CA2254948A1 - Detergent composition - Google Patents

Abstract

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

Description

2 PCT/US97/08372 DETERGENT COMPOSITION

Technical Field The present invention relates to a dete.gellt composition comI~nsin~ perca,l~onate bleach, a non-AQA surfactant and a bis-alkoxylated quaternary ~mmQnillm (bis-AQA) cationic surfactant.
Bacl~,lnd to the Invention The forrnulation of }aundry det~r~cnts and other cl~P~ning co...ro~;lions pl~sen~ a - considerable chqllP~ e~ since modern cG~ ositions are rcq~ cd to remove a variety of soils and stains from diverse s.lbsllates. Thus, laundry det~ t~, hard surface cleaners, ~l,a,..poos and other ~.~onal clP~ncin~ co...l)osi~ nc~ hand dishwashing del~E,e.lls and det~ int cG---I GS;l;onc suitable for use in aulo...alic dishwashers, all require the proper sel~tion and cGI~bination of ingredients in order to functioneffectively. In general, such dete,~,~nt co...l oC;~;onc will contain one or more types of 20 surf~ct~nts which are d~ ..fd to loosen and remove different types of soils and stains.
While a review of the l;~ ...c would seem to inrliMte that a wide sele~tiol- of surf~t~ntc and s,~ nt c4l-.1~h-qt;0llc are available to the de~lE,ent m~nuf~eturer, the reality is that many such in~l~lien~ are speciality çllf.~ qls which are not suitable in low unit cost items such as home-use laundry dete.~cn~. The fact ~,Il&ins that most 25 such home-use prod~;~ such as laundry det~cn~ still mainly co--,l,lise one or more of the con~en~ r~l ethoxylated nonioni~ andtor sulf~ted or sulfonal~xl anionic surf~rt~ntc, p-es.l",dbly due to economic considerations and the need to formulate composition~
which function re~n~l~ly well with a variety of soils and stains and a variety of fabrics.
The quick and effi~ient removal of dil~.~.-l types of soils and stains such as body soils, greasy/oily soils and certain food stains, can be problematic. Such soils co"~l,lise a lur~ of hydrophobic triglycerides, lipids, co.npl~ poly~cchatides, inol~ ic salts and ~ n-~~us matter and are thus notoriously difficult to remove. Low levels of 35 hydrophobic soils and residual stains often remain on the surface of the fabric after washing. Successive washing and wearing coupled with limited hydrophobic soil removal W 097/44432 PCT~US97/08372 in the wash c-llminAt~s in a build up of residual soil and stain which further entraps particulate dirt leading to fabric yellowing. Eventually the fabric takes on a dingy a~ealance which is perceived as unwearable and discarded by the consumer.

5 The lilGI~Lu-c suggests that various nitrogen-cont~ining cationic surfactants would be useful in a variety of cleaning compositions. Such materials, typically in the form of amino-, amido-, or ~ualell~ary ammonium or imiflA7olinium compounds, are often designed for ~peciAlity use. For e~ull~lc, various amino and quate.llaly ammonium surfactants have been suggested for use in shampoo compositions and are said to provide cosmetic benefi~
10 to hair. Other nitrogen-co..~ g surfactAntc are used in some laundry detcl~,en~ to provide a fabric softening and anti-static benefit. For the most part, however, the colll.lle..ial use of such materials has been limited by the difficulty encuullte.cd in the large scale mqmlfq.~ re of such compounds. An additional limit~tion has been the potential p,~ )ilalion of anionic active colllpo~ of the deterg.,.ll composition occasioned by their 15 ionic interaction with cationic ~ulrhr!A~ i The aforc.ne.llion~d noriollir and anionic surf~!qntc remain the major surfactant components in today's laundry colll~o~ilions.

It has now been disco~,~d that certain bis-alkoxylated qudte.llaly ~r~ onium (bis-AQA) compounds can be used in various detergenl compositions to boost det~,.gel1.;y ~.r~,nll~nce 20 on a variety of soil and stain types, particularly the hydlophobic soil types, commonly encountered. Unexpectedly, it has now been discovered that compositions cont~ining bis-AQA surf~rt-qntc and perc~bollate bleach deliver superior cl~n;..~ and ~l.i~ ss p.,.Ç~ re versus products co..~;~;..;.-g either technology alone.

25 The bis-AQA surf ~t-qntc of the present invention provide suhst~ntiql bell~rl~ to the form~ or, over cqtioni~ surf. ~tqntc previously known. For example, the bis-AQA
~u~r~ used herein provide mqrkPd iln~lovclllelll in cleqnir~ of "everyday" greasy/oily llydlu~hobic soils regularly encountered. Moreover, the bis-AQA sUl rh ~ C are co,ll~.atible with anionic surfartantc commonly used in detergent compositions such as alkyl 30 sulfate and alkyl benze~le sulfonate; illcoll~alibility with anionic colll~o-.ellls of the detelgcllt composition has commonly been one of the limiting factor in the use of cationic surf:~~t~ntc previously known. Low levels (as low as 3 ppm in the laundering liquor) of bis-AQA surf ~t~ntc gives rise to the benefits described herein. Bis-AQA ~ulr~ctallts can be forrn~ t~l over a broad pH range from 5 to 12. The bis-AQA surf~ct~ntc can be35 p~epaled as 30% (wt.) solutions which are pumpable, and therefore easy to handle in a W O 97/44432 PCT~US97108372 m~n.-f~ctl-ring plant. Bis-AQA surf~ct~ntc with degrees of ethoxylation above S are sometimPs present in a liquid form and can therefore be provided as 100% neat materials.
In addition to their beneficial h~n-lling p~ope~lies, the availability of bis-AQA surfact~ntc as highly conce~ at~d solutions provides a substantial economic advantage in transportation costs. The bis-AQA surf~t~nt~ are also compatible with various perfume ingredients, unlike some cationic surfa~t~nts known in the art.

Pelcall,onate, which delivers peroxide bleach into the wash, is a cornerstone technology of modern, ultra-compact granular laundry dcl~r~elll formulas. Peroxide bleach is hydrophilic and, while it cannot match the ble~r~lin~ effectiveness delivered by ~lacids (formed for example from peroxide hlte~d~;lion with TAED), it is effective at decolouration of pigm~onts (e.g. in particulate or beverage stains) and also can help remove the colour from the organic residues ~c~oci~t~rl with body soils.

It is believed that the greasy/oily soils are effectively solubilized by bis-AQA, thereby allowing access of the hydrophilic peroxide bleach to the colour bodies in the soil (e.g.
apped pigm~ntc) res~llting in improved soil decolouration. The present invention thus provides a dcl.,~cnt colll~o~ilion which delivers superior cleaning in such much as the composition provides marked cle~ning effectiveness against both hydrophobic greasy/oily and hydrophillic coloured soils.

BACKGROUND ART

U.S. Patent 5,441,541, issued August 15, 1995, to A. Mehreteab and F. J. Loprest, relates to anionic/cationic ~ulr~l Illu~lules. U.K. 2,040,990, issued 3 Sept., 1980, to A. P.
Murphy, R.J.M. Srnith and M. P. Brooks, relates to ethoxylated cationics in laundry detel~enls.

Sullllnal y of the Invention The present invention provides a composition comprising or prep~d by colllbinLng a ~ p~ ;âll,onate bleach, a non-AQA surfactant and an effective amount of a bis-alkoxylated 4uatelllal~ ammoniurn (bis-AQA) cationic surfactant of the formula:

R~ /ApR
N X
R2/ A qR

wherein Rl is a linear, branched or substituted Cg-Clg alkyl, alkenyl, aryl, alkaryl, ether or glycityl-ether moiety, R2 is a Cl-C3 alkyl moiety, R3 and R4 can vary independently and are 5 selected from hydrogen, methyl and ethyl, X is an anion, and A and A' can varyindependently and are each Cl-C4 alkoxy, p and q can vary indepe..dal.lly and are integers of from 1 to 30.

Detailed Desclil,tion of the Invention P,,.call,onate Bleach The first esser~ ColllpOIh,ll of the present invention is a l.el,_a.l,onate bleach. Alkali metal or alkali earth metal perca,l,onates, particularly sodium pe~all,onate are plef~--ed 15 ~Ica.bo.~ates for in~ lsion in compositions in accordance with this invention. Sodium call,onate is an addition co...~ u..d having a formula corresponding to 2Na2C03.3H202, and is available coml~ cially as a crystalline solid. Cou.me.cialsuppliers include Solvay, FMC, Tokai Denka and others.

20 A pl~fel~ed ~lcall~,~le bleach con,~.ises dry particles having an average particle size in the range from 0.5 mm to 1 mm, not more than 10% by weight of said partic}es being smaller than 0.2 mm and not more thanlO% by weight of said pa,licles being larger than 1.250 mm.

25 ~erca,l,onate can be present at levels of ~lwe~l 1% and 50%, pler~l,.bly ~I~.,.,n 1% and 30%, most preferably bel~een 5% and 20% by weight of detergellL colllpo~ilion.

The ~lca,l,onate is most ~}ef~lably h~colpo.~ted into such compositions in a coated form which provides in-product stability.
A suitable coating material providing in product stability compriçes mixed salt of a water soluble alkali metal sulphate and carbonate. Such co~tin~ together with coating processes W O 97144432 PCTrUS97/08372 s have previously been described in GB-1,466,799, granted to Interox on 9th March 1977.
The weight ratio of the mixed salt coating material to perca~L.onate lies in the range from 1 : 200 to 1: 4, more preferably from 1: 99 to 1: 9, and most p,efciably from 1: 49 to 1:
19. Preferably, the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na2SO4.n.Na2CO3 wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.

Other co~tin~c which contain silicate (alone or with borate salts or boric acids or other inolg~ics), waxes, oils, fatty soaps can also be used advantageously within the present invention Bis-AlkoxYlated Ouat~,na,~ Ammonium (bis-AOA) Cationic Surfactant The second esse~ l component of the present invention co~ es an tfrec~ive amount of a 15 bis-AQA ~u~ra~ l of the formula:

R~ /ApR
N X
*/ A~qR4 wl~.e.ll Rl is a linear, bl~nched or s~Jb~ d alkyl, alkenyl, aryl, alkaryl, ether, glycityl 20 ether moiety cont~inin~ from 8 to 18 carbon atoms, pref~,.dbly 8 to 16 carbon atoms, most preferably from 8 tol4 carbon atoms; R2 is an alkyl group cont~inin~ from 1 to 3 carbon atoms, preferably methyl; R3 and R4 can vary hlde~n~1Pntly and are selecte~l from the group co.~c;~;lh~ of hydrogen (preferred), methyl and ethyl; X~ is an anion such as chloride, blolllide, methyl sulfate, sulfate, sufficient to provide elecl,ical neutrality. A and 25 A' can vary h~ ntly and are each selected from Cl-C4 alkoxy, especially ethoxy, propoxy, butoxy and ~ UleS ~ r; p iS from 1 to 30, preferably 1 to 15, more preferably 1 to 8, even more preferably 1 to 4 and q is from 1 to 30, preferably 1 to 15, more preferably 1 to 8, even more preferably 1 to 4. Most preferably both p and q are 1.

30 Bis-AQA compounds whe~,Ul the hydloca,l,yl substituent Rl is Cg-C12, especially Cg-C1o, e..h~ e the rate of dissolution of laundry granules, especially under cold water conditions, as co",l)ared with the higher chain length materials. Accordingly, the Cg-C12 W 097/44432 PCT~US97/08372 bis- AQA surfact~ntc may be preferred by some formulators. The levels of the bis-AQA
surfactants used to prepare fini~hP~ laundrS delclgclll compositions can range from 0.1% to 5 %, typically from 0.45 % to 2.5 %, by weight. The weight ratio of bis-AQA to percarbonate bleach is in the range of from 1:100 to 5:1, preferably from 1:60 to 2:1, most 5 preferably from 1: 20 to 1:1.

The present invention employs an "effective amount" of the bis-AQA surfactants to improve the pPlru~ ce of clPqning compositions which contain other optional ingredients. By an "effective amount" of the bis-AQA surf~ ~Pntc herein is meant an 10 amount which is sufficient to improve, either directionally or sig~ificAI~îly at the 90%
confi-1~nre level, the pclrolll~llce of the cleqni~ co~ ,osition against at least some of the target soils and stains. Thus, in a composition whose targets include certain food stains, the formulator will use ~urric;e.ll bis-AQA to at least directionally improve cleqning pelrolmallce against such stains. Lil~ewise, in a composition whose targets include clay 15 soil, the forrn~lq-tor will use ~urr~riP-l~ bis-AQA to at least directionqlly improve clP-q-ning pe.rolll~ce against such soil.

The bis-AQA sulr;..~ may be used in combination with other detersive surfactants at levels which are effective for achieving at least a directional improvement in cleq-nin~
20 pelro~mance. In the context of a fabric laundry composition, such "usage levels" can vary depen~ing not only on the type and severity of the soils and stains, but also on the wash water ~elll~lUIC, the volume of wash water and the type of washing m~~hinP.

For example, in a top-loading, vertical axis U.S.-type ql~tomqtir washing ",~rll;n~. using 45 25 to 83 liters of water in the wash bath, a wash cycle of 10 to 14 ...; .~ s and a wash water Iclll~rature of 10~C to 50~C, it is p~fe,led to include from 2 ppm to 50 ppm, preferably from 5 ppm to 25 ppm, of the bis-AQA surfactant in the wash liquor. On the basis of usage rates of from 50 ml to 150 ml per wash load, this trn~lqtes into an in-plc-luct conce~ dlion (wt.) of the bis-AQA sulr~c~ull of from 0.1% to 3.2%, preferably 0.3% to 30 1.5%, for a heavy-duty liquid laundry dc~rg~nl. On the basis of usage rates of from 60 g to 9S g per wash load, for dense ("compact") granular laundry dete~gents (density above 650 g/l) this tr~n~l~tes into an in-product concentration (wt.) of the bis-AQA surfactant of from 0.2% to 5.0%, preferably from 0.5 % to 2.5 % . On the basis of usage rates of from 80 g to 100 g per load for spray~ried granules (i.e., "fluffy"; density below 650 g/l), this CA 02254948 l998-ll-l7 W O 97144432 PCTrUS97/08372 tr~ncl~ec into an in-product concentration (wt.) of the bis-AQA surfactant of from 0.1% to

3 .5 %, preferably from 0.3 % to 1.5 % .

For example, in a front-loading, horizontal-axis European-type automatic washing m~r~ in,o 5 using 8 to 15 liters of water in the wash bath, a wash cycle of 10 to 60 ~ çs and a wash water ~ pe~dture of 30~C to 95~C, it is pfel~.-ed to include from 13 ppm to900 ppm, preferably from 16 ppm to 390 ppm, of the bis-AQA surfactant in the wash liquor. On the basis of usage rates of from 45 ml to 270 ml per wash load, this tr~ncl~tto~c.
into an in-product concentration (wt.) of the bis-AQA ~ulr~ alll of from 0.4% to 2.64%, 10 preferably 0.55% to 1.1%, for a heavy-duty liquid laundry detelgelll. On the basis of usage rates of from 40 g to 210 g per wash load, for dense ("col.l~act") granular laundry dete~g~ (density above 650 g/l) this tr~ncl~tec into an in-product conce..l.alion (wt.) of the bis-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-dried granules (i.e., "fluffy";
15 dencity below 650 g/l), this tr~ncl~c into an in-product conc~ rd~ion (wt.) of the bis-AQA surfactant of from 0.13% to 1.8%, preferably from 0.18% to 0.76%.

For example, in a top-loading, vertical-axis JapAnf ce-type aulo..~ washing m~ fusing 26 to 52 liters of water in the wash bath, a wash cycle of 8 to 15 ...i..~lcc and a wash water t.".lpc~ e of 5~C to 25~C, it is p,erel.~d to include from 1.67 ppm to 66.67 ppm, preferably from 3 ppm to 6 ppm, of the bis-AQA ~u~racta,ll in the wash liquor. On the basis of usage rates of from 20 ml to 30 ml per wash load, this tr~nCl~t~c into an in-product conce.lL,ation (wt.) of the bis-AQA surfactant of from 0.25% to 10%, preferably 1.5% to 2%, for a heavy-duty liquid laundry d~ g~n~. On the basis of usage rates of from 18 g to 25 35 g per wash load, for dense ("co.. l ~rl") granular laundry d~t,.ge.lls (density above 650 g/l) this tr~ncl~tes into an in-product collce..L,~tion (wt.) of the bis-AQA ~ulrac~ll of from 0.25 % to 10%, prefe,dbly from 0.5% tol.0%. On the basis of usage rates of from 30 g to 40 g per load for spray-dried granules (i.e., "fluffy"; density below 650 g/l), this tr~n~l~t~s into an in-product conce.lllalio.. (wt.) of the bis-AQA surfactant of from 0.25% tolO%, 30 preferably from 0.5% to 1%.

As can be seen from the fol~,goillg, the amount of bis-AQA surfactant used in a m~hin-o-wash laundering context can vary, ~lepc~ g on the habits and practices of the user, the type of washing m~- hin~. In this context, however, one heretofore unaplJlc.,ia~d advantage of the bis-AQA surf~Gt~n~s is their ability to provide at least directional improvements in ~e-ror."ance over a spectrum of soils and stains even when used at relatively low levels with respect to the other surfactants (generally anionics or anionic/nonionic mixtures) in the finichP-I compositions. This is to be distinguished from other compositions of the art wherein various cationic surf~ct~ntc are used with anionic 5 surf~rt~ntc at or near stoichiometric levels. In general, in the practice of this invention, the weight ratio of bis-AQA:anionic surfactant in laundry compositions is in the range from 1:70 to 1:2, preferably from 1:40 to 1:6, preferably from 1:30 to 1:6, most preferably from 1:15 to 1:8. In laundry compositions which comprise both anionic and nonionic surfllet~ntc, the weight ratio of bis-AQA:mixed anionic/nonionic is in the range from 1:80 to 1:2, preferably 1:50 to 1:8.

Various other c!~nin~ compositions which comprise an anionic surfactant, an optional nonionic surfactant and speci~li7pd surf. ~t~n~C such as betaines, s--lt~in~s, amine oxides can also be forrmll~ted using an effective amount of the bis-AQA surfactants in the manner of 15 this invention. Such compositions include, but are not limited to, hand dishwashing products (especially liquids or gels), hard surface cleaners, shampoos, personal cl~n~ g bars, laundry bars, and the like. Since the habits and practices of the users of such compositions show ll.il-;...~l ~alialioll, it is s~ticf~ctory to include from about 0.25% to about 5 %, preferably from about 0.45 % to about 2 %, by weight, of the bis-AQA
20 surfactants in such compositions. Again, as in the case of the granular and liquid laundry col~ osilions, the weight ratio of the bis-AQA surfactant to other surfactants present in such compositions is low, i.e., sub-stoichiometric in the case of anionics. Preferably, such cle~ning compositions co~lprise bis-AQA/surfactant ratios as noted imme~ tely above for ;nr-Use laundry compositions.
In contrast with other cationic sw r~ n~ known in the art, the bis-alkoxylated cationics herein have s~ffiriçnt solubility that they can be used in colllbillaliOn with mixed surfactant ~y~el~s which are quite low in nonionic surf~rt~ntc and which contain, for example, alkyl sulfate surf~rt~ntc. This can be an hllpoll~llL consideration for form~ tors of de~elgellt 30 compositions of the type which are conventionally designed for use in top loading aulolllalic washing m~rllinPs, especially of the type used in North America, as well as under JapA..fse usage conditions. Typically, such compositions will com~lise an anionic ~ulÇàc~l~:nonionic surfactant weight ratio in the range from about 25:1 to about 1:25, preferably about 20:1 to about 3:1. This can be contrasted with Eulopeall-type formulas W O 97/44432 PCT~US97/08372 which ~pically will comprise anionic:nonionic ratios in the range of about 10:1 to 1:10, preferably about 5:1 to about 1:1.

The ~e~lled ethoxylated cationic surf~ct~n~s herein are available under the trade name 5 ETHOQUAD from Akzo Nobel Ch~rnir~l~ Company. Alternatively, such materials can be syr.~ si~Pd using a varie~r of dirr. ~ t reaction schclllcs (wherein "EO" r~les~nt~
-CH2CH20- units), as follows.

RIOH + N H3 H2/Cat/Heat ~ Rl N'H
EXCESS

Rl N~ + 2 nB BASECat, Rl N--[(EO)n~l2 Rl N--[(EO) Hk + CH Cl HEAT~ Rl N+--[(EO) H~
CH3 cr [( )2Hl2 H' 'H HÉAT

Br + N--[(EO)2H]2 HEAT, Rl N+ [(EO) H]
CH3 Br 'N--~(EO)2Hk + C H2 Cat , 3~N--[(EO) H]

R Br + N--[(EO)2H]2 HEAT ~ Rl N+ [(EO) H]
CH3 Br Cl--CH2CH2--OH + n~ 5 ~ Cl--CH2CH20[EO]n--H

R--N~CH + 2 Cl--CH2CH20~EO]n--H ~ Rl l-[CH2CH20[EO]nHk An econon~ical reaction scheme is as follows.

Rl OSO3~Na+ + H-N--~(EO)H]2 HEAT ~ Rl N--[(EO)H]2 Rl N--~(EO)H]2 + 2 n~ HEAT ' R--N--[(Eo)(Eo)r~ 2 Rl N--[(EO)(EO)nH~2 + CH3Cl ~ R--Nl--[(EO)(EO)nHk CH3 Cl The following ~ c~ e the optional and preferred reaction conditions of .~ch~mP 5. Step 1 of the reaction is preferably con~lcte~ in an aqueous m~-1inm Reaction W O 97/44432 PCTrUS97/08372 lel,lpf ~al~lres are typically in the range of 140-200~C. Reaction pressures are 50-1000 psig.
A base catalyst, preferably sodium hydroxide can be used. The mole ratio of re~ct~ntc are 2:1 to 1:1 amine to alkyl sulfate. The reaction is preferably con~lcte-l using Cg-C14 alkyl ~ sulfate, sodium salt. The ethoxylation and 4ualf ~ dtion steps are carried out using 5 conventional conditions and re~ct~ntc.

Under some ch.~ res reaction Schf~mf S results in products which are sufficiently soluble in the aqueous reaction mf~dillm that gels may form. While the desired product can be recovered from the gel, an ~Iternqte, two-step synthesis Schf mf 6, hereinafter, may be 10 more desirable in some CQI.llllf ~-;ial ci,~ n~es. The first step in Schf mP 6 is co.-.lvc~ed as in Schem~ 5. The second step (ethoxylation) is pl_fel~.bly con-~lcted using ethylene oxide and an acid such as HCI which provides the quate-l~a~ surfactant. As shown below, chlorohydrin i.e., chloroethanol, can also be reacted to give the desired bishydroxyethyl derivative.
- For reaction ~Schf mf 6, the following pal~ tel~ e the optional and pref~l.f d reaction conditions for the first step. The first step is preferably con~ cted in an ~qq~f ouc mf rlil-rn Reaction t~,lll~lalures are typically in the range of 100-230~C. Reactiorl prf s:,ules are 50-1000 psig. A base, preferably sodium hydroxide, can be used to react 20 with the HSO4-g."l.,.ated during the n,a;~ion, or an excess of the amine can be employed to also react with the acid. The mole ratio of amine to alkyl sulfate is typically from 10:1 to 1:1.5; preferably from 5:1 to 1:1.1; more preferably from 2:1 to 1:1. In the product recovery step, the desired substihlted amine is simply allowed to se~alate as a distinct phase from the ~ eol~e reaction me~ m in which it is insoluble. The second step of the 25 process is co~ u~-led under col~ ;on~l leaelioll condiliolls. Further ethoxylation and 4uatel 11;7~ ;on to provide bis-AQA surf~t~nts are con-4lrt~d under standard reaction conllitil)n.e.

SrhPm~ 7 can optionally be co~ e~l using ethylene oxide under standard eth~xylation 30 conditions, but without catalyst, to achieve monoethoxylation.

The following illustrates these additional reaction srhf~n.~, whcleill "EO" l~.esen~ the -CH2CH20- unit. In the reactions, either an inolganic base, an organic base or excess amine reactant is used to neutralize generated HSO4.

WO 97144432 PCTrUS97/08372 Scheme 6 Rl OSO3~Na+ + H,N--CH2CH2-OH ~ Rl N--CH2CH2-OH

, ,CH2CH20H
R NCH2CH20H + CICH2CH20H ~ R N~

Sch.o~n~ 7 ~ ,CH2CH20H
Rl N--CH2CH2OH NoCatalyst 'EO~I

The following further illustrates several of the above reactions solely for the conveni~nre of the formulator, but is not intended to be limitin~ thereof.

Synthesis A
Preparation of N.N-Bis(2-hydroxyethyl)dodecylamine To a glass autoclave liner is added 19.96 g of sodium dodecyl sulfate (0.06921 moles), 14.55 g of ~i~th~n~lamine (0.1384 moles), 7.6 g of 50 wt. % sodium hydroxide solution - (0.095 moles) and 72 g of ~listill~(l H20. The glass liner is sealed into a 500 ml, st~inless steel, rocking autoclave and heated to 160-180~C under 300400 psig nitrogen for 34 hours. The llli~lUl'~, iS cooled to room ~ lule and the liquid contents of the glass liner are poured into a 250 ml s~a~tol y funnel along with 80 ml of chlorofoilll. The funnel is shaken well for a few ~ s and then the lllLY.IU~, iS allowed to sepal~. The lower chlol~f{~llll layer is drained and the chlolofollll evaporated off to obtain product.

Synthesis B
Preparation of N.N-Bis(2-hydroxYethyl)dodecylamine 1 Mole of sodium dodecyl sulfate is reacted with 1 mole of ethanolamine in the plesence of base in the lllam~. described in Synthesis A. The res~t~in~ 2-hydroxyethyldodecylamine is recovered and reacted with l-chloroethanol to prepare the title compound.

Synthesis C
,ara~ion of N.N-Bis(2-hydroxyethyl~dodecylamine .

CA 02254948 l998-ll-l7 W 097/44432 PCTrUS97/08372 To a glass autoclave liner is added 19.96 g of sodium dodecyl sulfate (0.06921 moles), 21.37g of ethanolamine (0.3460 moles), 7.6 g of 50 wt. % sodium hydroxide solution (0.095 moles) and 72 g of distilled H20. The glass liner is sealed into a 500 ml, st~inlPsc steel, rocking autoclave and heated to 160-180~C under 300400 psig nitrogen for 3-4 hours. The ~ Lule is cooled to room l~",~e,dlure and the liquid contents of the glass liner are poured into a 250 ml separatory funnel along with 80 ml of chloroform. The fuMel is shaken well for a few ~ c and then allowed ~ lule to se~,a,ate. The lower chloroform layer is drained and the chloroform is evaporated off to obtain product. The product is then reacted with 1 molar equivalent of ethylene oxide in the absellce of base catalyst at 120-130~C to produce the desired final product.

The bis-substituted amines p,~;pa~ed in the foregoing Syntheses can be further ethoxylated in standard fashion. Quat~l",~tion with an alkyl halide to form the bis-AQA surfactants herein is routine.

According to the foregoing, the following are nonli~ , specific illustrations of bis-AQA
surf~ct~nt~ used herein. It is to be ~ de.~lood that the degree of alkoxylation noted herein for the bis-AQA surf~rt~nt~ is reported as an average, following common practice for conventional ethoxylated nonionic surf~-~t~nt~. This is because the ethoxylation reactions typically yield mixtures of materials with diff~lillg degrees of ethoxylation. Thus, it is not u~lco~l~lllon to report total EO values other than as whole l-u-~ , e.g., "E02.5n, "EO3.5" .

Design~tion R1 R2 ApR3 A~q~4 bis-AQA-l C12-C14 CH3 EO EO
(also l~fe.-cd to as Coco Methyl EO2) bis-AQA-2 C12-C16 CH3 ~EO~2 EO
bis-AQA-3 C12-C14 CH3 ~EO~2 ~EO~2 (Coco Methyl EO4) bis-AQA~ C12 CH3 EO EO

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

CA 022~4948 1998-11-17 W 097/44432 PCT~US97/08372 bis-AQA-6C12-C14 CH3 ~EO~2 (EO)3 bis-AQA-7 Cg-CIg CH3 (EO)3 (EO)2 S

bis-AQA-8 C12-C14 CH3 (EO)4 (E0)4 bis-AQ-A-9 C12-C14 C2H5 (EO)3 (EO)3 bis-AQA-10 C12-C18 C3H7 (EO)3 (EO)4 bis-AQA-ll C12-C18 CH3 (propoxy) (EO)3 bis-AQA-12 Clo~C18 C2H5 (iso-propoxy)2 (EO)3 - bis-AQA-13 Clo~C18 CH3 ~EO~PO)2 (EO)3 bis-AQA-14 Cg-Clg CH3 (EO)lS* (EO)15*
bis-AQA-lS Clo CH3 EO EO
bis-AQA-16 Cg-C12 CH3 EO EO

bis-AQA-17 Cg-Cll CH3 ~ EO 3.5 Avg. -bis-AQA-18 C12 CH3 ~ EO 3.5 Avg. -bis-AQA-l9 Cg-C14 CH3 ~EO~lO (EO)lo bis-AQA-20 Clo C2H5 ~EO~2 (EO)3 bis-AQA-21 C12-C14 C2H5 (EO)5 (EO)3 bis-AQA-22 C12-C18 C3H7 Bu (EO)2 W O 97/44432 PCT~US97/08372 *Ethoxy, optionally end-capped with methyl or ethyl.

Highly preferred bis-AQA compounds for use herein are of the formula;

Rl ~CH2CH20H
N X~
CH3/ \CH2CH2OH

wherein Rl is Cg-Clg hydlucalL,yl and mixtures thereof, preferably Cg, Clo, C12, C14 aLkyl and mixtures thereof. X is any convenient anion to provide charge balance,preferably chloride. With lef~ ,nce to the general bis-AQA structure noted above, since in 10 a pl.,fe,l~,d co"l~oulld Rl is derived from coconut (C12-C14 aLkyl) fraction fatty acids, R2 is methyl and ApR3 and A'qR4 are each monoethoxy, this p~fe.l~,d type of colll~ouild is lefell~d to herein as "CocoMeEO2" or "bis-AQA-l" in the above list.

Other bis-AQA surf~~t~ntc useful herein include compounds of the formula:

R\ +~(CH2CH20)pH

R2/ \(CH2CH20)C~H

wllel~,ill Rl is Cg-Clg hydrocdll,yl, preferably Cg-C14 alkyl, in~pf ~ ly p is 1 to 3 and q is 1 to 3, R2 is Cl-C3 alkyl, preferably methyl, and X is an anion, e~peci~lly chloride or 20 bromide.

Other co~ ullds of the fol~,goillg type include those wLleill the ethoxy (CH2CH20) units (EO) are replaced by butoxy (Bu) isopropoxy [CH(CH3)CH20] and [CH2CH(CH30] units(i-Pr) or n-propoxy units (Pr), or ll~i~Lul~S of EO and/or Pr and/or i-Pr units.
A highly pl~f~ll. d bis-AQA colllp.~ul~d for use in under built formnl~tions are of the formula whelcill p and/or q are integers in the range of belw~en 10 and 15. Thiscompound is particularly useful in laundry handwash detergent compositions.

30 Non-AOA Detersive Surf~rt~nt~

In addition to the bis-AQA surfactant, the compositions of the present invention preferably further comprise a non-AQA surfactant. Non-AQA surfactants may include essentially any anionic, nonionic or additional cationic surfactant.
s Anionic Surfactant Nonlimiting examples of anionic surfact~ntc useful herein typically at levels from l % to 55%, by weight, include the conventional Cll-C1g alkyl benzene sulfonates ("LAS") and primary ("AS"), b,~lched-chain and random Clo-C20 alkyl s~11f~t~s, the Clo-C1g secondary (2,3) allcyl sulfates of the formula CH3(CH2)X(CHOSO3-M+) CH3 and CH3 (CH2)y(CHOS03~M+) CH2CH3 where x and (y + 1) are h~ of at least 7, preferablyat least 9, and M is a water-solubilizing cation, especi~11y sodium, ul~alulaLe-d sulfates such as oleyl sulfate, the C12-C1g alpha-sulfonated fatty acid esters, the C1o-C1g su1f~tPd 15 polyglycosides, the C1o-C1g alkyl alkoxy sulfates ("AEXS"; especi~lly EO 1-7 ethoxy sulfates), and the C1o-C1g alkyl alkoxy carboxylates (especi~11y the EO 1-5 etho~yc~l,oxylates). The C12-Clg belaines and sulfub~t~ s ("s1~1t~inPs"), Clo-C1g amine oxides, can also be included in the overall co"lposilions. Clo-C20 conventional soaps may also be used. If high su(lsing is desired, the b,a"ched-chain Clo-C16 soaps may 20 be used. Other conventional useful surfactants are listed in standard texts.

Nonionic Sulr~ r.l~

Non1i~ ;..g examples of nonionir surfactants useful herein typically at levels from 1% to 25 55%, by weight include the alk-~ylal~d alcohols (AE's) and alkyl phenols, polyhydroxy fatty acid amides (PFAA's), allyl po1yglycosides (APG's), C1o-C1g glycerol ethers.

More specifir~lly, the con-~nC~til n products of p~ and second~y aliphatic alcohols with from 1 to 25 moles of ethylene oxide (AE) are suitable for use as the nonioni~
30 surfactant in the present invention. The alkyl chain of the aliphatic alcohol can either be straight or branch~d, p".nal~ or secondary, and generally contains from 8 to 22 carbon atoms. P~,fe.l~d are the condensation products of alcohols having an alkyl groupcont~ining from 8 to 20 carbon atoms, more preferably from 10 tol8 carbon atoms, with from 1 tolO moles, preferably 2 to 7, most preferably 2 to 5, of ethylene oxide per mole of 35 alcohol. Examples of co~ nclcially available nonionic surf~t~nt~ of this type include:

W 097/44432 PCTrUS97/08372 TergitolTM 15-S-9 (the con~en.cAtion product of Cl 1-Cls linear alcohol with 9 moles ethylene oxide) and TergitolTM 24-L-6 NMW (the con~ncAtion product of C12-C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; NeodolTM 45-9 (the conl1PnCAtinn product of C14-Cls linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-3 (the con-~P~nCA.~ion product of C12-C13 linear alcohol with 3 moles of ethylene oxide), NeodolT M 45-7 (the con-len.c~tion product of C14-Cls linear alcohol with 7 moles of ethylene oxide) and NeodolTM 45-5 (the con~P~C. tion product of C14-Cls linear alcohol with S moles of ethylene oxide) l-lall eled by Shell Ch~nAirAI Co~ ~ly; KyroTM EOB (the 10 con-lPn~~-ion product of C13-Cls alcohol with 9 moles ethylene oxide), n~all eled by The Procter & Gamble Colllydl~y; and Genapol LA 030 or O50 (the co~ P.~C~tion product of C12-C14 alcohol with 3 or 5 moles of ethylene oxide) mArketed by Hoechst. The l)lefe~l~d range of HLB in these AE nonionic surfA~tAntc is from 8-11 and most plefc.l~d from 8-10.
COn~lf n~ rs with propylene oxide and butylene oxides may also be used.
Another class of l.ncl~.lcd nonionic ~ulr~ s for use herein are the polyhydroxy fatty acid amide su, r.- ~ of the formula.

R2 I~ Z, - O R

~hPlcil~ Rl is H, or C14 hyd,ocalbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is Cs 31 hydrocarbyl, and Z is a polyhydro~cyhydlocarbyl having a linear hyd,oc~l~l chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Preferably, Rl is methyl, R2 is a straight C11 15 alkyl or 25 Cls 17 alkyl or alkenyl chain such as coconut alkyl or ll~Ll~Luleil thereof, and Z is derived from a ~c~ ci~ sugar such as glucose, fructose, maltose, lactose, in a reductive AAminA-iQn real~tion. Typical examples include the C12-Clg and C12-C14 N-methylgl-~oAmi-1es. See U.S. 5,194,639 and 5,298,636. N-alkoxy polyhydroxy fatty acid amides can also be used;
see U.S. 5,489,393.
Also useful as the nonionic surfactant in the present invention are the alkylpolysaccharides such as those disclosed in U.S. Patent 4,565,647, T.lenA~lo, issued January 21, 1986, having a hydrophobic group co.,lAini.~g from 6 to 30 carbon atoms, preferably from 10 to 16 carbon atoms, and a polysaccharide, e.g. a polyglycoside, hydlu~hilic group con~ining .

W O 97/44432 PCT~US97/08372 from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7 saccharide units.
Any reducing saccharide cont~inin~ S or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (optionally the hydrophobic group is attn~ l at the 2-, 3-, 4-, etc. positions thus giving a glucose or 5 galactose as opposed to a glucoside or galactoside). The intersaccharide bonds can be, e.g., between the one position of the adllition~l saccharide units and the 2-, 3-, 4-, and/or 6-positions on the preceAing saccharide units.

The prere.led alkylpolyglycosides have the fonnula:

R20(CnH2nO)t(glYC~sYl)x whclcill R2 is select~(3 from the group con~i~ting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and lnL.~ res thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to 10, preferably 0; and x is from 1.3 to 10, ~lc~.~bly from 1.3 to 3, most preferably from 1.3 to 2.7. The glyco~l is preferably derived from glucose. To ple~are these coll~oullds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (~tt7~hm~nt at the l-position). The additional 20 glycosyl units can then be ~tt;~ b~,l~eel1 their l-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominately the 2-position.

Polyethylene, polypropylene, and polybutylene oxide con~l~n~tes of alkyl phenols are also suitable for use as the nonionic surfactant of the surfactant systems of the present invention, 25 with the polyethylene oxide co~ f .~t~s being preferred. These compounds include the col-~e~ iQn products of alkyl phenols having an alkyl group cont~inin~ from 6 to 14 carbon atoms, prcr~.~bly from 8 to 14 carbon atoms, in either a straight-chain or l)l~lched-chain configuration with the aLkylene oxide. In a p~cre~l~,d embo~im~nt, the ethylene oxide is present in an ~ equal to from 2 to 25 moles, more prefeMbly from 3 30 tol5 moles, of ethylene oxide per mole of alkyl phenol. C~"l.~l~rcially available nonionic surfactants of this type include IgepalTM C0-630, marketed by the GAF Corporation; and TritonTM X-45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company.
These sur~ct~ntc are commonly referred to as alkylphenol alkoxylates (e.g., allyl phenol ethoxylates).

The con~1~ncAtion products of ethylene oxide with a hydrophobic base formed by the conA~ncqtion of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant in the present invention. The hydrophobic portion of these compounds will preferably have a molecular weight of from 1500 to 1800 and will exhibit 5 water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is 50% of the total welght of the conAçncq~tion product, which corresponds to conA~ncA~ion with up to 40 moles of ethylene oxide. Examples of co,-~pou-lds of this type include certain of the 10 co.~ ercially-available PluronicTM surfqctqntc"~.z.l~PI~A by BASF.

Also suitable for use as the nonionic surfactant of the nonionic surfactant system of the present invention, are the col-A~ ion products of ethylene oxide with the product res--lting from the reaction of propylene oxide and ethyl~n~AiA.~ P. The hydrophobic 15 moiety of these products COllSiSI~ of the reaction product of ethyl~ di~ n;"~ and excess - propylene oxide, and generally has a molecular weight of from 2500 to 3000. This hyd~ophobic moiety is conAen.ced with ethylene oxide to the extent that the conA~ncq-tion product contains from 40% to 80% by weight of polyoxyethylene and has a molecular weight of from 5,000 to 11,000. Examples of this type of nonionic surfactant include 20 certain of the co~ elcially available TetronicTM compounds, marketed by BASF.
Additional Cationic SUl[~C~

Suitable cq~tiQnic surfactAnt~ are preferably water disp~ il)le compound having surfactant 25 ~,ro~.lies colll~ ing at least one ester (ie -COO-) linkage and at least one calionlcally charged group.

Other suitable cationic surfArtAntc include the quatell~aly al,llllolliulll surfActAntc selected from mono C6-C16, preferably C6-Clo N-allyl or alkenyl a~l~lloniulll ~ cL~ls ~llcle.
30 the rçmqinir~ N position~ are sub~l;l.~l. d by methyl, hydroxyethyl or hydroxypropyl groups. Other suitable cationic ester surfactants, including choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.

Optional D~L~.~e1ll Ingredients W 097/44432 PCT~US97/08372 The following illustrates various other optional ingredients which may be used in the compositions of this invention, but is not intended to be limiting thereof.

Bleach Activators s Bleach activators are p.~ere~d cO~ of the composition of the present invention.
Where present, the amount of bleach activators will typically be at a level of from 0.1% to 60%, more typically from 0.5% to 40% of the bl~ g composition col~lising the ble~ching agent-plus-bleach activator.
The combination of peroxygen bIe~rlling agents, such as pe.~all,onate and bleach a~ atols results in the in silu production in aqueous solution (i.e., during the washing process) of the peroxy acid co~l~;,pondil~g to the bleach activator. Various nonlimiting e~ plcs of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934. The nonanoyloxyl.. ,l~.le sulfonate (NOBS) and leLIaac~lyl ethylene ~ .niI~ (TAED) activators are typical, and mixtures thereof can also be used.
See also U.S. 4,634,551 for other typical bleaches and activators useful herein.
Highly preferred amido-derived bleach activators are those of the formulae:
R1N(R5)C(o)R2C(o)L or R1C(o)N(R5)R2C(o)L

wherein Rl is an alkyl group cont~ining from 6 to 12 carbon atoms, R2 is an alkylene co.~ ninp from 1 to 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl co.l1 .;..;.~g from 1 25 to 10 carbon atoms, and L is any suitable leaving group. A leaving group is any group that is displaced from the bleach activator as a con~e~ nre of the nucleophilic attack on the bleach activator by the perhydrolysis anion. A p.el~ d leaving group is phenyl sulfona~e.

F~fell.,d examples of bleach ac~ tol~ of the above formulae include (6-o~ n~ i(lo-30 caproyl)c~ --Ifonate, (6-l~n~-.~.-.i~ocaproyl)oxyl,cllze,Rs,llfonate, (6~ec~n~ o-caproyl)oxyb~ nf ~IIfonate, and ~ Lul~S thereof as described in U.S. Patent 4,634,551, incorporated herein by lef.,l~l ce.

W O 97/44432 PCT~US97/08372 Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990, incorporated herein by ref~ence. A highly ~refell~d activator of the benzoxazin-type is:

o S N

Still another class of ~ fell~d bleach a;li~ato~ jnrh~Ps the acyl lactam activators, especially acyl caprol~ct~rn~ and acyl valerolP~t~m~ of the formulae:

o Cl--CH2--CH2~

CH2--CH2' O lC--CH2--ICH2 R6--C--N~

wllc;~ ~n R6 is H or an aLkyl, aryl, aL~coxyaryl, or aL~aryl group cont~ining from 1 to 12 15 carbon atoms. Highly ple~ d lactam activators include benzoyl capro1 ~t~m, octanoyl capro~ m, 3,5,5-~ k~lh~Y~noyl capro~ t~m, nonal~oyl caprolactam, decanoyl caprolactam, nn-lPcenoyl caprolac~rn, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, Imflecennyl valerolactam, nonanoyl valerolactam, 3,5,5-llelhylhP~n-yl valerolactam and rnixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, inrl~l~lin~ benzoyl caprolactarn, adsorbed into sodium perborate.

Bleach Catalyst CA 022~4948 1998-11-17 W O 97/44432 rCTrUS97/08372 Bleach catalysts are preferred components of the compositions of the present invention. If desired, the ble~hin~ compounds can be catalyzed by means of a m~ng~nPse compound.
Such compounds are well known in the art and include, for example, the ~ ng~ se-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat. 5,244,S94; U.S. Pat. 5,194,416; U.S.
Pat. 5,114,606; and Europeall Pat. App. Pub. Nos. 549,271A1, 549,272A1, 544,440A2, and 544,490A1; Preferred examples of these catalysts include MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclonollane)2(PF6)2, MnIII2(u-O)l(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2 (C104)2, MnIV4(u-0)6(1,4,7-triazacyclononane)4(C104)4, MnIII~
MnIV4(u-O)1(u-OAc)2 (1,4,7-Ll.n~ll-yl-1,4,7-triazacyclononane)2(ClO4)3~ MnIV(1,4,7-10 ~ elh.~l-1,4,7-triazacyclononane)- (OCH3)3(PF6), and mixtures thereof. Othermetal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat.
5,114,611. The use of ...~.~g~.lP3e with various complex ligands to el-h~nre ble~cllin~ is also reported in the following United States Patents: 4,728,455; 5,284,944; 5,246,612;
5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.
As a practical matter, and not by way of limit~ti-)n, the compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from 0.1 ppm to 700 ppm, more preferably from 1 ppm to 500 ppm, of the catalyst species in the 20 laundry liquor.

Cobalt bleach catalysts useful herein are known, and are described, for example, in M. L.
Tobe, "Base Hydrolysis of T~silioll-Metal Complexes", Adv. Inorg. Bioinor~. Mech., (1983), 2, pages 1-94. The most ~ fell~d cobalt catalyst useful herein are cobalt 25 p~nt~min~ acetate salts having the formula [Co(NH3)sOAc] Ty~ wll.,_.ll "OAc"
leple,SenlS an acetate moiety and "Ty" is an anion, and especi~lly cobalt p~ ; Z".;.~f acetate chloride, [Co(NH3)sOAc]Cl2; as well as ~Co(NH3)sOAc](OAc)2;
[Co(NH3)soAc](pF6)2; [Co(NH3)sOAC](sO4); [co(NH3)soAc](BF4)2; and [Co(NH3)sOAc](NO3)2 (herein "PAC").
These cobalt catalysts are readily ~l~aled by known procedures, such as taught for example in the Tobe article and the le~rences cited therein, in U.S. Patent 4,810,410, to Diakun et al, issued March 7,1989, J. Chem. Ed. (1989), 66 (12), 104345; The Synthesis and Chara~ dlion of Inolgal~ic Compounds, W.L. Jolly (Prentice-Hall; 1970), pp. 461-3; Inor~. Chem., 18, 1497-1502 (1979); Inorg. Chem., 21, 2881-2885 (1982); Inor~e.

CA 02254948 1998-ll-17 W O 97/44432 PCTrUS97/08372 Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-176(1960); and Journal of Physical Chemistry, 56, 22-25 (1952).

As a practical matter, and not by way of limitation, the automatic dishwashing compositions and cle~ning processes herein can be adjusted to provide on the order of at least one part per h~ dr~d million of the active bleach catalyst species in the aqueous washing mP~ m, and will preferably provide from 0.01 ppm to 25 ppm, more preferably from 0.05 ppm to 10 ppm, and most preferably from 0.1 ppm to 5 ppm, of the bleach catalyst species in the wash liquor. In order to obtain such levels in the wash liquor of an automatic dish~ashil1g process, typical ~ olll~ disllwashing collll,osilions herein will conlp.ise from 0.0005% to 0.2%, more preferably from 0.004% to 0.08%, of bleach catalyst, especi~lly m~ng~n~se or cobalt catalysts, by weight of the cleaning compositions.

Additional Bleach The del~,rg~ compositions herein may optionally conll)lise an additional bleachillg agent.
When present, such additional ble~ching agents will typically be present at levels of from 1 % to 30%, more typically from 5 % to 20%, of the detelgelll composition, especi~lly for fabric laundering.
The bl~arhing agents used herein can be any of the bleachi..g agents useful for detelgellt compositions in texti}e cle~nin~, hard surface cle~ning, or other cle~ning purposes that are now known or become known. These include oxygen bleaches as well as other b1earhin~
agents. P~.l,o.ate blea~ ,s, e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.

Another Càl~ Oly of bl~c~lin~ agent that can be used without l~ L,i.;lion enco...p~cses ~l~,a~l,oxylic acid bl~hing agents and salts thereof. Suitable examples of this class of agents include m~n~si.. monoperoxyph~h~l~te hexahydrate, the m~gn~sillrn salt of meta-chloro ~lI,~I~oic acid, 4-nonylamino4-oxoperoxybutyric acid and diperoxydoder~n~lioic acid. Such bl~arhing agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985, Euio~an Patent Application 0,133,354, Banks et al, published Feblualy 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued ~ovember 1, 1983. Highly ~lefell~,d ~ .

W O 97/44432 PCTrUS97108372 blea~ling agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S.
Patent 4,634,551, issued January 6, 1987 to Burns et al.

Peroxygen bleaching agents can also be used. Suitable peroxygen bl~chin~ compounds 5 include sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
Perborate bleach, persulfate bleach (e.g., OXONE, m~nuf.~ red co~ e,.;ially by DuPont.~ can also be used.

Bleaclling agents other than oxygen ble~chin~ agents are also known in the art and can be 10 utilized herein. One type of non-oxygen blearhing agent of particular interest inr!ll~1es photoactivated ble ~hin~ agents such as the sulfonated zinc and/or ~ .ni~ .n phthalo-cyanines. See IJ.S. Patent 4,033,718, issued luly 5, 1977 to Holcombe et al. If used, de~,gent compositions will typically contain from 0.025% to 1.25%, by weight, of such bleaches, especi~ y sulfonate zinc phthalo-;ya~ e.
- Mixtures of ble~-hin~ agents can also be used.

Builders 20 D.,t~,lgel-l builders can optionally, but preferably be inclllded in the compositions herein, for example to assist in controlling mineral, especially Ca2+ and/or Mg2+, h~.ll~ss in wash water or to assist in the removal of particulate soils from surfaces. Builders can operate via a variety of ,.,~ ."~ inrll-din~ folllimg soluble or insoluble complexes with hardness ions, by ion e~h~ , and by orf~,.ing a surface more favorable to the 25 p~C;~)ilalion of h~less ions than are the surfaces of articles to be cle;~n~ Builder level can vary widely rl~pe.~ upon end use and physical form of the COIIIpO;ailiOIl. Built dete~ typically co ~.ise at least 1% builder. Liquid form~ll?tiQn~ typically comp.ise 5% to 50%, more typically 5% to 35% of builder. Granular forrnl~l~ ions typically co,ll~.ise from 10% to 80%, more typically 15% to 50% builder by weight of the d~,t~,.g~
30 composition. Lower or higher levels of builders are not e~cl-JA~d. For example, certain detclgellt additive or highsurfactant formlllAtion~ can be unbuilt.

Suitable builders herein can be selecte~l from the group con~ g of phosph~l~s and polyphosphates, çspecii~lly the sodium salts; silicates in~ lin~ water-soluble and hydrous 35 solid types and including those having chain-, layer-, or three-dimensional- structure as W O 97/44432 PCTrUS97/08372 well as amorphous-solid or non-structured-liquid types; carbonates, bicall,onates, sesquicarbonates and carbonate minerals other than sodium carbonate or sesquicarbonate;
minQsilicates; organic mono-, di-, tri-, and tetracarboxylates especially water-soluble nonsurfactant carboxylates in acid, sodium, potassium or alkanolammonium salt form, as 5 well as oligomeric or water-soluble low molecular weight polymer carboxylates inrlllding aliphatic and aromatic types; and phytic acid. These may be compl~ P-~ by borates, e.g., for pH-buffering pulposes, or by sulfates, especially sodium sulfate and any other fillers or carriers which may be i~ )o.lallt to the engineering of stable surfactant and/or builder-conl~ in~ det~.g~ compositions.
Builder ~ ules, somPtim~S termed "builder systems" can be used and tyypically colll~.isc two or more conventional builders, optionally compl~ rd by ~h~ "~i, pH-buffers or fillers, though these latter materials are generally accoullted for s~,p~alely when des,~ g q~,qntiti-os of ma~erials herein. In terms of relative q~ s of surfactant and builder in 15 the present det~ c.l~, preferred builder ~y~ ns are typically form~ t~d at a weight ratio of surfactant to builder of from 60: 1 to 1:80. Certain plef. .led laundry dt~ ellts have said ratio in the range 0.90:1.0 to 4.0:1.0, more preferably from 0.95:1.0 to 3.0:1Ø

P-cont~ining det~rge.l~ builders often prel~ ,d where permitted by legislation include, but 20 are not limited to, the alkali metal, anllllol~ium and alkanol~l.lllorli~ll salts of polyphosphates exernrlified by the tripolyphosphates, pyrophosphates, glassy polymeric meta~phosphates; and phosrhon~tes.

Suitable silicate builders include alkali metal silir~tes, particularly those liquids and solids 25 having a SiO2:Na20 ratio in the range 1.6:1 to 3.2:1, inr~ lin~, particularly for ~ulol~ ic dishwashing purposes, solid hydrous 2-ratio 5ilirate$ .. ~ d by PQ Corp. under the traden~...r- BRITESIL~, e.g., BRITESIL H20; and layered silir~t~s, e.g., those described in U.S. 4,664,839, May 12, 1987, H. P. Rieck. NaSKS-6, so...e~in.Ps abbr~i&t~d "SKS-6", is a crystalline layered ~h..~iniu."-free ~-Na2SiOs morphology silicate ~ rt~d by 30 Hoerhct and is ~lefe.lcd especially in granular laundry colll~osiLions. See p~ ~aLi~re m~th~lc in German DE-A-3,417,649 and DE-A-3,742,043. Other layered cilil~t~s, such as those having the general formula NaMSix02x+ 1 YH20 wl~.~ m M is sodium or hydrogen, x is a lllllllbel from 1.9 to 4, preferably 2, and y is a llum~l from O to 20, preferably 0, can also or al~ ~tely be used herein. Layered silicates from Hoechst also 35 include NaSKS-5, NaSKS-7 and NaSKS-11, as the a, ,B and ~ layer-silicate forms. Other W O 97/44432 PCT~US97/08372 silicates may also be useful, such as m~g..~siùll~ silicate, which can serve as a cli~pc~ g agent in granules, as a stabilising agent for bleaches, and as a component of suds control systems.

Also suitable for use herein are synth~si7P~I crystalline ion exchange materials or hydrates thereof having chain structure and a composition replestllted by the following general formula in an anhydride form: xM2O ysio2.zMlo wll~ M is Na and/or K, M' is Ca and/or Mg; y/x is 0.5 to 2.0 and z/x is 0.005 to 1.0 as taught in U.S. 5,427,711, Sakaguchi et al, June 27, 1995.
Suitable c~l,onate builders include alk~lin~ earth and alkali metal call,ol~t~s as disclosed in ~errn~n Patent Applir~tion No. 2,321.001 published on November 15, 1973, although sodium bicarbonate, sodium carbonate, sodium ses4-1ical1,ol~le, and other carbonate minerals such as trona or any convenient multiple salts of sodium c~l,ol~dte and calcium ca,l,ona~e such as those having the composition 2Na2C03.CaC03 when anhydrous, and even calcium carbonates inrl~ in~ calcite, aragonite and vaterite, especi~lly forms having high surface areas relative to COI.~p~ -l calcite may be useful, for example as seeds or for use in synthetic dclcrgell~ bars.

.Ah)minosilicate builders are especi~lly useful in granular detelg.,llts, but can also be incol~lated in liquids, pastes or gels. Suitable for the present purposes are those having elll~ilical formula: [Mz(A102)z(SiO2)v] xH20 wherein z and v are integers of at least 6, the molar ratio of z to v is in the range from 1.0 to 0.5, and x is an integer from 15 to 264.
minos~ t~s can be crystalline or ~lloll,hous, naturally-occullillg or ~y.,~ lly derived. An ~ nsili~t.o pl~Ylu~ l;o~ method is in U.S. 3,985,~69, Klulll~nel, et al, October 12, 1976. ~,fi,li~ s~ ,lic crystalline ~ minnsilir,~te ion eY~h~n~e materials are available as Zeolite A, Zeolite P (B), Zeolite X and, to wl~t~iel extent this differs from Zeolite P, the so-called Zeolite MAP. Natural types, including clinoptilolite, may be used. Zeolite A has the formula: Na12[(AlO2)12(SiO2)12~-xH2O wheleill x is from 20 to 30, ecpeci~lly 27. Dehydrated zeolites (x = 0 - 10) may also be used. Preferably, the minnsilir~te has a particle size of 0.1-10 microns in r~ ter.

Suitable organic det.,rgelll builders include polycarboxylate colnpounds, including water-soluble nonsurfactant dicarboxylates and tricarboxylates. More typically builderpolycarboxylates have a plurality of carboxylate groups, preferably at least 3 carboxylates.

W 097/44432 PCT~US97/0~372 Carboxylate builders can be form~ te(l in acid, partially neutral, neutral or overbased fonn. When in salt form, alkali metals, such as sodium, potassium, and lithilln, or alkanolammonium salts are pl~fel,ed. Polycarboxylate builders include the ether polycarboxylates, such as oxydisuccinate, see Berg, U.S. 3,128,287, April 7, 1964, and S Lamberti et al, U.S. 3,635,830, January 18, 1972; "TMS/TDS" builders of U.S.

4,663,071, Bush et al, May 5, 1987; and other ether carboxylates including cyclic and alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163;
4,158,635; 4,120,874 and 4,102,903.

10 Other suit~~'~ builders are the ether hydroxyl~olycall~oxylates, copolymers of maleic al~lydlide with ethylene or vinyl methyl ether; 1, 3, 5-1lihydloxy benz.,,~e-2, 4, 6-triclllphnni~ acid; carboAy,.,.,ll,)lloxysl~rcini~ acid; the various alkali metal, ~~ o~ n and sulb~ d ammonium salts of polyacetic acids such as ethylenf ~ tetraacetic acid and nitrilolliacetic acid; as well as mellitic acid, succinic acid, polymaleic acid, ~.~,ne 1,3,5-15 tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
Citrates, e.g., citric acid and soluble salts thereof are illll)ullallt carboxylate builders e.g., for heavy duty liquid det~ , due to availability from renewable resources and biodegradability. Citrates can also be used in granular compositions, especially in 20 combination with zeolite and/or layered silicates. Oxydisuccinates are also especi~lly useful in such composhion~ and col..binations.

Where pe- ...illrd and especially in the formulation of bars used for hand-laullde,ing operations, alkali metal phn~h~teS such as sodium tripolyphosphates, sodium 25 y~lOphf;~lJh~t~' and sodium o-ll-.~l,hosphate can be used. Pl.osphonate builders such as et_ane-l-h~dlu~y-l~l~irhn~ hon~ and other known ~ho~hol~tes, e.g., those of U.S.3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137 can also be used and may have desirable ~nti.ccalin~ pro~.lies.

30 Certain detersive ~,llfi~ nl~ or their short-chain homologs also have a builder action. For unambiguous formula accoul~ g purposes, when they have surfactant capability, these materials are summPd up as detersive ~ulrac~llls. r~efel.~d types for builder functionality are illustrated by: 3~3-dicarboxy4-oxa-l~6-hex~nprlioates and the related compounds disclosed in U.S. 4,566,984, Bush, January 28, 1986. Succinic acid builders include the 35 Cs-C20 aLkyl and alkenyl succinic acids and salts thereof. Succinate builders also include:

W 097/44432 PCTrUS97tO8372 laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenyl~ cin~te (pleÇellcd), 2-pentadecenylsuccinate. Lauryl-succinates are described in Eulol~eall Patent Application 86200690.5/0,200,263, published November 5, 1986. Fatty acids, e.g., C12-C1g monocarboxylic acids, can also be incorporated into the compositions as surfactant/builder S materials alone or in colnbillaLion with the aÇc le~lle.llioned builders, especially citrate and/or the succinate builders, to provide additional builder activity. Other suitable polycarboxylates are disclosed in U.S. 4,144,226, Crutchfield et al, March 13, 1979 and in U.S. 3,308,067, Diehl, March 7, 1967. See also Diehl, U.S. 3,723,322.

10 Other types of inorganic builder materials which can be used have the for nula (MX)i Cay (CO3)z wl~c,eill x and i are il.le~e,~ from 1 to 15, y is an integer from 1 to 10, z is an integer from 2 to 25, Mi are cations, at least one of which is a water-soluble, and the equation ~i = 1 ls(xi multiplied by the valence of Mi) + 2y = 2z is sqticfiçd such that the formula has a neutral or "bqlqnred" charge. These builders are referred to herein as 15 "Mineral Builders". Waters of hydration or anions other than call,ullate may be added provided that the overall charge is bAlq-n~ed or neutral. The charge or valence effects of such anions should be added to the right side of the above equation. P~ef. l~bly, there is present a water-soluble cation select~-d from the group COI~.C;.~ of hydrogen, water-soluble metals, hydl~ell, boron, Alllll10~ , silicon, and .ni~lu~s thereof, more20 ~lcfe~ably, sodium, potassium, hydrogen, lithil~m, qmmonil~rn and l~ ules thereof, sodium and pot~csjllm being highly ~,lef~llcd. Nonli...il;.~ examples of nol~call,onate anions include those selected from the group consisting of chloride, sulfate, fluoride, oxygen, hydroxide, silicon dioxide, chlOlllal~, nitrate, borate and n~lules thereof.
~efe,l~,d builders of this type in their simplest forms are selectecl from the group con~;cl;.¢ of Na2Ca(CO3)2, K2ca(co3)2t Na2Ca2(C~3)3~ NaKCa(C~3) NaKCa2(C~3)3. K2Ca2(C~3)3. and combinations thereof. Anespeciallyp,ef~
material for the builder des.;lil~d herein is Na2Ca(C03)2 in any of its crystalline modifications. Suitable builders of the above-defined type are further illustrated by, and include, the natural or synthetic forms of any one or combinations of the following minerals: Afgl~ e, Andersonite, AshcroftineY, Beyerite, BolcaliLe, Burbankite, B-ltcchliit~, Can~;lillile, Carbocernaite, Carletonite, Davyne, DonnayiteY, Fairchildite, rc.lisulile, rl~ .;le, Gauderl~yile, Gaylussite, Girvasite, GregG"~ile, Jouravskite, K~...ph~ it~y, Kell~lclil~, Kh~ e, LepersonniteGd, Liottite, MckelveyiteY, Micloswlllllile, Mroseite, Natrofairchildite, Nyel~r~ , RemonditeCe, Saclur~lite, W O 97/44432 PCT~US97/08372 Schrockingerite, Shortite, Surite, Tunisite, Tl~ccanite, Tyrolite, Vishnevite, and Zemkorite.
Preferred mineral fonns include Nyererite, Fairchildite and Shortite.

Enzymes S

Enzymes can be inrhlded in the present detel~el,l compositions for a variety of purposes, includillg removal of protein-based, carbohydrate-based, or triglyceride-based stains from substrates, for the prevention of refugee dye ll~llsf~" in fabric laundering, and for fabric restoration. Suitable el.~y~lles include proteases, amylases, lipases, cellulases, peroxidases, 10 and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Preferred selections are inflllenred by factors such as pH-activity and/or stability optima, ll..,....o~ ility, and stability to active de~.genL~, builders. In this respect bact~,.ial or fungal enzymes are ,ulere.lcd, such as ba.;l.,.ial amylases and l~lul~,ases, and fungal cell~ s.
"Detersive enzymen, as used herein, means any enzyme having a cle~nin~, stain removing or otherwise beneficial effect in a laundry, hard surface cleaning or pe.~onal care detergent composition. ~,fi,.l~,d detersive el~yl~es are hydrolases such as proteases, amylases and lipases. Plefe.lcd el~y~,es for laundry purposes include, but are not limited to, proteases, cellnl~es, lipases and peroxidases. Highly p.~r.,.red for ~ o".al;r dishwashing are amylases and/or p,ol~ases.

Enzymes are normally incorporated into detelge." or de~lge~l additive co",posilions at levels ~l~rr.~ to provide a "cl~ning-effective amount". The term "cl-o~ning effective ~molmt" refers to any amount capable of producing a cle~nin~, stain removal, soîl removal, , deodorizing, or freshness improving effect on subsLl~tes such as fabrics, di~h~. ~e. In practical terms for current conL~ll.,.~;ial p~e~laliul~s~ typical amounts are up to 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the dete.gelll cc~ osilion. Stated otherwise, the coll.l~osilions herein will typically co-l-ylise from 0.001 % to 5 %, preferably 0.01%-1% by weight of a cc,n,llle.cial l,r~,~ c preparation. Protease enzymes are usually present in such con~ elcial plep~dtions at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of co",posilion. For certain d~l~r~;e.l~, such as in automatic disll~ashil,g, it may be desirable to increase the active enzyme content of the col~lln.,rcial plepalation in order to minimi7~
the total amount of non-catalytically active materials and thereby hllplo.~e spotting/filming W 097/44432 PCTrUS97/08372 or other end-results. Higher active levels may also be desirable in highly concellLldted detergent formulations.

Suitable examples of proteases are the subtilisins which are obtained from particular strains S of B. subtilis and B. Iichenfformis. One suitable protease is obtained from a strain of ~ri~ , having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE0 by Novo Industries A/S of De.~ all~, hereinafter "Novo". The ~lc~alion of this t~ C and analogous enzymes is described in GB 1,243,784 to Novo. Other suitable - proteases include ALCALASE0 and SAVINASE0 from Novo and MAXATASE0 from International Bio-S~ ti~s, Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756 A, January 9, 1985 and ~.)tease B as disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985. See also a high pH protease from Bacillus sp.
NCIMB 40338 described in WO 9318140 A to Novo. El~ynlalic df t~,lge.lls colllpIishlg protease, one or more other enzymes, and a reversible protease inhibitor are desclibed in WO 9203529 A to Novo. Other plf Çf .l~d proteases include those of WO 9510591 A to Procter & ~.~m1~le . When desired, a plot~ase having declcased adsol~ion and hlcl.ased hydrolysis is available as des~lil~d in WO 9507791 to Procter & Gamble. A recolllbil~1t trypsin-like ~roLf asc for dele.genl~ suitable herein is des~,lil,ed in WO 9425583 to Novo.

In more detail, an especially ~lef~ d protease, lerell~,d to as "Protease D" is a carbonyl hydrolase variant having an amino acid seq~en-~e not found in nature, which is derived from a pre-;ulsor carbonyl hydrolase by su~s~ g a different amino acid for a plurality of amino acid residues at a position in said call,unyl hydrolase equivalent to position +76, ~l~,felably also in colllbi~lion with one or more amino acid residue positions equivalent to those sek~~ from the group Co~ ~ng of +99, +101, +103, +104, +107, +123, +27, + 105, + 1J9, + 126, + 128, + 135, + 156, + 166, + 195, + 197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the llu~ hlg of R(7~ a~yloliquefaciens subtilisin, as described in the patent applications of A. Baeck, et al, entitled ~Protease-Co..~ g Cleaning Compositions" having US Serial 30 No. 08/322,676, and C. Ghosh, et al, "Bleaching Collll~o~iLions COmpliaing Pl~ âsc Enzymes" having US Serial No. 08/322,677, both filed October 13, 1994.

Amylases suitable herein, especially for, but not limited to automatic dishwashing purposes, include, for example, a-amylases described in GB 1,296,839 to Novo;
35 RAPIDASE0, Illt~lnalional Bio-S~ ,f lir~5, Inc. and TERMAMYL0, Novo.

W O 97/44432 PCT~US97/08372 FUNGAMYL~ from Novo is especially useful. Fn~ e~ g of enzymes for improved stability, e.g., oxidative stability, is known. See, for example J. Biological Chem., Vol.
260, No. 11, June 1985, pp. 6518-6521. Certain pref~lled embodillRnls of the present compositions can make use of amylases having improved stability in d~l~lgc,lls such as

5 qutomqtir dishwashing types, especially improved oxidative stability as measured against a leftl~,nce-point of TERMAMYL~ in colllmelcial use in 1993. These l refel,~,d amylases herein share the chalacl. lislic of being "stability-enhq-nred" amylases, chal,lcl~li ed, at a ,.. ;..;.. -, by a measurable improvement in one or more of: oxidative stability, e.g., to hydrogen peroxide/tetraacetylethylen~iqminP in l-llrf.,l- d solution at pH 9-10; thermal 10 stability, e.g., at collllnon wash te~ alu~s such as 60~C; or AlkqlinP stability, e.g., at a pH from 8 to 11, llleasul~,d versus the above-identified lcfel~ ce-point amylase. Stability can be lued~urcd using any of the art-disclosed techrlirq-l tests. See, for example, rcfel.,llces r1icclQsed in WO 9402597. Stability e~-h~ cd amylases can be obtained from Novo or from Ce~ ror TnternqtirJnal. One class of highly pl. f~ll.,d amylases herein have t_e15 comlllolldlity of being derived using site-directed mnt~q,gen~cis from one or more of the Rn~ amylases, especially the R~.cil1.1~ a-amylases, regardless of WIlcLllc- one, two or multiple amylase strains are the ill~ di~te pl~ rst.ls. Oxidative stability-el-h~nred amylases vs. the above-i~lentifi~od rcfe~ ce amylase are plcft~ d for use, especially in bl~rh;..g, more preferably oxygen ble~ ing, as distinct from chlorine ble;~ching, 20 de~ gcllt compositions herein. Such p~ef~ d amylases include (a) an amylase according to the helcillbefol~, incc)l~tJlated WO 9402597, Novo, Feb. 3, 1994, as further illustrated by a mutant in which s~b~ ;Qn is made, using alanine or threonine, preferably Ihleo~ e, of the methionine residue located in position 197 of the B lich~,.iJ~rl,ls alpha-amylase, known as TERMAMYL~', or the homologous position variation of a similar parent amylase, such 25 as B. arrryloliquefaciens, B. subtilis, or B. stearothermophilus; (b) stability~-h~.~l-ed amylases as desc~ibed by ~n~nror In~ ional in a paper entitled "Oxidatively R~sict~nt alpha-Amylases" prcsenled at the 207th Alllc.icall Ch~mir~l Society National Meeting, March 13-17 1994, by C. l~ eki..~oll. Therein it was noted that bleaches in ~ J...~ir dishw~shing dct.,.gell~ inactivate alpha-amylases but that improved oxidative stability 30 amylases have beenmade by Genencor fromB. Iichenifonnis NCIB8061. Mc~ io~ c (Met) was i(~entifi~ as the most likely residue to be mo~ifi~cl Met was ~ubsliluled, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to specific ".~
particularly hllpGII~ll being M197L and M197T with the M197T variant being the most stable ~Apl. ssed variant. Stability was ll.casllled in CASCADE(~ and SUNLIGHT~; (c) 35 particularly ~ ;Ç.,lled amylases herein include amylase variants having additional ,,, . ,, .. ., ~ ~ . . ~ .

W 097/44432 PCTrUS97/08372 mo-~ific~tion in the imm~ te parent as described in WO 9510603 A and are available from the assignee, Novo, as DURAMYL~. Other particularly l)refcllcd oxidative stability enh~nred amylase include those described in WO 9418314 to Genencor I~lLcl~ ional and WO 9402597 to Novo. Any other oxidative stability-çnh~nred amylase can be used, for 5 example as derived by site-directed mutagenesis from known chirneric, hybrid or simple mutant parent forms of available amylases. Other plef~ cd el~y--.c modifications are ~ccessihle. See WO 9509909 A to Novo.

Other amylase el~yllRs include those described in WO 95/26397 and in co-pe~ g 10 application by Novo Nordisk PCT/DK96/00056. Specific amylase e..~y~es for use in the de~rgelll colllposilions of the present invention include a-a nylases chalaclcli~cd by having a specifl~ activity at least 25% higher than the specific activity of Tel.ll~ullyl~ at a tclll~al~ range of 25~C to 55~C and at a pH value in the range of 8 to 10, llleas-lILd by the Ph~rleb~c~ a-~llylasc activity assay. (Such Phadebas~ a-amylase activity assay is described at pages 9-10, WO 95/26397.) Also inrl~ ed herein are a-amylases which are at - least 80% homologous with the amino acid seq~lerlres shown in the SEQ ID listings in the l~fe.~ ces. These enzymes are preferably incollJuldted into laundry det lgenl cc,lllposilions at a level from 0.00018% to 0.060% pure el~ylllc by weight of the total composition, more ~I~;felably from 0.00024% to 0.048% pure el~ylllc by weight of the 20 total composition.

C~ cçc usable herein include both bacterial and fungal types, preferably having a pH
Opl~lllllln b~ ,n 5 and 9.5. U.S. 4,435,307, Ball,esgo~.l et al, March 6, 1984, discloses suitable fungal ce~ ces from H~ ola insolens or Humicola strain DSM1800 25 or a cçlll'lqce 212-pro~ring fungus belonging to the genus Aeromonas, and ce~ ce extracted from the ~..tol)a~ as of a marine mollusk, Dolabella Auricula Solander.
~llit~ble ce~ es are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME~ and CELLUZYME~ (Novo) are especi~lly useful. See also WO 9117243 to Novo.
Suitable lipase el-~yllles for detergellt usage include those produced by microolga.~ of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB
1,372,034. See also lipases in J~ ,se Patent Application 53,20487, laid open Feb. 24, 1978. This lipase is available from Amano Pharrn~cel-ti~l Co. Ltd., Nagoya, Japan, 35 under ~e trade name Lipase P "Amano, " or "Amano-P. " Other suitable conlllll ~ial W097t44432 PCT/US97/08372 lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. Iipolyticum NMLB 3673 from Toyo Jozo Co., Tagata, Japan;
Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. LIPOLASE~ enzyme derived S from Humicola lanuginosa and co~ le~cially available from Novo, see also EP 341,947, is a plcfc~led lipase for use herein. Lipase and amylase variants stabilized against peroxidase enzymes are desclibed in WO 9414951 A to Novo. See also WO 9205249 and RD 94359044.

10 In spite of the large lllJul~l of publications on lipase enzymes, only the lipase derived from Hl~micola lanuginosa and pi~luced in Aspergillus oryzae as host has so far foundwidespread application as additive for fabric washing produ.;l~. It is available from Novo Nordisk under the tra~lenqm~ Lipolasen', as noted above. In order to Optil~ e the stain removal p~,ro.l,~l1ce of Lipolase, Novo Nordisk have made a ll~llbcl of variants. As described in WO 92/05249, the D96L variant of the native Humicola lanuginosa lipase improves the lard stain removal efficiency by a factor 4.4 over the wild-type lipase (enzymes compared in an amount l~n~ hlg from 0.075 to 2.5 mg protein per liter).Research Disclosure No. 35944 published on March 10, 1994, by Novo Nordisk discloses that the lipase variant (D96L) may be added in an amount col~ ,yonding to 0.001-100- mg 20 (5-500,000 LU/liter) lipase variant per liter of wash liquor. The present invention provides the benefit of improved wl~ n~s~ mqi.~ re on fabrics using low levels of D96L variant in dcL,ge.ll compositions contqining the bis-AQA surfiq.~t-qnt~ in the l,lal~llel disclosed herein, especially when the D96L is used at levels in the r,,nge of 50 LU to 8500 LU per liter of wash solution.

Cl~tinq~e e,~ es suitable for use herein are described in WO 8809367 A to C;ellel~cor.

Peroxidase e,~yllRs rnay be used in cull,bil~tion with oxygen sources, e.g., ~..;arl,o,~te, perborate, hydrogen peroxide, etc., for "solution ble-qrlling" or prevention of transfer of 30 dyes or pig~-~f~ removed from substrates during the wash to other substrates present in the wash solution. Known peroxidases include horseradish peroxidase, ligninqce, and haloperoxidases such as chloro- or bromo-peroxidase. Peroxidase-con~-qining dele,~ L
compositions are disclosed in WO 89099813 A, October 19, 1989 to Novo and WO
8909813 A to Novo.

CA 02254948 1998-ll-17 W O 97/44432 PCTrUS97108372 A range of enzyme materials and means for their incorporation into synthetic delerge, compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5,1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, Place et al, July 18, 1978, and in U.S.4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid d~le,ge formulations, and their incol~c,.aLion into such form.-l~tions, are disclosed in U.S.
4,261,8~8, Hora et al, April 14,1981. Enzymes for use in dtl~,lgenls can be stabilised by various techni(lues. Enzyme stabilisation tecllni~lues are disclosed and exemplified in U.S.
3,600,319, August 17,1971, Gedge et al, EP 199,405 and EP 200,586, October 29,1986, 10 Venegas. Enzyme stabilisation sy~ ms are also described, for example, in U.S.3,519,570. A useful R~cilh-c, sp. AC13 giving ~roteases, xylanases and cellll1~ces, is described in WO 9401532 A to Novo.

Enzyme Stabilizin~ System The enzyme-cont~inin~ cornpositiQns herein may optionally also col"~,lise from 0.001% to 10%, preferably 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 colllp,alible with the detersive enzyme. Such a system may be hlhele.llly provided 20 by other formulation actives, or be added sep&lal~ly, e.g., by the formulator or by a m~n--fartllrer of det~rge~ ready enzymes. Such stabilizing systems can, for example, colll~lise c~lci~-m ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, and ln~b~ eS thereof, and are ~lesign~d ~o address dirr~le." stabilization problems d~endillg on the type and physical form of the dele~ c~,lllpOSiLio,l .
One stabilizing approach is the use of water-soluble sources of c~l~i--m and/or m~g..fsiu ions in the finich~d composilions w_ich provide such ions to the tl~yllles. C~lcil~m ions are generally more effective than m~gn~si.. ions and are preferred herein if only one type of cation is being used. Typical det~,.ge.ll con~osilions, espec~lly liquids, will colllplise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 8 to about 12 milliml~les of c~,lci~lm ion per liter of finich~d d~ gelll coll~osilion, though variation is possible ~lepe.~ on factors including the multiplicity, type and levels of enzymes incorporated. Preferably water-soluble calcium or maglle;,iunl salts are employed, including for example calcium chloride, c~lci-lm hydroxide, calcium formate, calcium malate, c~lcillm m~lP~te, c~lrhlm hydroxide and calcium acetate; more generally, calcium CA 022~4948 1998-11-17 O 97/44432 PCTAjS97/08372 sulfate or magnesium salts corresponding to the exemplified calcium salts may be used.
Further increased levels of ~lci-lm and/or Magnesium may of course be useful, for example for promoting the grease-cutting action of certain types of surfactant.

Another stabilizing approach is by use of borate species. See Severson, U.S. 4,537,706.
Borate stabilizers, when used, may be at levels of up to 10% or more of the composition though more typically, levels of up to about 3% by weight of boric acid or other borate compounds such as borax or orthoborate are suitable for liquid detelge,ll use. Substitute~
boric acids such as phenylborollic acid, b~ nebo~onic acid, p-bromophenylboronic acid or the like can be used in place of boric acid and reduced levels of total boron in d.,telge compositions may be possil,lc though the use of such substituted boron derivatives.

Stabilizing systems of certain cl~P~ning compositions, for example a~tom~tic dish~..shing co~ )osilions, may further con,plisc from 0 to 10%, preferably from 0.01% to 6% by weight, of chlorine bleach scavengel~, added to prevent chlorine bleach species present i many water supplies from ~tt~ ing and inactivating the el~yl"cs, especially under ~lk~linP
condiliolls. While chlorine levels in water may be small, typically in the range from 0.5 ppm to 1.75 ppm, the available chlorine in the total volume of water that comes in contact with the enzyme, for example during dish- or fabric-washing, can be relatively large;
acco~hlgly, enzyme stability to chlorine in-use is somPtimPs problematic. Since ~elca~bol~ate has the ability to react with chlorine bleach the use of additional stabilizers against chlorine, may, most generally, not be P55~ 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 cont~inin~ I..O~ cations with sulfite, bisulfite, thioslllfitP, thios~llf~te, iodide, etc. Antioxidants such as call,~l,ate, ascorbate, etc., organic amines such as ethyk~ is~ acetic acid (EDTA) or alkali metal salt thereof, mol-oelh~ lamine (MEA), and mixtures thereof can likewise be used. Likewise, special e.~lllc inhibition ~yslt;llls can be incorporated such that dirr~,lel,l el.~y~es have m~ximllm cOlllpalibility. Other conventional scavengers such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium ~ ollate, as well as phosphate, conrlPn~ed phosphate, acetate, ben7O~e, citrate, formate, lactate, malate, tartrate, salicylate, etc., and n,L~lu~s thereof can be used if desired. In general, since the chlorine scavenger function can be pe.rollned by ingredients separately listed under better recognized functions, (e.g., hydrogen peroxide sources), there is no absolute re-luhelllent to add a separate chlorine .. . . ..

CA 02254948 1998-ll-17 W O 97/44432 PCT~US97/08372 scavenger unless a compound performing that function to the desired extent is absent from an enZyme-cont~ining embodiment of the invention; even then, the scavenger is added only for optimum results. Moreover, the formulator will exercise a chfn~ict's normal skill in avoiding the use of any enzyme scavenger or stabilizer which is majorly incompatible, as S forrn-~lq~e~, with other reactive ingredients. In relation to the use of an~l,o,l,uln salts, such salts can be simply n~1miYefl with the detel~gent composition but are prone to adsorb water and/or liberate qmmoniq during storage. Accordi.l~sly, such materials, if present, are desirably protec~ed in a particle such as that described in US 4,652,392, Rqgin~L-i et al.

10 Polvmeric Soil Release Agent Known polymeric soil release agents, hereinafter "SRA" or "SRA's", can optionally be employed in the present det~nl composition~s. If utili7~d, SRA's will generally comprise from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2~ to 3.0% by weight, oftne co~ osilion.

n~,felled SRA's typically have hydlulJhilic seg...f ..l~ to hy~ophilize the surface of l~dlol)hobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of vvaslliQg and rinsing 20 cycles thereby serving as an anchor for the hydrophilic se~ll~nts. This can enable stains occul~mg s~bseq~ent to tl~ f.~l with SRA to be more easily cleaned in later washing procedures.

SRA's can include a variety of charged, e.g., anionic or even cqtion ~ (see U.S.4,956,447), as well as n~.. rh~l~d ulollollle~ units and structures may be linear, branched or even star-shaped. They may include Cd~ moieties which are especiqlly err.,.,live in controlling molecular weight or altering the physical or surface-active L~lvpellies.
Structures and charge di;~llil~ulions may be tailored for application to di~r~ fiber or textile types and for varied dct~,.gell~ or dete~gc.ll additive products.
~efe.lc;d SRA's include oligomeric terephth~l~te esters, typically pr~alcd by processes involving at least one ~ e~ irlcation/oligollle..z~tion, often with a metal catalyst such as a ~ ko~ e. Such esters may be made using additional mononl~,.s capable of being incorporated into the ester slluclul'e through one, two, three, four or more positions, 35 without of course ~Illling a densely crosslink~l overall slluclul~e.

W 097/44432 PCT~US97/08372 Suitable SRA's include: a sulfonated product of a substAntiAIIy linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently AttArh~cl to the backbone, for example as described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P.
Gosselink: such ester oligomers can be plcl)a-~d by (a) ethoxylating allyl alcohol, (b) .,acl~ng the product of (a) with dimethyl terephthAlAte ("DMT") and 1,2-propylene glycol ("PG") in a two-stage ll~n~este~irlcation/ oligol-le.i~tion procedure and (c) reacting the product of (b) with sodium metabisulfite in water; the nonionic end-capped 1,2-10 propy1ene/polyoxyethylene tel~,~hl~.qlAt~ polyesters of U.S. 4,711,730, Dec~ e. 8, 1987 to Gosselink et al, for example those produced by lldnsc.,l~,.;r.catiorl/oligo~ ~dtion of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"); the partly-and fully- anionic-end-capped OligOIll~,-iC esters of U.S. 4,721,580, January 26, 1988 to ('Jocselin~, such as OligUlll,l~ from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-15 hydroxyocli~ne~lfonate; the n~l~ionic-capped block polyester oligomeric compounds of U.S. 4,702,857, October 27, 1987 to Gosselink, for example produced from DMT, Me-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimc~ 1-5-sulfoisop~.~l.AI~t~; and the anionic, especially sulfoaroyl, end-capped terephthAI~te esters of U.S. 4,877,896, October 31, 1989 to Maldonado, Gosselink 20 et al, the latter being typical of SRA's useful in both laundry and fabric conditioning products, an example being an ester composition made from m-sulfob.,,~oic acid monosodiurn salt, PG and DMT optionally but preferably further co~ ising added PEG, e.g., PEG 3400.

25 SRA's also include simple copolymeric blocks of ethylene t~"ephll.AI~ or propylene t.,,~h~ lAte with poly~tllyle.l~ oxide or polypropylene oxide te~ph~1.AIate, see U.S.
3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Ra~d~r, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; and the Cl-C4 alkylcelluloses and C4 hydroxyalkyl celluloses; see U.S. 4,000,093, 30 Dec~rnher 28, 1976 to Nicol, et al. Suitable SRA's chara~;~.iscd by poly(vinyl ester) hydrophobe se~n~ll~ include graft copolymers of poly(vinyl ester), e.g., Cl-C6 vinyl esters, prcfelably poly(vinyl acetate), graRed onto polyalkylene oxide backbones. See Eulo~an Patent Application 0 219 048, published April 22, 1987 by Kud, et al.
Col~ rcially available examples include SOKALAN SRA's such as SOKALAN HP-22, 35 available from BASF, (~Je ~ ny. Other SRA's are polyesters with repeat units cont~ining W O 97/44432 PCT~US97/08372 10-15% by weight of ethylene terephth~ e together with 90-80% by weight of polyoxyethylene terephth~l~te, derived from a polyoxyethylene glycol of average molecular weight 300-5,000. Collllllelcial examples include ZELCON 5126 from Dupont and MILEASE T from ICI.

Another ple~lled SRA is an oligomer having ell~ ical formula (CAP)2(EG/PG)s(T)s(SIP)l which comprises terephthaloyl (T), sulroiso~hLhaloyl (SIP), oxyethyleneoxy and oxy-1,2-propylene (EG/PG) units and which is preferably t.,...~ ed with end-caps (CAP), preferably modified isethionates, as in an oligomer compl,sing one 10 sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a defined ratio, plcf.,~ably about 0.5:1 to about 10:1, and two end-cap units derived from sodium 2-(2-hydroxyethoxy)-e~h~n~s~llfonate. Said SRA preferably further comprises from 0.5% to 20%, by weight of the oligomer, of a crystallinity-reducing stabiliser, for example an anionic surfactant such as linear sodium dodecylben~ ~f;,~lfonate 15 or a m~rnher se!ected from xylene-, Cl~..f -~-, and toluene- sulrolLat~,s or IlliAlules thereof, these stabilizers or m~ifiPrs being introduced into the ~y~lLllCSiS pot, all as taught in U.S.
5,415,807, Gosselir'c, Pan, Kellett and Hall, issued May 16, 1995. Suitable l,lollo~ for the above SRA include Na 2-(2-hydroxyethoxy) e!~ lfonate, DMT, Na- dimethyl 5-sulfoisophth~l~te, EG and PG.
Yet another group of preferred SRA's are oligome.ic esters colll~ ing: (1) a backbone comprising (a) at least one unit selected from the group c~ncictin~ of dihydroxysulÇol~tes, polyhydroxy sulrol~tes, a unit which is at least lliru-l.;lional whe.~by ester linkages are formed reslllting in a blalulled oligomer backbone, and combin~tionc thereof; (b) at least 25 one unit which is a te.~,~hlllaloyl moiety; and (c) at least one unsulfonated unit which is a 1,2-oxyallcylel~eoAy moiety; and (2) one or more ca~ing units sel~cte~1 from nonionic Cappill~, units, anionic cappil~; units such as al1coxylated, preferably ethoxylated, isethionates, alkoxylated prop~n~sl~lrona~es, alkoxylated propanerliclllfonates, aL~coxylated phenolsulfonates, sulfoaroyl derivatives and mixtures thereof. Preferred of such esters are 30 those of empirical forrmll~
{ (CAP)x(EG/PG)y ' (DEG)y " (PEG)y " ' (T)z(SIP)z ' (SEG)q(B)m}

wherein CAP, EG/PG, PEG, T and SIP are as defined h~ ,inabove, (DEG) repl~stllLsdi(oxyethylene)oxy units; (SEG) leplesenL~ units derived from the sulfoethyl ether of 35 glycerin and related moiety units; (B) represents bran~hing units which are at least W O 97144432 PCT~US97/08372 trifunctional wh~ by ester linkages are formed rec~lting in a branched oligomer backbone; x is from about 1 to about 12; y' is from about 0.5 to about 25; y" is from 0 to about 12; y"' is from 0 to about 10; y'+y"+y"' totals from about 0.5 to about 25; z is from about 1.5 to about 25; z' is from 0 to about 12; z + z' totals from about 1.5 to about 25; q is from about 0.05 to about 12; m is from about 0.01 to about 10; and x, y', y", y"', z, z', q and m l~pl~,se.ll the average number of moles of the corresponding units per mole o~said ester and said ester has a molecular weight ranging from about 500 to about 5,000.

10 ~erc.led SEG and CAP monomers for the above esters include Na-2-(2-,3-dihydro~y~ropoxy)t~h~nr~ fonate ("SEG"), Na-2-{2-(2-hydroxyethoxy) ethoxy}
.lh~ lfonate ("SE3") and its homologs and Uli~ lures thereof and the products ofethoxylating and sulfonating allyl alcohol. P~erell~d SRA esters in this class include the product of ~ esf~.irying and oligoll,eli~ g sodium 2-{2-(2-15 hydroxyethoxy)ethoxy}e~h~n~s~lfonate and/or sodium 2-[2-t2-(2-hydroxyethoxy)-ethoxy}ethoxy]~ nr~ lfonate, DMT, sodium 2-(2,3-dihydro~ypr~oxy) ethane sulfonate, EG, and PG using an &~n,yliale Ti(IV) catalyst and can be ~esi~ t~d as (CAP)2(T)5(EG/PG)1.4(SEG)2.5(B)0.13 whel~,.ll CAP is (Na+ -03S[CH2CH20]3.5)-and B is a unit from glycerin and the mole ratio EG/PG is about 1.7:1 as measured by 20 conventional gas chromatography after complete hydrolysis.

Additional classes of SRA's include (I) nonionic te~ s using diisocyanate coupling agents to link up polymeric ester SL~ ul_s, see U.S. 4,201,824, Violland et al. and U.S.
4,240,918 T~g~cce et al; (II) SRA's with carboxylate t~rmin~1 groups made by adding 25 trim~llitir al~dride to known SRA's to convert l.,~ al hydro~yl groups to trimellitate esters. With a proper se!ection of catalyst, the trimpllitir anhydride forms linl~ges to the tellllil~als of the polymer through an ester of the isolated carboxylic acid of trimf lliti~
anhydride rather than by o~ ulg of the anhydride linkage. Either nonionic or anionic SRA's may be used as ~ululg materials as long as they have hydroxyl terminal groups 30 which may be e~le.irlcd. See U.S. 4,525,524 Tung et al.; (m) anionic terephth~l~te-based SRA's of the llre~llal~c-linked variety, see U.S. 4,201,824, Violland et al; (IV) poly(vinyl caprolactam) and related co-polymers with ulollolllcrs such as vinyl pyrrolidone and/or dimethyl~min~thyl mPth~crylate, in~ ing both nonionic and cationic polymers, see U.S.
4,579,681, Ruppert et al.; (V) graft copolymers, in addition to the SOKALAN types from 35 BASF made, by grafting acrylic mo,.ulllcl~ on to sulfonated polyesters; these SRA's CA 02254948 l998-ll-l7 W 097144432 PCTrUS97/08372 assertedly have soil release and anti-redeposition activity similar to known cellulose ethers:
see EP 279,134 A, 1988, to Rhone-Poulenc Chemie; (VI) grafts of vinyl monomers such as acrylic acid and vinyl acetate on to proteins such as caseins, see EP 457,205 A to BASF
(1991); (VII) polyester-polyamide SRA's plc~aled by condensing adipic acid, caprolactam, 5 and polyethylene glycol, especially 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. Patents 4,240,918,4,787,989,4,525,524 and 4,877,896.

Clay Soil Removal/Anti-redeposition Agents The compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition pr~,~. Iies. Granular de~clgcnl compositions which contain these compounds typically contain from 0.01% to 10.0% by weight of the water-soluble ethoxylates amines; liquid detc~nl compositions 15 typically contain 0.01 % to 5% .

The most plef~ d soil release and anti-redeposition agent is ethoxylated tetraethylene-pe..~ . Exemplary ethoxylated amines are further des~,libed in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of ~Icfe~led clay soil removal-antiredeposition agents are the cationic colll~uu.~ds disclosed in Elm~pean Patent Application 111,965, Oh and Gosselink, published June 27, 1984. Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, ~,lblished June 27, 1984; the ~wiL~elionic polymers ~li.crlosecl in Eulù~eal Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985. Other clay soil removal and/or anti le~ iQn agents known in the art can also be utilized in the con~l)osilions herein. See U.S. Patent 4,891,160, VanderMeer, issued January 2, 1990 and WO 95/32272, published November 30, 1995.Another type of plefi_.led antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.

Polymeric Dispersing Agents Polymeric dispersing agents can advantageously be utilized at levels from 0.1 % to 7 %, by weight, in the compositions herein, especi~lly in the plesence of zeolite and/or layered , . . .

CA 022~4948 1998-11-17 silicate builders. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder pl.rol,l,al,ce, when used in combination with other builders 5 (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release peptization, and anti-redeposition.

Polymeric polycarboxylate materials can be pr~pal~d by pol~",e.izillg or copol~,ulc~ ng suitable unsa~ d ~ O..-~ ,~, preferably in their acid form. Unsaturated mol,o-"..ic 10 acids that can be poly"~.iLed to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, ,.esacol~ic acid, CiLlaCOniC acid and methylen~m~lonic acid. The ~lesellce in the polymeric polycarboxylates herein or ,llonc,ll,~.ic se~ , cont~inin~ no carboxylate radicals such as vill~lnlcLllyl ether, styrene, ethylene, etc. is suitable provided that such sc~5...- .l~i do not col~ ule more than 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water-soluble salts of poly"lc.iLed acrylic acid. The average molecular weight of such polymers in the acid form l,l.,fe.ably ranges from 2,000 to 10,000, more p~f.,.dbly from 4,000 to 7,000 and most preferably from 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ~l"nol~ m and substituted ammonium salts.
Soluble polymers of this type are known materials. Use of polyacrylates of this type in det~lge~t co.nl.o~ ons has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued March 7, 1967.

Acrylic/maleic-based copolymers rnay also be used as a ~,efel,ed component of the di~p~ lg/anti-l~del)osilion agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such30 copolymers in the acid form pl~,f._rably ranges from 2,000 to 100,000, more preferably from 5,000 to 75,000, most preferably from 7,000 to 65,000. The ratio of acrylate to m~ te seg~ nL~ in such copolymers will generally range from 30: 1 to 1: 1, more preferably from 10:1 to 2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ~ omum and s~hstihlt~d 35 allllllonilllll salts. Soluble acrylate/m~ te copolymers of this type are known materials WO 97/~4432 PCTrUS97/08372 which are described in European Patent Application No. 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also describes such polymers comprising hydroxypropylacrylate. Still other useful dis~ hlg agents include the maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP
193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.

Another polymeric material which can be included is polyethylene glycol (PEG). PEG can exhibit dispc~ g agent pelro,lllallce as well as act as a clay soil removal-allLiled~osition - agent. Typical molecular weight ranges for these purposes range from 500 to 100,000, preferably from 1,000 to 50,000, more ~ref~.ably from 1,500 to 10,000.

Polyaspartate and polygl~ ~re di~ ing agents may also be used, especially in conjullclion with zeolite builders. Dispe.sillg agents such as polyaspartate preferably have a molecular weight (avg.) of 10,000.
Bri~htener Any optical bri~l-lr~f .s or other bri~ or whiLellillg agents known in the art can be incorporated at levels typically from 0.01% to 1.2%, by weight, into the det~.35enL
compositions herein. Col,ullfrcial optical brigl.t~--f.~ which rnay be useful in the present invention can be c1~ccifiPd into subgroups, which include, but are not l~Pcess~ily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, ...f~ yanines, dil~ o~hiophene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other mi~r~ nPonc agents. FY~nlrle~ of such b~ pn .~ are disclosed in "The Production and Application of Fluolescent l~r;gl~t~ Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982).

Specific examples of optical bri~ which are useful in the present c~ osilions are those id~r~tifi~A in U.S. Patent 4,790,856, issued to Wixon on Decel~l~l 13, 1988. These bri~h~ .s include the PHORWHITE series of bright~onPrs from Verona. Other bri~}lr-u ~s disclosed in this Icfe~.lce include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artic White CC and Artic White CWD, the 2-(4-styryl-phenyl)-2H-naptho[1,2-d3triazoles; 4,4'-bis-(1,2,3-triazol-2-yl)-stilbenes; 4,4'-bis(styryl)bisphenyls; and the ~minocoumarins. Specific examples of these bri~l.lP~l~.s include 4-methyl-7-diethyl- amino coulll~h~;l,2-bis(ben7imiA~7c1-2-yl)ethylene; 1,3-diphenyl-pyrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-naptho[1,2-d]oxazole;
and 2-(stilben~-yl)-2H-naphthol1,2-d]triazole. See also U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton.

5 Dye Transfer Inhibiting Agents The compositions of the present invention may also include one or more materials effective for inhibiting the trallsrcl of dyes from one fabric to another during the cle~ning process.
Generally, such dye llal~r.,l inhibiting agents include polyvinyl pyrrolidone polymers, 10 polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimi~701e, gpn~SC phthalo~;~al~il1e, peroxi~l~ces, and ~ u~s thereof. If used, these agentstypically cc,nl~lise from 0.01% to 10% by weight of the co~nposilion, preferably from 0.01% to 5%, and more preferably from 0.05% to 2%.

15 More ~l ecirlcally, the polya.l~ine N-oxide polymers ~lcf~l.,d for use herein contain units having the following sLIu~;luldl formula: R-AX-P; wll~le,l1 P is a polyllle,i~able unit to which an N-O group can be at~h~l or the N-O group can form part of the polymerizable unit or the N-O group can be ~ ell 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 aliphatic, ethoxylated aliphalics, 20 aromatics, heter~cyclic or alicyclic groups or any combination thereof to which the nillogen of the N-O group can be att~e~od or the N-O group is part of these groups. Preferred poly~ml~e N-oxides are those ~lle~ R is a hele,o. yclic group such as pyridine, pyrrole, d~7ole, pyrrolidine, piperidine and derivatives thereof.

25 The N-O group can be l~,plese"~d by the following general structures:

1~ 1~
(R~ N--(R2)y; =N--(Rl)x (R3)z wherein R1, R2, R3 are ~liphqtir, aloll~tic, heterocyclic or alicyclic groups or30 colllbi~lions thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be c~ ~od or form part of any of the aÇ(),e"~l~ioned groups. The amine oxide unit of the polyamine N-oxides has a pKa < 10, preferably pKa < 7, more plef~,l,ed pKa < 6.

W O 97/44432 PCTrUS97108372 Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting propcl lies. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, 5 polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
The am~ne N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10: 1 to 1:1,000,000. However, the l,L-nb.,l of amine oxide groups present in the polyd.l~ e oxide polymer can be varied by a~r~;,lidte copolyul~,li~lion or by an a~ "idl~ degree 10 of N-o~ tion The poly~uni~le oxides can be obtained in almost any degree of pol~n~el i~Lion. Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferred 1,000 to S00,000; most plef.,l.~,d S,000 to 100,000. This plefelled class of materials can be referred to as "PVNO".

15 The most ~-efelle~ pol.~u"hle N-oxide useful in the dCt~,lgelltCOlll~OSiliOnS herein is poly(4-vinylpyridine-N-oxide) which has an average molecular weight of 50,000 and an amine to amine N-oxide ratio of 1 :4.

Copolymers of N-vinylpyrrolidone and N-vinyli...i-1~701e polymers (~f~ d to as a class as 20 "PVPVI") are also pl~fell~d for use herein. Preferably the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from S,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is .1~ t~...;..~d by light s~ as described in Barth, et al., Ch~ni~l Analysis. Vol 113.
"Modern Methods of Polymer Chal~ct, .-~tion", the disclosures of which are il~colpo~ated herein by ref~ ce.) The PVPVI copolymers typically have a molar ratio of N-vi~ cl~ to N-v.l"llp~,lolidone from 1:1 to 0.2:1, more pl.,f~,lably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or b~ rtl.

The present invention conll.osiLions also may employ a polyvinylpyrrolidone ("PVP") having an average molecular weight of from 5,000 to 400,000, preferably from 5,000 to 200,000, and more preferably from 5,000 to 50,000. PVP's are known to persons skilled in the d~ ,nL field; see, for example, EP-A-262,897 and EP-A-256,696, inco.~,uldted herein by rer.,., ,lce. Compositions cont~ining PVP can also contain polyethylene glycol ("PEG") having an average molecular weight from S00 to 100,000, preferably from 1,000 CA 02254948 l998-ll-l7 W 097/44432 PCTrUS97/08372 to 10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from 2:1 to 50:1, and more preferably from 3:1 to 10:1.

The detelgeilt compositions herein may also optionally contain from 0.005% to 5% by weight of certain types of hydrophilic optical bri~ en~rs which also provide a dye transfer - inhibition action. If used, the compositions herein will preferably com~lise from 0.01% to 1% by weight of such optical bri~ P~-f.s.

The hydrophilic optical brigl.l~ s useful in the present invention are those having the 10 stn~ctural formula:

Rl R2 N~O~ I ~C=C~ I ~(~N

R2 SO3M SO3M Rl whe~cill Rl is select~(1 from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is 15 selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassiulll.

When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the bri~l.t~ur is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-11i~h~e-2-20 yl)amino]-2,2'-stilben~di~ulfonic acid and disodium salt. This particular bl ;~ht~ l.f'. species is colnlllel~ially .~ 1 under the tra~len~mP Tinopal-UNPA-GX by Ciba-Geigy Cw~Ola~ . Tinopal-UNPA-GX is the ~refelled hydluphilic optical brigh-~n~r useful in the de~e.gelll col,lposilions herein.

25 When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M
is a cation such as sodium, the brightrn~r is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-ll;azh~c-2-yl)amino]2,2'-stilben~ ulfonic acid disodium salt. This particular bright~n~r species is colllllle~;ially mal~eled under the tr~ckl.~...r Tinopal SBM-GX by Ciba-Geigy Corporation.

W O 97/44432 PCTrUS97/08372 When in the above formula, R1 is anilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bisl(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilben~licl~lfonic acid, sodium salt. This particular bri~hten~r species is conll~ cially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Coll,o,dlion.
s The specific optical brigl-lrn~l species selected for use in the present invention provide especiqlly effective dye tla,~Çer inhibition pc.ro~ ance benefits when used in combination with the selçct~d polymeric dye llal~f~ inhibiting agents he.cil~l)cfore described. The combination of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such 10 selecte~l optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) provides signi~çqntly better dye transfer inhibition in aqueous wash solutions than does either of these two dete.genl composition collll O~ ts when used alone. Without being bound by theory, it is believed that such brigl.~ work this way because they have high affinity for fabrics in the wash solution and ~lle~folc deposit relatively quick on these 15 fabrics. The extent to which bri~ If :~ deposit on fabrics in the wash solution can be defined by a pa~n~t~,. called the "exhqll~tion coeffi~i~nt". The exhaustion cocrr~cicl~ is in general as the ratio of a) the brigl.~.... material deposited on fabric to b) the initial brigl~ r collce~lllation in the wash liquor. I~;gh~.-f-.s with relatively high eYh~ustion coerrlcitll~ are the most suitable for inhibiting dye ,l~r~ in the context of the present 20 invention.

Of course, it will be app~ciated that other, convçntionql optical bright~n~r types of col,ll,vu,~ds can optionally be used in the present colllpo~ilions to provide coll~enLiollal fabric "brightn~ss" ~,I.,rlls, rather than a true dye ~re. inhibilillg effect. Such usage is 25 conventionql and well-known to det~lge,ll form~ ion~.

Ch~l-qtin~ A~eents The d~.,.ge.ll composition~ herein may also optionally contain one or more iron and/or 30 ...~n~,,..-f sf chPl-q-ting agents. Such ch~ ting agents can be selected from the group con~ of amino carboxylates, amino phosphonates, polyfunctionally-sub~lilu~d aro-matic ch~l-qtin~ agents and ll~lul~s therein, all as h~.e.lldrleF defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and mqng,qn~se ions from washing solutions by 35 formation of soluble ch~l~tçs.

.

CA 02254948 l998-ll-l7 Amino carboxylates useful as optional chelating agents include ethylen~diA...inrlel. ~ce-At~os, N-hydroxyethylethylenediA~ .;AAretAAteC~ nitrilotriA et"~toc, ethylenP~ minr tell~proprionates, triethylenetetrAAAAmin~h~AAretAtes, diethyle.~L~ ,inep~.-lAAAretAAt~s, and S ethanoldiglycines, alkali metal, ammonium, and substituted a~ lol~iulll salts therein and mixtures therein.

Amino phosphonates are also suitable for use as ch~ ing agents in the compositions of the invention when at least low levels of total phosphorus are p~ d in dcl._rgell~
10 compositions, and include ethylenP~liz...in~tetrakis (methylen.opho~l,honates) as DEQUEST.
Plcfellcd, these amino phosl,hol~tes to not contain alkyl or alkenyl groups with more th~n

6 carbon atoms.

Polyfull~,liollally-~.Jb~ ed aloll~lic ch~lAAtin~ agents are also useful in the colll~o~ilions herein. See U.S. Patent 3,812,044, issued May 21,1974, to Connor et al. ~ler~,.led compounds of this type in acid form are dihydroxydisul~.-,f ~f S such as 1 ,2-dihydroxy-3,5-disulfobe.~e.l~.

A plefc.led biodegradable chelator for use herein is ethyl~n~iAmin~ disuccinate 20 ("EDDS"), especially the [S,Sl isomer as described in U.S. Patent 4,704,233, November 3,1987, to Hartman and Perkins.

The co...l.osilion~ herein may also contain water-soluble methyl glycine ~ etir acid (MGDA) salts (or acid form) as a chelant or co-builder useful with, for example, insoluble 25 builders such as zeolites, layered ~ilir~t~.

If ~ltili7~d, these chPI~ agents will geneMlly coll~plise from 0.1% to 15% by weight of the deterg~ co.llposiLions herein. More p.efe.ably, if ~Itili7~ the rh~!Atin~ agents will coll~,ise from 0.1% to 3.0% by weight of such compositions.
- Suds Su~lcssors Colllpoullds for lcducillg or supples~illg the formation of suds can be il~col~o,ated into the compositions of the present invention. Suds ~-lpl)lession can be of particular illlpGlL~llce in CA 02254948 l998-ll-l7 the so-called "high concentration cleaning process" as described in U.S. 4,489,455 and 4,489,574 and in front-loading European-style washing m~r~in~s.

A wide variety of materials may be used as suds suppressors, and suds s-l,plessor~ are well 5 known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Ch~mir~l Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category of suds ~upyressor of particular interest enconlpasses monocarboxylic fatty acid and soluble salts therein. See U.S. Patent 2,954,347, issued September 27,1960 to Wayne St. John. The monocarboxylic fatty acids and salts thereof used as suds~ ,sor typically have hydrocdll,yl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, po~c~ ..., and lithium salts, and ammonium and alkanolammonium salts.

The dct~"gc.lt col"~osilions herein may also contain non-surfactant suds su~lessors.
15 These include, for e..~u.~le: high molecular weight hydrocall,ons such as paraffin, fatty acid esters (e.g., fatty acid triglyce.ides), fatty acid esters of monovalent alcohols, ~liph~ti.
Clg-C40 ketones (e.g., slealonc)~ etc. Other suds Lnhil~ilo,~ include N-alkylated amino triazines such as tri- to hexa-alkylm~!~mines or di- to tetra-alkyl~ ;nP chlolLIi~h~es formed as products of C~ ;C chloride with two or three moles of a primary or secondary 20 amine cont~ining 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosph~te esters. The hydrocarbons such as paraffin and haloparaffin can be utili7~l in liquid form. The liquid hydrocall)ons will be liquid at room ~cnl~laLule and a~.-.o~ph-,.ic pr~i.;,ul~, and will have a pour point in the range of -40~C and 50~C, and 25 a ...i-~ n boiling point not less thanllO~C (atmospheric ples~ul~). It is also known to utili_e waxy hydroc~l,ons, preferably having a melting point below 100~C. The hydrocall~olls co~ 'e a ~ f.,.red c~tegol~ of suds su~plcssor for d~,t.,lg~
compositions. Hydloc&lbu.l suds su~pr,ssol~ are described, for example, in U.S. Patent 4,265,779, issued May 5, lg81 to Gandolfo et al. The hydrocall~olls, thus, include 30 aliphatic, alicyclic, aromatic, and hcl~,r~yclic saturated or w~a~ dted hydlocall,ons having from 12 to 70 carbon atoms. The term "paraffin," as used in ~is suds su~iessor Ai~Cucsion~ iS intt~nA~1 tO include mixtures of true paraffins and cyclic hydlocall~ulls.

Another pl~f~ ,d cat~ol ~ of non-surfactant suds suppressors comprises silicone suds 35 su~plessors. This calegoly includes the use of polyorganosiloxane oils, such as W O 97/44432 PCTrUS97/08372 polyd~ ylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyol~nosiloxane is chemisorbed or fused onto the silica. Silicone suds ~upplessors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and Eulopean Patent Application No. 89307851.9, published February 7,1990, by Starch, M. S.

Other silicone suds ~-lpl,le3sors are disclosed in U.S. Patent 3,455,839 which relates to compositions and processes for defoaming aqueous solutions by incollJolalillg therein small 10 amounts of polydimethylsiloxane fluids.

Mixtures of silicone and sil~nqt~(l silica are desclibed, for i~ rc, in ~'~çrrnqn Patent Application DOS 2,124,526. Silicone defoamers and suds controlling agents in granular delelgenl colll~)csilions are ~ closed in U.S. Patent 3,933,672, Bartolotta et al, and in U.S.
15 Patent 4,652,392, R~gin~i et al, issued March 24,1987.

An exc.llpl~ silil~.on.o based suds ~Uppl.,Sso~ for use herein is a suds ~ s~ing amount of a suds controlling agent co..~ ;ng ess~ lly of:
(i) polydillle~lylsiloxane fluid having a viscosity of from about 20 cs. to about 1,500 CS. at 25~C;
(ii) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxane resin composed of (CH3)3SiO1/2 units of SiO2 units in a ratio of from (CH3)3 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 gel.
In the p~felled silicone suds ~u~,plessor used herein, the solvent for a contimlo .c phase is made up of certain polyethylene glycols or polyethylene-pol~l,r~pylene glycol copolymers or ~ ul.,S thereof (plefe,l~d), or polyprowlene glycol. The primary silicone suds su~lessol is branched/crosslinked and prereldbly not linear.
To illustrate this point further, typical liquid laundry de~ llt compositions with controlled suds will optionally comprise from about 0.001 to about 1, preferably from about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5, weight % of said silicone suds ~uppressor, which colnplises (1) a non~queous emulsion of a primary 35 antifoam agent which is a Il~ e of (a) a polyorganosiloxane, (b) a resinous siloxane or a CA 022~4948 1998-11-17 W O 97/44432 PCT~US97/OB372 silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates;
(2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room te~ ture of S more than about 2 weight %; and without polypropylene glycol. Similar amounts can be used in granular coln~osi~ions, gels, etc. See also U.S. Patents 4,978,471, Starch, issued December 18, 1990, and 4,983,316, Starch, issued January 8, 1991, 5,288,431, Huber et al., issued February 22, 1994, and U.S. Patents 4,639,489 and 4,749,740, Aizawa et al at column 1, line 46 through column 4, line 35.
The silicone suds ~u~plessor herein preferably co"~ises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular weight of less than about 1,000, p~ere~dbly between about 100 and 800. The polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at 15 room telllyeldlule of more than about 2 weight %, pl.,f.,ldbly more than about 5 weight %.

The yrefell~d solvent herein is polyethylene glycol having an average molecular weight of less than about 1,000, more preferably ~t~cen about 100 and 800, most preferably~ ,ll 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, 20 preferably PPG 200/PEG 300. Preferred is a weight ratio of between about 1:1 and 1:10, most preferably between 1:3 and 1:6, of polyethylene glycol:copolymer of polyethylene-polypropylene glycol.

The l.r~felled silicone suds ~I~)IeSSC~l~ used herein do not contain polyprowlene glycol, 25 particularly of 4,000 molecular weight. They also plef~,.ably do not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC L101.

Other suds su~pl.,ssors useful herein colll~,lise the secolld&r~/ alcohols (e.g., 2-aLkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones (1isclosed in 30 U.S. 4,798,679, 4,075,118 and EP 150,872. The secondary alcohols include the C6-C16 allyl alcohols having a Cl-C16 chain. A p~ l.,d alcohol is 2-butyl octanol, which is available from Condea under the tr~dem~rk ISOFOL 12. Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from F.nirh~rn. Mixed suds su~l~ssors typically comprise n~ ules of alcohol + silicone at a weight ratio of ~:5 to 35 5:1.

CA 022S4948 l998-ll-l7 W 097/44432 PCT~US97/08372 51 For any dete,gcnl compositions to be used in ~tom~tic laundry or dishwashing m~hinPs, suds should not form to the extent that they either overflow the washing m~rhinP or negatively affect the washing merh~ni~m of the dishwasher. Suds ~llyplessors, when 5 ntili7Pcl are preferably present in a "suds su~ ssing amount. By "suds sup~ll,ssillg amount" is meant that the formulator of the composition can select an amount of this suds controlling agent that will s-lffiriPntly control the suds to result in a low-sudsing laundry or dishwashing delel ellls for use in ~lltom-~ir laundry or dishwashing m~rhin~.

10 The compositions herein will generally comprise from 0% to 10% of suds ~u~,essor.
When utilized as suds sul prcssors, monocarboxylic fatty acids, and salts therein, will be present typically in ~-I,o~ c up to 5%, by weight, of the dt~ gelll composition.Preferably, from 0.5% to 3% of fatty monocarboxylate suds ~ ssor is 1Itili7Pr~
Silicone suds s~lessols are typically utilized in ~hllUUlllS Up to 2.0%, by weight, of the 15 det~ t composition, although higher ~mo lntC may be used. This upper limit is practical in nature, due primarily to coll~;e~ll with k~pillg costs n~ and effectiveness of lower amounts for effectively controlling su~ci~. Preferably from 0.01% to 1% ofsilicone suds ~,lp~l~;,sor is used, more preferably from 0.25% to 0.5%. As used herein, these weight ~rcc,llage values include any silica that rnay be utilized in cc,-,lb,.~lion with 20 polyorganosiloxane, as well as any adjunct materials that may be utilized. Mono~a,~l phosphate suds su~ essors are generally utilized in ~mollntC ranging from 0.1% to 2%, by weight, of the composition. Hydrocarbon suds ~u~ essors are typically utilized in ~m~ nt.c ranging from 0.01% to 5.0%, although higher levels can be used. The alcohol suds ~u~ressc,~ are typically used at 0.2%-3% by weight of the finichPd compositions.
Alkoxylated Polycarboxylates Alko~Lylated polycarboxylates such as those pl.,~a~ed from polyacrylates are useful herein to provide additional grease removal ~c.ro".,allce. Such rnaterials are described in WO
30 91/08281 and PCT 90/01815 at p. 4 et seq., illco,po~at~d herein by ler~,el~ce.
ChPmir~lly, these materials Collll)liSC polyacrylates having one ethoxy side-chain per every

7-8 acrylate units. The side-chains are of the formula -(CH2CH2O)m(CH2)nCH3 wherein m is 2-3 and n is 6-12. The side-chains are ester-linked to the polyacrylate "backbone" to provide a "comb" polymer type structure. The molecular weight can vary, but is typically . . . ~ . , .

W O 97144432 PCTrUS97/08372 in the range of 2000 to 50,000. Such alkoxylated polycarboxylates can comprise from 0.05% to 10%, by weight, of the compositions herein.

Fabric Softeners Various th~ough-the-wash fabric softeners, especially the impqlpqhle smPctite clays of U.S.
Patent 4,062,647, Storm and Nirschl, issued Decelllbcr 13, 1977, as well as other softener clays known in the art, can optionally be used typically at levels of from 0.5% to 10% by weight in the present compositions to provide fabric softener bellcrl~s con.;ullclllly with 10 fabric cle~nin~. Clay SOrlC.~ can be used in colllbillation with amine and cationic softeners as disclosed, for example, in U.S. Patent 4,375,416, Crisp et al, March 1, 1983 and U.S. Patent 4,291,071, Harris et al, issued September 22, 1981 r~.r.~ s Pe.rl~llRs and p~,lrulll~,ly ingredients useful in the present colll~osilions and prucesses colllplise a wide variety of natural and ~y~ ic rhPmir~l in~l~.di~.lL~" inrl~l~in~, but not limited to, aldehydes, ketones, esters. Also inrl~ P-i are various natural extracts and ess~ ~re~ which can complise complex ll~LlLlules of ingredients, such as orange oil, lemon 20 oil, rose extract, lavender, musk, p~trhollli, balc~rni~ essence, sandalwood oil, pine oil, cedar. Finished p.,lrulll~s can co~ lise e~ llely complex llli~lules of such ingredients.
Finished perfumes typically comprise from 0.01% to 2%, by weight, of the del.,lgc.ll colll~osilions herein, and individual ~.rulll~ly hlgledients can colllplise from 0.0001% to 90% of a finichpd p~,lru~llc co,.~l OS;IiQIl.
Several pc.rull~e fonn~ tionc are set forth in Example XI, hcl~.~r~,. Non-li..,;l;.~
examples of ~clrullle iulgl~,diellLs useful herein include: 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7 t~halll~,~l n~ph~ lPnP; ionone methyl; ionone gamma methyl; methyl cedrylone;
methyl dihydroj~ e; methyl 1,6,10-11hll.,lllyl-2,5,9-cyclodoAeca~ l-1-yl ketone; 7-acetyl-1,1,3,4,4,6-hPY~mPthyl tetralin; 4-acetyl-6-tert-butyl-1,1-dimethyl indane; para-hydroxy-phenyl-l,.l~o~; bcnzophellollc; methyl beta-naphthyl ketone; 6-acet,vl-1,1,2,3,3,5-h~Y~.n. ~ d indane; 5-acetyl-3-isopropyl-1,1,2,6-teL~Ilc~ indane; 1-dQd~Pc~n~l, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde; 7-hydroxy-3,7-dimethyl oc~t~n~l; 10-nn~lPcPn-l-al; iso-hexenyl cyclohexyl carboxaldehyde; formyl tricyclodecane; con-lPn~tion products of hydroxycilloncllal and methyl alllhlallilate, W O 97/44432 PCTrUS97/08372 condensation products of hydroxycitronellal and indol, condensation products of phenyl ~cet~l~ehyde and indol; 2-methyl-3-(para-tert-butylphenyl)-propionaldehyde; ethyl vanillin;
heliotropin; hexyl cinn~mir aldehyde; amyl cinnqmic aldehyde; 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; coumarin; decalactone g~mmq; cyclopent~ec~nt)lide; 16-hydroxy-9-h.-x~lecenoic acid lactone; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyrane; beta-n~phthol methyl ether; ambroxane;dodecahydro-3a,6,6,9a-tetlalllclllylnaphtho[2,1b]furan; cedrol, 5-(2,2,3-t~inlelllylcyclopent-3-enyl)-3-methylpentan-2-ol; 2-ethyl4-(2,2,3-llimc~lyl-3-cyclo~ tell-1-yl)-2-buten-1-ol;
caryophyllene alcohol; tricyclodecenyl propionate; tricyclodecenyl acetate; benzyl 10 salicylate; cedryl acetate; and para-(tert-butyl) cyclohexyl acetate.

Particularly l,lere~ d perfume materials are those that provide the largest odorimproven,.,n~ in finiched product compositions cont~inin~ ce~ lq~es. These pclr~ll"es include but are not limited to: hexyl c;~ .ir aldehyde; 2-methyl-3-(para-tert-15 l)ulylp~nyl)-propionaldehyde; 7-acetyl-1,2,3 ,4,5,6,7,8-octahydro-1, 1 ,6,7-tell~,lethyl lu~ nP; benzyl salicylate; 7-acetyl-1,1,3,4,4,6-hPYz.,..~ ~I.yl tetralin; para-tert-butyl cyclohexyl acetate; methyl dihydro jasmonate; beta-napthol methyl ether; methyl beta-naphthyl ketone; 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; 1,3,4,6,7,8-hexahydro4,6,6,7,8,8-hP~ cyclopenta-gamma-2-benzopyrane; dodecahydro-3a,6,6,9a-teLI~ ylnqphthQ[2,1b]furan; ,qnicqld~hyde; C()UmllUl; cedrol; vanillin;
cyclopçnt-q-d~c~n-)lide; tricyclodecenyl acetate; and tricyclodecenyl propionate.

Other pc.rwlle materials include essF~ I oils, resinoids, and resins from a variety of sources inrl~ ing, but not limited to: Peru balsam, Olihqm~m resinoid, styrax, labdanum resin, nutmeg, cassia oil, bel~oh1 resin, coriander and lavandin. Still other pclrulllc ch~mi~q-lc include phenyl ethyl alcohol, terpineol, linalool, linalyl acetate, geraniol, nerol, 2-(1,1-dilll~,~lylethyl)-cyclohexanol acetate, benzyl acetate, and eugenol. Carriers such as diethylphthqlqte can be used in ~e finichPd perfume compositions.

Other In~redients A wide variety of other ingredients useful in detergent compositions can be inrJIlded in the coll,posilions herein, inrlu~ing other active ingredients, carriers, hydlotlo~s, p-oces~ g aids, dyes or pigm~ tc~ solvents for liquid forrnulations, solid fillers for bar co~ osilions, etc. If high sudsing is desired, suds boosters such as the Clo-C16 alkanolqmidPs can be .. . . .

W O 97/44432 PCTrUS97/08372 incorporated into the compositions, typically at 1%-10% levels. The C1o-C14 monoethanol and ~i~thAnol amides illustrate a typical class of such suds boosters. Use of such suds boosters with high s~ cing adjunct surf~ctAnt~ such as the amine oxides, betaines and sul~in~ noted above is also advantageous. If desired, water-soluble ma~lRsi~and/or calcium salts such as MgCl2, MgSO4, CaCl2, CaSO4, can be added at levels of, typically, 0.1%-2%, to provide additional suds and to enhance grease removal pc~ro~,J.ance.

Various detersive ingredients employed in the present compositions optionally can be 10 further stabilized by absorbing said ingredients onto a porous hydrophobic su~ dLe, then coating said ~ub~ with a hydrophobic coating. Preferably, the detersive ingredient is ~lmixed with a ~ulr~ l before being absorbed into the porous substrate. In use, the detersive ingredient is released from the substrate into the aqueous w_shing liquor, where it pclÇu'll,s its inten i~(l detersive function.
To illustrate this technitl~e in more detail, a porous l.~dl()phobic silica (tr~deTnark SIPERNAT D10, DeGussa) is ~t1mil~d with a proteolytic e~yllle solution contAining 3%-5% of C13 15 ethoxylated alcohol (EO 7) nonionic surfactant. The res~ltin~ powder is di~ ed with stirring in silicone oil (various silicone oil viscosities in the range of 500-20 12,500 can be used). The res~lting siliron~ oil dispersion is em~ ifi~od or otherwise added to the final detergenl matrix. By this means, in~ l~diell~ such as the afor~...f ~ oned el~ es, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, ~luoresccls, fabric conditioners and hydrolyzable s.llr~ A~ can be "plo~ected" for use in detelgellts, inr~ ing liquid laundry detel~elll compositions.
Liquid dete,g~nt conlrosition~ can contain water and other solvents as callie~. Low molecular weight primary or secQnr1A. ~ alcohols exemplified by m~th~nnl, ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are p,efell~d for solubilizing sul~hcLallt, but polyols such as those cont~inin~ from 2 to 6 carbon atoms and from 2 to 6 30 hydroxy groups (e.g., 1,3-plc,panediol, ethylene glycol, ~lycelillc, and 1,2-propànediol) can also be used. The compositions rnay contain from 5% to 90%, typically 10% to 50%
of such calli~,Is.

The detelgelll compositions herein will preferably be forrmll~ted such that, during use in 35 aqueous cle~ning operations, the wash water will have a pH of b~ .,n 6.5 and 11, W O 97144432 PCTrUS97/08372 preferably between 7.5 and 10.5. Liquid dishwashing product formulations p~er~lably have a pH between 6.8 and 9Ø Laundry products are typically at pH 9-11. Techniques for controlling pH at reco-,-...~n~1~Pd usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
s Granules ~mlf~rtllre Adding the bis-alkoxylated cationics of this invention into a c~ chel mix, followed by conventional spray drying, helps remove any resi~u~l, potentially malodorous, short-chain 10 amine cont~min~nf~. In the event the formulator wishes to pl~ale an ~1miY~hle particle cont~ining the alkoxylated cationics for use in, for example, a high density granular dete.g.,.ll, it is plcfell~,d that the particle composition not be highly ~lk~lin~o. Processes for prepaling high density (above 650 g/l) granules are described in U.S. Patent 5,366,652.
Such particles may be fonn~ d to have an ~rr~cLive pH in-use of 9, or below, to avoid 15 the odor of illlpulily amines. This can be achieved by adding a small amount of acidity source such as boric acid, citric acid, or the like, or an apl)rol)liate pH buffer, to the particle. In an alternate mode, the pros~ e problems associated with amine malodors can be masked by use of pe~rulllc il~g~diellls, as disclosed herein.

Examples The following examples are illustrative of the present invention, but are not meant to limit or ol~ ise define its scope. All parts, pe.,_~.l~ges and ratios used herein are e~ssed as ~.~enl weight unless oth~ P S~eC;fifA
In the following e~ les, the abbreviated component idPntifir~ ons have the following ,..P_ni-~,~

LAS : Sodium linear C12 alkyl be.~ e sulfonate TAS : Sodium tallow alkyl sulfate C45AS : Sodium C14-C1s linear aLkyl sulfate CxyEzS : Sodium Clx-C1y branched alkyl sulfate con~en~ed with z moles of ethylene oxide C45E7 : A C14 15 pred~ y linear primary alcohol con~on~ed with an average of 7 moles of ethylene oxide WO 97/44432 PCT/US97tO8372 C25E3 : A C12 15 blallchcd primary alcohol condensed with an average of 3 moles of ethylene oxide C25ES : AC12 15branchedp~ lalyalcoholcon-lPn~e(lwithan average of ~ moles of ethylene oxide CocoEO2 : Rl.N+(CH3)(c2H4OH)2 with Rl = C12 -C14 Soap : Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut oils.
TFAA C16-C18 alkyl N-methyl ~ rs.. ,~ e TPKFA : C12-C14 topped whole cut fatty acids STPP : Anhydrous sodium tripolyphosphate Zeolite A : Hydrated Sodium~ minnsilieate offormula Nal2(A1~2Si~2)12- 27H20 having a particle size in the range from 0.1 to 10 micr~llllet~
NaSKS-6 : Crystalline layered silicate offormula ~-Na2Si205 Citric acid : Anhydrous citric acid Carbonate : Anhydrous sodium calbonate with a particle size ~ . 200~1m and 900~1m Bicarbonate : Anhydrous sodium bica,l,(~l~dte with a particle size distribution between 400,um and 1200~1m Silicate : Amorphous Sodi--m Silicate (SiO2:Na2O; 2.0 ratio) So~ m sulfate : Anhydrous sodium sulfate Citrate : Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution b~ 425~1m and 850 ~m MA/AA : Copolymer of 1:4 maleic/acrylic acid, a~e.. g~ ola~ulqr weight 70,000.
CMC : Sodiumcarbo~ylll~llyl cellulose P~oteasc : Proteolytic enzyme of activity 4KNPU/g sold by NOVO
Industries A/S under the trdenq nP Savinase Alcalase : Proteolytic ~.~yll.c of activity 3AU/g sold by NOVO Ill~lusLIies A/S
Cellulase : Cellulytic el~yllle of activity 1000 CEVU/g sold by NOVO Industries A/S under the traden~qm~ Carezyme CA 022~4948 1998-11-17 W 097/44432 PCT~US97/08372 Amylase Amylolytic enzyme of activity 60KNU/g sold by NOVO
Industries A/S under the tr~den~m~ Termamyl 60T
Lipase Lipolytic enzyme of activity 100kLU/g sold by Lipolase Endolase Endoglunase el~yulc of activity 3000 CEVU/g sold by NOVO
Industries A/S
PB4 : Sodium p."bol~e tetrahydrate of nominal formula NaB02 .3H2o.H2o2 PB1 : Anhydrous sodium perborate bleach of nominal formula NaB~2 H2~2 Pereall~onate : Sodium Pelc&rl,onate of nomin~l formula 2Na2C03.3H202 NOBS : Nonanoylo~yl~nzel~ sulfonate in the form of the sodium salt TAED : TetraacetylethylenP~I;~.. i~.o DTPMP: : Diethylene ~ e penta (methylene phosphonate), malkeLed by MonQ~nto under the Trade name Dequest 2060 Photoactivated : Sulfonated Zinc Phthalocyanine el-raps~ tf~d in bleach dextrin soluble polymer ;gl.~ 1 : Dico~ .m 4,4'-bis(2-slllrhostyryl)l)iph.,.lyl ~l;gl~l~ .-f 1 2 : Dico~illm 4,4'-bis(4-anilino-6-morpholino-1 3.5-triazin-2-yl)amino) stilbene-2 2'-disulfonate HEDP : 1,1-hydroxyethane diphosphonic acid PVNO : Polyvinyl~ylidi~K N-oxide PVPVI : Copolymer of polyvinylpyrrolidone and vinylimi~701e SRA 1 : Sulfobc.~oyl endcappedesters with oxyethylene oxy and t~.ephlllaloyl backbone SRA 2 : Diethoxylated poly (1, 2 propylene t,_.ephll.~ P) short block polymer Silicone antifoam: Polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as disl,el~ulg agent with a ratio of said foa n controller to said dispelsing agent of 10 1 to 100:1 In the following Examples all levels are quoted as % by weight of the composition.

,, . ~ . ,, . . . ~ .. , CA 02254948 1998-ll-17 W O 97/44432 PCT~US97/08372 EXAMPLE I

The following delelgenl formulations according to the present invention are pl~aled, where A and C are phosphorus-cont~;nin~ det. rgenl compositions and B is a zeolite-cont~inin~ dele.ge.ll composition.
A _ C
Blown Powder STPP 24.0 - 24.0 Zeolite A - 24.0 C45AS 8.0 5.0 11.0 MA/AA 2.0 4.0 2.0 LAS 6.0 8.0 11.0 TAS 1.5 CocoMeEO2* 1.5 1.0 2.0 Silicate 7.0 3.0 3.0 CMC 1.0 1.0 0.5 Bri~hl. n~l 2 0.2 0.2 0.2 Soap 1.0 1.0 1.0 DTPMP 0.4 0.4 0.2 Spray On C45E7 2.5 2.5 2.0 C25E3 2.5 2.5 2.0 Silicone a~lliÇ~ 0.3 0.3 0.3 ~lrwllc 0.3 0 3 0 3 Dry additives C~l,ol~t~ 6.0 13.0 15.0 PB4 - 4.0 10.0 PB1 4.0 ~ ~
Pe~;all~onate 18.0 18.0 21.0 Photoactivated bleach 0.02 0.02 0.02 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.25 0.30 0.15 Dry mixed sodium sulfate 3.0 3.0 5.0 .

W O 97/44432 PCT~US97/08372 R~l~nre (Moisture &
Miscell~n~o~lc) To: 100.0 100.0 100.0 Density (g/litre) 630 670 670 *The bis-AQA-1 (CocoMeEO2) surfactant of the Example may be replaced by an 5 equivalent amount of any of surfact~nt~ bis-AQA-2 through bis-AQA-22 or other bis-AQA
surf~t~n-c herein.

EXAMPLE II
The following det ~ge.lL formulations, according to the present invention are ~ ed:
D _ F
Blown Powder 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 Bri~h~nPr 1 0.2 0.2 0.2 Carbonate 8.0 16.0 20.0 DTPMP - 0.4 0.4 Spray On C45E7 1.0 1.0 1.0 Dry additives PVPVI/PVNO 0.5 0.5 0.5 ~)t~ 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.1 0.1 0.1 Cellulase 0.1 0.1 0.1 NOBS - 6.1 4.5 P~a,l,onate 7.0 5.0 6.0 Sodiu n sulfate - 6.0 R~l~nre (Moisture W 097144432 PCT~US97/08372 & Miscellaneous) To: 100 100 100 *The bis-AQA-1 (CocoMeEO2) surfactant of the Example may be replaced by an equivalent amount of any of surfact~nt~ bis-AQA-2 through bis-AQA-22 or other bis-AQA
surfactants herein.
s EXAMPLE III

The following high density d~kl~c.lt fonnulations, according to the present invention are ~lc~aled:
G H
Blown Powder ZeoliteA 15.0 15.0 15.0 Sodium sulfate 0.0 5.0 0.0 L A S 3.0 3.0 3.0 CocoMeEO2~ 1.0 1.5 1.5 DTPMP 0.4 0.4 0.4 CMC 0.4 0.4 0.4 M A/A A 4.0 2.0 2.0 Agglo,l.e.dtes L A S 5.0 5.0 5.0 T AS 2.0 2.0 1.0 Silicate 3.0 3.0 4.0 Zeolite A 8.0 8.0 8.0 Carbonate 8.0 8.0 4.0 Spray On P~.Çuu~c 0.3 0.3 0.3 C45E7 2.0 2.0 2.0 C25E3 2.0 - -Dry additives Citrate 5.0 - 2.0 Bicdl~ollate - 3.0 C~l~t~ 8.0 15.0 10.0 T A E D 6.0 2.0 5.0 Perea~l~onate 13.0 7.0 10.0 Polyethylene oxide CA 02254948 l998-ll-l7 W O 97/44432 PCTfUS97/08372 of MW 5,000,000 - - 0.2 Bentonite clay - - 10.0 Ploteasc 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Arnylase 0.6 0.6 0.6 Cellulase 0.6 0.6 0.6 Silicone antifoam 5.0 5.0 5.0 Dry additives Sodium sulfate 0.0 3.0 0.0 R~l~nre (Moisture &
Miscellaneous) To:100.0 100.0 100.0 Densi~r (g/litre) 850 850 850 *The bis-AQA-l (CocoMeEO2) sulrae~lll of the Example may be replaced by an 15 equivalent amount of any of su~t~nt.c bis-AQA-2 through bis-AQA-22 or other bis-AQA
surf~rt~ntc herein.

EXAMPLE IV

20 The following high density ~te~g~ Lforml~lqtions accordil.g to the present invention are ~r~pal~,d:

M N
Blown Powder Zeolite A 2.5 2.5 So~ m sulfate 1.0 1.0 CocoMeEO2~ 1.5 1.5 Agglolnerdle C45AS 11.0 14.0 Zeolite A 15.0 6.0 Carbonate 4.0 8.0 MA/AA 4.0 2.0 CMC o.5 o 5 DTPMP 0.4 0.4 Spray On W O 97/44432 PCTrUS97/08372 C25E5 5.0 5.0 Perfume 0.5 0 5 Dry Adds SKS 6 13.0 10.0 Citrate 3.0 1.0 TAED 5.0 7.0 Percarbonate 15.0 15.0 SRA 1 0.3 0.3 Protease 1.4 1.4 Lipase 0.4 0 4 Ce~ Ce 0.6 0.6 Arnylase 0.6 0.6 Silicone ~llifOalll5.0 5.0 15 Brigl.l~-.. r 1 0.2 0.2 Bri~.ht~n~r 2 0.2 R~l~nre (Moisture &
~ cell~n~oous) To: 100 100 Density (g/litre) 850 850 20 *The bis-AQA-1 (CocoMeEO2) sùrfactant of the Example rnay be replaced by an equivalent amount of any of surfPct~ntc bis-AQA-2 through bis-AQA-22 or other bis-AQA
surf~ nt~ herein.

Any of the granular d- tc.ge.lt compositions provided herein may be tabletted using known 25 t~blettin~ m~tht~c to provide dete~ tablets.

The l"-.,..r;.,~l,..,, of heavy duty liquid d.,t~_.gelll compositions, especially those designed for fabric laundering, which COlll~)i;Se a non-aqueous carrier ..~Pd;~ can be co~ e~l in the lllamlel disclosed in more detail h~ ,r~i. In an alternate mode, such non-aqueous 30 compositions can be plee~aled according to the disclosures of U.S. Patents 4,753,570;
4,767,558; 4,772,413; 4,889,652; 4,892,673; GB-A-2,158,838; GB-A-2,195,125; GB-A-2,195,649; U.S. 4,988,462; U.S. 5,266,233; EP-A-225,654 (6116/87); EP-A-510,762 (10128/92); EP-A-540,089 (5/5/93); EP-A-540,090 (5/5/93); U.S. 4,615,820; EP-A-565,017 (10/13/93); EP-A-030,096 (6/10/81), h~col~ulated herein by ~eÇ~lence. Such 35 coll~osilions can contain various particulate detersive ingredients (e.g., bl~hi~g agents, , W O 97/44432 PCT~US97/08372 as disclosed hereinabove) stably suspended therein. Such non-aqueous compositions thus comprise a LIQUID PHASE and, optionally but preferably, a SOLID PHASE, all as described in more detail hereinafter and in the cited lefe.ellces. The AQA surfactants are incorporated in the compositions at the levels and in the manner described hereinabove for S the m~lufa~;lur~ of other laundry detergf .ll compositions.

LIQUID PHASE

The liquid phase will generally coll",lise from 35% to 99% by weight of the det~rgen~
10 compositions herein. More preferably, the liquid phase will co"ll)lise from 50% to 95%
by weight of the compositions. Most preferably, the liquid phase will co"ll,lise from 45%
to 75% by weight of the compositions herein. The liquid phase of the detel~e.ll composition~ herein esse~ lly contains relatively high conce"llalions of a certain type anionic surfactant colllbillf d with a certain type of non~q~lPo--s, liquid diluent.
(A) Essential Anionic Surfactant The anionic surfactant is an PssPnti~l coll,~oll~nl of the nonaqueous liquid phase and is selected from the alkali metal salts of alkylb.,.~_ne sulfonic acids in which the alkyl group 20 contains from 10 to 16 carbon atoms, in straight chain or branched chain configuration.
(See U.S. Patents 2,220,099 and 2,477,383, incorporated herein by r~fe.en~e.) Especially plcfe~led are the sodium and pot~c.~illm linear straight chain alkyl~.~e.lc sulfonates (LAS) in which the average llulllbe~ of carbon atoms in the alkyl group is from 11 to 14. Sodium Cll-C14 LAS is especi~lly l".,fe.~d.
The alkylhf n7~ sulfonate anionic surfactant will be dissolved in the nonaqueous liquid diluent which makes up the second ess~ col,ll,o~ of the nonaqueous phase. To form the structured liquid phase required for suitable phase stability and acce~lable rheology, the aL~cylb~ f sulfonate anionic surfactant is generally present to the extent of from 30% to 30 65 % by weight of the liquid phase. More preferably, the alkylbe~Le.~ sulfonate anionic surfactant will co",~lise from 35% to 50% by weight of the nonaqueous liquid phase of the compositions herein. Utilization of this anionic surfactant in these concentrations corresponds to an anionic ~ulracta"t conc~ lation in the total co,llposilion of from 15% to 60% by weight, more preferably from 20% to 40% by weight, of the composition.

..... . .. . _.. =. .... , , . . ~ .. ...

(B) Nonaqueous Liquid Diluent To form the liquid phase of the dctelgcll~ compositions, the heleil-before described alkylbenzene sulfonate anionic surfactant is combined with a nonaqueous liquid diluent 5 which contains two esse~.l;ql components. These two components are a liquid alcohol alkoxylate material and a nonaqueous, low-polarity organic solvent.
Alcohol AlkoxYlates One esse-~1;A1 cOIul)u~ of the liquid diluent used to form the co,llposilions herein 0 colll~lise,s an alkoxylated fatty alcohol material. Such materials are lll.,nlselves also nonionic surfa~tqntc. Such materials correspond to the general formula:
Rl(CmH2mO)nOH
wh~reu~ Rl is a C8 - C16 alkyl group, m is from 2 to 4, and n ranges from 2 to 12.
Preferably Rl is an allcyl group, which may be l,lilual,~ or secondaly, that contains from 9 to 15 carbon atoms, more preferably from 10 to 14 carbon atoms. Preferably also the aLkoxylated fatty alcohols will be ethoxylated materials that contain from 2 to 12 ethylene oxide moieties per molecule, more plef._,~bly from 3 to 10 ethylene oxide Illoi_ties per molecule.

20 The allcoxylated fatty alcohol component of the liquid diluent will rl. .lu~ tly have a h~drophilic-lipophilic balance (HLB) which ranges from 3 to 17. More ~l~,fe.ably, the HLB of this material will range from 6 to 15, most preferably from 8 to 15.

Examples of fatty alcohol aLkoxylates useful as one of the es~ colupullcn~ of the 25 nnn~ qlleo~l~ liquid diluent in the composition~ herein will include those which are made from alcohols of 12 to 15 carbon atoms and which contain 7 moles of ethylene oxide. Such materials have been co....~ ially ...~ fte~ under the trade names Neodol 25-7 and Neodol 23-6.5 by Shell ~h~mir,q,l COul~ . Other usefill Neodols include Neodol 1-5, an ethoxylated fatty alcohol avcl~.gin~ 1} carbon atoms in its alkyl chain with 5 moles of 30 ethylene oxide; Neodol 23-9, an ethoxylated primary C12 - C13 alcohol having 9 moles of ethylene oxide and Neodol 91-10, an ethoxylated Cg - Cll E,lh~ alcohol having 10moles of ethylene oxide. Alcohol ethoxylates of this type have also been .~ rled by Shell Ch~nirq-l Company under the Dobanol tr~onqm~. Dobanol 91-5 is an ethoxylated Cg-C
fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated W 097144432 PCTrUS97/08372 C12-C1s fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.

Other examples of suitable ethoxylated alcohols include Tergitol 15-S-7 and Tergitol 15-S-9 5 both of which are linear secondary alcohol ethoxylates that have been commercially eted by Union Carbide Corporation. The former is a mixed ethoxylation product ofCll to C1s linear secondary alkanol with 7 moles of ethylene oxide and the latter is a similar product but with 9 moles of ethylene oxide being reacted.

10 Other types of alcohol ethoxylates useful in the present composition~ are higher molecular weight noniol~cs, such as Neodol 45-11, which are similar ethylene oxide conden~ ~ion products of higher fatty alcohols, with the higher fatty alcohol being of 14-15 carbon atoms and the l..l.u~l of ethylene oxide groups per mole being 11. Such products have also been commercially .nslh~,ted by Shell C~hFmi~l Co~
The alcohol alkoxylate culll~n~nt which is esCF .l;qlly utilized as part of the liquid diluent in the nonaqueous compositionc herein will generally be present to the extent of from 1%
to 60% of the liquid phase colllyosilion. More preferably, the alcohol alkoxylate component will cG"lylise 5% to 40% of the liquid phase. Most preferably, the ess~ lly utilized alcohol alkoxylate colllyoll~nl will colny,ise from 5% to 30% of the dete~ ,nl composition liquid phase. Utilization of alcohol alkoxylate in these concF.lll~lions in the liquid phase collF jpollds to an alcohol aLkoxylate concellL.~Iion in the total collll)o~ilion of from 1% to 60% by weight, more preferably from 2% to 40% by weight, and most preferably from 5 % to 25 % by weight, of the composition.
ii) No~ql)eous Low-Polarity Organic Solvent A second ec.cF ~~1 ;ql colly)~ t of the liquid diluent which forms part of the liquid phase of the d~t,.genl colnposi~iorc herein collll,lises nonaqueous, low-polarity organic solvent(s).
The term "solvent~ is used herein to col~nole the non-surface active carrier or diluent 30 portion of the liquid phase of the conlyosilion. While some of the essF~ ;ql and/or optional colllpollt;lll~ of the compositions herein may actually dissolve in the "solvent"~o~ g liquid phase, other components will be present as particulate material dis~ ed within the "solvent"-cont~ining liquid phase. Thus the term "solvent" is not meant to require that the solvent material be capable of actually dissolving all of the detelg~ colll~osilion 35 co,llponF;llls added thereto.

W O 97/44432 PCTrUS97/08372 The nonaqueous organic materials which are employed as solvents herein are those which are liquids of low polarity. For purposes of this invention, "low-polarity" liquids are those which have little, if any, ten-~n~y to dissolve sodium pel~,all,onate. Thus relatively polar S solvents such as ethanol should not be utilized. Suitable types of low-polarity solvents useful in the nonaqueous liquid de~r~nl compositions herein do include non-vicinal C4-Cg alkylene glycols, alkylene glycol mono lower alkyl ethers, lower molecular weight polyethylene glycols, lower molecular weight methyl esters and amides.

10 A p,~fe.r~ type of nonaqueous, low-polarity solvent for use in the compositions herein coul~lises the non-vicinal C4-Cg branched or straight chain alkylene glycols. Materials of this type include hexylene glycol (4-methyl-2,4~ n~ ol)~ 1,6-h~nediol, 1,3-butylene glycol and 1,4-butylene glycol. Hexylene glycol is the most ~ Ç~ d.

15 Another plcfcll.,d type of nonaqueous, low-polarity solvent for use herein co",~lises the mono-, di-, tri-, or tetra- C2-C3 alkylene glycol mono C2-C6 alkyl ethers. The specific examples of such colll~ ullds include diethylene glycol Illul ~ll~yl ether, ~ hylene glycol monobutyl ether, dipro~lene glycol monoethyl ether, and di~,o~ylene glycol Illollo~.llyl ether. Diethylene glycol monobutyl ether and dipropylene glycol monobutyl 20 ether are especi~lly p,~ere.l~,d. Compounds of the type have been co~ lelcially ."~rl~led under the tra~ n ~ s Dowanol, Carbitol, and Cellosolve.

Another ~lcrell~ type of n-~n~qneous~ low-polarity organic solvent useful herein comprises the lower molecular weight polyethylene glycols (PEGs). Such materials are those having molecular ~.. ,igl~ls of at least 150. PEGs of mol~c~ r weight ,a"~i~ from 200 to 600 are most pl~re.l~,d.

Yet another ~ler~"~d type of non-polar, nonaqueous solvent co,~,ises lower molecular weight methyl esters. Such materials are those of the general formula: R1-C(O)-OCH3 30 W~ ll Rl ranges from 1 to 18. Examples of suitable lower molecular weigllt methyl esters include methyl acetate, methyl propionate, methyl oct~n~- ~, and methyl ~lodec~n-.ate.

The nonaqueous, low-polarity organic solvent(s) employed should, of course, be 35 cGIllpdtillle and non-reactive with other composition components, e.g., bleach and/or W O 97/44432 PCT~US97/08372 activators, used in the liquid delergellt compositions herein. Such a solvent co~ onent will generally be utilized in an amount of from 1% to 70% by weight of the liquid phase. More preferably, the nonaqueous, low-polarity organic solvent will comprise from 10% to 60 by weight of the liquid phase, most preferably from 20% to 50% by weight, of the liquid 5 phase of the composition. Utilization of this organic solvent in these concellll ~tions in the liquid phase corresponds to a solvent concenllation in the total composition of from 1% to 50% by weight, more preferably from 5% to 40% by weight, and most preferably from 10% to 30% by weight, of the composition.
iii) Alcohol Alkoxylate To Solvent Ratio The ratio of alcohol alkoxylate to organic solvent within the liquid diluent can be used to vary the rheological ~ropellies of the dete~gellt colllposilions eventually formed.
Generally, the weight ratio of alcohol alkoxylate to organic solvent will range from 50:1 to 1:50. More preferably, this ratio will range from 3:1 to 1:3.
iv) Liquid Diluent Conce,llldlion As with the concelll.alion of the alkyl~ nf sulfonate anionic surfactant ~lliAlule, the amount of total liquid diluent in the nonaqueous liquid phase herein will be ~lete, ..~ d by the type and amounts of other composition com~one.lt~ and by the desired composition 20 ~lo~llies. Generally, the liquid diluent will comprise from 35% to 70% of thenonaqueous liquid phase of the culllposi~ions herein. More plefel~bly, the liquid diluent will conlplise from 50% to 65 % of the non~queous liquid phase. This coll~ oilds to a non~ q~leous liquid diluent collcel~Llalion in the total co~u~osilion of from 15% to 70% by weight, more preferably from 20% to 50% by weight, of the cv~ )osil;on.
SOLID PHASE

The nnn~queous de~l~e.lt co.~.i o~;l;o~s herein also cssel~ lly complise from 1% to 65%
by weight, more preferably from 5 % to 50% by weight, of a solid phase of particulate 30 material which is di~persed and ~ .u~d within the liquid phase. Generally such particulate material will range in size from 0.1 to 1500 microns. More plere.ably such material will range in size from 5 to 200 ll~icruns.

The particulate material utilized herein can comprise one or more types of delcl enl 35 colllposilion co.llpo~en~ which in particulate form are substantially insoluble in the W 097/44432 PCT~US97/08372 68 nonaqueous liquid phase of the composition. The types of particulate materials which can be utilized are described in detail as follows:

COMPOSITION PREPARATION AND USE

The nonaqueous liquid delerge..l compositions herein can be pre~a~,d by combining the eSsenti~l and optional components thereof in any convenient order and by mixing, e.g., ~git~ting, the resnlting component combinalioll to form the phase stable con.posilions herein. In a typical process for pr~illg such compositions, essenti~l and certain 10 pler~ d optional components will be combined in a particular order and under certain conditions.

In the first step of such a typical p~epalàlion process, an adl~lul~ of the alkylbcnze.l~
sulfonate anionic surfactant and the two esc~nti~l con~o~ ~ of the nonaqueous diluent is formed by heating a c~.lllbhlalion of these materials to a t~ alule from 30~C to 100~C.

In a second plocess step, the heated adllli~lu~e formed as he,elllbefolc; desclil~d is m~int~in~i under shear a~ilalion at a ~,ll~-alul~ from 40~C to 100~C for a period of from 2 ...;.-- t..s to 20 hours. Optionally, a vacuum can be applied to the ~ ..e at this point.
20 This second plocess step serves to coll-pletely dissolve the anionic surfactant in the nonaqueous liquid phase.

In a third process step, this liquid phase co.,l~il.ation of materials is cooled to a tem~ alule of from 0~C to 35~C. This cooling step serves to form a ~ ul~d, ~ulra~ cont~inin~
25 liquid base into which the particulate material of the dete,g.,,l~ co..~,o~il ;on~ herein can be added and di~

Particulate material is added in a fourth p~ocess step by con.~h~ing the particulate material with the liquid base which is ...~ d under conditions of shear ~git~tion When more 30 than one type of particulate material is to be added, it is pl~r,_,l.,d that a certain order of addition be obsc;~ ~ed. For example, while shear agitation is m~int~inlocl, es.senti~lly all of any optional ~u- r~ in solid particulate form can be added in the form of particles langillg in size from 0.2 to 1,000 microns. After addition of any optional surfactant particles, particles of ~ubsl;~ ly all of an organic builder, e.g., citrate andlor fatty acid, 35 and/or an ~lk~linity source, e.g., sodium carbonate, can be added while CG.~ g to ., . ,, . , . _ _ , , _ .

mAinrAin this A-h..;xl~.e of composition components under shear agitation. Other solid form optional ingredients can then be added to the composition at this point. Agitation of the mixture is contin~ed, and if nPcess-Ary, can be increased at this point to form a uniro disl,eisioll of insoluble solid phase partic~ulAtps within the liquid phase.

After some or all of the foregoing solid materials have been added to this ~git~t~d the par~cles of the highly ~ler~,.~d peroxygen bleaching agent can be added to the composltlon, again while the mixture is mAint~inPd under shear agitation. By adding the peroxygen blPr~ching agent material last, or after all or most of the other colll~o~ s, and 10 especially after alk~linity source particles, have been added, desirable stability benefits for the peroxygen bleach can be realized. If elL~ c prills are hlcol~.~ldted, they are yl~Ç.,~bly added to the nonaqueous liquid matrix last.

As a final process step, after addition of all of the particulate material, agitation of the 15 mixture is continued for a period of time ~rr~rie~l to form cG.ll~osilions having the requisite viscosity and phase stability ch&la~t.,li~lics. Frequently this will involve agitation for a period of from 1 to 30 ~ s.

As a variation of the co~ )osilioll prepa-alion pr~cedule he-eillbefore described, one or 20 more of the solid co".po~ may be added to the AgitrAt~Pd mixture as a slurry of particles prernixed with a minor portion of one or more of the liquid con.~on~ . Thus a premix of a small fraction of the alcohol aL~oxylate and/or nonaqueous, low-polarity solvent with particles of the organic builder material and/or the particles of the in~)lganic ~IIrA1;n;tY
source and/or ~allicles of a bleach activator may be st~ala~ly formed and added as a 25 slurry to the Agjt~tP~ Il~i~lule of composition co,.,pollen~. Addition of such slurry premixes should p.~,cede addition of peroxygen bler~ching agent and/or e.~"e- particles which may th~mcelves be part of a premix slurry formed in analogous f~chion The compositions of this invention, pl.,paled as hel~lb~ e described, can be used to 30 form aqueom washing solutions for use in the laundering and bl~r-hing of fabrics.
Generally, an effective alllOUIII of such compositions is added to water, preferably in a conventional fabric laundering automatic washing mA~hin~, to form such aqueous laundering/ble~rhing solutions. The aqueous washing/bl~hi.~g solution so formed is then con~cted, preferably under agitation, with the fabrics to be laundered and bleached 35 t~

,.. .

An effective amount of the liquid detelge..t compositions herein added to water to form aqueous laundering/bl~rhin~ solutions can comprise amounts sufficient to form from 500 to 7,000 ppm of composition in aqueous solution. More preferably, from 800 to 3,000 5 ppm of the del~rgellL compositions herein will be provided in aqueous washing/blear}ling solution.

EXAMPLE V

10 A non-limiting example of a bleach-cont~inin~ nonaqueous liquid laundry dcter~ is y~ d having the composition as set forth in Table I.
Table I
Component Wt. % Ran~e (% wt.) Liquid Phase Na C12 Linear aL~cyl~ sulfonate (LAS) 25.3 18-35 C12 14, EO5 alcohol ethoxylate 13.6 10-20 Hexylene glycol 27.3 20-30 F~lrullle 0.4 0-1.0 bis-AQA-1 * 2.0 1-3.0 Solids r~aS~ IC 0.4 0-1.0 Na3 Citrate, al~lyd~s 4.3 3-6 Sodium ~albol ate 3.4 2-7 Sodium no~ oylo~l~-~,f l~ sulfonate (NOBS) 8.0 2-12 Sodium carbonate 13.9 5-20 Diethyl ll~llC p~ ' acid (DTPA) 0.9 0-1.5 t~ ............................... 0.4 0-0.6 Suds Supylessor 0.1 0-0.3 Minors Ral~nre ----*CocoMeEO2. bis-AQA-1 may be replaced by bis-AQA surf~t~n~ 2-22 or other bis-AQA surf~rt~n~ herein.

The composition is l,iepalcd by mixing the bis-AQA and LAS, then the hexylene glycol and alcohol ethoxylate, together at 54~C (130~F) for 1/2 hour. This mi~luie is then cooled W O 97/44432 PCTrUS97108372 to 29~C (85~F) whereupon the rem~inin~ col"pone,lt~ are added. The resultin~
composition is then stirred at 29~C (85~P) for another 1/2 hour.

The res-lltin~ col~posilion is a stable anhydrous heavy du~ liquid laundry del~g~ which 5 provides excellent stain and soil removal p~,l Ç . ~ n~e when used in normal fabric laundering operations.

EXAMPLE VI

10 The following hand wash det.,~ l form~ tions, accor~ing to the present invention, are p~ ,d by mixing the h,gr~,dienl~ together in the perce.,~ge weight ;..I~.ln~ as in~ie~t~d below.

A B C D
LAS 15.0 12.0 15.0 12.0 TFAA 1.0 2.0 1.0 2.0 C25E5 4.0 2.0 4.0 2.0 AQA-9* 2.0 3.0 3.0 2.0 ST 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 DTPMP 1.0 1.6 1.6 1.6 Carbonate 2.0 2.0 5.0 5.0 Bicarbonate - - 2.0 2.0 Silicate 7.0 7.0 7.0 7.0 ~ o ~a~ 1.0 - 1.0 1.0 Amylase 0.4 0.4 0.4 Lipase 0.12 0.12 - 0.12 Photoactivated bleach 0.3 0.3 0.3 0.3 Sulfate 2.2 2.2 2.2 2.2 E~rcalbonate 4.0 5.4 4.0 2.3 NOBS 2.6 3.1 2.5 1.7 SRA 1 0.3 0.3 0.7 0.3 Bri~ht.on~r 1 0.15 0.15 0.15 0.15 W 097/44432 PCT~US97/08372 Rql~nre misc./water 100.0 100.0 100.0 100.0 to 100 AQA-9*; May be replaced by any AQA surfactant desc.ibed herein. ~efell~,d AQA
surfart~ntc for use in this example are those with from 10 to 15 ethoxy groups; for example AQA-10, AQA-16.

The folegoillg FY~m~ I S illustrate the present invention as it relates to fabric laulldF~ g compositionc~ wll~,as the following Examples are intended to illustrate other types of cle~nin~ compositions accor~ g to this invention, but are not int~ n-1~d to be li...i~
thereof.
Modern, high ~Ço~ ce hand dishwashing compositions can contain illgl~,.lie~ which are (lesignP~ to provide s~ ;fir in-use product aulib,l~s such as grease cutting ability, high su(lsin~ mil-lnPsc and skin feel ~rl~. Such ~ngledie~ for use with the bis-AQA
surf~rt~nts herein include, for example, amine oxide surfactants, betaine and/or s~llti~in 15 ~ulr~ t~, alkyl sulfate and alkyl ethoxy sulfate surfactants, liquid c~~ " especi~lly water and water/propylene glycol n~lul~s, natural oils such lemon oil. In a~ ition~
plef~,lled liquid and/or gel hand dish~vasl,ing coll~po~ilions may also contain calcium ions, m~ Fsi.. ions, or l~lùres of r~lcil~m/m~.. F,i.~.. ions, which afford additional grease cutting pe,rollllance advantages especi~lly when used in colllbil~lion with det~20 ln~lul. s collll,lisi~g the bis-AQA ~,llr~c~nt herein in colll~ ion with, for example, amine oxide, alkyl sl~lf~t~s and alkyl ethoxy sulfates. M~n~si~lm or calri~-m or mixed MglCa ion sources typically cOl~l;5e from 0.01% to 4%, preferably from 0.02% to 2%, by weight, of such co..~i)osilio..c. Various water-soluble sources of these ions include, for example, sulfate, chloride and acetate salts. Moreover, these colll~o~ilions may also contain 25 ~Ol~io~ic s~fi~ ...t~i, especiqlly those of the polyhydroxy fatty acid amide and alkyl polygh)c~ci~1e classes. ~ef. d are the C12-C14 (cocollul alkyl) ~F ~ of these classes. An esrec~ y pl~f~ ,d nonionic ~ulrac~n~ for use in hand disll~aslling liquids is C12-C14 N-methylgl.lc~...i~e. E~re.l~,d amine oxides include C12-C14 dimethylamine oxide. The aL~cyl sulfates and aLkyl ethoxy sulfates are as desclibed he,e.llabove. Usage 30 levels for such surf;~ct~ntc in disll-. ashing liquids is typically in the range from 3 % to 50%
of the fini.ch-od com~osilion. The formulation of dishwashing liquid compositions has been W 097/44432 PCT~US97/08372 described in more detail in various patent publications in~ 1ing U.S. 5,378,409, U.S.
5,376,310 and U.S. 5,417,893, incorporated herein by reference.

Modern automatic dishwashing det,lgellL~c can contain bleaclling agents such as S hypochlorite sources; ~.I,ol~te, percarbonate or persulfate bleaches; enzymes such as proteases, lipases and amylases, or mixtures thereof; rinse-aids, ecpeciqlly nonionic surf~rtqntc; builders, inrlntli~ zeolite and phosph~te builders; low-sudsing detersive surfact~ntc, especially ethylene oxide/propylene oxide co.~e.~c~t~s. Such co~ )osilions are typically in the form of granules or gels. If used in gel form, various gelling agents known 10 in the literature can be employed.

The following Examples A and B further illustrate the invention herein with respect to a granular phosphate-col-t~ auLolll~tic dishw~shillg det~l~enl.
EXAMPLE VII
% by weight of active material INGREDIENTS A
STPP (anhydlous)l 31 26 Sodium Carbonate 22 32 Silicate (% SiO2) Surfactant (nonionic) 3 1.5 NaDCC Bleach2 2 --bis-AQA-l * 0.5 1.0 Sodium r,rcalbollate 3.2 5 TAED -- 1.5 Savinase (Au/g) -- 0.04 Te.ma~ rl (Amu/g) 425 Sulfate 25 25 ~,rullle/Minors to 100~ to 100%
lSodium tripolyphosphate 2Sodium dichlol~;ydllulate *The bis-AQA-l surfactant can be replaced by bis-AQA-2 through bis-AQA-22.

Various gelling agents such as CMC, clays, can be used in the composition~ to provide 35 varying degrees of viscosity or rigidity, according to the desires of the fo~ lqtor CA 022s4948 1998-11-17 W 097/44432 PCT~US97/08372 EXAMPLE VIII
The following illustrates ~ ules of bis-AQA surf~cP-nt~ which can be substituted for the bis-AQA surf~ctqntc Iisted in any of the foregoing Examples. As disclosed hereinabove, S such ~lIhl~lul~,s can be used to provide a S~ lUn1 of p~Irollnallce be.~rl~ and/or to provide cle~ning compositions which are useful over a wide variety of usage conditions.
Prefera~y, the bis-AQA swr~ in such Il~lul~,s differ by at least 1.5, preferably 2.5-20, total EO units. Ratio ranges (wt.) for such mixtures are typically 10:1-1:10. Non-limitin~ eYqnlrles of such ll~L~LulCS are as follows.
Co,nl oncIlt~ Ratio (wt.) bis-AQA-1 + bis-AQA-5 1:1 bis-AQA-l + bis-AQA-10 1:1 bis-AQA-l + bis-AQA-15 1:2 bis-AQA-1 + bis-AQA-5 + bis-AQA-20 1:1:1 bis-AQA-2 + bis-AQA-S 3:1 bis-AQA-S + bis-AQA-15 1.5:1 bis-AQA-l + bis-AQA-20 1:3 20 Mixtures of the bis-AQA s~llr~ herein with the corresponding c~tion:, ~uIr~C~which contain only a single ethoxylated chain can also be used. Thus, for ~
Illi~lUQs of ethoxylated cationic surfq-rtqntc of the fonnula RlN+CH3[EO]x[EO]yX~ and RlN+(CH3)2[EO]zX-~ wh~,.c~ Rl and X are as disclosed above and wh~.c,lI one of the cationics has (x+y) or z in the range 1-5 preferably 1-2 and the other has (x+y) or z in the range 3-100, ~I.,Ç~,lably 10-20, most preferably 14-16, can be used herein. Suchco~ )o~iliol~s adv~nta~oucly provide improved detergcIlcy pelroI...~ e (especiqlly in a fabric la~deli,lg context) over a bI~adel range of water haldness than do the cationic surf ~tqntc herein used individually. It has now been discovered that shorter EO cationics (e.g., EO2) improve the cle~.;~ pclruIl~l~ce of anionic surfq-ct~ntc in soft water, whereas 30 higher EO cqtionirs (e.g., EO15) act to il~I~love hardl~ss tolclOIlce of anionic surf.~tqntc, llrC~ improving the rleqni~ ~.ro..~ e of anionic ~uIr~ nl~ in hard water.
Conventional wisdom in the d~ ;y art suggests that builders can OYI~ Le the ~clÇù"I~nce "window" of anionic surf~rt~ntc. Until now, however, bro~leni~ the window to encu~ )ass esce ~ 1ly all coI~dilions of water harlI~ss has been impossible to 35 achieve.

. .

W O 97/44432 PCTrUS97/08372 The laundry detergellt compositions prepared using one or more folegoing cull.bil~alions of ingredients can optionally be built with any non-phosphate or phosph~te builders, or nli~lul~;s thereof, typically at levels of from 5% to 70%, by weight of finich~-l 5 c~ osilioll.

EXAMPLE IX

The following illu~llalts ll~L~Iul~,S of con~elllionâl non-AQA surf~ct~nt~ which can be used 10 in combination with the bis-AQA surfact~ntc in any of the f~.egoillg Examples, but is not intton~tl to be 1;Q~ thereof. The ratios of non-AQA surf~~t~nt~ in the ~lu-~,s are noted in parts by weight of the surfactant l~ lul~s.

Mixtures A-C
In~l~di~ Ratios AS*/LAS 1: l AS/LAS 10:1 (pref. 4:1) AS/LAS 1:10 (pref. 1:4) *In the fo.~,going, the primary, s~lb~ ;ally linear AS ~u,ra.;~t can be r~ pl~ceA by an 20 equivalent amount of seco--daly AS or blallched-chain AS, oleyl sulfate, and/or lllL~LlUl.,S
thereof, in~ in~ lul~,s with linear, plillla~y AS as shown above. The "tallow" chain length AS is particularly useful under hot water con-litions, up to the boil. "Coconut" AS
is p.~fe.l~d for cooler wash Lelll~.alu~s.

25 The ll~lul~s of alkyl sulfate/anionic sulr~ l;.,~t~ noted above are ~--~ir~A by incol~Gld~ g a no.l.ol~ic non-AQA sulr~;~l therein at a weight ratio of anionic (total) to ~ n;oni~r~ in the range of 25:1 to 1:5. The llvlliol~c ~u~r~ can collll)lise any of the col.-~,.lliollal classes of ethoxylated alcohols or alkyl phenols, alkylpolyglycosides or polyllyd~oxy fatty acid amides (less preferred if LAS is present), or ll~L~lul~s thereof, such as those di~closed 30 hereinabove.
Mixtures D-F
AS*/AES 1: 1 AS/AES 10:1 (pref. 4:1) AS/AES 1:10 (pref. 1:4) 35 *Can be replaced by secondaly, bl~.chcd or oleyl AS as noted above.

,, ~ .

The mixtures of AS/AES noted above can be modified by incol~oldlh,g LAS therein at a weight ratio of AS/AES (total) to LAS in the range from 1:10 to 10:1 5 The ~ es of AS/AES or their res-lltin~ AS/AES/LAS lllLX.IUl~;S can also be colllbil~ed with nonionic surf~t~ntc as noted for Mixtures A-C at weight ratios of anionic (total) to nonionic in the range of 25:1 to 1:5 Any of the fole~,oillg mixtures can be m ~ifi~d by the illc~l~oldlion therein of an amine 10 oxide surfactant, whcle~ the amine oxide COlll~liSFS from 1% to 50% of the total Sulra~ l~lu~

Highly plefi .led co,llbinalionc of the folegoillg non-AQA ~ull~ will coll.l,li;.e from 3% to 60%, by weight, of the total finichPd laundry del~lge.ll cclllyo~ on The finichPd compositions will preferably conlplise from 0.25% to 3 5%, by weight, of t_e bis-AQA
surfactant Example X
This Example illustrates ~lrurl~ formulations (A-C) made in aceol~lce with the 20 invention for il~ol~olalion into any of the foregoing FY~ es of bis-AQA-cont~inin~
d~ te.genL co nposil ions. The various ili~lediell~ and levels are set forth below.
(% Weight) F~,rulllc In~slcdielll A B C
Hexyl ci~ ir aldehyde 10.0 - 5.0 2-methyl-3-(para-tert-~ rl~he~l)-propio~ql-lFk~e 5.0 S.0 7-acetyl-1 ,2,3,4,5,6,7,8-octahydro-1, 1,6,7-t~ ~lJ~ l naphth~ 5 0 10.0 10.0 Benzyl salicylate 5.0 7-acetyl-1,1,3,4,4,6-h.~ . !hylt~ tlalin 10.0 5.0 10.0 Para-(tert-butyl) cyclohexyl acetate 5.0 5.0 Methyl dihydro j~ n~lP 5.0 Beta-napthol methyl ether - 0.5 Methyl beta-naphthyl ketone - 0.5 2-methyl-2-(para-iso-1,lo~"~lph~.lyl)-propionaldehyde - 2 0 1,3,4,6,7,8-hexahydro4,6,6,7,8,8-h~

W O 97/44432 PCT~US97108372 cyclopenta-ganma-2-b~ yrane - 9.5 Dodecahydro-3a,6,6,9a-tetramethylnaphtho-[2, lb]furan 0.1 ~ni~l(iehyde ~ ~ 0 5 Coumarin - 5.0 Cedrol - - 0.5 Vanillin - - 5.0 Cyclopent~c~nolide 3.0 - 10.0 Tricyclodecenyl acetate - - 2.0 ~ ..... resin - - 2.0 Tricyclodecenyl propionate - - 2.0 Phenyl ethyl alcohol 20.0 10.0 27.9 Te.~,h~eol l0.0 5.0 Linalool 10.0 10.0 5.0 Linalyl acetate 5.0 - 5.0 Geraniol S.o Nerol 5.0 2-(1,1-di llc~llylethyl)-cyclohexanol acetate 5.0 Orange oil, cold pressed - 5.0 Benzyl acetate 2.0 2.0 Orange t~.,llcs - 10.0 F.llgennl - 1.0 Di~,ll~ll.l.lh~l~ _ 9.5 Lemon oil, cold pressed - - l0.0 Total 100.0 100.0 100.0 The fo~,going pwfill-.e conlrosition.C are ?~miY~d or sp~ ed-onto (typically at levels up to about 2% by weight of the total detelgelll collll o~iLion) any of the bis-AQA
surfactant-cont~ining cle~ni~ (inrlu~ling ble,7chin~) compositions disclosed herein.
I~llploved deposition and/or retention of the pelrulllc or individual components thereof on 30 the surface being cleaned (or bl~?~ d) is thus secured.

Claims (16)

WHAT IS CLAIMED IS:

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

wherein R1 is a linear, branched, 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, and A and A' can vary independently and are each C1-C4 alkoxy, p and q can very independently and are integers in the range of from 1 to 30.

2. A composition according to Claim 1 which is prepared by mixing the non-AQA
surfactant and the bis-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 any of Claims 1 to 3 wherein the ratio of bis-AQA to non-AQA surfactant is from 1:15 to 1:8.

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

6. A composition according to any of Claims 1 to 5 wherein said bis-AQA surfactant has the formula such that R1 is C8-C18 alkyl, R2 is methyl A and A' are ethoxy or propoxy groups and p and q are each integers of 1 to 4.

7. A composition according to any of Claims 1 to 6 wherein the formula of the bis-AQA
cationic surfactant is such that p and/or q are integers in the range of from 10 to 15.

8. A composition according to any of Claims 1 to 7 comprising two or more bis-alkoxylated AQA surfactants, or a mixture of a bis-AQA surfactant and a mono-ethoxylated cationic surfactant.

9. A composition according to any of Claims 1 to 8 comprising two or more non-AQA
surfactants and a mixture of two or more bis-AQA surfactants.

10. A composition according to any of Claims 1 to 9 in a granular, bar, aqueous liquid or non-aqueous liquid, or tablet form.

11. 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 10.

12. A method according to Claim 11 for removing bleach sensitive soil from fabrics.

13. A method according to any of Claims 11 or 12 which is conducted in an automatic machine.

14. A method according to any of Claims 11 to 13 which is conducted by hand.

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

16. A method according to Claim 15 which is conducted using a perfume or perfumeingredient in combination with a detergent composition comprising a bis-AQA.