CA2247499A1 - Agglomerated high density detergent composition containing secondary alkyl sulfate surfactant and processes for making same - Google Patents

Abstract

An agglomerated high density detergent composition comprising a detersive surfactant system and a builder is provided. Two processes for producing the agglomerated high density detergent composition are also presented herein. The agglomerated detergent composition is preferably free of phosphates and has a density of at least 650 g/l. The detersive surfactant system comprises linear alkylbenzene sulfonates, alkyl sulfates, alkyl ethoxy sulfates, secondary (2, 3) alkyl sulfates and demonstrates improved solubility in an aqueous laundering system.

Description

AGGLOMERATED HIGH DENSITY DETERGENT COMPOSITION CONTAINING
SECONOARY ALKYL SULFATE SURFACTANT
AND PROCESSES FOR MAKING SAME

FIELD OF THE INVENTION
Secondary alkyl sulfate (SAS) surf~ctAntc are processed using variolis ingredients to provide improved water solubility. The resulting SAS particles are useful in laundry detergents and other cleaning compositions, especially under cold water washing conditions.
BACKGROUND OF THE INVENTION
Most conventional detergent compositions contain mixtures of various detersive surfArtAntc in order to remove a wide variety of soils and stains from surfaces. For exarnple, various anionic surfactants, especially the alkyl benzene sulfonates, are useful for removing particulate soils, and various nonionic surfactants, such as the alkyl ethoxylates and alkylphenol ethoxylates~ are useful for removing greasy soils. While a review of the literature would seem to suggest that a wide selection of surfactants is available to the detergent manufacturer~ the reality is that many such materials are specialty chemicals which are not suitable for routine use in low unit cost items such as home laundering compositions. The fact remains that many home-use laundry detergents still comprise one or more of the conventional alkyl b~nze.,c sulfonate or primary alkyl sulfate surfactants.
One class of surfActAntc which has found limited use in various compositions where eml~lcification is desired comprises the secondary alkyl sulfates. The conventional secondary alkyl s~lfates are available as generally pasty, random mixtures of sulfated linear and/or partially branched alk~nes Such materials have not come into widespread use in laundry detergents, since they offer no particular advantages over the alkyl benzene sulfonates.
Modern granular laundry detergents are being forrnlllAtPd in "condenced" form which offers snbstAntiAI advantages, both to the consumer and to the m~nllf~turer. For the consumer, the smaller package size Atten~lAnt with con~lencecl products provides ease-of-hAn-~ling and storage. For the rnAnl~fAeturer, unit storage costs, shipping costs and pA~k~ginE~ costs are lowered.
The m~nllfActllre of acceptable condence~ granular detergents is not without its difficulties. In a typical con~nced forrnulation, the so-called "inert" ingredients such as sodium sulfate are mainly deleted. However. such ingredients do play a role in enhancing the solubility of conventional sprav-dried detergent: hence, the condensed form will often suffer from solubility problems. Moreover, conventional low-density detergent granules are usually prepared by spray-drving processes which result in porous detergent particles that are quite amenable to being solubilized in aqueous laundry liquors. By contrast, condensed formulations will typically comprise substantially less porous, high density detergent particles which are less amenable to solubilization. Overall, since the condensed forrn of granular detergents typically comprises particles which contain high levels of detersive ingredients with little room for solubilizing agents, and since such particles are intentionally manufactured at high bulk densities, the net result can be a substantial problem with regard to in-use solubility.
It has now been discovered that a particular sub-set of the class of secondary alkyl sulfates, referred to herein as secondary (2,3) alkyl sulfates (SAS), offers considerable advantages to the formulator and user of dete.gellt compositions. For example, the secondary (2,3) alkyl sulfates are available as dry, particulate solids. Accordingly, they prospectively can be forrnulated as high-surfactant (i.e., "high-active") particles for use in granular laundry detergents. Since, with proper care in m~nllf~rtllring, the secondary (2,3) alkyl sulfates are available in solid, particulate form, they can be dry-mixed into granular detergent compositions without the need for passage through spray drying towers. In addition to the foregoing advantages seen for the secondary (2,3) alkyl sulfates, it has now been determined that they are both aerobically and anaerobically degradable, which assists in their disposal in the en~ ent. Desirably, the secondary (2,3) alkyl sulfates are ~uite compatible with detersive enzymest especially in the presence of calcium ions.
The present invention converts SAS powder which has a relatively slow dissolution rate into fast-dissolving del~rgellt agglomerates. Importantly, the SAS
agglo.~lelales provided herein are free-flowing, and can be readily arlrn~ d with other ingredients to provide fully-formulated granular detergents. Accor.lh.gly, the present invention overcomes many of the problems associated with the use of SAS in granular laundry detergents or other granular cleaning compositions.
BACKGROUND ART
D~Ie~ L compositions with various "secondary" and branched alkyl sulfates are disclosed in various patents; see: U.S. 2,900,346~ Fowkes et al, August 18, 1959; U.S.
3,234,258, Morris, February 8, 1966; U.S. 3,468,805, Grifo et al, September 23, 1969;
U.S. 3,480,556, DeWitt et al. November 25, 1969; U.S. 3,681,424, Bloch et al, August 1, 1972: U.S. 4~052.342~ Fernley et al. October 4. 1977; U.S. 4.079.020. Mills et al. March 14. 1978; U.S. 4.226.797. Bakker et al.. October 7. 1980; U.S. 4.235.7j2. Rossall et al.
November 25. 1980; U.S. 4.317.938. Lutz. March ~. 1982: U.S. 4,529.541, Wilms et al.
July 16, 1985; U.S. 4.614.612. Reillv et al. September 30. 1986; U.S. 4,880~569. Leng et al, November 14, 1989; U.S. 5,075,041, Lutz December 24~ 1991; U.S. 5,349.101, Lutz et al.. September 20, 1994; U.S. 5,389,277. Prieto. February 14, 1995; U.K. 818,367?
Bataafsche Petroleum, August 12, 1959; U.K. 85X.500. Shell. January 11, 1961; U.K.
965,435, Shell, July 29, 1964; U.K. 1,538,747, Shell, January 24, 1979; U.K. 1,546,127, Shell, May 16. 1979; U.K. 1,550,001, Shell, August 8, 1979; U.K. 1,585,030, Shell, February 18, 1981; GB 2,179,054A, Leng et al, February 25, 1987 (referring to GB2.155,031). U.S. Patent 3.234,258, Morris, February 8, 1966, relates to the sulfation of alpha olefins using H~S04? an olefin reactant and a low boiling, nonionic, organic cryst~lli7~tion medium.
Various means and appa~ s suitable for ~,cp~ing high-density granules have been disclosed in the literature and some have been used in the detergency art. See, fo!
example: U.S. 5,133,924; EP-A-367,339; EP-A-390,251; EP-A-340,013; EP-A-327,963;EP-A-337,330; EP-B-229,671; EP-B2-191,396; JP-A-6,106,990; EP-A-342,043; GB-B-2,221,695; EP-B-240,3S6; EP-B-242,138; EP-A-242,141; U.S. 4,846,409; EP-A-420,317;
U.S. 2,306,698; EP-A-264,049; U.S. 4,238,199; DE 4,021,476.
See also: WO 94/24238; WO 94/24239; WO 94/24240; WO 94/24241; WO
94/24242; WO 94/24243; WO 94/24244; WO 94/24245; WO 94/24246; U.S. 5,478,500 Swift et al, December 26, 1995; U.S. 5, 478,502, Swift, December 26, 1995; U.S. 5, 478,503,December26, 1995.
SUMMARY OF THE INVENTION
The present invention meets the needs identified above by providing an agglo~ d high density d~ ge~l~ composition cont~ining secondary (2,3) alkyl sulfate surfactant. Two processes for producing the agglomerated high density detergent co"~posilion are also pl~ese~.led herein. The agglomerated detergent composition is subst~nti~lly free of phosphates, has a density of at least 650 g/l and comprises a detersive surfactant system and a builder. The detersive surfactant system comprises linear alkylbenzene s--lf~tes, alkyl sl~lf~tes, alkyl ethoxy sulfates and secondary (2,3) alkyl sulfates and demonstrates improved solubility in an aqueous laundering system.
As used herein, the term "agglomerates" refers to particles formed by agglomerating or "building-up" d~l~.g~.,l granules or particles which typically have a smaller median particle size than the formed agglomerates.

As used herein. the phrase "median particle size" means the particle size at which 50% of the particles are smaller and 50% are larger in size and refers ~o individual agglomerates and not individual particles or detergent granules.
All percentages, ratios and proportions used herein are by weight, unless otherwise specified. All viscosities described herein are measured at 70~C and at shear rates between about 10 to 50 sec~ I . preferably at 25 sec~ l All documents~ including patents and publications cited herein. are incorporated by reference.
In accordance with one aspect of the invention, an agglomerated detergent composition having a density of at least 650 g/l is provided herein. The agglomerated detergent comprises from about l % to about 70% by weight of a detersive surfactant system comprising C 10-20 linear alkylbenzene sulfonates, C 10-20 alkyl sulfates, C 10-18 alkyl ethoxy sulfates having from about l to about 7 ethoxy groups and C 10-20 secondary (2,3) alkyl sulfates. Additionally, the agglomerated detergent composition contains at least about l % by weight of a detergency builder. The surfactant system and the detergency builder are agglomerated to form detergent agglomcl~les which have improved solubility in an aqueous laundering solution.
In accordance with another plef~ d aspect of the invention, a granular detergentcomposition comprises conventional formulation ingredients and at least about 10% to about 65%, by weight, of the agglomerated detergent composition.
In another preferred composition embodiment of the invention an agglomerated del~lgent composition having a density of at least 650 g/l comprises from about 5% to about 30%, more preferably from about 10% to about 25%, and even more preferablyfrom about 15% to about 22% Cl2 14 alkylbenzene sulfonate. The agglomerated det~.ge.lt composition can optionally also comprise about 15% to about 35%. morepr~f~lably from about 22% to about 24% and even more preferably from about 21% to about 22% C 14 15 alkyl sulfate. In addition, the agglomerated detergent composition prefe.ably includes from about 15% to about 35%, more preferably from about 10% to about 25% and most preferably from about 5% to 15% Cl0 20 secondary alkyl (2,3) sulfate. Further, the agglomerated d~L. .ge.,l composition contains from about 15% to about 35%, more preferably from about 10% to about 25% and most preferably from about 5% to about 15% aluminosilicate. Also included in agglomerated d~le.~g~.ltco~ osilion is from about from about 10% to about 40%, pl~:fe.,lbly from about 5% to about 30% and most preferably from about 5% to about 25% sodium carbonate. rhe balance of the aggloll~ ed detelg~,nt composition is made up of water and optionally other unreacting minor ingre-liPnt~

WO 97t32954 PCT/US97/04690 In a process aspect of the invention~ referred to herein as the "paste" process. a process for making an agglomerated detergent composition comprising blending, mixing, and drying steps is provided. The first step of the paste method comprises blending secondary (2.3) alkyl sulfate with detergency builder to form a homogeneous powder mixture. The detergency builder is preferably a member from the group consisting of carbonate. aluminosilicate and zeolite. The homogeneous powder mixture is then combined with a surfactant paste mixture which includes from about 1% to about 80% by weight of a detersive surfactant system comprising C 10-20 linear alkyl benzene sulfonates. C 10-20 alkyl sulfates, C 10-18 alkyl ethoxy sulfates having from about 1 to about 7 ethoxy groups, alcohol ethoxylates, and polyethylene glycol. This step results in the formation of detergent agglomerates.
Next, the detergent agglomerates are mixed in a moderate speed mixer/densifier so as to further form the detergent agglomerates. Lastly, the detergent agglomerates are dried so as to form an agglomerated detergent composition has a density of at least about 650 g/l. The paste process preferably further comprises the step of adding a coating agent. The agglomerates of the agglomerated detergent composition have a median particle size of from about 300 microns to about 600 microns. The viscosity of the surfactant paste is preferably from about 10,000 centipoises to about 100,000 centipoises.
In another aspect of the invention, a second process for making the agglomerateddetergent composition, referred to herein as the "neutralization" process. is provided. The first step in the neutralization method comprises blending secondary (2,3) alkyl sulfate with a detergency builder to form a homogeneous powder mixture. Next, a liquid acid precursor for C 10-20 linear alkyl benzene sulfonate is combined with the homogeneous powder mixture in a high speed mixer/den~ifier to form dete~ agglomerates. A final optional step in the neutralization process involves mixing the detergent agglomerates in a moderate speed mixer/densifier to further form and build-up the detergent agglomerates.
The agglomerated detergent composition has a density of at least about 650 g/l.
Optionally, the dt:lergc.l~ agglomerates formed by the neutralization process can be cooled.
In accordance with another aspect of the invention, a method for laundering soiled fabrics is provided. The method comprises the step of cont~eting the soiled fabrics with an effective amount of a granular deL~ composition as described herein in an aqueous laundering solution.
Accordingly, it is an object of the present invention to provide an agglomerated35 high density detergent composition co.~ g secondary (2,3) alkyl sulfate surfactant and processes for making the agglomerated high density detergent composition. These and other objects. features and attendant advantages of the present invention will become apparent to those skilled in the art from reading of the following detailed description of the preferred embodiment and the appended claims.
DETAILED DESCR~PTION OF THE PREFERRED EMBODIMENT
The invention is directed to an agglomerated high density detergent composition cons~ining secondary (2,3) alkyl sulfate and to a process for producing the agglomerated detergent composition. Secondary (2,3) alkyl sulfates are useful in the formulation of granular and agglomerated detergent compositions because they are biodegradable and because they are compatible with enzymes, a common ingredient in commercially available detergent compositions. However, poor solubility of the secondary (2.3) alkyl sulfates. especially in cold wash water environrnents, precludes their extensive use in most detergent formulations.
The present invention overcomes problems associated with the use of secondary (2,3) alkyl sulfates and provides an agglomerated high density detergent composition and a method for producing the detergent composition. The secondary (2,3) alkyl sulfate agglomerate and its processing in the manner of the present invention are described in detail, hereinafter. Other ingredients which can be used to prepare fully-form~ t~d detergent compositions are also disclosed for the convenience of the formulator, but are not intended to be limiting thereo~
The detergent composition of the present invention must include the aforementioned detersive surfactant system and a detergency builder. Adjunct detergent ingredients, which include conventional formulation ingredients for use in d~le.ge~
optionally may be included in the detergent composition, as well. Nonlimiting examples of the surfactant, builder and preferred adjunct enzymes, ble~rhing compounds, ble~clling agents and bleach activators, polymeric soil release agents, dye transfer inhibiting agents, cllPI~ting agents, clay soil removal and anti-redeposition agents, suds suppressors, fabric softeners and other miscellaneous ingredients are described in detail hereinafter.
Surfactant Nonlimiting exarnples of surf~t~nt~ which can be used herein in addition to or as part of the SAS agglomerates, typically at levels from about 1% to about 50%, by weight, include the conventional C l l -C l g alkyl bc~ c sulfonates ("LAS") and primary, branched-chain and random C I o-C20 alkyl sulfates ("AS"), unsaturated sulfates such as oleyl sulfate, the C I o-C 18 alkyl ethoxy sulfates (''AEXS''; especially EO 1-7 ethoxy sulfates), C 1 o-C 18 alkyl ethoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), WO 97/329~4 PCT/US97/04690 the C 10-1 B glycerol ethers. the C I o-C 18 alkvl polyglycosides and their corresponding sulfated polyglycosides~ and C 12-C 18 alpha-sulfonated fatty acid esters. The detergent agglomerates described herein preferably comprise C12-CI~ alkyl benzene sulfonates. If desired. the conventional nonionic and amphoteric surfactants such as the C 1 2-C 18 alkyl 5 ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxvlates and C6-C12 alkyl phenol alkoxvlates (especially ethoxylates and mixed ethoxy/propoxy), Cl~-CIg betaines and sulfobetaines ("sultaines"), C l o-C 1 8 amine oxides, and the like. can also be included in the overall compositions. The C I o-C 18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical exarnples include the C 1 2-C 18 N-methylglucarnides.
See WO 9.206.154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides. such as C 1 o-C 18 N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C 1 2-C 18 glucamides can be used for low sudsing. C I o-C20 conventional soaps may also be used. If high sl~lcing is desired, the branched-chain C l o-C 16 soaps may be used. Mixtures of anionic and nonionic surf~ct~ntc are especially useful. Other conventional useful surf~t~nt~ are listed in standard texts.
Conventional secondary alkyl sulfate surfactants, which are incorporated in the agglomerated detergent composition disclosed herein, are those materials which have the sulfate moiety distributed randomly along the hydrocarbyl "backbone" of the molecule.
Such materials may be depicted by the structure:
CH3(cH2)n(cHoso3-M+)(cH2)mcH3 wherein m and n are integers of 2 or greater and the sum of m + n is typically about 9 to 17, and M is a water-solubilizing cation.
The selected secondary (2,3) alkyl sulfate surfactants used herein comprise structures of formulas A and B:
(A) CH3(CH2)X(CHOSO3-M+) CH; and (B) CH3(cH2)y(cHoso3-M+)cH2cH3 for the 2-sulfate and 3-sulfate, reaye~ ely. Mixtures of the 2- and 3-sulfate can be used herein. In forrnulas A and B, x and (y+ I ) are, respectively, integers of at least about 6, and can range from about 7 to about 20, preferably about 10 to about 16. M is a cation, such as an alkali metal, ammoniurn, alkanolammonium, ~lk~line earth metal, or the like.
Sodium is typical for use as M to prepare the water-soluble secondary (2,3) alkyl s~lf~tes, but ethanolarnmoniurn, diethanolammonium, triethanolammonium, potassiurn, ammonium, and the like, can also be used. Materials A and B, and mixtures thereof, are abbreviated "SAS", herein.
With regard to the random secondary alkyl sulfates (i.e.. secondary alkyl sulfates v~ith the sulfate group at positions such as the 4. 5. 6, 7, etc. secondary carbon atoms), such maeerials tend to be tacky solids or. more generally, pastes. Thus. the random alkyl sulfates do not afford the processing advantages associated with the solid SAS when formulating detergent granules. Moreover. SAS provides better sudsing than the random S mixtures. It is preferred that SAS be substantially free (i.e., contain less than about 20%, more preferably less than about 10%. most preferably less than about 5%) of such random secondary alkyl sulf~tes One additional advantage of the SAS surfactants herein over other positional or "random" alkyl sulfate isomers is in regard to the improved benefits afforded by said SAS
with respect to soil redeposition in the context of fabric laundering operations. As is well-known to users, laundry detergents loosen soils from fabrics being washed and suspend the soils in the aqueous laundry li~uor. However, as is well-known to detergent formulators, some portion of the suspended soil can be redeposited back onto the fabrics.
Thus, some redistribution and redeposition of the soil onto all fabrics in the load being washed can occur. This, of course~ is undesirable and can lead to the phenomenon known as fabric "graying". (As a simple test of the redeposition characteristics of any given laundry detergent formulation, unsoiled white "tracer" cloths can be included with the soiled fabrics being laundered. At the end of the laundering operation the extent to which the white tracers deviate from their initial degree of whiteness can be measuredphotometrically or estim~te~l visually by skilled observers. The more the tracers' whiten~ss is retained, the less soil redeposition has occurred.) It has also been determined that SAS affords substantial advantages in soil redeposition characteristics over the other positional isomers of secondary alkyl sulfates in laundry detergents, as measured by the cloth tracer method noted above. Thus, the selection of SAS surfactants according to the practice of this invention which preferably are subst~nti~lly free of other positional secondary isomers unexpectedly assists in solving the problem of soil redeposition in a manner not heretofore recognized.
It is to be noted that the SAS used herein is quite different in several hl~
p~ope. lies from the secondary olefin sulfonates (e.g., U.S. Patent No. 4,064,076, Klisch et al, 12/20/77); accordingly, such secondary sulfonates are not the focus of the present mventlon.
The ~l~p~dlion of SAS of the type usefill herein can be carried out by the addition of H~SO4 to olefins. A typical synthesis using a-olefins and sulfuric acid is disclosed in U.S. Patent 3,234,258, Morris, or in U.S. Patent 5~075,041, Lutz, granted December 24, 1991, both of which are incorporated herein by reference. The synthesis, WO 97132954 ' PCT/US97/04690 conducted in solvents which afford the SAS on cooling, yields products which. when purified to remove the unreacted materials randomly sulfated materials lln~lllfated by-products such as C l o and higher alcohols, secondary olefin sulfonates. and the like are typically 90+% pure mixtures of 2- and 3-sulfated materials (up to 10% sodium sulfate is typically present) and are white, non-tacky, app~ently crystalline solids. Some 2.3-disulfates may also be present, but generally comprise no more than 5% of the mixture of secondary (2 3) alkyl mono-sulfates.
If stil} further increases in the solubility of the "crystalline" SAS surfactants are desired the forrnulator may wish to employ mixtures of such surf~ct~nt~ having a mixture of alkyl chain lengths. Thus, a mixture of C l 2-C 18 alkyl chains will provide an increase in solubility over an SAS wherein the alkyl chain is say, entirely C 16 When formulating detergent compositions using the soluble particles provided by this invention it may be desirable that the SAS surfactants contain less than about 3% sodium sulfate preferably less than about 1% sodium sulfate. In and of itself, sodium sulfate is an innocuous material. However, it provides no cleaning function in the compositions and may constitute a load on the system when dense granules are being form~ tecl Various means can be used to lower the sodium sulfate content of the SAS. For example, when the H2SO4 addition to the olefin is completed, care can be taken to remove unreacted H2SO4 before the acid forrn of the SAS is neutralized. In another method. the sodium salt form of the SAS which contains sodium sulfate can be rinsed with water at a t~ re near or below the Krafft temperature of the sodium SAS.
This will remove Na2SO4 with only minim~l IOSS of the desired, purified sodium SAS.
Of course, both procedures can be used, the first as a pre-neutralization step and the second as a post-neutralization step.
The terrn "Krafft temperature" as used herein is a term of art which is well-known to workers in the field of surfactant sciences. Krafft t~ dl~lre is described by K.
Shinoda in the text "Principles of Solution and Solubility", translation in collaboration with Paul Becher, published by Marcel Dekker, Inc. 1978 at pages 160-161. Statedsuccinctly, the solubility of a surface active agent in water increases rather slowly with te.l~l,elal~lre up to that point, i.e., the Kra~ft tcll~l)e.dlllre, at which the solubility evidences an extremely rapid rise. At a telll~c.dlllre ~",loxilllately 4~C above the Krafft telllpcldlwe a solution of almost any composition becol,les a homogeneous phase. In general, the Krafft t~ .dlure of any given type of surfactant, such as the SAS herein which comprises an anionic hydrophilic sulfate group and a hydrophobic hydrocarbyl group, will vary with the chain length of the hydrocarbyl group. This is due to the change in water solubility with the variation in the hvdrophobic portion of the surfactant molecule.
The fo~nulator may optionally wash the SAS surfactant which is cont~min~ted with sodium sulfate with water at a temperature that is no higher than the Kraffl S t~"~ alure~ and which is preferably }ower than the Krafft temperature. for the particular SAS being washed. This allows the sodium sulfate to be dissolved and removed with the wash water, while keeping losses of the SAS into the wash water to a minimum.
Under cirCllmct~nces where the SAS surfactant herein comprises a mixture of alkyl chain lengths, it will be appreciated that the Krafft temperature will not be a single point but, rather. will be denoted as a "Krafft boundary". Such matters are well~known to those skilled in the science of surfactant/solution measurements. In any event~ for such mixtures of SAS. it is preferred to conduct the optional sodium sulfate removal operation at a te,l,p~ldlllre which is below the Krafft boundary, and preferably below the Krafft tcln~.lalllre of the shortest chain-length surfactant present in such mixtures, since this avoids excessive losses of SAS to the wash solution. For example, for C16 secondary sodium alkyl (2,3) sulfate surf~ t~nts, it is preferred to conduct the washing operation at teln~e,al lres below about 30~C, preferably below about 20~C. It will be ap~leciated that changes in the cations will change the pref.l,~id ~elll~;lal~lres for waching the SAS
surf~ct~ntc, due to changes in the Krafft temperature.
The washing process can be conducted batchwise by suspending wet or dry SAS
in sufficient water to provide 10% to 50% solids, typically for a mixing time of at least 10 minutes at about 22~C (for a C 16 SAS), followed by pressure filtration. In a preferred mode, the slurry will comprise somewhat less than 35% solids, inasmuch as such slurries are free-flowing and ~m~hle to agitation during the washing process. As an additional benefit, the washing process also reduces the levels of organic cont~min~nts which comprise the random secondary alkyl sulfates noted above.
SAS powder has poor solubility, especially in cold water conditions. The discovery that SAS powder solubility can be improved by agglol,lcla~ g SAS with various surfactant paste mixtures and detergency builders is un~ e.;ted. Two processes have been discovered which result in improved solubility of SAS. The first is referred to herein as the paste process. In this process, SAS and detergency builders powders are agglomerated with a surfactant paste ll~ ule. The second process is Ic~ d to herein as the neutralization process. In this process, SAS and detergency builders are mixed with a liquid acid ~ or of linear alkylbenzene sulfonate to form d~lcrgelll agglomerates.
The soluble agglolnclales provided in the agglomerated del~lg.l.~ composition W O 97/32954 PCTrUS97/04690 and processes herein preferably contain from about 10% to about 70%. more preferably - from about 15% to about 50%, and most preferably from about 20% to about 30% of a secondarv (2.3) alkvl sulfate surfactant.
While not intended to be limited by theorv. it is hypothesized that the mechanical input from the high speed mixing device to the surfactant paste mixture and the blended secondary (2.3) alkyl sulfate surfactant provide sufficient energy to provide a phase change to the crystalline secondary (2,3) alkyl sulfate surfactant. The phase change to a less crystalline surfactant phase thus affords the improved solubility.
While not intended to be limited by theory, it is also hypoth~ si7~(1 that the mechanical input from the mixing device(s) and the additional chemical energy from the exothermic heat of neutralization of the liquid acid pre-cursor for C l 0-20 linear alkyl benzene sulfonate with the detergency builder (specifically, sodium carbonate) to the secondary (2,3) alkyl sulfate surfactant provide sufficient energy to provide a phase change to the crystalline secondary (2,3) alkyl sulfate surfactant. The phase change to a less crystalline surfactant phase thus affords the improved solubility.
SAS Processin~
The agglomerates of the invention can be made by two methods: one involving the use of a surfactant paste (hereinafter the "paste process") and a second involving the use of liquid acid precursors of C 10-20 linear alkylbenzene sulfonate, (hereinafter the "neutralization process"). In the first step of the paste process, secondary (2,3) alkyl sulfate is blended with d~le.~ cy builder to form a homogeneous powder mixture. The preferred detergency builders comprise those selected from the group consisting of carbonate. aluminosilicate, zeolite and mixtures thereof.
In the next step of the paste process, the homogeneous powder mixture is agglomerated ~,vith a surfactant paste mixture to form detergent agglomerates. The surfactant paste mixture preferably comprises from about 1% to about 80% by weight of a detersive surfactant system which comprises C10 20 linear alkylbenzene sulfonates, C10-2o alkyl sulfates, Clo l8 alkyl ethoxy sulfates having from about 1 to about 7 ethoxy groups, alcohol ethoxylates, and polyethylene glycol.
To achieve the desired density of 650 g/l, the above-mentioned mixing steps of the paste process can be carried forth initially in a high speed mixer/densifier after which a moderate speed mixer/densifier can follow, wherein the starting detergent materials are agglomerated and densified to produce particles having a density of at least 650 g/l and more preferably from about 700 g/l to about 800 g/l. Preferably, the mean residence time of the starting detergent materials in the high speed mixer/densifier (e.g. Lodige Recycler CB30) is from about I to 30 seconds while the residence time in low or moderate speed mixerldensifier (e.g. Lodige Recycler KM 300 "Plongh~hz~re") is from about 0.25 to 10 minutes. Alternativelv. the agglomeration step of the paste process contemplatesachieving the desired density of the starting detergent materials by agglomeration in a 5 single moderate speed mixer/densifier wherein the residence time is increased. for example, up to about 15 minutes.
For purposes of facilitating agglomeration. detergency builders are blended withSAS just prior to adding the surfactant paste mixture. While not inten~ing to be limited by theory, it is believed that the free flowing, high density det~gent agglomerates 10 produced by the present invention is attributed to the absorption of the excess water typically contained in the viscous surfactant paste by the detergency builder during or just prior to agglomeration.
The surfactant paste mixture described above is highly viscous. In the instant invention, the surfactant paste preferably has as viscosity of from about 10,000centipoises (cps) to about 100,000 cps. More preferably, the viscosity of the surfactant paste used in the paste process is from 10,000 cps to 80,000 cps.
The detergent agglomerates produced by the paste process preferably have a surfactant level of from about 1% to about 70%, more preferably from about 20% to about 55%, even more preferably from about 35% to about 50% and, most preferably20 from about 40% to about 45%. Such det~ t agglomerates are particularly useful in the production of low dosage detergents. An attribute of dense or densified agglomerates is the relative median particle size. The present paste process typically provides delelge~
agglomerates having a median particle size of from about 300 microns to about 600 microns, and more preferably from about 400 microns to about 600 microns. The above-25 ref~lel.ced particle si~ results in an agglomerated detergent composition having densityvalues of 650 g/l and higher. Such a feature is especially useful in the production of low dosage laundry d~ nts as well as other granular compositions such as dishwashingcompositions. A preferred embodiment of the invention is a granular detergent composition comprising conventional formulation ingredients and at least about 5% by 30 weight of the agglomerated detergent composition prepared according to the paste process. In another preferred embodiment of the invention, a method for laundering soiled fabrics is provided. The method comprises the step of cont~cting soiled fabrics with an effective amount of a granular detergent composition which comprises at least about 10% to about 65% by weight of the agglomerated detergent composition described 35 herein.

W O 97/329S4 rCTrUS97/04690 As mentioned above. the agglomerates of the invention can be produced by the neutralization process. The neutralization process comprises the steps of first~ blending secondarv (2.3) alkyl sulfate with a detergency builder to form a homogeneous powder mixture. The detergency builder is preferably one selected from the group consisting of S alkali metals. ammonium phosphates, substituted ammonium phosphates. citric acid, aluminosilicates. carbonates. silicates. borates~ polyhydroxy sulfonates. polyacetate carboxylates, polycarboxylates. zeolite and mixtures thereof.
Next, in the neutralization process, the homogeneous powder mixture described above is mixed with a liquid acid precursor of C 10-20 linear alkylbenzene sulfonate in a 10 high speed mixer/densifier to from detergent agglomerates. Preferably, the mean residence time of the starting detergent materials in the high speed mixer/densifier (e.g.
Lodige Recycler CB30) is from about I to 30 seconds. The detergent agglomerates formed at this stage are then optionally further mixed in a moderate speed mixer/densifier. The residence time in the low or moderate speed mixer/densifier (e.g.
Lodige Recycler KM 300 "Plol-ghch~re") is from about 0 to 10 min-ltes Preferably, the detergent agglomerates are then cooled so as to form a detergent composition which has a density of at least about 650 g/l. In another embodiment of the neutralization process, a coating agent can be added at the step carried out in the moderate speed mixer/densifier.
The particles of the agglomerated detergent composition produced by the 20 neutralization process preferably have a median particie size of from about 300 microns to about 600 microns. In a pl~r.,..ed embodiment of the invention, a granular detergent composition is made by combining at least about 10% to about 65% by weight of the agglomerated detergent composition, made according to the neutralization process. with conventional formulation ingredients. In another preferred embodiment of the invention 25 involving a method of laundering soiled fabrics, the fabrics are contacted with an effective amount of a granular detergent composition, comprising d~l.,.gent agglomerated made according to the neutralization process, in an aqueous laundering solution.Optional A~glomeration Process Steps Either the paste or the neutralization process can comprise the additional step of 30 spraying an additional binder in the mixer/densifier(s) used in the agglomeration step to facilitate production of the desired detergent agglomerates. A binder is added for purposes of enhancing agglomeration by providing a "binding" or "sticking" agent for the detergent components. The binder is preferably selected from the group consisting of water, anionic surfactants. nonionic surfactants, polyethylene glycol, polyacrylates, citric 35 acid and mixtures thereof. Other suitable binder materials including those listed herein W 097/32954 PCT~US97/04690 14 are described in Beerse et al. U.S. Patent No. 5 108.6~6 (The Procter & Gamble Company).
Another optional step contemplated by the present process includes conditioning the detergent agglomerates by either drying, cooling, or adding a coating agent to 5 improve flowability after they exit the mixerldensifier(s) used in agglomeration. This furthers enhances the condition of the detergent agglomerates for use as an additive or to place them in shippable or pac~g~hle form. The coating agent can be any ingredient which enh~nces the flowability or low characteristics of the detergent SAS agglomerates.
By way of exarnple, various aluminosilicates, zeolites and carbonates can be used. Those 10 skilled in the art will appreciate that a wide variety of methods may be used to dry as well as cool the exiting detergent agglomerates without departing from the scope of the invention. By way of example, apparatus such as a fluidized bed can be used for drying and/or cooling while an airlift can be used for cooling should it be necess~ry Builders Detergent builders must be included in the compositions herein to assist in controlling mineral, especially Ca andlor Mg, hardness in wash water or to assist in the removal of particulate soils from surfaces. Builders can operate via a variety of mPch~niem~ including forming soluble or insoluble complexes with hardness ions, by ion exchange, and by offering a surface more favorable to the precipitation of hardness ions 20 than are the surfaces of articles to be cleaned. Builder level can vary widely depending upon end use and physical form of the composition. Built dt;~rgents typically co~ lise at least about 1% builder. Granular forrnulations typically comprise from about 10% to about 80%, more typically 15% to 50% builder by weight of the detergent composition.
The agglomerated detergent composition described herein comprises at least about 1% by 25 weight of a detergency builder. Lower or higher levels of builders are not excluded. For example, certain d~ gellt additive or high-surfactant formulations can be unbuilt.
Suitable builders herein can be selected from the group con.cistir~g of phosph~tes and polyphosph~tçs, especially the sodium salts; silicates including water-soluble and hydrous solid types and including those having chain-. Iayer-, or three-~iim~oneiona 30 structure as well as amorphous-solid or non-structured-liquid types; carbonates, bic~l,ona~es, sesquicarbonates and carbonate minerals other than sodium carbonate or sesquicarbonate; aluminosilicates; organic mono-, di-, tri-, and tetl~ca l)oxylates especially water-soluble nonsurfactant carboxylates in acid, sodium, potassiurn or alkanolammonium salt form. as well as oligomeric or water-soluble low molecular weight 35 polymer carboxylates including aliphatic and aromatic types; and phytic acid. These may ~e complemented by borates~ e.g.. for pH-buffering purposes or by sulfates~ especially sodium sulfate and anv other fillers or carriers which may be important to the enginPering of stable surfactant and/or builder-cont~ining detergent compositions. The agglomerated detergent composition according to the present invention preferably contains builder 5 selected from the group consisting of alkali metal, arnmonium phosphates~ substituted ammonium phosphates. citric acid. aluminosilicates, carbonates, silicates. borates~
polyhydroxy sulfonates, polyacetate carboxylates, polycarboxylates, zeolite and mixtures thereof. More preferably, the agglomerated detergent composition of the invention contains aluminosilicates, zeolites~ and/or carbonates as builder.
Builder mixtures~ sometimes termed "builder systems" can be used and typically comprise two or more conventional builders, optionally complemented by chelants, pH-buffers or fillers~ though these latter materials are generally accounted for separately when describing quantities of materials herein. In terms of relative quantities of surfactant and builder in the present detergents, preferred builder systems are typically formulated at a weight ratio of surfactant to builder of from about 60:1 to about 1:80. The surfactant to builder ratio of the agglomerated detergent composition of the present invention preferably ranges from 1:5 to about 5:1.
Phosphate-cont~ining detergent builders often ~lef~ d where perrnitted by legislation include, but are not limited to, the alkali metal, amrnonium and alkanolammonium salts of polyphosphates exemplified by the tripolyphosphates, pyrophosphates, glassy polymeric meta-phosph~tes; and phosphonates. The agglomerated detergent composition contained herein is substantially free of phosphates.
Suitable silicate builders include alkali metal silicates, particularly those liquids and solids having a SiO2:Na2O ratio in the range 1.6:1 to 3.2:1, including, particularly for automatic dishwashing purposes, solid hydrous 2-ratio silicates marketed by PQ Corp.
under the tr~c~en~me BRITESIL(~9, e.g., BRITESIL H20; and layered silicates, e.g., those described in U.S. Patent No. 4,664,839, May 12, 1987, H. P. Rieck. NaSKS-6, sometimes abbreviated "SKS-6", is a crystalline layered alllminl~m-free o-Na2SiOs morphology silicate marketed by Hoechst and is preferred especially in granular laundry compositions. See pl~ ~Jdldlive methods in German DE-A-3,417,649 and DE-A-3,742,043. Other layered silicates, such as those having the general formula NaMSixO2x+l yH2O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0, can also or alternately be used herein. ~ayered silicates from Hoechst also include NaSKS-5, NaSKS-7 and NaSKS- 1 1, as the a, ,B and y layer-silicate forms. Other silicates may also be useful, such as magnesium silicate~ ~~hich can serve as a crispening agent in granules. as a stabilizing agent for bleaches. and as a component of suds control systems.
Also suitable for use herein are synthesized crystalline ion exchange materials or hydrates thereof having chain structure and a composition represented by the following S general formula in an anhydride form: xM2O.ySiO2.zM'O wherein M is Na and/or K. M' is Ca and/or Mg; ylx is 0.5 to 2.0 and z/x is 0.005 to 1.0 as taught in U.S. 5,427.711, Sakaguchi et al. June 27, 1995.
Suitable carbonate builders include ~Ik~line earth and alkali metal carbonates as disclosed in German Patent Application No. 2.321,001 published on November 15, 1973.
although sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, and othercarbonate minerals such as trona or any convenient multiple salts of sodium carbonate and calcium carbonate such as those having the composition 2Na2CO3.CaCO3 when anhydrous, and even calcium carbonates including calcite, aragonite and vaterite, especially forrns having high surface areas relative to compact calcite may be useful, for example as seeds or for use in synthetic detergent bars.
Aluminosilicate builders are especially useful in granular detergents, but can also be incorporated in liquids, pastes or gels. Suitable for the present purposes are those having empirical formula: [Mz(AlO2)z(SiO2)v]-xH2O wherein z and v are integers of at least 6, the molar ratio of z to v is in the range from 1.0 to 0.5, and x is an integer from 15 to 264. Aluminosilicates can be crystalline or arnorphous, naturally-occurring or synthetically derived. An aluminosilicate production method is in U.S. 3,985,669, Krummel, et al. October 12, 1976. Pl~fe.l~d synthetic crystalline aluminosilicate ion exchange materials are available as Zeolite A, Zeolite P (B), Zeolite X and, to whatever extent this differs from Zeolite P, the so-called Zeolite MAP. Natural types, including clinoptilolite, may be used Zeolite A has the formula: Nal2[(A1~2)12(Si~2)12] XH2~
wherein x is from 20 to 30, especially 27. Dehydrated zeolites (x = 0 - 10) may also be used. Preferably, the aluminosilicate has a particle size of 0.1-10 microns in dia~neter.
Suitable organic detergent builders include polycarboxylate compounds, includingwater-soluble nonsurfactant dicarboxylates and tricarboxylates. More typically builder polycarboxylates have a plurality of carboxylate groups, preferably at least 3 carboxylates. Carboxylate builders can be forrnulated in acid, partially neutral, neutral or overbased form. When in salt form, alkali metals, such as sodiurn, potassium, and lithiurn, or alkanolarnmonium salts are preferred. Polycarboxylate builders include the ether polycarboxylates, such as oxydisuccinate, see Berg, U.S. 3,128,287, April 7, 1964, and Lamberti et al, U.S. 3,635.830, January 18, 1972; "TMS/TDS" builders of U.S.

4~663~071. Bush et al. May 5. 1987; and other ether carbo:cylates including cyclic and ~ alicyclic compounds such as those described in U.S. Patents 3 923 679: 3 835.163;
4.158.635; 4.120.874 and 4.102.903.
Other suitable builders are the ether hydroxypolycarboxylates. copolymers of S maleic anhydride with ethylene or vinyl methyl ether; 1, 3. 5-trihydroxy benzene-2, 4, 6-trisulphonic acid; carboxymethyloxysuccinic acid: the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenP~ mine tetraacetic acid and nitrilotriacetic acid; as well as mellitic acid, succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
Citrates. e.g., citric acid and soluble salts thereof are important carboxylate builders e.g., for heavy duty liquid detergents, due to availability from renewable resources and biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silic~tes. Oxydisuccinates are also especially useful in such compositions and combinations.
Where permitted and especially in the formulation of bars used for hand-laundering operations, allcali metal phosphates such as sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethane-l-hydroxy-l,l-diphosphonate and other known phosphonates, e.g., those of U.S.
3.159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137 can also be used and may have desirable ~nti~calin~ plol)c.lies.
Certain detersive surfactants or their short-chain homologs also have a builder action. For unambiguous formula accounting purposes, when they have surfactant capability, these materials are summed up as detersive surf~ct~ntc Preferred types for builder functionality are illustrated by: 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S. 4,566,984, Bush, January 28, 1986. Succinic acid builders include the Cs-C20 alkyl and alkenyl succinic acids and salts thereof. Succin~te builders also include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-do~ecenylc~lccin~te (preferred), 2-p~nt~lPc~nyls~cin~te~ and the like. Lauryl-succinates are described in European Patent Application 86200690.5/0,200,263, published November S, 1986. Fatty acids, e.g., C 12-C 18 monocarboxylic acids, can also behlcol~,olated into the compositions as surfactant/builder materials alone or in combination with the aforementioned builders, especially citrate and/or the succinate builders, to provide additional builder activity. Other suitable polycarboxylates are disclosed in U.S.
4,144,226, Crutchfield et al, March 13, 1979 and in U.S. 3,308,067, Diehl, March 7, 1967. See also Diehl. U.S. 3.723.32~.
Optionally. inorganic builder materials can be used which have the formula (MX)iCav (CO3)z wherein x and i are integers from 1 to 15, y is an integer from 1 to 10. z is an integer from 2 to 2~. Mj are cations. at least one of which is a water-soluble and the 5 equation ~ 1 5(x; multiplied by the va}ence of Mi) + 2y = 2z is satisfied such that the formula has a neutral or "b~l~n~e.l" charge. Waters of hydration or anions other than carbonate may be added provided that the overall charge is balanced or neutral. The charge or valence effects of such anions should be added to the right side of the above e~uation. Preferably, there is present a water-soluble cation selected from the group 10 consisting of hydrogen, water-soluble metals, hydrogen, boron, ammonium, silicon, and mixtures thereof. more preferably, sodium, potassiurn, hydrogen~ lithium, ammonium and mixtures thereof. sodiurn and potassium being highly ple~ d. Nonlimiting examples of noncarbonate anions include those selected from the group conci~ting of chloride, sulfate, fluoride, oxygen, hydroxide, silicon dioxide, chromate, nitrate, borate and mixtures 15 thereof. Preferred builders of this type in their simplest forms are selected from the group consisting of Na~Ca(C03)2, K2Ca(C03)2, Na ~Ca2(CO3)3, NaKCa(C~3)2, NaKCa2(C03)3, K2Ca2(C03)3, and combinations thereof. An especially l,le~.led material for the builder described herein is Na2Ca(CO3)2 in any of its crystalline modifications. Suitable builders of the above-defined type are further illustrated by, and 20 include, the natural or synthetic forms of any one or combinations of the following minerals: Afghanite, Andersonite, AshcroftineY, Beyerite, Borcarite~ Burbankite,Butschliite. Cancrinite, Carbocernaite, Carletonite, Davyne, DonnayiteY, Fairchildite, Ferrisurite. Franzinite, Gaudefroyite, Gaylussite, Girvasite, Gregoryite, Jouravskite, KamphaugiteY, K~t~ e, ~h~ sl-ile, Lepe.ao~ iteGd, Liottite. MckelveyiteY, 25 Microsornmite, Mroseite, Natrofairchildite, Nyerereite, RemonditeCe, Sacrofanite, Sch.uc~ e, Shortite, Surite, Tunisite, Tuscanite, Tyrolite, Vishnevite, and Zemkorite. ~f~ ,d mineral forms include Nyererite, Fairchildite and Shortite.
Adiunct Formulation InRredients The fully-forrn~ te~ granular d~l~.genl compositions which are ~ aled using 30 the SAS agglomerates of this invention will typically comprise various other forrnulation ingredients to provide ~ ry cleaning and fabric care benefits. aesthetic benefits and ploce~;.-g aids. The following are non-limiting exarnples of builders, en~;~/llles, enzyme stabilizers, ble~ ing compounds, including ble~hing agents and bleach activators, polymeric soil release agents, dye transfer inhibiting agents, c~Pl~ting agents. clay soil 35 removal and anti-redeposition agents, fabric softeners, detersive surf~rt~ntc and other miscellaneous in~redients v,,hich are typical for use in the comn~ercial practice of the present invention. especially to provide high quality fabric laundrv detergent compositions.
Enzvmes - Enzymes can be optionally included in the formulations herein for a S wide variety of fabric }aundering purposes. including removal of protein-based, carbohydrate-based. or triglyceride-based stains. for example, and for the prevention of fugitive dye transfer, and for fabric restoration. Enzymes preferably included in the agglomerated detergent composition herein are those selected from the group consisting of proteases, amylases, lipases. cellulases, lipases and mixtures thereof. Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal. bacterial. fungal and yeast origin. However, their choice is govemed by several factors such as pH-activity and/or stability optima. thermostability, stability versus active detergents, builders and so on. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
En~ymes are normally incorporated at levels sufficient to provide up to about S
mg by weight. more typically about 0.01 mg to about 3 mg, of active enzyme per gram of the composition. Stated otherwise, the compositions herein will typically comprise from about 0.01 % to about 2%, preferably 0.01 %- I % by weight of an enzyme. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
Suitable examples of proteases are the subtilisins which are obtained from particular strains of Bacillus subtilis and Bacillus licheniforms. Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade narne ESPERASE~). The ~lep~alion of this enzyme and analogous enzymes is described in British Patent Specification No. 1,243,784 of Novo. Proteolytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the tr~ n~mes ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. ~The Netherlands). Other proteases include Protease A (see European Patent Application 130,756, published January 9, 1985) and Protease B (see Eu.ope~ Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130,756, Bott et al, published January 9, 1985).
Amylases include, for example, x-amylases described in British Patent Specification No. 1,296,839 ~Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries.

The cellulase usable in the present invention include both bacterial or fungal cellulase. Preferably. thev will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4.435.307. Barbesgoard et al. issued March 6, 1984. which discloses fùngal cellulase produced from Humicola insolens and Humicola strain DSM 1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander). suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME (Novo) is especially useful.
Suitable lipase enzymes for detergent usage include those produced by microorg~nicmC of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372.034. See also lipases in J~p~n~se Patent Application ~3,20487, laid open to public inspection on February 24~ 1978. This lipase is available from Amano Pharm~reutical Co. Ltd., Nagoya, Japan, under the trade narne Lipase P
"Arnano," hereinafter referred to as "Amano-P." Other commercial lipases includeAmano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
Iipolyticurn NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan;
and further Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. The LIPOLASEenzyme derived from Humicola lanuginosa and commercially available from Novo (see also EPO 341,947) is a plefe.l~d lipase for use herein.
Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution ble~rhing," i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, lignin~ce and haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-co..l~;..i..g d~l~,g.ll~ compositions are disclosed, for example, in PCT Tnt~ tional Application WO 89/099813, published October 19, 1989, by O. Kirk, ~ccign~d to Novo Industries A/S.
A ~vide range of enzyme materials and means for their incol~oldlion into synthetic 30 detergent compositions are also disclosed in U.S. Patent 3,553,139, issued January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. Patent 4,101,457, Place et al, issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued March 26, 1985, both. Enzyme materials useful for detergent formulations, and their inco~o~dlion into such formulations, are disclosed in U.S. Patent 4,261,868, Hora et al, issued April 14, 35 1981. Enzymes for use in detergents can be stabilized by various techniques. Enzyme W O 97/32954 PCT~US97/04690 stabilization techniques are disclosed and e:~emplified in U.S. Patent 3~600.319. issued August 17. 1971 to Gedge, et aL and European Patent Application Publication No. 0 199 405. Application No. 86200586.5. published October 29, 1986. Venegas. Enzvme stabilization svstems are also described, for exarnple, in U.S. Patent 3.519,570.
Bleachin~ Compounds - Bleaching Aeents and Bleach Activators - The detergent compositions herein may optionally contain bleaching agents or bleaching compositions cont~ining a ble~ching agent and one or more bleach activators. When present, bleaching agents will typically be at levels of from about 1% to about 30%, more typically from about 5% to about 20%, of the detergent composition, especially for fabric laundering. If presenL the amount of bleach activators will typically be from about 0.1 % to about 60%, more typically from about 0.5% to about 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.
The ble~ching agents used herein can be any of the ble~chine agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other ble~r~ing agents. Perborate bleaches, e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
Another category of ble~ching agent that can be used without restriction enComr~csee perc~boxylic acid ble~hing agents and salts thereof. Suitable examples of this class of agents include m~n~siurn monoperoxyphth~l~te hexahydrate, the m~gneSium salt of metachloro ~ I,e,lzoic acid, 4-nonylamino~-oxoperoxybutyric acid and diperoxydo~ler~nedioic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985, Eun~peall Patent Application 0,133,354, Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983.
Highly l,.ef~ d ble~c-hin~ agents also include 6-nonylarnino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.
Peroxygen bleaching agents can also be used. Suitable peroxygen ble~ ing compounds include sodium carbonate peroxyhydrate and equivalent "pel~;~bollat~"
bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, m~nufartllred comrnercially by DuPont) can also be used.
A ~l~f.,.led pe.c~l,onate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 W O 97/32954 PCTrUS97/04690 micrometers and not more than about 10% by weight of said particles being larger than about 1.'50 micrometers. Optionally, the percarbonate can be coated with silicate. borate or water-soluble surfactants. Percarbonate is available from various commercial sources such as FMC. Solvay and Tokai Denka.
Mixtures of bleaching agents can also be used.
Peroxygen bleaching agents. the perborates. the percalbollates~ etc.~ are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e.! during the washing process) of the peroxy acid corresponding to the bleach activator.
Various nonlimiting examples of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990toMaoetal,andU.S.Patent4,412~934. Thenonanovloxybenzene sulfonate (NOBS) and tetraacetyl ethylene ~ mine (TAED) activators are typical, and mixtures thereof can also be used. See also U.S. 4,634,551 for other typical bleaches and activators useful herein.
Highly preferred amido-derived bleach activators are those of the formulae:
RIN(R5)C(o)R2C(o)L or Rl C(O)N(R5)R2C(o)L
wherein Rl is an alkyl group cont~ining from about 6 to about 12 carbon atoms, R2 is an alkylene con~inin~ from I to about 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl cont~ining from about 1 to about 10 carbon atoms, and L is any suitable leaving group. A
leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion. A l)~ef~ d leaving group is phenyl sulfonate.
Preferred examples of bleach activators of the above forrnulae include (6-oct-anamido-caproyl)oxyb~ Psulfonate, (6-nonanamidocaproyl)oxyben7PnPsl-lfonate, (6-~ec~n~miflo-caproyl)oxybel.~P~ fonate, and mixtures thereof as described in U.S.Patent 4,634,551, incorporated herein by reference.
Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990, incorporated herein by reference. A highly preferred activator of the benzoxazin-type is:
o [~(N"C~

Still another class of preferred bleach activators includes the acyl lactarn activators, especi~lly acyl caprolactams and acyl valerol~t~m~ of the formulae:

O O
Il 11 O C--CH2--CH2\ 0 C--CH2--CH2 R6--C--N~ ,C H2 R6--C--N~

wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group cont~ining from I to about 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactarn.
octanoyl caprolactam~ 3,5~5-trimethylhexanoyl caprolactam. nonanoyl caprolactam~decanoyl caprolactam, llndecPnoyl caprolactam, ben_oyl valerolactam, octanoyl valerolactarn, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam.
3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784. issued to Sanderson. October 8, 1985. incorporated herein by reference. which discloses acyl caprolactams, including benzoyl caprolactarn, adsorbed into sodium perborate.
Ble~chin~ agents other than oxygen ble~ching agents are also known in the art and can be utilized herein. One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or all-minllm phthalocyanines. See U.S. Patent 4~033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from about 0.025% to about 1.25%, by weight, of such bleaches. especially sulfonate _inc phthalocyanine.
If desired, the ble~ching compounds can be catalyzed by means of a m~ny~nese compound. Such compounds are well known in the art and include, for example, them~n~;~nPse-based catalysts disclosed in U.S. Pat. 5.246,621. U.S. Pat. 5.244.594; U.S.
Pat. 5,194,416; U.S. Pat. 5,114,606; and European Pat. App. Pub. Nos. 549,271Al,549,272Al, 544,440A2, and 544.490Al; Preferred examples of these catalysts include MnIV2(u-O)3( 1 ,4,7-L~ hyl- 1 ,4,7-tria_acyclononane)2(PF6)2, MnIII2(u-O) 1 (u-O-Ac)2( 1 ,4,7-lrilllclhyl- 1 ,4,7-tri~7~cyclononane)2 (CI04)2, MnIV4(u-O)6( 1 ,4,7-triazacy-clononane)4(ClO4)4, MnIIIMnIV4(u-o) 1 (u-OAc)2 ( 1 ,4,7-trimethyl- 1 ,4,7-triazacyclo-nonane)2(C1O4)3, MnIV(1,4,7-trimethyl-1,4,7-tri~7~cyclononane)- (OCH3)3 (PF6), and mixtures thereof. Other metal-based bleach catalysts include those disclosed in U.S. Pat.
4,430,243 and U.S. Pat. 5,114,611. The use of m~n~n~se with various complex ligands to çnh~nre ble~çhing is also reported in the following United States Patents: 4,728,455;
~ 5.284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227.084.
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 W O 97/32954 PCT~US97/04690 preferably provide from about 0.1 ppm to about 700 ppm. more preferably from about I
ppm to about 500 ppm. of the catalyst species in the laundry liquor.
Polvmeric Soil Release A~ent - Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and processes of this S invention. Polymeric soil release agents are characterized by having both 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 and, thus~ serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to lren~ p~t 10 with the soil release agent to be more easily cleaned in later washing procedures.
The polymeric soil release agents useful herein especially include those soil release agents having: (a) one or more nonionic hydrophile components con.cistinp eccenti~lly of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segmentc with a degree of polymerization of lS from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30 oxypropylene units wherein said mixture co-l~ins a sufficient amount of oxyethylene units such that the hydrophile component has hydrophilicity great enough to increase the 20 hydrophilicity of conventional polyester synthetic fiber surfaces upon deposit of the soil release agent on such surface, said hydrophile segments preferably comprising at least about 25% oxyethylene units and more preferably, especially for such components having about 20 to 30 oxypropylene units, at least about 50% oxyethylene units; or (b) one or more hydrophobe components comprising (i) C3 oxyalkylene terephth~l~te se~mPntc,25 wherein, if said hydrophobe components also comprise oxyethylene terephth~l~tP,7 the ratio of oxyethylene te.epl.~ te: C3 oxyalkylene terephth~te units is about 2:1 or lower, (ii) C4-C6 alkylene or oxy C4-C6 alkylene seg.... I,ti, or mixtures therein, (iii) poly (vinyl ester) se~mPntc~ preferably polyvinyl acetate), having a degree of polymerization of at least 2, or (iv) C I -C4 alkyl ether or C4 hydroxyalkyl ether substituents, or mixtures 30 therein, wherein said substituents are present in the form of C I -C4 alkyl ether or C4 hydroxyalkyl ether cellulose derivatives, or mixtures therein, and such cellulose derivatives are ~llphiphilic, whereby they have a sufficient level of C I -C4 alkyl ether and/or C4 hydroxyalkyl ether units to deposit upon conventional polyester synthetic fiber surfaces and retain a sufficient level of hydroxyls, once adhered to such conventional 35 synthetic fiber surface, to increase fiber surface hydrophilicity, or a combination of (a) and (b).
Typically, the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from about 200~ althou~h higher levels can be used. preferably from 3 to about 150, more pre~erably from 6 to about 100. Suitable oxy C4-C6 alkylene hydrophobe segments include, but are not limited to~ end-caps of polymeric soil release agents such as MO3S(CH2)nOCH2CH~O-, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent No. 4,721,580, issued January 26, 1988 to Gosselink.
Polymeric soil release agents useful in the present invention also include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephth~l~te or propylene terephth~l~te with polyethylene oxide or polypropylene oxide terephth~l~te, and the like. Such agents are cornmercially available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group con~i~ting of C l-C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al.
Soil release agents characterized by poly(vinyl ester) hydrophobe segmlonts include graft copolymers of poly(vinyl ester), e.g., C 1 -C6 vinyl esters, preferably poly(vinyl acetate) grafted onto poiyalkylene oxide backbones, such as polyethylene oxide backbones. See European Patent Application 0 219 048, published April 22, 1987 by Kud, et al. Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Gerrnany).
One type of l)lc;~.,ed soil release agent is a copolymer having random blocks ofethylene tc.~ h~l~te and polyethylene oxide (PEO) t~.~phlh~l~te. The molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000.
See U.S. Patent No. 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent No.
3,893,929 to R~c~dl~r issued July 8, 1975.
Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephth~l~te units contains 10-15% by weight of ethylene tere~hth~l~tp units together with 90-80% by weight of polyoxyethylene terephth~l~t~ units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000. Examples of this polymer include the commercially available m~t~i~l ZELCON 5126 (from DuPont) andMILEASE T (from ICI). See also U.S. Patent No. 4,702,857, issued October 27, 1987 to Gosselink.
Another pl~fe.l~d polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone ofterephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently ~ ehed to the backbone. These soil release agents are described fully in U.S. Patent 4 968.451.
issued November 6. 1990 to J.J. Scheibel and E.P. Gosselink. Other suitable polvmeric soil release agents include the lerephth~l~te polyesters of U.S. Patent 4,711,730. issued December 8, 1987 to Gosselink et aL the anionic end-capped oligomeric esters of U.S.
Patent 4,721,580~ issued January 26~ 1988 to Gosselink. and the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
Preferred polymeric soi} release agents also include the soil release agents of U.S.
Patent No. 4,877,896. issued October 31, 1989 to Maldonado et al, which discloses anionic, especially sulfoaroyl, end-capped terephth~l~te esters.
Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy- l ,2-propylene units. The repeat units form the backbone of the oligomer and are preferably termin~tPd with modified isethionate end-caps. A particularly ~"e~.led soil release agent of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-eth~nesulfonate. Said soil release agent also comprises from about 0.5% to about 20%, by weight of the oligomer, of a crystalline-reclucing stabilizer, preferably selected from the group con.~i~ting of xylene sulfonate, c.-mPnP sulfonate, toluene sulfonate, and mixtures thereof.
If ~Itili7P~ soil release agents will generally comprise from about 0.01% to about 10.0%, by weight, ofthe de~elgel,l compositions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0%.
Dye Transfer Inhibitin~ A~ents - The compositions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process. Generally, such dye ,.dn~r~. inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, m~ng~nPse phthalocyanine, peroxidases, and ~ lull_S thereof. If used, these agents typically comprise from about 0.01% to about 10% by weight of the composition, preferably from about 0.01 % to about 5%. and more preferably from about 0.05% to about 2%.
More specifically, the polyamine N-oxide polymers pleI~ d for use herein contain units having the following structural formula: R-AX-P; wherein P is a 35 polymerizable unit to which an N-O group can be ~ he~ or the N-O group can form part W O 97132954 rcTrusg7/o4690 of the polymerizable unit or the N-O group can be attached tO both units; A is one of the ~ following structures: -NC(O)-, -C(O)O-. -S-. -O-, -N=; ~c is 0 or l; and R is aliphatic ethoxylated aliphatics aromatics. heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group can be attached or the N-O group is part of these groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole. imidazole, pyrrolidine~ piperidine and derivatives thereof.
The N-O group can be l~resented by the following general structures:

(Rl )X--IN ~ )y; --N--(R~ )x (R3)z wherein Rl, R~. R3 are aliphatic. aromatic. heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be attached or form part of any of the aforementioned groups. The amine oxide unit of the polyamine N-oxides has a pKa <10, preferably pKa <7, more preferred pKa <6.
Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting plop~.lies. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
The amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by ~pr~ iate copolymerization or by an al,plopliate degree of N-oxidation. The polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; more ~lef~ d 1,000 to 500,000; most preferred 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO".
The most p~efe.,ed polyamine N-oxide useful in the detergent compositions hereinis poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1:4.
Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as a class as "PVPVI") are also preferred for use herein. Preferably the PVPVI has an average molecular weight range from 5,000 to l,000,000, more preferably from 5,000 to 200,000, and most preferably from l O,000 to 20,000. (The average molecular weight range is ~ terrnined by light scattering as described in Barth, et al., Chemical Analvsis, WO 97/329~4 PCT/US97/04690 Vol 113. "Modern Me~hods of Polvmer Characterization". the disclosures of which are incorporated herein by reference.) The PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from l: l to 0.2:1~ more preferably from 0.8:1 to 0.3:1. most preferably from 0.6: l to 0.4:1. These copolymers can be either linear or 5 branched.
The present invention compositions also may employ a polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5.000 to about 400~000,preferably from about 5,000 to about 200,000, and more preferably from about 5.000 to about S0,000. PVP's are kno~vn to persons skilled in the detergent field; see, for exarnple, EP-A-262,897 and EP-A-256~696~ incorporated herein by reference. Compositions cont~ining PVP can also contain polyethylene glycol ("PEG") having an average molecular weight from about 500 to about 100,000~ preferably from about l~000 to about 10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2:1 to about 50:1, and more preferably from about 3:1 to about 10:1.
The detergent compositions herein may also optionally contain from about 0.005%
to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from about 0.01% to 1% by weight of such optical brighteners.
The hydrophilic optical bri~hteners useful in the present invention are those having the structural formula:
R, H H N~

R2 SO3M SO3M Rl wh~,le~ll Rl is selectç(l from anilino, N-2-bis-hydroxyethyl 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 forrnula, Rl is anilino, R2 is N-2-bis-hydroxyethyl and M is acation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)arnino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular br ghter er species is commercially m~rketeA under the tr~en~nle Tinopal-UNPA-GX by Ciba-Geigy Coll,o,dlion. Tinopal-UNPA-GX is the l,lef~lled hydrophilic optical bright~ner useful in the detergent compositions herein.
When in the above formula, R1 is anilino. R~ 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-hydroxveth~;l-N-methylamino)-s-triazine-~-yl)arnino]2.2'-stilbenedisulfonic acid diso-dium salt. This particular bri8htener species is commercially marketed under thetradename Tinopal SBM-GX by Ciba-Geigy Corporation.
When in the above forrnula. Rl 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 is commercially marketed under the tM~en~me Tinopal AMS-GX by Ciba Geigy Corporation.
The specific optical brightener species selected for use in the present invention provide especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents hereinbefore described. The combination of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than does either of these two detergent composition components when used alone. Without being bound by theory, it is believed that such brighteners work this way because they have high affinity for fabrics in the wash solution and therefore deposit relatively quick on these fabrics. The extent to which brightPnPrs deposit on fabrics in the wash solution can be defined by a parameter called the"exhaustion coefficient". The exhaustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightPner concentration in the wash liquor. Bright~nPrs with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention.
Of course, it will be appreciated that other, conventional optical brightPtlPr types 25 of compounds can optionally be used in the present colposi~ions to provide conventional fabric "briF;htnPss" benefits, rather than a true dye ~ sre. inhibiting effect. Such usage is conventional and well-known to deter~ell~ formulations.
Chelating A,eents - The detergent compositions herein may also optionally contain one or more iron and/or m~ng~nPsp chPI~tinp agents. Such chel~ting agents can beselected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intP~ing to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and m~ng~nPse ions from washing solutions by formation of soluble chelates.
Arnino carboxylates useful as optional cho!~ting agents include W O 97/32954 PCTnUS97/04690 ethvlene~ minetetracetates. N-hydroxyethylethylene~ minetriacetates. nitrilotriacetates, ethylene~ mine telld~lo~lionates. triethylenetetr~minehexacetates. diethylene-triaminepentaacetates (DTPA). and ethanoldiPlycines. alkali metal, ammonium. andsubstituted ammonium salts therein and mixtures therein.
Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are perrnitted in detergent compositions. and include ethylent ~i~.ninetetrakis (methylenephosphonates) as DEQUEST. Preferred, these arnino phosphonates to not contain alkyl or alkenylgroups with more than about 6 carbon atoms.
Polyfunctionally-substituted aromatic chPl~ting agents are also useful in the compositions herein. See U.S. Patent 3.812.044. issued May 21, 1974, to Connor et al.
Pl~f~.~cd compounds of this type in acid forrn are dihydroxydisulfoben7erl~s such as 1,2-dihydroxy-3 ,5 -disulfobenzene .
A l~lef~ d biodegradable chelator for use herein is ethylçnerli~rnine disuccinate ("EDDS"), especially the [S,S~ isomer as described in U.S. Patent 4,704.233, November 3, 1987. to Hartman and Perkins.
If ~ltili7~.1 these ch~l~ting agents will generally comprise from about 0.1% to about 10% by weight of the d~lelgell~ compositions herein. More preferably, if l~tili7PA
the chel~tin~ agents will comprise from about 0.1% to about 3.0% by weight of such compositions.
Clav Soil Removal/Anti-redeposition A~ents - The compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition l~lo,oellies. Granular detergent compositions which contain these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylates ~rnin~s~
The most ~ ,f."l~,~ soil release and anti-redeposition agent is ethoxylated tetraethylc,l~,~c.,~ o Exemplary ethoxylated arnines are further described in ~hS.
Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of plefel.cd cl~y soll removal-antiredeposition agents are the cationic compounds disclosed in Eulope~ Patent Application 1 1 1,965, Oh and Gosselink, published June 27, 1984. Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S. Patent4,548,744, Connor, issued October 22, 1985. Other clay soil removal and/or anti W O 97/32954 PCTAUS97/046gO

redeposition agents knov~n in the art can also be utilized in the compositions herein.
Another type of preferred antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.
Suds Suppressors - Compounds for reducing or suppressing the formation of suds S can be incorporated into the compositions of the present invention. Suds suppression can be of particular importance in the so-called "high concentration cleaning process" as described in U.S. 4,489~455 and 4,489,574 and in front-loading European-style washing m~-~hines.
A wide variety of materials may be used as suds suppressors, and suds ~u~ ssors 10 are well known to those skilled in the art. See, for example, Kirk Othrner Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc.,1979). One category of suds suppressor of particular interest enco",p~cses monocarboxylic fatty acid and soluble salts therein. See U.S. Patent 2,954,347, issued September 27,1960 to Wayne St. John. The monocarboxylic fatty acids and salts thereof 15 used as suds suppressor typically have hydrocarbyl chains of 10 to about 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.The detergent compositions herein may also contain non-surfactant suds suppressors. These include, for example: high molecular weight hydrocarbons such as 20 paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C l g-C40 ketones (e.g., stearone), etc. Other suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylme!~min~s or di- to tetra-alkyl~ mine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine con~ining 1 to 24 carbon atoms, propylene oxide, and 25 monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosph~te esters. The hydrocarbons such as paraffin and halopdldfrln can be utilized in liquid form. The liquid hydrocarbons will be liquid at room te.~ ,.al~lre and atmospheric ples~ule, and will have a pour point in the range of about -40~C and about 50~C, and a minimllm boiling point not less than 30 about 110~C (~tmosph~ric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below about 100~C. The hyd~oc~l,ons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5,1981 to Gandolfo et al. The hydrocarbons, thus, include ~liph~tic, alicyclic, aromatic, and 35 heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The terrn "paraffin." as used in this suds suppressor discussion. is inten-lecl to include mixtures of true paraffins and cyclic hydrocarbons.
Another preferred category of non-surfactant suds suppressors comprises siliconesuds suppressors. This category includes the use of polyorganosiloxane oils~ such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the si}ica. Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4.265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No. 89307851.9, published February 7, 1990, by Starch. M. S.
Other silicone suds suppressors are disclosed in U.S. Patent 3.~55.839 which relates to compositions and processes for defoaming aqueous solutions by incorporating therein small arnounts of polydimethylsiloxane fluids.
Mixtures of silicone and sil~n~tec~ silica are described, for in~il;.n~e, in GelTnan Patent Application DOS 2,124,526. Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al, and in U.S. Patent No. 4,652,392. R~ginc~i et al, issued March 24, 1987.
An exemplary silicone based suds ~u~ eSSOr for use herein is a suds suppressing amount of a suds controlling agent conci~ting e~centi~lly of:
(i) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about 1.500 cs. at 25~C;
{ii) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxane resin composed of (CH3)3SiO1/2 units of SiO2 units in a ratio of from (CH3)3 SiO1/2 units and to SiO2 units offrom about 0.6:1 to about 1.2:1;
and (iii) from about 1 to about 20 parts per 100 parts by weight of (i) of a solid silica gel.
In the ~l~f, .l~d silicone suds suppressor used herein, the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol. The pnmary silicone suds suppressor is branched/cros~linked and preferably not linear.
To illustrate this point further, laundry detergent compositions with controlledsuds will optionally comprise from about 0.001 to about 1, preferably from about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5, weight % of said silicone suds suppressor. which COM~I ises (1) a nonaqueous emulsion of a primary antifoam agent which is a mi~cture of (a) a polyorganosiloxane. (b) a resinous siloxane or a silicone resin-producing silicone compound. (c) a finely divided filler material. and (d) a catalyst to promote the reaction of mixture components (a). (b) and (c). to form silanolates: (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of S polyethylene-polypropylene glycol having a solubility in water at room t~ cldlllre of more than about 2 weight %; and without polypropylene glycol. Similar amounts can be used in granular compositions, gels. etc. See also U.S. Patent Nos. 4,978,471, Starch.
issued December 18, 1990, and 4,983,316, Starch, issued January 8, 1991, 5,288,431, Huber et al.. issued February 22, 1994, and U.S. Patent Nos. 4,639,489 and 4,749,740, Aizawa et al at column 1, line 46 through colurnn 4. line 35.
The silicone suds suppressor herein preferably comprises polyethylene glycol anda copolymer of polyethylene glycol/polypropylene glycol. all having an average molecular weight of less than about I ,000, preferably between about 100 and 800. The polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than about 2 weight %, preferably more than about 5 weight %.
The preferred solvent herein is polyethylene glycol having an average molecular weight of less than about 1,000, more preferably between about 100 and 800, mostpreferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300. Preferred is a weight ratio of between about 1: 1 and 1: 10, most preferably between I :3 and I :6, of polyethylene glycol:copolymer of polyethylene-polypropylene glycol.
The prefe.l.d silicone suds SU~u~)l'eSSOIa used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC L 101.
Other suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872. The secondary alcohols include the C6-C 16 alkyl alcohols having a C I -C 16 chain. A preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12. Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem. Mixed sudssuppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1 :5 to 5:1 .
For any dete~.,nt compositions to be used in automatic laundry washing m~hin~s~ suds should not form to the extent that they overflow the washing m~hine.

Suds suppressors. when llti~i7P~l are preferably present in a "suds suppressing arnount.
By "suds suppressing arnount" is meant that the fo~nulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry v~ashing machines.
The compositions herein will generally comprise from 0% to about 5% of suds suppressor. When utilized as suds suppressors, monocarboxylic fatty acids, and salts therein. will be present typically in amounts up to about 5%, by weight, of the detergent composition. Preferably. from about 0.5% to about 3% of fatty monocarboxylate suds suppressor is lltili7Pf~ Silicone suds suppressors are typically utilized in arnounts up to about 2.0%, by weight, of the detergent composition, although higher arnounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimi7P-l and effectiveness of lower amounts for effectively controlling sudsing.
Preferably from about 0.01% to about 1% of silicone suds suppressor is used. more preferably from about 0.25% to about 0.5%. As used herein. these weight pel~e~llage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be lltili7P.l Monostearyl phosphate suds suppressors are generally utilized in arnounts ranging from about 0.1 % to about 2%. by weight, of the composition. Hydrocarbon suds su~pl~Jsors are typically utilized in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used.
The alcohol suds SU~ ,5SO1:; are typically used at 0.2%-3% by weight of the fini~hP-~
composltlons.
Fabric Softeners - Various through-the-wash fabric softeners, especially the impalpable smectite clays of U.S. Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as other softener clays known in the art, can optionally be used typically at levels of from about 0.5% to about 10% by weight in the present compositions to provide fabric softener benefits concurrently with fabric clean;ng Clay softeners can be used in combination with arnine and cationic softeners as disclosed, for exarnple, in U.S.
Patent 4,375,416, Crisp et al, March 1, 1983 and U.S. Patent 4,291,071, Harris et al, issued September 22, 1981.
Other In~redients - A wide variety of other ingredients useful in dc:l~ ,gent compositions can be included in the compositions herein, including other active ingredients, carriers, processing aids, dyes or pigments, etc. If high sudsing is desired, suds boosters such as the C l o-C 16 alkanolamides can be incorporated into the compositions, typically at 1%-10% levels. The Clo-C14 mon-~eth~nol and diethanolamides illustrate a typical class of such suds boosters. Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides. betaines and sultaines noted above is also advanta_eous. If desired. soluble magnesium salts such as MgCl2~ MgSO4, and the like. can be added at levels of~ typically, 0.1%-2%. to provide additional suds and to enhance grease removal perforrnance.
Various detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate~
then coating said substrate with a hydrophobic coating. Preferably, the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate.
In use. the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
To illustrate this technique in more detail, a porous hydrophobic silica (trademark SIPERNAT DlO, DeGussa) is admixed with a proteolytic enzyme solution cont~inin~
3%-5% of C 13 l 5 ethoxylated alcohol (EO 7) nonionic surfactant. Typically, theenzyme/surfactant solution is 2.5 X the weight of silica. The resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used). The resulting silicone oil dispersion is emulsified or otherwise added to the final delel~ent matrix. By this means, ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected" for use in d~l~rgents.
The detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about l l, preferably between about 7.5 and 11Ø Fabric laundry products are t,vpically at pH 9-l l. Techniques for controlling pH at lecol.ll..e~-lecl usage levels include 25 the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.

EXAMPLES I - X
Two processes for producing agglomerates according to the invention are exemplified below in Exarnples I and II. In addition, several detergent compositions 30 made in accordance with the invention are exemplified in Exarnples III to X.

EXAMPLE I
Example I ill~ dles the process of the invention which produces free flowing, high density d~l~.gent agglomerates using the "paste process". A batch version of the 35 present process is described hereinafter. Initially, 200 grarns of a powdered builder W O 97/32954 PCTrUS97/04690 mixture (hereinafter ret'erenced as the "builder") comprising zeolite A and sodium carbonate in a weight ratio of 1.7:1 (47% by weight) and 100 grams of C16 secondary (2,3) alkyl sulfate surfactant are blended into a lab-scale high-shear mixer ~Regal La Machine(~ II) to form a homogeneous powder mixture. Thereafter. 200 grams surfactant 5 paste (at 65~C) are fed into the mixer and blended with the homogeneous powdermixture. The surfactant paste comprises an aqueous paste composition comprising 73%
by weight of C 1 1-C 18 alkyl benzene sulfonates ("LAS") and C 12-1 S alkyl sulfate and in a ratio of 25 :75~ and 20% water. The mixer is run until agglomerates are forrned. In a continuous version of this process. the detergent agglomerates would be further built-up 10 in a moderate speed mixer/densifier. Subsequent oven drying (2-4 hours at 75~C) will reduce the moisture to the desired level. The resulting detergent agglomerates have a density in a range from about 650 to 750 g/l and a median particle size between about 400 to about 600 microns.

EXAMPLE II
Example II illustrates the process of the invention which produces free flowing,high density de~e. g~ agglomerates using the neutralization process. A batch version of the present process is described hereinafter. Initially, 280 grarns of a powdered builder mixture (hereinafter referenced as the "builder") comprising zeolite A and sodium carbonate in a weight ratio of 1:2.2 (56% by weight) and 100 grams of C 16 secondary (2,3) alkyl sulfate surfactant are blended into a lab-scale, high-shear mixer (Regal La Machine~) II) to form a homogeneous powder mixture. Thereafter, the liquid acid precursor of C 10-20 linear alkylbenzene sulfonate (hereinafter referred to as "acid"), at 60~C, is continuously fed into the high shear mixer/densifier at a rate of 100 g/min until agglo~ .aLes are produced. The resnlting detergent agglomerates have a density in a range from about 650 to 750 g/l and a median particle size between about 400 to about 600 microns.

EXAMPLES III - VI
SAS agglomerates ~ p~d in the foregoing manner are used to provide fully-forrn~ t~d d~ lg~llt compositions, as illustrated by the following, non-limitingformulations in Examples III to VI. Example III exemplifies detergent agglomerates which it is possible to malce using the paste process and Examples IV - VI exemplify detergent agglo,ll~aLes which it is possible to make using the neutralization process.

W O 9~/32954 PCTrUS97/04690 ComponentsIII IV V Vl C12 14alkylbenzenesulfonate 7.5 20.2 20.2 25.4 C 14_ 15 alkyl sulfate 22.5 - ~ - ~
C10 20 secondary alkyl (2,3) sulfate 18.5 17.8 17.8 29.4 Neodol C~3 E6.5 - 2.4 2.5 Polyethylene glycol (MW=4000) 1.5 1.3 Aluminosilicate 24.0 29.1 17.3 16.3 Sodium carbonate 14.5 17.7 35.0 18.5 Minors (water. unreactants) 11 5 11 5 7 2 10 4 100.0 100.0 100.0 100.0 EXAMPLES VII - X
SAS agglomerates ple~)ared in the foregoing manner are used to provide fully-form~ ted detergent compositions, as illustrated by the following, non-limiting S Exarnples. In Examples VII to X, the overall weight percent of the ingredients is listed in the vertical columns. C10 20 secondary alkyl (2,3) sulfate agglomerates are p~e~)ared by the paste process in Example VII and by the neutralization process in Examples VIII
through X.

Components$ VII VIII IX
Surfactants C10 20 secondary alkyl (2,3) sulfate 7.2 8.0 8.0 7.3 C4s alkyl sulfate 12.8 2.6 2.6 3.2 C14-Cls alcohol ethoxylate (1-3) sulfate 1.6 1.0 1.0 1.2 C 12 13 linear alkyl benzel1e sulfonate7.2 15.8 15.8 9.6 Neodol C23 26E6.5-9 1.5 1.4 1.7 1.5 Salts/Builder Zeolite A 23.4 26.5 22.3 28.0 Sodium silicate (1.6r) 0.6 0.6 0.6 0.6 Polyacrylate Na (MW = 2,000-6,000) 2.4 2.4 2.4 2.4 Polyethylene glycol (MW = 4,000) 1.6 1.1 1.1 1.0 Sodiurn Carbonate 24.5 21.2 28.2 25.4 Sodiurn perborate 1.0 1.1 1.1 1.0 Sodium sulfate 5.5 5.6 5.6 5.6 Others Perfurne 0.4 0.4 0.4 0 4 W O 97/32954 rCT~US97/04690 Soilreleasepol,vmer 0.4 0.4 0.~ 0,4 Brighteners 0.2 0.2 0.2 0.2 Enz,vmes 0.6 0.6 0.6 0.6 Fumed silica 0.4 0.4 0.4 0.4 Miscellaneous Unreacted 0.5 0.5 0.5 0.5 Moisture 8.2 10.2 71 11 7 Total: 100 100 100 100 * In Examples VII to X, the abbreviations used for certain Ingredients are defined as follows: ~EODOL g) refers to nonionic surfactants commercially available from Shell Chemical Company; soil release polymer is an anionic polyester (see Maldonado and 5 Gosselink and other patents cited above); Brighteners are TINOPALS~. available from Ciba-Geigy.

Having thus described the invention in detail, it will be clear to those skilled in the art that various changes may be made without departing from the scope of the invention 10 and the invention is not to be considered limited to what is described in the specification.

Claims (9)

WHAT IS CLAIMED IS:

1. An agglomerated detergent composition having a density of at least 650 g/l comprising:
(a) from 1% to 70% by weight of a detersive surfactant system comprising C10-20 linear alkylbenzene sulfonates, C10-20 alkyl sulfates, C10-18 alkyl ethoxy sulfates having from 1 to 7 ethoxy groups, C10-20 secondary (2,3) alkyl sulfates; and (b) at least 1% by weight of a detergency builder, preferably selected from the group consisting of alkali metals, ammonium phosphates, substituted ammonium phosphates, citric acid, aluminosilicates, carbonates, silicates, borates, polyhydroxy sulfonates, polyacetate carboxylates, polycarboxylates, zeolite and mixtures thereof;
wherein said surfactant system and said builder are agglomerated to form detergent agglomerates; wherein said surfactant system has improved solubility in an aqueous laundering solution.

2. An agglomerated detergent composition according to Claim 1 wherein said detersive surfactant system and said detergency builder are in a weight ratio offrom 1:5 to 5:1.

3. An agglomerated detergent composition having a density of at least 650 g/l comprising:
(a) from 1% to 70% by weight of a detersive surfactant system; wherein said detersive surfactant system comprises from 5% to 30% by weight of C12-14 alkylbenzene sulfonate, from 15% to 35% C10-20 secondary alkyl (2,3) sulfate;
(b) from 15% to 35% aluminosilicate;
(c) from 10% to 40% sodium carbonate; and (d) the balance water.

4. A process for making an agglomerated detergent composition comprising the steps of:
(a) blending secondary (2,3) alkyl sulfate with a member selected from the groupconsisting of carbonate, aluminosilicate, zeolite and mixtures thereof to form ahomogeneous powder mixture;
(b) agglomerating said homogeneous powder mixture with a surfactant paste mixture in a high speed mixer/densifier to form detergent agglomerates, said surfactant paste mixture comprising from 1% to 80% by weight of a detersive surfactant system comprising C10-20 linear alkylbenzene sulfonates, C10-20 alkyl sulfates, C10-18 alkyl ethoxy sulfates having from 1 to 7 ethoxy groups, alcohol ethoxylates, and polyethylene glycol, and preferably having a viscosity of from 10,000 centipoises to 100,000 centipoises;
(c) mixing said detergent agglomerates in a moderate speed mixer/densifier so asto build-up said detergent agglomerates, and optionally further comprising the step of adding a coating agent; and (d) drying said detergent agglomerates so as to form said agglomerated detergentcomposition which has a density of at least 650 g/l, and preferably said detergent agglomerates of said agglomerated detergent composition have a median particle size of from 300 microns to 600 microns.

5. A process for making an agglomerated detergent composition comprising the steps of:
(a) blending secondary (2,3) alkyl sulfate with a detergency builder to form a homogeneous power mixture, preferably selected from the group consisting of alkali metals, ammonium phosphates, substituted ammonium phosphates, citric acid, aluminosilicates, carbonates, silicates, borates, polyhydroxy sulfonates, polyacetate carboxylates, polycarboxylates, zeolite and mixtures thereof; and (b) agglomerating a liquid acid precursor of C10-C20 linear alkylbenzene sulfonate with said homogeneous power mixture in a high speed mixer/densifier toform detergent agglomerates so as to form said agglomerated detergent composition which has a density of at least 650 g/l, and preferably said agglomerated detergent compositions have a median particle size of from 300 microns to 600 microns.

6. A process according to Claim 5 further comprising the step of mixing said detergent agglomerates in a moderate speed mixer/densifier so as build-up said detergent agglomerates.

7. A granular detergent composition comprising conventional formulation ingredients and at least 5% by weight of the agglomerated detergent composition prepared according to the process of any of Claims 4-6.

8. A granular detergent composition comprising conventional formulation ingredients and at least 10% to 65% by weight of the agglomerated detergent composition according to any of Claims 1-3.

9. A method for laundering soiled fabrics comprising the step of contacting saidsoiled fabrics with an effective amount of a granular detergent composition according to either of Claims 7 or 8 in an aqueous laundering solution.