CA2255005A1 - Detergent composition - Google Patents

Abstract

A detergent composition comprising a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant, a non-AQA surfactant and a photobleach.

Description

DETERGENT COMPOSITON

Technia-l Pield The present invention relates to a dete~ nt cG~ ~c;tion comprising phoLoble;~ch, a non-AQA surfactant and a bis-alkoxylated quate,-la~y q. ~ oniu~ (bis-AQA)c?tionic 10 ~ulf~ctant.

~und to the Invention The formulation of laundry dete.genLs and other cleDning co~ nc p~sents a 15 con~;dP-rable chqllen~e~ since modern co.. I~sitionc are ,~uired to remove a variet,v of soils and stains from diverse substrates. Thus, laundry d~t~ .E,ent~ hard surface cleanc~, chDmpoos and other pe.~nal cle~ncing c~ po~;~;or~c~ hand dishwc.sh.ng d~t~rgenl~ and deL~.gent cou~ ;Qnc suitable for use in automatic dishwashers allrequire the proper se~ ;0l- and combination of ingredients in order to function 20 effectively. In g~el~e~l~ such d~tcrg~nt col~positions will contain one or more types of surf ~t~ntc which are designed to loosen and remove dif~rent types of soils and stains.
While a review of thc lit~ ul~ would seem to indi~atP that a wide sçle~tion of surf~tDntc and surfactant cGlnkin~;ollc are available to the dete~gent manufacturer, the reality is that many such ingredients are s~i~lity ch~rni~lc which are not suitable in 25 low unit cost items such as home-use laundry dete~,ents. The fact remains that most such home-usc ~ such as laundry detelg~;nls still mainly co",l,.i~ one or more of the con~ t;on~l etho~cylated nonionic and/or s~llfated or sulfonated anionic surfaet~ntc, e~ ly due to c~nv~o .;c c~ncidçrations and the need to formulate co"~ ;onc which function l~n~bly well with a variety of soils and stains and a variety of 30 fabrics.

The lite~alule ~ug~-~ jtC that various niL,~gen-cont~ining c~tionic surfart~ntc would be useful in a variety of clYnin~ c~lnpositir)nc Such materials, typically in the form of amino-, amido-, or quaternary ammonium or imi~i~701inium colllpounds, are often designed for 35 c~i~lity use. For e~mrle, various amino and quaternary ~mmonium surf~rt~n~c have been suggested for use in shampoo compositions and are said to provide cosmetic benefits WO 97/43394 PCT/US97tO8445 to hair. Other nitrogen-cont~inin~ surfart~ntc are used in some laundry detc.gen~ to provide a fabric softening and anti-static benefit. For the most part, however, the conl~ue--;ial use of such materials has been limited by the difflculty encountered in the large scale m~nllfactllre of such compounds. An additional limitation has been the potential S plecipiLation of anionic active colllpollcn~ of the detelge,l~ composition occasioned by their ionic interaction with cationic sul r~ . The afor~ tioned nonionic and anionic surf~t~ntc remain the major surfactant COIll~Ol~ s in today's laundry compositions.

The quick and efficient removal of different types of soils and stains such as body soils,~0 greasy/oily soils and certain food stains, can be problematic. Such soils comprise a re of triglycerides, lipids, complex polysaccharides, il~lg~ic saltc and p.ute;~ eo!.c matter all of which, are to some extent, composed of hydrophobic moieties and are thus notoriously ~iffi~.llt to remove. Low levels of hydrophobic soils and residual stains often remain on the surface of the fabric after washing.
A wide variety of bk~Ch~s~ for example peroxygen bleach, chloride bleaches and photobleaches are commonly used in dct~.~enl conlpo~ilions in addition to ~ulr;-c~ ts as mPntion~A above. Photobleachs are conv~ ,I;o~ y used under ch~ l;.n~es where launde~ed fabrics are subjected to coll,el~ t,d light sources, such as direct s~mlight as in a 20 line drying operation. Photobleach is a relatively mild bleach particularly effective at decolouration of coloured pig.. 1~ (e.g. in particulate or beverage stains) and removal of colour from the organic residues associated with body soils. The blP ~r~ power of the photobleach is derived from e~"~s.lle to ultra violet s~mlight It is believed that sunlight converts the photobleach into an active bk~fhi~ species which then oxidises coloured 25 stains present on the fabric. One ploble.ll associated with the use of any blesch, i.~ln~ the pholobleach is the inability to completely remove residual soil and stain from the surface of the fabric. Sl~ccescive washing and wearing coupled with limited soil removal in the wash c~lmin ~.~S in a build up of residual soil and stain which further entraps particulate dirt leading to fabric yellowing. Eventually the fabric takes on a dingy 30 al,~a~ ce which is perc ~ ed as ~l~e~able and discarded by the col~uule~.

It has been discovered that certain bis-alkoxylated quate~ ammoniwn (bis-AQA) col.lpounds can be used in various dete.~~ compositions to boost detelgen~r pelrollllance on a variety of soil and stain types, particularly the hydrophobic soil types, comrnonly 35 cllcc~ullleled. Une~ecledly, it has now been discovered that compositions cont~ining bis-AQA surf~t~ntc and photobleach deliver superior cleal~ing and whiten~ss pelrolllldnce versus products contAinin~ either technology alone.

The bis-AQA surfact~ntc of the present invention provide substantial ~n.rl~ to the S fonnulator, over cationic surf~t~ntc previously known. For example, the bis-AQA
~ul r~ used herein provide marked improvement in cle~nin~ of "everyday" greasy/oily hydrophobic soils regularly el~counl~ed. Moreover, the bis-AQA surf~rt~ntc are co..lpatible with anionic surfaçt~ntc comnlonly used in deterg~"lt colll~osilions such as alkyl sulfate and alkyl be.~e,~ sulfonate; hlcollllJalibility with anionic cOI~ .lLs of the 10 dete.gf .-l composition has commonly been the limiting factor in the use of c~ti~nir ~ulr~tA~c previously known. Low levels (as low as 3 ppm in the h.lllde.ing liquor) of bis~AQA SUrraCI~n~c gives rise to the ~n,rlL~ des~libed herein. Bis-AQA surf~rt~ntc can be form~ ~d over a broad pH range from S to 12. The bis-AQA ~u r~ can be p~. d as 30% (wt.) solutions which are ~ hle, and Ille~fu~ easy to handle in a 15 m~ml~ l.-. hlg plant. Bis-AQA s~ r~e~ with degrees of ethoxylation above 5 are SOI~f,~ f S present in a liquid form and can Ll.~ fore be provided as 100% neat materials.
In addition to their beneficial h~n~ling plo~lLies, the availability of bis-AQA surf~rt~ntc as highly conce.ltlatLd solutions provides a s~b~ l econol.lic advantage in Lldns~lL~tion costs. The bis-AQA ~wr~ n~ are also col~-p~;hlE with various ~.rullle ingredients, 20 unlike some cationic surfi~ct~ntc known in the art.

It is believed that the greasy/oily soils are effectively solubilized by bis-AQA, ILe.,_b~
allowing access of the photobleach to the colour bodies in the soil (e.g. e.l~rdp~cd P;r"-~ ls) res~ltin~ in improved soil decolouration. The present invention thus provides a 25 detefgelll co~ o ;l;on which not only delivers superior cle~ning of both hydruphobic greasy/oily soils and h~r~ol)hilic coloured soils by way of a dete.~.ll colll~o~ilion col~ g a bis-AQA surfactant and a photobleach.

BACKGROUND ART
U.S. Patent 5,441,541, issued August 15, 1995, to A. Mehreteab and F. J. Loprest, relates to anionic/c~tionir sulrac~t ll~uLIules. U.K. 2,040,990, issued 3 Sept., 1980, to A. P.
Murphy, R.J.M. Smith and M. P. Brooks, relates to ethoxylated cationics in laundry de~.gcnts.

Summary of the Invention The present invention provides a composition co,llp,isil1g or pl~tJar~,d by combining a photobleach, non-AQA surfactant and an effective amount of a bis-alkoxylated quat. ~ y S ~~ -onium (bis-AQA) cationic sulri c~nt of the formula:

R~ /A~R
N\ X
R2/ A qR

wh~ in Rl is a linear, bl~ched or sl~bstitlltçd Cg-C1g alkyl, aL~cenyl, aryl, aLkaryl, ether or 10 glycityl ether moiety, R2 is a Cl-C3 aL~cyl moiety, R3 and R4 can vary i lde~ ntly and are select~ from hydlogen, methyl and ethyl, X is an anion, and A and A' can vary infl. ~.~ 1y and are each Cl-C4 aLlcoxy, p and q can vary inf~e~ and are i~ ,ge~a of from 1 to 30.

Detailed Des~ tion of the In~ ion Photobleach The co.ll~osilions of the present i~ve~,lion Culll~,lisc a photobleach as an esse;~ l feature 20 thereof. Photobleaches suitable for use herein include sulfonated zinc and/or qhl...i..;.....
phthalo~;y~ilKs. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. The phthalo~ e photobleaches are available for e~"ple under the lui-~e ~lllf TINOLUX or as zinc phthql~anine sulfonate.

25 In general the phthql~ ines can be pn,parcd in the ll~mel descril)ed by T.in~te,q~d and co~o,~ , as ~.t~d in "Journal of the Ch~mi~ql Society" (pl719,1936). As is well lcnown, ~ b~ te~ metal phthalocyanines are soluble in water to an nmlcllqlly lowdegree and are ~ .,fo.e used as pi~ f.~C. However water solubility can be improved by the introduction of h~dlophilic groups such as sulfo, carboxy, or other sl~ctit~ent groups 30 into the phthalocyanine s~ ule by the use of hot oleum. Sulfonated phthalocyanines are useful dyes because they have an affmity for cellulose in the form of either cotton or paper pulp.

As noted hereinabove, phthalocyanines can be readily sulfonated by heating with oleum.
Thus zinc and aluminium phthalocyanines which are monosulfonated, disulfonated, trisulfonated and tetrasulfonated can be prepared. The trisulfonated and tetrasulfonated S species are p.er~lred for use as photobleaches. The zinc tetrasulfonated and zinc trisulfonated phthalocyanines are most pr~f~,l~d.

Detergelll compositions employed herein contain from 0.025 % to 1.25 % by weight, of such bleaches.
Bis-Alkoxvlated Ouatel,.aly A~ ,ol~iLu~, (bis-AOA) Cationic Surfactant The second essc.~ l Coll~ of the present invention COlllpliSCS an effective ~mollnt of a bis-AQA ~ulr~ll of the formula:

R~ /ApR
N\ X
R2/ A qR

wherein Rl is a linear, bl~lchcd or subsli~u~d alkyl, alkenyl, aryl, alkaryl, ether, glycityl ether moiety cont~ini~ from 8 to 18 carbon atoms, preferably 8 to 16 carbon atoms, most 20 preferably from 8 tol4 carbon atoms; R2 is an allcyl group cont~ining from 1 tO 3 carbon atoms, preferably methyl; R3 and R4 can vary independently and are selecte~ from the group co..~ g of hydrogen (pl~f~ d), methyl and ethyl; X~ is an anion such as chloride, l~l~o.l.ide, methyl sulfate, sulfate, S--r~ to provide electrical neutrality. A and A' can vary i~ epr ~ntly and are each selected from Cl-C4 aLkoxy, especially ethoxy, propoxy, butoxy and ~ lUl~,S thereof; p is from 1 to 30, p,e~e~bly 1 to 15, morepreferably from 1 to 8, even more preferably 1 to 4 and q is from 1 to 30, preferably 1 to 15, more preferably from 1 to 8, even more plefe~ably 1 to 4. Most preferably both p and qare 1.

Bis-AQA compounds wllcle~ t_e l~dloc~lJyl substituent R1 is Cg-C12, especially Cg-C1o, el-hA.-~e the rate of dissolution of laundry granules, especially under cold water conditions, as com~,~cd with the higher chain length materials. Accordingly, the Cg-C12 bis- AQA surfartAntc may be preferred by some formulators. The levels of the bis-AQA
surfactants used to prepare finich~od laundry del~.gelll compositions can range from 0.1% to 5%, typically from 0.45% to 2.5%, by weight. The weight ratio of bis-AQA to pe.. all~onate bleach is in the range of from 1:100 to 5:1, preferably from 1:60 to 2:1, most preferably from 1: 20 to 1:1.

The present invention employs an "effective amount" of the bis-AQA surfartAnt.~ to improve the pc.ro~ alue of cle~ning col.lpo~;~ions which contain other optional ingredients. By an "effective amount" of the bis-AQA surf~t~nt~ herein is meant an ~mollnt which is sufficient to improve, either directio~lly or si~ llirlc~llly at the 90%
confi~lenre level, the ~.rolllla~ce of the cle~ning composition against at least some of the target soils and stains. Thus, in a composition whose targets include certain food stains, the formulator will use sufficient bis-AQA to at least directionally irnprove cle~nin~
~lr~/llllance against such stains. Likewise, in a colllposilion whose targets include clay soil, the fonn~ tor will use s~fflieient bis-AQA to at least directionally improve cle~nir~
.rl,lll~ce against such soil.

The bis-AQA s~ may be used in colllbi~dlion with other detersive surf. ~t~ntc- at levels which are erf~,~,live for achieving at least a directional improvement in cleaning ~.Ç.llllallce. In the context of a fabric laundry composition, such "usage levels" can vary ~pen-ling not only on the type and severity of the soils and stains, but also on the wash water t~.ll~dl~lre, the volurne of wash water and the type of washing ,ll~rki"r.
For example, in a top-loading, vertical axis U.S.-type automatic washing m t-hin~ using 45 to 83 liters of water in the wash bath, a wash cycle of 10 to 14 minll~çs and a wash water lC~ ~.d~ of 10~C to 50~C, it is pfer.,.l~d to include from 2 ppm to 50 ppm, preferably from 5 ppm to 25 ppm, of the bis-AQA surfactant in the wash liquor. On the basis of usage rates of from 50 ml to 150 ml per wash load, this tr~nc~tçs into an in-pr~lu._l co~ c llrdlion (wt.) of the bis-AQA sulra.;~l.L of from 0.1% to 3.2%, preferably 0.3% to 1.5%, for a heavy-duty liquid laundry det.,.~el~t. On the basis of usage rates of from 60 g to 95 g per wash load, for dense (ncompact") granular laundry de~lge.lts (density above 650 g/l) this trAncl~t~çs into an in-product concentration (wt.) of the bis-AQA surfactant of from 0.2% to 5.0%, preferably from 0.5% to 2.5%. On the basis of usage rates of from 80 g to 100 g per load for spray-dried granules (i.e., "fluffy"; density below 650 g/l), this .. . . . .

WO 97/43394 PCT/US97tO8445 translates into an in-product concentration (wt.) of the bis-AQA surfactant of from 0.1 % to 3.5 %, preferably from 0.3 % to 1.5 % .

For example, in a front-loading, horizontal-axis European-type automatic washing mq-rhinlo 5 using 8 to 15 liters of water in the wash bath, a wash cycle of 10 to 60 ...i.~ ,s and a wash water Lel,l~.dl~re of 30~C to 95~C, it is p~ d to include from 13 ppm to 900 ppm, preferably from 16 ppm to 390 ppm, of the bis-AQA surfactant in the wash liquor. On the basis of usage rates of from 45 ml to 270 ml per wash load, this trqn~lqtrs into an in-product collcenllation (wt.) of the bis-AQA surfactant of from 0.4% to 2.64%, 10 preferably 0.55% to 1.1%, for a heavy-duty liquid laundry dele.~ L. On the basis of usage rates of from 40 g to 210 g per wash load, for dense (ncompact") granular laundry dete.gen~ (density above 650 g/l) this trqnClqtes into an in-product collcentldlion (wt.) of the bis-AQA s-llracta,l~ of from 0.5 % to 3.5 %, preferably from 0.7 % to 1.5 %. On the basis of usage rates of from 140 g to 400 g per load for spray-dried granules (i.e., "fluffyn;
15 density below 650 g/l), this trqnCl~-e~ into an in-plo l-lcl concelltlàlion (wt.) of the bis-AQA surfactant of from 0.13% to 1.8%, preferably from 0.18% to 0.76%.

For example, in a top-loading, vertical-axis Japa~-~se type ~ ..AI;c washing ...~h;..r using 26 to 52 liters of water in the wash bath, a wash cycle of 8 to 15 ...;.~ s and a wash 20 water te,ll~.dl-lre of 5~C to 25~C, it is plef~ d to include from 1.67 ppm to 66.67 ppm, preferably from 3 ppm to 6 ppm, of the bis-AQA surfactant in the wash liquor. On the basis of usage rates of from 20 ml to 30 ml per wash load, this tranclqtes into an in-product conc~.lL.dlion (wt.) of the bis-AQA surfactant of from 0.25% to 10%, preferably 1.5% to

2%, for a heavy-duty liquid laundry dct.~ . On the basis of usage rates of from 18 g to 35 g per wash load, for dense (nco.. ,~ cln) granular laul~dry dc;ler~e~t~ (density above 650 g/l) this translates into an in-product CO~ dtiOll (wt.) of the bis-AQA surfactant of from 0.25% to 10%, preferably from 0.5% tol.0%. On the basis of usage rates of from 30 g to 40 g per load for spray-dried granules (i.e., "fluffy"; density below 650 g/l), this tr~nCl?tes into an in-product col~cenLIdlion (wt.) of the bis-AQA surfactant of from 0.25% tolO%, 30 preferably from 0.5% to 1%.

As can be seen from the for~goillg, the amount of bis-AQA surfactant used in a m~rhin~-wash laundering context can vary, depending on the habits and practices of the user, the type of washing m~cllin~. In this context, however, one heretofore unappreciated35 advantage of the bis-AQA surfact~ntc is their ability to provide at least directional CA 022SSoOS 1998-11-17 improvements in l)c~ro~ dl ce over a sl,e,~ of soils and stains even when used at relatively low levels with respect to the other surf~rt~ntc (generally anionics or anionic/nonionic mixtures) in the finich.o-l compositions. This is to be distinguished from other compositions of the art wherein various cationic surf~rt~n-c are used with anionic S surfact~ntc at or near stoichion~el,ic levels. In general, in the practice of this invention, the weight ra~io of bis-AQA:anionic surfactant in laundry compositions is in the range from 1:70 to 1:2, preferably from 1:40 to 1:6, preferably from 1:30 to 1:6, most preferably 1:15 to 1:8. In laundry co,,,yosilions which con,~ise both anionic and nonionic surfact~ntc, the weight ratio of bis-AQA:mixed anionic/nonionic is in the range from 1:80 to 1:2, ~., f~.dbly 1:50 to 1:8.

Various other cle~ning coml~osilions which colll~lise an anionic aulra~ , an optional nonionic surfactant and specialized aul~-gc~nlc such as betaines, svlt~inlos, amine oxides can also be form~ t~d using an effective ~mmmt of the bis-AQA surf:~t~ntc in the l.lalllKr of 15 this invention. Such co,.,l~osil;on~ include, but are not limited to, hand dishwashing products (especi~lly liquids or gels), hard surface cleaners, shampoos, pe,~ol~al cle~ncing bars, laundry bars, and the like. Since the habits and practices of the users of such ColllpOsiliG~I5 show ~ /~ialiOn, it is satisfactory to include &om about 0.25% to about 5%, preferably &rom about 0.45% to about 2%, by weight, of the bis-AQA
20 surf ~t~nts in such co,~oailions. Again, as in the case of the granular and liquid laundry composition., the weight ratio of the bis-AQA surfactant to other surfi ~t~ntc presen~ in such composilions is low, i.e., sub-sloichiolll ~ic in the case of anionics. Preferably, such cle~nin~ compositions co,J~ise bis-AQA/surfactant ratios as noted immP~ trly above for in~ use laundry co,,,posilion~.
In co,l~,~l with other c~ nir surf~t~ntc known in the art, the bis-aLkoxylated cationics herein have S-~rr.ri~ solubility that they can be used in combination with mixed surfactant S~at~ s which are quite low in no"io~ic surf~t~nts and which contain, for example, alkyl sulfate ~ul G.( ~n~. This can be an il..~ ~ll consideration for formulators of de~erge, 30 c~,l"~osilions of the type which are conve.llionally ~esign~i for use in top loading o~ ;r washing ~ rl~ 5, especi~lly of the type used in North America, as well as under Jap~n~e usag col~dilions. Typically, such compositions will comprise an anionic au.r~ nonionic surfactant weight ratio in the range from about 25:1 to about 1:25, preferably about 20:1 to about 3:1. This can be contrasted with E~o~an-type formulas which typically will comprise anionic:nonionic ratios in the range of about 10:1 to 1:10, preferably about 5:1 to about 1:1.

The preferred ethoxylated cationic surf~rt~ntc herein are available under the trade name S ETHOQUAD from Akzo Nobel Ch~mi~qlc Company. Alternatively, such materials can be 5y~ f s-~d using a variety of dirr~fc.~ ,aclion sch~-.-rs (wl~c~ l "EO" r~ escn~-CH2CH2O- units), as follows.

RIOH + N H3 H2/Cat/Heat ,Rl N ~H
EXC ES S

Rl N~ + 2 n~ BASECat, Rl N--[(EO)nH~2 Rl N--[(EO)nH]2 + CH3CI ~Rl Nl--[(EO)nHk CH3 cr 'N--[(EO)2Hk + C H2/Cat, ~N--[(EOkH]2 RlBr + N--[(EO)2H~2 HEAT, Rl Nl--[(EO)2H]2 CH3 Br [( 2 ]2 H' 'H HÉAT

R~Br ~N--[(EO)2Hl2 HEAT ~ R--I--[(EO)2Hk CH3 Br Cl--CH2CH2--OH + n~ ~ Cl--CH2CH20[EO~n--~

R--N~cH + 2 Cl--CH2CH20[EO]n--H ~ Rl l-[CH2CH20[EO]nH]2 An economical reaction scheme is as follows.

Rl OSO3~Na+ + H-N--[(EO)H]2 HEAT ~ Rl N--[(EO)H~2 R--N--[(EO)H]2 + 2 n~ BAHEACTAT~ Rl N--[(EO)(EO)~

Rl N--[(EO)(EO)nH32 + CH3CI ~ Rl I--[(EO)(EO)r~k CH3 Cl The following p~ll~,t~ .. s. ize the optional and plefelled reaction conditions of ~ Scll~m~ 5. Step 1 of the reaction is preferably conAl~ct~ in an ;~ Ollc mPAil~m. Reaction . ~ . ... . . . .

t~l'peldlures are typically in the range of 140-200~C. Reaction ple3sules are 50-1000 psig.
A base catalyst, preferably sodium hydroxide can be used. The mole ratio of l~c~ r~ are 2:1 to 1:1 amine to alkyl sulfate. The reaction is preferably con~ cted using Cg-C14 all~yl sulfate, sodium salt. The ethoxylation and qudt~ dtion steps are carried out using 5 conventional con~litiQnc and re?,ct~ntc.

Under some cil.-.. ~l;~nres reaction SchPmP 5 results in products which are sllfficipntly soluble in the a~l~Po--c reaction mPf~ m that gels may form. While the desired product can be recovered from the gel, an alternate, two-step synthesis .SchPmP 6, hereinafter, may be 10 more desirable in some collull~.~;ial ch~ res. The first step in SchPmP 6 is con~ ctPd as in .SchPmP 5. The second step (ethoxylation) is preferably con~lllrted using ethylene oxide and an acid such as HCI which provides the quat~ surfactant. As shown below, chlorohydrin i.e., chloroell~ol, can also be reacted to give the desired bishydroxyethyl derivative.
For reaction .SchPrnP 6, the following palalllct .s s~n....~.~e the optional and pn.fe,l.,d reaction conditions for the first step. The first step is plef, ,dbly con~ ctPd in an aqueous ...P~ .. Reaction t~"ll~,atures are typically in the range of 10~230~C. Reactionp~,S~ S are 50-1000 psig. A base, preferably sodium hydroxide, can be used to react 20 with the HSO4-ge,~,ated during the reaction, or an excess of the amine can be employed to also react with the acid. The mole ratio of arnine to aLkyl sulfate is typically from 10:1 to 1:1.5; preferably from 5:1 to 1:1.1; more preferably from 2:1 to 1:1. In the product l'eco~ r step, the desired s~b~ nled amine is simply allowed to se~)alate as a distinct phase from the ~ qneo~ls reaction mPdillm in which it is insoluble. The second step of the 25 p~cess is co~ cr~ cl under conv..llional reaclion conditions. Further ethoxylation and uuàte~l~;7~ir~n to provide bis-AQA surf. ~t~n~c are con~ cted under standard reaction con~ ;on~

.~rhPmP 7 can optionally be co~ cled using ethylene oxide under standard ethoxylation 30 conditions, but ~ill.uul catalyst, to achieve monoethoxylation.

The following illustrates these additional reaction schPmPs~ wherein "EO" le~ ,sc.l~ the -CH2CH2O- unit. In the reactions, either an inorganic base, an organic base or excess amine l~ac~ul is used to neutralize generated HSO4.

. . . . . . . . ..... . .

Scheme 6 Rl OSO3Na+ + H,N--CH2CH2-OH ~ Rl N--CH2CH2-OH

I ,CH2CH20H
R--NCH2CH20H + ClCH2CH20H ' RN~

Srl-P.nP 7 B ,CH2CH2OH
R N--CH2CH2OH NoCatalyst 'EOnH

The following further illustrates several of the above reactions solely for the conveniP~ e of the fonmllq~or, but is not intPrl-lPd to be 1;...;~ thereof.

Svnthesis A
~?ar~tion of N.N-Bis(2-hydroxyethYl)dodecylamine To a glass autoclave liner is added 19.96 g of sodium dodecyl sulfate (0.06921 moles), 14.55 g of ~ .olan~ine (0.1384 moles), 7.6 g of 50 wt. % sodiwn hydroxide solution (0.095 moles) and 72 g of r1ictill~pd H20. The glass liner is sealed into a 500 ml, stainless steel, rocking autoclave and heated to 160-180~C under 300400 psig nitrogen for 34 15 hours. The llli~Ule iS cooled to room ~ alul~, and the liquid contents of the glass liner are poured into a 250 ml sel)al,.to.y funnel along with 80 ml of chloroform. The funnel is shaken well for a few minutes and then the ~ ule is allowed to sepa,ate. The lower chloluful,.l layer is drained and the chloroform e~a~o.~led off to obtain product.

20 Sy~ esis B
. "al~lioll of N.N-Bis(2-h~loA~ l)dodecylamine 1 Mole of sodium dodecyl sulfate is reacted with 1 mole of ethanolamine in the pl~se.lce of base in the ..~cr described in Synthesis A. The resllltin~ 2-hydroxyethyldodecylamine is 25 r~co~el~d and reacted with l-chloroethanol to pl,~,are the title co..ll,uund.
Synthesis C
ralion of N~N-Bis(2-hydroxyethYl)dodecvlamine To a glass autoclave liner is added 19.96 g of sodium dodecyl sulfate (0.06921 moles), 21.37g of ethanolamine (0.3460 moles), 7.6 g of 50 wt. ~ sodium hydroxide solution (0.095 moles) and 72 g of tli.~tillP~ H20. The glass liner is sealed into a 500 mL st~inl~ss steel, rocking autoclave and heated to 160-180~C under 300400 psig nitrogen for 3~
hours. The ll~clul~ is cooled to room le.~ alul~ and the liquid colltenls of the glass liner are poured into a 250 ml separatory funnel along with 80 ml of chloroform. The funnel is shaken well for a few ~ Jt~s and then allowed llliAIul~ to scp~dLe. The lower chloroform layer is drained and the chlorofollll is eva~o~àl~d off to obtain product. The product is 10 then reacted with 1 molar equivalent of ethylene oxide in the absence of base catalyst at 120-130~C to produce the desired final product.

The bis-su~liluled amines pl~l,arcd in the Çol~oulg Syntheses can be further ethoxylated in standard fashion. Quaternization with an alkyl halide to form the bis-AQA surfactants 15 herein is routine.

According to the fol~go.l.~, the following are non~imi~in~, specific illustrations of bis-AQA
surf~rt~nts used herem. It is to be lmdc.~lood that the degree of aLkoxylation noted herein for the bis-AQA surf~ct~ntc is le~,led as an average, following co~ on practice for 20 conventional ethoxylated nulliOlliC Slll rh~ . TlliS iS because the ethoxylation rcaC~ionS
typically yield llfi~lul~s of materials with differing degrees of ethoxylation. Thus, it is not unCO-n~un to report total EO values other d~an as whole Illllllbc~ e.g., "E02.5~, "EO3.5 n .

De~ ................ Rl R2 ApR3 A~qR4 bis-AQA-1 C12-C14 CH3 EO EO
(also ~,f.,,.~ to as Coco Methyl EO2) bis-AQA-2 C12-C16 CH3 ~EO~2 EO
bis-AQA-3 C12-C14 CH3 ~EO~2 ~EO~2 (Coco Methyl EO4) bis-AQA4 C12 CH3 EO EO

bis-AQA-5 C12-C14 CH3 ~EO~2 (EO)3 , ~

CA 022~00~ 1998-11-17 bis-AQA-6 C12-C14 CH3 ~EO~2 (EO)3 bis-AQA-7 C8-C 18 CH3 (EO)3 (EO)2 s bis-AQA-8 C12-C14 CH3 (EO)4 (EO)4 bis-AQA-9 C12-C14 C2H5 (EO)3 (EO)3 bis-AQA-10 C12-C18 C3H7 (EO)3 (EO)4 bis-AQA-ll C12-C18 CH3 (propoxy) (EO)3 bis-AQA-12 Clo~C18 C2H5 (iso-~l~ol)o~-~)2 (EO)3 bis-AQA-13 Clo~C18 CH3 (EO/po~2 (EO)3 bis-AQA-14 Cg-Clg CH3 (E~)15* (EO)l5*
bis-AQA-15 Clo CH3 EO EO
bis-AQA-16 Cg-C12 CH3 EO EO

bis-AQA-17 Cg-Cl l CH3 ~ EO 3.5 Avg. -bis-AQA-18 Cl2 CH3 - EO 3.5 Avg. -bis-AQA-l9 Cg- C14 CH3 ~E~~10 (EO)10 bis-AQA-20 Clo C2H5 ~EO~2 (EO)3 bis-AQA-21 C12-C14 C2H5 (EO)5 (EO)3 bis-AQA-22 C12~C18 C3H7 Bu (EO)2 CA 02255005 l998-ll-l7 WO 97/43394 rCT/US97/08445 *Ethoxy, optionally end-capped with methyl or ethyl.

Highly plefell~d bis-AQA compounds for use herein are of the formula;

Rl /CH2CH2OH
N ~ X~

wherein Rl is Cg-Clg hydrocarbyl and mi~Llul s thereof, preferably Cg, Clo, C12, C14 aLkyl and lllLl~lules thereof. X is any convenient anion to provide charge balance, preferably chloride. With lefe..,nce to the general bis-AQA s~luclule noted above, since in 10 a ~-. fe.led compound Rl is derived from coconut (C12-C14 alkyl) fraction fatty acids, R2 is methyl and ApR3 and A'qR4 are each monoethoxy, this pl~fc~led type of co,ll~u~d is ref.,...,d to herein as "CocoMeEO2" or "bis-AQA-l" in the above list.

Other bis-AQA ~UI fi.~ useful herein include coml~oullds of the formula:

R~ +~(CH2CH2O)pH

R2/ \(CH2CH20)qH

whc~h~ Rl is Cg-Clg hy~oca.b~l, preferably Cg-C14 al}cyl, independently p is 1 to 3 and q is 1 to 3, R2 is Cl-C3 aLtcyl, p~,f, ,ably methyl, and X is an anion, especi~lly chloride or 20 blollude.

Other co..~ s of the folcgolng type include those ~he,e~ the ethoxy (CH2CH20) units (EO) are replaced by butoxy (Bu) isopropoxy [CH(CH3)CH20] and [CH2CH(CH30] units(i-Pr) or n-propoxy units (Pr), or I~ ules of EO andlor Pr and/or i-Pr units.
A highly piefe.l~d bis-AQA col~l~wld for use in under built formulations are of the formula wherein p andlor q are integers in the range of bel~.~,.,n 10 and 15. This compound is particularly useful in laundry handwash de~lgelll compositions.

30 Non-AOA Detersive Sul ri.. ,;.."~

CA 02255005 l998-ll-l7 In addition to the bis-AQA surfactant, the compositions of the present invention preferably further comprise a non-AQA surfactant. Non-AQA surf~rt-q-nts may include essentially any anionic, nonionic or additional cationic surfactant.
s Anionic Su.r~ctant Nonlimiti~ exarnples of anionic ~.ulr;~ , useful herein typically at levels from 1% to 55%, by weight, include the conventional C11-C1g alkyl benzene sulronahs ("LAS") and 10 plilll~y ("AS"), branched-chain and random Clo-C20 alkyl sl~lfq-tes, the Clo-C1g secondary (2,3) alkyl sulfates of the formula CH3(CH2)X(CHOSO3-M+) CH3 and CH3 (CH2)y(CHOSO3~M+) CH2CH3 where x and (y + 1) are illhge. . of at least 7, plefel~ly at least 9, and M is a water-solubilizing cation, especiqlly so~ m, u~.alulated s-llfqtPs such as oleyl sulfate, the C12-C1g alpha-sulfonated fatty acid esters, the C1o-C18 slllf~
15 polyglycosides, the Clo-C1g alkyl alkoxy s~llfq-t~s (nAEXSn; especiqlly EO 1-7 ethoxy sl~lfqtes), and the Clo-C18 aL~cyl aLkoxy carboxylates (especiqlly the EO 1-5 ethoxycarboxylates). The C12-Clg betaines and sulfobet-q-in~s ("s~lt~in~s"), Clo-C~8 amine oxides, can also be inrll~ded in the overall compositions. Clo-C20 conventional soaps may also be used. If high su~lsin~ is desired, the branched-chain Clo-C16 soaps may 20 be used. Other conventional useful ~.ul r;~ are listed in standard texts.

Nonionic Surfartq.~ltc Nonlimitin~ examples of nonionic surf-q-ct~ntc useful herein typically at levels from 1% to 25 55%, by weight include the alkoxylated alcohols (AE's) and alkyl phenols, polyhydroxy fatty acid amides (PFAA's), aL~cyl polyglycosides (APG's), C1o-C1g glycerol ethers.

More "~ jfi~lly, the con~l~n~qtiQn products of primary and secondary ~lirh~tir alcohols with from 1 to 25 moles of ethylene oxide (AE) are suitable for use as the llOlllOnlC
30 surfactant in the present hl~elllio.l. The aL~cyl chain of the alirh-q-tir alcohol can either be straight or b~ rh~d, primary or secondary, and generally contains &om 8 to 22 carbon atoms. P~l,fel.~,d are the conrl~ncation products of alcohols having an alkyl group cont-q-ini~ from 8 to 20 carbon atoms, more preferably &om 10 tol8 carbon atoms, with &om 1 tolO moles, preferably 2 to 7, most preferably 2 to 5, of ethylene oxide per mole of 35 alcohol. Examples of co-n-ll.,.;ially available nonionic surfact-q-ntc of this type include:

CA 02255005 1998-ll-17 TergitolTM 15-S-9 (the con~encqtion product of Cll-Cls linear alcohol with 9 moles ethylene oxide) and TergitolTM 24-L-6 NMW (the con-l~nC~ion product of C12-C14 prirnary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; NeodolTM 45-9 (the condensation product of C14-C1s linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-3 (the conrl~ncqtion product of C12-C13 linear alcohol with 3 moles of ethylene oxide),NeodolTM 45-7 (the co~ ;on product of C14-Cls linear alcohol with 7 moles of ethylene oxide) and NeodolTM 45-5 (the co~ t~;on product of C14-C1s linear alcohol with 5 moles of ethylene oxide) 1~l eled by Shell ChPmicq-l Compqny; KyroTM EOB (the 10 con~lencq-tion product of C13-C1s alcohol with 9 moles ethylene oxide), In~l~eled by The Procter & Gamble Colnl)any; and Genapol LA 030 or 050 (the con-lencqtion product of C12-C14 alcohol with 3 or 5 moles of ethylene oxide) marketed by Hoechst. The ~ref~ ~cd range of HLB in these AE nonionic sulra~;lants is from 8-11 and most preferred from 8-10.
Con-l~nc-q-t~s with propylene oxide and butylene oxides rnay also be used.
Another class of p,efe.l~d nol~ionic ~ulr~ t~ for use herein are the polyhydroxy fatty acid amide surfactants of the formula.

R2--C~ Z
O R

wherein R1 is H, or C14 I.~dloc~byl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is Cs 31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear l~ydlocdlt"rl chain with at least 3 hydroxyls directly co....~clr~l to the chain, or an aLkoxylated derivative thereof. Preferably, Rl is methyl, R2 is a straight C11 1s alkyl or 25 Cls 17 alkyl or aL~enyl chain such as coconut aL~cyl or nuxtures thereof, and ~ is derived from a re~ c;-~g sugar such as gll~cose, fructose, mqltose, lactose, in a reductive qminqtion reaction. Typical examples include the C12-Clg and C12-C14 N-methylglllcqmidec. See U.S. 5,194,639 and 5,298,636. N-aL~coxy polyhydroxy fatty acid amides can also be used;
see U.S. 5,489,393.
Also useful as the nonionic ~ulr~c~nt in the present invention are the alkylpolysaccharides such as those disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group contqining from 6 to 30 carbon atoms, preferably from 10 to 16 carbon atoms, and a poly~accha~ide, e.g. a polyglycoside, hydrophilic group contqining , .. . .. . .. .

from 1.3 to 10, preferably from 1.3 to 3, most preferably &om 1.3 to 2.7 saccharide units.
Any reducing saccharide cont~inin~ 5 or 6 carbon atoms can be used, e.g., glucose, galactose and g~lqrtosyl moieties can be substituted for the glucosyl moieties (optionally the hydrophobic group is artqrhPd at the 2-, 3-, 4-, etc. positions thus giving a glucose or 5 galactose as opposed to a glucoside or galactoside). The intersaccharide bonds can be, e.g., bc~ eell the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6-positions on the prece~ g saccharide units.

The l,refellcd aL~cylpolyglycosides have the formula:
R20(CnH2nO)t(glycosyl)x wherein R2 is selected from the group con~;cl;ng of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalk~l~h~nyl, and lllib~ les thereof in which the alkyl groups contain from 10 to 18, plcr lably from 12 to 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to 10, preferably 0; and x is from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7. The glycosyl is preferably derived from glucose. To pr~,~are these col~o~lnds, th alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (att~ at the l-position). The a~ itionql 20 glycosyl units can then be qtt~ Pd between their 1-position and the prece~line glycosyl units 2-, 3-, 4- and/or 6-position, preferably pre~ominqtely the 2-position.

Polyethylene, polypropylene, . nd polybutylene oxide con~ C~t~s of alkyl phenols are also suitable for use as the ~ ;onir, surfactant of the surfactant systems of the present invention, 25 with the polyethylene oxide con~ C~t~s being pl~fe.led. These compounds include the co~ nc~irJn products of alkyl phenols having an alkyl group contqining from 6 to 14 carbon atoms, pl~,f~"ably from 8 to 14 carbon atoms, in either a straight-chain or bl~ched~hain configuration with the aIkylene oxide. In a pref~.l.,d embo~limPnt, the ethylene oxide is present in an Z~ O~ t equal to from 2 to 25 moles, more preferably from 3 30 tol5 moles, of ethylene oxide per mole of alkyl phenol. Co.lllllel~eially available nonionic surf~t~ntc of this type include IgepalTM CO-630, ll~rl~eted by the GAF Corporation; and TritonTM X~5, X-114, X-100 and X-102, all marketed by the ~ohm & Haas Company.
These surfactants are conllllonly referred to as alkylphenol aL~coxylates (e.g., alkyl phenol ethoxylates).

W O 97/43394 P~r~US97/08445 The con~ncation products of ethy}ene oxide with a hydrophobic base formed by thecondensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant in the present invention. The hydrophobic portion of these compounds will preferably have a molecular weight of from 1500 to 1800 and will exhibit 5 water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid chal~cL~r of the product is retained up to the point where the polyoxyethylene content is 50% of the total weight of the co.~ ca~ion product, which cG...,sponds to co~ nC~Iion with up to 40 moles of ethylene oxide. Examples of compounds of this type include certain of the 0 co~ frcially-available PluronicTM surf~ctantc, marketed by BASF.

Also suitable for use as the nonionic surfactant of the nonionic ~.nr~ system of the present invention, are the con~nC~tion products of ethylene oxide with the product resultin from the reaction of propylene oxide and ethylen~~ ;ne. The hydrophobic15 moiety of these products cor~ of the reaction product of ethylen~li~ r and excess propylene oxide, and generally has a molecular weight of from 2500 to 3000. Thishydrophobic moiety is co~ nced with ethylene oxide to the extent that the co~-del.r-l;ol-product contains from 40% to 80% by weight of polyoxyethylene and has a molecular weight of from 5,000 to 11,000. Examples of this type of nonionic ~u~ ra~ include 20 certain of the con~,crcially available TetronicTM compounds, marketed by BASF.

Additional Cationic surfactants Suitable cationic surf~ ntc are preferably water dis~l~il,lc compound having ~u~raclant 25 plo~,lies CGIl~ iSil~g at kast one ester (ie -COO-) linkage and at least one cationically ch~gc~ group.

Other suh~J- c~tinnir surf~ct~ntc include the quate,~y ~ onillm surf~t~ntc selected from mono C6-C16, preferably C6-Clo N-aL~yl or aL~cenyl al~ lOlliUIII surfaetantc whcle 30 the re~n~ining N positions are SU~G5~ ~ by methyl, hydroxyethyl or hydroxypropyl groups. Other suitable cationic ester ~ulr;~ I;tntc, inrhldjng choline ester surfarr~ntc~ have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.

Optional Dete.~el,l In~redients The following illustrates various other optional ingredients which may be used in the compositions of this invention, but is not intended to be limi~ing tnereof.

Additional Bleach The dete.gent comrositions herein rnay optionally comprise an additional ble~ching agent.
When present, such additional bleqching agents will typically be at levels of from 1% to 30%, more typically from 5% to 20%, of the dctelge.lt co.llposilion, especiqlly for fabric lq-l-n-l~ring.
The bk,~hin~ agents used herein can be any of the bl~hi.-g agents useful for det~,.~.ll compositions in textile cleqni~ hard surface cleaning, or other cle-q-ning purposes that are now known or becolllc known. These include oxygen bleaches as well as other ble~,chin~
agents. ~.l,uiate bleachcs, e.g., sodium pe.l,o~ c (e.g., mono- or tetra-hydrate) can be used herein.

AL~ali metal or aL~ali earth metal pe.~arl,ondtcs, particularly sodium ~lc~lJollate are pl~.fi ~led percarl,o.~tes for inclusion in compositions in accordalKe with the invention.
Sodium ~rcall~nate is an addition compound having a formula coll. s~nding to 2Na2C03.3H202, and is available collllll~.~;ially as a crystalline solid. Colllllle.cial suppliers include Solvay, PMC, Tokai Denka and others.

A pler~lcd ~ l~t~, bleach co.ll~lises dry particles having an average particle size in the range from 0.5 mm to 1 mm, not more than lO~ by weight of said particles being smaller than 0.2 mm and not more than 10% by weight of said particles being larger than 1.250 mm.

The ~.~l,ollat~ is most plef. .ably incorporated into such compositions in a coated form which provides in-produ~l stability.
A suitable coating material providing in product stability C~ liScS mixed salt of a water soluble alkali metal slllphqt~ and carbonate. Such coatings together with coating processes have previously been desc,ibed in GB-1,466,799, granted to Interox on 9th March 1977.
The weight ratio of the mixed salt coating material to ~I~ ~nate lies in the range from 1 : 200 to 1: 4, more preferably from 1: 99 to 1: 9, and most preferably from 1: 49 to 1:
19. Preferably, the mixed salt is of sodium sulphate and sodium carbonate which has tne , .... . . . .

general formula Na2SO4.n.Na2CO3 wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.

Other coatings which contain silicate (alone or with borate salts or boric acids or other 5 h1o~g~lics), waxes, oils, fatty soaps can also be used advantageously within the present invention Another categol y of ble~ching agent that can be used without l~,;,lriCliOn enco...p~ses ~icarl,oxylic acid ble~rhin~ agents and salts thereof. Suitable examples of this class of 10 agents include m~gnPsil-m Illon~loxyphthql-q-te hexahydrate, the mq~ sill~ll salt of meta-chloro pe.b~,nzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydo~ecqn~-lioic acid. Such ble~qching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued Nov~mber 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent Appli~qtion 0,133,354, Banks et al, published reb,udly 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued Nove~.ber 1, 1983. Highly plef~ ed blearl-in~ agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S.
Patent 4,634,551, issued January 6, 1987 to Burns et al.

Peroxygen bleac~ agents can also h,e used. Suitable peroxygen ble~ching coll.~unds 20 include sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
Perborate bleach, persulfate bleach (e.g., OXONE, m~nllf~t~tured co.lllllercially by DuPont) can also be used.

Mixtures of bleac~ agents can also be used.
Bleach Activators Bleach activators are ylcf~ ~lcd components of the composition where a peroxygen bleach is present. If present, the ~ n~ of bleach activators will typically be from 0.1 % to 60%, 30 more typically from 0.5% to 40% of the ble~.rhing composition collly~ g the bl~l~hi.~g agent-plus-bleach activator.

The combination of peroxygen blenclling agents and bleach activators results in the in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid 35 collc;,l,ol~ding to the bleach aclivdlor. Various nonlimiting examples of activators are . ,, .~.

disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934. The nonanoyloxyl~llzc"c sulfonate (NOBS) and tetraacetyl ethylene ~ min~
(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 plefe,-cd amido-derived bleach activators are those of the formulae:

R1N(R5)C(o)R2C(o)L or R1C(o)N(R5)R2C(o)L

10 wl~ Rl is an alkyl group corlt~ining from 6 tol2 carbon atoms, R2 is an alkylene co~ g from 1 to 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl cont~ining from 1 to 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 con~eqllenre of the nucleophilic attack on the bleach activator by the perhydrolysis anion. A prer.,.led leaving group is phenyl sulfonate.
~ef~ll.,d examples of bleach activators of the above formulae include (6-oc~ Q-caproyl)o~ylA ,~ f~ fonate, (6-n~ Qcaproyl)oxyb.n,- ~rs~lfonate, (6~ o-caproyl)oxyb~n~ a~lfonate, and n~lules thereof as described in U.S. Patent 4,634,551, incorporated herein by rer~ce.
Another class of bleach a~;livato.~ colll~lises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990, incorporated herein by r~,f~,~e.lce. A highly l"efelled activator of the benzoxazin-type is:

~N~C~

Still another class of pfefel.ed bleach activators includes the acyl lactam activators, especi~lly acyl caprolactarns and acyl valerolactams of the formulae:

R--C--N~

S ~hele.n R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group con~ining from 1 to 12 carbon atoms. Highly p.ef~ d lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5~ hyll~x~noyl caprolactam, nonanoyl caprolact~m, decanoyl caprolac~m, ..,--lece.~yl caprolact~m, benzoyl valerolactam, octanoyl valerolactarn, decanoyl valero!act~m, ~ Pcenoyl valerol;~ct~m"lol~loyl valerolactam, 3,5,5-hil~ Lhylh ~noyl valerolactamand Il~ r~s thereof. Seealso U.S. Patent4,545,784, issued to Sanderson, October 8, 1985, incorporated herein by ~,f; ,e~ce, which discloses acyl caprolactams, including benzoyl caprol~rt~m, adsorbed into sodium perborate.

Bleach Catalyst Bleach catalysts are ~lefe.led components of colllposilions of the present invention that, in addition to the photobleach, comprise an oxygen rel~c;--~ bleaching agent. Bleach catalysts are well known in the art and include, for example, the m~ se-based catalysts lose~l 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 Eulo~ Pat. App. Pub. Nos. 549,271Al, 549,272Al, 544,440A2, and 544,490A1; ~,fe~.ed ~les of these catalysts include MnIV2(u-O)3(1,4,7~ hyl-1 ,4,7-L,i~acyclo~onane)2(PF6)2, Mnm2(u-O)l(u-OAc)2(1,4,7-~ thyl-1 ,4,7-triazacyclo-nonane)2 (C104)2, MnIV4(u-0)6(1,4,7-tri~7~cyclononane)4(CI04)4, MnmMnIV4(u-O)l(u-OAc)2 (1,4,7-~ le~llyl-1,4,7-triazacyclonollane)2(Cl04)3, MnIV(1,4,7-L~.,IIeLhyl-1,4,7-triazacyclol.o.~ )- (OCH3)3(PF6), and mixtures thereof. Othermetal-basedbleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611. The use of .~n~ se with various complex ligands to enhance ble~rl ing 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 co~ )osilions 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 ~qtleOl~ washing liquor, and will preferably provide from 0.1 ppm to 700 ppm, more preferably from 1 ppm to 500 ppm, of the catalyst species in the laundry liquor.

Cobalt bleach catalysts useful herein are known, and are desc.ibed, for example, in M. L.
Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inor~. Bioinor~. Mech., 10 (1983), 2, pages 1-94. The most plef~ d cobalt catalyst useful herein are cobalt pent~qmin~ acetate salts having the formula [Co(NH3)sOAc] Ty~ wL~ "OAc~
es~ an acetate moiety and "Tyl' is an anion, and especi~lly cobalt pent~ acetatechloride, [Co(NH3)sOAc]C12; as well as [Co(NH3)sOAc](OAc)2;
[C~(NH3)5OAc](pF6)2; [Co(NH3)sOAC](sO4); [Co(NH3)sOAc](BF4)2; and 15 [Co(NH3)sOAc](NO3)2 (herein "PAC~).

These cobalt catalysts are readily plcpar~,d by known p,ocedules, such as taught for example in the Tobe article and the rcfefe,~ces cited therein, in U.S. Patent 4,810,410, to Diakun et al, issued March 7,1989, J. Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis 20 and Chdldc~1izdlion of IllOlganiC Compounds, W.L. Jolly (Prentice-Hall; 1970), pp. 461-

3; Inor,e. Chem., 18, 1497-1502 (1979); Inor~. Chem., 21, 2881-2885 (1982); Inor~.
Chem.. 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Physical Ch.,ulisllY, 56, 22-25 (1952).

25 As a pld.;lical matter, and not by way of limit~tion, the automatic dishwashing col,.~osilions and cle~ P plocesses herein can be adjusted to provide on the order of at least one part per hundred million of the active bleach catalyst species in the aqueous washing ...Pd; ~.., and will preferably provide from 0.01 ppm to 25 ppm, more preferably from 0.05 ppm to 10 ppm, and most preferably from 0.1 ppm to 5 ppm, of the bleach 30 catalyst species in the wash liquor. In order to obtain such levels in the wash liquor of an auluu~dtic dishwashing process, typical d~llUllldliC dishwashing compositions herein will col~ ise from 0.0005% to 0.2%, more preferably from 0.004% to 0.08%, of bleach catalyst, especi~lly ~ AI~se or cobalt catalysts, by weight of the cleaning compositions.

35 Builders

4 PCT/US97/08445 Detelge"l builders can optionally but preferably be included in the compositions herein, for example ~o assist in controlling mineral, especially Ca and/or Mg, hardness in wash water or to assist in the removal of particulate soils from surfaces. Builders can operate via a

5 variety of mPrhqni~mc inr!l-~iing forming soluble or insoluble complexes with hardness ions, by ion el~ch~n~e, and by ol~.hlg a surface more favorable to the precipitation of ha~ ess ions than are the surfaces of articles to be cleaned. Builder level can vary widely d~ending upon end use and physical form of the CG~ oSilion. Built det. Ige.,~. typically Co~ iSC at least 1% builder. Liquid forrm~l~tirJns typically comprise 5% to 50%, more 10 typically 5% to 35% of builder. Granular formulations typically colll~lise from 10% to 80%, more typically 15% to 50% builder by we}ght of the del~lge.ll composition. Lower or higher levels of builders are not PYrluderl. For example, certain detelgelll additive or high-surfactant form~ tions can be llnbuilt.

15 Suitable builders herein can be sekc~ d from the group co~cictin~ of ~ho~hates and polypho~h~l~s, esppc~ y the sodium salts; silir~t~Ps inrlu~i~ water-soluble and hydrous solid types and in~ ling those having chain-, layer-, or three~impncion~l- structure as well as ~llol~/hous-solid or non-stluctured-liquid types; call,o,~tes, bic~l,o,lates, s~s~ ira~ l,onates and c~l~llalt: minerals other than sodium calbOI~ or ses~ .l,o,~le;
20 ~ silir~tPs; organic mono-, di-, tri-, and tetracarboxylates especially water-soluble no~ulrac~ll carboxylates in acid, sodium, pot~csillrn or aL~canolammonium salt form, as well as oligonlc,lic or water-soluble low molecular weight polymer carboxylates inrluAi aliphatic and aromatic types; and phytic acid. These may be compl~ Pd by borates, e.g., for pH-burf~"ing ~ull~oses, or by sl~lf~t~Ps, especially sodium sulfate and any other 25 fillers or carriers which may be h"~l~l to the engil-~ .,ng of stable surfactant and/or builder-co..~ g det~l~enl co.~ ilions.

Builder ~ S, s.-...- t;...Ps termed "builder systems" can be used and typically col..l..ise two or more conventional builders, optionally complem~tPd by chPI~ntc, pH-buffers or 30 fillers, though these latter materials are generally ~cco~ ed for sepalately when describing q~z~ s of materials herein. In terrns of relative qu~ntitips of surfactant and builder in the present d~ genLs, p~fe,l.,d builder systems are typically forTn~ ted at a weight ratio of surfactant to builder of from 60:1 to 1:80. Certain prcf.,l,ed laundry dc;Lerge"l~ have said ratio in the range 0.90:1.0 to 4.0:1.0, more preferably from 0.95:1.0 to 3.0:1Ø

P-cont~ining dete~ge~ll builders often preferred where permitted by legislation include, but are not limited to, the alkali metal, a~ oluum and alkanolammonium salts of polyphosphates exemplified by the tripolyphosphates, pyrophosphates, glassy polymeric meta-phosphates; and phosphonates.

Suitable silicate builders include alkali metal .cilirqtPs, particularly those liquids and solids having a SiO2:Na2O ratio in the range 1.6: 1 to 3.2: 1, inrlu.ling, particularly for automatic dish~ashil g purposes, solid hydrous 2-ratio silir-q-tPs ~lal~ted by PQ Corp. under the tra~k~ f BRITESIL~, e.g., BRITESIL H20; and layered silir-q-~es, e.g., those desclibcd in U.S. 4,664,839, May 12, 1987, H. P. Rieck. NaSKS-6, so.. ~t;.. ~s abbreviated "SKS-

6", is a crystalline layered qlltrninillm-free ~-Na2SiOs morphology silicate marketed by Hoechst and is preferred especiqlly in granular laundry compositions. See ple~a,dli~re m~th~s in German DE-A-3,417,649 and DE-A-3,742,043. Other layered silicates, such as those having the general formula NaMSixO2x+ 1 YH2O wherein M is sodium or l~y-lrogen, x is a ,.~llber 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. Layered silir~tPs from Hoechst also include NaSKS-5, NaSKS-7 and NaSKS-11, as the a, ~ and y layer-silicate forms. Other silicates may also be useful, such as l--a~ ... silicate, which can serve as a c.;~ g agent in granules, as a stabilising agent for bleaches, and as a component of suds control systems.

Also suitable for use herein are ~ c; -,d crystalline ion exchqnge materials or hydrates thereof having chain ~L~u~lur~, and a cou.~o,ilion ~ ese.lled by the following general formula in an anhydride form: xM20 ySiO2.zM'O wlle~ M is Na and/or K, M' is Ca and/or Mg; ylx is 0.5 to 2.0 and ztx is 0.005 to 1.0 as taught in U.S. 5,427,711, Sakaguchi et al, June 27, 1995.

Suitable calbo~L~ builders include ~ lin~ earth and aLkali metal c~ll,ol~tes as disclosed in German Patent Applir~tion No. 2,321,001 published on November 15, 1973, ~Itho~lgh sodium bica,l~l~a~e, sodium carbonate, sodium sesquicalbo~Le, and other carbonate minerals such as trona or any convenient multiple salts of sodium c~bG.~te and c~lcinm c~l,onate such as those having the co"ll)osition 2Na2C03.CaC03 when anhydrous, and even calcium c~l,onates inrl~l~ling calcite, aragonite and vaterite, especially forms having high surface areas relative to co--li)act calcite may be useful, for example as seeds or for use in synthetic dete.ge.lt bars.

Aluminosilicate builders are especially useful in granular detergents, but can also be incol~,uldted in liquids, pastes or gels. Suitable for the present purposes are those having empirical formula: [MZ(Alo2)z(sio2)v] xH2O wl.c.~in z and v are integers of at least 6, S 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.
~lmninosilicates can be crystalline or amorphous, naturally-ocwlli,~g or syn~h~tirqlly derived. An al~ osil~cate production m~thod is in U.S. 3,985,669, Krummel, et al, October 12, 1976. ~f~_.led ~ lh.lic crystalline all~..i..ns;li~ate ion exchq~e materials are available as Zeolite A, Zeolite P (B), Zeolite X and, to ~hat~,ve. extent this differs 10 from Zeolite P, the so-called Zeolite MAP. Natural types, inrll~lin~ clinoptilolite, may be used. Zeolite A has the formula: Na12[(AlO2)12(SiO2)12] xH2O wherein x is from 20 to 30, especiqlly 27. Dehydrated zeolites (x = O - 10) may also be used. Preferably, the q.~ nnsilirqte has a particle size of 0.1-10 lllicrolls in ~ trl .

15 Suitable organic d~,t_-~gent builders include polycarboxylate colll~ul~ds, in~ water-soluble l~o,~ulr~ctant dica,lo~ylates and tricarboxylates. More typically builder polycarboxylates have a plurality of carboxylate groups, preferably at least 3 carboxylates.
Carboxylate builders can be forrm~ e~ in acid, partially neutral, neutral or ovelbascd form. When in salt form, alkali metals, such as so~ m, ~!-~CS; ~ , and Ihhil~m, or 20 aL~canolanùllo~i~ll salts are plefi,.l~d. Polycarboxylate builders include the ether polycarboxylates, such as oxycli~-~cc;nz~e, see Berg, U.S. 3,128,287, April 7, 1964, and i 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 carboxylates including cyclic and alicyclic colll~uilds, such as those described in U.S. Patents 3,923,679; 3,835,163;
2S 4,158,635; 4,120,874 and 4,102,903.

Other suitable builders are the ether h~dl~ypolycarboxylates, copolymers of maleic anhydride with ~ ",e or vinyl methyl ether; 1, 3, S-kihydroxy 'Ge.~.le-2, 4, 6-trisulphonic acid; carboAy~ yloxysuccinic acid; the various alkali metal, allul~o~ m and ~.ub~.l;U~ .. O~ .. salts of polyacetic acids such as ethyl~-P~iiz~.. inf tetraacetic acid and nitriloLIiace~ic acid; as well as mellitic acid, succinic acid, polymaleic acid, ben~ene 1,3,5-~lic~ul,o~ylic acid, ca,boAy~ loxysuccinic acid, and soluble salts thereof.

Citrates, e.g., citric acid and soluble salts thereof are important carboxylate builders e.g., 35 for heavy duty liquid dc~lgell~., due to availability from renewable resources and biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicates. Oxydisuccinates are also especially useful in such compositions and combinations.

Where pe.l~ ed, and especially in the formulation of bars used for hand-laundering operations, alkali metal pho~l,hates such as sodium tripol~yhos~hat~s, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethane-l-hydroxy-1,1-dipho~l.honate 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 10 desirable anticcq1ing ~lo~lies.

Certain detersive surfartantc or their short-chain homologs also have a builder action. For u~ biguous formula ilCCO~ oses, when they have surfactant capability, these ,l~t~,.ials are ~ d up as detersive surfactants. I~efe,.ed types for builder functionality 15 are illustrated by: 3,3-dicarboxy4-oxa-1,6-h~YanPAio~tes and the related co~ lds disclosed in U.S. 4,566,984, Bush, January 28, 1986. Succinic acid builders include the Cs-C20 alkyl and alkenyl sl~ccini~ acids and salts thereof. Succinate builders also include:
laurylsuccinate, myristyl~.,cc;..~l~, palmitylsuccinate, 2~odecenylcllccin~t~ (pler.,lle~), 2-pent dec~nylsuccinate. Lauryl-succ~ . s are described in European Patent Application 86200690.5/0,200,263, published Nov~,,n~l 5, 1986. Fatty acids, e.g., C12-C1g monocalboxylic acids, can also be incorporated into the colnposi~ions as surfactant/builder materials alone or in combination with the afof~ oned builders, especially citrate and/or the s~lccinqtç builders, to provide additional builder activity. Other suitable polycarboxylates are ~icclosed in U.S. 4,144,226, Cmtchfiel~ et al, March 13, 1979 and in U.S. 3,308,067, Diehl, March7, 1967. See also Diehl, U.S. 3,723,322.

Other types of inolgao~c builder materials which can be used have the formula (MX)i Cay (CO3)z ~.h~ ,~ x and i are i~tegels from 1 to 15, y is an integer from 1 to 10, z is an integer from 2 to 25, Mi are cations, at least one of which is a water-soluble, and the 30 equation ~i = l 1s(xi multiplied by the valence of Mi) + 2y = 2z is 5qticfi~1 such that the formula has a neutral or '~bqlqnredll charge. These builders are referred to herein as "Mineral Builders". Waters of hydration or anions other than carbonate may be added provided that the overall charge is balqn~ed or neutral. The charge or valence effects of such anions should be added to the right side of the above equation. ~lably, there is 35 present a water-soluble cation selected from the group concicting of hydrogen, water-soluble metals, hydrogen, boron, ammonium, silicon, and mixtures thereof, more preferably, sodium, potassium, hydrogen, lithillm, ammonium and mixtures thereof, sodium and potassium being highly pl.,fell~d. Nonlimiting examples of noncarbonate anions include those selected from the group co~ g of chloride, sulfate, fluoride, 5 oxygen, hydroxide, silicon dioxide, chromate, nitrate, borate and uu~lul.,S thereof.
~,fell~ d builders of this type in their simplest forms are sel~t~ d from the group conci~ g of Na2Ca(C03)2, K2Ca(C03)2, Na2Ca2(C03)3, NaKCa(C03)2, NaKCa2(C03)3, K2Ca2(C03)3, and conlbinations thereof. An çspçci~lly p~f~ d material for the builder described herein is Na2Ca(C03)2 in any of its crystalline 10 mo~1iflc~tions. Suitable builders of the above-defined type are further illustrated by, and include, the natural or syl~ ic forms of any one or combinations of the following minerals: Af~ e, Andcljonile, AshcroftineY, Beyerite, Bol~;~i~, Burbankite, R~ltcchliite, Caml,llile, Calboc.,.u~ite, Carletonite, Davyne, Dol~ndyi~Y, Fairchildite, F."li~ e, rl~-7i.~ , (J~defroyite, Gaylussite, Girvasite, Gregolyile, Jouravskite, 15 Kaml,haugiteY, Kc~L~.ile, Kh~nnPchit~ ol~ ,Gd, Liottite, MckelveyiteY, Microsoll~.lile, Mroseite, Natrofairchildite, Nye.~r~ite, R~ Ce, Sacrofanite, Schrocki.-ge.ile, Shortite, Surite, Tunisite, Tl~sc~nite, Tyrolite, Vishnevite, and Zemkorite.
~.,f~ d mineral forms include Nye.e.ile, Fairchildite and Shortite.

20 Enzvmes El~l,les can be inrhl-le.~ in the present det~,rgenl co.ul)osilions for a variety of l,lJl~ses, inrhl<~ing removal of protein-based, carbo~ ~c-based, or triglyceride-based stains from ~ub~llate-s, for the prevention of refugee dye ~ Ç.,r in fabric laundering, and for fabric 25 l ,i,lo.alion. Suitable ~",es include ~ lut,ases, amylases, lipases, cellulases, peroxidases, and l~lu.cs thereof of any suitable origin, such as vegetable, animal, baclelial, fungal and yeast origin. R.,fe,l~,d selecliol~s are i..~ red by factors such as pH-activity and/or stability optima, th- ~...osl~bility, and stability to active det~lge,lls, builders. In this respect bac~.ial or fungal elL~ Rs are ~l~r~.l~, such as bacl~,lial amylases and pluteases, and 30 fungal cel~ ces.

"Detersive enzyme~, as used herein, means any enzyme having a cle~ning, stain removing or ollle.v~ise beneficial effect in a laundry, hard surface cle~ning or personal care dete.~n~
composition. ~er.ll~,d detersive enzymes are hydrolases such as pro~eases, amylases and 35 lipases. P~,fell~d enzymes for laundry purposes include, but are not limited to, proteases, cf~ U~s, lipases and peroxidases. Highly l.lefe~ d for automatic dishwashing areamylases and/or proteases.

Enzymes are normally hlcGl~ated into de-t~ t or dete.gf ~ll additive compositions at 5 levels sufficient to provide a "cle~ni~-effective amo~nt~. The term "clf~nil~ effective ~mount" refers to any amount capable of producing a cl~ning, stain removal, soi~ removal, wl.it~ g, deodoli~i~, or frechn~oss improving effect on ~ dt~s such as fabrics, di;~h~ àle. In l,ldclical terms for current cc.ll~l~c.cial p..,palalions, typical sllwul1~s are up to 5 mg by weight, more typically 0.01 mg to 3 mg, of active c~,l,e per gram of the 10 det~.gf nt composition. Stated oth.,. wise, the compositions herein will typically co,llp.ise from 0.001% to 5%, preferably 0.01%-1% by weight of a col~llc..;ial e~y.l.e ,l. pa,alio~ t,_ase e.~u~cs are usually present in such co~ ~ial ~ alations at levels s~lrr~ie-~l to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of culll~osilion. For certain d.,~.ge.lt~, such as in alllulllalic dish.. asl~ing, it may be desi.a~le 15 to incl~âse the active e~c content of the co~ .f~..;ial preparation in order to ~ f the total ~ nt of non-catalytically active materials and thereby improve spotting/filming or other end-results. Higher active levels may also be desirable in highly conce.ll,,.ted d~,t,.~e.ll formulations.

20 Suitable examples of proteases are the subtilisins which are obtained from particular strains of B. s~btilis and B. Iic/.~,.iro",.is. One suitable protease is obtau~ed from a strain of Rg~ , having .~ - . activity thro~ ghol)t the pH range of 8-12, developed and sold as ESPERASE~ by Novo ~ if S A/S of De,~ , hereinafter NNovo". The p~p~alion of this e~rll,e and analogous e es is described in GB 1,243,784 to Novo. Other suitable 25 p~Dt~,ases include ALCALASE~ and SAVINASE~ from Novo and MAXATASE~ from Intc...-lio~ Bio-S~ .- l;cs~ Inc., The NelL.,.lands; as well as E~ut~,asc A as disclosed in EP 130,756 A, January 9, 1985 and Protease B as disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985. See also a high pH ~lotedse from R ~ ilh-~ sp.
NCIMB 40338 dcselibet in WO 9318140 A to Novo. Enzymatic dct,.gen~ conlpli~ g 30 protease, one or more other c.~llles, and a reversible protease ~nhibilOl are desclibed in WO 9203529 A to Novo. Other plefe~led proteases include those of WO 9510591 A toProcter & l'~mhle . When desired, a protease having decreased adsorption and incleased hydrolysis is available as des~lil,cd in WO 9507791 to Procter & Gamble. A l~combinaut trypsin-like plut~ase for d~,t.,.~e.l~ suitable herein is described in WO 9425583 to Novo.

W O 97/43394 PCTrUS97/08445 In more detail, an especially p~cfe~l~d protease, referred to as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to po~iLioll +76, S preferably also in co~ inalion with one or more amino acid residue positions equivalent to those select~P~ from the group con.~ g of +99, +101, +103, +104, +107, +123, +27, + 105, + 109, + 126, + 128, + 135, + 156, + 166, + 195, + 197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 accolding to the llulllbe~ing of R(7ri(lr~ anryloliquefaciens subtilisin, as des~lil~d in the patent applications 10 of A. Baeck, et al, entitled "Protease-Contqining Cleaning Col.lposilions" having US Serial No. 08/322,676, and C. Ghosh, et al, "BlParh;~ Co.-~ ions Co~ lisillg ~o~ ce Enzynnes" having US Serial No. 08/322,677, both filed October 13, 1994.

Amylases suitable herein, especjqlly for, but not limited to ~ on,~l;r dishwashing 15 ~ul~oses~ include, for e~al~plc, a-amylases described in GB 1,296,839 to Novo;
RAPIDASE~, Ll~...-l;orlql Bio-Sy.lll.- t;~s, Inc. and TERMAMYL~, Novo.
FUNGAMYL~ from Novo is especiqlly useful. F.-.gi.-~ . ing of enzymes for hllplu~.d stability, e.g., oxidative stability, is known. See, for example J. Biological Chem., Vol.
260, No. 11, June 1985, pp.6518-6521. Certain plefe.l~d embc~i~..f nl~ of the present 20 CGIlll~oSiLions can make use of amylases having improved stability in dete.gc.lLs such as aulumalic dishwashing types, especiqlly improved oxidative stability as measured against a l~f~,r~nce point of TERMAMYL~9 in comlll~,rc;al use in 1993. These plef~ d amylases herein share the chalaL~.islic of being "stability~h~nred" amylases, chalacL~,.ized, at a ...;n;....-..., by a measurable improv.,~ll,nl in one or more of: oxidative stability, e.g., to 25 hydrogen peroxide/tetraac~l~lelh~ nfdi-...;n~ in buffered solution at pH 9-10; thermal stability, e.g., at co.. on wash te~ .. ...ul~s such as 60~C; or ~ lin~ stability, e.g., at a pH from 8 to 11, ~easul~d versus the above-identifi~d l~,f, rence-point amylase. Stability can be ll,easul ~ using any of the art~icrlosed ~ech.~ l tests. See, for example, r~.f~ ~e.~ces ~licclosetl in WO 9402597. Stability l ..h~ ed amylases can be obtained from Novo or from 30 t~ .- nror International. One class of highly preferred amylases herein have the collllllonality of being derived using site-directed mutagenesis from one or more of the Rn~ amylases, especiqlly the R~ a-amylases, regardless of whether one, two or multiple amylase strains are the ;.... ed;qte precursors. Oxidative stability-enhqnred amylases vs. the above-i~l~ntifiPd ~fe~ence amylase are plefe,l.,d for use, especially in 35 bl~hi~g, more preferably oxygen ble2~hing, as distinct from chlorine blevqching, .. ...

detelge.-t compositions herein. Such preferred arnylases include (a) an arnylase according to the hereinbefore incorporated WO 9402597, Novo, Feb. 3, 1994, as further illustrated by a mutant in which substitution is made, using alanine or threonine, preferably tll,~,onilK, of the methionine residue located in position 197 of the B lich~i~iJ'or,,.is alpha-amylase, known 5 as TERMAMYL~, or the homologous position variation of a similar parent arnylase, such as B. amyloliql ~iens, B. subtilis, or B. stearothermophilus; (b) stability enh~nced amylases as desclibed by Cenellcor L~ alional in a paper entitled "Oxidatively R~sict~nt alpha-Amylases" pr~s.~ Pd at the 207th A l.e.ican ChPmir~l Society National Meeting, March 13-17 1994, by C. ~~ on. Therein it was noted that bleaches in ~J~o"~t 10 dishwashing de~ergel-ts inactivate alpha-amylases but that improved oxidative stability amylases have been rnade by Ce~ ror from B. Iicl~ o",.~s NCIB8061. Melt.io~
(Met) was i~entifi~d as the most likely residue to be m~ified. Met was substi~ d one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to specific m~ nts, particularly iu~ t being M197L and M197T with the M197T variant being the most 15 stable eA~r~,ssed variant. Stability was nR8~ d in CASCADE~ and SUNLIGHT~9; (c) particularly ~.ef.,~ed amylases herein include amylase variants having additional mf-(lifir~tion in the ;..~ te parent as desc.ibed in WO 9510603 A and are available from the ~c.ci~n~e~ Novo, as DURAMYL~g). Other particularly pl~f~-c;d oxidative stability enh~--red amylase include those desc.ibed in WO 9418314 to C;e ~ .ror Int. .l18lional and WO 9402597 to Novo. Any other oxidative stability e-~h~nce~l amylase can be used, for example as derived by site-directed m~ en~si~ from known chimeric, hybrid or simple mutant parent forms of available amylases. Other plef. .-~ enzyme ~I~o~l;lic~ions are accessible. See WO 9509909 A to Novo.

Other amylase enzymes include t_ose desc~il~d in WO 95/26397 and in co-~
application by Novo Nordisk PCT/DK96/00056. Specifi~ amylase e.l~.~llRS for use in the dete~ co o;~;l;olls of the present invention include a-amylases ch8l8cle.i~d by having a s~if.c activity at least 25 % _igher than the specific activity of Termamyl~ at a te.n~alulc range of 25~C to 55~C and at a pH value in the range of 8 to 10, measured by the Phadebas~9 a-amylase activity assay. (Such Ph~e~ a-amylase activity assay isdescribed at pages 9-10, WO 95/26397.) Also in~lu(le~ herein are a-amylases which are at least 80~ homologous with the amino acid seq~len~es shown in the SEQ ID listings in the ~efe.~ ces. These enzymes are preferably h~cOll,olated into laundry det~,.g~
compositions at a level from 0.00018% to 0.060% pure enzyme by weight of the total composition, more preferably from 0.00024% to 0.048% pure enzyme by weight of the total composition.

C'ell~ c~s usable herein include both bact~,.ial and fungal types, preferably having a pH
Optillllllll bel~,.een 5 and 9.5. U.S. 4,435,307, Barbesgoard et al, March 6, 1984, discloses suitable fungal celll~l~ces from Humicola insolens or Humicola strain DSM1800 or a celh~l~ce 212-pro~h~ci~ fungus belonging to the genus Aeromonas, and cell~ ce eAlla~lcd from the hepatc.p~as 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-10 2.247.832. CAREZYME~ and CELLUZYME~ (Novo) are especi~lly useful. See also WO 9117243 to Novo.

Suitable lipase enzymes for det~r~,el~t usage include those produced by microorg~;cl~lc of the Pseudomonas group, such as Pseudomonas stu~zen ATCC 19.154, as disclosed in GB
15 1,372,034. See also lipases in Jap~n~se Patent Application 53,20487, laid open Peb. 24, 1978. This lipase is available from Amano ph~ ie?l Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," or ~Amano-P." Other suitable co,lu,,.rcial lipases include Amano-CES, lipases ex Chromoba~ter viscosum, e.g. Chromobacter viscosum var. Iipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan;
20 Chromobacter vi~eosl<m lipases from U.S. Bioc~ r~l Corp., U.S.A. and Disoynth Co., The Nc~ ds, and lipases ex Pseudomonas gladioli. LIPOLASE~ enzyme derived from Humicola lanuginosa and collu~r~idlly available from Novo, see also EP 341,947, is a l)ref~ d lipase for use herein. Lipase and amylase variants stabilized against peroxidase enzymes are desclibed in WO 9414951 A to Novo. See also WO 9205249 and 25 RD 94359044.

In spite of the large l~ber of publications on lipase enzymes, only the lipase derived from Humicola lanuginosa and produced in Aspergill~s oryzae as host has so far found widesl,l. ad a~lication as additive for fabric washing products. It is available from Novo 30 Nordisk under the tra~ ç Lipolasen', as noted above. In order to o~ the stainremoval perfo~ ce of Lipolase, Novo Nordisk have made a llum~. of variants. As des_lil~d in WO 92/05249, the D96L variant of the native Humicola lanuginosa lipase i~llpl~o~.s the lard stain removal efficiency by a factor 4.4 over the wild-type lipase (enzymes CO"",al. d in an amount r~gh~g from 0.075 to 2.5 mg protein per liter).35 Research Disclosure No. 35944 published on March 10, 1994, ~y Novo Nordisk discloses that the lipase variant (~:)96L) may be added in an amount coll~sl,o~lding to 0.001-100- mg (5-500,000 LU/liter) lipase variant per liter of wash liquor. The present invention provides the benefit of improved ~ll;t~ SS mq;..~ n-e on fabrics using low levels of D96L variant in detelgent compositions contqining the bis-AQA surfq-rtq-ntc in the ~ icclosedherein, especially when the D96L is used at levels in the range of 50 LU to 8500 LU per liter of wash solution.

C~ltinqce enzymes suitable for use herein are described in WO 8809367 A to ~e--r l~'Or.

Peroxidase enzymes may be used in combination with oxygen sources, e.g., p~lc~l,onate, ~,.I,ol.-te, hydrogen peroxide, etc., for "solution blP'~hi.~g" or prevention of ll~f~l of dyes or pigm~ntc removed from substrates during the wash to other SUb~llat~S present in the wash solution. Known peroxidases include hul~e.adish peroxidase, ligninqce, and haloperoxidases such as chloro- or bromo-peroxidase. Peroxidase-co..~ g det.,l~.lt compositions are disclosed in WO 89099813 A, October 19, 1989 to Novo and WO
8909813 A to Novo.

A range of er~y-llc n~lials and means for their incorporation into ~ ic d~.t. l~lll compositions is also disclosed in WO 9307263 A and WO 9307260 A to G. I~ ,~or Int~"~lional, WO 8908694 A to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further ~ clQsed in U.S. 4,101,457, Place et al, July 18, 1978, and in U.S. 4,507,219, ~ gh~s, March 26, 1985. Enzyme materials useful for liquid det~"E,e forrn~lq-tions~ and their illcol~lalion into such formulations, are disclosed in U.S.
4,261,868, Hora et al, April 14, 1981. Enzymes for use in deterge.l~ can be stabilised by various techni~l~es. Enzyme stabili~q~ion t~hniT-es . re disclosed and exemplified in U.S.
3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilisation ~ ~s are also described, for eA~I~ple, in U.S.
3,519,S70. A useful Rarillllc, sp. AC13 giving prot~ases, xylanases and cellulases, is de~c~,bed in WO 9401532 A to Novo.
Enzyme Stabilizing System The enzyme-cont-q-ining colll~sil ;(mc herein may optionally also comyl,se from 0.001 ~ to 10%, preferably from 0.005 % to 8 %, most preferably from 0.01 % to 6%, by weight of an el~llR stabilizing system. The enzyme stabilizing system can be any stabilizing system WO 97/43394 rCT/US97/08445 which is compatible with the detersive enzyme. Such a system may be i~ ,e,llly provided by other formulation actives, or be added set)alately, e.g., by the formulator or by a mqmlfart lrer of detelgelll-ready enzymes. Such stabilizing systems can, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic S acids, and I~ ures thereof, and are design~d to address dirr. ,~ t stabilization problems de~n~ling on the type and physical form of the dct~ ~ge,ll composition.

One stabilizing app.oach is the use of water-soluble sources of c~lril~m and/or l..ag.-f,si~
ions in the finich~ colll~osilions which provide such ions to the enzymes. ~lri~lm ions 10 are generally more effective than m~ ... ions and are plcÇ~ ,d herein if only one type of cation is being used. Typical detergc~ll co~ osilions, especi~lly liquids, will co",l.lise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 8 to about 12 millimoles of c~lril~m ion per liter of finichrd detc,g~ t collll)osiliol~, though ValialiOIl iS possible ~ 1;ng on factors inrlu(ling the multiplicity, type and levels of lS enzymes illCO~lat d. P~felably water-soluble c~lri~rn or m~.~f si~.. salts are employed, inrl~ for example c~lrillm chloride, c~lri~m hydroxide, c~lrillm fol~Lt, c~lcil~m malate, c~lci~m m~ te, c~lrillrn hy~vxide and c~lrillrn acetate; more generally, c~lri~lm sulfate or ma~-rs;-l... salts coll~,spolldillg to the exemplified c~lrillrn salts may be used.
hCl h~leased levels of C~lri~m and/or l~g..~ci~ may of course be useful, for 20 example for promoting the grease-cutting action of certain types of surfactant.

Another stabilizing a~l,foach is by use of borate species. See Scve.soll, U.S. 4,537,706.
Borate stabilizers, when used, may be at levels of up to 10% or more of the co,ll~silion though more typically, levels of up to about 3% by weight of boric acid or other borate 2S culll~uunds such as bora~ or oll~lobolaLe are suitable for liquid det~ use. .S~bsl;l.JI~
boric acids such as p~lylboro"lc acid, bu~neborol~ic acid, p-blonlophe.lylbolol~ic acid or the like can be used in place of boric acid and reduced levels of total boron in d~l. .E,ent co"lpos;l ;on~ may be possible though the use of such s~lb~ boron derivatives.

30 Stabilizing ~ ~"ls of certain cl~ni..g compositions, for example ~-tom~~ir dishwashing compositions, may further comprise from 0 to 10%, preferably from 0.01% to 6% byweight, of chlorine bleach scavengers, added to prevent chlorine bleach species present in many water supplies from ~ rL i,~g and inactivating the enzymes, especially under ~Ik~lin~
condiliûns. While chlorine levels in water may be small, typically in the range from 0.5 35 ppm to 1.75 ppm, the available chlorine in the total volume of water that comes in contact with the el~y~l~c, for example during dish- or fabric-washing, can be relatively large;
accordingly, enzyme stability to chlorine in-use is som~timPs problematic. Sincepercarbonate has the ability to react with chlorine bleach the use of additional stabilizers against chlorine. may, most generally, not be essentiql, though improved results may be 5 obtainable from their use. Suitable chlorine scavenger anions are widely known and readily available, and, if used, can be salts contAinin~ .l,.oni lm cations with sulfite, bisulfite, thioslllfite, thioslllf~t.~, iodide, etc. Antioxidants such as call,amate, ascorbate, etc., organic amines such as ethyl~ iA...in.~ .acetic acid (EDTA) or alkiali metal salt thereof, monoelllanolamine (MEA), and mixtures thereof can likewise be used. Likewise, 10 special enzyme inhibition ~y~L.,Ills can be incorporated such that different ~ .lLy-lles have m~ximllm compatibility. Other conventional scave,lgels such as bisulfate, nitrate, cloride, sources of hydrogen peroxide such as sodium pell~l_te tetrahydrate, sodium perborate Illo,lohydrate and sodium pe,cOll,onate, as well as phosphate, co.~ e~l phosphate, acetate, ber,7.5)~te, citrate, follllate, lactate, malate, tartrate, salicylate, etc., and Il~ ,S
15 thereof can be used if desired. In general, since the chlorine scavenger function can be .r~"..lcd by ingredients sel,a._tely listed under better ..,cogniL~d rul~;liG~s, (e.g., hydrogen peroxide sources), there is no absolute reyuile,.l~ to add a separate chlorine scaveng~l unless a cc,...~ performing that function to the desired extent is absent from an el~rme conrAini~ embod;~ of the invention; even then, the scavenger is added only 20 for o~lim~lll, results. Moreover, the formulator will exercise a ch~ s normal skill in avoiding the use of any enzyme scavenger or stabilizer which is majorly i~-ro,..l.Alible, as form~ t~1, with other ~acli~e ingredients. In relation to the use of ammonium salts, such salts can be simply ~lmiYed with the det~ .~e,lt composition but are prone to adsorb water and/or liberate A--IIIIOI~ during storage. Accordingly, such materials, if present, are desirably prot~,~t~d in a particle such as that described in US 4,652,392, P~agin~l~i et al.

Polymeric Soil Release AQent Known polymeric soil release agents, hereinafter "SRA" or "SRA's", can optionally be 30 employed in the present d~,tergenl cc,llposilions. If u~ili7~d, SRA's will generally coll,p~ise from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight, of the colllposiLion.

~efe"~,d SRA's typically have hydrophilic se~llRnt~ to hydrophilize the surface of 35 hydrophobic fibers such as polyester and nylon, and hydrophobic seg~ rl~ to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles thereby serving as an anchor for the hydrophilic segments. This can enable stains oc~ ing subseql~en~ to tl~-t- f n~ with SRA to be more easily cle~n~A in later washing l,loce.l-lr~s.
SRA's can include a variety of charged, e.g., anionic or even cationic (see U.S.4,956,447), as well as l-o~ a~ged mQno...fl units and structures may be linear, b~ clled or even star-chaped. They may include capylllg ll.oieties which are especiqlly effective in controlling molecular weight or altering the physical or surface-active pluy.,lies.
10 Slluclu~es and charge di~ lions may be tailored for application to dirf~.ent fiber or textile types and for varied d.te.gelll or det.,.~e.ll additive ~,i~lu.,ls.

~f._~led SRA's include oligolll..ic tere~.h~ te esters, typically ple~ ed by processes involving at least one ~ t,~,irlcalion/oligolll..i~lion, often with a metal catalyst such as 15 a ~ ..(IV) qlkoxide Such esters may be made using additional Illo~ol~ , ca~)âbl~ Of being i~oll,olat~,d into the ester SLIuClulc through one, two, three, four or more positions, wilhuul of course fol.lling a densely crosslinked overall sl.uclul .

Suitable SRA's include: a sulronated product of a sul.~ lly linear ester oligomer 20 co.~ ised of an oli~,om~lic ester backl.olle of t,lephlhqloyl and oxyaLkyleneoxy repeat units and allyl-derived sulronat~,d ~ l moieties covalently q~ d to the backbone, for e~ le as described in U.S. 4,968,451, No~ ~l 6, 1990 to J.J. Sch~ibPl and E.P.GocsPlin' such ester oligolllcl~ can be plel)~C;I by (a) ethoxylating allyl alcohol, (b) lle?cti~ the product of (a) with dimethyl tel~lJh~ q~P ("DMT") and 1,2-propylene glycol 25 (nPGn) in a two-stage ~ crification/ oligol,Rli~tion ploce.lure and (c) le~cl~ng the product of (b) with sodium metabisulfite in water; the non.ollic end-capped 1,2-propylene/pol~u~ lene tel~h~ l~te polyesters of U.S. 4,711,730, Dece-..kl 8, 1987 to G~osselirlk et al, for c~ple those produced by ~ c j~ ir~caliol~/oligoll~ ~lion of poly(ethylel~l~/col) methyl ether, DMT, PG and poly(ethyleneglycol) (nPEGn); the partly-30 and fully- anionic-end-capped oligo~ ,lic esters of U.S. 4,721,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-hydroxyoct-q-nPs~llfonate; the nonionic-capped block polyester OligOnh~iC col.lpo~l"ds of U.S. 4,702,857, October 27, 1987 to Gosselirlk~ for example produced from DMT, Me-capped PEG and EG and/or PG, or a coll,bil~ation of DMT, EG and/or PG, Me-capped35 PEG and Na~i,lle~ l-S-sulfoisophthql3t~o; and the anionic, especially sulfoaroyl, end-WO 97/43394 pcTrus97to844s capped te.elJh~ te esters of U.S. 4,877.896, October 31, 1989 to Maldonado, Gosselink et al, the latter being typical of SRA's useful in both laundry and fabric conditioning products. an example being an ester composition made from m-sulfobenzoic acid monosodium salt, PG and DMT optionally but preferably further comprising added PEG, e.g., PEG 3400.

SRA's also include simple copolymeric blocks of ethylene t~.ephlh~l~t~P or propylene t,repht~ e with polyethylene oxide or polypropylene oxide le~,})hlh'~l~tP~ see U.S.
3,959,230 to Hays, May 25,1976 and U.S. 3,893,929 to R~c~ , July 8,1975; cell--losic 10 derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; and the Cl-C4 alkylcelluloses and C4 hydroxyalkyl celluloses; see U.S. 4,000,093, Decenlbe. 28,1976 to Nicol, et al. Suitable SRA's charac~ ised by poly(vinyl ester) hydrophobe scE...- ~Ic include graft copolymers of poly(vinyl ester), e.g., C1-C6 vinyl esters, preferably poly(vinyl acetate), grafted onto polyalkylene oxide backbones. See Euro~all Patent Applir~ioll 0 219 048, published April 22, 1987 by Kud, et al.
Co,lull~ ;ially available examples include SOKALAN SRA's such as SOKALAN HP-22, available from BASF, C~ .y. Other SRA's are polyesters with repeat units cont~ini~
10-15% by weight of ethylene ~ .lh~ tP together with 90 80% by weight of polyoxyethylene le~c~ tP, derived from a polyoxyethylene glycol of average molecular weight 300-5,000. Collul~ ;ial examples include ZELCON 5126 from Dupont and MILEASE T from ICI.

Another plefe.l.,d SRA is an oligomer having e.llpirical formula (CAP)2(EG/PG)s(T)s(SIP)1 which co~ .lises terephthaloyl (T), sulfoisophthaloyl (SIP), 25 oxyethyle.l~o~y and oxy-1,2-propylene (EG/PG) units and which is preferably t~_in~e~
with end caps (CAP), preferably m~ifi~d isethionates, as in an oligomer Colll~ illg one sulfoico~h~ )yl unit, S t~,r~lllaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a defined ratio, preferably about 0.5:1 to about 10:1, and two end~ap units derived from sodium 2-(2-hyd~ yethoxy)~ll.znP~.~Ifonate. Said SRA preferably further colll~iises from 0.5% to 20%, by weight of the oligomer, of a cryst~llinity-re~ ci.~g stabiliser, for example an anionic ~ulr~ such as linear sodium dodecyl~.-7~.-fs~1fonate or a ~lle,ll~l selPctP~ from xylene-, ~ f-, and toluene- sulfonates or mixtures thereof, these stabilizers or modifiers being introduced into the synthesis pot, all as taught in U.S.
5,415,807, Gosselin~, Pan, Kellett and Hall, issued May 16, 1995. Suitable monomers for the above SRA include Na 2-(2-hydroxyethoxy)-eth~n~sl~lfonate, DMT, Na- dimethyl 5-sulfoisophrh~l~te, EG and PG.

Yet another group of preferred SRA's are oligomeric esters colllplising: (1) a backbone 5 comprising (a) at least one unit selected from the group consisting of dihydroxysulfonates, polyhydroxy sulfonates, a unit which is at least trifunctional wllereby ester linkages are formed resl~lting in a bl~nched oligomer bac~one, and combinations thereof; (b) at least one unit which is a tel~hlhaloyl moiety; and (c) at least one unsulfonated unit which is a 1,2-oxyalkyleneoxy moiety; and (2) one or more capping units select~l from nonionic 10 capping units, anionic capping units such as alkoxylated, preferably ethoxylated, isethionates, allcoxylated prop~n~s.llfol~t~,s, alkoxylated proy~--r~ lfonates, alkoxylated phenolsulforlates, sulfoaroyl derivatives and ~ ules thereof. P~fel.~d of such es~ers are those of c.llyilical formula:
{ (CAP)x(EG/PG)y ' (DEG)y n (PEG)y " ' (T)z(SIP)z ' (SEG)q(B)m}
wll~le~ CAP, EG/PG, PEG, T and SIP are as defined hereinabove, (DEG) l.,~l~s_~b di(oxyethylene)oxy units; (SEG) ~ lc.se~ls units derived from the sulfoethyl ether of glyce,in and related moiety units; (B) ~ep.es..lts bl~nl~hi~g units which are at least ,lir ~ whereby ester linl~ges are formed resultir~ in a b~ ched oligomer 20 bac~l.une; x is from about 1 to about 12; y' is from about 0.5 to about 25; y" is from 0 to about 12; y" ' is from 0 to about 10; y' +y" +y" ' totals from about 0.5 to about 25; z is from about 1.5 to about 25; z' is from 0 to about 12; z + z' totals from about 1.5 to about 25; q is from about 0.05 to about 12; m is from about 0.01 to about 10; and x, y', y", y"', z, z', q and m ~e~les~ the average ~ of moles of the corresponding units per 25 mole of said ester and said ester has a molecular weight raulging from about 500 to about 5,000.

~ef~ ed SEG and CAP ...~ for the above esters include Na-2-(2-,3-dihydroxypropoxy)~ s ~lfonate ("SEGn), Na-2-{2-(2-hydroxyethoxy) ethoxy}
30 ~lh~n~ fonate ("SE3n) and its homologs and n~ixtures thereof and the products of ethoxylating and sulfol~ling allyl alcohol. ~.~ lcd SRA esters in this class include the product of ~IA...~ J . irying and oligolll~ lg sodium 2-{2-(2-hydroxyethoxy)ethoxy}e~ n~..1fonate and/or sodium 2-[2-{2-(2-hydroxyethoxy)-ethoxy}ethoxy]e~ nP,.~Ifonate, DMT, sodiurn 2-(2,3-dihydroxypropoxy) ethane sulfonate, 35 EG, and PG using an a~ oylialc Ti(IV) catalyst and can be ~lesipn~ted as WO 97/43394 PCT/US97/0844!;

(CAP)2(T)5(EG/PG)1.4(SEG)2.5(B)0.13 wherein CAP is (Na+ -O3S[CH2CH2O]3.5)-and B is a unit from glycerin and the mole ratio EG/PG is about 1.7:1 as measured by conventional gas chromatography after complete hydrolysis.

5 Additional classes of SRA's include (I) nonionic terephth~l~tes using diisocyanate coupling agents to link up polymeric ester structures, see U.S. 4,201,824, Violland et al. and U.S.
4,240,918 ~g~se et al; (II) SRA's with carboxylate tcllnil~al groups made by adding trim~lliti~ anhydride to ~nown SRA's to convert te.ll.inal hydroxyl groups to trimellitate esters. With a proper selection of catalyst, the trim~llitic anhydride forms linkages to the 10 tc.llf.llals of the polymer through an ester of the isolated carboxylic acid of trim~olliti~
anhydride rather than by opening of the anhydride linkage. Either nonionic or anionic SRA's may be used as starting materials as long as they have hydroxyl terminal groups which may be e;.l~ified. See U.S. 4,525,524 Tung et al.; (m) anionic te~ te-based SRA's of the u~~ c-linked variety, see U.S. 4,201,824, Violland et al; (IV) poly(vinyl 15 caprolactam) and related co-polymers with nlollunRl~ such as vinyl pyrrolidone and/or ,lhyl~minoethyl ..~ ~ylate, inrl~ in~ both l~O~iOlllC and calion,c polymers, see U.S.
4,579,681, Ruppert et al.; (V) graft copolymers, in addition to the SOKALAN types from BASF made, by g~afling acrylic lllUnUIII~ on tO sulfol~t~d polyesters; these SRA's assertedly have soil release and anti-redeposition activity sirnilar to known ce~ ose ethers:
see EP 279,134 A, 1988, to Rhone-Poulenc Chemie; (VI) grafts of vinyl ~llono-l.~.s such as acrylic acid and vinyl acetate on to pro~cills such as caseins, see EP 457,205 A to BASF
(1991); (VII) polyester-polyamide SRA's pll,pal~d by con~len~ing adipic acid, caprolactam, and polyethylene glycol, especially for llca~ g polyamide fabrics, see Bevan et al, DE
2,335,044 to Unilever N. V., 1974. Other useful SRA's are described in U.S. Patents 4,240,918, 4,787,989, 4,525,524 and 4,877,896.

Cla~,r Soil Removal/Anti-led.,~;,ilion A~ents The coll.l,osiliol~s of the present invention can also optionally contain water-soluble 30 ethoxylated amines having clay soil removal and antiredeposition pro~. Lies. Granular ~telge.lL compositions which contain these compounds typically contain from 0.01 % to 10.0% by weight of the water-soluble ethoxylates amines; li~uid d~,tel~ent compositions typicallycontainO.01% to5%.

WO g7/43394 PCI/US97/08445 The most pref~ ,d soil release and anti-redeposition agent is ethoxylated tetraethylene-pem~min~. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of plefell~d clay soil removal-aIlli.edeposition agents are the cationic coll.puunds disclosed in European Patent Application 111,965, Oh and Gosselin'c, published June 27, 1984. Other clay soilremoval/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselinlc, published June 27, 1984; the ~vilL.,.ionic polymers ~icclosecl in Euro~an PateM Application 112,592, Go.sselirlc, published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, 10 issued October 22, 1985. Other clay soil removal and/or anti redeposition agents Icnown in the art can also be utilized in the compositions herein. See U.S. Patent 4,891,160, Vande.Meer, issued January 2, 1990 and WO 95/32272, published Nov~l"~, 30, 1995.Another type of pref~ d antiredeposition agent ~n~ludes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.
Polymeric Dl~ A~ents Polymeric disL~ g agents can advantageously be utilized at levels from 0.1 % to 7 %, by weight, in the colll~o~ilion~ herein, especially in the p.es~.~ce of zeolite and/or layered 20 silicate builders. Suitable polymeric di~ lg agents include polymeric polycarboxylates and polyethylene glycols, ~lthol)gh others known in the art can also be used. It is believed, though it is not intPn~ to be limited by theory, that polymeric disl,c.sillg agents enh~n~e overall del.,.ge.ll builder pe.~u~lllance, when used in co...bi~ation with other builders (in~ .ting lower molecular weight polycarboxylates) by crystal growth inhibition, 25 particulate soil release peptization, and anti-redeposition.

Polymeric polycarboxylate materials can be plet)~cd by polyl..e.~ing or copolyllR~ g suitable uns,.lu-at._d ...O~ , prLf~,,ably in their acid form. Unsaturated muno.l.elic acids that can be poly.--c.ized to form suitable polymeric polycarboxylates include acrylic 30 acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylerl~m~lonic acid. The l,.esence in the polymeric polycarboxylates herein or monom~ric seE,..~ , con~ining no carboxylate radicals such as vill~ lctllyl ether, styrene, ethylene, etc. is suitable provided that such s~ ,nls do not constitute more than 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from 2,000 to 10,000, more preferably from 4,000 to 7,000 and most preferably from 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted aln~lloniL~Ill salts.
Soluble polymers of this type are known materials. Use of polyacrylates of this type in dete.gelll compositions has been ~ close~ for example, in Diehl, U.S. Patent 3,308,067, issued March 7, 1967.
Acrylic/maleic-based copolymers may also be used as a plefe.l..d colll~l~ t of the dis~,~ing/anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of suchco~olyll.~l~ in the acid form pl.,fe.abl~ ranges from 2,000 to 100,000, more preferably from 5,000 to 75,000, most pl~f.,lably from 7,000 to 65,000. The ratio of acrylate to mqlP~te se~lll.,n~ in such copolymers will generally range from 30: 1 to 1: 1, more preferably from 10: 1 to 2: 1. Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for t~llple, the aL~cali metal, ammonium and S~lbS~ t~d ~Illlloniulll salts. Soluble acrylate/m~lPqte copolymers of this type are known materials which are desclibcd in Eulu~an Patent Application No. 66915, published Dec~mher 15, 1982, as well as in EP 193,360, published Sel)telllber 3, 1986, which also des. libes such polymers colllplisillg hydro~Ly~ropylacrylate. Still other useful dis~lsii~g agents include the maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP
193,360, inr!u(~ing, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
Another pol~u~.,lic material which can be in~ludPd is polyethylene glycol (PEG). PEG can exhibit di;.~ ing agent pelf.~ e as well as act as a clay soil removal-all~ir~eposition agent. Typical molecular weight ranges for these purposes range from 500 to 100,000, preferably from 1,000 to 50,000, more plefelably from 1,500 to 10,000.
Polyaspal~e and polygl..~ dis~ g agents may also be used, especially in conjun~lion with zeolite builders. Dis~sing agents such as polyaspartate preferably have a molecular weight (avg.) of 10,000.

B~ r W O 97/43394 PCT~US97/08445 Any optical bri~l.t~ ~-1... or other brighte~ ing or whitening agents known in the art can be incorporated at levels typically from 0.01 % to 1.2%, by weight, into the dete;g~
compositions herein. Co~ .c,cial optical brig~lrl~ 1'7 which may be useful in the present 5 invention can be clq-ccified into subgroups~ which include, but are not ~ Cf ss~rily lhnited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, ...r!l.;nfcyanines, u~lliophf nf -5~5-dioxide~ azoles, 5- and 6-..u ~~'~rf d-ring h~t~,lo~;ycles, and other miccellqnf ous agents. Examples of such bri~ -f ~. are disclosed in "The Production and Application of FluorescellL ~ t~ g Agents", M. Zahradnik, Published by Jonn Wiley 10 & Sons, New York (1982).

Specifil ~Aa ll~les of optical bri~l.t-r n., ~. which are useful in the present c~ posilions are those iderltifi~ in U.S. Patent 4,790,856, issued to Wixon on Decf. ..l;~r 13, 1988. These bri~l~t~ include the PHORWHITE series of brigl~ from Verona. Other lS bright'F'- lS rlicclosed in this l~f~.ellce include: Tinopal UNPA, Tinopal CBS and Tinopal SBM; available from Ciba-Geigy; Artic White CC and Artic White CWD, the 2-(4-styryl-phenyl)-2H-naptho[1,2-d]triazoles; 4,4'-bis-(1,2,3-triazol-2-yl)-stilbPnPs; 4,4'-bis(styryl)bi~h~,lyls; and the ~ oco~-..q. ins. Specific exarnples of these bri~ f ~f ~s include 4-methyl-7-diethyl- amino colullalin; 1,2-bis(~n~;,..iA~7Ol-2-ylkthylene; 1,3-diphenyl-pyrazolines; 2,5-bis(ben7oxq-7Ql-2-yl)thiophene; 2-styryl-naptho[1,2-d]oxazole;
and 2-(stilben4-yl)-2H-n~rhtho[1,2-d]triazole. See also U.S. Patent 3,646,015, issued February 29, 1972 to E~miltc-n Dye Transfer Inhibitinp Agents The COI~ ;0~ of the present invention may also include one or more rnaterials effective for inhi~ g the ll~f~,r of dyes from one fabric to another during the cleqning process.
Generally, such dye ~ , ulhi~ g agents include polyvinyl pyrrolidone polymers, polyamine N~xide polyrners, copolymers of N-vinylpyrrolidone and N-vinylimi~J~7ole, 30 ~gi~nrse phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from 0.01 % to 10% by weight of the composition, preferably from 0.01% to 5%, and more preferably from 0.05% to 2%.

More specifically, the poly~ul.il1e N-oxide polymers preferred for use herein contain units having the following structural formula: R-AX-P; wherein P is a polymerizable unit to which an N-0 group can be ~ rh~d or the N-0 group can form part of the polymerizable unit or the N-0 group can be ~ ~h~-~ to both units; A is one of the following structures -NC(0)-, -C(0)0-, -S-, -0-, -N=; x is 0 or 1; and R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen S of the N-0 group can be alt~rh~l or the N-0 group is part of these groups P~f~ d polyamine N-oxides are those wherein R is a h~,t, lu ~clic group such as pyridine, pyrrole, imi~l~701e, pyrrolidine, piperidine and derivatives thereof The N-0 group can be .~p~se,lt~d by the following general sL~u~;lulcs:

1~
(Rl)x 7 (R2)y; =N (Rl)x (R3)z wllc. hl Rl, R2, R3 are ~lirh"~i~, al~ulatic, h~ro~;yclic or alicyclic groups orco..lbil~lions thereof; x, y and z are 0 or 1; and the nitrogen of the N-0 group can be 15 ~tt ~h~d or form part of any of the afo.~ nlioned groups The amine oxide unit of the polyamine N-oxides has a pKa c 10, preferably pKa <7, more p..,fe..ed pKa c6 Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye ~f._, inhibi~ g pio~.lies. Examples of suitable polymeric 20 backbones are polyvinyls, polyaL~ylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and llli~ lCS thereof. These polymers include random or block copolymers where one mono~ r type is an amine N-oxide and the other l~lollu~ type is an N-oxide The amine N-oxide poly~ s typically have a ratio of amine to the amine N-oxide of 10:1 to 1 1,000,000. However, the u~ ber of arnine oxide groups present in the pol~d.~.e 25 oxide polymer can be varied by ap~ropl.atc copolyl~ ion or by an applu~liate degree of N-oxidation The pol~e oxides can be obtained in almost any degree of pol~ll.e~alion. Typically, the average molecular weight is within the range of 500 to 1,000,000; more prcf~ d 1,000 to 500,000; most plefe,led 5,000 to 100,000 This p.cfe,.~d class of materials can be r~,fe,led to as "PVNOn The most l).cfell~d polyamine N-oxide useful in the del_lgent compositions herein is poly(4-vinylpyridine-N-oxide) which has an average molecular weight of 50,000 and an amine to amine N-oxide ratio of 1:4.

5 Copolymers of N-vinylpyrrolidone and N-vinyl;...i-1~70le polymers (referred to as a class as "PVPVI") are also plef._..ed for use herein. Preferably the PVPVI has an averagemolecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is .,..in~l by light scalte~u~g as described in Barth, et al., Ch~mi~l AnalYsis. Vol 113.
10 "Modern Methods of Polymer Chara~;le.~lionn, the disclosures of which are incorporated herein by r~fcrf,lce.) The PVPVI copolymers typically have a molar ratio of N-vinylimi~1~7ole to N-vi~l~ olidone from 1:1 to 0.2:1, more p.cf~,,dbly from 0.8:1 to 0.3: 1, most preferably from 0.6: 1 to 0.4:1. These copolymers can be either linear or b,~lched.
The present invention co...~ilions also may employ a polyvinylpyrrolidone ("PVPn) having an average molecular weight of from 5,000 to 400,000, preferably from 5,000 to 200,000, and more pl~Çf~ably from 5,000 to 50,000. PVP's are known to persons skilled in the d~t~ige.ll field; see, for example, EP-A-262,897 and EP-A-256,696, iulco~at~d 20 herein by ~f~_re.~ce. Co.-.posiliolls cont~inin~ PVP can also contain polyethylene glycol (nPEG") having an average molecular weight from 500 to 100,000, preferably from 1,000 to 10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from 2:1 to 50:1, and more preferably from 3:1 to 10:1.

The d t,~g~ con~rositi~ns herein may also optionally contain from 0.005% to 5% by weight of certain types of hydrophilic optical bri&l.t~ rs which also provide a dye L.ar~r.,r inhibition action. If used, the co.~lpo~i~;o~c herein will preferably collll).ise from 0.01% to 1 % by weight of such optical ~ t~ r~.,~,.

The hydrophilic optical brigh~ nf,~ useful in the present invention are those having the structural formula:

RI~N H H N ~ 2 ~\ /~\ I I / ~\ /~
N~)~N~C=C~ ~ I ~, /N

R2 SO3M SO3M Rl wherein Rl is selectPd from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is select~d from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro 5 and amino; and M is a salt-folllling cation such as sodium or pot~csil~m When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as so~ m, the bri~htPrPr is 4,4',-bis[(4-anilino~-(N-2-bis-hydroxyethyl)-s-~ ine-2-yl)amino]-2~2~-stilb-pnp~ic~llfonic acid and tlico~ m salt. This particular brightener species 10 is COI~ rcially Illa~ted under the trade~ c Tinopal-UNPA-GX by Ciba-Geigy Col~oldlioll. Tinopal-UNPA-GX is the pltr~ d hydrophilic optical bri~htPnPr useful in the dete.~ colllpo~;l;onc herein.

When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M
is a cation such as so ~ m, the bri~ .f ~ is 4,4'-bisl(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-~ -2-yl)amino]2,2'-stilbel-f~ fonic acid disodium salt. This particular ~ htenfr species is collllllel~ially ll~t~d under the tr~d~Pn~mP Tinopal SBM-GX by Ciba-Geigy Col~l on.

20 When in the above formula, Rl is anilino, R2 is morphilino and M is a cation such as so~ m, the bri~l~t~ is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilhe~ fonic acid, sodium salt. This particular bri~ f l species is col~ ciallyrl.. ~d uDder the tradename Tinopal AMS-GX by Ciba Geigy Col~olalion.

25 The specific optical bri~ht~npr species selected for use in the present invention provide especi~lly effective dye ~l~r~. inhibition performance bel~rl~ when used in colllbil~tion with the selectP~l polymeric dye ,l~r~r inhibiting agents hcleillbcfore dcsclibed. The colllbi~ ion of such sel~ polymeric materials (e.g., PVNO and/or PVPVI) with such sele~ d optical bri~l.t~ ~rls (e.g., Tinopal UNPA-GX, Tinopal SBM-GX and/or Tinopal 3Q AMS-GX) provides signifir~ntly better dye transfer inhibition in aqueous wash solutions than does either of these two dete~gent composition colllpoll..lts when used alone. Without . ~

being bound by theory1 it is believed that such brigl.lPrl ., 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 brighlene.~, deposit on fabrics in the wash solution can be defined by a pararneter called the "exh~ lstion coefficient". The exhqlJstion coefficient is in 5 general as the ratio of a) the br;gl~ material deposited on fabric to b) the initial brigl.l~ nf ~ conc..~ tion in the wash liquor. Bri~ f .~ with relatively high e xh-qn~tion coefficients are the most suitable for inhibiting dye ~ ,r~. in the context of the present invention.

10 Of course, it will be appl~ciated that other, conventional optical brightf nPr types of co...pou,lds can optionally be used in the present cclllposilions to provide conv.ul;Qnql fabric '~briehtnf ss~ benef~" rather than a true dye ~ r~. inhibiting effect. Such usage is conventional and well-known to dcl~ lg~nt formulations.

15 Chf 1~ Ag~nt~

The df te~gf ~1l compositions herein may also optionally contain one or more iron and/or nf'Sf. rh~l~li"~ agents. Such chelating agents can be selec~ed from the group cnnC;~ of amino car'ooxylates, amino phospho~ s~ polyfunctionally-s~lbsl;n.~d aro-20 matic chFl~ agents and mixtures therein, all as hereinafter defined. Without intf n~lin~to be bound by theory, it is believed t'nat the benefit of these rnaterials is due in part to their exce~lional ability to remove iron and l..~eAn~se ions from WdShing solutions by forrnqtion of soluble chfl~t. r7 25 Amino carboxylates useful as optional ch~lAI ;-~g agents include ethylen-P~ . aretA~ s, N~ lro~lethylen-P~ ..;n. h;~et-q-t~s, nitrilo~ fs, ethyl~ ~fliA~...n~
t~ a~iO~IiOnateS~ triethYIen~te~ hr}~ et-q-t~OS~ diethYIe~ ;n~PenlA-qret~qtPS, and eth~ lycines, aL~cali metal, ~.. nn;.~.. " and ~ub~lilut~d qmmonillm salts therein . nd lUlCS therein.

Amino phosphonqtes are also suitable for use as ch-Pl-q-ting agents in the compositions of the invention when at least low levels of total phosphorus are ~I.liued in d~t~ ,enlcolllposilions, and include ethylen-P~iq-min-Pt~Ptrakis (methylenephosphol~hs) as DEQUEST.
~ fe,l~d, these amino phosphonates to not contain alkyl or aLkenyl groups with more than 35 6 carbon atoms.

WO 97143394 PCTtUS97/08445 Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et ah P~f.,.l~,d compounds of this type in acid form are dihydroxydisulfobenzel~es such as 1,2-dihydroxy-5 3,5-disulfobel~Le.l~.

A y~efe.l. d biodegradable chelator for use herein is ethylen~ min~ disuccinate ("EDDSn), especiqlly the [S,S] isomer as dcsclibed in U.S. Patent 4,704,233, Nove~
3, 1987, to Hartman and Perkins.
The compositions herein may also contain water-soluble methyl glycine .1i~retir acid (MGDA) salts (or acid form) as a chelant or co-builder useful with, for example, insoluble builders such as zeolites, layered .cilir~e~.

If Utili7~1, these chr!~ agents will generally co,--y.ise from 0.1 % to 15 % by weight of the dcte~ge.ll con.yosilions herein. More p~efelably, if lltili7Pf1, the chP~ agents will co.l.y.ise from 0.1 % to 3.0% by weight of such comyosilions.

Suds Suy~)~ssors Conlyo~ ds for reducing or ~uyyu~,~sillg the formation of suds can be incolyolal~d into the colll~osilions of the present invention. Suds ~iUyp~eSsioll can be of particular irnportance in the so-called "high COllC~.~t~aliOl1 cle~ni~ process" as described in U.S. 4,489,455 and 4,489,574 and in front-loading Eul~l~ean-style washing m~rllin.os.
A wide variety of materials may be used as suds sLIl~plessors, and suds ~uyyleSSOrS are well known to those skilled in the art. See, for ex~--yle~ Kirk Otluner Encyclopedia of Ch~mi~l Te~hn~ gy~ Third Edition, Volume 7, pages 430~47 (John Wiley & Sons, Inc., 1979). One catL~o.~ of suds ~uy~lesso~ of particular interest encol~p~cses Illolloc~l,oxylic fatty acid and soluble salts therein. See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The ...onoc~.boxylic fatty acids and salts thereof used as suds ~uyylessor typically have hy-lroc&-l~yl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the aLkali metal salts such as so ~ m, pot~csillm~ and lithium salts, and an,..lon,ull, and a1~canola,l,moluum salts.

WO 971433g4 PCT/US97/08445 The det~ e.ll compositions herein may also contain non-surfactant suds suppressors.
These include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic Clg-C40 ketones (e.g., ~l~alone), eu. Other suds inhi~ilors include N-alkylated amino S lli~il.es such as tri- to hexa-alkylm~l~min~s or di- to tetra-alkyl~ min~ chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or sccondalr amine cont~ini~ 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monost~ryl alcohol phos~h~te ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters. The hydl~carl,ons such as pa,arrl" and halolJararful 10 can be utilized in liquid form. The liquid hydroc~l,ons will be liquid at room tc~llpelatllle and atmosph.,lic p~ u~, and will have a pour point in the range of 40~C and 50~C, and a l..in;....~ boiling point not less thanllO~C (atmo~l,}~lic ~ s~e). It is also known to utilize waxy hydrocarbons, preferably having a ...~ ..g point below 100~C. The hy-llvc~l,u"s constitute a plefel,~d Cà~gOlr of suds supp.~sûr for dct~lg~ t 15 col,.posiliolls. Hydrocalllol1 suds su~ ssors are dcs.,libed, for example, in U.S. Patent 4,265,779, issuedMay5, 1981 toGandolfoetal. Theh~ocall,ons, thus, include ~lirh~tir, alicyclic, aromatic, and het~,.~yclic satula~d or unsaturated h~ldlocd,l,olls having from 12 to 70 carbon atoms. .The term "pdlaîrlll," as used in this suds ~upl)ressûr ~ic~-..csion, is intPn~ed to include nIL~lUIeS of true paraffins and cyclic hydrocdrl,ulls.
Another plcf~.lcd cdtegolr of non-surfactant suds ~ulJplessors comprises silicone suds ~U~pl~SSvl~. This category inrllld~s the use of polyor~allosiloxane oils, such as polydill~ hylsiloxane, dis~.~ions or em~lcions of polyorganosiloxane oils or resins, and co."b~ations of polyo,g~-o~iloxqn~ with silica particles wll~.eil1 the polyorganosiloxane is 25 c~ o,l~ or fused ûnto the silica. Silicone suds ~u~p~ssors are well known in the art and are, for e~u~>le, ~;~1QS~1 in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and ~o~ Patent Application No. 89307851.9, published Pebruary 7, 1990, by Starch, M. S.

30 Other silicone suds ~u~pressol~ are disclosed in U.S. Patent 3,455,839 which relates to compositions and processes for defoaming aqueous solutions by inco.~.~lating therein small of polydil~ lsiloxane fluids.

Mixtures of silicone and sil~qnqt~d silica are desclil~d, for incl~ e, in German Patent Application DOS 2,124,526. Silicone defoa.nel~ and suds controlling agens in granular detelge-~t compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al, and in U.S.
Patent 4,652,392, R~gin~ki et al, issued March 24, 1987.

An exemplary silicone based suds ~u~yl.,ssor for use herein is a suds SU~pl~SSillg amount of a suds controlling agent col-c;~ sse~ 1y of:
(i) polydu-,.,lhylsiloxane 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 co.l,~osed of (CH3)3SiO1/2 units of SiO2 units in a ratio of from (CH3)3 SiO1/2 units and to SiO2 units of from 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 ~lefe.l~,d silicone suds ~upplessor used herein, the solvent for a contimlo~-~
phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol 15 copolymers or ~ ules thereof (~l~f~ ,d), or polyl,~o~lene glycol. The primary silicone suds ~upplessor is b~ hed/crosslinl~d and preferably not linear.

To illustrate this point further, typical liquid laundry d~.t~.ge.ll co.llposilions with controlled suds will optionally co~JI,lise from about 0.001 to about 1, preferably from 20 about 0.01 to about 0.7, most pl~fe.~bly from about 0.05 to about 0.5, weight % of said silicone suds sllyplessor~ which comprises (1) a nonaqueous emulsion of a primary ~lliroa.ll agent which is a ~ , of (a) a polyolg~nosiloxane, ~b) a resinous siloxane or a siliccn~ resin-pro~uci~ silicone colll~ul.d, (c) a finely divided filler material, and (d) a catalyst to proll-~le the reac~iol~ of Ini~UI~ components (a), ~b) and (c), to forrn silanolates;
25 (2) at least one ~ ;o~iC~ siliron~ ~.ur~c,~ll; and (3) polyethylene glycol or a copolymer of polyethylene-poly~lop,lene glycol having a solubility in water at room te~llpel~lule of more than about 2 weight %; and without polypropylene glycol. Similar amounts can be used in granular co~osi~io~, gels, etc. See also U.S. Patents 4,978,471, Starch, issued Dec~ 18, 1990, and 4,983,316, Starch, issued January 8, 1991, 5,288,431, Huber et 30 al., issued I~eblu~ 22, 1994, and U.S. Patents 4,639,489 and 4,749,740, Aizawa et al at column 1, line 46 through column 4, line 35.

The silicone suds ~u~ lessor herein preferably co..ll,lises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular weight of less than about 1,000, preferably between about 100 and 800. The polyethylene CA 022SSoOS 1998-11-17 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, most preferably ,ell 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300. Pr~fe,l~,d is a weight ratio of ~I~ n about 1:1 and 1:10, most preferably ~t~ .n 1:3 and 1:6, of polyethylene glycol:copolymer of polyethylene-polypropylene glycol.
The preferred silicone suds SulJ~iessolS 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 L101.

15 Other suds auppl~ SSOl~ useful herein conlplise the secondary alcohols (e.g., 2-alkyl aL~canols) and ll~h~lures 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-C16 aLkyl alcohols having a Cl-C16 chain. A ~r~fe.l~,d alcohol is 2-butyl octanol, which is available from Condea under the llade~ ISOFOL 12. Mixtures of secondary alcohols20 are available under the trademark ISALCHEM 123 from F.nif ll~rn. Mixed suds s,~ .ssors typically collll,lise nli~ules of alcohol + silicone at a weight ratio of 1:5 to 5:1.

For any d,_ler~,elll conlrositionc to be used in automatic laundry or dishwashing m~hin~s, 25 suds should not form to the extent that they either overflow the wdShillg ~ C~ or negatively affect the washing ...~ ... of the dishwasher. Suds suppressors, whenili7Pd, are preferably present in a "suds :~up~-essing ~mollnt. By "suds supl)~ssing ~mmlnt" is meant that the formulator of the composition can select an amount of this suds controlling agent that will s~ffi~iently control the suds to result in a low-sudsing laundry or 30 dishwashing detelgel.ls for use in " ~lo~ r laundry or dishwashing m~ in~s.

The colllposi~ions herein will generally comprise from 0% to 10% of suds ~u~ essor.
When utili_ed as suds ~u~L"essol~, monocarboxylic fatty acids, and salts therein, will be present typically in amounts up to 5 %, by weight, of the d~lergen~ composition.35 Preferably, from 0.5% to 3% of fatty monocarboxylate suds sul l"essor is utili_ed.

Silicone suds au~ressors are typically utilized in amounts up to 2.0%, by weight, of the deterge.,l composition. although higher amounts may be used. This upper limit is practical in nature, due primarily to conc~ll, with k.,epin~ costs minimi7eC~ and effectiveness of lower ~mountC for effectively controlling sudsing. Preferably from 0.01 % to 1 % of silicone suds ~up~ssor is used, more preferably from 0.2S% to O.S%. As used herein, these weight ~,~;c.,Lage values include any silica that may be urili7~-l in co",bination with polyolganosiloxane, as well as any optional materials that may be utilized. Monostearyl phosph~te suds Sup~l~SSO15 are generally utilized in amounts lan~ing from 0.1 % to 2%, by weight, of the composition. Hydl~ocallJon suds ~upp,~ssors are typically utilized in 10 ~ o~ r~l~h~g from 0.01 % to 5.0%, ~Ithol)gh higher levels can be used. The alcohol suds ~upplessors are typically used at 0.2%-3% by weight of the finich~d compositions.

AlkoxYlated PolycarboxYlates 15 ALlcoxylated pol~;a~l,o~ylates such as those ~ ,d from polyacrylates are useful herein to provide additional grease removal p~Ç~.I.llal~ce. Such materials are desclibed in WO
91108281 and PCT 90/0181S at p. 4 et seq., incorporated herein by refel~.lce.
Ch~o~nir~lly, these materials colllplise polyacrylates having one ethoxy side-chain per every

7-8 acrylate units. The side-chains are of the formula -(CH2CH20)m(CH2)nCH3 wlie.~,in 20 m is 2-3 and n is 6-12. The side-chains are ester-linked to the polyacrylate "bacl~bone" to provide a "comb" polymer type structure. The molecular weight can vary, but is typically in the range of 2000 to 50,000. Such alkoxylated polycar~oxylates can colllylise from 0.05% to 10%, by weight, of the compositions herein.

25 Fabric Sor~n~.~

Various through-tlle-. ~sh fabric sor~e.~, ecpeci~lly the imr~lp~hle S...~C~ clays of U.S.
Patent 4,062,647, Storm and Nirschl, issued Dec~-..her 13, 1977, as well as other softener clays known in the art, can optionally be used typically at levels of from 0.5% to 10% by 30 weight in the present co~ o~il;onc to provide fabric softener ~n~fi~ co~i~;ull.,.llly with fabric cl~w.g. Clay sur~el~ can be used in co.llbil~tion with an~ine and cationic softeners as Aisclose~1. for t;A~Ilyle, in U.S. Patent 4,375,416, Crisp et al, March 1, 1983 and U.S. Patent 4,291,071, Harris et al, issued Se~t~.l.ber 22, 1981 35 ~. rwlles WO 97/43394 PCTtUS97/08445 Perfumes and perfumery ingredients useful in the present compositions and processes comprise a wide variety of natural and synthetic ch~mi~q-l ingredients, in~ludin~, but not limited to, aldehydes, ketones, esters Also in~ ded are various natural extracts and 5 ess~ r~s which can con~lise complex ~ ul'~S of ingredients, such as orange oil, lemon oil, rose extract, lavender, musk, p~. hollli, bal~qmi~ essc .~e, sandalwood oil, pine oil, cedar Finished pe.rw-Rs can comprise ~l.c.llcly complex mixtures of such ingredients Finished pc.rull.cs typically COIIl~lisc from 0 01% to 2%, by weight, of the dete~el.l composiliulls herein, and individual p~ru~ y ingredients can co..lplise from 0 0001% to 10 90% of a r. .iChrd pelrunlc co.llposilion.

Non-limitin~ ples of pe.rulllc ingl~di~ s useful herein include: 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7 tel.~ne~.yl ~-aph~ PnP; ionone methyl; ionone gamma methyl; methyl cedrylone; methyl dihydrojasmonate; methyl 1,6,10-l-i.1,~ 1-2,5,9-cyclo~lod~P~q~rien-1-yl ketone; 7-acetyl-1,1,3,4,4,6-hP~ hyl tetralin; 4-acetyl-6-tert-butyl-l,l~imethyl indane; para-hydroxy-phenyl-b~ .-on~ zoph~nolx; methyl beta-naphthyl ketone; 6-acetyl-1,1,2,3,3,5-h ~ 1 indane; 5-acetyl-3-iso~.opyl-1,1,2,6-te~ l-yl indane; l-do~Pcqnql~ ~(4-hydroxy4-u~ll.yl~ yl)-3-cyclohexene-1-carboxaldehyde; 7-hydroxy-3,7~i n~ yl ocqt~n-q-l; 10-~ ce~--l-al; iso-hexenyl cyclohexyl carboxaldehyde; formyl tricyclodecqnP; con~len~qtiQn products of hydroxycitronellal and methyl al,lh,allllate, co~ F ~ on pi~lu.;~ of hydroxycitronellal and indol, con~encqtion products of phenyl ~cet-q~ hyde and indol; 2-methyl-3-(para-tert-butylph~.-~l)-propionaldehyde; ethyl vanillin; heliotropin; hexyl C-~-n~n-il~ aldehyde; amyl ci~-n~ ~ ir aldehyde; 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; COUIl~lill; ~lec-q-l""tone g,qmm~; cyclopent-dec~n~ P; 16-L~d~o~y-9-hPY d~e~-oic acid lactone; 1,3,4,6,7,8-hexahydro4,6,6,7,8,8-kf~ lcyclopenta-~amm~ 2-h.,~opyrane; h-eta-naphthol methyl ether; ambroxane; ~Pc~hydro-3a,6,6,9a t~ t~a.nell.ylnaphtho[2,1b]furan; cedrol, S-(2,2,3-Llh~l.,LI-ylcyclopent-3-enyl)-3-methylpentan-2-ol; 2-ethyl-4-(2,2,3-t.hll~tllyl-3-cyclopel.le.l-1-yl)-2-buten-1-ol; caryophyllene alcohol; tricyclodecenyl propionate; tricyclodecenyl acetate; henzyl salicylate; cedryl acetate; and para-(tert-butyl) cyclohexyl acetate.

Particularly ~ref.,~, d ~,ru l.e materials are those that provide the largest odor improve,l,~ s in fini~hPd pr~lucL colllposilions cont~inin~ cellulases These ~Çullles include but are not limited to: hexyl cinn~mic aldehyde; 2-methyl-3-(para-tert-butylphenyl)-propionaldehyde; 7-acetyl-1,2 ,3 ,4,5 ,6,7 ,8-octahydro-1, 1 ,6,7-tl ~l~ne~.yl n~phth~1ene; benzyl salicylate; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin; para-tert-butyl cyclohexyl acetate; methyl dihydro jasmonate; beta-napthol methyl ether; methyl beta-naphthyl ketone; 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; 1,3,4,6,7,8-hexahydro-4,6,6,7,8.8-h~s~m~thyl-cyclopenta-g~mm~ 2-bellzopyrane; do~ec~hydro-5 3a,6,6,9a-tellalllel]lylt~ hlllo[2~lb]fura~ nic~l~ellyde; COIllllalin; cedrol; vanillin;
cyclopent~ ec~n~lide; tricycloA~cenyl acetate; and tricyclodecenyl propionate.

Other pe.ru---c ~..ate.ials include ~ccenti~t oils, resinoids, and resins from a variety of sources inrlu-ling, but not limited to: Peru bqlc~m~ Olih~m~m r~si~loid, styrax, l~1~1~l..l...
10 resin, nutmeg, cassia oil, benzoil- resin, coriander and lavandin. Still other ~.rull.e ch~mir~1c include phenyl ethyl alcohol, l~ eol, linalool, linalyl acetate, geraniol, nerol, 2-(l,l-dimethylethyl)-cyc1Oh~ nol acetate, benzyl acetate, and eugenol. Carriers such as diethylrhthql~te can be used in the r..~;~h~d pe.r~,ll.e co~ o~ ;o~-c.

15 Other Ingl~,di.,ll~

A wide variety of other i-~l~;di.n~ useful in det~,.ge.ll co..ll os;~ions can be inrl~ eA. in the co~,.posi~ions herein, inrh1Ain~ other active in~l~,die.~, carriers, hydlo~lopcs, processing aids, dyes or E);gl~ t~, solvents for liquid forrnlll~tions, solid fillers for bar compositions, 20 etc. If high sl~Aci~ is desired, suds boosters such as the Clo-C16 aL~canol~miAes can be h1col~ ated into the co...pos;liol-c, typically at l %-10% levels. The C lo-Cl4 and ~ nol amides illustrate a typical class of such suds boosters. Use of such suds boosters with high s~cing optional s~ r~ such as the amine oxides, betaines and s~1t~ir Pc noted above is also advantageous. If desired, water-soluble I.. agnf S;ll~.~ andJor c~lri1~rn salts such as MgC12, MgSO4, CaC12 CaS04, can be added at levels of, typically, 0.1%-2%, to provide additional suds and to enh~nre grease removal p~lrOI.l~.

Various detersive ingredients employed in the present co.~pos~;ons optionally can be 30 further stabilized by absoll,mg said i~l~dic.~ onto a porous hydrophobic substrate, then coating said substrate with a hyd~ ,hobic coating. Preferably, the detersive ingredient is a~1miYed with a surfactant before being absorbed into the porous ~ul~ te. In use, the detersive i~l~die.ll is .~leased from the substrate into the a~ons washing liquor, where it pe.ro~ s its int~n3ed detersive fimrtjon To illustrate this techniq-le in more detail, a porous hydrophobic silica (tr;~emqrk SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution cont~inin~ 3%-5% of C13 15 ethoxylated alcohol (EO 7) nonionic surfactant. Typically, the c.~lne/surfactant solution is 2.5 X the weight of silica. The resl~ltin~ powder is dijl,el~ed 5 with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used). The res~lltin silicone oil di~el~ion is em~lcifi~od or otherwise added to the final dete.ge,ll matrix. By this means, ingredients such as the afole.... ~lioned enzymes, bleaches. bleach activators, bleach catalysts, photoactivators, dyes, lluolesc~"~, fabric conditioners and hydrolyzable ~ul r.~ tc can be "p~ot~,c~,d" for use in dct.lgellts, 10 in~lu~lin~ liquid laundry det~l~gel~l colll~osilions.

Liquid d~l.,lg.,ln colllpos;l;~ c can contain water and other solvents as Cdlli.,l~. Low molecular weight primary or secondary alcohols exemplified by ...~ ol, ethanol, I,rop~ol, and isopr~l,~,ol are suitable. Monohydric alcohols are p~fell~ for solubilizing 15 sulra~ t, but polyols such as those cont~inir~ from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups (e.g., 1,3-pro~ iol, ethylene glycol, glycerine, and 1,2-prop~-~iol) can also be used. The co,upo~i~;orl~ may contain from 5% to 90%, typically 10% to 50%
of such carriers.

20 The det~ ,~ cou~po~ nc herein will preferably be forrml1~d such that, during use in a(ll)eollC cle~ning opelaliolls, the wash water will have a pH of between 6.5 and 11, p,~fe.~bly ~ 7.5 and 10.5. Liquid dishwashing product formulations preferably have a pH ~t~ ,n 6.8 and 9Ø Laundry products are typically at pH 9-11. Tec~lni~lues for controlling pH at r.~o~ d usage levels include the use of buffers, alkalis, acids, 25 etc., and are well known to those skilled in the art.

Granules ~ re Adding the bis-alkoxylated cationics of this invention into a clulchcl mix, followed by 30 col~ lional spray drying, helps remove any residual, I,oterltially malodorous, short-chain amine co~ lc. In the event the formulator wishes to pl.,pale an ~miY~ble particle cont~ini~ the aL~oxylated c~l;o.~irs for use in, for example, a high density granular de~r~nl, it is l,l.,f,.led that the particle composition not be highly ~Ik~lin~o. Processes for piCp~i~lg high density (above 650 g/l) granules are desclibed in U.S. Patent 5,366,652.
35 Such particles may be form~ d to have an effective pH in-use of 9, or below, to avoid the odor of in,lJu-ily amines. This can be achieved by adding a small ~mo~nt of acidity source such as boric acid, citric acid, or the like. or an a~ ol,liate pH buffer, to the particle. In an alternate mode, the prospective problems associated with amine malodors can be m~c~d by use of perfwne ingredients, as disclosed herein.

Examples The following examples are illustrative of the present invention, but are not meant to limit or otherwise define its scope. All parts, ~ ges and ratios used herein are e~r~ssed 10 as ~ent weight unless otherwise specified.

In the following examples, the abbreviated component i-le~-~;r.r-lions have the following ,..P~ni~e.~

LAS : So~ m linear C12 aL~cyl b~ n~ sulfonate TAS : Sodil~m tallow allcyl sulfate C45AS : So~ m C14-C1s linear alkyl sulfate CxyEzS : .Sodi~m Clx-C1y bl~lched alkyl sulfate co--A~ ~e~ with z moles of ethylene oxide C4SE7 : AC14 15 predo.. ~in~tly linearprimary alcohol co~-A~ ed with an average of 7 moles of ethylene oxide C25E3 : A C12 15 branched primary alcohol co.-A~n~ed with an average of 3 moles of ethylene oxide C25E5 : A C12 15 ~l~ched primary alcohol conAPnc~Pd with an average of 5 moles of ethylene oxide CocoEO2 : Rl.N+(cH3)(c2H4oH)2 with Rl = C12 ~

Soap : Sodium linear alkyl carboxylate derived from an 80/20 mi~lule of tallow and coconut oils.
TFAA : C16-C18 alkyl N-methyl glllc~miA~P
TPKFA : C12-C14 topped whole cut fatty acids STPP : Anhydrous sodium tripolyphosphate Zeolite A : Hydrated Sodium ~ minosilicate of forrnula Nal2(A1~2Si~2)12- 27H20 having a primary particle size in the range from 0.1 to 10 NaSKS-6 : Crystalline layered silicate offonnula ~ -Na2Si20S
Citric acid : A~ dlous citric acid Carbonate : Anhydrous sodium calbol~t. with a particle size ~ 200~1m and 900~1m BicalL,unate : Anhydrous sodium bicarbonate with a particle size di~llibulion ~l..__n 400~1m and 1200~m Silicate : Amorphous SoAil~m Silicate (SiO2:Na2O; 2.0 ratio) Sodium sulfate : Anhydrous sodium sulfate Citrate : Tri-sodium citrate dihydrate of activity 86.4%
with a particle size dis~ ion ~t~ ,n 425~1m and 850 llm MA/AA : Copolymer of 1:4 maleic/acrylic acid, average molecular weight 70,000.
CMC : So li~m carboxymethyl ce~ lose d5e : Proteolytic C~ 111_ of activity 4KNPU/g sold by NOVO Ind~ if s A/S under the tradf~ n~
Savinase Alcalase : Proteolytic e.~llle of activity 3AU/g sold by NOVO L~llif s A/S
Cçlll.lsc.... : Cellulytic c.lL~llle of activity 1000 CEVU/g sold by NOVO IJ~ ies A/S under the tra(lf~ .. r Carezyme Amylase : Amylolytic enzyme of activity 60KNU/g sold by NOVO Industries A/S under the ~ f n-.nr Tennamyl 60T
Lipase : Lipolytic el~llle of activity 100kLU/g sold by Lipolase WO 97/43394 PCT/USg7/08445 Endolase : Endoglunase enzyme of activity 3000 CEVU/g sold by NOVO Industries A/S
PB4 : Sodium pe,bG,~te te~rahydrate of nominal formula NaBo2.3H2o-H2o2 PB1 : Anhydrous sodium perborate bleach of nominql formula NaBo2.H2o2 Pe..,all,ollate : Sodium r~rc~l~O~IA~ of nominal formula 2Na2C03 3H2~2 NOBS : Nonanoylo~yl~ sulfonate int_e formof the sodium salt.
TAED : Tetraacetylethyk.-P~ .. inP
DTPMP : Diethylene ~ e penta (methyhne phosphon~~), llla~ d by Monsanto under the Trade name Dequest 2060 Photoactivated bleach: Sulro.~t~d Zinc Phthaloc~rani~ ell~a~ t~
in bleach dextrin soluble polymer Bri~l~lfner 1 : Di~o~ m4,4'-bis(2-sulphostyryl)biph~,~l 13l igl~ 2 : Disodium 4,4'-bis(4-anilino~-morpholino-1.3.5-triazin-2-yl)amino) stilbene-2:2'-disulfonate.
HEDP : 1,1-hydro~yelllane dil,hosl,honic acid PVNO : Polyvi~ll,yridine N-oxide PVPVI : Copolymer of polyvinylpyrrolidone and vinyli..~ ole SRA 1 : SulÇobe~o~l end capped esters with oxyethylene oxy and t~ hll.~loyl bacl~l~n~
SRA 2 : Diethoxylated poly (1, 2 propylene lele~hll,alate) short block polymer Silicone aJ liroa~.l: Polydimethylsiloxane foam controller with ~ilo~r~nP-oxyaLkylene copolymer as di~ g agent with a ratio of said foam controller to said di~ sing agent of 10:1 to 100:1.

In the following Examples all levels are quoted as % by weight of the composition.

EXAMPLE I

The following d~tergent formulations according to the present invention are ~re~aled, where A and C are phosphorus-cont~inin~ del~ rge.lt compositions and B is a zeolite-cont~ininp dele.ge.lt composition.
B C
Blown Powder STPP 24.0 - 24.0 Zeolite A - 24.0 C45AS 8.0 5.0 11.0 MA/AA- 2.0 4.0 2.0 LAS 6.0 8.0 11.0 TAS 1.5 CocoMeEO2~ 1.5 1.0 2.0 Silicate 7.0 3.0 3.0 CMC 1.0 1.0 0.5 Bri~h~r.~r 2 0.2 0.2 0.2 Soap 1.0 1.0 1.0 DTPMP 0.4 0.4 0.2 Spray On C45E7 2.5 2.5 2.0 C25E3 2.5 2.5 2.0 Silicone a~liro~.l 0.3 0.3 0.3 F~.ru.l~e 0.3 0.3 0 3 Dry additives Carbonate 6.0 13.0 15.0 PB4 - 4.0 10.0 PB1 4.0 0 ~ICa~ 18.0 18.0 21.0 TAED 3.0 3.0 Photo~rtivated bleach 0.05 0.05 0.05 aSC 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.25 0.30 0.15 sodium sulfate 3.0 3.0 5.0 R~l~n-~e (Moisture &
Miscellaneous) To: 100.0 100.0 100.0 Densi~y (g/litre) 630 670 670 *The bis-AQA-l (CocoMeEO2) surfactant of the Example may be replaced by an 5 equivalent amount of any of surfact~ntc bis-AQA-2 through bis-AQA-22 or other bis-AQA
surf~t~nt~ herein.

EXAMPLE II
The following dete.~ t form~lqtions, according to the present invention are 10 ~ alC~:
D E F
Zeolite A 30.0 22.0 6.0 Sodium sulfate 19.0 5.0 7.0 MA/AA 3.0 3.0 6.0 LAS 13.01 1 .0 21 .0 C45AS 8.0 7.0 7.0 CocoMeEO2* 1.0 1.0 1.0 Silicate - 1.0 5.0 Soap - - 2.0 Bri~ht~n~r 1 0.2 0.2 0.2 Carbonate 8.0 16.0 20.0 DTPMP - 0.4 0.4 C45E7 1.0 1.0 1.0 PVPVI/PVNO 0.5 0.5 0.5 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Arnylase 0.1 0.1 0.1 Ce~ lq~e 0.1 0.1 0.1 NOBS - 6.1 4.5 PB1 - 2.0 4.1 Pl.. ~o~ ated bleach 1.05 0.5 0.2 Sodium sulfate - 6.0 n~e (Moisture & ~ cell~nPous) To: 100 100 100 PC~rrUS97/08445 *The bis-AQA-l (CocoMeEO2) surfactant of the Example may be replaced by an equivalent amount of any of surfactants bis-AQA-2 through bis-AQA-22 or other bis-AQA
surfactants herein.

EXAMPLE m The following high density dete~gellt formulations, according to the p~esent invention are ple~ d:
G H
Blown Powder Zeolite A 15.0 15.0 15.0 Sodium sulfate 0.0 5.0 0.0 LAS 3.0 3 0 3 0 CocoMeEO2~ 1.0 1.5 1.5 DTPMP 0.4 0.4 0.4 MA/AA 4.0 2.0 2.0 Agglo~ al~:S
LAS 5.0 5 0 5 0 TAS 2.0 2.0 1.0 Silicate 3.0 3.0 4.0 Zeolite A 8.0 8.0 8.0 Call,Gnate 8.0 8.0 4.0 Spray On E~-ru~e 0.3 0.3 0.3 C45E7 2.0 2.0 2.0 C25E3 2.0 - -Dry additives Citrate 5.0 - 2.0 Bicdl~lLat~ - 3.0 Carbonate 8.0 15.0 10.0 TAED 6.0 2.0 5.0 PBl - 2.0 3.6 Photoactivated bleach 1.0 0.75 0.5 Polyethylene oxide of MW 5,000,000 - - 0.2 Bentonite clay - - 10.0 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0 4 Amylase 0.6 0.6 0.6 Ce~ e 0.6 0.6 0.6 Silicone a~ltifo~ll 5.0 5.0 5 0 Dry additives Soli~m sulfate 0.0 3.0 0.0 R~l~n~e (Moisture &
~i~cell~n~ous) To:100.0 100.0 100.0 Density (g/litre) 850 850 850 *The bis-AQA-1 (CocoMeEO2) surfactant of the Example may be ~placed by an 15 equivalent amount of any of slll r~ bis-AQA-2 through bis-AQA-22 or other bis-AQA
~ulr~el; ..l~ herein.

EXAMPLE IV
20 The following high density dete.~ t formulations according to the present invention are d:

M N
Blown Powder Zeolite A 2.5 2.5 So~ m sulfate 1.0 1.0 Coc~o~r-r.02~ 1.5 1.5 om~orate C45AS 11.0 14.0 Zeolite A 15.0 6.0 Carbonate 4.0 8.0 MA/AA 4.0 2.0 CMC 0.5 0.5 DTPMP 0.4 0 4 Spray On Wo 97/43394 ~.ru~ O
Dry Adds HEDP 0.5 0.3 SKS 6 13.0 10.0 Citrate 3.0 1.0 TAED 5.0 7.0 PB1 8.0 15.0 Photoactivated bleach 0.27 0.8 SRA 1 0.3 0.3 ~ot~ase 1.4 1.4 Lipase 0.4 0.4 Cellul. se 0.6 0.6 Amylase 0.6 0.6 Silicone ~,tiroaLu 5.0 5.0 igl.l~ nf- 1 0.2 0.2 Brigh~nPr 2 0.2 Rqlqn~e (Moisture &
~Siccellqn~ool~c) To: 100 100 Density (g/litre) 850 850 *The bis-AQA-l (CocoMeEO2) ~Çhc~lt of the Ex. mple may be replaced by an equivalent ~mount of any of ~"~ r ~ bis-AQA-2 through bis-AQA-22 or other bis-AQA
~ulr; ~r~"1~ herein.

EXAMPLE V

The following hand w. sh d~bc~g~ form~lq~ion~ acco~i,lg to the present invention, are d by mi~cing the ingre~ie,l~ tGg~ r in tne ~lcelllage weight 5'~1U~ as in~irq-~below.

A B C D
LAS 15.0 12.0 15.0 12.0 TFAA 1.0 2.0 1.0 2.0 C25E5 4.0 2.0 4.0 2.0 CA 02255005 1998-ll-17 PCTrUS97tO8445 AQA-9* 2.0 3.0 3.0 2.0 STPP 25.0 25.0 15.0 15.0 MA/AA 3.0 3.0 3.0 3.0 CMC 0.4 0.4 0.4 0 4 DTPMP 1.0 1.6 1.6 1.6 Cal~n~t~ 2.0 2.0 5.0 5.0 Bic~l~olLa~e - - 2.0 2.0 Silicate 7.0 7.0 7.0 7.0 ~o~a3e 1.0 - 1.0 1.0 Amylase 0.4 0.4 0.4 Lipase 0.12 0.12 - 0.12 Pl-o~o~cl;vated bleach 0.3 0.3 0.3 0.3 Sulfate 2.2 2.2 2.2 2.2 PB1 4.0 5.4 4.0 2.3 NOBS 2.6 3.1 2.5 1.7 SRA 1 0.3 0.3 0.7 0.3 Brigl~r~ ~f ~ 1 0.15 0.15 0.15 0.15 Rqlqnre misc./water 100.0 100.0 100.0 100.0 to 100 AQA-~; May be replaced by any AQA ~u~rac~ described herein. ~f,.led AQAsurf: ~tq-nts for use in this example are those with from 10 to 15 ethoxy groups; for example AQA-10, AQA-16.
s The for~go~ Examples illustrate the present invention as it relates to fabric laullde.illg colllpo~ but are not ;~.t. ~ d to be limitin thereof.

EXAMPLE VI
The following illustrates ll~ Ules of bis-AQA surfactants which can be ~lb~ te~ for the bis-AQA s~r~e~ listed in any of the folegoilg E~ les. As disclosed hereinabove, such I~ lu~.,s can be used to provide a ~ Ull of ~hlrullllallce bcnff.l~ and/or to provide cle~ning compositions which are useful over a wide variety of usage conditions.
is Preferably, the bis-AQA surf~ ntc in such mixtures differ by at least 1.5, preferably 2.5-20, total EO units. Ratio ranges (wt.) for such mixtures are typically 10:1-1:10. Non-limiting examples of such lni~lulcs are as follows.
Components Ratio (~,vt.) bis-AQA-l + bis-AQA-5 1:1 bis-AQA-1 + bis-AQA-10 1:1 bis-AQA-1 + bis-AQA-15 1:2 bis-AQA-1 + bis-AQA-5 + bis-AQA-20 1:1:1 bis-AQA-2 + bis-AQA-5 3:1 bis-AQA-5 + bis-AQA-15 1.5:1 bis-AQA-1 + bis-AQA-20 1:3 Mixtures of the bis-AQA ~ulr ~ i herein with the co..~iponding cationic ~ulr~ 1cwhich contain only a single ethoxylated chain can also be used. Thus, for eY- . 'e, 15 ~ Lul_S of ethoxylated cationic aulr~ of the formula RlN+CH31EO]x[EO]yX~ and R1N+(CH3)2[EO]zX-~ wLe.~,~ Rl and X are as ~licclose-l above and Wll,;~l one of the cationics has (x+y) or z in the range 1-5 preferably 1-2 and the other h_s (x+y) or z in the range 3-100, preferably 1~20, most pre&rably 14-16, can be used herein. Such colllposil;onC advantageously provide ill~)~'OVed dc~.g~ pelrulll.ance (especi~lly in a 20 fabric l~und. .u~g context) over a bloader range of water hal:llleSS than do the cationic ~ulr~r~ herein used individually. It has now been discovered th_t shorter EO c~tionics (e.g., EO2) ill~.o-e the clP~ ~.rull.-a lce of anionic s~llr~ in soft water, ~he~as higher EO cationics (e.g., EO15) act to improve hardness tolerance of anioniC surfa~t~n~c, thereby improving the ck~ pc.rulmar.ce of anionic sulrac~lls in hard water.
25 Co..~Y-~ ;on~l wisdo~ in the d~,t,.ge~y art suggests that builders can olJti l~ze the pc.Çolll~ce "wi-do~." of anionic surf~ ntc. Until now, however, bro~ning the wil~dow to ~ l~O"~p~c~ e~ lly all conditions of water ha~dl1ess has been i l-~ossil~le to achie~e.

30 The laundry dete.ge.ll colll~osilioils p-epaled using one or more Çol~,going COIlllill~liOnS of i~ledien~ can optionally be built with any non-pho~l)hate or phosphate builders, or l..S thereof, typically at levels of from 5 % to 70%, by weight of finich~l C~ )OSilioll.

EXAMPLE VII

The following illustrates mixtures of conventional non-AQA surfactants which can be used in combination with the bis-AQA surfact~ntc in any of the foregoing Examples, but is not int~nll~od to be limiti~ thereof. The ratios of non-AQA sulr~rl~nl~i in the nli}~lu~s are S noted in parts by weight of the ~ racLdlll mixtures.

Mixtures A-C
In~l.,di~ Ratios AS*/LAS 1: 1 AS/LAS 10:1 (pref. 4:1) AS/LAS 1:10 (pref. 1:4) *In the fo.~,going, the plilllary~ s--b~ lly linear AS surfactant can be let,laced by an equivalent A.llO~ of seco~ AS or branched-chain AS, oleyl sulfate, and/or miAIUI~S
thereof, in~lu~ ul~,s with linear, primary AS as shown above. The "tallow" chainlS length AS is particularly useful under hot water co~ ;on~ up to the boil. "Cocon!~tn AS
is l,lef,-l~d for cooler wash ~ ules.

The Illi~lules of alkyl sulfate/anionic surf~t~nt~ noted above are moAifi~d by illCOl~lalillg a nonionic non-AQA surfactant therein at a weight ratio of anionic (total) to nonionic in the range of 25:1 to 1:5. The nonionic ~ulra~ can colll~ e any of the conventional classes of ethoxylated alcohols or alkyl phenols, alkylpolyglycosides or polyhydroxy fatty acid amides (less l)lcf .le~ if LAS is present), or nnA~ s thereof, such as those disclosed hereinabove.
Mixtures D-F
AS*/AES 1:1 AS/AES 10:1 (pref. 4:1) AS/AES 1:10 (pref. 1:4) *Can be replaced by s~-o~ y, ~.a,~ched or oleyl AS as noted above.

30 The Il~L~lUl~,s of AS/AES noted above can be modified by ulCOl~OIdlillg LAS therein at a weight ratio of AS/AES (total) to LAS in the range from 1:10 to 10:1.

The ll~lures of AS/AES or their reslllti~ AS/AES/LAS nlixLules can also be colllbil ed with nonionic surfactants as noted for Mixtures A-C at weight ratios of anionic (total) to nolliol~ic in the range of 25:1 to 1:5.

Any of the foregoing mixtures can be modified by the incorporation therein of an amine oxide surfactant, wherein the amine oxide comprises from 1% to 50 % of the totalsurfactant mixture.

Highly ~ . d co"lbinations of the fo,egoil g non-AQA surf: ~t~ntc will co",~,ise from 3% to 60%, by weight of the total fini~h~d laundry deterg_nt composition. The finich.od culllposilions will l.,ef, .ably co",~,ise from 0.25% to 3.5%, by weight of the bis-AQA
~r~ t.

Claims (19)

WHAT IS CLAIMED IS:

1. A composition comprising or prepared by combining a photobleach, a non-AQA surfactant and an effective amount of a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant of the formula:

wherein R1 is a C8-C18 alkyl or alkenyl moiety, R2 is a C1-C3 alkyl moiety, R3 and R4 can vary independently and are selected from hydrogen, methyl and ethyl, X is an anion, and A
and A' can vary independently and are each C1-C4 alkoxy, p and q can very independently and are integers in the range of from 1 to 30.

2. A composition according to Claim 1 which is prepared by mixing the non-AQA
surfactant and the AQA surfactant.

3. A composition according to Claim 1 or 2 wherein the non-AQA surfactant is an anionic surfactant.

4. A composition according to any of Claims 1 to 3 wherein the ratio of bis-AQA to non-AQA surfactant is from 1:15 to 1:8.

5. A composition according to any of Claims 1 to 4 comprising an additional bleaching agent.

6. A composition according to any of Claims 1 to 5 additionally comprising an oxygen-releasing bleach and a bleach activator.

7. A composition according to any of Claims 1 to 6 additionally comprising a bleach catalyst.

8. A composition according to any of Claims 1 to 7 wherein said bis-AQA surfactant is of the formula where R1 is C8-C18 alkyl, R2 is methyl A and A' are ethoxy or propoxy groups and p and q are each integers of from 1 to 8.

9. A composition according to any of Claims 1 to 8 wherein said bis-AQA surfactant is of the formula where R1 is C8-C18 alkyl, R2 is methyl A and A' are ethoxy or propoxy groups and p and q are each integers of from 1 to 4.

10. A composition according to any of Claims 1 to 9 wherein the formula of the bis-AQA
cationic surfactant is such that p and/or q are integers in the range of from 10 to 15.

11. A composition according to any of Claims 1 to 10 comprising two or more bis-AQA
surfactants, or a mixture of a bis-AQA surfactant and a mono-ethoxylated cationic surfactant.

12. A composition according to any of Claims 1 to 11 comprising two or more non-AQA
surfactants and a mixture of two or more bis-AQA surfactants.

13. A composition according to any of Claims 1 to 12 in a granular, bar, aqueous liquid or non-aqueous liquid, or tablet form.

14. A method for removing soils and stains by contacting said soils and stains with a detergent composition, or aqueous medium comprising said detergent composition, according to any of Claims 1 to 13.

15. A method according to Claim 14 for removing bleach sensitive soil from fabrics.

16. A method according to either of Claims 14 or 15 which is conducted by hand.

17. A method according to any of Claims 14 to 16 which is conducted in an automatic machine.

18. A method for enhancing the deposition or substantivity of perfumes or perfume ingredients onto fabrics or other surfaces, comprising contacting said surfaces with a perfume or perfume ingredient in the presence of a bis-AQA surfactant.

19. A method according to Claim 18 which is conducted using a perfume or perfumeingredient in combination with a a detergent composition comprising a bis-AQA.