CA2254946A1 - Detergent composition - Google Patents

Abstract

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

Description

DETERGEN~ COMPOSITON

Techni~l Field The present invention relates to a detergent cG.~os;tion comprising photobleach, a non-AQA sulrd~;tdnt and an alkoxylated quat~l,.~y ammonium (AQA) cationic surfactant.

l~l~und to the Invention The forrnulation of laundry dct~.~c.lts and other cle~ning co"l~itions pl~sellts a considerable çhqllPn~e~ since modern cou-~it;ons are required to remove a variety of soils and stains from diverse substrates. Thus, laundry detergents, hard surfacecleaners, ch~ oos and other pe~aonal cl~ncing co..,~;l;o~c, hand dishwashing 15 dete.E,~nts and det,.E,cnt ~I~ oc;l;onc suitable for use in ~to~ t;c dishwashers all re~uire the proper s~ and co"lbindtion of ingredients in order to function effectively. In general, such det~-gent col-.poC;~;onc will contain one or more types of surf~t~r~tc which are decigned to loosen and remove different types of soils and stains.
While a review of the lite.dtuçc would seem to indi~?~ that a wide sel~tion of 20 surf~~t~ntc and ~u~ t&ll combin~;Q- s are available to the ~te~ent m~nufactllrer~ the reality is that many such ingl~Jic.l~ are spe~ ity c~-~...ic~lc which are not suitable in low unit cost items such as home-use laundry d, hl~nts. The fact ~ll~ains that most such home-use l~iu~,~ such as laundry deb_.~,enti still mainly co",~.ise one or more of the conve .L;- n~l e~hu.~ ted nonioniG and/or sl~lf: ~ or sulfo2lat~ anionic surf~ct~ntc, 25 P1eJ~ Y due to ~4n~ con~iderations and the need to forrnulate co",~;l;onc which ~une~ion r~conqbly well with a variety of soils and stains and a variety of fabrics.

The lit~ y.~ ~e~l~ that various nil~o~el)-conl~;ning C~tiQ~i~ surf~t~nts would be 30 useful in a variety of cl~nin~ co~c;l;onc Such materials, typically in the form of amino-, amido-, or .~uat~ q-mmorlium or imi~7~1inium co,,.pounds~ are often ~eci~ned for c~q1ity use. Por example, various amino and qll-t~ .,; . y q.,.~..o~lium surfactqntc have been s.~ggesled for use in shamroo co.nl~s;l;onc and are said to provide cos~..e!;c ben~fitc to hair. Other nitrogen-con~inin~ surfactants are used in 35 some laundry d~ nts to provide a fabric softening and anti-static benefit. For the most part, however, the co".~ ..;ial use of such materials has been limited by the W 0 97/43393 PCTrUS97/08441 -~ifficlllty enco~nt~Pred in the large scale manufacture of such compounds. An ~d~itior limi~tion has been the pot~n-i~l pre~ipit~tion of anionic active coll,l)onen~ of the dete.gent co...roS;tion oc~cioned by their ionic interaction with c~tionic surf~rt~r~tc The afore.-lcntioned nQnio~ic and anionic surf~t~-lts remain the major surfactant S co.,.~ f ntc in t~day's laundry co~ ;tionC

The quick and efficiP.nt removal of different types of soils and stains such as body soils, greasy/oily soils and certain food stains, can be problematic. Such soils COlllpli~ a Illi~lUl~ of triglyc~,ndes, lipids, complex poly~e~h~lidçs inorganic salts and 10 lnutein~u~ matter all of which, are to some extent, col.~ d of hydn)phobic moieties and are thus notoriously ~1ifficult to remove. Low levels of hyd~phobic soils and residual stains often remain on the surface of the fabric after w~hing.

A wide variety of ble~l~rs for exarnple peroxygen bleach, ~hlorill~ bleaches and15 photobleaches are cornn~Qnly used in d- t~.b~nt c~ l~5;~ nC in ~drlition to SUlfi~
as m~n~ienPd above. Photobleachs are conven~;Q~ ly used under cu~u~- r~ 5 where laundered fabrics are ~lbj~hcl to c~n~n~ated light sources, such as direct sllnlight as in a line drying ope~tiQn. Photobleach is a relatively mild bleach particularly effective at d~olQu~tion of coloured ~ tnen~s (e.g. in particulate or beverage stains) 20 and removal of colour from the Ol,~alUC residues ~Ccoci~ with body soils. Theb'e3rhiltg power of the photobleach is derived from e~posure to ultra violet s~nli~ht It is bd~;e.l~d that s ~light converts the photoble~-h into an active bl~~h;~g species which then O.i~ic~c coloured stains present on the fabric. One problem lc~ t~d with the use of any 25 bleach, including the phot~bleach is the inability to completely remove residual soil and stain from the surface of the fabric. Succ~scive washing and ~ ~ing coupled withlimited soil removal in the wash c~ n~tf s in a build up of residual soil and stain which further entraps particulate dirt leading to fabric yellowing. Eventually the fabric talces on a dingy ~ r~ which is perceived as ur ~ lc and discar~ed by the 30 con~-~.-. r.

It has been discovered that certain alko~ylated quaternary ~mmoni~m (AQA) c~...~u---lc can be used in various d~t~ nt co...l~c;tionc to boost det~.~,enc~
~.r~"..an~ on a variety of soil and stain types, particularly the hydr~phobic soil types, 35 co,,-~only e-~c~ur~t~ . Un~ct~11y, it ha now been discovered that co~ oc;t;~nc CA 02254946 1998-ll-17 W O 9~/43393 PCT~US97/08441 -Cont~q-ining AQA surf;~qntc and photobleach deliver superior cle-q-ning and ~~ PnPcc pclrol..-ance versus products contqining either t~nQlQgy alone.

The AQA sur~q-r'q~ts of the present invention provide subst-q-ntiql benefits to the 5 formulator, over cqtionic surf~ q-ntc previously known. For eYq-mrle, the AQA
surf~rtqntc used herein provide marked improvement in cle-q-nin~ of "everyday"
greasy/oily hydrophobic soils regularly encountered Moreover, the AQA surf~t~ ltc are cG~ lible with anionic surf~~tqntc cQrnmo~ly used in d~te.gel l co...~ ;Qns such as alkyl sulfate and alkyl ~ e sulfonate; inco.-.patibility with anionic co-~l~n~Pnl~ of 10 the dete~gent co--lpo,;~ n has commonly been the linlitinE~ factor in the use of cqtionic r.- ~I;.n~c previously known. Low levels (as low as 3 ppm in the l~ ,, ;ne liquor) of AQA surf~t-q-ntc gives rise to the benefitc described herein. AQA s~ ntC can be forrn~1qtPd over a broad pH range from S to 12. The AQA surf~rtqntc can be p.~ das 30% (wt.) solutionc which are pumpq~ le, and lhe;~_rule easy to handle in a 15 ~--qrur~ t~ing plant. AQA surf~rtqntc with degrees of etho~ylation above S are som~tim~c p~esent in a liquid form and can ll..,..,fo~ be provided as 100% neat materials. In ~ iti~ n to their ben r~ qn~ling ~.~pe.lies, the availability of AQA
lr~ nlc as highly concPn~ t~,d solutions provides a ,,~bs~.t;~l economic advantage in llanspollation costs. The AQA S.,lll i are also co-~t;ble with various ~ ru"le 20 ingre~icontc~ unlike some ati~ ric S~lr~ known in the art.

It is beli.,~/~ that the greasy/oily soils are effectively soluhi~ d by AQA, thereby aUowing access of the photobleach to the colour bodies in the soil (e.g. entlapp~d pigmPnts) rec~lting in improved soil decolouration. The present invention thus provides 25 a d~ ,u~t c~ t;on which not only delivers superior cl~ning of both hydlophol)ic greasy/oily soils and h~dr~philic coloured soils by way of a d~te.gent co-.~s:t;~
comp~ g a AQA s.,lrd~ nt 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/cationic ,-llr~ nt Ini~lu~s. U.K. 2,040,990, issued 3 Sept., 1980, 5 to A. P. Murphy, R.J.M. Smith and M. P. Brooks, relates to ethoxylated rqtionics in laundry detL.~ents.

Summ-q-~y of the Invention 10 The present invention provides a co...~ci~;Qn comprising or p~d by c~ h..n;np a photobleach, non-AQA surfactant and an effective qmount of an alkoxylated q,J~ yqmmnni--m (AQA) cqti~nic surfactant of the forrnula:

R~ /ApR
N\ X
R2' R3 wherein Rl is a linear, ~I~ ched or s,~b~l;t.-t~ Cg-Clg alkyl, alkenyl, aryl, al~aryl, ether or glycityl ether moiety, R2 is a Cl-C3 alkyl moiety, R3 and R4 can vary in~cprl-de~ y and are s~lc~t~ from h~ en, methyl and ethyl, X is an anion, A is Cl-C4 all~o~y and p is an integer in the range of from 2 to 30.
D~tqil~ De~~ tion of the Invention ph~toblea~h 25 The compositions of the present in~c~.lion cornrri~e a ~hotob'~~h as an css.~r~ti~l feature thereof. Photobl~ches suitable for use herein include sulfonated zinc and/or qlll..,.r.;~ phthq~ ~ines. SeeU.S. Patent4,033,718, issuedJuly5, 19~7to osnhe et al. The phthql~cyanine photoble~hPs are available for example under thetradPnqmP TINOLUX or as zinc phthqlocyanine sulfonate.
In general the phthqlQcyanines can be prepared in the ~~ ner described by Linstead and c~ . Jlh~ as r~ .~ in "Journal of the Chemi~ql Society" (p1719, 1936). As is well hlown, unc~ s~ metal phthql~cyanines are soluble in water to an unus--qlly low CA 02254946 l998-ll-l7 W O 97/43393 PCTrUS97/08441 ' s degree and are the~fole used as pigments. However water solubility can be improved by the introduction of hydrophilic groups such as sulfo, carboxy, or other ~J>~;Iue~
groups into the phthql~cyanine structure by the use of hot oleum. Sulfonated phth~locyanines are useful dyes berq~e they have an affinity for cellulose in the form 5 of either cotton or paper pulp.

As noted he.~;nabo~e, phUhqlocyanines can be readily sulfonated by heating with oleum. Thus zinc and qlumini~m phthqk~ ines which are mo~os~llfonated~
disulfonat~d, trisulfonated and tetrasulfonated can be pl~paç~. The trisulfonated and 10 tetrasulfonated species are piefe~r~d for use as photobklr.h~s The zinc tetrasulfonated and zinc trisulfonated ~hthqlocyanines are most ~ fc~

nt c~ ~c;l;o~ employed herein contain from 0.025 % to 1.25 % by weight, of such bleaches.
Alkn~yl~tPA Oll~t~ ~ Ammonium ~OA) Cationic Sulr;- IAn~

The second ec~nt;~l col.~n~ -~t of the present invention CGlllpli~:S an effective amount of an AQA surfactant of the forrnula:
R~ /ApR
N X
R2/ \R3 wherein Rl is a linear, b~-'ch~d or s~bstil~lt~ al~yl, alkenyl, aryl, ll~ryl, ether or glycityl ether moiety containing from 8 to 18 carbon atoms, preferably 8 to 16 carbon atoms, most preferably from 8 to 14 carbon atoms; R2 and R3 are each ind~ .ntly allcyl groups co~t-~'i~ from 1 to 3 carbon atoms, p-~,fe,~bly me~yl; R4 is ~1r~
25 from h~,,en (t~l~ f~), methyl and ethyl, X~ is an anion such as rhlondr, bromide, methylsvlfvq~r., sulfate to provide e~ neutrality; A is s~lr~ from Cl-C4 allco~y, r~riqlly etho~cy (i.e., -CH2CH2~), pl~Ay, butoAy and ~ ut~sth~,~or, and p is an integer from 2 to 30, p~fe~dbly 2 to 15, more ~lefe~ably 2 to 8, most pl~felably 2 to4.
AQA coll-~unds wherein the hydloc~l,yl substituent R1 is Cg-C12 esp~iqlly Cg-1o,enhqnc~ the rate of disY)lutiQn of laundry granules, es~i~lly under cold water c4l~;t;Qnc~ aSC41llpKu~ with the higher chain length materials. AGcoi~ingly, the Cg-, ... . ., .. . , ... . . . . , . . , .... ~ . ..

W O 97/43393 PCT~US97/08441 C12AQAsurfartqntc may be preferred by some formulators. The levels of the AQA
surf~ q-ntc used to p-e~e finish~i laundry delergent COn~pOSitiOnS can range from 0.1% to 5 %, typically from 0.45 % to 2.5 %, by weight.

5 The present invention employs an ~effective ~mount" of the AQA surf~~tq-ntc toimprove the pe.ru~ anc~ of cl~qning co.~l~sitionc which contain other adjunct ingredients~ By an "effective amount" of the AQAsurfqrtqnts and adjunct ingl~ients herein is meant an amount which is sufficient to improve, either dire~ionqlly orcigtlifirqntly at the 90% confidence level, the ~lÇul,..ance of the clc~ning c~ ~s;tio~
10 against at least some of the target soils and stains. Thus, in a cG...I~s;l;Qn whose targets include certain food stains, the formulator will use sufficient AQA to at least dire~tionqlly improve rl~qning pe.Ço.".ance ag.,inst such stains. Likewise, in ac~ ~C;~;on whose targets include clay soil, the formulator will use sufficientAQAto at least d~l;onqlly impmve clo~ pc~oi.nanc~ ag inst such soil. Importantly, in alS fully-for~n-~lqt~d laundl.~ d~te~ nt the AQAs~l~C'~ can be used at levels which provide at least a directionql improve.,.ent in cl~nil~g ~.Çol-..ance over a wide variety of soils and stains, as will be seen from the data ~ ~nted hereinafter.

As noted, the AQA slll r~ are used herein in d~te~enl co~ ;nnc in 20 cG,.~bir.ation with other detersive su.r~ at levels which are effective for achic~h~g at least a d..C~;on~l improve~l.ent in cleqning pe~l-.-ance. In the conte~t of a fabric laundry c4-..~s;L;nn~ such ~usage levels~ can vary d~ n~ not only on the type and severity of the soils and stains, but also on the wash water t~ .~pe~OI~ ,, the volume of wash water and the type of washing ~..lcl~ine For e~ample, in a top-loading, vertical axis U.S.-type ~u~ 5~;c washing l"~Ghi~ using 45 to 83 liters of water in the wash bath, a wash cycle of 10 to 14 minutes and a wash water t~ t~ of 10~C to 50~C, it is p~fe..~d to include from 2 ppm to 50 ppm, ~l~f~.dbly from S ppm to 2S ppm, of the AQA su~r~:t~nt in the wash liquor. On the basis of usage rata of from 50 ml to 150 ml per wash load, this l.~fi~ r ~ into an in-~l~luel co~ a~n (wt.) of the AQA surfactant of from 0.1% to 3.2%, p~fe.~ly 0.3% to 1.5%, for a heavy-duty liquid laundry det~.~ent. On the basis of usage rates of from 60 g to 95 g per wash load, for dense ("compact") gran~ r laundry ~oe.~cnts (density above 650 g/l) this tr~CI~t~s into an in-product co~c~nn~llion (wt.) of the AQA
su~ra~;~nt of from 0.2% to 5.0%, preferably from 0.5% to 2.S%. On the basis of usage rates of from 80 g to 100 g per load for spray-dried granules (i.e., ~fluffyn;

W 0 97143393 PCTrUS97/0844 density below 650 g/l), this tnqnC~ ps into an in-product concentration (wt.) of the AQA surfactant of from 0.1~o to 3.5%, preferably from 0.3% to 1.596.

For e~mple, in a front-loading, horizontal-axis European-type automatic washing 5 ~n~~hine using 8 to lS liters of water in the wash bath, a wash cycle of 10 to 60 I~l;n~ s and a wash water tclll~.dlurc of 30~C to 95~C, it is pr~fe.fud to include from 13 ppm to 900 ppm, preferably from 16 ppm to 390 ppm, of the AQA sulra~ t in thewash liquor. On the basis of usage rates of from 45 ml to 270 ml per wash load, this n~n!;~ s into an in-product c~ne~nl~dtion (wt.) of the AQA sulrdc~nt of from 0.4% to 10 2.64%, preferably 0.55% to 1.1%, for a heavy-duty liquid laundry det~c~t. On the basis of usage rates of from 40 g to 210g per wash load, for dense (~compact") gr~ qr laundry dct~-gents (density above 650 g/l) this tr~ncl~tes into an in-product c~nC~ ;Qn (wt.) of the AQA surfactant 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-15 dried granules (i.e., ~fluffy~; density below 650 gll), this translates into an in-lnudu~;t U~nrw~t~ ;orl (wt.) of the AQA surfactant of from 0.13% to 1.8%, p~fe.ably from 0. 18% to 0.76%.

For e~cample, in a top-loading, vertical-axis Jap'n~5e type au~ ic washing .. ~,hi~F
using 26 to S2 liters of water in the wash bath, a wash cycle of 8 to 15 .--;n~lteS and a wash water ~.u~, ~ of 5~C to 25~C, it is ~f.~ d to include from 1.67 ppm to 66.67 ppm, preferably from 3 ppm to 6 ppm, of the AQA s~ ac~nt in the wash liquor.
On the basis of usage rates of from 20 ml to 30 ml per wash load, this t~ sl~tPs into an in-~l~lu.;t c4~ "-t;on (wt.) of the AQA surfactant of from 0.25% to 10%, preferably l.S% to 2%, for a heavy~uty liquid laundry dete.~ent. On the basis ofusagc ~ of from 18 g to 35 g per wash load, for dense ("c4lnp~l") gr~n~ r laundry deterg_nts (dcnsiq above 650 g/l) this tr~n~l~tes into an in-pr~lucl eQnC~ ~n r;Or (wt.) of thc AQA a~r-- t~nt of from 0.25% to 10%, plefe.dbly from 0.5% to 1.09G. On the basis of usage rates of from 30g to 40g per load for spray~ried granules (i.e., ~fluffy"; density below 650 g/l), this t~nCI~tes into an in-product c~ erl-dtion (wt.) of thc AQA s~lrf~t~n~ of from 0.25% to 10%, preferably from 0.5% to 1%.

As can be seen from the fole6oillg, the amount of AQA surfactant used in a ...Q~ ;ne wash hund~ling conte~ct can vary, depe~din~ on the habits and pr~rticçs of the user, the 35 type of washing ~ h;ne, and the like. In this conte~t, however, one he~etofoIe llnappl~;dl~l advantage of the AQA surf~c!~n~c is their ability to provide at least CA 02254946 1998-ll-17 W O 97/43393 PCTrUS97/08441 -directionql improvements in performance over a spectrum of oils and stains even when used at relatively low levels with respect to the other surf~P-ntc (generally ~ ~ionics or anionic/nonionic mixtures) in the finis~led compositionc~ This is to be distinguished from other c~l-,~s;tionc of the art wherein various c~tionic surfilct-qntc are used with 5 anionic surf-q-rtqntc at or near s~ichi~!net ic levels. In general, in the practice of this invention, the weight ratio of AQA:qrio~ surfactant in laundry C4~ ~s;~;~ ns is in the range from 1:70 to 1:2, l~f~bly from 1:40 to 1:6, more p~f~ ~ably from 1:30 to 1:6, most prefe,ably from 1:15 to 1:8. In laundry co...l~s;l;~.ne which con~ i~ bothanionic and nQniQnic surf~tql~tc the weight ratio of AQA:mi~ed anionic/rQricniC is in 10 the range from 1:80 to 1:2, p~fe.dbly 1:50 to 1:8.

Various other cl~-qnine c4l,.l~s;tiQns which comprise an anionic surfactant, an optional nQ~ic?nir surfactant and s~iqli7ed surf~t~ntc such as b~ inp~s~ sult-q-ines~ amine o~cides, nd the lilce, can also be fonn~lqt~l using an effective qlnollnt of the AQA i....r~
15 in the ~.,anner of this invention. Such c~-.l~s;l;QnC in.~ de, but are not limited to, hand dishwashing ~luducls (es~iqlly liquids or gels), hard surface cleq~e~
~h~...~5 pe.~nal clp~ ;ne bars, laundry bars, nd the like. Since the habits and practices of the users of such co,l"~s;l;~ns show rninimql variation, it is sqticf?~tQry to include from 0.2S% to 5%, preferably from 0.459G to 2%, by weight, of the AQA
20 sulr~ n~ in such a~ ~s;t;QnC. Again, qs in the case of the ~r~qtllllqr qnd liquid lau..d~ po~ nc~ the weight ratio of the AQA surfactqnt to other s,llr;- ~;-ntc present in such cG ~ ;nnC is low, i.e., sub-stoi~hiomptric in the case of ~in~ s~f~bly, such ck~ ng co!,.l~l;Qns comprise AQA/~ ~nt ratios a noted i..-.-~:~tely above for machine-use laundry co.~pQs;t;nnC
In cont~a~t with other cationic ~ulr~l~nts known in the art, the al~o~ylatod c~'io~;cs heran have s~rr~ solubility that they can be used in co .bin~;on with mi~ced sur&ctant systems which are quite low in nonioric s~llr1~c~n~c and which con~;n~ for e~cample, allyl sulfate ~ r-~ t~ This can be an i-l,~l~nt con~;de~ nn for 30 forn~ qt~ s of d~t,~c.~l co--.po.;l;orlc of the type which are con~len~;on~lly d~ n~d for use in top loading a ~o--~';c washing m~hines, especi~lly of the type used in North Plica _s well as under Ja~nP s~ usage conditions. Typically, such C~ ;nnc will ;~ an anionic s.-~f~l~nt:noniQnic surfactant weight ratio in the range from 25:1to 1:25, pl~fe~ably 20:1 to 3:1. This can be contrasted with European-type forrnulas 35 which typically will comprise anionic:nonionic ratios in the range of 10:1 to 1:10, pl~f~.~bly5:1 to 1:1.

CA 02254946 1998-ll-17 PCTrUS97/08441 The preferred ethoxylated c~ior~iC surfa~t~ntc herein can be syr~~h~i7~d using a variety of different ~ Lion s~h~..es (wherein "EO~ l~,?re~nls -CH2CH20- units), as follows.
SCHF.l~IE 1 R OH + CH3N~2 H2/catlHeat I ~CH3 EXCESS

N,CH3 ~ BASE Cat~ Rl N--(EO)--H

Rl N--(EO)n--H + CH3Cl ~ R--Nl--(E~)n--H

SCH~I~F. 2 H,N--(EOhH + 2 ,C~ HH2ÉCAaT ~ CH ~N--(EO)2H
"DIGLYCOLAMI~IE"

RlBr + ~N--~EO~2H HEAT ~ Rl N--~EO~2--H

SC~F.~F. 3 CH ~N--(EO)H + n~ HEAT CH3 R Br + N--(EO)"+l H ~Rl N~(EO)n+l H
CH3~ CH3 Br Cl--CH2CH2--OH + n ~ ~ Cl--CH2CH20[EO]n--H

Rl N~ + Cl--CH2CH20[EO]n--H HEAT~ R'N--CH2CH20[EO]n--H
CH3 cr An economical reaction scheme is as follows.
SCHEME S

Rl--OSO3Na+ + ~N--CH2CH2-OH HEAT- Rl N--CH2CHrOH+ Na2SO4 + H2O
H

C~
Rl N--CH2CH2-OH + n~ HEAT ~ R--Nl ~H2CH2O[Eoln--H

Rl N--CH2CH20lEO]n--H + CH3CI ~ Rl N--CH2CH201EOln--H
CH3 CH3 Cr For reaction Sçhen~e S, the following ~ t~.s su~ q-ize the optiQn~l and pr~f~lodl~dction contlitionc herein for step 1. Step 1 of the reaction is pl~fe dbly conduc~d in an ~yu~--~ .. P I;----- R~tion t~ ~,atul~s are typically in the range of 100-230~C.
i~ p~ S are 5~1000 psig. A base, preferably sodium hydro~cide, can be used to ~t with the HSO4- geAe.at~d during the r~ction. In anothe, mode, an e~ce~ of the amine can be employed to also react with the acid. The mole ratio of amine to allcyl sulfate is typically from 10:1 to 1:1.5; plefe. lbly from 5:1 to 1:1.1;
15 more pl~f~bly from 2:1 to 1:1. In the product recovery step, the desired ~ ul~
amine is simply allowed to s~dte as a distinct phase from the aqueous reaction .~-P.i;u--~ in which it is in~olu~'c. The product of step 1 is then etho~ylated and e~ ~ using ~,~d r~~tir~ as shown.
~0 The following ill.~ s the fol~oing for the convenie~C~e of the formul~or, but is not i to be li~;t;~e thereof.

W O 97/43393 PCT~US97/08441 Pre~A~ation of N-(2-hydroxyethyl)-N-methyldodecylamine - To a glass autoclave liner is added 156.15 g of sodium dodecyl sulfate (0.5415 moles), 81.34 g of 2-(methylamino)ethanol (1.083 moles), 324.5 g of ~iStill~d H2O, and 44.3 g of 50 wt. %
sodium hydroxide s~ tion (0.5538 moles NaOH). The glass liner is sealed into 3 L, 5 st~inlec~ steel, rocking autoclave, purged twice with 260 psig nihogen and then heated to 160 180~C under 700-800 psig nitrogen for 3 hours. The lldAIu~ is cooled to room te.--~.dl~lre and the liquid content.~ of the glass liner are poured into a 1 L S~dtOly funnel. The mi~cture is sep~dt~d into a clear lower layer, turbid middle layer and clear upper laya. The cle~r upper layer is i~ol~t~l and placed under full v~uul" (<100 mm 10 Hg) at 60 65~C with mixing to remove any residual water. The clear liquid turns cloudy upon removing residual water as ~lition~l salts cryst~lli7~s out. The liquid is vacuum filtered to remove salts to again obtain a clear, colorless liquid. After a few days at room L.l.pe.al~lre, ~~ ition~l salts crystallize and settle out. The liquid is vacuum filtered t~ ~~.I.O~ solids and again a clear, colollei~ liquid is o~t~;n~d which 15 ~.,lains stable. The i~!~ted clear, colorless liquid is the title product by N~ analysis and is >90% by GC analysis with a ty~pical recovery of ~90%. The an~ine is then etho~tylated in standard f~cllion~ Quaterni7~tion with an alkyl halide to form the AQA
surfA~nt~ herein is routine.

20 According to the Çon~going~ the following are nonlimiting, S ~ ific ill--,t ~;..,.c of AQA
s~lr;~ s used herein. It is to be und~.~lood that the degree of alko~cylation noted herein for the AQA s-- r~ t~ is lc~31t~ as an average, following co..-.l,on pr~cfor conventionql etho~cylated ~~"niol~ic surf~ t~ntc~ This is boc~ ~ the ell~Ayl~tion ;nnQ typically yield n~i~tures of mqt~iqlc with differing degrees of etho-Aylation.
25 Thus, it is not ~ - on to report total EO values other than a whole nu~ e.g., ~EO2.S~, ~EO3.5~, and the like.

~Cur~qti~n Bl ~,2 R3 Alko~ n AQA-l C12-C14 CH3 CH3 EO2 .. ..... ..

CA 022~4946 1998-11-17 W O 97/43393 PCTrUS97/08441 -s AQA-7 C14-C16 CH3 C3H7 (EO/PrO)4 AQA-8 C12-C14 CH3 CH3 (PrO)3 AQA-10 Cg-Clg CH3 CH3 EOlS

AQA-ll Clo C2Hs C2H5 EO3.5 AQA-12 Clo CH3 CH3 EO2.5 AQA-13 Clo CH3 CH3 EO3.5 AQA-14 Clo C4Hg C4H9 EO30 AQA-lS C8C14 CH3 CH3 EO2 AQA-16 Clo CH3 CH3 EO10 AQA-17 C12-C18 C3H9 C3H7 Bu4 AQA-l9 C8 CH3 CH3 i~3 AQA-21 Cl2 CH3 CH3 EO3.5 AQA-22 Cl2 CH3 CH3 EO4.5 W O 97/43393 PCTrUS97108441 - Highly y~efe~l~ AQA compound for use herein are of the formula /(C H2C H2O )2-5 H
N X~
CH3/ ~CH3 wherein Rl is Cg-CIg hy~ll~l,yl and mixtures thewf, e~i~lly Cg-C14 alkyl, S ~efe.dbly Cg, Clo and C12 allcyl, and X is any convenient anion to provide charge b~l~nGe, plef~.ably chloride or bromide.

As noted, cG~ unds of the folcgoing type include those wherein the etho~y (CH2CH20) units (EO) are r~pl~ed by butoxy, is..plopo~.y [CH(CH3)CH20] and 10 [CH2CH(CH30] units (i-Pr) or n-propoxy units (Pr), or ~ ulos of EO and/or Pr and/or i-Pr units.

A highly p~f~l~ AQA c~ ~vl.d for use in under built formnl-~ionc are of the formula wherein p is an integer in the range of between 10 and 15. This con~pol~n~l is 15 particularly useful in laundry handwash d~ te.E,ent col~.po~;tiQn~.

Non-AOA Detersive Surf~r~

In ~'~ition to the AQA ~ f~;t~lt, the co.~s;tinnc of the present invention pl~fe.dbly 20 fur~er comprise a non-AQA surfactant. Non-AQA surfart~nt~ may include e~ y any anionic, nonionic or ~ ;on~l c~tiQnic surfactant.

Anionic Surfac~ant Nonlimiting el~mp!es of anionic surf~~t~ntc useful herein typically at levels from 1% to 55%, by weight, include the conventio~-q~ Cl1-C1g alkyl brn7~ne sulfonates ("LAS") 5 and primary ("AS"), branched-chain and random Clo-C20 alkyl s~lf-q-tes, the C1o-Clg ~con~l-q-ry (2,3) alkyl SUIfq-tPS of the formula CH3(CH2)X(CHOSO3 M+) CH3 and CH3 (CH2)y(CHOS03 M+) CH2CH3 where A and (y + 1) are intcgels of at least 7, ~ fe ~bly at least 9, .~nd M is a water-solubilizing cation, eC~ qlly so~ lm~
unsaturated s~llf?t~s such as oleyl sulfate, the C12-CIg alpha-sulfonated fatty acid 10 esters, the Clo-cl8 s~lf-q-t~ polyglyc~c~des, the Clo-C18 alkyl alkoxy sulfates ("AEXS"; e~iqlly EO 1-7 etho~cy sulfates), and the Clo-C1g alkyl all~o-Ay call,oA~lates (e F~iqlly the EO 1-5 etho~c~l,o~ylates). The C12-Clg ~t~n~ and sulfobc~in~c ("sultqin~s~), Clo-Clg amine oxides, can also be inrlud~ in the overall co...~os;l;Qns. Clo-C20 convention~l soaps may also be used. If high sudsing is 15 desired, the b~ched-chain Clo-C16 soaps may be used. Other conventi~nql useful s.ll rg ~ are listed in ~ndard texts.

Nonionic Surfactants 20 Nonlimiting e~camples of noniQnic surfYq~t~ntc useful herein typically at levels from 1%
to 55 %, by weight include the, ll~oxylated ql,~hQIc (AE~s) and alkyl phF.~ c, polyhydro~cy fatty acid amides (P~AA's), ~kyl polyglycosides (APG's), Clo-C1g glycerol ethers.

25 More ~ifirq11y, the con~n~q i~n pr~lu~ls of primary and s~con~q y qliphqti~
_lr~hQlc with~ f~m 1 to 25 moles of ethylene oxide (AE) are s~it~ for use as thenoni~ nV s..l~ in the present invention. The allcyl chain of the ~liph~ti~ alcohol can either hue s~ight or ~ or ~eco~ ~, and generally cQr~-;nC from 8 to 22 carbon atoms. P~fe.l~d are the condPn~qti~l- products of qlcohnls having an al~yl 30 group contqinin~ from 8 to 20 carbon atoms, more preferably fr~m 10 tol8 carbon atoms, with from 1 tolO moles, preferably 2 to 7, most plefel~bly 2 to 5, of ethylene oxide per mole of q1r~hol Esamples of cornmP~cially available nonionic ~ r~ nt!~ of this type inrh~de: TergitolTM 15-S-9 (tbe cQndPnc?tion product of Cl l-Cls linear alcohol with 9 moles ethylene oxide) and TergitolTM 24-L-6 NMW (the cQI~en~qtiQn35 product of C12-C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both ~na~ket~ by Union Carbide CO~aliOn;

CA 02254946 1998-ll-17 W O 97/43393 PCTrUS97/08441 NeodolTM 45-9 (the con~e~lsation product of C14-Cls linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-3 (the condçnc~tion product of C12-C13 linear alcohol with 3 moles of ethylene oxide), NeodolTM 4s 7 (the condenQ~tiQn product of C14-C1s linear alcohol with 7 moles of ethylene oxide) and NeodolTM 45 S (the conden~ on product of C14-Cls linear alcohol with 5 moles of ethylene oxide) ",~t~l by Shell Ch~micvl Company; KyroTM EOB (the condenQqtion product of C13-Cls alcohol with 9 moles ethylene oxide), Inalketed by The Procter & ~.~mbleCo!~l~ny; and Genapol LA 030 or 050 (the cQ~enC~tion product of C12-C14 alcohol with 3 or 5 moles of ethylene oxide) ~n~Lted by Hoe~hct The p.~ r. nge of HLB in these AE no~ )nic surf~c!~ntc is from 8-11 and most preferred from 8-10.
C~on(~enC~trS with propylene oxide and butylene oxides may also be used.

Another class of plefe.l~ d noni~-nic surf~-t~rltc for use herein are the polyhydroAy fatty acid amide s~ r~n~ of the formula.

R2 fi--I--Z' O R

wherein Rl is H, or Cl~ hydro~ul yl, 2-hydroxy ethyl, 2-hydro~y propyl or a .l~l~e thereof, R2 is Cs 31 h~d.~ l, and Z is a polyhydroxyhyd~l,yl having a linear hydio~l.yl chain with at least 3 h~d.~DA)~ls directly c~nn~ d to the chain, or an all uAylat~d derivative thereof. Preferably, R1 is methyl, R2 is a straight Cll l5 alkyl or C1S 17 allcyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a l~dur;~g sugar such as gl~lcose, ~ close, m~ltose, l~tos~, in a Ju~L~ io~ rnrtion. Typical eY~mplPs include the cl2-clg and C12-C14 N-2S methylgluc~nidcs. See U.S. S,194,639 and 5,298,636. N-all~o~y pol~l yd~.-y fatty acid amidcs can also be used; see U.S. S,489,393.

Also useful as the ~';OQ;'' s~lr~l in the present invention are the allcylpol~cchalides such as those ~ clos~ in U.S. Patent 4,565,647, T len~lo, issued January 21, 1986, having a h~d.~phobic group cont~;ni-Qg from 6 to 30 carbon atoms, preferably from 10 to 16 carbon atoms, and a pol~aacch~ide, e.g. a polygl~ ide, hydrophilic group c4nt~ ng from 1.3 to 10, p~f~.~,bly from 1.3 to 3, most p~f~dbly from 1.3 to 2.7 s~cha,ide units. Any reducing ~ccha,ide cor-t~ining 5 or 6 carbon atoms can be used, e.g., gl~cose, g~l~ctos~ and galactosyl moieties can be S,J~.Sl;t~
for t~he glucosyl moietics (OptiQ~ y the hydrophobic group is ~tt~ed at the 2-, 3-, 4-, ... . . .

etc. positions thus giving a glucose or ~ ctose as opposed to a gl~lc~ide or g;~l~~tosi~le). The intersaccharide bonds can be, e.g., between the one pocitiQrt of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the p~l;n~
saccharide units.
s The ~lefe.-~d alkylpolyglycosides have the formula:
R20(CnH2nO)t(glycosyl)x 10 wherein R2 is Sf kcte.,d from the group concistin~ of alkyl, alkylphenyl, hydro~cyal~l, hydroxyalkylphenyl, and ",i~lu~s thereof in which the alkyl groups contain from 10 to 18, p~f~.dbly from 12 to 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to 10, preferably 0; and ~ is from 1.3 to 10, preferably from 1.3 to 3, most p.~fe.~bly from 1.3 to 2.7. The glycosyl is preferably derived from glucose. To ple~ these 15 c~ ~u~ c, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with g1UCOSf, or a ource of gl-)c~s~, to form the glucosile (~tt~~~ment at the l-position).
The :~Aitic!n~l glycosyl units can then be ~ hed between their l-p~citi~ n and the pifx~ing glycosyl units 2-, 3-, 4- and/or ~positir~n~ p~fel~bly p~Jo...in~.ly the 2-pQctttQn.
Polyethylene, polyl,.opylenf, and polybutylene oxide con~e~ t~ C of alkyl ~.k. ~-olc are also s,~ ble for u e as the nQnio~ir surfactant of the s~l.rac~nt systems of the present invention, with the polyethylene o~cide c~n~e~-~tf s being p.~fe.-~d. These cc.~ c include the c~n~lc1n~ n products of alkyl phPnolc having an alkyl group c4n'~ini ~e 25 from 6 to 14 carbon atoms, p~fe.ably from 8 to 14 car'oon atoms, in either a straight-chain or b~ chain config-~lalion with the . lkylene oxide. In a p~fe.-~
embodiment, the ethylene oxide is present in an qmount equal to from 2 to 25 moles, more pf~f~bly from 3 tol5 moles, of ethylene oxide per mole of Ikyl phenol.
Co-~".lc~;ally available nnni~nit surf ~c~q~tc of this type include IgepalTM ca630, .. -~-L- ~J by the GAF CO1~ ; and TritonTM X~5, X-114t X-100 and X-102, all ...~.L- ~ ~ by the Rohm & Haas Comp,qny. These surf?c!-q-ntc are co.Y ...~u~1y ~.,f~,l.xt to as al~tl)hPnol allcoxylates (e.g., alkyl phenol ethoxylates).

The conde ~c~t;nn p.~luc~s of ethylene oxide with a hydrophobic b. se formed by the 35 conden~q~iQn of propylene oxide with propylene glycol are also suitable for use as the q~litionql nnniQniC surfactant in the present invention. The hydrophobic portion of CA 02254946 1998-ll-17 these compounds will preferably have a molec~ r weight of from 1500 to 1800 and will exhibit water insolubility. The addition of polyoxyethylene moie~ies to this hydrophobic portion tends to increase the water solubility of the Innl~ulp as a whole, and the liquid chal.-cter of the product is retained up to the point where the 5 polyo~yethylene content is 50% of the total weight of the con~len~qtion product, which co.,~ ds to cQI~d~n~t;on with up to 40 moles of ethylene oxide. E~ les of c4.~ ds of this type include certain of the cornmercially-available PluronicTM
surfq,ctqn~c7 ~ t~d by BASF.

10 Also suitable for use as the no~ioniC surfactant of the nollioltic surfact. nt system of the present invention, are the c~nden~qtion produc~s of ethylene oxide with the pl~uel res ~lting from the reaction of propylene oxide and ethyler~Aiqmine. The hydl~phobic moiety of these ~ioducl~ concists of the reaction product of ethyleneAis...;n~ and e~ccess propylene o~ide, and gene-ally has a mol~ulq~ weight of from 2S00 to 3000. This 15 hydlvphobic moiety is condenc~ with ethylene oxide to the extent that the cQn~enC~tion p~ Qnl-inS from 40% to 80% by weight of polyoxyethylene and has a mnle~ qr weight of from 5,000 to 11,000. FYqmrles of this type of notlin~ic surfactant include certain of the commercially available TetronicTM col"pounds, nlall~d by BASF.

20 A~itinnql ('qtinnicrcllrfqntqntc Suitablc ~;onie s~lr;~ t~ are l"~efe.ably water dispersible co.~ having ~Ç~t p.~ p"lies cQn~pri~;ng at least one ester (ie -COO ) linluge and at least one onil~qlly cl-ar~,~d group.
Other suitable rqtioni~ s.uf~ tc include the quatc.-~ry q~nmQnium surfactants fmm mono C6-C16, preferably C6-Clo N-allcyl or alkenyl qm..,on;u~u surfactants ~ h~.~. the remqining N pqsitiol~s are subs~ituted by methyl, hydlu.~yethyl or hyd uA~r~yl groups. Other suitable cq~ionic ester surfq-rt-q-ntc~ including choline 30 ester surfactants, have for ~mple been ~icclos~d in US Patents No.s 4228042, 4239660 and 4260529.

Op~ir)nql D~t~.~cnt ~n~ienlS

3S The following illustrates various other optional ingredients which may be used in the c~ ~s:l;rns of this invention, but is not int~nde~ to be limitin~ thereof.

CA 02254946 1998-ll-17 W O 97/43393 PCTrUS97/08441 -Additional Bleach The dele~ent co.l.~os;l;ons herein may optionally comprise an additional ble~ching S agent. When present, such ~d~litior~l ble~hing agents will typically be at levels of from 1% to 30%, more typically from 5% to 20%, of the detergent co.~l~s;l;on, e~ qllyfor fabric laundering.

The ble~ ing agents used herein can be any of the bl~hing agents useful for 0 det~lgentCO~ OS;~;Qn~ in textile cl~ning, hard surface cle~ning, or other cle~ning )O~S that are now Icnown or be~ome known. These include o~cygen bleaches as well as other bleaching agents. I~ ate bleac~-~s e.g., sodium pe~ ale (e.g., mono or tetra-hydrate) can be used herein.

15 Alkali metal or alkali earth metal per~bo~t~s, particularly sodium perc~bonate are p,~fe ,~d pc~l,onates for incl~ on in c~ll~C;tion~ in accordance with the invention.
.So~lium pe.~r~onate is an ;~it~ co~ ound having a formula C~ ,pontling to 2Na2C03.3H202, and is available commercially as a crystalline solid. Corr~rnPrcial suppliers include Solvay, FMC, Tokai Denka and others.
A pl.,fen~sd pe.~l,onate bleach comprises dry particles having an average pa~ticle size in the range from 0.5 mm to 1 mm, not more than 10% 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 ~c~l~nat~. is most pl~.fe.d'bly incol~ ted into such c4~ t)nc in a coated form which ~ idc~ in-product stability.
A suitable coating material providing in product stability comprises mixed salt of a water soluble alkali metal s~lphate and carbonate. Such co~ing.~togetl,er with coating pl~CeS ~ have previously been described in GB- 1,466,799, granted to Intero~c on 9th March 1977. The weight ratio of the mi~ed salt coating material to ~r~llonale lies in the range from 1: 200 to 1: 4, more preferably from 1: 99 to 1: 9, and most pl~feldbly from 1: 49 to 1: 19. Preferably, the mixed salt is of sodium sulE~hq~e and sodium c~l onate which has the general formula Na2S04.n.Na2C03 wherein n is from0.1 to 3, ~ ,fe.dbly n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.

Other ~tingC which contain silicate (alone or with borate salts or boric acids or other inorganics), waAes, oils, fatty soaps can also be used advantageously within the present invention S Another CatCgGIy of bl~ching agent that can be used without restriction enComp~c~s ~r~luAylic acid bl~ ~hi-le agents and salts thereof. Suitable eY-q-mples of this class of agents include m-q~gr-ecil-m n~o~op~roA~ qte hexahydrate, the ~ gnPc;llm salt ofmet~-~hloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and oAydQd~ oie acid. Such bleaching agents are ~lisclo~d in U.S. Patent 10 4,483,781, Hartman, issued Nove.l,ber 20, 1984, U.S. Patent ~rplicq~ion 740,446, Burns et al, filed June 3, 1985, European Patent Applic~ion 0,133,354, Banks et al, published I~lu~y 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued ~J~ ~r 1, 1983. Highly ~.~fe~led ble, ching agents also include 6-nonylamino-6-o~ ycap~ acid as described in U.S. Patent 4,634,551, issued January 6, 1987 15 to Burns et al.

Peroxygen bleaching agents can also be used. S~itqble peroxygen bl~ching cG,-.l~undc include sodium p)rlo~,hosph~ pero~c~hydl~t~, urea ~.oAyl,ydrate, and sodium pero~cide. Pe~l~latc bleach, persulfate bleach (e.g., OXONE, n~qnuf~tllred 20 cc~ ,r~ially by DuPont) can also be used.

tures of bleaching agents can also be used.

~ch Activ~
Bleach a~ are Inefe.l~d coln~nen~ of the c~l..~s;~ion where a peroxygen bleach is present. If present, the q-~nount of bleach activators will typically be ~from 0.1% to 609C, more typically from 0.S% to 40% of the bkl~hing c~
c~ y ;~ing the bleaching agent-plus-bleach activator.
The c~...h~ n of p~ g_~l bleaching agents and bleach activators results in the in sinl pl~3~c~ n in aqueous Sl!l~t~ (i.e., during the washing process) of the pero~cy acid to the bleach acdvator. Various nonlimi~ing e~p'e~ of activators are ~li~los~ in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et a~, and U.S.
Patent 4,412,934. The nonanoylo~yl~n~ne sulfonate (NOBS) and ~lldacel~rl ethylene W O 97/43393 PCT~US97/08441 -minP ( rAED) 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 p~cfcllcd arnido-deAved bleach activators are those of the formulae:

RlN(R5)C(o)R2C(o)L or RlC(O)N(R5)R2C(O)L

wh~,~in Rl is an al~yl group c~n'~;nill~ from 6 tol2 carbon atoms, R2 is an allcylene c~ining from 1 to 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl c4~ ;nin~ from 10 1 to 10 carbon atoms, and L is any s~it~h!P leaving group. A leaving group is any group that is ~lispl lr~d from the bleach activator as a consequence of the n~ 4phili~
attack on the bleach activator by the perhydrolysis anion. A plCL~l~d leaving group is phenyl sulfonate.

15 ~. f~.l xl e~camples of bleach activators of the above formulae include (6~.1ido-caproyl)u,-yb~ Pnf ,-~lfonate, (6 non~n ~midoc ~l~yl)oxyb~ a.~lfonate, (~
dcc~n~-.id~caproyl)o~ f j~Jlfonate, and mixtures thereof as dP~ri~l in U.S.
Patent 4,634,551, inco~ t~d herein by ~fe,ence.

20 Anotha class of bleach activators co~ lises the bc~ ;n-type activators ~ os~l by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990, incolltola~d herein by ~fen~ncc. A highly p~fe.l~d activator of the bçn7or-q7in-type is:
~C~

Still another class of ~ d bleach activators includes the acyl lactam ac~i~ra~
e-~iqlly acyl capfolA ~ s and acyl valero!A~tqms of the formulae:

O Cl--CH2--CH2~
R6--C--N~ ,C H2 CA 02254946 1998-ll-17 W O 97/43393 PCT~US97/08441 -o c c H2--f H2 wherein R6 is H or an alkyl, aryl, al~oxyaryl, or alkaryl group c~ ;nin~ from 1 to 12 S carbvn atoms. Highly p,~fe.,~d lactam activators include benzvyl ca~lv~ .n, ~;~noyl caprc~l~~tam, 3,5,5-trimethyll-c-~noyl caprolactq-m, nonanoyl caprol~-tqm, decanoyl cap.sl u~ nde~ oyl caprol~c!~q~m, benzoyl vale,~la~m, v~;~no~l vale.~ 'A~--, decanoyl valerol~~t~m, ~nd~enoyl valerolact-q-m.., nonanoyl valer~l~rl~....
3,5,5-h~ ylh~ ~~no~l valerol~~tqm and mi~tures thereof. See also U.S. Patent 10 4,545,784, issued to Sanderson, October 8, 1985, incol~latcd herein by l~Çe~nce, which ~lic~ ~s acyl caprolvq~tqn~s~ inc]lJdill~ benzoyl capr~ .., ads~ d into sodium ~bol~.

~açh (~t-qlyst Bleach catalysts are pl.,fe.l~xl co".l~onPn~c of co"~po~;l;ol~C of the present invention that, in :~dditir~n to the photobl-~~h, comprise an oxygen ,~ ;ng bleaching agent. Bleach catalysts are well l~own in the art and in~lude, for e~-q-rn. '~, the mqll~,, nr~based catalysts ~licslos~d in U.S. Pat. 5,246,621, U.S. Pat. S,244,594; U.S. Pat. 5,194,416;
20 U.S. Pat. 5,114,606; and Elllop~n Pat. App. Pub. Nos. 549,271Al, 549,272A1, 544,440A2, and 544,490Al; ~fe~lod ~r~mp'es of these catalysts include MnIV2(u-0)3(l~4~7~ methy~ 4~7-hia~ejcl~nQn~ne)2(pF6)2~ MnIII2(u-0)1(u-OAc)2(1~4~7-hill~ ,4~7-h~ )2-(clo4)2~ MnIV4(u-0)6(1,4,7-hia~ lononane)4(C104)4, MnmMnIV4(u-O)l(u-OAc)2 (1,4,7-~ 1,4,7-triaza~ lQn~n~ne~2(ClO4)3, MnIV(1,4,7-trimethyl-1,4,7-h;az.. cycl~no~ e)-(OCH3)3(PP6~, and Illialu~s thereof. Other metal-based bleach catalysts include those oscd in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611. The use of .-. lg~ se with various comple~c ligands to c~ nce bleaching is also fe~O.ted in the following United States P~tents. 4,728,455; S,284,944; S,246,612; S,256,779; 5,280,117; 5,274,147;
30 5,153,161; and 5,227,084.

As a p,~lical matter, and not by way of limit~tion~ the co".l~~;tiQ~c and pn~ss~s herein can be adjusted to provide on the order of at least one part per ten million of the CA 02254946 1998-ll-17 W O 97/43393 PCTnUS97/08441 active bleach catalyst species in the aqueous 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.

S Cobalt bleach catalysts useful herein are known, and are described, for e~qmplc, in M.
L. Tobe, "Base Hydrolysis of Tr ~ ion-Metal Complexes~, Adv. Inor~. Bioinore.
Mech., (1983), 2, pages 1-94. The most pl~ f~ d cobalt catalyst useful herein are cobalt p~ e acetate salts having the formula [Co(NH3)sOAc] Ty~ wherein "OAc"
an acetate moiety and ~Ty~ is an anion, and esF~iqlly cobalt pentqqmine 10 acetate r~l~ncle, [Co(NH3)sOAc]C12; as well as [Co(NH3)sOAc](OAc)2;
tCo(NH3)sOAc](PF6)2; [Co(NH3)sOAc](SO4); [Co(NH3)sOAc](BF4)2; and ~Co(NH3)sOAc](NO3)2 (herein "PAC").

These cobalt catalys~s are re. dily ~ d by known p~lu~s, such as taught for lS e~carnple in the Tobe article . nd the rcf~rcnces cited therein, in U.S. Patent 4,810,410, to Diakun et .,1, issued March 7,1989, J. Chem. Ed. (1989), ~ (12), 1043-45; TheSynthesis and ~hq~- t~ ;on of Ino~ ic Compollnds~ W.L. Jolly (~n~ce-Hall;
1970), pp. 461-3; Inorp. Chem., 18, 1497-1502 (1979); Inorg. Chem.. 21, 2881-2885 (1982); Inor~. Chem.. 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and 20 Journql of Physir-q-l Chernistry, 56, 22-25 (1952).

As a pr~~ti~ql matter, and not by way of limit~tion~ the au~---dtic dishwashing co...~ ;ons and cleaning p~ccss~s herein can be adjusted to provide on the order of at least one part per hur,LI~ million of the active bleach catalyst species in the -queous 25 washing ~ ~, and will preferably provide from O.Ol ppm to 25 ppm, more p.~f~ from 0.05 ppm to 10 ppm, and most preferably from 0.1 ppm to 5 ppm, of the bleach catalyst species in the wash liquor. In order to obtain such levels in the wash liquor of an ~ ';c dishwashing process, typical ~ ~lo-..-l;c di~h. ~lung c4- ~llQc;lionc herein will C4~ ;~, from 0.0005% to 0.2%, more p~fe.ably from 0.004% to 0.08%, 30 of bleach catalyst, çsp~iqlly l,.ar~g,arl~"~ or cobalt catalysts, by weight of the c compositions.

R--iltl~rS
.

35 D~.gent builders can op~ nqlly but preferably be inçluded in the c4~pcc;l;onc herein, for ç~qmple to assist in controlling mineral, espe~iqlly Ca and/or Mg, h~dness in wash W O 97143393 PCT~US97/08441 -water or to assist in the removal of particulate soils from surfaces. Builders can operate via a variety of m~h~ni.cmc inclu~ling forming soluble or insoluble complexes with hardness ions, by ion eY~c~l~n~e~ and by offering a surface more favorable to the pr~ipit; tion of hanlness ions than are uhe surfaces of articles to be cle~q-nPd. Builder 5 level can vary widely ~epPnAing upon end use and physical form of the cû.~.po~ n.
Built de~.~,~ ta typically comprise at least 1% builder. Liquid formnlq-ti~ ns typically comprise 5% to S0%, more typically 5% to 35% of bùilder. Granular forrn-~vq.tio~-c typically comprise from 10% to 80%, more typically 15% to 50% builder by weight of the d~t~.gcnt c~ pos;~iom Lower or higher levels of builders are no~ eYcluded For 10 e~cample, certain d~te.gcint additive or high-surfactant forrnn1~ir)nc can be unbui~t Suitable builders herein can be ~l~i from Lhe group comicting of phosl~h~t~ s and polypho~h-q-t~Ps~ ec~i~lly the sodium salts; silir~t~Ps incluAing water-soluble and hydrous aolid types and including those having chain-, layer-, or three~i~nPn~io15 structure as well as a-,lw~hous-solid or non-structured-liquid types; C~hbvn~t~,5, bic~n~s, s~cqu~ bo~t~s and c~ubûnate minerals other than sodium c~l,ona~ or s~ui~l~ona~; Lqlu l.il~os;licqt~s: organic mon~, di-, tri-, and tehdcd l,oxylates P~C~iqlly water-soluble nonsurfactant carboxylates in acid, sodium, ~l~c~;u~ or qlL~no~ monium salt form, as well as oligomeric or water-soluble low molecular 20 weight polymer carbo~ylates in~luding vliphqtic and aromatic types; and phytic acid.
These may be complemented by boP~s e.g., for pH-buffering pUl~)CiSeS, or by sulfates, eq~ciq11y sodium sulfate and any other fillers or carAers which may be~nt to the e~ ;r.P~ ~ ;ng of stable surfact~nt and/or builder~Qn~ g det~gent C~l..~ c Builder mi~tures, SG~ P5 termed ~builder systems~ can be used and typically C4 Ul~-;gC two or more con~n~;Q~1 builders, optionql1y complc~.c--~t~d by c~ pH-buffers or fillers, though these latter mqtP~iqr1S are gener-q-11y ~ou~ted for s~p~at~l~
when descAbing quqntitips of materials herein. In terms of relative qu~t;t;Ps of30 surfactant and builder in the present dete~E,ent~s, ~iefe~.~i builder systems are typically formu1q~ at a weight ratio of surfactant to builder of from 60:l to 1:80. Certain ~,~f~,xi laundry d~t .E,~.Ils have said r. tio in the range 0.90:1.0 to 4.0: l.0, more preferably from O.9S:l.0 to 3.0:1Ø

35 P con~ ng d~~el t builders often preferred where permitted by legic1qti~n include, but are not limitod to, the all~ali metal, amn~onium . nd q11~qno!qmm~ nium salts of polyphosph~es exemplified by the tripolyphosph~t~s, pyrop~osph~tes, glassy polymeric meta-ph~sE)h~Ps; and phosphonates.

Suitable silicate builders include alkali metal c~ tPs, particularly those liquids and S solids having a SiO2:Na20 ratio in the range 1.6:1 to 3.2:1, inchlding~ particularly for au~ol.latic dishwashing pu.~ses, solid hydrous 2-ratio cili~Ps ~I~keted by PQ Corp.
under the tr~n~mÇ BRlTESIL~, e.g., BRlTESIL H20; and layered Ci~ t~s~ e.g., those described in U.S. 4,664,839, May 12, 1987, H. P. Riec~. NaSKS-6, somrtim~Sabbreviated ~SKS-6", is a crystalline layered aluminium-free ~-Na2SiOs morphology silicate l~ ~t~d by ~hct and is ~,. fe.l~d espe~i~lly in granular laundry compositions. See pre~a,dlive rrlethodc in German DE-A-3,417,649 and DE-A-3,742,043. Other layered cilic~es such as those having the general formula NaMSix02~+ 1-yH2O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a nulub~ r from 0 to 20""~ fcl~bly 0, can also or alternately be used herein. Layered silir~t~s from ~hct also include NaSKS-5, NaSKS-7 and NaSKS-l l, as the a, ~ and y layer-silicate forms. Other silir~tes may also be useful, such as rnagnF-C;~ cilir~t~!, which can serve as a cricp~ning agent in granules, as a stabilising agent for bleaches, and as a COI .l~onent of suds control systems.

20 Also suitable for use herein are s~t~C; -~ crystalline ion eYch~rlge materials or hydrates thereof having chain structure and a CO-~ ;Qn r~scnted by the followinggeneral formula in an anhydride form: xM20ySiO2.zM'O wherein M is Na and/or K, M' is Ca and/or Mg; y/~ is 0.S to 2.0 and z/x is 0.005 to 1.0 as hught in U.S.
5,427,711, Sa}~,~lchi et al, June 27, l99S.
Suitable c~bolute builders include ~l~lin-~ earth and alkali mehl ~iLll on ~ 5 as clo~ in German Patent A~ ';o~- No. 2,321,001 published on Nove...be~ lS, 1973, although sodium bic~l,on~te, sodium c~l,onat." sodium sesquicarbonate, andother c~b~i~tc mir~P~lc such as trona or any convenient mlllt ~ 'e salts of sodium 30 c~l,onate and c~lcil~m c~ul,ona~ such as those having the c~ ~c;t;~ l-2Na2CO3.CaCO3 when anhyd-~us, and even calcium c~l~natcs in~h~Aing calcite, aragonite and vaterite, espe~i~lly forms having high surface areas relative to CCI ~'t calcite may be useful, for example as seeds or for use in synthetic de~.Ecnt bars.

3S ~ll....inos;li~tp builders are ~PSp~iqlly useful in granular de~.~cnts, but can also be inc~ dt~d in li.luids pastes or gels. Suitable for the present pul~)OSeS are those W O 97/433g3 PCTrUSg7/08441 having empirical formula: [MZ(Alo2)z(sio2)vlxH2o wherein z and v are in~g~,~ of at least 6, the molar ratio of z to v is in the range from 1.0 to O.S, and ~ is an integer from 15 to 264. Aluminocilirq~es can be crystalline or amorphous, natu~lly~ul.ing or srthetirqlly derived. An alu~ os;licqte productiolt method is in U.S. 3,985,669, Krummel, et al, ~ct~ber 12, 1976. ~fel,ed synthetic crystalline q~ minosilirqte ion exchqnge materials are available as 7~1ite A, _eolite P (B), Zeolite X and, to whatever e~ctent this differs from 7~1ite P, the so called _eolite MAP. Natural types, inclu~ing clinoptilolite, may be used. 7~1ite A has the formula:
Nal2[(AlO2)12(SiO2)12~ aH2O whcnc,n ~c is from 20 to 30, es~riqlly 27. Dehydrated ~li~s (~c = O - 10) may also be used. P~fe~ably, the alllminocilirqt~ has a particle size of 0.1-10 microns in ~ ..ct~,..

Suitable organic d~tc~g~nt builders include polyca,l,o..ylate cQmr~ n~ls inr~ ing water-soluble nons~.,r~ctant dicarbo~cylates and tricarboxylates. More typically builder poly~l,oAylates have a plurality of carboxylate groups, ~l~ably at least 3 carboxylates. Carboxyhte builders can be formul-q-ted in acid, partiaUy n~u~l, neut~al or ov~la~d form. When in salt form, allcali metals, such as s~ n, pOtqCCil~m, and lithium, or qlL;-n~ nil~- - salts are p.~ d. Poly~l.oaylate builders include theetherpolyc~rloxylates, suchaso-Ay~icucçinqte~ seeBerg, U.S. 3,128,287, April7, 1964, and ~ q~ li et al, U.S. 3,635,830, January 18, 1972; "TMS/TDS~ builders ofU.S. 4,663,071, Bush et al, May S, 1987; and other ether carboxylates including cyclic and alicyclic co.-~un~k, such as those d~sc.il,ed in U.S. Patents 3,923,679;
3,835,163; 4,158,63S; 4,120,874 and 4,102,903.

O~er c~ ~ble builders are the ether hydroxypol~c~l~Aylates, copolymers of maleicanh~d i~c with c lhyh~c or vinyl methyl ether; 1, 3, 5-trihydroxy ~n~ e-2, 4, 6-tnsulphonic acid; c~b~A~,--I~Lh~ ysuc~iniG acid; the various allcali metal, z ~"~ C!n;~
and substituted S~ ....t~ .... salts of ~ c.,tic acids such as ethyler~ G 1~ ~ t;r acid and n;tri1O~ ;r acid; as well as mellitic acid, suc~iniC acid, polymaleic acid, 30 b~ ~ 1,3,5-11ic&bo~lic acid, carboAymethyloxysuc~inic acid, and soluble salts thereof.

S e.g., citnc acid and soluble salts thereof are i~l,po.~nl carboxylate builderse.g., for heavy duty liquid dete~. nts, due to availability from .~n~.~able ,~ so~,~s and 35 biodegr~ahility. Cit~qt~os can also be used in granular co~ os;l;Qns, es~e.ciqlly in , .. --. .... . . .

CA 02254946 1998-ll-17 W O 97/43393 PCTrUS97tO8441 -co,llbination with zeolite and/or layered silicates. Oxy~icuccin~tes are also espe~iqlly useful in such cGml)osi~ions and combinations.

Where permitted, and çs~iqlly in the form~ tion of bars used for hand-launderingC!p~P ,qtionC all~ali metal ph~ hqt~s such as sodium tripol~l~h~cl~h~t-~s sodiumpyrophosphqte and sodium orthoph~sph-q-te can be used. phGs~ n~ builders such asethane-1-hydroxy-l,l~iphQsrh~nqtP and other known phosphon-q-tPs e.g., those of U.S. 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137 can also be used and may have desirable qntic~qling }J~ s.
Certain detersive su- r-~rl;~t~ or their short-chain homologs also have a builder action.
For unambiguous forrnula ~counting purposes, when they have surfactant c-q~ps~ ility, these materials are sU~nmp~ up as detersive surf: c tqntc Pn fe.lxl types for builder fi~neti ~nqlity are illu~at~d by: 3,3-dicarboxy-4-oxa-1,6-h- ~~n~;oqtPs and the related 15 c~ c di~l~C~d in U.S. 4,566,984, Bush, January 28, 1986. .Sucrinic acid builders include the Cs-C20 alkyl and alkenyl suc~inic acids and s. lts thereof.S~c~ ~ builders also in~lude laurylcucri~qte, myristylcucrinqtP. palmitylsuccinate, 2-~o~l~Pc~nylcuc~;nqtp (pl~L.l~d), 2-pPnt~dp~c~pnylcuccinqtp~ Lauryl-su~;n~trs arede~~libed in E~upean Patent ~pplic~ti~n 86200690.5/0,200,263, published Nove..l~.
5, 1986. Fatty acids, e.g., C12-Clg m~no~ rlic acids, can als~o be i~ o.a~ed into the c~ ~s:tiQn~ as surfactantlbuilder materials alone or in co.l~b~ ;~ with the aîo,~ t;on~ builders, es~;qlly citrate and/or the sue~in~r builders, to provide ~A;I;~n~l builder activity. Other suitable polyc~ylates are disclQsed in U.S.
4,144,226, C-~f kfi~l~ etal, March 13, 1979 and in U.S. 3,308,067, Diehl, March 7, 1967. Seealso Diehl, U.S. 3,723,322.

Other types of I~ ,af~lc builder materials which can be used have the formula (MX)i Cay (CO3)z wherein x and i are int~ from 1 to 15, y is an integer from 1 to 10, z is an integer from 2 to 25, Mi are cqtiQns, at least one of which is a water-soluble, and 30 the e.~udtion ~i = l ls(xi multirli~ by the valence of Mi) ~ 2y = 2z is 5qticfied such that the formula has a neutral or ~bqlqr~ charge. These builders are l~ fe.lcd to herein as ~Mine~l Builders". Waters of hydration or anions other than c~ may be added provided that the overall charge is bq-lq~ced or neutral. The charge or valence effects of such anions should be added to the right side of the above equation.
35 ~efe ably, there is present a water-soluble cation sele~t~ from the group consi~ting of hydrogen, water-soluble metals, hydrogen, boron, qmmrmium, silicon, and .~ur~s thereof, more preferably, sodium, potassium, hydrogen, lithium, ammonium and mi~tures thereof, sodium and po~Ccillm being highly preferred. Ncnlimitin~ ~ .~ r'es of noncarbonate anions include those ~ ted from the group concictin~ of chloride, sulfate, fluoride, oxygen, hydroxide, silicon dioxide, ch~nate~ nitrate, borate and S mi~ctures thereof. P~ fe..cd builders of this type in their ~imrlest forrns are s~
from the group con~i~tin~ of Na2Ca(C03)2, K2Ca(C03)2, Na2Ca2(C03)3, NaKCa(C03)2, NaKCa2(C03)3, K2Ca2(C03)3, and combin~tionc thereof. An lly ~,r fe~d material for the builder described herein is Na2Ca(C03)2 in any of its crystalline n Y~ific~iQIl~ Suitable builders of the above-defined type are further 10 illl.ct-~d by, and in~lude, the natural or synthe~c forrns of any one or cG...b;~ ;onc of the following minerals: A~gl~ e, Andersonite, Ashc-ufLineY, ~y_.i~e, Bol~it4, Bur~ Rut~rh~ C~ncrinite~ Call~..-aite, Carktonit~ Davyne, Do.uuyit~Y, PairrhilAi~ Ferrisurite, F~n7ir~ . G7udeffroyite, Gaylussite, Girvasite, Cr~o.~tc, Jouravslcite, ~ rh~.~g;t~ry, Kf~t~nerit~ Kh~nne~llite, I~pe~ ;tf,Gd, ~ iottit~, 15 Mcl~elveyiteY, Mic~ ~ ;te, Mroseite, Natrofairchildite, Nye it~i" P.e~ .on~:t~e, Saclofarit " Sch~ gerite, Shortite, Surite, Tunisite, T~ nite" Tyrolite, Vishnevite, and 7Pm~rite. P~t;fe.l~ d mineral forms include Nyererite, Fairchildite and Shortite.

rn4~lll&s Enzymes can be i-~r1vded in the present dete.E,_nt co, ~po~;t;onc for a variety of p~ S, i~rl~,-l;ng removal of protein-based, carbohydrate-based, or trigly~.~de-based stains from s~bs~tes, for the p.~ ,ntion of refugee dye transfer in fabric laundering, and for fabric l~s~.~l;on Suitable enzymes include prot~,s amylases, lipases, 25 cellulasa, pc, ~ ~s, and llfi~lul~s thereof of any suihble origin, such as v~animal, b~r~";~l, fungal and yeast origin. I~,fc.l~d s~l~ti~ ns are inflvenc~d by factors such as pH-activity and/or shbility optima, th~ osl ~ ty, and stability to active det~,.gcnls, b~i1Aers In this respect bacterial or fungal enzymes are pl~,fe,l~d, such as bac~ial amylases and prot~q-~s and fungal ce~ ~s ~Detersive ~ C'', as used herein, means . ny enzyme having a rleq~ing~ stain removing or otherwise be~efi~iq1 effect in a laundry, hard surface cle-~in~ or pe~o~
care dc~,.E,cnt col~ om r~,fe.l~d detersive enzymes are hydrolases such as plot~s amylases and lipases. ~,fe.l~d enzymes for laundry l.ul~o~s include~ but 35 are not limited to, proteases, cellulases, lipases and pero~ q~s Highly ~fe.l~,d for O! ~at;c dishwashing are amylases and/or prot~-q-~s ~ . .. , . ~ ...

WO 97/433g3 PCT/US97/08441 Enzymes are normally incorporated into detelgellt or det~ "t additive compositionc at levels suffirient to provide a ~cle~ning-effective amountn The term "cle~ning effective ~mollnt" refers to any ~rnount capable of producing a clç~nin~, stain removal, soil S removal, whiter~ g~ deodorizing, or fre~hnPss improving effect on substrates such as fabrics, dishware. In practical terms for current commercial pr~p- ~tion~. typical ~moUnt~ are up to S mg by weight, more typically 0 01 mg to 3 mg, of active enzyme per gram of the det~nt co, ~c;l;nn Stated otherwise, the C~! pGs;l;Qns herein will typically c~ , from 0 001% to 5%, preferably 0.01 %-1% by weight of a 10 CO~ r~;al enzyme p~ ;nn. Protease enzymes are usually present in such commercial p~ t;onc at levels sufficient to provide from 0 005 to 0.1 Anson units (AU) of activity per gram of col~l~silion For certain de~cnts, such as in automadc dishwashing, it may be desirable to increase the active enzyme content of the c~ ial p.~ tion in order to minimi7~ the tot. l qmount of non-catalytically acdve 15 materials and thereby illlp~.e ~ll;nglfllming or other end-results. Higher active levels may also be desirable in highly c~nc~ ted de~.~,cnt forrn l~iQn~

Sui'~l le e~amples of pr~t~ses are the subtilisins which are obtained from panticular strains of B. s~nlis and B. Iicl~en~formis. One suitable prot~ is obt~ntd from a20 strain of R~invs, having mq-im~m activity l~lrou~hout the pH range of 8-12, developed and sold as ESPERASE~ by Novo Indu~llies A/S of Denmark, h~.~;n~L~
"Novo~. The pl~pa~alion of this enzyme and analogous enzymes is described in GB
1,243,784 to Novo. Other suitable proteases include ALCALASE~ and SAVINASE~
from Novo and MAXATASE~ from Inter~qtion~l Bio-Synth~ti~s Inc., The 25 Netherlands; as well as Protease A as di~closed in EP 130,756 A, January 9, 1985 and Protea~c B as ~ d in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 198S. See also a high pH protease from Bacillus sp NCIMB 40338 des~7bec1 in WO 9318140 A to Novo. Enzymatic dete.genls comprising piot~, one or more other c~nL~ es, and a reversible y~e inhibitor are deselibcd in WO 9203529 A to 30 Novo. Other p~f~ Ot~S include those of WO 9510591 A to Procter & Gamble When desired, a protease having de~;,~d adsorption and inc,~d hydlol~;.;s is available as d~i~cl in WO 9507791 to Procter & Gamble A r~C~! k; ~1 trypsin-lilce p~t~ for d~ nls suitable herein is described in WO 9425583 to Novo.

35 In more detail, an es~i~lly plefe.,~d plote~, l~ fe.l~ to as "F~ot~se D~ is acarbonyl hydr~ldse variant having an amino acid sequence not found in nature, which is denved from a p~ or carbonyl hydrolase by snbstihlting a different amino acid for a plurality of arnino acid residues at a poCition in said carbonyl hydrolase equivalent to position +76, preferably also in cornbin~tion with one or more arnino acid residue po~jtiOnc equiva~ent to those sflP~t~J from the group concictin~ of +99, +101, +103, 5 + 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 acco~ding to the ~ lg of R~ loliquefaciens s~btilicin, as des~libed in the patent a~plic~t;onc of A. Baec~, et al, entitled "Protease-C~or.l;-ini-~g Cleaning Co..~ ;onc~ having US Serial No. 08/322,676, and C. Ghosh, et al, ~Bleaching 10 Compositions Comprising ~r~t~e Enzymes~ having US Serial No. 081322,677, both filed Octo~r 13, 1994.

Amylases suit~ herein, çs~~ y for, but not limited to ~ O~ ;c dish~ g IJU~ rlvdç, for e~ample, a-arnylases d~ ibed in GB 1,296,839 to Novo;
15 RAPIDASE~, Illlc~ r~l Bio-Syr~hPti~s Inc. and TI~RMAMYL~, Novo.
~UNGAMYL~ from Novo is es~iqlly useful. Fn~ ce g of enzymes for improved stability, e.g., o~idative stabiliq, is lcnown. See, for e~ample J. RiolQgjrql Chem., Vol. 260, No. 11, June 1985, pp. 6518-6521. Certain p~fcll~ em~ Pnts of the present c4-..~C;l;Qnc can make use of amylases having i~ ed stability in dct~.E,e.lts 20 such as j~"~o~"~l;r, dish~hing qpes, es~iqlly improved oxidative stabiliq as measured against a refe~nce point of TERMAMYL~9 in commerci~ l use in 1993.
These p.ef~ d ~,.yl~s herein share the cl~ . ;stir of being ~st. biliq~nhqn~
amylases, ch~- - t~ d, at a minimum, by a l..~.uable improve.llc~l in one or more of: o~idativc stability, e.g., to hydrogen peroxide/tl ~oetylethylen~l;~ e in 25 bur~ soludon at pH 9-10; thermal stabiliq, e.g., at co.lll,lon wash ~.~I~.a~ s such as 60~C; or q~ q~ e stability, e.g., at a pH from 8 to 11, ...e~-,cd versus the above~ ;re~ f,~ ce point arnylase. Stabiliq c. n be Illc~lsul~d using any of theart~isclosod t~ tests. Soe, for e~nple, r~fe~nc~s ~ osed in WO 9402S97.
Stabiliq enhanced ~nylases can be o~t-in~d from Novo or from CeA~n~r 30 T~ ol. One class of highly p~fc.l~xi . mylases herein have the c~ ty of being derived using site d;~Lct~ v~ P~;c from one or more of the ~
amylases, e~srecjqlly the f~ril/~s a-amylases, regardless of ~ l,clh~ one, two or multiple amylase strains are the j~nm~iqte ploeurso.~. Oxidative stabiliq-enhqnr~
amylases vs. the above-identifi~d ~fe.ence . mylase are ~ fell~d for use, es~iqlly in 35 b~ hing, more preferably oxygen bl~~hing, as distinct from chlorine bleaching, de~genl co~ os;~;on~ herein. Such p.efe.,~ arnylases include (a) an amylase according to the hereinbefore incol~,dled WO 9402597, Novo, Feb. 3, lg94, as further illustrated by a mutant in which sU~stitution is made, using alanine or lhl~ine, preferably tl~r~nil-e, of the methionine residue located in pocition 197 of the B
licheniformis alpha-amylase, known as TERMAMYL~9, or the homologous y.,.C;~
5 vqriqtion of a similar parent amylase, such as B. anryloliqu~faciens, B. subtilis, or B.
stearothennophil~ b) stability-enhanced amylases as described by G~e~lc4r ~n~.rnqtiorql in a papcr entitled ~O~idatively R~ci~t-q-nt alpha-Amylases~ p~"t~d at the 207th ~ " jr~n C~h~ ,ql Society ~qti~nql ~tin~, March 13-17 1994, by C.
~f;~hi~ Therein it was noted that bleaches in au~n~a~c dishwashing detc.~nts 10 inactivate alpha-amylases but that improved oxidative stability amylases have been made by Geu~el~r~r from B. Iichenifonnis NCIB8061. MethiQ~ine (Met) was id~-.lir.
as the most likcly residue to be modificd. Met was sl~bs~ ,~, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to ~ifir ~n~ t~, particularly i".po~nt being M197L and M197I with the M197T variant being the most stablc lS eAy.~d variant. Stability was measured in CASCADE~9 and SUNLIG~I~; (c) particularly pl.,f~l~,d amylases herein include arnylase variants having ~ditionsl n~lifi~ti~ n in the i...-..~h,~le parent as described in WO 9510603 A and are available from the q-Ccign~, Novo, as DURAMYL~9. Other particularly ~,~felled o~cidative stability enhq~ c~ arnylase include those d~.ibed in WO 9418314 to qcnP-~r 20 Int~ ;o~ and WO 9402597 to Novo. Any other oxidative st~bility enh~ ~c~d ~ rlase can be used, for e~carnple as derived by site~il~ d mutaeenPcic from hlown chimeric, hybrid or simple mutant parent fonns of available a~nylas~s. Other pref~
en,~ ~ifi~tion~ are ~rc~c~;ble. See WO 9509909 A to Novo.

Other amyla_e ~ S include those described in WO 95/26397 and in co-p~nAing application by Novo Nordislc PCI/DK96/00056. Sp~ific amyla e enzymes for use in the ddag0t compo~tions of the present invendon include ~-a nylases char~ ~ by having a ~ ;r.~ activity at least 2S!~i higher than the cp~ ;r.e activity of T ,1l~ll~1~9 at a te~-~r~ e range of 2S~C to 55~C and at a pH value in the range of 8 to 10, 30 mea ~d by the ~ ~9 a-arnylase activity assay. (Such Pl.~ b~C~ a-arnylase activity assay is ~P~.ikd at pages 9-10, WO 95/26397.) Also in~lud~d herein are a-amylases which are at least 80% ho, o'ogous with the amino acid s~ue.lc~ shown in the SEQ ID listings in the 1~ fe.~nc~. These enzymes are pl~ f~ ly inco.po.~t~ into Iau.~ ,ent compositions at a level from 0.00018~o to 0.060% pure enL~.ne by weight of the total c4l~ ;0~, more preferably from 0.00024% to 0.048% pure enL~.~ by weight of the total c4~n~s;l;Qn~

CA 02254946 1998-ll-17 W O 97/43393 PCT~US97/08441 Ce~ q-~Ps usable herein include both bacterial and fungal types, preferably having a pH
optimum between S and 9.5. U.S. 4,435,307, Barbesgoard et al, March 6, 1984, di~losos suitable fungal cçlll~lq~s from Humicola insolens or Humicola strain S DSM1800 or a cellulase 212-producin~ fungus belol ging to the genus Aeromonas, and c~ q~ e,.t~ ~ from the h~ o~ncreas of a m.,rine nlollusl~ Dolabella ~uricula 5Olq~r. Suit~ e c~llulq~s are also ~i~los~d in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME~9 and CELLUZYME~ (Novo) are eq~iqlly useful. See also WO 9117243 to Novo.
Suitable lipase enzymes for deb~rge~lll usage include those produced by .llicl~rg~ c of the Pseudomonas group, such as Pseudomor~s sn~zen ATCC 19. lS4, as ~li~los~
in GB 1,372,034. See also lipases in J~p~qne~ Patent Applirqtion 53,20487, laid open Feb. 24, 1978. This lipace is available from Amano Pha..n ~ ql Co. Ltd., Nagoya,15 Japan, under the trade name Lipase P ~Amano,~ or ~Amano-P.~ Other suitable col.. ercial lipases include Amano-CES, lipas~s e~c Chromob~7cter wscosum, e.g.Chromr~ ter uscosum var. Iipo~yticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromoborter viscosum lipases from U.S. Pi~.l P ..;~l Corp., U.S.A. and Disoynth Co., The Nethe~lands, and lipases ex Pseudomonas gladioli. LWLASE~9 enzyme derived from Humicola lanuginosa and commercially available from Novo, see also EP 341,947, is a pl~fe.l-xl Iipase for use herein. Lipase and amylase variants s~ i7ed against ~.o.~ ~, enzymes are described in WO 9414951 A to Novo. See also WO 9205249 and D 94359044.

In s~pite of the large number of publications on lipase enzymes, only the lipase derived from Hwluaola l~nuginosa and produced in ~spergillus oryz~c as host has so far found ~.;~,h~ad application as additi~c for fabric washing plodu.:~. It is available from Novo Nordislt under the ~ r~-.c ~ qce, as noted above. In order to optimize the stain removal p~Ç~ , ance of Lipolase, Novo Nordisk have made a nul,l~. of variants.
As des~ d in WO 92/05249, the D96L variant of the native Hurnicola lanuginosa lipase improves the lard stain removal efficiency by a factor 4.4 over the wild-type lipase (cY~I.es c~ a~ in an ~mQUnt l~nging from 0.075 to 2.5 mg protein per liter). Research Diccl~s~-e No. 35944 published on March 10, 1994, by Novo Nordisk .I;eclQs~s that the lipase variant (D96L) may be added in an ~m- un~ co,~ ~nA;ng to 0.001-10~ mg (5-500,000 LU/liter) lipase variant per liter of wash liquor. The present invention provides the benefit of improved whitenesc ~ nten~1r~ on fabrics using low ,..... , . . . . . . , .. , . . ~

W 097/43393 PCTrUS97/08441 -levels of D96L variant in detergent co.~,l~s;tiQnc contqinine the AQA surfactqntc in the ~l~anner ~iC~los~ herein, especi-q-lly when the D96L is used at levels in the range of 50 LU to 8500 LU per liter of wash l~lution.

S CUtinqc~ enzymes suitable for use herein are described in WO 8809367 A to ( ~nenC~l.

Pero~ qce P~ .les may be used in col"kin~l;on with oxygen sources, e.g., p~r~bondt~, pe~ ate, hydrogen peroxide, etc., for nsolution b1~ in~" or p~ lion of ll~sfer of dyes or pigm~ntC removed from s~ll,sl,at,~s during the wash to 10 other s~lbs~ s present in the w. sh solutinll. Known pero~ q-cps include horseradish perO~ qc~ ligninqcP, . nd halope~o~iAqcps such . s chloro- or bromo-pero~ q~P
Pe O~ q~cQ~ g dete.~ent col~.pos;tionc . re ~isclos~ in WO 89099813 A, October 19, 1989 to Novo arhd WO 8909813 A to Novo.

15 A range of c~r,..e rqteriqlc . nd me. ns for their incol~.ation into ~nthetic d~
c~...~ is also di~-los~l in WO 9307263 A a nd WO 9307260 A to (~-'f"'CO~
Int~nqti~rql, WO 8908694 A to Novo, and U.S. 3,553,139, J.nuary 5, 1971 to McCarty et al. ~~ .nes a re further ~liQrlosed in U.S. 4,101,457, Place et ~, July 18, 1978, ~nd in U.S. 4,507,219, Hl~ghrs, March 26, 1985. Enzyme materials useful for 20 liquid dete.be.~t forrnt~qtions, and their inco.~ .Lion into such for nl~]~innQ~, are ~liQ~-lQS~d in U.S. 4,261,868, Hora et ..1, April 14, 1981. Enzymes for use in d~.gents can be stabilised by v. rious techniques. Enzyme stqbiliQqtion t~hniques are and e~c ~ r~cd in U.S. 3,600,319, August 17, 1971, Gedge et al, EP
199,405 and EP 200,S86, October 29, 1986, Venegas. Enzyme stabiliQqti~n systems are also de~cribed, for e~ample, in U.S. 3,519,570. A useful R~ .5~ sp. AC}3 giving pr~ es, Ayl~uscs and c~ lqQ~s, is described in WO 9401532 A to Novo.

rn~l~ P '~;tabili7i~ ~yct~m The c .L~".e ~.~I_.n ~g c~ ;ons herein may optionally also comprise from 0.001 %to 10%, ~ ,f~.dbl~ from 0.005% to 8%, most preferably from 0.01% to 6%, by weight of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system which is co..~t;~le with the detersive enzyme. Such a system may be inherently provided by other formulqtion actives, or be added s~ r.Jy, e.g., by the 35 fo~mulq~or or by a manufacturer of de~,~,~,nt-ready enzymes. Such stabilizing systems can, for e~ample, comprise c~lri-lm ion, boric acid, propylene glycol, short chain CA 02254946 l998-ll-l7 W O 97/43393 PCTrUS97/08441 ~

carboxylic acids, boronic acids, and mixtures thereof, and are decign~ to address different stabili7~tion problems ~e~n-ling on the type and physical form of the d~t~ t c~ tiQn.

S One stabilizing approach is the use of water-soluble sources of r~lci~rn and/or . sgn~ ions in the finiched e4~ !5il;Qr~C which provide such ions to the enzymes.
ium ions are genPr~lly more effective than magnçsiunl ions and are p~f~ l~d herein if only one type of cation is being used. Typical dete.~eYll CG ~poC;~ n~esF~~ y liquids, will cQmpri~e from about 1 to about 30, p.~ f~ ~, bly from about 2 to 10 about 20, more p~f~bly from about 8 to about 12 mi11imcl~s of c~ nn ion per liter Of finich~d detefgent CG~ s;tion~ though variation is possible de~ ;n~ on factors in~lu~lin~ the ml~ y, type and levels of enzymes inc~ ated. P~f~, bly water-soluble ~lrjllrn or ...~.~c-:lJm salts are employed, includin~ for example c~
~ hlorir~P, c~lri-~n hydroxide, c~lrium fG..,-ate, calcium malate, r~ ll~ maleate, lS c~lri..m hyd~Aide and c~lcium ~ ; more generally, cqlcillm sulfate or magnesium salts coll~q~ Ain~ to the e~en plified c~lri~l~ salts may be used. Further inc~dlevels of C~4 i~m and/or M~g~c~;~.... may of course be useful, for e~ample for p.u-~.n~ g the g.~ cutting action of certain types of surfactant.

20 Another st~'~ili7~ app~oach is by use of borate spa~iPs. See 5ev~.~on, U.S.
4,537,706. Borate s~ 7prs~ when used, may be at levels of up to 10% or more ofthe con.~ n though more typically, levels of up to about 3% by weight of boric acid or other borate C~ Q~ such as bora~ or or~llûbo~ P are suitable for liquid det~ use. SUbstihltcd boric acids such as phenylboronic acid, but~ o.~ic acid, 25 p-b.~---o~hPnylbo.~,. ic acid or the lilce can be used in place of boric acid and reduced levds of total boron in det~r~,enl co~?os;~;nllc may be possible though the use of such substituted boron derivatives.

st~' ili7ir~g systems of certain cle~ni~g c~ )os;l;ons, for exarnple a'~"'~t;e 30 dish. ~shin g cQI~l~s;~ c may further comprise from 0 to 10%, p~fe.~bly from 0.01% to 6% by weight, of chlorine bleach scavenge~, added to prevent ch1~rin bleach species present in many water s~pplies from ~ cL ;ng and inactivating theerL~..~s, e~ ly unda ~ e c~n~ Qnc~ While chlorine levels in water may be small, typically in the range from 0.5 ppm to 1.75 ppm, the available chl~-nne in the 35 total volume of water that comes in contact with the enzyme, for e~mpl~ during dish-or fabric-~.~hing, can be relatively large; accordingly, enzyme stability to clllorine in-CX 02254946 l998-ll-l7 W O 97/43393 PCTrUS97/08441 use is solnP~tim~ps problematic. Since pe.~onate has the ability to react with chlorine bleach the use of ~Ai~ionq1 stabilizers against chlorine, may, most generally, not be ess~ l, though improved results may be obtainable from their use. Suitable chlorine scavenger anions are widely known and readily available, and, if used, can be salts S co~ in;l~ qmm~nill~ cations with sulfite, bic~lfit~P, thiosnlfite~ ~hi~s.llfq~tP, iodide, etc.
~ntioYi-~qntc such as car~qmqte~ ~ll,ale, etc., organic amines such . s ethytpn-pA;s~ F~hdce~c acid (EDTA) or alkali met. l salt thereof, ...o.~ t.~noldmine (MEA), and m~lul~s thereof can lilcewise be used. Likewise, special enzyme inhibition systems can be inc~l~lat~d such that different enzymes have I~G~
10 ~,- ~;hility. Other conventinnql scaveng~ such as bisulf-q-tP, nitrate, rhl~ e, sources of hydrogen peroxide such as sodium pe~lJOldte tetrahydrate, sodium ~ l~ldle ,.onohydrate and sodium per~bondtl" as well as phos~h~, conden~d p h~,~, ~Pt:~te, benzoate, citrate, f~.,.,at~, lactate, malate, tartrate, salicylate, etc., and ll~lules thereof can be used if desired. In e~nPr~q~l, since the ch1~rin~ s~a-cn~
lS run~lion can be pe~rol"led by ingn~ient~ sc~uatcly listed under better ~~~
functi~nc, (e.g., h~d~n peroxide sources), there is no ~solute ~uhe.,.ent to add a ~ te chl~in~ scavenger unless a co,-~l o~ d ~.l~l",ing that function to the desired e~ctent is absent from an e..L~..,e co~ e en~ mPn~ of the invention; even then, the scavenger is added only for op~ ----- results. Moreover, the forn~ t~r will 20 e~cercise a chrr~ict~s nonnal sl~ll in avoiding the use of any cnL~".e sca~eng~r or s~ i7P which iSI majorly inl~4..~p~';bl~, as forrnu1~t~, with other reactive ~h~gf~l;~C
In relation to the use of ammonium salts, such salts can be simply ~mi~ed with the det~. ~ t c4--~ n but are prone to adsorb water and/or liber~ ...n~ni~ during st~ra~. AccorLngl~, such materials, if present, are desirably protected in a particle such as that d~P~-kd in US 4,652,392, Ragins~i et al.

p~~ S~ Pq~ A.pent Known pol~.,.e~ic soil rele~se agents, he.e;naller ~SRA" or ~SRA's~, c. n optionqlly be 30 employed in the present d,t~,a~t co..~ s If utilized, SRA~s will genPr.q11y compri e from 0.01% to 10.0%, typically from 0.1% to 5%, pl. felably from 0.2% to 3.0% by weight, of the ~--~s:l;o-~.

P~f~l.d SRA's typic~ly have h~dlùphilic s~gm~n~C to hydrophi1i7P the surface of 3S h~dl~h~b r fibers such . s polyester and nylon, and hy.llu~hob;c sel~. nlc to deposit upon h~dl~phobic fibers and remain adhered thereto through completion of waching CA 022S4946 1998-ll-17 W O 97/43393 PCTrUS97/08441 and rinsing cycles thereby serving as an anchor for the hydrophilic s~g~cl-tc This can enable stains occurring subsequent to L~ nt with SRA to be more easily ckq~ed inlater washing p~lules.

S SRA's can include a variety of charg~, e.g., . nionic or even cqtionic (see U.S.
4,956,447), as well as nonc~ ..ono...er units and structures may be linear, b.,~ch~ or even star-shaped. They may include capping moieties which are e~iqllyeffecdve in controlling m~'~ulqr weight or altering the physical or surface-acdve pr~pellics. Structures and charge dLl-;bulions may be tailored for applic?~ n to10 different fiber or te~ctile types and for varied dete.~,ent or d~t~ nt additive pl~lucls.

Pref,.l~ SRA's include oligol..c~ic t~.phth~l~te esters, typically p,e~ by p.~cc~cs involving at least one transest rific~ti~ n/oligo~ ,i~tion, often with a metal catalyst such as a titanium(IV) ~ e Such esters may be made using ~dditi~nq~ nn ~
lS capable of being inco.~.dted into the ester structure through one, two, three, four or more ~ s rs, wilhG~ll of course fo.-,.ing a densely cro~cli~1 overall slluctu~.

Suitable SR~'s inrlud~P- a sulfonated pr~lu~;l of a s.lbs~r.t;3l1y linear ester oligomer comprised of an oligomeriG ester h~~LI~Qne of terephthaloyl and o~cyalkylw~A~ repeat 20 units and allyl-derived sulfonat~ terminal moieties covalently ~ - hcd to the b~ one, for e~cample as desen~l in U.S. 4,968,451, November 6, 1990 to J.J. SchPi~l and E.P. ~ elinlr- such ester ~I;go- ~s can be p,~ od by (a) etho~ylating allyl ql~ohQl, (b) ~lil~g the pr~h. t of (a) with di--.~ lhyl t~.epklh~lq~te (~DMT~) and 1,2-~.opyl~,ne glycol (~ ) in a two-stage t~l~st..;l~ t;on/ oligomerization pl~luic and (c) 2S reacting the ~vd~l of (b) with sodium metabisulfite in water; the nnnionic end-capped 1,2-propybnelpol~o.~ hyl~c ~ ht~lqtP polyesters of U.S 4,711,730, D~
8, 1987 to C~J; ~1~ d al, for e~cample those produced by tIanxsbrificaoon/oligom~ of poly(ethyleneglycol) methyl cther, DMT, PG and poly(c~ cglycol) (~PEG~); the partly- and fully- anionic-end~apped oligomeric 30 esters of U.S. 4,721,S80, Janu~ 26, 1988 to Gosselink, such as oligomers fromethylene glycol (~ ), PG, DMT and Na-3,6-dioxa-8-hyd,uAy~l- F~.~lfonate; the lU~n;Q.';''--Capped bloclc ~ ~t~ oligoln~ric compounds of U.S. 4,702,8S7, October 27, 1987 to G~s~l;nk, for e~arnple produced from DMT, Me-capped PEG and EG
and/or PG, or a co-~bin~;ol~ of DMT, EG and/or PG, Me-capped PEG and Na-35 di,..clhyl-5-sulfoi~)ph~latc; and the anionic, es~ci~lly sulfoaroyl, end capped tc~ ~ estcrs of U.S. 4,877,896, Oc~ober 31, 1989 to M~ldon~lQ~ occ~link et .. . ...

WO 97/43393 pcTruss7lo844 al, the latter being typical of SRA's useful in both laundry and fabnc c~n~iti~ning products, an e~mple being an ester co...~s;tio~ made from m-sulfobçn-~ie acid mQnosalium salt, PG and DMT optinn~lly but preferably further comprising added PEG, e.g., PEG 3400.
s SRA's also inr~ude simple copolymeric blocks of ethylene te~p~th~ e or propyleneterephthql~'o with polyethylene o~cide or polypropylene oxide tc~k~hql~, see U.S.
3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to F~r~dl~r, July 8, 1975;
cellulosic derivatives such as the hydro~yether c~ lo~ic polymers available as 10 METHOCEL from Dow; and the Cl-C4 al_ylc~ -lo~es and C4 h)dloayallcyl c~ s~s see U.S. 4,000,093, Dec~-mbçr 28, 1976 to Nicol, etal. SuitableSRA's chq~rt~ by poly(vinyl ester) hydr~phobe ~g~ t~ indude graft copolymers of poly(vinyl ester), e.g., Cl-C6 vinyl esters, p~fe.ably poly(vinyl acetate), grafted onto polyal~ylene o~ide b~LI~oncs See Eur~n Patent J~pplirqtion 0 219 048, p~lJlishcdApril 22,1987 by Kud, et al. 1~ ~ially available e~arnples include SOKALAN
SRA's such as SOKALAN HP-22, availablc from BASF, Germany. Othcr SRA's are polyesters with repeat units cQntS ;nil~g 1~15% by weight of ethylene te~hl~q~
~E.~h r with 90 80% by weight of polyo~yethylene te~ph~h~l~te~ derived from a polyoAyethylene glycol of average molecular weight 300-5,000. Co..----c-- ;al e~amples 20 include ZELCON S126 from Dupont and MILEASE T from ICI.

Another p.~f~.l. d SRA is an oligomer having cmpiric~l formula (CAP)2(EG/PG)s(T)S(SIP)l which comprises ~ oyl (1), ~ î4;~h~ oyl (SIP), oAyethyl~A~ and o-Ay-1,2-propylene (EG/PG) units and which is p~f~ably~S t~ t~l with end caps (CAP), preferably Incdified ic Ih;nn,at~5, as in an oligomer B one sulfoi~p~.th~lQyl unit, S t~ )klh~l~yl units, oxyethyl~n~A~r and OAY-1t2-P~ AY units in a defined ratio, pl~fe.ably about 0.S:1 to about 10:1, andtwo end cap units derived from sodium 2-(2-hyd~A~_lhoA~) e'~ fonate. Said SRA preferably further oQn~pr-~-s from 0.5% to 20%, by weight of the oligomer, of a 30 crystallinity-l~Juci-~g stabiliser, for e-Aample an anionic aUlrd~ such as }inear sodium dodec~ ulfonate or a ~ .ul~r sel~t~d from Aylene-, cumene-, and toluene-sulfonates or l~ub~lul~S thereof, these stabilizers or m~ifiers being introduced into the s~.,~is pot, all as taught in U.S. S,415,807, ~Jo~linl~, Pan, Kellett and Hall, issued May 16, 1995. C ~it-'~Je ,.-ono..-~ ~ s for the above SRA include Na 2-(2-35 h~droA~retho~cy) e~h~ , -lfonate, DMT, Na- dimethyl 5-sulfois~phthalate, EG and PG.

Yet allotl,~ group of p.cfel-~d SRA's are oligomeric esters comprising: (1) a b~t~ne comprising (a) at least one unit selPct~ from the group con~ictin~ of dihydroxysulfonales, polyhydroxy sulfonates, a unit which is at least trifi~n~ on~l wl.~y ester lin~g~s are formed rçsul2in~ in a branched oligomer ~ bone, and S c~ b;n~ c thereof; (b) at least one unit which is a tereph~hqlQyl moiety; and (c) at least one unsulfonated unit which is a 1,2~xyaJkyleneoxy moiety; and (2) one or morc capping units ~Pl~P~t~ from nonif~nir cqppi-~ units, anionic wppin~ units such as al~A~latcd, p ~fe.~bly etho~cyhted, icethionatPs~ alkoAylated pro~P,-.Ifonates, allcoAyhted p~ ~ic~lronat~s~ o..~ht~ ph~nols~lfonates, sulfoaroyl derivatives~0 and l~ lu~S thereof. ~fe.l~d of such esters are those of empirical formuh:
~ (CAP)%(EGlPG)y ' (DEG)y ~ (PEG)y " ' (T)z(SIP)z ' (SEG)q(B)m}

wherein CAP, EG/PG, PEG, T and SIP are as defined he~.na~e, (DEC;) ~
di(o~yethylene)w~y units; (SEG) f~.~nt~ units derived from the sulfoethyl ether of lS glyc~ and related moiety units; (B) r~Ats b.-r~cl~ g units which are at leastt ihn~tional whereby ester lin~gcs are formed resulting in a branched oligomer ~LI ~ e;~cis 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.S to about 2S; z' is from 0 to about 12; z + z' totals from about 1.5 20 to about 25; q is from about 0.05 to about 12; m is from about 0.01 to about 10; and %, y', y", y"', z, z', q and m r~ ~nt the average number of moles of the CO.I~ ~?~ units per molc of said estcr and said ester has a ~ weight rangingfrom about 500 to about 5,000.

2S ~f~ l~ SEG and CAP l.~on--."r.~ for the above esters include Na-2-(2-,3-dihy~LoA~p,opoAy)~lhq~-~lfonate (~SEG~), Na-2-{2-(2-hydro~yetho~cy) etho~y~
ethancwlfonate (~SE3~) auld its ~'0mr'~8q and ~ tur~s thereof and the p,~du;ts of e~.~yl~, and sulfonating allyl ~lcohol. ~.,fe.-od SRA esters in this class include the product of t~lsest~,.ifying and oligomerizing sodium 2-~2-(2-30 hyJ.o..y~l.u.~yktho~y~e~h~ncs~lfonate and/or sodium 2-[2-~2-(2-hydro~yetho~cy)-etho~y~ ~.oAy]~lh~n/~lfonate, DMT, sodium 2-(2,3-dihydro~cy~.u~..~) ethane sulfonate, EG, and PG using an a~.up-iate Ti(IV) catalyst and can be ~le-~ign~ed as (CAP)2(~S(EG/PG)1.4(SEG)2.S(B)0. 13 wherein CAP is (Na+
03StCH2CH20]3.5)- and B is a unit from glycerin and the mole ratio EG/PG is about 35 1.7:1 as l~.~bu~.,d by conv~ ;on~l gas chromq~ograrhy after complete hydrolysis.

... , .. . .. . , . ........ ~ ... ...

W O 97/43393 rCTnUS97/08441 -~dditionql classes of SRA's include (I) nonionic ~ qlqt~s 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 I q&~q-Cce et al; (II) SRA's w}th carboxylate t~"~ al groups made by adding trimellitic anhydride to known SRA's to convert terminal hydro~yl5 groups to trimPllitqte esters. With a proper ~le~!inn of catalyst, the tnmP11itin anhydride forms linkages to the terminals of the polymer through an ester of theisolqted carbo~ylic acid of trim~llitir anhydride rather than by opPn~ of the anhydride linl~e~ Either nor innic or anionic SRA's may be used as starting n~qteriqls as long as they have hydroAyl h.l.,inal groups which may h~e esterified. Ses U.S. 4,525,524 Tung 10 et al.; (m) anionic tere~hthqlqte-based SRA's of the UlCIh~e linked vadety, see U.S.
4,201,824, Violland et al; (IV) poly(vinyl caprol~~tqm) and related co polymers with ~"on~ -a such as vinyl pyrrolid~n~ and/or dimethylq...;nG~Ih~l ...- lh~ late, in~h)~
both n~ OniC and ~t;Q-~ir polymers, see U.S. 4,579,681, Ruppert et al.; (V) graft copol~..-e.s, in ~;~;Q~ to the SOKALAN types from BASF made, by graf~ng acrylic 15 ,.,OIu~ s on to sulfonated pOl~h~a; these SRA's assertedly have soil release and an~ n activity similar to Icnown cellnlQse ethers: see EP 279,134 A, 1988, to Rhone-Poulenc Ch~ ; (Vr) grafts of vinyl monolners such as acrylic acid and vinyl acetate on to proteins such as c~inc~ see EP 457,205 A to BASF (1991); (V~) polyester-polyamide SRA's p~pa~d by cond~ ~~;ng adipic acid, ~~ "" and 20 polyethylene glycol, es~i~lly for treating polyamide fabrics, see Bevan et al, DE

2,335,044 to Unilever N. V., 1974. Other useful SRA's are described in U.S. Pat~:nts 4,240,918, 4,787,989, 4,525,524 and 4,8M,896.

W O 97/43393 PCTrUS97/08441 Clay Soil Remov~l/Anti-~de~osition Agents The CQ~ ~S l;OtlS of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antired~position pn~ ies. (~
5 de~,~5,e.lt C~ rO~;tiQllc which contain these COmpOl~n~lS typically contain from 0.01 %
to 10.0% by weight of the water-soluble etho~ylates ~mines; liquid det~r~ht co.npos;l;onc typically contain 0.01% to S%.

The most ~l~ f~ d soil release and anti-~ po~;t;--n agent is etho~ylated tetraethylene-10 pentan~ine. F-~mpl~ry ethoxylated amines are further descl;hed in U.S. Patent4,597,898, VanderlI~er, issued July 1, 1986. Another group of pr~fe.l~d clay soil removal-~lth~l~ t;~n agents are the c~tif~nir co~npou~ os~ in European Patent ~llp1jr~tion 111,965, Oh and ~30CC~linlr~ p~h!iched June 27, 1984. Other clay soil removal/a..ti~l~;t;~ agenL which can he used include the etho~ylated amine polymers Ai~lo~l in I:ur~p~n Patent Applir~tion 111,984, t~Joss~linlr~ published June 27, 1984; the zwiltL.;OlUC polymers ~isclos~d in Eulop~ Patent ~ inn 112,592,(3~C~l;n1f p~.b~ ~ July 4, 1984; and the amine oxides ~ Qs~d in U.S. Patent 4,548,744, Connor, issued C~tober 22, 1985. Other clay soil removal and/or anti redeposition agents Icnown in the art can also be utilized in the co~s~ nc herein.
20 See U.S. Patent 4,891,160, V~dPr~Pr, issued January 2, 1990 and WO 95/32272, published Novc."~. 30, 1995. Another type of p.~fc,l~d ant~dcpQ~;Iion agent ;n~l~ldes the carboxy methyl ce~ se (CMC) materials. These materials are well Imown in the art.

2S Pol.~ ic n ~ c Polymaic dl~ ~g agents can ad~ g~'4usly be utilized at levels from 0.1 X to 7%, by weight, in the co..~c l;ons herein, es~iqlly in the p~nce of zeolite and/or layered silicate b~ ors. Suitable polymeric dispersing agents include pol~."c~,c30 polyc~bo.~lates and polyethylene glycols, ~l~hough others known in the art can also be used. It is bel;cv~, though it is not in~e~d<d to be limited by theory, that ~ m~.;c di~l~& agents enh ~ce overall dete.E,~.lt builder ~Çu....ancc, when used in combination with other builders (inrlu~ling lower molecular weight polyc~l~Ayla~) by c~ystal growth inhibition, particulate soil release ~ p~ ;on~and anti-l~dc~t;on ... . . . . . . .

O 971433g3 Polymeric polyc~l~ylate materials can be prepared by polymerizing or copolym~liLi~g suitable unsaturated mQno~ , preferably in their aeid form.
Unsaturated monomeric acids that can be polymerized to form suitable polymerie polye~l~w-ylates inelude acrylic acid, maleic acid (or maleic anhydride), fumarie aeid, it~ niG acid, ~conitir acid, .~ nie aeid, eitraconic aeid and methylempfnqlnl~ir aeid.
The pl~ lce in the polymerie polyc~l,oxylates herein or ~--o~o,---~ ;c sle~ P ~t~, in~ no earboxylate ~dieals such as vinylmethyl ether, styrene, ethylene, ete. is~ui~ble provided that sueh .se~ eM~i do not constitu~p more than 40% by weight.

Partieularly s~it~le polymerie pol~ .ylates can be derived from aerylie acid. Such acrylic aeid-based polymers whieh are useful herein are the water-soluble salts of polyfnPri7~ aerylie aeid. The average rnol~culqr weight of such pol~ e.~ in the aeid form ~ fe.ably ranges from 2,000 to 10,000, more plefe~ly from 4,000 to 7,000 and most preferably from 4,000 to 5,000. Water-soluble salts of sueh aerylie aeid polymers ean inrlude, for e~ample, the alhli metal, ~m....~ .... and s~l,s~ ned q~ -n~ m salts.
Soluble pol~ of this type are lcnown mqtPfiqlc Use of pol~ lat~s of this type indetergent co---pos l;nnC has been ~;c~4s~d, for example, in Diehl, U.S. Patent

3,308,067, issued Mareh 7, 1967.

Aerylie/maleie-basod copolymers may also be used as a plef~l~d CO~pQn~'~ of the dis~ g/anti-redeposition agent. Such materials include the water-soluble salts of eo~ l..e,a of acrylic acid and maleic acid. The average ~ 'e~ qr weight of such ajpd~l..~a in ~c acid form pl~fe~ably ranges &om 2,000 to lQO,OOO, more p~f~bly from 5,ûOO to 7S,OQO, most p~f~.ably from 7,000 to 65,000. The ratio of acrylate to maleate S~e,J~ lo in such copolymers will generally range from 30:1 to 1:1, moreprefe~bly from 10: 1 to 2: 1. Water-soluble salts of such acrylic acid/maleic acid copolymers Gm in~lude, for e~cample, the allGlli metal, ~ Q~ and substituted ammoNium salts. Solvblc acrylate/mql~te copolymers of this type are hlown ~q~ c which are d~3, ~;~d in I;UlOpean Patent ~Mli- ~ion No. 66915, pvbliched ~
15, 1982, as well as in EP 193,360, publish~d S~t~ - ~r 3, 1986, which also ~escrib~s such yol~"~ ~ ;s,ng h~d~.~ pylacrylate. Still other useful ~ ne agents incl~de the maleic/acrylic/vinyl alcohol terpolymers. Such ~nqteriqlC are.,lso .t~ os~
in EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl q~ C!hnl~

W O 97143393 PCTrUS97/08441 Another polymeric material which can be include~ is polyethylene glycol (PEG). PEG
can exhibit dispersing agent pe,rol",ance as well as act as a clay soil removal-antiredeposition agent. Typical molecular weight ranges for these purposes range from 500 to 100,000, preferably from 1,000 to 50,000, more preferably from 1,500 to 5 10,000.

Poly~latc and polyglut~m~te dispersing agents may also be used, es~i~lly in conjunction with zeolite builders. Dis~.~ing agents such as polyas~te preferabl have a molecular weight (avg.) of 10,000.
Bri~,htç,ner Any optical b, ;ght~--~ 5 or other bri~htenirlg or whitening agents Icnown in the art can be i~col~l.-t~d at levels typically from 0.01% to 1.2%, by weight, into the d~~ t lS C4~ ;QI~S herein. ~olnmPrcial optical briehh~ which may be useful in thc present invention can be c~ ;fi~d into subgroups, which in~lude, but are not n~cc--;ly limited to, derivatives of ~tilhenç, pyrazoline, ~)~ .;11, carbo%ylic acid, .~c~ p~anines~ o!hiophcne S,5-dio~cide, azoles, S- and 6-...~ ed-ring het~rocycles, and other rni~ ous agents. Fl~ples of such bri~ c n~ ~ are 20 ~i~los~d in ~The Productior~ and Ap~!ir~tion of Fluorescent Brieh~c~ g Agents~, M.
Zahradnik, PUblich~ by John Wiley & Sons, New York (1982).

Sp~ifi~ e%amples of optical brigh~n~s which are useful in the present Co,--pC~iti~ c are those irlpntifipd in U.S. Patent 4,790,856, issued to Wixon on Decrmher 13, 1988.
25 These br.ight0ers include thc PHORW~TE series of bri~h~c ~ from Verona. Oth_rbrighten~s disclosed in ~is 1~,fe.~ nce include: Tinopal UNPA, Tinopal CBS and Tin~pal SBM; availablc from Ciba-Geigy; Artic White CC and Artic White CWI), the2-(q ~.~l-phenyl)-2II r~pthotl ,2-dl~i. zoles; 4,4'-bis-(1 ,2,3-triazol-2-yl)-ctilh~n~s

4,4'-bis(styryl)b~ hr .~ls; and the q-mi~oumq ins. Specific e~-q- ?!~s of these 30 brighteners include 4-methyl-7-dieuhyl- -q-mino coumarin; 1 ,2-bis(ben7in~ q7QI-2-yl)ethylene; 1~3-diphenyl-pyrq-7nlinPs 2,5-bis(benz~ l-2-yl)thiophPnP; 2-styryl-napthotl,2-d~o~cazole; and 2-(stilben~-yl)-2H-r.~ 1,o[l,2~]tDle. See also U.S.
Patent 3,646,01S, issued reb,~,a.., 29, 1972 to ~qmilton.

35 Dye Tr-q-ncfer Inhib;l;,~ A~nt~

CA 02254946 1998-ll-17 W O 97143393 PCTrUS97/08441 The co~nl~s~tioll~ of the present invention may also include one or more materials effecdve for inhibit~ng the ~ansfer of dyes from one fabric to another during the cle~ning pr~ss. Generally, such dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone

5 and N-viny~ Aq7n~e~ mqng~ne~e phthalocy-qnine, peroxidases, and mixturcs thereof.
If used, these agents typically comprise from 0.01% to 10% by weight of thc CO.~pQS;~ , yl~fe,ably from 0.01% to 59~, and more preferably from 0.05% to 296.
More ~Cificqlly~ the polyamine N-oxide polymers p~fe.lcd for use herein contain 10 units ha~ing the following s~ ;tu-dl formula: R-AX-P; wherein P is a polymerizable unit to which an N-O group can be ~q~hed or the N-O group c. n form part of the polymerizable unit or the N-O group can be qtt;~~hed to both units; A is one of the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=; x is 0 or 1; and R is ~liph~~
e~.~ tcd ql;l~h~ 5~ alo!.~7t;cc, heterocyclic or alicyclic groups or any combination 15 thereof to which the nillugen of the N-O group c~n be ~t~~~hed or the N-O group is p~t of these g~oups. ~fe,led polyamine N-oxides are those ~4hc~ ;n R is a heterocyclic group such as pyridine, pyrrole, imi~7~1e, pyrrolidine, piperidine and derivatives ~ereof.

20 The N-O group can ,h,e~ t~ by the following general structures:

(Rl)X--I ~2)y; =N--(Rl)X
(R3)z whe2~n Rl, R2, R3 are ~lirh~~ic, aromatic, h~te,~clic or alicyclic groups or 25 combina~ons lhe,~f, x, y and z arc 0 or 1; and the nitrogen of the N-O group can bc attached or form part of any of thc af~ nl;oned groups. The arnine oxide unit of the polyamine N-o~idcs has a pKa < 10, }"ef~.~bly pKa < 7, more p,efe~lod pKa < 6.

Any polymer l~Lko.le can bc used as long as the amine oxide polymet formed is 30 watcr-soluble and has dye transfer inhibiting pr~,lies. FY~mpl~s of suitable pol~ ,ic b~~~n~-s are polyvinyls, polyalkylenes, polyesters, polyethers, poly.unide, polyimides, I)ol~a.;.ylates and ~ s thereof. These polymers include random or blocL copolymers where one monomer type is an amine N-oxide and the other monomer CA 02254946 1998-ll-17 W O 97/43393 PCTnUS97/08441 -type is an N-oxide. The amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to l :1,000.000. However, the number of amine oxide groupspresent in the polyamine oxide polymer can be varied by appropriate copolymerization or by an ap~n.~liate degree of N-o~ tion. The polyamine oxides can be obtained in 5 almost any degree of polymeri7qtion~ Typically, the average molecular weight is within the range of S00 to 1,000,000; more ~fe.,~;l 1,000 to S00,000; most piefe.-~xl S,000 to 100,000. This p~fe.l~ d class of materials can be refe.l~xl to as ~PVNO~.

The most p~fe.-~ polyamine N-o~ide useful in the deh.E,ent co...poC;l;onc herein is 10 po~y(4-vinylpyridine N o~cide) which has an average mole~ulqr weight of S0,000 and an amine to amine N-o~ide ratio of 1:4.

Copolymers of N-vinylpyrrQ1idone and N-viny1imi~l~7~1e polymers (~I~ d to as a class as ~PVPVI~) are also plcfe~l~d for use herein. ~efe.ably the PVPVI has an lS average molecular weight range from S,000 to 1,000,000, more pf~f~bly from 5,000 to 200,000, and most ~l~fe~ably from 10,000 to 20,000. (The average ~'e.ulqr weight range is deh.l,lin~d by light s~lh.ing as described in Barth, et al., Chemi~-q-l Anq~ Vol 113. ~Modern ~le~hcds of Polymer Characterization~, the ~ clos~res of which are inco~ ~ herein by 1~ f~.cnce.) The PVPVI copolymers typically have a 20 molar ratio of N-vin~ 41e to N-vinylpyrrolidone from l:l to 0.2:1, more pl~,f~ bly from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can h~e either linear or ~ ehcd.

The present invcntion c4~ ns also may employ a polyvinylpyrrolidone (~PVP~) 25 having an ave.~g~ molecular weight of from 5,000 to 400,000, plcf,.ably from S,000 to 200,000, and more pl~fe~ably from S,000 to 50,000. PVP's are Icnown to ~.~ns sl~illed in the d~ l field; see, for e~mple, EP-A-262,897 and EP-A-2S6,696, inco~ld~d hercin by l~fe~nce. ('~ 'I Gs;l;ons cont~ nE PVP can also contain polyethylene glycol (~PEG") having an average rnole~ul~r weight from S00 to 100,000, 30 pl~f~,~bly from 1,000 to 10,000. I~fe~ably, the ratio of PEG to PVP on a ppm b~is delivered in w~h solutionc iS from 2:1 to 50:1, and more plefel~ bly from 3:1 to lO: 1.

The d~te~E,ent c~ po.il;ons herein may also op~ionally contain from 0.005% to 5% by weight of certain types of hydrophilic optical brigh~ençrs which also provide a dye 35 ~ sr~ inhibition action. If us~d, the co,l.positions herein will p~f~,~ably comprise from 0.01% to 1% by weight of such optical brighteners.

The hydrophilic optical bri~htPnPrs useful in the present invention are those having the structural forrnula:

N~ ~C=c~H N~
R2 SO3M SO3M Rl ~ n Rl is s~l~P~l~ from anilino, N-2-bis-hydroxyethyl and NH-2-hyd~ l; R2 is ~1P,~I from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino,chloro and amino; and M is a salt-fo"lling cation such as sodium or po!~;r When in the above formula, Rl is anilino, R2 is N-2-bis-hydro~yethyl and M is a cation such as sodium, the bri~hte~P~ is 4,4',-bist(4-anilino-~(N-2-bis-hyd~ hyl)-s-triazine-2-yl)amino]-2,2'-stilben~iclllfonic acid and di~illm salt. This particular bl;gh~ species is co--~ r~dally l--~k t~ under the t~Vlen~me Tinopal-UNPA-GX
by Ciba-Gdgy Col~,-; ~;nm Tinopal-UNPA-GX is the p.~fe.-~d hydf~philic optical brightener useful in the d~ _nt C~ ;t;nr~C herein.

When in the above formula, Rl is anilino, R2 is N-2-hydroxyethyl-N-2-methylaminoand M is a cation such as sQ~illm~ the bl;gh~ r is 4,4'-bis[(4-anilin~(N-2-hyd~uA~ -N-methylamino)-s-l-iazinc-2-yl)amino]2,2'-stilbe~islllfonic acid disodium salt. This particular br~ht~ner species is CQI .n~rcially 1 .~.~. tJ~;I under the ne Tinopal SBM-GX by Ciba-Geigy Col~l t;. --When in ~# above fo~-~lq Rl is anilino, R2 is morphilino and M is a cation such as C~ , thebrighteneris4,4'-bist(~ q~ ino-~molphilino-s-triazine-2-yl)amino]2,2'-stilb~nFA;c~lfonic acid, sodium salt. This p. rticular bri~htener species is C(~ ;ially d under the L~ ns-~c Tinopal AMS-GX by Ciba Geigy CO ~atiOi~.

The .c~ifir optical brigh4~rr species crlerted for use in the present invention provide ~c~iql1y effective dye l-~nsf~ inhibition performance ben~fi~c when used in co...bh~alion with the s~kct~ polymeric dye t~ansfer inhibjtin~ agents hefein~fo.~
described. The ui.llb;nq~t;QI~ of such C~l~t~ polymeric materials (e.g., PVNO and/or CA 02254946 1998-ll-17 W O 97t43393 PCT~US97/08441 PVPVI) with such sfl~ l optical bngh~ (e.g., Tinopal UNPA-GX, Tinopal SBM-GX and/or Tinopal AMS-GX) provides cignifi~qr,tly better dye transfer in~ tion in aqueous wash olutions than does either of these two de~.gcnt col~S;~;rm c4~..~nc ~
when used alone. Without being bound by theory, it is believed that such brighteners S work this way be~q~oe they have high affinity for fabrics in the wash solution and the~fo~ deposit relatively quiclc on these fabrics. The extent to which brigl-ten -~deposit on fabrics in the wash solution can be defined by a pararneter called the "e~hqllction coefficierlt~. The e~hq~stion cQefficient is in gener~ as the ratio of a) the brig~t ne~ material ckposit~1 on fabric to b) the initial bright~n~ co.-c~t.; l;nn in the 10 wash liquor. Brighteners with relatively high eYhq-uction coeffirientc are t~he most suitable for inhibiting dye transfer in the context of the present invention.

Of course, it will be app.~iatod that other, conventirnql optical bl;ght~n~ types of c~ n~ lc can option. lly be used in the present C4...~;t;0nC to provide conv~ iQn~1 lS fabric ~bngh'n~ss~ efitc rather than a truedye hdr,sre. inhibiting effect. Such us~ge is conventiQnql and well-lcnown to det~ ,ent forrnul-q-tionc.

Chel~t;i~ ApP.ntc 20 The dete~ent co. ~l~L I;nnc herein may also optionally contain one or more iron and/or ",~g"nf ~ lh~ g agents. Such ch~ g agents can be c~l&ted from the group conL CI;~e of an~ino carbo~ylates, amino pho.~holl~tes, polyfi~nrti qlIy-s~lb~ ~ rd aro matic chc~ agents and ~ u~s therein, all as hereinafter defin~. Without intending to be bound by theory, it is beliei~ that the benefit of these materials is due 2S in part to their ~~ c.~ ;o~l ability to remove iron and rnqng~qnese ions from washing L;ollIti~ by Ço l-lation of soluble ch~lqt~S

An~ino carbo~yla~s useful as optio~ql che~ g agents include ethylr~ ...;nct~ ~x-tate~, N-h~Lv.~ le~ nfA;~ r~h;~-~t 1-s~ nitril~ t~5 ethyl~ A~ P-30 t~t~pl;~ s, triethy1c~Pt~ ehc~a~ tes, diethyIen ~;z...;ne~nt~ t~t~gand ~ '- w'~i~lycines, allcali metal, qmmonium, and s~,sI;~ ...,..o~ -.. salts therein an~ cs therein.

Amino ~hos~hc~ trs are also suitable for use as chelq~ting agents in the c~ ~s;t;onc Of 35 the invention when at least low levels of total phosphol~ls are pe.lllilt~d in d~t~.~nt c4~ ~sitions~ and include ethykon~iq~inct~ s (metbylen~phosph~n~fs) as CA 02254946 1998-ll-17 W O 97143393 PCT~US97/08441 DEQUEST. Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than 6 carbon atoms.

Polyfunrtionqlly-sul~s~ d aromatic chel-q-ting agents re also useful in the S c~"~.c;l;onc herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et .,1. ~f. .-~d c~ ds of this type in acid form are dihydroxydisulfob~n7~nes such as 1~2-dihydro~cy-3~5-disulfobfn ~

A pl*fe.l~xl bi~ de~. ~~'-le çh~ or for use herein is ethyknediqmine (li~lcc h~e("EDDS"), e~iqlly thc [S,S] isomer as desc~ibod in U.S. Patent 4,704,233, No~re...~r 3, 1987, to Hartman and Perkins.

The c4~ ;QJlc herein may also contain water-soluble methyl glycine ~ ;r . cid (MGDA) salts (or acid form) as a chel. nt or co-builder useful with, for e~campk, lS insoluble builders such as 7e~lites~ layered silir~t~s If u~ili7~d~ these ch~ ;n~ agents will generally comprise from 0.1% to 15% by weight of the det~ ~ent C4~ OC;I ~Onc herein. More preferably, if u~ili7~d, the c h~ ;ne agent will C41~pl ;~G from 0.1 X to 3.0% by wdght of such CGIll~S;l;nnc W O 97/43393 PCTrUS97108441 Suds Suy~lesso.s Compounds for re~ucirle or ~ ressillg the formation of suds can be inco.~ dtod into the co~ ;tiQl~s of the present invention. Suds suppression can be of paniculqr 5 i~--yo~l~nce in the so called ~high co~ .dtion cle~nin~ process~ as deselibcd in U.S.
4,489,455 and 4,489,574 qnd in front-loading European-style washing ~ h;n~s A wide variety of rnaterials may be used as suds allpp~ssul~, and suds aupp ~i.s~la qre well known to those skilled in the . rt. See, for e~-q-~r le, Kirlc Othmer Encycl~pe.J:q of 10 ~ nicql T~.hr~lcgy, Third FAi~ol-, Volume 7, pages 43~447 aohn Wiley & Sons, Inc., 1979). One cat~GI~ of suds s,J~ ssor of particular interest enco...p~cs~s l~A~lic &tty acid and soluble s~ts therein. See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The nlonQcq-~oxylic fatty acids and salts thereof used qs suds a.~ a~r typically have hydro~byl chains of 10 to 24 carbon 15 atoms, preferably 12 to 18 carbon atoms. Suit~ salts include the alkali metal salts such as so~ um~ CC !~ and lithium salts, and qm.~o~-;tl... and qlL~Ilc~l~.,...~n;~
salts.

The d~ t~ nt co-~ l~oC;l;onS herein may also conhin non-surfact. nt suds s.~ppl~s~ls.
20 These incl~P~ for e~ample: high ~ qr weight h~druc~ns such as p~-,-r~
fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent q,lc4hol~, ~tip'~qtic C18~40 l~etones (e.g., stearone), etc. Other suds inh;b;~ include N-allcyhted amino t~;~ ;n~s such as tri- t~ he~a-alkyl nelqmines or di- to tetra-allcylA~ chlu,~ formed as pr~lucla of cyanuric chl~ de with two or tbree 2S moles of a primary or ~r~o~ amine contqinin~ 1 to 24 carbon atoms, propylene o~cidc, and monostcaryl ph~h~tes such as ",onost~--yl alcohol phosphate ester and ryl di-~li metal (e.g., K, Na, and Li) pho~l-h~t~s and p,ho~hot~ esters. The h~d~uu such ~ ~ ~rr. ~ and haloparaffin can be utilizod in liquid forrn. The liquid l~d~;hl~.~s will be liquid at room te.,lpe.atur~ and ~hno~h~ ic ~ " and 30 will have a pour point in the range of ~0~C and 50~C, and a .--in;.~ , boiling point not less thanllO~C (.~ -o~ph- ~ic ~ ). It is also known to utilize wa~y h~/dn~l.ùfls, prefe~ably having a melting point below 100~C. The hyd~l,ùns c4rq;l~ne a p~f.,.l~ cat gol~f of suds ~-lpp~ssor for del~,ge.~t ~x~.np~;l;srC
H~d,~l on suds ~p~ SSOl~ are de~clibed, for eY~mple, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. The hydl~rl,ons, thus, include ~lirh~ ic, alicyclic, ar~"~atic, and het. .~clic saturate~ or unsaturated hydfocalboi,s having from . ,_, . .. ........ . ... .. .

CA 02254946 l998-ll-l7 W O 97/43393 PCTrUS97/08441 12 to 70 carbon atoms. The term ~paraffin," as used in this suds supy~sor ~icruc~ n~
is int~n~ed to include mixtures of true paraffins and cyclic hydr~bons.

Another p~f~-. d catLgo.~ of non-surfactant suds SUPP1~,SS'OI~ comprises sili~ne suds 5 s~pl, ~s30r~. This category includes the use of polyorgq-nocilQY~ne oils, such as polydimethylcilol~qne~ dispersions or emlllcir~nc of polyo.~nns;l~sqne oils or resins, and ~ ~,hin~l;onc of polyor~q-nQs~ q~-P with silica particles wherein the polyolE~nQs;l~rqn~- is ch~Pmi.c~rbed or fused onto the silica. Silicone suds SU~are well known in the art and are, for e~ample, ~iccl~s~ in U.S. Patent 4,26S,779, 10 issued May 5, 1981 to ~lqnd~lfo et al qnd Eulo~ean Patent ~Mlirqtior~ No.
89307851.9, published February 7, 1990, by Starch, M. S.

Other cilir.l!n~ suds SU ~l~SS~l~ are ~;C~1QS~ in U.S. Patent 3,455,839 which relates to c~ ;t;~ c and p~scs for def~..,ng aqueous ~lu~innc by incol~ thcrein 15 small q.~ tc of pol~ "~ lhylcilo~qn~ fluids.

Mixtures of cilic~e and cilqnq~ silica are described, for j~s~ r~ in German Patent Appli~q~ion DOS 2,124,526. ~ilicQne defoarners and suds controlling agents in granular d- t~l~;e- t oo~ ~C;l;onc are ~{icclQs~ in U.S. Patent 3,933,672, Bartolotta et 20 al, and in U.S. Patent 4,652,392, RaginC1~i et al, issued March 24, 1987.

An ~e~ y cili~n~. based suds sup~,iessor for use herein is a suds s~lpl,l~ing ~m~un~ of a suds controlling agent cQnCicting ec~ "~;~lly of:
(i) ~l~di~lc~ cilox ~ ~e fluid having a viscosity of from about 20 cs. to about 1,500 cs. at 2S~C;
(ii) from about S to about 50 parts per 100 parts by weight of (i) of silo~cane resin C4 "~0~ of (CH3)3SiOl/2 units of SiO2 units in a ratio of from (CH3)3 SiOl/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 gd.
In the pl~fe.,~ cili~one suds su~ ssor used herein, the solvent for a con~ uC phase is made up of certain polyethylene glycols or poly_lhylene-pol~ ul~yl~e glycol copolymers or mixtures thereof (pl~f~ d), or yol~l"uyylene 3S glycol. The primary cilicQne suds s.~ ssor is branched/crosc1inl~ed and ~l~f~ably not linear.

W O 97/43393 PCTrUS97/08441 To illust~.q~t~ this point further, typical liquid laundry d~rg~nt co~..pos;t;~nc with controlled suds will optionally comprise from about 0.001 to about 1, ~ fe.dbly from about 0.01 to about 0.7, most prcf~.~,bly from about 0.05 to about 0.5, weight % of S said CilieQne suds ~upp~sol~ which comprises (1) a nonaqueous emUlsiQn of a primary antifoam agent which is a n,~tule of (a) a polyol~nr.s;lo~q~le, (b) a n .~nous cilo ~ne or a cilir,one resin-prod~cirlg cilieQne C4!~po~lnd~ (C) a finely divided filler material, and (d) a catalyst to promote the reaction of mLl~ture Wl~)l enLc (a), (b) and (c), to form cil~nc-l~t~ S (2) at least one l.oniQni~ cilic~e surfactant; and (3) polyethylene glycol or a copolymer of poly_lhylene polypropylene glycol having a solubility in water at room .I~Iature of more than about 2 weight %; and without polypropylene glycol. Similar ~-.-o.~ can be used in granular c~.,.pQc;t;onc, gels, etc. See also U.S. Patents4,978,471, Starch, issued I~e--~r 18, 1990, and 4,983,316, Starch, issued January 8, 1991, 5,288,431, Huber et al., issued r~ual~ 22, 1994, and U.S. Patents lS 4,639,489 and 4,749,740, Aizawa et al at column 1, line 46 tllr~Jugh coll~mn 4, line 35.

The cilic~ne suds ~Uppl~ ~or herein yl~f~bly compri es polyethylene glycol and acopolymer of polyethylene glycoVpolypropylene glycol, all having an average molecular weight of less than about 1,000, preferably beh.~n about 100 and 800. The pol~_lhyl~ glycol and polyethylene/polypropylene copolymers herein have a s~ ility in water at room t~ ~ of more than about 2 weight %, ~ c.ably more than about S weight %.

The pl~f~ d solv0t herein is polyethylene glycol having an average m~ lqr weight2S of less than about l,OûO, more p~fe. bly between about 100 and 800, most pl~f~ably between 200 and 400, and a copolymer of polyethylene glycoVpolry.~ylene glycol, prefe~bly PPG 200/PEG 300. ~fe.,~d is a weight ratio of between about 1:1 and 1:10, most preferably between 1:3 and 1:6, of polyethylene glycol:copol~,ner of polyethylene-polypropylene glycol.
Ille preferred Qilirone suds Sul)p~ a used herein do not contain pol),~upylene glycol, particularly of 4,000 mo~ulqr weight. They also p.efe.ably do not contain bloclc copolymers of ethylene o~cide and propylene oxide, like PLURONIC L101.

3S Other suds S~lpp~SSOl~ useful herein comprise the ~cc~n~-y ~Ir~hols (e.g., 2-alltyl nlQ) and ~ ules of such ~ICQhQlc with cilic~ne oils, such as the cilir~ s disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872. The seco~dqry ~lr~hnl~
include the C6-C16 alkyl alcohols having a Cl-C16 chain. A p~fe..~ alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12.
Mixtures of sC~on~uy alcohols are available under the trademark IS~T C~F-~ 123 S from F.nichPn~. Mi~ed suds s~p~ ssors typically comprise mixtures of alcohol + cilicone at a weight ratio of 1:5 to 5:1.

For any det~gent Co~pQc;~ n~ to be used in ?~ C~ 5~;C laundry or dishwashing m~~.hinec, suds should not form to the e~tent that they either overflow the ~. asl~illg 10 m~~hinP. or negatively affect the washing ~..~'h~nicm of the dishwasher. Sudsa~ when utili7ed, are plefe,dbly present in a "suds S~lp~a;llg ~moun~ By "SUdS~~ ng ~ Q~ iS meant that the formulator of the Go~r~s:l;nn can select an ...ou~t of this suds controlling agent that will s~ffici~Pntly control the suds to result in a low-su~si~ l~n.ll~ or diah~ ing det~rgen~ for use in ~ ;c laundry or dishwashing n-~~hinf~

The compositions herein will generally comprise from 0% to 10% of suds ;.~.p~ ~r.
When utilized as suds su~n,~la, ~-.o~ .l,oxylic fatty acids, and salts therein, will be present typically in ~--o~ up to 5%, by weight, of the d~ t~.genl c4 ~pQ~ ';O~.
~cf~.~bly, from 0.5% to 3% of fatty mo~ ylate suds suyyrej~or is utili7~d.
~iliro~ suds aupp.e~ls are typically utili~d in amountC up to 2.0%, by weight, of the det~.L ' composition, although higher qmollntC may be used. This upper limit is prr~ti~ql in nature, due primarily to concern with ~ n~ costs minimi7~ and effectiveness of lower z ~o~ for effectively controlling su~lsin~ . fe.~bly from0.01% to 1% of Q;l;~ suds s~.yp~ss~r is used, more preferdbly from 0.2SX to 0.5%. As uscd he~an, these weight percentage vlues include any silica that may be utilized in c~ with polyo ~;a~o~;lo~P, as well as any optionql n~qt-riqlc th. t may be u~lizod. Monostearyl phG_,Jha~ suds ~pp~la are g~ne~lly utilized in ~mQU~tC Pngjng from 0.1% to 2%, by weight, of the cG-~-i~s;~ n. Hydn~L~on suds S~lpp~ ~ laaIC typically utilized in qmollntc ~nging from 0.01 % to 5.0%, ~l~ouph higher levds can be used. The alcohol suds S~lp~leSSD15 are typically used at 0.2%-3%
by weight of the finichr~ C4~ ~C I;~

All~ntyl~t~ Polyn~ ylates CA 02254946 l998-ll-l7 W O 97/43393 PCTrUS97/08441 -Alko~cylated polyc~u~ylates such as those prepared from polyacrylates are usefulherein to provide ~ tionql gre. se removal pe~Çol".ance. Such materials are de-~cri~d in WO 91/08281 and PCT 90/01815 at p. 4 et seq., inco~ d herein by l~fe~nce.
Chemicqlly~ these materials co",p.i~ polyacrylates having one ethoxy side-chain per 5 every 7-8 acrylate units. The side-chains are of the formula -(CH2CH2O)m(CH2)nCH3 wherein m is 2-3 and n is ~12. The side-chains are ester-linlced to the polyacrylate "b~ e~ to provide a "comb" polymer type ~L,uclur~. The lqr weight can vary, but is typically in the range of 2000 to 50,000. Such allco%ylated pol~c~ul~Aylates can comprise f~om 0.05% to 10%, by weight, of the 10 c4m~ c herein.

Fabric Soften~

Various ~Ilu.lgh-the-wash fabric oftenc.~, e~periqlly the irnF~ql~ c-, ~ clays of U.S. Patent 4,062,647, Storm and Nirschl, issued ~e~ 13, 1977, as well as other ~rtencr clays h own in the art, can optionqlly be used typically at levels of from 0.5%
to 10% by weight in the present c4...~s;t;0~c to provide fabric sorLner bene~t~
con~ nlly with fabric rleqning. Clay softene~ can be used in c4..~bin-~;on with amine and c-q-tionic soft_ners as di~lo~l for example, in U.S. Patent 4,37S,416, Crisp 20 et al, March 1, 1983 and U.S. Patent 4,291,071, Harris et al, issued September 22, ~.ru.,.~,s 25 Pe ru---w and pe~r...,-~ y ing~.cnt~ useful in the present CGI~ ;O~S and ~ S
comprise a wide variety of natur. l and s~nth~c chemicq-l ing~;e7~c, including, but not limited to, aldehydes, lrPtoncs esters. Also i~ lucled are various natural ~ nt~
and ~<s which can comprise comple~ IlliJ.tUI~S of in~ , such ag orange oil,lemon oil, rose ~ t lavender, muslc, patchouli, hqlcqmir e~C~nc~p.~ sandalwood oil, 30 pine oil, cedar. Finished ~rullles c_n comprise e ~ n,ely comple~ "u~lules of such ing~ s. Finished ~,rullles typic. lly comprise from 0.01 X to 2%, by weight, of the dlct~ t C4~ ;0l~C herein, and individu. l p~.ru,n.,.y ing-~ien~s can comrri~from 0.0001 % to 90% of a ~nichcd pe~rullle co",posi~ion.

35 Non-li...il;n~ a~amples of perfume ingredien~ useful herein in~l~de 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7 t~t~.u"~ lhyl naphth~l~ne; ionone methyl; ionone CA 02254946 1998-ll-17 W O 97/43393 PCT~US97/08441 -gamma methyl; methyl cedrylone; methyl dihydroj~rnon~qtP; methyl 1,6,1~trimethyl-2,5,9-cyclodod~l~ic.--1-yl ketone; 7-acetyl-1,1,3,4,4,6-heY-q-m..~Pthyl tetralin; 4-acetyl-

6-tert-butyl-1,1-dimethyl indane; para-hydroxy-phenyl-butqnone; benzo~h.~none; methyl beta-naphthyl ketone; 6-acetyl-1,1,2,3,3,5-heY-q-methyl indane; 5-acetyl-3-isopropyl-1,1,2,6 t~ - lhyl indane; l~o~ nql, 4-(4-hydroxy-4-methylpentyl)-3-c~k-h~ .enP-l~arbol~-q-l~ehyde; 7-hydl~,Ay-3,7-dimethyl oCvtqn~ t-d~c~ --l-al; iso hexenyl cyclohe~cyl ca,l~v -q-ldPhyde; formyl tricycl~le~qn~; condPr rqtion products of hydloA~citronellal and methyl ~ .nilqt~ condPn~qtil~n products of hydro~c~cihu.Kllal and indol, conAen~ n products of phenyl ~ P~qldehyde and indol; 2-methyl-3-(para-tert-b~ lphenyl)-propionaldehyde; ethyl vanillin; heliol~op;n; he~yl cinn~ icaldehyde;
amyl ~ n~ ic aldehyde; 2-methyl-2-(para-iso propylphenyl)-propionqld~P~-yde;
l; d~Pcql~tone ~mma; cyclop~ nolide; 16-hydroYy-9-he~ad~P~oic acid e; 1~3~4~6~7~8-heyahydro-4~6~6~7~8~8-hey~methylcyrlQppnt~-garnma-2-benzo pyrane; beta-na~hlhûl methyl ether; al,lbroAane; dod~qhydro-3a,6,6,9~ te~ ethyl-n~.h~l o[2, 1b]furan; cedrol, 5-(2,2,3-trimethylcyclopent-3-enyl)-3-,ne~hyl~r.tan-2-ol;
2-ethyl~-(2,2,3-~i---. lhyl-3-cyclopentcn- 1 -yl)-2-buten- 1 -ol; c~ ~ophyllene ql~hnl;
tricyclo l~enyl propionate; tricyrlo~P~nyl: cPtqt~P; benzyl ~licylate; cedryl acetate;
and para-(tert-butyl) cyclohe~yl acetate.

Particularly p.-_f~-~ ~.rull.c materials are those that provide tne largest odorimproYel..enls in finiched product c~ ..~,;~;onC cor-tqinin~ c~ qc~s These ~lru-,-es include but are not limited to: he~yl cinnqmi~ aldehyde; 2-methyl-3-(para-tert-butylphenyl)-propionaldehyde; 7-.,cetyl- 1,2,3,4,5 ,6,7,8-octahydro 1,1 ,6~7-tptr-q-mpthyl naphthalene; benzyl salic~la~, 7-acetyl-1,1,3,4,4,6-herqmethyl tetralin; para-tert-butyl 2S cycld~yl acetate; methyl dihydro j~ o~; beta-napthol methyl ether; methyl beta-l~hth~l lcetonc; 2-methyl-2-(para-iso propylphenyl)-propionql~1~Phyde; 1,3,4,6,7,8-he~cahydro 4,6,6,7,8,8-1~ hyl-cyclopPn~q-~,qmm- 2-b~ ~ahydro-3a,6,6,9a-tP~r~ethyln~l~h~o[2,1b]fu~n; q-nisqldehyde; cou,-~in; cedml; vanillin;Op~ oli~e; tricyc~ yl acetate; and tricyrlodc~nyl propio Otlher pe~ "e materiqls include eCCpntiql oils, rçsinoids . nd resins from a variety of sources inclu~iin~ but not limited to: Peru bq-lQqn~, Olihqn~lm reCinoi~ styra~c, labdanum resin, r~tmP~, cassia oil, b~--~in resin, cori~nder and lavandin. Still other ~lru-.,e chemi~qlc include phenyl ethyl alcohol, terpineol, linqlool, linalyl acetate, 35 e~-ni~?l, nerol, 2-(1,1-dimethylethyl)-cyclohe~nol lretqte, benzyl ~ t~, and W O 97/433g3 eugenol. Carriers such as diethylphth~l~t~ can be used in the finished pe~ru,..e C~lllpO.Citionc, Other Inpredients s A wide variety of other ingredients u eful in detel "~t colllpos;t;nnc. can be include~l in the c~"~po~;l;nnC herein, inCludi~lp other active ingre~ n~c~ carriers, hyd,~pes, pr~ ss;ng aids, dyes or piP.rn~ntC, solvents for liquid form~lqtionc solid fillers for bar nc, etc. If high su(lcirlp is desired, suds boo t~a such as the Clo-C16 10 ql~rq~-olqn-ides can be incol~latcd into the co~pocitiQllc~ typically at 1%-10% levels.
The Clo-C14 m-noeth ~ ~ol qnd ~iethqnol arnides illustrate a typical clqss of such suds boosters. Use of such suds boo~t ,a with high sudsing optional surf~ ts such as the amine o~ide,s, ~l~ines and Cl~ ines noted above is also advantageous. If desired, water-soluble, .~g,-cc;u-,~ and/or cqk~ium salts such as MgC12, MgSO4, CaC12 CaSO4, 15 can be added at levels of, typically, 0.1%-2%, to provide ''~litionql suds and to en~qnC~ grease removal ~Çol,.,ance.

Various detersive ingf~licnts employed in the present co,npoc;l;nnc optionqlly can be fur~er stabilized by absolL,in~; s. id ingredients onto a porous hydrol,hobic s~lbsh~e, 20 then coating said substrate with a hydlu~.hob;c coating. Preferably, the detersive ing~xlient is ~ ed with a surfactant before being ab~ll,cd into the porous subsh~
In use, the detersive .n~l~iient is l~l~d from the ~lb~ te into the a~lue:uus wastling liquor, whcre it p~fu~ s its in~d~d detersive funrtion.

25 To illustrate this technique in more detail, a porous hydrophobic silica (~ ?.L
SIPERNAT D10, DeGussa) is ~ lmi-~d with a proteolytic enzymc sr)lutiQ~ co~;.ini~3%-59~ of C13 15 etho-~lat~d alcohol (EO 7) no~ nir, S~ ~1. TypicaUy, the enzyme/su~ ~nt ssl~;Qn is 2.S X the weight of silica. The res~ ing po. dcr is dispersod with stirring in Q;licQne oil (various cilicol-e oil vi~s;l;~5 in the range of 30 50~12,500 can be used). The resulti~lg silicQne oil dis~.aion is ern~lcifi~d or otherwise added to the final dete.~cnt matrix. By this means, in~~Yxlic~t~ such as the afole--~ent;Qn~d e..LJrl,.es, bleaches, bleach activators, bleach catalysts, pho'Q~ ators, ~ dyes, fluOl~.a, fabric conditiQners and hydrolyzable sull;.c~ tc can be ~protected"
for use in d~ ts, inclutlin~ liquid laundry dctergent cCS~.po5;1innC, CA 02254946 1998-ll-17 Liquid de te.~,.nt co...l~sitiQn~ can contain water and other solvents as carriers. Low mole Illq~ weight primary or s~ConAq~y ~lroh~l~ el~mp1ified by m~thq~lol~ ethanol, propanol, and isopr~)panol are suitable. Monohydric alcohols are pl~ufell~d for solubilizing surfactant, but polyols such as those containing from 2 to 6 carbon atoms S and from 2 to 6 hydro~y groups (e.g., 1,3-propqn~iol, ethylene glycol, glycerine, and 1,2~ o~iol) can also be used. The co...~o~;tio~ may contain from 5% to 90%, typically 10% to 50% of such c~ulle~.

The d. t~ ,genL co..~ ;tiol-s herein will ~ fe.~-bly be form~ t~_ such that, during use 10 in ~ ~US ck~-;ng o~,i-~;o~C the wash water will have a pH of beh.'~.l 6.5 and 11, prefe..,bly b~h.~l 7.5 and lO.S. Liquid dishwashing product formulqtions pr~f~
have a pH b~ n 6.8 and 9Ø I~undry p,udu. ~ are typicalUy at pH 9-11.
Te~h~ s for controlling pH at ~o ....~d~1 usage levels include the use of buffers, alkalis, acids, etc., and are well Icnown to those skilled in the art.
Gr~n..l~ ,f; l"~

Adding the allcoxylated rqtiorirs of this invention into a crutcher mi~, followed by con~ ;o~ spray drying, helps remove any resid~q1, ~t~ lly m?lodon)lls, short-20 chain asnine CQn~ in"~ In the event the formulator wishes to 1~ ~ an ~mi-~b1~particle ~o~ini~ the all-uAylat~cl rq~ nirc for use in, for ~ n~lc~ a high density g~anular det~.~,cnl, it is ~fell.xl that the particle co- .~ ;on not be highly q11r-q-line.
~occs~s for pr~ high density (above 650 g/l) gran~1Ps are dcer~;kd in U.S.
Patent S,366,6S2. Such ~licl~s may be form~~1qt~ to have an effective pH in-use of 2S 9, or bdow, to avoid the odor of impurity qminP~ This can be achic~cd by adding a sn~ll ~nount of acidity source such as boric acid, citric acid, or the lilce, or an app.~p~i~te pH buffer, to the p~Lclc. In an alternate mode, the plu~ te problemsassoc~ted with an~ine m~1odors can be masked by use of pclfu~e ingl~ s, as os~ herein.

Examples The following e~mples are illustrative of the present invention, but are not meant to limit or otherwise define its scope. All parts, percentages and ratios used herein are 5 e .~p.~d as percent weight unless otherwise spe~ified In the following exarnples, the abbreviated co-uponent iden~ific~inll~ have the following ll,f ,,.;~

LAS : So-iium linear C12 alkyl benzcne sulfonate TAS : Sodium tallowalkyl sulfate C45AS : So~ m C14-C1s linear alkyl sulfate C~cyEzS : Sodium Clx-Cly branched alkyl sulfate c4,~drn~d with z moles of ethylene o~ide C45E7 : A C14 1s pl~domin~ntly linear primary alcohol con~en~d with an average of 7 moles of ell~ylen c o~ide C25E3 : A C12 1S branched primary alcohol c4~d~ d with an average of 3 moles of ethylene o~cide C25E5 : A C12 15 br~ch~ primary alcohol c~n~nsed with an ave.age of 5 moles of ethylene o~ide COCD.r~? : Rl~N+(cH3)(c2H4oH)2 with Rl = C12 ~

Saap : Sodil~m linearalkyl carboxylatederived from an 80/20 ~ ule of tallow and cc~4r~l oils.
TFAA C16-C18 alkyl N-methyl ~ c~mi~
TPKFA : C12~14 topped whole cut fatty acids STPP : Anhydrous sodium tripol~Jhos~h~te Zeolite A : Hydrated Sodium Alumin~silicatP of formula Nal2(A1~2Si~2)12- 27H20 having a primary particlc size in the ~ange from 0.1 to 10 miclo-l.ct~.s 3S NaSKS~ : Crystallinelayered silicate of formula ~ -Na2Si205 CA 02254946 l998-ll-l7 W O 97/43393 PCTrUS97/08441 Citric acid : Anhydrous citric acid Carbonate : Anhydrous sodium carbonate with a particle s1ze bet veen 20011m and 900~m S Bicarbonate : Anhydrous sodium bic~l,onate with a particlesize distribution bet veen 40011m and 1200~m Silicate : Amorphous So~i~lm Silicate (SiO2:Na2O; 2.0 ratio) Sof~ sulfate : Anhydroussodium sulfate Citrate : Tri-sodium citrate dihydrate of activity 86.4%
with a particle size distribution between 425~1m and 850 ~m MA/AA : Copolymer of 1:4 maleic/acrylic acid, average -lec~lqt weight 70,000.
CMC : Sodium carboxymethyl c~ lQse ~t~ : Proteolytic enzyme of activity 4KNPU/g sold by NOVO Industries A/S under the tr~nqm~
Savinase ~lr~lq~P : Proteolydc enzyme of activity 3AU/g sold by NOVO Industnes AIS
Ce~ q~ : Cellulydc enzyme of activity 1000 CEVU/g sold by NOVO Industries A/S under the t1;1r~nqm~ Cal~L~
Amylase : Amylolydc enzyme of activity 60KNU/g sold by NOVO Ir.d.~ ;es A/S under the 1. ~ n~-.. C
Termamyl 60T
Lipase : Lipolytic enzyme of activity 1001~LU/g sold by ~ ipol~, Fn~olq~e : Endoglunase enzyme of activity 3000 CEVUtg sold by NOVO Ind~ ies AIS
PB4 : Sodium perborate tetrahydrate of nominal formula NaBo2.3H2o-H2o2 PBl : Anhydrous sodium pe~lJOlale bleach of nominal forrnula NaB02.H202 Percar'oonate : Sodium Pe.cdll,onate of nominal formula 2Na2C03.3H202 NOBS : Nonanoyloxybenzene sulfonate in the forrn of the sodium salt.
TAEO : Tetraacetylethylen~~ ine DTPMP : Diethylene triaminepenta (methylene pho;phonq~), .,.~ed by MoncqntQ under the Trade name Dequest 2060 Pho~Q~ ated bleach: Sulfonated Zinc Phthalocyanine ç~eqrs~
in bleqch de~trin soluble polymer Rrightf,-~f~ 1 : Dic~liun~ 4,4'-bis(2-sulphostyryl)biphenyl Rnght~ 2 : Disodium 4,4'-bis(4- nilino-~morpholino-1 .3.5-tri. zin-2-yl) mino) ctilhene-2:2'-disulfonate.
HEDP : 1, l-hydroxyethane diphos~honic acid PVNO : Polyvinylpyridine N-oxide lS PVPVI : Copolymer of polyvinylpyrrolidone . nd vinylimi~lq~ole SRA 1 : Sulfo~,nzo~l end capped esters with oxyethylene o~cy and terephthaloyl barlrt onP
SR~ 2 : Dietho~ylated poly (1, 2 propylene t~ .~pht~ q~e) short block polymer SilironP antifoam: Polydimethylsilo~ane foam controller with silo-~n~ oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dis~.~ing agent of 10:1 to 100:1.
In thc following E~amples all levels are quoted as % by weight of the c~ pC;~ nn.

P.XAMPI F. I

30 The following ~b~,E,c~l forn~ tionc according to the present invention are p,. palcd, where A and C are phos~h~ s~ ;nillg dete.y,ent co,..~c;t;onc and B is a zeolite- ining det~,rgc.lt C~ ~c tinrl~
C
Blown Powder STPP 24.0 - 24.0 Zeolite A - 24.0 wo 97143393 PCT/USg 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~ t~ner 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.S 2.5 2.0 C25E3 2.5 2.5 2.0 Silirone antifoam 0.3 0.3 0.3 Pe.~,Qe 0.3 0.3 0.3 Dry additives Carbonate 6.0 13.0 15.0 PB4 - 4.0 10.0 PBl 4.0 - 0 Pe,~l~ute 18.0 18.0 21.0 TAED 3.0 3.0 ph-~tQs~tivated bleach 0.05 ~.~S 0.05 ~t~ 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.25 0.30 0.15 ~odium sulfate 3.0 3.0 5.0 B~ e &
MjcrP~ 5) To: 100.0 100.0 100.0 Density (g/litre) 630 670 670 30 *The AQA-l (Co oMeEO2) s.llÇa~nt of the Fl~mple may be rep1~d by an equivalent ~ t of any of surf~~t~ntc AQA-2 through AQA-22 or other AQA
S.~lr;~ At~ herein.

F.xAMPLE II
The following detergent formulqtionc, according to the present invention are E F
S 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 13.0 11.0 21.0 C45AS 8.0 7.0 7.0 CocoMeEO2* 1.0 1.0 1.0 Silicate - 1.0 5.0 Soap - - 2.0 Brightener 1 0.2 0.2 0.2 C~l)onate 8.0 16.0 20.0 DTPMP - 0.4 0.4 C45E7 1.0 1.0 1.0 PVPWPVNO 0.5 0.5 0.5 Prote.~se 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.1 0.1 0.1 ('P111l1qcç 0.1 0.1 0.1 NOBS - 6.1 4.5 PBl - 2.0 4.1 Plwlo~li~.ted bkach 1.05 0.5 0.2 Sodium sulfatc - 6.0 Balancc (~ e & Mi~dlaneous) To: lû0 100 100 *The AQA-l (~C~ u~f~t~t of the F~q . 'e may be ~ ~ by ~n equivalent q-- o ~ of .~ny of S~ll r~ tc AQA-2 through AQA-22 or other AQA
30 surf ~tq~c herein.

F.XAMpT.F. III

The following high density d~ nt form~ or c, accol~ling to the present invention are~
S ~ H
Blown Powder _eoliteA 15.0 15.0 lS.0 m sulfate o.o 5.0 0.0 LAS 3.0 3.0 3 0 ~oco~ 2~ 1.0 1.5 1.5 DTPMP 0.4 0.4 0.4 CMC 0.4 0.4 0.4 MA/AA 4.0 2.0 2.0 ~&~ t"5 LAS 5.0 5.0 5.0 TAS 2.0 2.0 1.0 SUicate 3.0 3.0 4.0

7~1ite A 8.0 8.0 8.0 C~L~nat~ 8.0 8.0 4.0 Spray On ~,rull,e 0.3 0.3 0.3 C4SE7 2.0 2.0 2.0 C2SE3 2.0 - -Dry aWiti~es Cit~atc 5.0 - 2.0 Bic&l,onate 3 0 Cubcn~ 8.0 15.0 10.0 TAED 6.0 2.0 S.0 PBl - 2.0 3.6 Phot~-~;./ated bleach 1.0 0.7S 0.5 P~bl~ lene o~cide of MW s,ooo,oao - - 0.2 nent~!n;t~ clay - - 10.0 ~ 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 CA 02254946 1998-ll-17 W O 97/43393 PCTrUS97/08441 CÇI1U1~CP. 0.6 0.6 0.6 .Silic~neantifoam 5.0 5 0 5 0 Dry additives Sodium sulfate 0.0 3.0 0 0 pql~ncr (Moictllre &
Mi ~ s) To:100.0 100.0 100.0 Density (gllitre) 850 850 850 ~he AQA-l (Coco~ )2) s.~ ct~nt of the F~mple may be ~l~cd by an 10 equivalent ~mount of any of surf~ nts AQA-2 through AQA-22 or other AQA
surf~~t~-tc herein.

FXA~Pr F IV

lS The following high density det~g_nt fonn~ tinnc accGlding to the present i~ on are p~e~

M
Blown Powder Zeolite A 2.5 2.5 .So~ n sulfate 1.0 1.0 CocoM~~?~ 1.5 1.5 A~l~ t~v C45AS 11.0 14.0 Zeolite A 15.0 6.0 C~na~ 4.0 8.0 MA/AA 4.0 2.0 DTPMP 0.4 0.4 Spray On C2SE5 5.0 5.0 P~.ru,.. e o.S 0-5 Dry Adds HEDP 0.5 0.3 SKS6 13.0 10.0 Citrate 3.0 1.0 W O 97/43393 PCTrUS97/08441 TAED 5.0 7.0 PBl 8.0 15.0 Photoactivated bleach 0.27 0.8 S R A 1 0.3 o 3 S Protease 1.4 1.4 Lipase 0.4 0.4 Ce~ q~e 0.6 0.6 Amylase 0.6 0.6 .~ili~n~ antifoun 5.0 5.0 R-ig,h~ - ~r 1 0.2 0.2 Brigh~ e~ 2 0.2 Balance (~loict~re &
Mi~Pll~nff)~s) I'o: 100 100 Density ~g/litre) 850 850 15 *The AQA-l (Coc~'~ 2) surfactant of the Example may be ~l~d by an equivalent 5"'0~ of any of a,ll r~ -j A Q A-2 through A Q A-22 or other AQA
s r~ ts herein.

F,XAMP! F V
The following hand wash deterg~l formul~ c, according to the present invention, are p~pal~Dd by tmi~ing the Llg~;enta together in the ~.~ ~e weight ~-ou~ as ~ below.

A B C D
LAS 15.0 12.0 lS.0 12.0 TFAA 1.0 2.0 1.0 2.0 C25E~S 4.0 2.0 4.0 2.0 AQA-9~ 2.0 3.0 3.0 2.0 Sl~PP 25.0 25.0 15.0 15.0 MA/AA 3.0 3.0 3.0 3.0 C M C 0.4 0.4 0.4 0.4 D TP~P 1.0 1.6 1.6 1.6 C~a~bDnate 2.0 2.0 5.0 5.0 Bic3lbi~natc - - 2.0 2.0 CA 02254946 l998-ll-l7 W O 97/43393 PCTrUS97/08441 Silicate 7 o 7 o 7 o 7 o Protease 1.0 - 1.0 1.0 Amylase 0.4 0 4 0 4 Lipase 0.12 0.12 - 0.12 photrL~c~ivated bleach 0.3 0.3 0.3 0.3 Sulfate 2.2 2.2 2.2 2.2 PBl 4.0 5.4 4.0 2.3 NOBS 2.6 3.1 2.5 1.7 SRAl 0.3 0.3 0.7 0.3 Brigh~n~ 1 0.15 0.15 0.15 0.15 r~ misC./water 100.0100.0 100.0 100.0 to 100 AQA-9~; May be l~pl~d by any AQAs.,lÇ~t described herein. ~f~.~l AQA
aulr~ tc for use in this example are those with from 10 to 15 ethoxy groups; for ; r ~ AQA-lO,AQA-16 s The fo~. going E~carnples i~ ct~t~ the present invention as it relates to fabric laundering nC but are not intended to be ~ litin~ thereof.

Fx~MpLE Vl The following illustrates l~tu~S of AQAsurfact~ntc which can be c-~I,s~ d for the AQA surfactants listed in any of the foregoing E~arnples. As~isclo~d h~ e, such n~i~tu~ can be used to provide a s~lrum of pe.~G.,.~nc4 brn~f.tc and/or to provide cl~aning compositions which are useful over a wide variety of usage c~n~;l;ons.
15 Prefe~ably, the AQA surfactants in such mixtures differ by at least 1.5, p.~f~dbly 2.S-20, total EO units. Ratio ranges (wt.) for such ".ixtu~es are typically 10:1-1:10. Non-;ng e~camples of such ,..~lu~s are as follows.
Co.. ~. n~ . Ratio (wt.) AQA-l+ AQA-5 1:1 AQA-l+ AQA-10 1:1 AQA-l+ AQA-15 1:2 AQA-l+ AQA-5 + AQA-20 1:1:1 CA 02254946 1998-ll-17 W O 97143393 PCT~US97/08441 -AQA-2 + AQA-5 3:1 AQA-5 + AQA-15 1.5:1 AQA-1 + AQA-20 1:3 5 Mi~ctures of the AQA surf~-tqntc herein with the co~ ,onding c~ti- nic surfi~~~nt~
which contain only a single etho~ylated chaun can also be ussd. Thus, for e~qn~pl~, ules of ethoxylated cqtionic s~ri~1;nlc of the forrnula RlN+CH3[EO]xtEO]yX~
and RlN+(CH3)2[EO]zX~~ wl,c~ Rl and X are as diC~lo~d above and ~ h~.n one of the cqtionirs has (I~+y) or z in the range 1-5 preferably 1-2 and the other has (~+y) 10 or z in the range 3-100, preferably 10-20, most preferably 14-16, can be ussd herein.
Such co,.~s;~;Qnc advqnt~llsly provide improved d~ te~ r,~ ance (e-spe~iqlly in a fabric laundering context) over a br~ader range of water ha dness than do the c~tir~ni~ s~ -n~s herein ussd individually. It has now been discovered that shorter EO r~tionics (e.g., EO2) improve the cl~ning pe,Çùl."ance of anionic 15 s~r--~ n~c in soft water, ~.I,~as higher EO c~;onics (e.g., EO15) act to illllJlU~Ie ha.dl~ss tolerance of anionic ~ t~, thereby improving the cl~nine p~,lÇol",ance of anionic ~ulr~ in hard water. ConventiQn~l wisdom in the det~.g~n-;~ art ~ugg~ that builders can optimize the ~lru~ nce "window~ of anionic s~l~r; ~ C
Until now, ho~ r, bl~f---ing the window to enc~j"l~,ass ec~nt;~lly all cQfi~J;~;on~ of 20 water hanJtless h.,s been i..~poc~ le to achieve.

The laundry d~L~.~,ent ~.,.~ ;O~c p.~ d using one or more fol~oing cli...bin~;on~
of ir.g-.~iienLs can optionqlly be built with any non-phocphqt~ ûr phos~ te builders, or W~S thereof, typically at levels of from 5% to 70~, by weight of finiched 25 composition.

F.XA~p~ F.~nn The following ~ Js~ s ~ Lur~s of conven~ n~l non-AQA sl~lri-e~n~c which can be 30 used in c~..-binalion with the AQA surfa~tqntc in arty of the folegoing E~camples, but is not; t~ ~ to be limiting thereof. The ratios of non-AQA surf~tqntc in the ~ u-~sare noted in parts by weight of the sulractant mixtures.

. . . ~

CA 02254946 l998-ll-l7 W O 97/43393 PCTrUS97/08441 Mixtures A-C
Tru~redientC Ba~,.
AS*/LAS 1: 1 AS/LAS 10:1 (pref. 4:1) AS/LAS l:lO(pref. 1:4) *In the fol~oing, the primary, substqntiqlly linear AS surfactant can be ~ ~ by an equivalent ~q~moun~ of ser~n~q~y AS or blanched-chain AS, oleyl sulfate, and/or s thereof, including Illv~l~es with linear, prim ry AS as shown above. The ~tallow~ chain length AS is particularly useful under hot water c4n~lit~ s~ up to the 10 boil. ~CQCOQUt~ AS is p~f~.,ed for cooler wash t~ res.

The n~lu.~~ of ~yl sulfate/~nionic surf-q~ ntc noted above .,re ,..~; fiPd by il~cu~ n~ a nonionic non-AQA a.-~r~t~t therein at a weight ratio of anionic (total) to n- Q;onic in the range of 25:1 to l:S. The nQni~nic s.~ 4nt can co~pr-~ any of 15 the conven~nql classes of etho~yhtD~ qlcQh~lc or alkyl phenc!lc, alkylpolygly~sides or pol~h~dlu~.y fatty acid amides (less pr~fe.l~d if LAS is present), or ~,~lu~s thereof, such as those ~icrlosed hc.e;nabove.
Mi~n- es D-F
AS*/AES 1: 1 AS/AES 10:1 (pref. 4:1) AS/AES 1: 10 (pref. 1:4) *Can be 1el)l~ ~ by s~Q~ q~ y, b.~nch~d or oleyl AS as noted above.

The mL~turw of AS/AES noted above can be m ~ifi~d by incol~ g LAS therein at a wdght ~atio of AS/AES (totl) to LAS in the range from 1:10 to 10:1.

The mi~tu~es of AS/AES or their rrswlti-lp AS/AES/LAS II~ UI~.S can also be combinod with ~ ol~ic surfa~tqn~c as noted for Mixtures A-C at weight ratios of anionic (to~al) to ~ Qnir, in the range of 25:1 to 1:5.
Any of the fc,.~oing m~lufC~S can be mo~lified by the inco-~lation therein of an amine o~cide s~r~ t~ ~ h~;n the amine oxide comprises from 1% to 50% of the total r~.t ~-~lUl~.

35 Highly ~ref~l~d co"~bin~l;Qn~ of the fol~going non-AQA s"lri~ c will comprisefrom 3% to 60%, by weight, of the total finished laundry dete,ge.lt co..,l)osition. The W 097/43393 rCT~US97/08441 -fini.ched c~"lpositions will preferably comprise from 0.25% to 3.5%, by weight, of the AQA surfactant.

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 an alkoxylated quaternary ammonium (AQA) cationic surfactant of the formula:

X-wherein R1 is a linear, branched or substituted C8-C18 alkyl, alkenyl, aryl, alkaryl, ether or glycityl ether 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, A is C1-C4 alkoxy and p is an integer in the range of from 2 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 either of Claims 1 or 2 wherein the non-AQA surfactant is an anionic surfactant.

4. A composition according to Claim 3 wherein the ratio of 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 Claim 5 additionally comprising a bleach activator.

7. A composition according to either of Claims 5 or 6 additionally comprising a bleach catalyst.

8. A composition according to any of Claims 1 to 7 wherein said AQA surfactant is of the formula where R1 is C8-C18 alkyl, R2 is methyl, is an ethoxy or propoxy group and p is an integer of from 2 to 8.

9. A composition according to any of Claims 1 to 8 wherein said AQA surfactant is of the formula where R1 is C8-C18 alkyl, R2 is methyl, A is an ethoxy or propoxy group and p is an integer of from 2 to 4.

10. A composition according to any of Claims 1 to 9 wherein the formula of the AQA
cationic surfactant is such that p is an integer in the range of from 10 to 15.

11. A composition according to any of Claims 1 to 10 comprising two or more AQA
surfactants, or a mixture of a 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 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 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 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 AQA.