CA2148096A1 - Detergent compositions containing polyhydroxy fatty acid amide, sulfated polyhydroxy fatty acid amide and soap - Google Patents

Abstract

Mixed nonionic/anionic surfactants which comprise polyhydroxy fatty acid amides and their sulfated analogs are used with soaps in various cleaning functions. Thus, C10-C22 fatty acid N-alkyl glucamides are partly sulfated to form mixtures of the nonionic glucamide and the anionic glucamide sulfate. The resulting mixtures are admixed with soaps to provide extremely low interfacial tensions and good cleaning of fabrics, dishware, skin and hair.
Excellent removal of cosmetic stains from fabrics is also provided.

Description

:~o ~4~u~lo 21 ~ 8 0 9 6 PcTrusg3lll4ss Detergent compos~t10ns contaln~ng polyhydroxy f~ty ac1d am~de, sulfated polyhydroxy fatty acld am1de and soap.

The present ~nv~nt~on relates to fully-formulated detergent compositions contatning a nonionic surfactant, an anionic surfactant and soaps,.all 3f wh~ch are prepared from mainly renewable resources such as n~tural fats and oils, f~tty esters ~nd reducing sugars. The compos~t~ons yield extre~ely low interfacial ~ensions in aqueous ~edia9 especially in the presence of calcium ~ons, and are th~s useful for cleaning operations.

15Most conventional detergent composttions contain mix~ures of.
various detersive surfactants in order to r*mov~ a wide variety of soils and stains from surfaces. For exa~ple, various anionic surfactants, espec~al~y the alkyl ~enzene sulfonates, ~re useful for removing part~ula~ s01ls7 and various nonion~c surfactants, 20such as the alkyl ethoxylates 3nd al ~lphe~ol ethoxylates are useful for removing greasy soils. Accordingly, mixtures of anionic and nonionic surfactants are used in many modern det2rgent ; composlti~ns. Unfortunately,:many such surfactants are prepared mainly from petroche~ical feedstocks.
25Soaps, î.e., the salts of fatty acids, comprise a traditional : and time-hon~red class of surface-ac~ive agents. Soaps have the :;~ advantag~ that~ th~y are ava~iable via the hydrQ~ysis of ren~wable : resources sush as plant and animal oils and fats. Un~ortunately, soaps are quite susceptlble to the: formation of ~curd" in the ~ 30ipresence of wàter hardness. Moreover, soaps ~re not asleffiec~ive :: across conditions of pH and wate~ hardness for lowering so~ution :~: `interfacial: tensions as are theîr synthetic counterpart surfact-, ants, and are less e~eoti~e~cleaners, especially ~or grease and oil ~eposits. ~ :~
~ , 35~h~ile~a:review of the literature would seem to sugges~ that a : wide selectio~ o~ :surfactants is :available to the detergent manufacturer, the reality is that many such ~aterials are : ~ - specialty chemi~als which are not suitable f~r r~utine use in tow ~ unit ~ost~ items~such ~as home laundering compositions. The fact WO 94112610 ~/US93111455 ``.
214~096 - 2 ~
remains that most home-use detergents still comprise one or more of the conventisnal ethoxyl~ted nonionic and sulfated or sulfon-atkd anionic sur~actant , presumably due to the economic and performance considerations noted belo~
Conslderab~e attention has lately been directed to nonionic surfactants which can be prepared using mainly renewable resources, such as fatty acid esters and sugar.s. One such class o~ surfactants includes` the polyhydroxy `fat~y aeid amides.
1 Msreover, the combination of such nonionic surfactants with conventional anionic surfactants such as ~he alkyl sulfates, alkyl benzene sulfonates, alkyl ether sul~ates, and the like, has also been studied.
The formulation of ~ixed nonionic/anionic surfactant systems lS generally requires qu~te different raw materials, with attendant extra costs in storage, handling and m~nufacturing wlth respect to the individual nonionic and anion~c sur~aetant components.
Accordingly, once eap~tal has been invest@d to ~anufacture and handle a given type of s~r~actant system, 1t m~y become economic-atly unattractive to change to a di fferent surfactank system, even in the face of ~ther advantages ~hat the new system ~ight afford.
Moreover, it is generally true that the alkyl benzene sulfonate surfactants do provide superior cleaning over a wide variety o$ usage conditlons, especially in ho~e fabric la~ndering operations. ~lt is ~nderstandable that the for~ulator would be : . ~5 disinclined to ~change fro~ the alkyl benzene sù~f~nates ~o other ~ .
detersive systems, ~f do~ng so would lower overall product per-formanc~ and, as noted above, would also be economicatly disadvantageous. :
In ~ight of the ~oregoing, it would be adv~ntageou~s to employ surfactant systems which comprise a mixture of nonionic and anionic surfactan~s, both of~which can be prepared ~rom renewable, non-p2troche~ica1 Nsources. It would additlona1ly be advantageous to d~vise such ~ixed nonioniC/aniQni~ surfact:ant systems which are ~ompatib1e: with oth~r det~rc:ive:surfactants and other detersiv2 ingredients~in or~er to enable the formulator to provide superior detergent compositions~ It would be of consider~ble~ddition~l economic advantage for such surfactant .
:

`WO 94/12610 214 8 0 9 6 PCT/US93111455 e ~ 3 ~
systems to be manufactured mainly ~rom the same basic feedstock materials.
It has now been discovered that the combination of nonionic polyhydroxy fatty acid amides with their anionic sulfated analogs qu~ckly and easily provides superior m~xed nonionlc/anionic surfactant systems which are derivabl~ from the same feedstocks and which are available from renewable resources such as plants.
It has further been unexpectedly found that the combinatiDn of such nonionie/anionic surfactant mixtures with soaps le~ds to overall polyhydrox-y fatty acid am~de/sul~ated polyhydroxy fatty acid amide/soap surfactant systems which provide ~x~remely low interfacial tensions in aqueous media. Furthermore, ~t has been determined that the mixed nonionictanioniG/soap eombinations herein provide excellent removal of greasy and oily jsoils and stains from a variety of substrates, even in the absence of phosphate builders. To ach~eve this goal using surfactants made ~rom renewabie resources and ~thout the use of phosphates has been a substantial challenge to detergent for~ulators heretofore.
S~ch mlxed nonphosphate-bu~lt9 nonionic/anion~c/soap combinations . are the subject matter of the present inventiQn.
~AC~6RPUNQ AR~
A method for preparing crude polyhydro%y fatty aeid amides (glucamides) is descr~bed in U.S. Patent 19985,424, Piggott9 and . in U.S. Patent 2,703,798, Schwartz. The use of such glucamides with various synthetic anionic surfactants is described in U~SD
Patent 2,96~,576, corresponding to &.B. Patent 809,060. The sulfuric esters of acylated gluca~ines ar~ disclosed in U.S.
Patent 2,717,394, ~ch~artz.

the pres~nt invention encompasses detergent compssitions comprising a mi~ed nonionie/anionic surf~ctant system which comprises a polyhydroxy fatty acid amide (a) of the formula O Rl ,, : R2 - C - N - Z
3~ wherein ~1 is H, C1-C8 hydrocarbyl 7 2-hydroxyethyl 9 2-hydroxy-propyl, or a mixturc therein, R2 is C5-C3~ hydroearbyl~ and ~ is a polyhydroxyhydrQcarbyl moiety having a line~r hydrocarbyl chain with at least two (in the case of glyceraldehyde) or preferably at 2~8096 - 4 - .
least three (in the case ~f other reducing sugars) hydroxyls.
directly connected to the chain; and (b) an anionic surfactant which is a memb~r selected fro~
the group consisting of sulfated polyhydroxy fatty ac~d a~ides o~ sa~d formula ~a)9 at a welght ratio of (a):~b) of fr4m about 10:1 to about lolO; and (c) a soap. .
The term ~soaps~ herein is intç~ded to encompass the classk, conventional wat@r-soluble salts of Cl~-C~ near saturated and ~ unsaturated fatty acids. Compositions according ~o the pr~sent invention containing~ such soaps exh~blt qu~te lo~ interfaoial tensions and good grease remoYal praperties, even at pH's near neutral~ty, i.e., over the range of c~. 7-11Ø As a general proposition, the.improved qual~t~es of the co~pos~tions herein app~ar to peak with soaps of about C12, and decre~se somewhat w~th soaps which are longer ghan abou~ C13 and shor~er than about C~
especially w~th respect to spontaneous emulstfication of greasy soils. Accordingly, the C12 soaps are preferred herei~. The ~soaps~ can be employed in any water-soluble salt fOr~7 e-g~
alkali metal, alkaline earth~metals~, ammoniu~, alkanolammon~um, di-alkanola~onlum, ~ri-alkanolam~on~u~, Cl 5 alkyl s~bst~tutQd am~onium9 basi~ a~ino acid ~roups~ and t~e like~ all of~h kh are wetl-known to ~anufacturers. The sodium salt form is comen~ent, .
cheap and ~ffective. The fatty acid form can also be used, but will usually be converted into ion Po~m ~y pH adjustmenks~ which~
ar~ ~ade during processing of the compos~tions. S~nce~water-soluble soaps are g~n~rally easSer to ~ork with, lt ~s preferr~d that th2y be used, rather than the fatty acld form~
Nqnlim~ting examples o~ soaps~us~ul herein~ bnclude: deca-noate; undecanoate; laurate; undecyl~n~ate; 2-dodecenoate;
tridecanoate; and mixtures thereof.
The soaps :~ypically comprise at least abnut 1% by weight of : : the total compositions berein and preferably c~mpri~e fro~ about 4X to about 10% by:weight o~ the compositiQns. Stated oth~rwi~e, the weight ratio of soap (G) to the eo~bined ~ixturs nonionic/ani-on i c ( a ~ ~ b) l S i n the range c: ( a ~ b) from about 1: 20 to about 2, preferably about 1:8 to about 1:3.

~VO 94112610 Preferred cornp~sitions herein contain at least about 10~, preferably from about 25% to about 65X, by weight of said lonionlc/anionic/soap surfactant system. Such c~mpositions may :omprise from about 3X to abmlt 58X of the nonionic surfactant ~nd rom about 3% to about 50X of its sulfated anionic ocunterpart ;urfactant. Highl~ preferred are compos~tions which additionally :ontain from about 2X to about 40% by weight of an additional ~etersive sur~actapt, as well as othe~ optional detersive adjuncts as di scl osed hereinaFter . Al koxyl ated al cohol s or al koxyl ated alkyl phenols at le~ls of at least about 1%, preferably about 2X
to about 6X, are especially preferred for such use.
The invention eneolnpasses prgferred compositions which comprise from about 10% to about 65X :by weight of sa~d mixed nonionic/anionicjsoap sur~actant system, from about 1% to about 15X by weight of an ethaxylated Cg-C2~ alcohol, and optional builders and deters~ve enzymes. Such c:ompos~til~ns exh~bit ~specially good removal of cosmetic stains froln fabrics.
~ he preferred compositlons herein w111 also contain l~rom about 0% to about 2%, preferably from about OX to about 1.0%, by weight, of calcium ions. H~gh sudsing compos~tions will contain from about 0% to about 2%, preferably from about 0% to about 1.~, by weight of magn~sium ions~ Sources of Caltiillll and ~agnesium can be any c~nvenient water-sollJble ar.d toxicolog~cally acceptable salt, including but not 1 imited to, CaC12, MgC12~ Ca(OH)2, Mg~OH)2, CaBr2, Mg~r2,: Ca mal ate, Mg mal ate; Ca maleate, ~9 maleate, calcium formate, CaSD4, M9504 or the calc~um and/or magnesillm salts of ~n~onic surf~ctants or hydrotropes. CsC~2 and MgC12 are con~fenient and preferred heretn.
The in~lentiGn there~ore al so er.eom~asse~ an improvea mel;nw far removing cosmetic stains from fabrics, comprising contaeting the fabrics thus sl;ained with an aqueous bath containing at least about 0.02% by weight of a compos~ion which comprises said nonionic/anionic/soap sur~actant system and, preferably also containing said C~-C2~ alkoxylated (preferably ethoxylaged) alcohol or alkaxylated Cg ~24 alkyl phenol (preferably ethoxyl ated) .:

,09 Pcrluss3lll4s~ ~
~ - 6 - ~.
All perce,;ivages, rat~os and proportion~ herein are by weight, unless otherwise specified. All documents cited are incorporat2d herein by reference.

S The composit~ons and procssses of this invention most prefer-ably employ high quality polyhydroxy fatty acid ~mide surfactants whieh are substantially free of cyclized and ester-amide by-products. While the polyhydroxy fatty acid amide-based sur- ~`-factants used herein can b~ prepared, for example, by the methods disclosed in the Schwartz references above, this invention most ~-preferably employs high quality polyhydroxy fatty acid amide surfactants which are subskantially free of cycl~zed by-produets, As an overall propos~tion9 the preparative ~ethQds described ~n ~0-9,206,154 and W0-9,206,984 w~ll afford high quality ~oly-hydroxy fatty acid am~des~ The mQthods co~prise reacting N-alkylamino polyols w~h, pr~ferably, fatty ac~d ~ethyl esters in a solvent using an alkox~de eatalyst at temperatures of about 85~C
to prov~de h~gh yields ~90-9~X~ of polyhydroxy fatty acid amides having desirabl~ low levels (typ~cally, less than about 1.~%~ of sub-optimally degradable cyclized by-produc~s and also ~th improved color and impr~ved color stabitity~ e.g., Gardner Colors below about 4, preferably between 0 and 2O Use of N-methyl and N-hydroxy~l ~1 amine compounds provides h~gh suds~ng mater~als.
Use of N~C2-Cg alkyl a~ine compounds pr~vides low suds~rs. (~ith some of the low sudsers, e.g~, n-butyi, iso-butyl, n-hexyl, the methanol ~ntroduced wlth the catalyst or gen~rated during the r~action provides suffici@nt fluid~zation that the use of add~ional reaction solvent may be optional.~ If desired, any unreacted ~^alkylamino potyol remaining in the pr~duct can be 3d acylated with an ac~d anhydride, e.g., acetic anhydride~ ~aleic anhydride, or the like, to ~inimize the oYerall level of amines in the p~oduct.
~y ~cyclized by-products~ herein is meant the undesirable reaction b~-products of the pri~ary reaction wherein it appe~rs that the multiple hydroxyl groups in the p~lyhydroxy fatty acid amides can fonm ring structures which may not be readily biode-gradabtR. It *ill be appreciated by those skilled in t~e chemical arts that the preparation of the polyhydroxy fatty acid amides 21~8096 ~O 94/12610 PCT/VS93/114~5 herein using the di- and higher sacfharides such as maltose will result in the formation of polyhydroxy fa~ty acid amides wherein linear substituent Z (which contains multiple hydroxy substitu-ents) is naturally ~capped~ by a polyhydroxy ring structure. Such mater~als are not cycltzed by-products, as defined herein.
More specifically, the compos~tions and processes herein use pclyhydroxy fatty acid amide surfactants of the formula:
O
(I) R2 - ~ ~ N - ~
wherein: Rl ~s H, C1-Cg hydrocarbyl, 2-hydroxyethyl, 2-hydroxy-propyl, or a mixture thereof, preferably ~l-C4 alkyl, ~ore prefer-ably Cl or C2 alkyl, most preferably C1 alkyl (i.e., methyl); and R2 is a ~s-C31 hydrocarbyl moiety, preferably straight chain C7-Cl~ alkyl or alkenyl, more preferably straight chain Cg-C1 alkyl or alkenyl, most preferably straight chain Cl1-C19 alkyl or alkenyl, or mixture thereof; and Z is a polyhydraxyhydrocarbyl moiety having a linear hydrocarbyl chain w~th at least 2 (in th~
case of glyceraldehyde) or 3 hydro%yls ~n the case of other reducing sugars) directly connected to the chain, or an a~koxyl-ated derivative (preferably ethoxylated or propoxylated) thereof.
Z preferably will be derived from a reducing sugar in a reductive amination reaction; more prefer?bly Z is a glycityl mo~ety.
Suitable r~ducing sug~rs include glucose, fructose, maltose, lactose, ga~actose, mannose, and xylose, as wel~ as glyceralde-hyde. As raw materials, high dextrose co~n syrup, high fructose corn syrup, and h~gh maltose corn syrup can be util~zed as well as the indi~idual sugarç listed above. These corn syrups may yield a mix of sugar co~ponents for Z~ It should be understood that it is i by no means ~ntended to exclude other suitable raw ~aterials. Z

3~ preferably will be selected from the group cons~sting of -CH2~
:~ (CHOH)n-CH20H, -CH(CH20H)-(CHOH)~ 1-CH20H, -C~2-~CHOH~(CHOR')-; (CHOH)-CH2~H, where n is an integer fro~ 1 to 5, inclusive, and R' is H or a eyelic mono- or poly- saccharide, and alkoxylated derivatives thereof. Most pre~erred are glycityls wherein n is 4, : 35 particularly -CH2-(CHOH)4-CH20H.
In Formula ~ , Rl can be, for exa~ple~ N-methyl, N-ethyl, N-n-propyl, N-isopropyl, N-n-butyl, N~isobutyl, N-n-hexyl, N-2-ethylhexyl, ~ hydroxy ethylq or N-2-hydroxy propyl.
, WO 94/126108 ~ 9 6 PCT/US93/11455 :

~. - 8 - :
R2-CO-N~ can ~e, for example, cocamide, ste2ramide, o~eamide lauramide, myrista~ide, capr~camide, palm~tamide, tallowamide, etc.
Z can be l-deoxyglucityl, 2~deoxyfructityl, 1-deoxyxylityl, "
; 5 l-deoxymaltityl, l-deoxylactityl, l-deoxygalactityl, l-deoxyman-nttyl, l-deoxymaltotriot~tyl, 2,3-dihydroxypropyl ~from glyceral-dehyds), etc. ~; ``
It wlll be appreciated that the polyhydroxy fatty acid amide surfactants used herein as the nonion k surfactant component can be mixtures of materials having various subst~tuents Rl and R2.
SUl.ElEoN REA~TTON . . .' It is to be understood tlhat the sulfation pruducts herein are bel ieved t~ be mainly mono-sul~ates on the terminal hydroxyl substituent of the polyhydroxy fatty acid amides. HoweYer, since ::
the amides do contain multiple hydroxyl groups where sulfation can occur, the di-, tri-, tetra, ~t~. sulfates can b~ formed in varying amounts an;d be co-present tn the compos~tions. Indeed, ~t appears that using the syntheses disclosed herein, approximately lOX di -sul fation can routinely occur. The presence of such poly-sulfated ~aterials does not detract fro~ khe performance herein, and no special pur~Fieation steps need be used to remove them.
- Coconut glucose amide 1, (C11H23c~Me)~H2[c~OH~4cH2oH~ made fr~m 95X C12 ~ethyl ester3, ! 25 75.4 ~ (0.20 mole) is dissolved in 2200 9 chlorofsrm. Note chloroform ~s passed through silica gel to dry and to remov@
ethanol. Dry apparatus is used. ~hlorosulfonic acid 11.8 9 (0.10 mole) is dissolved in 50 ml chlorofonm. Acid solution is dripped into glucose a~ide solutio~ at 54-54~C ~15~mi~utes) with sti~ring 30 ! under a nitrogen blanket. Solution is stirred an addition~l 45 minutes with a nitrogen sweep at ~O~C to e~aporate off about hal~
: of the chlorofor~ and cooled below 30C. Th~ ae7d solution is slowly poured into a vigorously stirr~d, ice cooled base solution, ` The pH is monitored to assure that lt remains basic at all times.
A mixture with a final pH o~ 9.0 is achieved with a total of 157 ml 1H sodiu~ hydroxide and 400 ~l water. The mixture is evaporated at a~bient in a dish in hood ~ air stream for one week w~th occasional ~tirrillg to remove chlorofonn. Up to 8560 9 is ' .

~o 94/12610 21 ~ 8 0 9 6 pcTluss3lll4ss b- _ 9 _ made with wate~ to give approximately 1~ solution at pH 8.6 Cationic S03 analysis indicates 0.13 mole fraction sulfation. The resulting produot is a ~ixed nonionlc/anionic surfactant accorting ~o this invention.
In an alternatiYe process, the polyhydroxy fatty acid a~ide is ~ulfated as follows. St~ Two hundred grams of the C12 14 N-methyl gll~camide~ are dissolved in one liter of methylene chloride and transferred to a 2 l reaction flask. Ste~ - 66.8 grams of a 1:1 ~mole basis) pyr~dine/503 comple% obtained ~rom Aldrich Chemica? Company are added to the r~action flask, The reaction is allowed to proceed at:room ~emperature for three days (a matter of convenienoe, other reaction times can be used, depending on te~perature, etc. ) . Step 3 - 25 grams of sodi~m carbonate are dissolved in 80 mls. water and added to the reaction 15 flask ~ith mixîng for f~ur huurs. ~eQ~ - The crude reaction mixture is evaporated and the residue taken up in methanol ~total volume 1.4 l). ~ - The methanol is dried over MgS04 and the sol ~ds renloved by vasuum filtrat~on~ SteQ~ - The methanol solution is decolorized w~$h chircoal~; the charcoal is re~ved by 20 filtration through a Celite bed. ~t~ - Excess methanol is evapQrated on a rotary evaporator (60-C; vacuum). The residue is slurried with ethyl acetate (slightly warm). ~ - The ethyl acetate slurry is cooled to room ten~perature and 1;he solids allowed to settle. The ethyl acetate containing the desired sulfated glucamid~ surfactant is decanted from the solids and the so~Yent removed by evaporat~on. ~ - The sol ids remaining after evaporation of the ethyl acetate are grollnd by ~Qrtar and pestle and dried in a Yacuum oven (25-C; 20 n~ pressure~O Thc y~eld ;is 205 g/84.7X of theoretkal. ~ j I
Tallow (C16-Clg~ N-lnethylglucamide is sul~ated similarlyt except that pyridine is used in place of ~ethylene chloride as the sol~ent in the first step. ~ precipitate forms in Step 5, and is rem~ved by filtration. ~he sulfated tallow N-methyl glucamide regllires no decolori~ation.
~5 The sulfated polyhydroxy fatty acid amides used herein as the anionic surfactant component can a~so comprise the sulfAted seaction product ~f polyhydro%y fatty acid amides having a mixture of R1 ~n~ ~2 substituentS-WO 94/12610 PCT/lLJS93/11455 ~4~096 - 10 ~
~Ca Salts The suï~ated polyhy~roxy fatty acid amide surfaet~nts herein are con~ntionàlly prepared in their acid or alkali metal (e.g.~
Na, K) salt forms, or as a~non~um or aikanola~monium salts, e.y., 5 triet~anolan~nonium. These counte~;~on salts are non-limiting examples of typical sul~ated de$ePgents. However, in circum-stances where hi~h grease removal performance i s of parti cul ar importance, the formulator may fir,d ~t advantageous to incorporate at laast about OfSXg preferably from about 0.6X to about 2%, by 10 we~ght of ~agnesiuRI ions, calcium ions, or m1xtures the7~eof5 into the finished d~tergent compos1tioll. This can be done by simply adding vari~us water-soluble saltS such as the chlor~de~, sul -fates, acetates, etc. of magnesiu~ or calcjum to the compos~t~ons.
It is also useful to generate the nlagnesiu~ and/or ca~cium salts 1~ of the sulfated polyhydroxy ~atty ac~ds her~in byreacting Mg(OH)2 or Ca(OMj~ ~lth the acid fon~l of the sulfated polyhydroxy fatty acid a~ide9 and ~h~s can conventently be done in situ durling ~he formulation of the finished detergent co~pos~tions or as a separ-. ate step durliny the manufac~ure of the sulfated surfactant, i tsel f .

Under some circumstances the forlnulator of det~rgen~ co~po~
tions may f~nd lt des~rable to provi~ low suds~ng compostt~ons.
For estample, low su~slng is a desirable - feature of window cl~an-2~ ers, floor and wall cteansers9 and other hard surPace clQansers ~here ~xcess sudsing would require inconven~enl; rinsing steps in the overall cleaning process. Dishwashing detergents folo use in alltomatic maeh~nes ~ust be formulated to have ~ss@nt~ally no suds, i .I since~excess suds can actually spill out of th~ ~achinesO L~ke wise, European-style front load~ng fabric washing machines require low sudslng detergents to avoid suds sp~llage~ Low suds~ng ~an also be advantageous in concentsoated laundering pi~oc~sses such as descr~bed in U.S. Patents 4,489,45~ and 4,4899574.
It transpires that the polyhydrQxy fatty ac~d amides of ~5 formlJla (I3 herein having H, hydroxyalkyl and/or ~thyl subst~tu-ents as ~roup Rl are h~gh slJdsers, whereas the compounds with Rl - as ~3-C~ (straight-chain, branched ch~in or eyc-~ ic) are low sudsers. Importantly for cleaning purposes, the low sudsers, --~NO 94/12610 PCT/US93/11455 , ~,. ` - 11 -especially C2 and ~-3 alkyl, still lower interfacial tensions very substantially and ar~ thus quite aetive detersive surfactants.
Accordin~ly, when fo~mulating low sudsing CQ~positions herein the formulator may wlsh ~o e~ploy compounds of ~ormula (II~, con~eniently and preferably wi~h their`correspsnding sulfates, :~, O . Rl -(II) R~ C - N - Z
wherein R2 and Z are as 1n formula (I), above, and wherein R~ is C3 to about C8 alkyl, e.g., n-propyl, n-butyl, isobutyl, isopro-pyl, n-pentyl~ cyclopentyl, n-hexyl, cyclohexyl, and also inelud-ing various alkyl-branched substi~uents such as 2-ethylhexyl, and the like. Low sudsers preferably are substant~ally free ~f N-hydrogen, N-methyl, N-ethyl and N-hydroxyalkyl substituents.
Alternativelyj the sulfates with shorter alkyl chains, disc~osed above, can be used w~th these longer ehain polyhydroxy fatty aeid amides, but this is less convenient ~from a.manufacturing stand-point. The synthesis of such eompounds follows the steps noted above. Of course, for low sudsers the fonmulator may opt not to conduct the hereinbefore described steps (~Secondary ReactionW) to diminish the levels of fatty acids in the reaction products9 since .
the fatty acids can, themselves, help controi sude. For solub~l-ity r~asons, preferred composit~ons herein are those wherein the total number of carbon atoms in the N-alkyl subst~tuent plus ~atty acid substituent is no greater:than about 20-21. This is e~pe-cially true when formulatin~ homogeneous l~quid co~positions.
By ~low sudsing~ herein is meant a suds he~ght or suds vo~ume ; for the low sudsing detergent eompositlons herein containing the N-C3-C~ alkyl polyhydroxy fatty acid a~de surfactant which is substantiall~ less than that~which is: aehiev~d i~ comp~rab~!e compos~t~ons containing the N~methyl polyhydroxy ~atty ac~d a~ide :surfactant. Typically, the compositions ~herein provide sudsin~
~ which is no greater, on average,: than about 70~, preferably no : greater than about SOX, of that prod~ced with the N-methyl sur-f~ctants. Of course, the sudsing can be still further reduced by means of standard: suds control a~ents such :as the silieones, various fatty materials and the like.
For the convenience: of the formulator, a useful test proeedure for c~paring the sudsing of the low-suds eompositions .

w o 94/12610 21 4 8 0 9 6 PcTruss3/114ss herein is provided hereinafter. The test compr~ses agitating aqueous solutions eontaining the deterg~nt being tested in a standardized fashion and comparing sudsing against equivalent detergents containing the N-~ethyl polyhyd~oxy fatty acid amide.
. 5 This partieular test is run at ambient tempsrature (ea. 23-C) and at 60C~ and at water hardness (3:1 Ca:Mg) levels of 10.4 gr/gal ~179 pp~) and 25 gr/gal (428 ppm~ to mimic a wide variety of prospective usage conditions. Of co~rse, the formulator may modify the test condltions to ~o~c~s on prospect~ve usage conditions and user hab}ts and pract~ces throughoug the world.
. ~a~ , .
Suds cylinders having the d1~ensions 12 inch (30.4 cm) he~ght and 4 inch (10.16 c~3 d~ameter are releasably attached to a machine which rota~es the cyl~nders 360- around a fiX~d axis. ~
typical test uses four cylinders, two for the standard comparison detergent product and two for the lo~ sudsing detergent test product.
' In the test, 500 ~L of aqueous solution of the respective i detergents is placed in the cyl~nders. Conveniently, the; 20 solutions comprise 3 9 o~ the detergent, but o~her amounts can be used. The temperature of the solutions and their hardness are adjusted as noted above. Typically, CaCl2 and MgCl2 salts are used to suppl~ hardness. The cylinders are sealed and the 500 ml level 0arked with tape. The eylinders are rotated through two ~5 complete revolutions, stopped and vented.
APter the forego~ng preparatory matters have been co~pleted, the test begins. The cylinders are allowed ta rotate 360~ on the ~achine at a rate of 30 reYolutions per minute. The machine is stop~ed at one minute interYals~ the suds~height ~rom the top of the solution to the top of the suds is ~asured, and the machine is restarted. The test proceeds tbusly for 10 minutes. A suds ~volum~ is calculated by taking the average suds height over the te~t ti~e (10 minutes) and can be expressed as suds volu~e per minute (cm3, which conforms with: suds volume per minute ~ sum of 3~ suds height at each time of ~easurem@nt di~ded by total ti~e (10 ~inutes).
It is to be-un~erstood that .the forego~ng test pro~ides a relative comparison between low sudsing detergent co~posit~ons cf ~o 94/12610 214 8 0 ~ 6 PCT/US93/114ss the type provided herein vs. standard comparison products. Stated otherwise, absollJte Yalues of suds heights are meaningless, since they can Yary widely with solut;ion temperature and water hardness.
To illustrate this point furtller, arl N-n-propyl polyhydroxy fatty 5 acid amide low sudser exh~bits suds volumes per minute in the above test of~: 0.5 cm a~ T~ambient, hardness 10.4; 2.1 cm at T~ambient, hardness 25. In co~parison, the respective figures for a tallowalkyl N-methyl glucamide high sudser are 1 cm and 3.3 cm.
~ITIONAI~INGB~D~NTS
The ~detersive adjunct~ materials preferably used in fully-formul ated detergent ompositions containing the surfactants of the present inventlon will vary1 depending ~n the intended end-use of the final compositions. The following are intended only to be nonlimiting illustrations of su~h adjuncts, more examples of 4~hich 15 will readily come to ~ind of the skilled forlllulator.
O~ional Additional Su fdct~nts - The compos~tions here~n are designed to proY~de good clea~tng. However, if the formulatur w~shes, various additional surfactants can b~ incorporat~d ~nto the cQmpositions t~ provide variolls auxiliary cleaning benefits.
20 Typically, such iddltional surfactant~ will be used at levels up to 30% by w~ight o~ the ~inal/ ~ully-fonnulated compositions.
Nanlimiting examples of optioDal surfactants useful herein include the conYentional C~ 6 alkyl benzene sulfnnates, the C12-Cl~ primary and secundary alkyl sulfates and C12-Clg 2~ unsaturated (alkenyl) sulfates such as oleyl sulfate, the Clo-Clg alkyl alkoxy sulfates tespecially etho3ty sulfates~, the Clo^~lg alkyl polyglycosides and their corresponding sulfated polyglyco-sides, C12-Clg alpha-sulfonated fa1;ty acid esters? Cl~ C1~
betiijnes and sulfobetaines, Clo-Clg alnine oxides, and the, ~ike, 30 having due~regard for the effects on sudsing noted above, Other :~: conventiona1 useful surfactants are listed in standard texts. As noted herein, the conYenti~nal nonionic alcohol- and alky~phenol-:: : ethoxylates ~EO 1-7) are preferred for use in the present COlllpOSi-. tions to remove "non-polar, greasy" stains such as cosmetks~
35 lipstick, and the~like, from various fabrks and surfaces.
~zYm~: ~ Detersive enzymes can opti~onally be inclllded in the - detergent formul~ations for~a wide variety of purposes, especially for fabric laundering, including remov~l of protein-based1 - ,, wo 94/12610 21 ~ ~ O ~ 6 PCT~Sg3/114~5 ~. - 14 -ca~bohydrate-based~ or triglyceride-based stains, for e%ample, and prevention of refuge~ dye transfer. The enzymes to be incorpor-ated include proteases, a~ylases, lipases, cellulasesg and per-oxidases, as well as ~ixtures thereof. Other types of enzymes may also be included. They may be of any su~ta~le origin, such as vegetable, animal, baeterial~ fungal and yeast origin. However, the~r choiee is governed by several fa ~ors sueh as pH-aetivity and/or stability optima9 thermostabili~y`, stability vers~s active d~tergents, builders and so on. In this respect bacterial or fungal enzymes ~re preferred, such as bacterial amylases and proteases, and ~un~al cellulases.
I . Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by wei~ht, more typically about 0.05 mg . to about 3 m97 of active enzyme per gram of thg composi~ion.
Suitable examples of proteases are the subtillsins whieh are obtained fro~ particular strains of ~.subtilis and B.licheniforms.
Another suitable protease is obtain~d fro~ a strain of Bacillus, having maximu~ activ~ty throughout the pH range of 8-12, developed and sold by Novo lndustries A/S under the registered trade name . ESPERASE. The preparation of this enzyme and an~logous enzymes is described in British Patent Specifieation ~o. 1,243,784 of N~vo.
Proteolytic enzymes suitab7e for removing protein based stains ! th~t are com~ercially available include those sold under the tradenames ALCALASE and SAVINASE by ~ovo Industries A/S (Den~ark~
and M~XATASE by lnternational Bio-Synthetics, Ine. ~The Netherlands~. Other proteases include Prot~ase A (see European Patent Application 130,756, published January 9, 1~85) and Protease B (see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Applicatio~ 1:30~756t Bott et al, publishsd January ~9 1985).
~ylases ~nclude, for example, ~-amylases descr~bed in ; British Paten~ Sp~cification No. 1,2967839 (No~o), RAPIDASEt Internatlonal Bi~o-Synth~tics, Inc. and TERMAMYL, Novo Industries.
The cellulases ~sable in the present invention include buth bacterial ~r fungal cellulase. Preferably, they will have a pH
optimum ~f between S and 9.5. Suitable cell~lases are disclosed in U.S. ~atent 4~435,307,- Barbesgoard et al, issued March 6, 1~84, which discloses ~ungal cellulase produced from Humicola insolens 21~096 `iVO 94/12610 PCT/~S93/11455 .~ - 15 -and Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cetlulase extracted frsm the hepatopanoreas of a marine mollusk (Dolabella Auricula Solander3.
Su~table cellulases are also disclosed in GB-A-2.075.028;
6B-A 2.095.275 and DEoOS-2.24~.832~
Su~table lipase enzymes for deteryent usage include those produced by m~croorganisms of the Ps~udomonas group, such as Pseudomonas stutzer~ ~TCC 19.1~4, as d~sclosed in British Paten~
1,3?2,034. See also lipases in Japaness Patent Appl~cation S3-20487, laid open to public inspect1On ~on February 24, 1978.
This lipase is available from Amano~ Pharmaeeutica~ ~o. Ltd., Nagoya, Japan, under the trade name Lipase P ~Amano,~ hereinafter referred to as ~mano-P.~ Other comm2rcial lipases inelude Amano-CES, lipases ex Chromobaet@r viscosu~, e.g~ Chromobdcter viscosum var. 7ipo7yticw NRRLB 3673, commerctally available from ~oyo Jozo Co., Tagata, 3apan; ~nd f~rth~r Chro~ob~cter viscos~
lipases from U.S; B~oche~ical Corp., U.S.A. and D1soynth Co., The Netherlands, and lipa~es ex Pseudomonas g~adlol i ~`
Peroxidase enzymes are used in combination with oxygen sources, e.~., percarbonat~? p~rborate? persulfate, hydrogen peroxide, etc. ~hey are used for ~solution bleaching,~ i.e. to prevent ~ransfer of dyes or pi~e~ts removed ~rom substrates during wash operat~ons to other substrates ~n the wash solution.
. Peroxidase enzymes are known in the art, and ~nclude, for exampte, horseradish perox~da~e, ligninase, and haloperaxid~s~ such as : chloro- and bromo-perox~dase. Perox~dase-containing detergent compositions are disclosed, for example, in PCT In~ernational Application WO 89jO99a13, published October 19, 1989, by 0. Kirk, assigned to!Novo Industries A/S. ~
A wide range of enzyme materlats and ~eans for their incorp-:: oration into syothetic detergent granules is also discloed in . U.S. Patent 3,553:,~139, issued January 5, 1971 tQ Mctarty et al (~.
Enzymes are further disclosed in U.S. Patent 4,1al,457, Place et ~; ; al, issued July; 18t 197~, and in U.S. Patent 4,507,219, Hughes, issued Mar~h 25~ 1985, both:. Enzyme mat@rials useful ~or ~i4uid detergent ~ormulations, and their incorporation into such : formulations,: are;dislosed in U.S. Patent 49261,868, Hora et al, issu~d April 14, 1981. Enzymes for use in det~rgents can be wo g4tl26l0 o 9 6 ~CT/US93/11455 stabilized by various techniques~ Enz~fme stab~lization techniques~
are disclosed and exemplified in U.S. Patent 4,261,868, issued April 14, 19B1 to Horn~ et al, U.S. Patent 3,6û0,319, is~ued August 17, 1971 to 6ed~eS, et al, and Europesn Pat~nt Appl ieation Publication No. 0 199 405, Apptication Ho. 862û0586.5, published ûctober 29, 1986, Venegas. Enzyne stab~ ation systems are also deser~b~d, for example, in U.S. Patents 4,261,868~ 3,600,319,. and 3,519,570. '3~
In add~tion to enzymes, the ~m~s~tions herein can option-ally inelude one or more other deter~ent ~djunct ~ater~als or other materials for assis~ing or enhancing cleaning performan~e9 treat~nent of the substrate to be el~2ned~ or to modify the aesthetics of the detergent compos~t~on (e.g., perfumes, col orants g dyes, etc . ) .
~g~ - Detergent builders can optionally be included i~
the compositions herein to assist in controll~ng min~ral hardness.
Inorganic as well as organ~c bu~ders can b~ usedO Bu~ld~rs are typkally used ~n fabric laundering composit~ons to ass~st in the removal of parti cul ate soi l s .
The level of builder san vary widely dependbng upon the end use of the co~position and its desired physisal form. 3~he~
present~ the composltions will typically comprise at least about 1% builder. Liquid fo~ulations typical~y co~p~tse from about 5%
to about 5~%~ more typically about 5~ to abollt 30X, by weight, o~
. 25 del;erg~nt builder. Granul~r fornlJlations typically co~prise ~romabout 10% to about 80~ more typ~c~lly fro~ about 15X to about 50X
by weight9 of the detergent builder. Lower or higher levels uf builder, however9 are not ~eant ~o be excludedc Ino~anic detergent builders incl~de, ~ut are not l~ it~d to, the alkali m~tal, ~an~onium and alkanola~oon~um salts of polyphos-phates (exemplified by the tr~polyphQsphates~ pyrophosphat~ 9 and glassy polyneric meta-phosphates~, phosphonates, phytic acid, silicates, carbonates ~including bicarbonates and sesquicarbon-ates), sulphates, and aluminosilical;esn Howe~er, non phosphate builders are required in some lo~alQsO Importantly, the composi-tions herein: function surprisingly well even in the presence of the so-called ~weaka buil~ers (as compared w~th phosphates) such '.

.

~O 94112610 21~ 8 0 9 6 PCT~US93/11455 .t~ - 17 -as c~trate, or in the s~-callad ~underbuilt~ situation t~at may occur w~th zeol~te or layered silicate builderc.
Examples of silicate builders are the alkali ~etal silicates, ' partieularly those having a SiO2:Na20 rati~o in the range 1.6:1 to 302:1 and 1 vered silicates, such;as the layered sodium sil~cates '` ' described in U.S. P~tent 4~664,839, issued May 12, 1987 to H. P.
Rieck. Howev~', other s~l~c~tes~ may also be useful such as ~or example magnesium'~silicate, which can serve as a crispening agent in granular formuiat~ions, ~as `a stab~lizing~ agent for oxygen bleaches,~and~as~a component of suds control syste-s.
Examples ~of carbonate build~rs~are the alkaline earth and ~' alkali metal~carbonates~as disclosed in~6erman Patent Appl kation No. 2,321,001 published on Hovember 15, 1~73. '-~
Aluminosil1cate1bui~1ders~are especially~useful in the~'present ~nve~tion. ~ Aluminosilicate ;bu~lders~ ar- of great ~importance ~n~
most currently marketed~heavy~duty grànular detergent compos~
t~ons,~and can~al~so bè~ s~gni~cant bu~lder in~red~ent~in l~qutd detergent~ form~lations.~ ~;Alumlnos~licste bu~ilders ~include those having the empirical~formul;a~
` ; 20 ~ Mz~zA102-ySiO2~) wh~reia M is~;s;odium,~'~potassium,~;ammoniu~or substi`tuted a~ on~um,~
z is from~about~0.~5~to~ab~out~2;~and~y~is~1; this~mater~al~ having a magnesium ion~ exchange~capa~c~ty of ~at least ;about~ 50 m~l~li;gram equiYal ents~ of~C~C03~hardness~ per~gram of anhydrous alu~inosili~
25~ ;cate.~ Preferrèd aluminos~ cates';are zeolite builders'wht~ch have~
the formula~
Naz~ (A 02)z~ ~(s 02)Y] ~XH20 where~n z and y~are ~'integers;of~at ~le-st 6, the molar ratio of z ~
to yl~s~ n the~range~from~l~.O ~to'iabout-0.5,~and ix is àn~in~eger ~' ~ ~ro~sbo~u ~15`to~bout~264.
Use~ alu~lnos~ cate~ Qn~exchange~materials~are co ~er~
cially~ 1 e ~T ese~: no~ icates~ ca ~be~c~ sta:lline~or amo~phou~s~in~structur ~and ~n~be~natural~ly-occur~ n' alum'nosill~
ca~es~or~-synth 'ic llg~de i;ved.~ A~method for produclng ~alum1no-3~ sill;cate~ion~ xchange~ ' terial~s ~is ~disclosed~`in~U.S.~ Patent~
3,985~,~6 ,~ t~al,~ issu ~October 12~1976. Pre~ rred ~
synthet1c~ c ~ lli~ alu inosil~lcate~ lon~ exchange~ matérials ~ ;
useful~herein are~ avail~abl~e~ ùnder ~the designations~`~eol;~te; A, wo 94112610 2 ~ 48 0 9 6 ~T/IIS9311145~ `~

Zeolite P (B), and Zeolite X. In an especially preferr~d enlbodiment, the crystall ine al uminosil icate ion exchange material has the formula~
Nal2t(A12)12(S~2)12]XH20 wherein x is f~om about 20 to about 30, especially about 27. This material ~s known as Zeol~te A. Preferably, the aluminos~licate has a particle size of about 0.1~10 ~icrons in diameter.
Organic detergent ~uilders suitab~è:~for the purposes olF the present invention include, but are ~ n`ot restr~cted to, a wide variety of polycarboxylate ea~pollnds. As used herein, "polycarboxylate" refers to compounds having a plurall ity of earboxylate groups, preferably at least 3 carboxylates.
Polycarboxylate builder can generally be added to the eomposition in ~cid form, but can also be added in ~he form of a neutralized salt. When utilized in salt form, alkali metals, such as sod~um, potassium, and l~thlllm, or alkanolan~nonium salts are preferred.
lneluded ~ong the polycarboxylate bu~lders are a varle~y of categories of useful ~at~r;als. One i~portarlt cat~gory of polycarboxyl~ke builders enco~passes the eth~r polycarboxylates, 20 . including oxydisuceinate, as dis~losed in Ber~, U.S. Patent 39128,287~ issued April 7, 1964, and Lamberti et al, U.S. Patent . 3,635,830, isslled January 189 1972. See also "TMSlTDS~ builders of U.S. Patent 4~663,0?1, ~ssued t~ Bush et al, on May 59 1987.
Su~table ether polycarboxylates also include cyclic co~pounds, particularly al~cyclic compounds, such as those described in U.S.
Patents 3,923~79; 3,835,163; 4,15E,635; 4,120,874 and 4,102,903 Other useful detergency builders ~nclude the ~ther hydroxy-polycarbQxylates, copolymers of ~aleic anhydride w~th ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy b~zgne-2, 4, $-trisul-phonic acid, and carbo%ymethylo%ysuccinic acid, the various alkali : ~etal~ ammonium and substituted ammonium salts of polyacetlc acids such a5 ethylenediamine tetraacegie acid and n~trilotriacetic :~ acid, as well as polyc~rboxylates such as ~ell~tic acid, succinic acid, oxydisuccin:k acid, polymaleic acid, ~nzene 1,3,5-tricar-boxylic :acidj carboxy~ethyloxysuccinic ac~d, ~nd soluble salts thereof. :
. : : Citrate builders, e.g., citric acid and soluble salts thereof ~particularly sodium salt), are polycarboxylat@ builders af .

.

~WO 94/12610 21 4 8 0 9 ~;` PCTIUS93/11455 ' ~

.e ^ 19 ~
particular importance ~or heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. ~Citrates can also be used in granular oomposi-ti~ns, especially in c~mbination with zeollte and/or layered silicate builders. ::
Also suitable ~n the detergent composi~ions of the present invention are the 3,3-dicarboxy-4-oxa-1,6~h@xanedi3ates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, lssued January 28, 1986. Us2fu~ succin1c aoid builders inelude the Cs-C20 alkyl and alkenyl succinic ac~ds and salts thereof. A
particularly pre~erred compQund of th~s type is dodec~nylsuccinic acid. Spe~ific examples of succinate builders include: laurylsuc-cinate, myristylsuccinate, pallllitylsuccinate, 2-dodecenylsuccirlate (preferred~, 2-pentadecenylsucoinate, and the l~ke. Laurylsuccin-ates are the prefe~red bui 1 ders of ~hi s grQup, and are descri bed ¦ in European Pa~ent Appl~cation ~86200690.S/0,200,263, published I NoYember 5, 1g86. -Othèr suttable polycarboxylates are disclosed in U.S. Patent 4,144, Z 6, Crutchf~eld et al, issued March 13, 1979 and in U~S.
Patent:3,308,067,~ Diehl,` issued March 7, 196~. S~e also Diehl U.S. Patent ~,723 7 322. :
. Fatty acids, e.g., C12-C~3 monocarboxylic acids, can als~ be ~: ineorporated into the compositions alone, or in combination with :~ : the aforesaid b~tlders, espeoially citrate and/or the succinate : ~ 25 builders, to: provide add~ti:onal builder activity. Such use of fatty ~cids will generally result.in a :diminution of sudsing, :`
:~ ~ which~should~be~taken into account by the fonmul~ator In situations where phosphorus-based builders can be used, i ! j the various alkali ~etal phosphates such as thQ;well-known sodium : 30 tripolyphosphates, sodium pyrophosphates and sodium orthophos-: phates can be used. ~ Phosphonate builders such ~as ethane-1-hydroxy~ diphosphanate:~and other:known phosphonates (seet ~or example, U.S. Patent 3,159,581; 392131030; 3,422,021; 3,400,14~;
and 3~422,137) can also:be used.
35:~
~ The detergent::~co~positions herein may optionally contain :~ ~ bleaching agents or~ bleaching composi:tions conta~ning a bleaching : agent and one or more bleach activatorsO When :present, bleaching WO 94112filO PC:T/US93/114~$ -2~d~80~6 - ~0 - .
agents will typically be at levels of from about lX to about 2~
more typically from about lX t~ about 1~%, of the detergent composition, especially for ~abric la~ndering. If present9 the amount of bleach act~vators w~ll typ~cally be from about 0.1X to about 6~, more typically from about; O.5X to about 40X of the bleaching composition comprising the bl~aching agent-plus-bleach activat~r. ~
The bleaching agents used herein can be any of the bleaching agents useful for detergent campositions in textile cleaning, hard surface cleaningt or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents. Perborate bleaches, e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein, but, under some conditions, may undesirably interact with the p~lyol nonionic surfactant.
One category of bl~aching agent that can be used without restricti~n encompasses percarboxyl~c (~percarbonate~) acid bleaching agents and :salts therein. Su~table examples of th~s claes of agents include magnes~um monoperoxyphthalate hexahydrate, 20 the ~agnesium salt o~ meta^chloro perbRnzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S~ Patent 4,483,781~ Hartman, issued Nov~mber 20, 1984, U.S. Patent Appl~cation 740,446, Burns et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al, publ~shed February 20, 1985~ and U.S. Patent 4,412f934, Chung et al, issued November 1, 1983. Highly preferreJ
bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued ~anuary 6, 1987 go Burns et al .~
Peroxygen bleaching agents can also be used~ Suitable peroxygcn bleaching compounds include sodiu~ carbonate peroxy hydrate, sodium pyrophosphate peroxyhydrat~, ur~a peroxyhydrake, and sudiu~ peroxide, Persutfate bleach (e.9., OXON~9 manufactured commercially by DuPontj can also be used.
Mixtures of bleaching agents can also be used.
P~roxygen bleaching agents and the perborates are preferably eombined with bleach acti~ator~, which lead tu the in situ produc-tion in aqueous solution (i.e., during the washing pruc@ss) o~ the 214~096 ^ PcTnuss3/l14ss h - 21 -peroxy a~id corresponding ~o the bleach aetivator. ~ari~us nonli~iting examples of activators are disclosed in U.S. Patent 4,915,8~4, issued April lO, 1990 to Mao et al, and U.S. Patent 4,412,934. The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (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.
Bleaching agents other than oxygen bl~aching agents are also known in the a~t and can be utilized herein. One type ~of non-oxygen bleach~ng agent of par~icular lnterest includes photo-act1vated bleaching agents such as ~the: sulfonated ~inc and/or aluminum phthaloeyanines. See U.S. Patent 4,033,718, issu~d July 5, 1977 to Holcombe et al. Typically, detergent composltions will contain about 0.025% to about 1.25Z, by weight, of sulforated~zinc phthalocyanine.
~ ~L~se Aqen_ - Any polymeric soil release agent~ known to those skilled ~n the :art can optionally be employed in the ompositions ~and processe~s of th~s~:lnvention. Polymeric : soil release ~agents~:are characterized by~:havlng both hyd~ophi1ic segments, to hy:~rophilize thè~surface ~f hydrophobic fibers, such:
as polyester and ny~on, and hydrophobic seg~ents,~to deposlt upon hydrophobic fi:bers and remain adhered thereto through eompletlon~
of washing and~:rlnslng cycles and, thus, serYe as an anchor~ for . the hydrophilic ~segm~nts. This can enàble stains occurrin g ; 25 : subsequent to:~ treatment~ w~th the~soi~l~release~agent~to be~ moreeasily~cleaned~ln;later w~shing pr~cedures.:
~ : The :am~unt of ~ixed:nonionic/ani:onic:surfactant:~:needed:~to : enhance`deposltlffn~will vary ~with the~ partieular~:soil release:`
agen,~ ichosqnl,~ the optional~presence or a~sence~of oth!er anionic : 30 surfactants,;:and :their type:~ as ~ well as~:~ the~ particular nonioni~/an~ionic~;:chosen.~ Genèrally,~ com~osi::t~ons will~ comprlse from:about~;0.01%~o:~aboue~ 1~X,~ by~weight;9~of the pol~ymerie~ soil elease~ agent,~ typitally~from~about:~;0.1X ~to~:about~ 5X, and~:~from about~:4%~to~:about~50X,`~mor~e typically from~about 5% t~about 3~%
35~ : of anionic~surfactant.;~Sueh~compositions should:gene~ally contain at least aboùt~l%, preferably~at least about:3X, by weight, o~ ~he m1xed~ nonionictanlonic surfa~ctant of:this invention, though it is not`intended to necessar1:1y be limited thereto. ;

WO 9V12610 21~ 8 0 9 6 PCT/US93/11455 `

~. - 22 -The polymerio soi~ release agents for whieh performance ~s enhanced herein especially include thosa soil release agents having: (a~ one or more nonionic hydrophil~ compoRents consisting ~ssengially of (i) polyoxyethylene segments wlth a degr~e of polylnerization ~f at least 2, or (ii).roxypropylelle or polyoxy-propylene segm~nts w~th a degree of pslymerization of from 2 to 10, wherein said hydrophile seg~ent does not encompass any oxypropylene unit unless ~t is bonded to adjacent moieties at each end by ether linkages, or (~i) a mixture of oxyalkylene unlts compris~ng oxyethylene and fro~ 1 to about 3û oxypropylene units whereill said mixture contains a sufficient amount of oxyethyl~ne units sueh that the hydrophile component has hydro-philicity great enough to increase the hydrophil~ci~ of conventional polyester synthetie fib~r surfaces upon d~posit of the soil release agent on such surf~ce, caid hydrophile segments preferably compris~ng at least about 25X oxyethyl~ne un~ts and more preferably, espec~ally for such components haY~ng about 20 to 30 oxypropylene unlits, ~t least about 50X oxyethylen~ un~ts; or tb? one or morQ hydrophobe compollents compr~sing (i) C3 oxyalkyl ene terephthalate segments~ ~herein, if said hy~rophobe co~ponents also comprise oxyethylene terephthalate, the ratio of oxyethylene terephthalate:C3 oxyal kylene terephthalate un~ts is ~bout 2:1 or lower, (ii) C4-t6 alkylene or oxy C4-C~ alk~lene seg~enlts, or m1%tures therein, ~i~i) poly (~inyl *ster) segments, pr~ferably poly(vinyl acet~t~)9 baving a degree of polymerlzation of at least 2, or (~v~ Cl-C4 alkyl ether or C4 hydroxyallkyl ether subsîitu-ents9 or m~x~ures therein, wherein sa~d substitu~lats are present in the form of Cl-C4 alkyl ether or C4 hydroxyalkyl ether cellu-lose derivativesl or Illixtures therein, and s~ch ce~lulo$e deriva-tiYes are amphiph~lic, whereby they h~ve 2 sufficient level o~
Cl-C~ alkyl ether and/or C4 hydroxyalkyl ether units to deposit upon conven~ional polyester synthetic fiber surPaces and retain a sufficient level of hydroxyls, once adher@d to such con~e7ltional synthetic fiber surface, to increase fiber surface hydrophiliclty~
or a combination of 5a) and (b3~
Typically, the polyoxyethyl~ne segments of ~a3~ willl have a degree of polymerization of ~ro~ 2 to about 200, although higher .

'~10 94/l:Z610 2 1 ~ 8 0 9 6 PCTIUS93/11455 ~ ;~

~. - 23 - -levels can be used, preferably ~rom 3 to about 150, more prefer- :
ably from 6 to about lûO. Suitable oxy C4-C6 alkylene hydrophobe segments include, but are not li~ited to, end-eaps of polymeric -~
so~l release agents such as M03S(CH2)nûClt2CH~O-, where M is sodium and n is an integer from 4-69 as d~sclosed in U.S. Patent 4,721,580, issued January 26, 1988 to 60sselink.
Polymeric soll rele~se agents ~Iseflll ln the present invention `:
also include cellulosic d~rivatives such as hydroxyether cellu~
losic polymers, copolymeric blocks of ethylene terephthalate or . -propylene t~rephthal~te with polyethylerle oxide or polypropylene o%ide terephthalate, and the l~ke. SuGh agents are con~nercially aYailable and include hydr~xyethers of cellulose such as METHOCEL -:
(~ow). Cellulosio soil r~l~ase agents for use herein also include th~se selected from the group consisting of Cl-~4 all~l and C4 hydroxyalltyl cellulose; see U.S. Patent 4,000,09, issued December 28, 1976 to Nicol, et al. ~ ~ .
Soil release agents charaeterized by poly(~rinyl es~er) hydrophobe segments ~nclude graM copolymers of poly(~inyl ester)9 , e.g., Cl-C6 vinyl esters~ preferably poly(vinyl acetate) graft~d `~
~: 20 onto polyalkylene oxide backbones, such as polyethylene oxide backbones. See European Patent Applic~t10n 0 219 048, publ~shed i~
Apr~l 22, 1987 by Kud, et al. Commercially a~va~lable soil release ~`
: agents of this kind include the SOKALAN type of ~aiterial, e.g., SOKALAN HP-22, avail~ble from BASF (~est Germany). ~
One type of preferred soil release agent is a copol ~ er ~ .
: having random blocks of ethylene terephthalate and polyethylene ;`/~
oxide (PEoj terephthalate. The molecular weight of this poly~eric i'.
soil release agent ~s in the range of ~rom ar.sut 25,000 ~o about 55,000. See~ U.S. Patent 3,~59,230 to Hays,~issued Ma~ 25,,1976 ~.
and U.S. Patent 3,893,929 to Basadur issued July 8,~ 1975.
Another preferred polymeric soil~rel~ase agent is a polyester ;~
with repeat uni;ts of ethylene ter~phthalate units: conta~ning 10-15% by weight of ethylene terephthalat~ units togeth~r with 90-8~Z by wei~ht of polyoxyethylene terephthalate un~ts, derived ~rom a polyoxyethylene glyool ~f averag~ molecular weight `:-300-5,0004 Examples of this polymer include the con~nercially ,~
, WO 94/12610 PCT/US93/11455:

21~8096C. . - 24 -available material ZLCON 5126 (~rom Dupont) and MILEASE T (from~
ICI). S~e also U.S~ Patent 4,702,857, issued October 279 1987 to 60ssel ink.
Another preferred pol~ymeric so~ rslease ~gent is a sul fonat~d product of a substant~a~,ly l in~ar ~ster ol igomer comprised of an ol igomeric ester ~a,ckbone of terephtha~oyl and oxyalkyleneoxy repeat unlts and`~ term~nal mo~ties covalently attached to the backbone. Thes~ soil release agents are described fully in U.S. Patent 4,968,4~ ssued Novemb~r 69 1990 to J. J~
lû Sche~bel and E. P60sselink.
Other suitable polymeric soil rele`ase agents include the terephthalate polyesters of U.S~ Patent 4,711,730, issued December 3, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S. Patent 4,721,580, issued January 26. 1988 to . 15 Gosse?ink, and the block polyester oligom~ric compounds of U.S.
Patent 4,702,857, issued October 27, 1987 t:o Gossel ink.
Preferred polymertc so~l release agents also ~nelude l:he oil release agents of U.S. Patent 4,877,8g6, issued October 3I, 1989 to Maldonado et al, wh~ch discloses anionic, especiatly sulfo-aroyl, end-capped terephthalate esters.
If utiliz~d, soil releas~ agents will g~nerally comprise from about 0.01X to about 10.0%, by weight, of the detQrgent composi-tions here1n, typically from absut 0.1% to ~boult 5X, pref~rably from sbout 0.2% to ~bout 3.0%. ~
~L~g~ - The deter~ent co~posltions herein may alsa optionally contain one or more: iron and/or :manganese chelatirlg agents . Such chel ating agents can b~ sel ected from the ~roup cons~st~ny of amino carboxylates, amino phosphonates, polyfunctionally-substitut~d aromatic chelatilng agentsl and mixtures therein, all as hereinafîer defined. ~l~thout intending to be bound by theory9 it is believed that the benefit o~ these materials is due in part to their exceptional a~ility to remove iron and manganes~ ions from washing solutions by formation of sol ubl e chel ates .
Amino carboxylates useful as optional chelating agents include ethylenedia~inetetraacetates, N-hydroxyethylethylenedi~
aminetriacetates, nitrilotriacetates, ethylenediamin~ tetrapropri-onates, triethylenetetraaminehexaacetates, diethylenetriamine-~ .

``'10 94/12610 21 ~L 8 0 9 6 PCT/U593/114$5 ~ - 25 -pentaacetal;es, and ethanoldiglyeines, alkali metal 9 a~nonium, and subst~tuted an~nonium salts therein and mixtures therein.
Anino phosphonates are also suitable for use as chelating agents in the compos~tions of the invention when at least low levels of total phosphorus are permitted in detergent composi^
tions, and include ethylenedianlinetetrakis ~methylenephosphon-ates)9 nitrllotris (~ethylenephosphonates) and diethylenetriam~ne-pentakis (methylenephosphonates). Preferably, these amino phos-phonates do not contain alkyl or alkenyl groups w~th more than I 10 about 6 earbon atomsO
¦ Polyfunctionally-substituted aromat k chelating agents are ¦ also useful in the somposltions herein. See U.S. Patent 3,812,044, issued May 21, 19747 to Connor et al. Preferred compounds of this type in acid form ar~ dihydroxydisulfobenzenes . 15 such as 1,2-dihydroxy -3,5-disulfobenzene.
A pref~rred biodegradable chelator for use here~n is ethyl-enediamine disuc~inate (nEDDS~), as descr~bed in U.S~ Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
If ut~lized, these chelating agents w~ll generally comprise from about 0.1% to about 10~ by weight of the detergent composi-tions herein. More preferably9 if utilized, the chelating agents wi11 comprise from about 0.1% to a~out 3.0% by weight of such compQsitions.
y ~ ~ ~ - The compositions 2S of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil remo~al and anti-redeposition properties. Granular detergent compositlons which cont~in these compounds ~ypically contain from about 0.01% to about 10.0Z by.
~ weight of the water-sol~ble ethoxylated a~ines; liquidl d~ter~nt 3Q compositions typically contain about 0.01% to about 5%.
Th~ most:preferred soil: r~lease and anti-redeposition agent is ethoxylated tet~aethylenepentamine. ~xe~plary etho%ylated amines are f~rther described in U.S. Patent 4,5~7,8989 YanderMeer, issued July 1,~:19B6. Another group of preferred clay soll removal/antiredepositinn agen~s are the catiDnic coRlpoullds dis-closed ~n EIJropean~ Patent Application 111,965, Oh and Gosselink, published June 27, 1984. Other clay soil remoYal/anti7edeposition agents whieh can be used include the ethoxylated amine polymers .

W094tl2610 ~ 8096 PCT/IJS93/11455 h~ - 26 -disclosed in European Patent Application 111,984, Gosselink, published June 27, 1934; the zwitterionic polymers d~sclosed in European Patent Application 1127592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S. Pa~ent 4~5487744, ~onnor, issued October 22, 1985. Other clay soil removal and/or anti redeposition agents known in~h~ art can also be utilized in the compositions herein. Another type of preferred anti-redeposition agent includes the carboxy methyl cellulose (CMC~
materials. Thes~ materials are well known in the ~rt.
e5~Ye~ L~s~s~ Pnlymeric d~spersing agents ean advantageously be utilized at levels from about 0.1X to about 7X, by weight, in the compositions herein. Thase materials can also aid in cak ium and magnesium hardness control. Suitable poly~eric dispersiRg agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be ~sed. It is believed, though ~t is not intended to be limit~d by theory, that polymer~c dispersing ~gents enhance over~ll detergent builder perfo~mance, ~hen used in combination with other builders (including lower molecular weight polycarboxylates) by crystal 20 growth inhibition, particulate soil release peptization, and anti-redeposition.
Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable u~saturated mononlers, preferably in their acid forR~. Unsaturated monomeric acids that can be pollymerized to farm suitabl~ polymeri~ polycarboxylates include acryl ic acid, Inaleic acid ~or mal~ic anhydride), fumark acid, ~taconie acid, aconitic acid, mes~c~nic acid, citraconic acid and methylenemalonic acid. The presence in the polymeric polycarboxylates herein of ~anomeric seg~ents,, containing no carboxylate radicals such as vir,ylmethyl ether, styrene, ethylel)e, etc. is suitable proYided that such segments do not corlstitute more than about 40X by weight.
Particularly su~table polymeric polycarboxylates can be dertved from acrylic acid. Such acrylic aeid-based polyners which are useful herein are ths water-soluble salts of polymerized acrylic acidO The aver~ge molecular weight of such polymers ifl the acid ~orm prefe~ably ranges ~rom about 2,t)ûO to 10~0~0, more preferably from about 4,000 to 7,-0~0 and most preferab~y from ~VO 94/12610 214 8 0 9 ~ PCT/US93/11455 .

about 4,000 to 5,000. ~ater-soluble salts of such acrylic acid polymers can include, for example9 the alkali metal, ammonium and substi~uted ammvnium salts. Soluble polymers of this type are known mat@rials. Us~ of polyacrylates of this type in deter~ent composlttons has be~n disclosed, for example, in Diehl, U.S, Patent 3,308,~679 issued March 7, 1967.
Acryl k/maleic-based copolymers ~ay also be used as a preferred component of the dispersing/anti-redepos~tion agent.
Such materials include thg water-solu~le salts of cspolymers of acrylic acid and maleic aci~. The average molecular weight of such copolymers in the acid form pr~ferably ranges. from about 2,000 to 100,000, more preferably fro~ about 5~000 to 75,000, most preferably from about: 7,000 to 65,~00. The ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about l:l, more preferably from about 10:1 to 2~
~ater-soluble salts o~ such ~crylic actd/maleis acid copolymers can inc7ude, h r example, the alkali ~tal, am~oniu~ and subst~tuted am~onium salts. Soluble acrylate~aleate copolymers of this type are known materials which are described in European , 20 Patent Application No. 66915, published ~ecember 15, 1982.
j Another polymeric materi~l whieh can be included is poly-ethylene glycol (PEG). PEG can exhibit dispersing aggnt perf~rm-ance as well as act as a clay soil renovall~nt~redep~sition agent.
Typical ~olecular weight ranges for these purposes range fr~m about 500 to about 100,0009 preferably fro~ about 1,000 to about 50,0007 more preferably from about l,S00 to about 109000.
Polyaspartate and polyglutamate dispersing a~ents may also be used, especially in-conjunction with zcolite builders.
5r~htener - Any opkical brighteners or other briglhtening or whitening agènts known ~n the art can be incorporated ~t leYels typically ~ro~ about 0.05% to about 1.2%, by weight, into the detergent compositioQs herein. Commergial optical` brighteners *hich may be useful in the pr@sent invention can be classifiad into subgroups which inc~ude, but are not necessarily limited to~
~5 derivatives of s~ilbe~e, pyrazoline, coumarin~ carboxylic acid~
~ethinecyanines, dibenzothiphene-575-dioxide, azo~es, 5- and .6-membered-ring heterocycles, and other ~iscellaneous ag@nts.
Examples oF such brighteners are diselosed in ~The Production and WO 94/12610 . PCT/US93/11455 2~ ~80 - o - 28 -App~ication of Fluorescent Brightening Agents~, M. Zahradnik, Published by John Wiley & Sons~ New York (1982).
Spec~fic examples o~ optieal brighteners which are useful in the present compositions are those ~tentified in U.S. Patent 4,790,856~ issued to ~ixon on December 13, 1988. These brighten-ers include the PHORWHI~E series;;~f brighteners from Verona.
Other brighteners disclosed in th~s~ ref~rence incl~d~: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; ~vailable from Ciba-6eigy;
Arct~c ~hite CC and Artic ~hite CWD, a~ailable fro~ H~lton-Davis, located in Italy; the 2-(4-styryl-ph~nyl)~2H- naphthol[1,2-d]-triazoles; 4,4'-bis- (1,2,3-triazol-2-yl)-st~l- benes; 4,4'-bis-(styryl)bisphe~yls; and the y-aminocoumarins. Specific e%amples of these~brighteners include 4-methyl-7-diethyl- amino coumarin;
1,2-bis(-benzimidazol-2-yl3ethylene; 1~3-diphenylphrazolines, 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-naphth-~1,2-d~oxazol@;
and 2-(stllbene-4-yl)-2H-naphtho- [1,2-dl~r~azole. See also U.S.
Patent 3,646~015, issued February ~99 1972 to Ham~lton. -~
~b~ 5 e.l::~5~r5 - ~ompounds for r~ducing or suppr~s~ng the formation of suds can be incorporated ~nto the co~pos~tion$ of the present tnv0nt~0n. The ~ncorporation of such mater7als, herein-after ~su~s suppr~ssors,~ can be desirab7e to further reduce the already-low sudsing of the mixed nonionic/anionic surfactants herein. Additional suds suppression can be of part~cular i~port-ance when the detergent compos~tione hergin optionally inelude a : ~ 25 relatively high s~dsin9 surfa~tant in co~bination ~lth th~ low-sudsing m~xed nonionic/anionic s~rfactants of th~s lnvgnt~on.
A wide var1ety of materials ~ay be used as suds suppressors9 and suds suppressQrs.are ~ell known to those sk~lled in the art.
See, ~or example, Kirk Othmer Encycloped~a of Chemical Technologyt Third Ed~tion, Volume 7, pages 430-447 (John Wiley ~ Sons, Inc., 1979). One~ cat~gory of suds suppressor of particular interest encompasses monocarboxylic fatty aci~s an~ soluble salts th~rein.
See U.S. Patent 2,9S4,347, issued September 279 1960 to ~ayne St.
John. The ~onocar~oxyl~k fatty acids and salts ther~of us~d as :~ ~ 35 suds suppressor typically haYe hydrocarbyl chains of 10 ~o about 24 carb~n atoms9 preferably 12 to }8 car~on atoms. Su~table salts include the alkali metal salts suoh as sodium, potassium, and ~; ~ lithium salts,. and ammonium and alkanola~monium salts.

~-~WO 94/12610 2 1 ~ 8 0 9 6 rCT/U593/11455 ;

~ - 29 - .
The detergent compositions herein n~ay also cont~in non- 6 -~:
surfactant suds suppressors. These inelude, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.~., fatty acid tri~lyc~rides~, fatty ac~d esters of monovalent alcohols, al~phatic Cl~-C4~ ketones (e.g. stearone), etc. Other suds inh~b1tors include H-alkylated amino triazines such as tri-to hexa-~lkylmelamines or di to tetra-alkyldtamine ehlortriazines formed as products of cyanuric chloride with two or three moles of a pr~ary or secondary amine ~ontain~ng 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and ~onostearyl di~alkal~ metal ~e.g. K, Na, and L~ ) phosph~tes and phosphate esters. The hydrocarbons such 3S paraffin and haloparaffin can be utilized ~n liquid form.
. The 1 iquid hydrocarbons will be 1 iquid at room tempera$llre and atmospheric pressure, and will have a pour point in the range o~
about -409C and about 5~C, and a minimum boiling point not less than about 110~C (atmospheric pressure3. It is also known to ut~l ize waxy hydrocarbons, preferrably having a melting point bel ow about 100-C. The hydrocarbons constitute a ~r~ferred category of suds supprèssor for deltergent eomposit~ons.
Hydrocarbon suds suppressors are describsd, for example9 in U.S.
Paîent 4, 265, 779, i ssued May 5, 1981 to Gandol fo et al . The . hydrocarbons, thus, incl ud~ al iphatiG, al icycl ic, aromatic, and heterocycl i c saturated or unsaturated hydrocarbons havi ng ~ro~
about 12 to about 70 carbon atoms. The term ~paraffln,~ as used ~n this suds ~uppressor discussion, is ~ntended to i~clllde mixtur~s of true paraffins and cyclic hydrocarborls.
Another pref~rred category of non-surfactarlt suds suppressors comprises s~licone suds suppressors. This category ijncludes the ' 1 ` 30 use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins9 and combinations of polyorg`anosiloxan~ with silica particles wherein the polyorganosiloxane is chemisorbed of fused onto the silica.
Silicone sllds: suppressors are well known in the art and are9 for example9 disclose~ in lJ.S. Patent 4,265,779, issued May 5" 1981 to ~andolfo et al and European Paten~ Application No. 89307851.9, published February 77 1990, by Starch, M. S.

~,~,'.'.''"~"' '' '........ ....... .; ' ' WO g4112610 PCTIUS93/11455 - ~
2 ~ ~ 8 0 Other silicone suds suppressors are disclosed in U.S. Patent 3j455,839 which relates to compositions and processes for defoam-~ng aqueous solutions by incorporating therein small amounts of polyd~thylsiloxane fluids.
Mixtures of sil icone and silanated sil ica are described, for ~nstanee, in Gernlan Patent Appl ication DOS 2,1247526. Sil icone defoamers and suds controll~ng .agents in granular detergent compositions are disclosed in U.S. Patent 3,9~39672, Bartolotta et at9 and in U.SO Patent 4,652,392, Baginsk~ et al, issu~d March 24, 1987.
An exemplary s~licone based suds suppress~r for use herein is a suds s~ppressing anlount of a suds controlling agent cvnsisting es entially of: ~
(i) polydimethylsiloxane fluid having a viseosity of from , 15 about 20 cs. to about lSOO cs. at 25-C;
. (~3 from: about 5 to about 50 parts per 100 parts by we~ght of (i) ~f siloxane res~n composed of ~CH3~3 S~01/2 untts ~: of S~02 un~ts in a ratio of from (CH3)~ SiO1/2 un~ts and to SiO2 un~ts of from about û.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 preferred silkone suds suppressor used herein, the solvent for a continuous phase ~is made up of certain polyethylene glycols or po~yethylene-polypropylene glycol oopolymers or : 25mixturss thereof ~preferred~, :and not polypropylene glycol. The ~:: prima~y sil~cone suds~ suppressor is branch~d/crossl~nked and not near.
To illustrate this point further~ typical liqu~d l~undry detergent composit~ons with controlled~ suds will ! optio,nally 3~comprise from:about O.OQ1 to about 1, preferably fro~ about 0~01 :~:: to about 3O7, most preferably~from abut 0c05 ts about 0.5, weight X of said~ silicone suds suppressor, whieh comprises ~1) a non-aqueous emulsion of a primary ant~foam agent which is a mlxtur@ of a~ a polyorganosiloxane,~ (b) a resinous siloxane or a s~l icone :~: 35resin-produciny sil icone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reac~ion of miatture ~: components (a), (b) and (c), to fora silanolates; (2~ at least one nonionic sil icone surfactant; and (3) polyethylene glycol or a 21~8~9~ `
~~wo 94/126~ /USg3/11455 *. - 31 -copolymer of polyethylene-polypropylene glycol havin~ a solubility in water at rooM temperature of more than about 2 weight X; and without polypropylene glycol. Simitar amounts can be used in granul ar co~positions, ~els? etc.See al so UOS. Patents 4~978,471, Starch, issued December18, 1990, and 4,983,316, Starch, issu~d Januar~y 8, 1991, and U.S. Patents 4,639,489 and ~, 749 . 740, Ai awa et al at col umn 1, l i ne 46 through col umn 4, line 35.
The silicone suds suppressor herein pref@rably comprises polyethylene glycQl and a copolymer of polyethylene glycol/poly~
propylene glycol, all ha~ing an average molecular ~eight of less than about 1,000, preferably bet~een about 1ûû and 800. The polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature ~f more than lS about 2 weight ~, preferably Inore than about 5 weight %.
The preferred so~vent herein ~s polyethylene glycol having an average ~oleoular we~ght of less than about 1,000, more preferably - between about 100 and 800, most preferably batween 230 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, ~o preferably PP6 200/PEG 300. Preferred is a weight ratio of between about 1:1 and 1:10, ~ost prefer~bly between 1:3 and 1:6, of polyethylene glyeol :copolymer of polyethylene-polypropylene glycol .
The preferred sil icolle suds suppressors used herein do not contain polypropylene glycol, particul2rly of 47000 Ç~lOlgClllar weight. They~ also prelFerably do not contain block copolymers of ethylene oxide and propylsne oxide, like PLURONIC L1~1.
- Other suds suppressors useful here~n eolnprise ths secondary akohols (e 9-, ?-alkyl alkallols~ and mixtures of such alçohols with silicone oils, such as the silicones disclQsed in U.S.
4,798,679, 4,075,118 and EP 15û7872. The seeordary alcohols include the C~-C16 alkyl alcohols having a G1-C16 chain. A
preferred al cohol i s 2-butyl octanQl, whi ch i s avai 1 abl e ~rom Condea under the tradema~k ISOFOL 12. Mixtures of sscondary alcohols are availabls under the trademark ISALCliEM 123 from Enichem. Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1:5 to 5:1.

WO 94/12~1~ PCT/US93/11455 - ~
2~ 1~8 ~ 9 ~ - 32 -For any detergent cnmpositions to be used in automatic laundry washing machines9 suds should not form to the extent that they overflow the washiny machine. Suds suppressors, when utilized, are preferably present in;:a asuds suppressing amount. N
By ~suds suppressing amount~ is~m~ea~t that the formulator o~ the composition can select an amount of this suds controlling agent that will sufficiefltly control the suds to result in a low-sudsing laundry detergent for use in automat~c laundry washing machines.
The compos~tions h~rein will generally comprise from ~% to about 5% of suds suppressar. When utilized as suds suppressors, . monocarboxylic fatty acids, and salts therein, will be present i typically in amounts up to ~bout 5%, by weight, of the detergent .
composition. Preferably, fro~ about 0.5% to about 3X of fatty monocarboxylate suds suppressor is util~zed. Silicone suds suppressors are typically uti~ized in amounts up to about 2.&Z, by I ~eight, of the detergent composition, although higher amounts may ! be used. Thi~ upper limit is practical in nature, due primarly to concern with keeping costs minimized and e~fectiveness of lower amounts for effectively controlling sudsing. Preferably fro~
about O.OlX to about 1% of silicone suds suppressor is used, ~ore preferably from about 0~25~ to about n.sx. As used herein, these weight percQntage values include any silica that may be util ked in comb~nation with polyorganosiloxane, as well as any adjunct materials that may be utilize~. Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from about 0.1% to about 2~, by weight, of the compositlon. ~ydrocarbon suds suppressors~are typically utiliYed~in amounts ranging from about 0.01% to about S.~%, although htgher levels can be used.
; In addition to the foregoing i~gred1ents which: are generallyemployed in fabric laundry~ dishwashing and hard surface cleaners or cleansing and sanitizing purposes, the sur~ac~ant compositions here~n can also be used with~a~:variety of other adjunct ingredi-:~ ents which~ provide still other benefits in various compositions within the scope of this invention. The follow~ng illustrates a : 35 variety of: such adjunct ingredients, but is not intended to be limiting therei~n.
: Fabric So~L~ Varinus through-the-wash fabric softeners, ~` especia~ly the impalpable s~ectite tlays of U.S. Patent 4~062,647, 21~8096 ";VO 94/12610 PCT/IJS93/11455 ~ - 33 -r Storm and Ni rschl, i ssued Deeember 13 , 1977 , as wel l as other softener elays known in the art, can be used typically at levels o~ ~rom about 0.5Y. ~o about 10X by weight in ~he present eomposi-tions tn provide fabric softener benef1ts concurrently with fabric eleaning. The polyhydroxy fatty acid a~ides of the present invention eause less int2rferenee with the softening performance of the clay than do the co~non polyethylene oxide nonio~ic sur-factants of the art. Clay so~teners can be used in combination with amine and cationic softeners" as disclDsed, for example, in U.S. Patent 4,375,416, Crisp et al, March 1, 1983 and ll.S. Patent 4,291,071" Harris et al, issued September 22, 1981.
Hair Care_ Ingredients - Shan3poo compositions formulatcd in the manner of this invention can contain froln about 0.05% to a~out 10% by weight of various ayents such as: conditionQrs, e.97, silicones (see, for example, U~S. Patents 4~152,416 and 4,364,847); antidandruf~ agents such as the pyridlinethiones, espeeially zinc pyrid~nethionè ~see U.S. Patents 4,379,753 and 4,345,0~0)9 selen~um compounds such as selenium sulfide and OCTOPIR0X; hair styling polyners (see U.S. Patents 4,01?,501 and 4,272,511~; and pedklllicides (anti-lice agents) such as LINDANE
and various p~rethrins ~see Br~tish Patent 17593,601 and U.S~
Patent 4,668,666) .
b~gr~: (e~ts - A wide variety of other ingredients . useful in detergent compositions can be included in the c~mpositions herelin, including other active ingredients, carriers, hydrotrapes9 processing aids, dyej or pi~ments, solvents for 1 i qui d formul ati ons, etc .
Various d~tersive ingredients employQd in the present co~positions adv~ntageously can be stabilized b~ abs~rbing 1 said insredients onto a porous hydrophobic su~strate, then co~ting said substratg wtth a hydrophobic coating. Preferably, the detersive ingredient is admixed wtth a sur~actant before being absorbed into the porous substrate. In use, the detersive ingredient is released froln the substrate into the aqueous washing liquor, where it performs its intended detersiYe functiollO
To illustrate this technique in more detail, a porous hydro-phobic silica (trademark SIPERNAT D10, DeGussa~ is admixed with a -proteolytie enzyme solution containing 3%-5~ of C13 15 ethoxylated WO 94112610 21 ~ 8 0 9 6 PCT/US93tll455 ;

alcohol E0(7) nonionic surfactant. Typically, the enzyme/surfact-ant solution is 2.5 X the weight of silica. The resll~ting powder is disp~nsed w~th stirring in sil~cone oil (various sil~cone oil viscos~ties in the range of 50~-12,500 can b~ used). The result-ing s~l icone oil dlspersion ~s emuls~fied or otherwise added to the final detergent matrix. By this;~:n~eans, ~ngredients such as the aforement~oned enzymes, bleaGh~, bleach actiwators, bleach catalysts, photoact~Yators, dyes, ~luorescers, fabric conditioners and hydrolyzable surfactants can be protectedb for use in deter-gents, ~ncllading l~qu~d laundry detergent so~posltions.
Liquid d~tergent compositions can contain wate~ and other solvents as carriers. Low molecular we1ght primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are preferred for . ~ 15 solubilizing surfacta1lt, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3~pr~panediol, ethylene :glycol ~ glycer~ne, and 1,2-propanediol) can also be used.
EQ~!~ - The fonnulation of effective, Insdern detergent . 20 compositions ~poses a considerable chal}enge, especially in the absence of phosphate bu~lders. For fabric launder~ng, the . formulator is required to address the removal o~ a wide variety of :~
soils and stains, many of which are terRad ~greasy/oily~ soils~
such as- foods, cos~etics, motor oil9 and the llke, from a wide ~ : 25 variaty of fabric surfaces and under ~ spectrum of usage eondi-: tions, ranging fro~ boil wash temperatures preferred by som~ users to l aundering temperatures as cold as S-C preferred by others .
Local factors,~ esp@cial7y water hardness levels ~nd the presence or absenc~ of metal cations such as iron in llæcal ~ash ~ater - 3a suppii~s~ can dramatically impaet detergency performance. Like-wise, th2 ~ormulator of hand dishwashing comp~sitions ~nus~ provide ~ :~ compositions whish re~nove high loads of:greasy food res~dues, but : ~ ` which do: so: under: conditions~ which are not irr~tating to the use~'s :skin nor damaging to the arttcles being washed. It ~s 35 especially d1ffieult to provide good grease removal at near neutral pHis.
It w;ll~:~: be appreciated by the formulators of det~rgent compos~tions~that, at suf~iciently low interf~cial ~ensions~ it is .
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--~ WO 94/12610 ~ 1 1 8 0 9 6 PCT/US93/11455 ~. - 35 -theoretically pnssible to provide what ~ight be tenned "spontane-ous emulsification" of greasy/oily soil. If such spontaneous emulstfication were to be secur~d, it would very considerably enhance greas~toi 1 removal from substrates such as fabri cs, dishwar~, enYironmental hard surfaces, and the likeO ~Ihile extremely low interfaoial tensions and, presumably, spontaneous emlllsificat~on, have possibly been achievable ~ith spec~alized surfactants such as the fluorinated surfaetants known in the art, the present invention provides a new~ mild surfactant system to . 10 achieve th~s desirable result. Moreover, spofltaneous emul sifica-tion may be achievable w~h some spectalized surfactants only at relatiYely high pH's in the range of 10-11, whereas this deslrable result is also achievable with the present compositions ev~n in the. near-neutral pH range of about 7-9, as well as from 9-11.
This is particularly iRlportant for hand-washing ~perations, for examp~e, hand dishwashing, where skin mildness is of concern to the user.
The polyhydroxy fatty acid amides employed in the practice of ~h~s invention are, str~c~urally, nonionie-type surfactants and are refer~ed to herein as ~n~elionics". It now appears that the conformation o~ the polyhydro%y fatty ~cid amide ~nay be changed due to interaetion between water hardness ions, esp~lally calcium cations, and the soap or anionic $ur~actant. This ~ay increase the molecular packing of the polyhydroxy fatty acid amides at the a~r/water interface. ~Jhatev@r the explanation at the ~olecular level, the net :result is the lower interfacial tensiQns and i~proved cl~anin~ bebefits wh~ch are assoeiated w~th the composi-~ons of this invention, especially with respect to ren~oval of greasy 50ils.
While the presence of calcium ions improves the grease/oil re~oval performance of the compositions, the presQnce of magnesiu~
ions provides increased suds level~. Inasmuch as ~ost consumers have eome to expe~t high suds l evel s i n hand-wash products, especially hand dtshwashing compositions, lthe form~lator may advantageously employ both calcium and ma~nesium ions in such compositions to ~rovide dual cleaning/sudsing beneflts~ If lower-sudsing ~ompositions are desired, thg ~agnesium ions may b~
del eted .

WO94/12610 ~ o96 PC'rlU593/1145; `~

Calcium and magnesium ions, if used, can be incorporated into~
the present ecmpositions in the form of their chloride, sulfate, bromide, formate, aoetate, malate, or maleate salts, or as salts of anionic hydrotropes or ahionic surfactants. Usage levels are S typioally from about 0.5% to`about 2% of the total compositions.
~hen such cati~ns are d~esired to be present, and if a builder is prasent, it is preferr~ that the builder be a non-phosphate builder suoh as citrate, zeolite or layered silicate.
It will ~urther be appr~iated that, while the salcium and/or optional magnesium ions may be ~ncorporated into the compositions herein, the formulator may determine that it is acoeptable prac-tice to rely on natural water hardness to provide such ions to the compositions under in-use situations. This may be a reasonable expedient, since :as little as 2 gr/gal calcium hardness can lS provide substantial benefi~s. However9 the formulator will most likely decide to add: the cakium and/or sptional~ agnes~um ions diractly to the compositions, thereby assuring their presence in ~- the i~-use situation. Under suoh circumstances, and especially when formulating liquid products wherein the presence of : ~ 20 precipitates may be undesirable, it may be preferrQd to add the calcium and/or rflagnesium ~o the composit~oris ~n the form of a .;. li~htly complexed chelate, such as cakium malate or maleata, magnesium malate or maleate, or the like.
The det~rgent com~ositions herein will preferably be formulated such th~t tluring use in aqueous clean~ng operations, : the wash water will hav~ a pH of between abollt 6.5 and about 11, ~: . preferably ~between about 7.0 and about 1û.5.~ Llq~Jid product formulations preferably have a pH between abou~ 7.S and about 9.S,.
ore p~efe~ab~y~between about 7.5 and labout ~9.~. Te~hn:iq~s for c~ntroll:ing pH at recommended usage levels include the use of buffers~ alkal~s, acids, ~t~., and:are well known ~o ~hose sk~ d in the art.
The ;following are typical, non7imiting examples wh k h :
illustrate: the: use o~ the mixed nonionie/anionic surfactant systems provided ~y this~ invention to prepare fully-formulated detergent composi t~i ons .

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--~WO 94/12610 2 I ~ 8 0 9 6 PCT/US93/114~

. s '' A liquid detergent composition herein comprises ~he following.
, . ~ ~ '.'.
: 5 Nonionic/anionic* 15.0 ;
Laurate, Na 5.0 ;-Sodium citrate 1.~
C1o alcohol ethoxylate (3) 13.0 I ~onoethanolamine 2.5~ater/propylene glycollethanol (100~ alance *1:1 mixture of coconutalkyl N-methyl glucamide and its sulfated counterpart surfactant.
EXAMPLE II
A granular detergent herein comprises the following.
Ing~edient Noni~nic~anionic* 1D.O
Laurate, Na 5.0 Zeolite A (1 10 ~icrometer) 30.0 Sodium citrate 10.0 Sodium carbonatc 20.0 Optical brightener o.i Detersive enzyme~* 1.0 C12 14 alkyl sulfate, Na. 5.0 Sodium sulfate 15.0 : 2S Water and minors . Balance *1:1 m~xture of tallowalkyl N~methyl gluca~ide and ~ts sulfated counterpart sur~actant~ Na sa~t.
**Lipolytic enzyme preparation (LIPOLASE).
, , , ~ I l The co~positions of Example I and I~ are each modifiQd by including Q.5% ~of ~a com~ercial proteolytic enzy~e preparation ~ (ESPERASE) therein:, Option~lly~ 005% of a com~ercial amylase : preparation (TE ~ YL) and~ 0.5X of a commercial lipolytic enzyMe preparation 5LIPOLASE) can be co-incorporated in such liquid and 3S solid detergent co~pos~tions. The composition of Example III can : be further:improved by the a~dition of 1.2% CaCl2.

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WO 94/12610 ` PCTlUS93tll45 o96 38-EXAMPlE IV
A di shwashi ng composi ti on wi th high grease removal properti esis as follows..

Nonionic/anionic* 20.0 Undecanoic acid 4.~
C12 sulfobetaine*~ 5.0 . Coconut ~onoethanolamid~ : 1.0 Water - Bal ance *Cl~-Cl,~ fatty acid amide of N-nlethyl glucamine or N-Qthyl fructamine, sulfatet to~; provide a 3:1 nonionic:sulfa~ed anionic mixture and neutralized partly with MgS04 and:partly with NaOH to provide an over Mg content in finished detergent compositions of 1. 6%.
. **Suds boosting surfactant aka ~sultaine~.
E~EL~Y , A sha~poo compos1tion is p~epared:accord~ing to Example IV by deleting the magnestu~ ~ons.
: It has also;now been deter~ined that the prPsent co~positions : : ; ~ 20 are :esp~cial:ly use~ul for remoYing :cos~etic stains from fabrics.
~: ~ ~ :: ; This is an especially important technical imprDvem~nt in d~ter-~ ~` gency performance. Cosmctics, or ~acîal "make-upff, lipstick and ` : the like, typ~cally~compr~se a;complex~ mixture of ~inely-ground, ~; h~ghly ~olored ~particulate~matertal which is intimately admixed ~:: : ~5with a greasy or waxy~carrier.:~ Cosmett~cs are spee~ically formu-:~ ~: lat~d to re~ain~on the~:surface to wh:ich:they~are applied, and:~or ;~ thts reason ~the~r~ carriers ~ are :w~ter-~nsoluble and/or water ;~ ~ repellent. ~As is wel~l-known, once a lipstick ~r other cosmetic:
smear is established on a ~abric, ~ts re~oval can prove exltrie~nely~
30 ~ : difficult.~By~comparison, the remoYal~ of cosmetic stains: ~rom fabrics::is~substan~ially~:;more:;d~icult than is ~h~ r~moval of common grea~sy:stains:such~as~lard.~ Compositions accordi~ng to the present~invention~:which ~add~tiona11y eomprise from about lX to about: 2~%~by:we1ght ~of an::ethoxy1ated (E0~ 7; prefera~ly 2 3~
35 ~ :C12~ g~ al~cohol :~or:alkyl ~phenol are preferably used ;n su~h :: formu1at1Ons~ to further boost performanceO

WO 9~/12610 - PCT/US93/11455 The fore~oing disclosure and Examples illustrate the practice of this invention in eonsiderable detail. It is to be appreci-ated, however, that the advan~ages afforded by the compositions and processes of this invention are broadly useful with a variety of other technologies which have been de~eloped for use in a wide va~iety of mvdern, fully-fo~flulated cleaning compositions, espe-cial~y laundry detergents~ The compositions herein will typically be used in aqueous media at coneentrations of at least about 200 ppm, e.g., for lightly-soil~d fabrics and/or hand dishwashing.
Higher usage concentrations in the range of ltOOO ppm to B9009 ppm, and h~gher, are used for heavily-soiled fabrics. However, usage levels can vary, depending on the desires of the user, soil loads, soil` types, and the like. Wash temperatures ean rangP from 5-~ to the b~il. . .

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Claims (7)

WHAT IS CLAIMED IS:

1. A detergent composition comprising a mixed nonionic/anionic/-soap surfactant system which comprises a polyhydroxy fatty acid amide (a) of the formula wherein R1 is H, C1-C8 hydrocarbyl, 2-hydroxyethyl, 2-hydroxy-propyl, or a mixture therein, R2 is C5-C32 hydrocarbyl, a Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least two hydroxyls directly connected to the chain; and (b) an anionic surfactant which is a member selected from the group consisting of sulfated polyhydroxy fatty acid amides of said formula (a), at a weight ratio of (a):(b) of from about 10:1 to about 1:10; and (c) a soap.

2. A composition according to Claim 1 which contains at least about 10% by weight of said mixed surfactant system.

3. A composition according to Claim 2 which additionally contains from about 2% to about 40% by weight of an additional detersive surfactant.

4. A composition according to Claim 3 wherein the additional surfactant comprises an alkoxylated alcohol or alkoxylated alkyl phenol.

5. A composition according to Claim 1 which comprises from about 15% to about 50% by weight of said mixed nonionic/anionic/soap surfactant system, from about 1% to about 10% by weight of an ethoxylated C8-C24 alcohol, and optional builders and detersive enzymes.

6. A method for removing cosmetic stains from fabrics, compris-ing contacting the fabrics thus stained with an aqueous bath containing at least about 0.05% by weight of a composition which comprises a mixed nonionic/anionic/soap surfactant system which comprises:

wherein R1 is H, C1-C8 hydrocarbyl, 2-hydroxyethyl, 2-hydroxy-propyl, or a mixture therein, R2 is C5-C32 hydrocarbyl, a Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least two hydroxyls directly connected to the chain; and (b) an anionic surfactant which is a member selected from the group consisting of sulfated polyhydroxy fatty acid amides of said formula (a), at a weight ratio of (a):(b) of from about 10:1 to about 1:10;
(c) a soap; and (d) optionally, an alkoxylated C8-C24 alcohol or alkoxylated C8-C24 alkyl phenyl.

7. A method for removing soils and stains from solid substrates such as fabrics, dishware and the like, comprising contacting said substrates with a composition according to Claim 1 in the presence of water.