to 8 carbon atoms, R 4 is H or R 3 , and Y is H or a solubilizing group. Any of R 1 , R and R 4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups. The preferred solubilizing groups are -SO, " M , -CO- ' M , -SO/M , -N (R ) 4 X and O<~N(R 3 )., and most preferably -SO, - M + and -CO- - M + wherein R 3 is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion. Alkyl Percarboxylic Acid Bleach Precursors Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis. Preferred precursors of this type provide peracetic acid on perhydrolysis. Preferred alkyl percarboxylic precursor compounds of the imide type include the N- ,N,N NI tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1 , 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred. The TAED is preferably not present in the agglomerated particle of the present invention, but preferably present in the detergent composition, comprising the particle. Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose. Amide Substituted Plkyl Peroxyacid Precursors Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae: N R N R' O R^ O or R° O O wherein R is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene group containing from 1 to 14 carbon atoms, and R* is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. Amide substituted bleach activator compounds of this type are described in EP-A-0170386. Perbenzoic Acid Precursor Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas. Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole. Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid. Cationic Peroxyacid Precursors Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis. Typically, cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammmonium group, preferably an ethyl or methyl ammonium group. Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion. The peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore. Alternatively, the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter. Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015; 4,988,451 ; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332. Examples of preferred cationic peroxyacid precursors are described in UK Patent Application No. 9407944.9 and US Patent Application Nos. 08/298903, 08/298650, 08/298904 and 08/298906. Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams. Benzoxazin Organic Peroxyacid Precursors Also suitable are precursor compounds of the benzoxazin- type, as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula: wherein R, is H, alkyl, alkaryl, aryl, or arylalkyl. Preformed Organic Peroxyacid The detergent composition may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 1% to 15% by weight, more preferably from 1% to 10% by weight of the composition. A preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae: R 1 — C - - N R 2 — C — OOH R 1 - — N — C R 2 - C OOH O R 5 O or R 5 O O wherein R is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, 2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms, and R-> is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386. Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N- phthaloylaminoperoxicaproic acid are also suitable herein. Bleach Catalyst The builder component or the composition herein can contain a transition metal containing bleach catalyst. One suitable type of bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as copper, iron or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. Pat. 4,430,243. Other types of bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include MnIV2(u-O)3(l,4,7-trimethyl-l,4,7-triazacyclononane)2-(PF6)2, MnH 2(u-O)ι(u- OAc)2( 1 ,4,7-trimethyl- 1 ,4,7-triazacyclononane)2-(Clθ4)2, Mn IV 4(u-O)6( 1 ,4,7- triazacyclononane)4-(Clθ4)2, Mn m Mn V 4(u-O)ι (u-OAc)2-(l ,4,7-trimethyl- 1 ,4,7- triazacyclononane)2-(ClO4)3, and mixtures thereof. Others are described in European patent application publication no. 549,272. Other ligands suitable for use herein include 1 ,5 ,9-trimethyl- 1 ,5,9-triazacyclododecane, 2-methyl- 1 ,4,7-triazacyclononane, 2-methyl- 1,4,7-triazacyclononane, l,2,4,7-tetramethyl-l,4,7-triazacyclononane, and mixtures thereof. The bleach catalysts useful herein may also be selected as appropriate for the present invention. For examples of suitable bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear manganese (IV) complexes such as Mn(l,4,7-trimethyl-l,4,7-triazacyclononane)(OCH3)3_(PF6). Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is a water- soluble complex of manganese (III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups. Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, meso- erythritol, meso-inositol, lactose, and mixtures thereof. U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand. Said ligands are of the formula: R 2 R 3 R 1 -N=C-B-C=N-R 4 wherein R , R , R->, and R4 can each be selected from H, substituted alkyl and aryl groups such that each R! -N=C-R and R3-C=N-R4 form a five or six-membered ring. Said ring can further be substituted. B is a bridging group selected from O, S. CR->R", NR and C=O, wherein R^, R6, and R? can each be H, alkyl, or aryl groups, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings. Optionally, said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro. Particularly preferred is the ligand 2,2'-bispyridylamine. Preferred bleach catalysts include Co, Cu, Mn, Fe,-bispyridylmethane and -bispyridylamine complexes. Highly preferred catalysts include Co(2,2'-bispyridylamine)Cl2, Di(isothiocyanato)bispyridylamine-cobalt (II), trisdipyridylamine-cobalt(II) perchlorate, Co(2,2-bispyridylamine)2θ2Clθ4, Bis-(2,2'- bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and mixtures thereof. Other examples include binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including [Bipy2MnIH(u-O)2Mn "v' bipy2]- (ClO 4 ) 3 . Other bleach catalysts are described, for example, in European patent application, publication no. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711,748 and European patent application, publication no. 224,952, (absorbed manganese on aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019 (cobalt chelant catalyst) Canadian 866,191 (transition metal-containing salts), U.S. 4,430,243 (chelants with manganese cations and non-catalytic metal cations), and U.S. 4,728,455 (manganese gluconate catalysts). The bleach catalyst is typically used in a catalytically effective amount in the compositions and processes herein. By "catalytically effective amount" is meant an amount which is sufficient, under whatever comparative test conditions are employed, to enhance bleaching and removal of the stain or stains of interest from the target substrate. The test conditions will vary, depending on the type of washing appliance used and the habits of the user. Some users elect to use very hot water; others use warm or even cold water in laundering operations. Of course, the catalytic performance of the bleach catalyst will be affected by such considerations, and the levels of bleach catalyst used in fully-formulated detergent and bleach compositions can be appropriately adjusted. As a practical matter, and not by way of limitation, the compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 1 ppm to about 200 ppm of the catalyst species in the wash liquor. To illustrate this point further, on the order of 3 micromolar manganese catalyst is effective at 40°C, pH 10 under European conditions using perborate and a bleach precursor. An increase in concentration of 3-5 fold may be required under U.S. conditions to achieve the same results. Additional builder material Water-Soluble Builders The builder component or preferably compositions herein may contain a water-soluble builder compound, typically present in detergent compositions at a level of from 1% to 80% by weight, preferably from 10% to 60%> by weight, most preferably from 15% to 40% by weight of the composition. The detergent compositions of the invention may comprise phosphate-containing builder material, preferably comprises tetrasodium pyrophosphate or even more preferably anhydrous sodium tripolyphosphate, present at a level of from 0.5% to 60%, more preferably from 5% to 50%, more preferably from 8% to 40. It may be preferred that the composiitons are free of phosphate-containing builder material. Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, and mixtures of any of the foregoing. The carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance. Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates or their acids containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-l,l,3-propane tricarboxylates 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 from 0.1% to 15%, more preferably from 0.5% to 8% by weight of the composition. Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1, 3, 3 -propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398.421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates. The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components. It may be preferred that the polymeric or oligomeric polycarboxylates are present at levels of less than 5%, preferably less than 3% or even less than 2% or even 0% by weight of the compositions. Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions are useful water-soluble builders herein. Insoluble Builder Compound The builder component or the compositions herein may contain an insoluble builder compound, but preferably only present at a level of from 0% to 25% by weight, most preferably from 0% to 15% weight of the composition, or even 0% to 10% by weight of the composition. Examples of largely water insoluble builders include the sodium aluminosilicates. Suitable aluminosilicate zeolites have the unit cell formula Na z [(Alθ2) z (Siθ2)y]- 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 are in hydrated form and are preferably crystalline, containing from 10% to 28%. more preferably from 18% to 22% water in bound form. The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula: Na 12 [AlO 2 ) 1 2 (SiO 2 )i2]- *H 2 O wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nagg [(AlO 2 )g6(SiO2)i06]- 276 H 2 O. Another preferred aluminosilicate zeolite is zeolite MAP builder. Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2. Of particular interest is zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07. In a preferred aspect the zeolite MAP detergent builder has a particle size, expressed as a d$Q value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres. The d5o value indicates that 50% by weight of the particles have a diameter smaller than that figure. The particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods of establishing d5Q values are disclosed in EP 384070 A. The builder component or the compositions herein may also comprise additional silicate material, including amorphous silicate material, metaa-silicates, additional coarse crystalline layered silicate material of particle size of above 150 microns. The additional silicate material is preferably present at a level of less than 20% by weight of the compositions, preferably less than 15% by weight or even less than 10% by weight. Heavy metal ion sequestrant Heavy metal ion sequestrant are also useful additional ingredients herein. By heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper. Heavy metal ion sequestrants are generally present at a level of from 0.005% to 10%, preferably from 0.1 %> to 5%, more preferably from 0.25% to 7.5% and most preferably from 0.3% to 2% by weight of the compositions. Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1 -hydroxy disphosphonates and nitrilo trimethylene phosphonates. Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate, 1,1 hydroxyethane diphosphonic acid and 1,1 hydroxyethane dimethylene phosphonic acid. Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof. Other suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2- hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3- sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein. The 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- 528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane-l,2,4-tricarboxylic acid are alos suitable. Glycinamide- N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable. Especially preferred are diethylenetriamine pentacetic acid, ethylenediamine-N,N'- disuccinic acid (EDDS) and 1,1 hydroxyethane diphosphonic acid or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof. Enzyme Another preferred ingredient useful herein is one or more additional enzymes. Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139. Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist- Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001% to 4% active enzyme by weight of the composition. Preferred amylases include, for example, α-amylases obtained from a special strain of B licheniformis, described in more detail in GB-1.269,839 (Novo). Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl, Duramyl and BAN by Novo Industries A/S. Highly preferred amylase enzymes maybe those described in PCT/ US 9703635, and in WO95/26397 and WO96/23873. Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition. Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001% to 1% by weight, preferably 0.001% to 1% by weight, most preferably from 0.001% to 0.5% by weight of the compositions. The lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein. A preferred lipase is derived from Pseudomonas pseudoalcaligenes. which is described in Granted European Patent, EP-B-0218272. Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge- Jensen et al, issued March 7, 1989. Organic Polymeric Compound Organic polymeric compounds are preferred additional components of the compositions herein or the agglomerates herein, where they may act such as to bind the agglomerate components together. By organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as binder, dispersants, and anti-redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein, including quatemised ethoxylated (poly) amine clay-soil removal/ anti-redeposition agent in accord with the invention. Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.01%) to 30%, preferably from 0.1% to 15%, most preferably from 0.5% to 10% by weight of the compositions. Examples of organic polymeric compounds include the water soluble organic homo- or co-polymeric 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. Polymers of the latter type are disclosed in GB-A-1, 596,756. Examples of such salts are polyacrylates of MWt 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 2000 to 100,000, especially 40,000 to 80,000. The polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629. Terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein. Other organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose. Further useful organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000. Highly preferred polymeric components herein are cotton and non-cotton soil release polymer according to U.S. Patent 4,968,451, Scheibel et al., and U.S. Patent 5,415,807, Gosselink et al., and in particular according to US application no.60/051517. Another organic compound, which is a preferred clay dispersant/ anti-redeposition agent, for use herein, can be the ethoxylated cationic monoamines and diamines of the formula: wherein X is a nonionic group selected from the group consisting of H, Ci -C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof, a is from 0 to 20, preferably from 0 to 4 (e.g. ethylene, propylene, hexamethylene) b is 1 or 0; for cationic monoamines (b=0), n is at least 16, with a typical range of from 20 to 35; for cationic diamines (b=l), n is at least about 12 with a typical range of from about 12 to about 42. Other dispersants/ anti-redeposition agents for use herein are described in EP-B-011965 and US 4,659,802 and US 4,664,848. Suds Suppressing System The detergent compositions of the invention, when formulated for use in machine washing compositions, may comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.02% to 10%, most preferably from 0.05% to 3% by weight of the composition. Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds. By antifoam compound it is meant herein any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution. Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component. The term "silicone" as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types. Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units. Other suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, for use as 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 antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic 18-C40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexa- alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters. A preferred suds suppressing system comprises: (a) antifoam compound, preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination (i) polydimethyl siloxane, at a level of from 50%> to 99%, preferably 75% to 95% by weight of the silicone antifoam compound; and (ii) silica, at a level of from 1 % to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound; wherein said silica/silicone antifoam compound is incorporated at a level of from 5% to 50%, preferably 10% to 40% by weight; (b) a dispersant compound, most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of from 1 :0.9 to 1 : 1.1 , at a level of from 0.5% to 10%, preferably 1% to 10% by weight; a particularly preferred silicone glycol rake copolymer of this type is DCO544, commercially available from DOW Corning under the tradename DCO544; (c) an inert carrier fluid compound, most preferably comprising a C \ g-C \ g ethoxylated alcohol with a degree of ethoxy lation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight; A highly preferred particulate suds suppressing system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50°C to 85°C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point offrom 45°C to 80°C. Other highly preferred suds suppressing systems comprise polydimethylsiloxane or mixtures of silicone, such as polydimethylsiloxane, aluminosilicate and polycarboxylic polymers, such as copolymers of laic and acrylic acid. Polymeric Dye Transfer Inhibiting Agents The compositions herein 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, polyvinylpyrrolidonepolymers or combinations thereof, whereby these polymers can be cross-linked polymers. Optical Brightener The compositions herein also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners. Hydrophilic optical brighteners useful herein include those having the structural formula: wherein R\ is selected from anilino, N-2-bis-hydroxy ethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming 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-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine- 2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba- Geigy Corporation. Tinopal-CBS-X and Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein. When in the above formula, Rj is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl- N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation. When in the above formula, R\ is anilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'- stilbenedisulfonic acid, sodium salt. This particular brightener species are commercially marketed under the tradename Tinopal-DMS-X and Tinopal AMS-GX by Ciba Geigy Corporation. Polymeric Soil Release Agent Polymeric soil release agents, hereinafter "SRA", can optionally be employed in the present compositions. If utilized, SRA's will generally comprise from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight, of the compositions. Preferred SRA's typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles, thereby serving as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the SRA to be more easily cleaned in later washing procedures. Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium(IV) alkoxide. Such esters may be made using additional monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosslinked overall structure. Suitable SRA's include a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Such ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1 ,2-propylene glycol ("PG") in a two-stage transesterification/oligomerization procedure; and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRA's include the nonionic end-capped 1 ,2-propylene/polyoxyethylene terephthalate polyesters of U.S. 4,711,730, December 8, 1987 to Gosselink et al., for example those produced by transesterification oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"). Other examples of SRA's include: the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8- hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S. 4,702,857, October 27, 1987 to Gosselink, for example produced from DMT, methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S. 4,877,896, October 31, 1989 to Maldonado, Gosselink et al., the latter being typical of SRA's useful in both laundry and fabric conditioning products, an example being an ester composition made from m- sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably further comprising added PEG, e.g., PEG 3400. SRA's also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the C1-C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S. 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 from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20°C as a 2% aqueous solution. Such materials are available as METOLOSE SMI 00 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK. Additional classes of SRA's include: (I) nonionic terephthalates using diisocyanate coupling agents to link polymeric ester structures, see U.S. 4,201,824, Violland et al. and U.S. 4,240,918 Lagasse et al.; and (II) SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. With the proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals of the polymer through an ester of the isolated carboxylic acid of trimellitic anhydride rather than by opening of the anhydride linkage. Either nonionic or anionic SRA's may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U.S. 4,525,524 Tung et al.. Other classes include: (III) anionic terephthalate-based SRA's of the urethane-linked variety, see U.S. 4,201,824, Violland et al.; Other Optional Ingredients Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes, speckles, colours or dyes, filler salts, with sodium sulfate being a preferred filler salt. Also, minor amounts (e.g., less than about 20% by weight) of neutralizing agents, buffering agents, phase regulants, hydrotropes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti-oxidants, bactericides and dyes, such as those described in US Patent 4,285,841 to Barrat et al., issued August 25, 1981 (herein incorporated by reference), can be present. Form of the Compositions The composition of the invention can be made via a variety of methods, including dry- mixing, agglomerating, compaction, or spray-drying of the various compounds comprised in the detergent component, or mixtures of these techniques. The compositions herein can take a variety of physical forms including liquid, but preferably solid forms such as tablet, flake, pastille and bar, and preferably granular or tablet forms. The compositions in accord with the present invention can also be used in or in combination with bleach additive compositions, for example comprising chlorine bleach. Detergent compositions herein, in particular laundry detergents, preferably have a bulk density of from 280 g/litre to 200 g/litre, or preferably from 300 g/litre or even 350g/litre or 420g/litre to 2000g/litre or more preferably to 1500g/litre or 100 g/litre or even to 700g/litre. Laundry Washing Method Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention. By an effective amount of the detergent composition it is meant from lOg to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods. The composition may also be formulated such that it is suitable for hard-surface cleaning or hand washing or for pre-treatment or soaking of soiled and stained fabrics. Abbreviations used in Examples In the detergent compositions, the abbreviated component identifications have the following meanings: LAS Sodium linear Cj j_i3 alkyl benzene sulfonate MES α-sulpho methylester of C lg fatty acid TAS Sodium tallow alkyl sulfate CxyAS Sodium Cj x - Ciy alkyl sulfate C46SAS Sodium Cj4 - Ci g secondary (2,3) alkyl sulfate CxyEzS Sodium C] x -Ci y alkyl sulfate condensed with z moles of ethylene oxide CxyEz lχ-C] v predominantly linear primary alcohol condensed with an average of z moles of ethylene oxide QAS R 2 .N+(CH3)2(C2H 4 OH) with R 2 = C n - C 14 QAS 1 R 2 .N+(CH3)2(C 2 H4OH) with R 2 = Cg - Ci i SADS Sodium C ]4 -C 22 alkyl disulfate of formula 2-(R).C 4 H 7 .- l,4-(SO 4 -) 2 where R = C 10 _C 18 SADE2S Sodium C l4 -C 22 alkyl disulfate of formula 2-(R).C 4 H 7 .- l,4-(SO 4 -) 2 where R = C 10 -C 18 , condensed with z moles of ethylene oxide APA Cg - CI Q amido propyl dimethyl amine Soap Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut fatty acids STS Sodium toluene sulphonate CFAA Ci 2-Cι 4 (coco) alkyl N-methyl glucamide TFAA Cι g-Cι g alkyl N-methyl glucamide TPKFA Ci g.Ci g topped whole cut fatty acids STPP Anhydrous sodium tripolyphosphate TSPP Tetrasodium pyrophosphate Zeolite A Hydrated sodium aluminosilicate of formula Nai 2(Alθ2Siθ2)i2- 7H2θ having a primary particle size in the range from 0.1 to 10 micrometers (weight expressed on an anhydrous basis) NaSKS-6 (I) Crystalline layered silicate of formula δ- Na2Si 2 O5 0 f weight average particle size of 18 microns and at least 90% by weight being of particle size of below 65.6 microns. NaSKS-6 (II) Crystalline layered silicate of formula δ- Na 2 Si2θ5 0 f weight average particle size of 18 microns and at least 90%) by weight being of particle size of below 42.1 microns. Citric acid Anhydrous citric acid Borate Sodium borate Carbonate Anydrous sodium carbonate with a particle size between 200μm and 900μm Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400μm and 1200μm Silicate Amorphous sodium silicate (SiO2:Na2O = 2.0:1) Sulfate Anhydrous sodium sulfate Mg sulfate Anhydrous magnesium sulfate Citrate Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425μm and 850μm MA/AA Copolymer of 1 :4 maleic/acrylic acid, average molecular weight about 70,000 MA/AA (1) Copolymer of 4:6 maleic/acrylic acid, average molecular weight about 10,000 AA Sodium polyacrylate polymer of average molecular weight 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, having 3.3% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Savinase Protease I Proteolytic enzyme, having 4% by weight of active enzyme, as described in WO 95/10591, sold by Genencor Int. Inc. Alcalase Proteolytic enzyme, having 5.3% by weight of active enzyme, sold by NOVO Industries A/S Cellulase Cellulytic enzyme, having 0.23% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Carezyme Amylase Amylolytic enzyme, having 1.6% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Termamyl 120T Amylase II Amylolytic enzyme, as disclosed in PCT/ US9703635 Lipase Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase Lipase (1) Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase Ultra Endolase Endoglucanase enzyme, having 1.5% by weight of active enzyme, sold by NOVO Industries A/S PB4 Sodium perborate tetrahydrate of nominal formula NaBO 2 .3H2O.H 2 O 2 PB1 Anhydrous sodium perborate bleach of nominal formula NaBO2.H 2 O 2 Percarbonate Sodium percarbonate of nominal formula 2Na 2 Cθ3.3H 2 θ2 DOBS Decanoyl oxybenzene sulfonate in the form of the sodium salt DPDA Diperoxydodecanedioc acid NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt NACA-OBS (6-nonamidocaproyl) oxybenzene sulfonate LOBS Dodecanoyloxybenzene sulfonate in the form of the sodium salt DOBS Decanoyloxybenzene sulfonate in the form of the sodium salt DOBA Decanoyl oxybenzoic acid TAED Tetraacetylethylenediamine DTPA Diethylene triamine pentaacetic acid DTPMP Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Tradename Dequest 2060 EDDS Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer in the form of its sodium salt. Photoactivated Sulfonated zinc phthlocyanine encapsulated in bleach (1) dextrin soluble polymer Photoactivated Sulfonated alumino phthlocyanine encapsulated in bleach (2) dextrin soluble polymer Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-l .3.5-triazin-2- yl)amino) stilbene-2:2'-disulfonate HEDP 1,1 -hydroxy ethane diphosphonic acid PEGx Polyethylene glycol, with a molecular weight of x (typically 4,000) PEO Polyethylene oxide, with an average molecular weight of 50,000 TEPAE Tetraethylenepentaamine ethoxylate PVI Polyvinyl imidosole, with an average molecular weight of 20,000 PVP Polyvinylpyrolidone polymer, with an average molecular weight of 60,000 PVNO Polyvinylpyridine N-oxide polymer, with an average molecular weight of 50,000 PVPVI Copolymer of polyvinylpyrolidone and vinylimidazole, with an average molecular weight of 20,000 QEA bis((C2H5θ)(C2H4θ) n )(CH3) -N+-C 6 H 12 -N+-(CH 3 ) bis((C2H5O)-(C 2 H O)) n , wherein n = from 20 to 30 SRP1 Anionically end capped poly esters SRP2 Diethoxylated poly (1, 2 propylene terephtalate) short block polymer PEI Polyethyleneimine with an average molecular weight of 1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen Silicone antifoam Polydimethylsiloxane foam controller with siloxane- oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1 Opacifier Water based monostyrene latex mixture, sold by BASF Aktiengesellschaft under the tradename Lytron 621 Wax Paraffin wax Example 1 The following are detergent formulations according to the invention: Example 2 The following are detergent formulations according to the present invention: Example 3 The following are detergent formulations according to the present invention: Example 4 The following are high density and bleach-containing detergent formulations according to the present invention: Example 5 The following are high density detergent formulations according to the present invention: Example 6 Example 7 The following laundry detergent compositions Y to AB are prepared in accord with the invention: Example 8 The following laundry detergent compositions AC to AG are prepared in accord with the invention: Example 9 The following formulations are examples of compositions in accordance with the invention, which may be in the form of granules or in the form of a tablet.

Claims: What is claimed is: 1. A builder component comprising ground crystalline layered silicate which comprises at least 95% or even 98% or even 100%) by weight of crystalline layered silicate having a particle size of less than 150 microns or even 102 microns, whilst having a weight average particle size of more than 15.0 microns, preferably from 16.0 to 48.8 microns. 2. A builder component according to claim 1, comprising ground crystalline layered silicate of the formula NaMSi 2 O 5 y H 2 O, wherein M is H, K, or preferably Na, or mixtures thereof, y is from 0 to 20, preferably 20. 3. A builder component according to claim 1 or 2 wherein at least 90% by weight of the crystalline layered silicate has a particle size of from 17.3 to 88.2. 4. A builder component according to any preceding claim, being in the form of a particle comprising from 40% to 80% by weight of the crystalline layered silicate intimately mixed with from 20%> to 50% by weight of a surfactant, preferably comprising at least an anionic surfactant. 5 A builder component according to claim 4 wherein the surfactant is an anionic sulphonate surfactant, preferably an alkyl benzene sulphonate salt, or a mid-chain branched alkyl sulphate or sulphonate surfactant . 6. A builder component according to any preceding claim, being in the form of an agglomerate, preferably having a weight average particle size of from 300 microns to 1100 microns. 7. A builder component according to any preceding claim comprising less than 10%> by weight, preferably less than 5% by weight of free moisture. 8. A detergent composition comprising the builder component according to any preceding claim, preferably at a level of from 1% to 60%> by weight of the composition, or even from 5% to 45% by weight. 9. A method for making a builder component according to claim 4 by forming a mixture of the crystalline layered silicate and the surfactant, and granulation of the mixture to form a particle, preferably by agglomeration to form an agglomerate. 10. Use of a builder system comprising a ground crystalline layered silicate which comprises at least 95% or even 98% or even 100% by weight of crystalline layered silicate having a particle size of less than 150 microns or even 102 microns, whilst having a weight average particle size of more than 15.0 microns, preferably from 16.0 to 48.8 microns, in a detergent composition, comprising a surfactant and other detergent components, for improving the dispensing of the detergent component.

Inventors: FENNEY MICHAEL KEITH, FIGUEROA FRANCISCO RAMON, HARTSHORN RICHARD TIMOTHY, FENNEY, MICHAEL, KEITH, FIGUEROA, FRANCISCO, RAMON, HARTSHORN, RICHARD, TIMOTHY
Applicants: FENNEY MICHAEL KEITH, FIGUEROA FRANCISCO RAMON, HARTSHORN RICHARD TIMOTHY, PROCTER & GAMBLE, FENNEY, MICHAEL, KEITH, FIGUEROA, FRANCISCO, RAMON, HARTSHORN, RICHARD, TIMOTHY, THE PROCTER & GAMBLE COMPANY
Application year: 1999
Main classification: C11D3
IPC codes: C01B33, C11D3