CA2148097A1 - Cleaning with low-sudsing mixed polyhydroxy fatty acid amide nonionic/anionic surfactants - Google Patents

Abstract

Mixed nonionic/anionic surfactants which comprise polyhydroxy fatty acid amides and their sulfated analogs are used in various cleaning functions where low sudsing is desired. 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 exhibit good cleaning of fabrics, dishware, skin and hair.

Description

~WO 94/12~98 2 I q 8 0 9 7 PCT/US93/11451 - ! -1- ~ .
CLEANING WITH LOW-SVDSING MIXED POLYHYDROXY
FATTY ACID PMIDE NONI~NIC/ANIONIC SURFAGTA~TS

,, ~e{~
The present inYention relates to cl~aning compusitions and methods which employ low sudsing detergent mixtures comprising a 1~ nonionic surfaetant and an anionic surfactant~ both of which are prepared from mainly renewable resourc~s such as fatty esters and reducing sugars.

Most conventional detergen~ compositions eontain mixtures of various detersiYe surfactants in order to re~ove a wide variety of soils and stains from surfaces. for ~xample, various anionic s~rfaotants, especially the alkyl benzene sulfonates, are useful for removing particulate so~ls,~and var~ous nonionic surfactants, such as the alkyl ethoxylates and alkylphenol ethoxylates are ~seful ~or removing greasy soils. Accordingly, ~ixtures of anionic and no~ionic surfactants are used in many modern detergent composition~. Unfortunate~y, ~any such surfactants are prepared mainly from petrochem~cal ~eeds~oek ~hile a review of the literature would seem to suggest that a : 25 wide selection of surfactants is~ av~jlable to the de~ergent manufacturer, the r~ality is that ~any such materials are : sp~ialty che~icals which are not su~table for routine use in low `~ unit cost i~ems such as home laundering compos~tions. ~he fact :~ remains that ~ost~home-use detergents still c~mprise one or ~ore of the conventional ethoxylated nonionic and sul~ated or sulfonat!ed anionic sur~actants, presumably due to ~he econo~ic and per~ormance considerations ~oted below. ~ ~
Considerable attention has lately been directed to nonionic :~ surfactants whic~. can be prepared ~sin~ mainly renewable : 35 r~sources~ such as fatty ~cid esters and sugars. One such class ~; of surfactants comprises the polyhydroxy fat~y acid amides.
: Moneover, the combination of such ~onionic surfactants with : conYentional anion~c surf~ctants such as the alkyl sulfates, alkyl WO 94/1:~598 PCT/US93/11451 21~8097 benzene sulfona,tes, ~lky~ ether sulfates, and the like, has also been studied.
The formulation of mixed nonionic/anionic surfactant systems general~y requires quite different raw materials, with attendant extra c~sts in storage, handling and manufacturing with respect to the individual nonionic and anionic surfactant components.
Accordingly, once capital has~A:been invested to manufacture and handle a given type of surfactant system, it may become ecsnomic-ally ~nattractive to change to a different surfaotant system, even in the face of other advantages that the new system might affoYd.
In 1 ight of the foregoing, it wou~d be adva~tageous to provide surfactant systems which comprise a mixture of nonionic and anionic surfactants, both of which can be prepared from r~newable, non-petrochemical resources. It would additionally be advantageous to deYise such surfactant systems which provide good detergency performance~ as compared with current formulations. It would be of considerable add~tiona,l economic advantage for such mixed nonionic/an~onic surfactant syste~s to be manufactured mainly from the same basic feedstock mater~als.
An add~tional ~actor to be considered is that the for~ulation of detergent composltions:containlng typtcal detersive surfactants usuàlly results in products whkh have, to a more or less degree, the inherent tendency to form suds when the compositions are agitated in an aqueous medium. In ~any cireumstances the . 25 formation of suds is desirable, and con,sum~rs have come to exp~ct high, r~ch suds in var~ous shampoo, personal cleans~ng and hand dishwashing compos~t~ons. On the other hand, in certain other composit~ons the presence of suds ean be problematic~ For exa~ple, most har~ surface cleansers are d~signed to have lnw suds levels, thereby obviating the `need for extensive r~nsin~ of the surfaces after the clean~er has been appl~ed~ L~kewise, so~e washing machlnes, esp~cially European-style front-loading machines ~ : which are designed to use subs~antially l~ss water than the ~ore ;~ famillar American styl~e top-loading mach~nes, typieally employ ~ ~5 higher~oncentrations of detersive surfactants. Suds levels must `~ be kept low or els~ ~the suds ean actually sp~ rom surhmachines. :A ~si~ilar~ situation occurs with most automatic ~: : dishwashing machine~ whsre sur~actant ~evels are kept Yery ~ow and .

.

suds controll ing agents are used extensively to provide a nearly sudsless cleaning of dlshware. Low sudsing can als~ be advantageous i n concentrated ~aundering processes such as those deseribed in ll.S. Patents 4,489,455 and 4,4~9,574.
Unfortunately, many of ~he potyhydroxy fatty acid amide surfactants are suds boosters and stabilizers, especially when used in combination with conventional ;anionie surfactants.
Accordingly, the formulator of low sudsing detergent compositions either must curtail the use of this desirable class of surfactants when formulating low sudsing detergents,:or must use relatively high amounts of suds cDntrolling agents in such compositions.
It has now been discovered that the combination o~ properly selecte~ nonionic polyhydroxy fat~y aeid amides with ~he`ir anionic sulfated analogs quickly and easily prov~des s~peri~r mixed nonionic/anionic surfactant syste~s which are low-sudsing, which are ~erivable from tha same feedstocks, there~y affording the ~anufacturing advantages noted above, and wh k h are ~vail~ble from renewable resources such as plants.
I ~CKGROUND ART
1 20 A method for preparing crude polyhydroxy ~atty ac;d amides ¦ (glucamides~ is deseribed in U:.S. Patent ~,985t424, Piggot~, and l ~ U.S. Patent 2,703,798, ~ch~artz; The use o~ such glucamides with v~rious synthetio anionic surfactants ~s describsd in U.S.
Patent 2,965~,576, corresponding to G.~. Patent 809,050. The : ~ 25 sulfuric esters of acylated slucamines are disclosed in U.S.
Patent 2,717,894, Schwartz.

The present inven~ n encompasses a method for cleaning surfaces with lo~ sudsing, :comprising contacting the surfaGe to be cleaned w~th an aqueous medium contaibing:: a low-sudsihg m~xed surfact3nt syste~ whieh conlprises: (a) a nonionic polyhydroxy fatty acid amide of the fon~ula: :
O Rl R~ - C - N - Z - ~ I 3 wherein Rl is C2-C~ hydrocarbyl, especially when Rl is n-propyl, is~propyl~ ~ n-butyl, isobutyl, n-pentyl, n-hexyl, cyrlohexyl, ~ ~ : : 2-ethylhexyl, and the like, or a mixture thereof9 R2 is ~5-C32 ;~ ~
~:: : -hydrocarbyl, especially Cl2-Clg hydrocarbyl, and Z is a polyhy-droxyhydrocarbyl moiety having a linear hydrocarbyl chain with at ~east two ~in the case of glyceraldehyde), or at least three 5in the case of other reducing sugars), hydroxyls Birectly connected to the chain; and ~b) an anionic surfactant which is a member ; selected from the gr~up consistin~ of the sul~ated reaction products of said polyhydroxy fatty~ acid amides of formula (a), at a weight ratio of (a):(b) of~rom about lO:l to about l:lO, preferably from about 1:3 to about 3:1, most preferably about 1:1.
The in~ention also encompasses the mixture of said nonionic and anionic compounds ~a) and (b3 in the proportions undicated in the above method.
The method herein is suitable ~or a varie~y of cleaning purposes, including but not limited to: laundering fabrics;
washing eating and cooking utensils~ glassware and dishes in automatic washing machines; cleaning other hard surfaces~ such as walls, floors, and other environmental surfaces including automo-biles, windows and the like; ~f low suds~ng ls desired, for person~l cleansing such as cleaning skin or shampooing hair; or any other use where low sudsing is desired, or fo~ other circumstances where a low interfacial tensinn is required, e~9O~
oi1 rscovery.
Methods for cleaning wh~rein low sudsing is requir~d prefer-ably uses compounds (both nonionic and the corresponding sulfated compound) wh~rein Rl is C3-C8 ~lkyl, espec~ally C3 (i.e., n-propyl or iso-propyl) or C4 (n-butyl or iso~butyl), or C~ ~n-hexyl3 and ~ithout hydroxyalkyl, and especially where Rl ~ R2 totals no ~ore than about 20 carbon atoms so as to ensure good solubil~ty even in liqu~d for~ulations. Such methods are partic~larly us~ful in ~0 automatic washing machines for fabric launderin~.
The invention also provides a ~ow~sudsing co~posi~ion of : matter which is especially adapted fsr use as the surfactant mixture in a fully-formulated detergent composition comprising said nonion k surfactant (aJ and said sul~ated nonionic surfactant (b) at a ~ei~ht ratio of from about 1:10 t~ about 10 1~ preferably about 1:3 to about 3~ ost preferably about l:l.
The inv~ntion also encompasses fully-fQ~mulated low sudsing - detergent compos~tions comprtsing from about 2~ to about 6~% of .. . ,. . .. , . ~ ~ ....... ..

WO 94/12~98 214 8 0 9 7 PCT/VS93/11451 such mixtllre of surfactants (a) and (b~, together with various detersive adjuncts such as builders, enzymes, bleaches and the like.
Al1 percentages, ratios and proportions herein are by weight, unless otherwise specified. All documents cited are incorporated herein by reference.
DE~AI LE~ . DEscRI~oNllE~NyE~lQN
~hile the polyhydroxy fatty acid amides used herein can be prepared, ~or examp~e, by the methods disclosed in the Schwartz or Pig~ott references above, this invention most preferably employs high qual ity polyhydroxy fatty acid am~de surfactants whioh are substantially free of cyclized by-products.
As an overall proposition, the preparative n~ethods described in ~0-9,~06,154 and ~ 9,206,984 will afford h~gh quality poly-15 . hydroxy fatty acid amides. The methods comdrise reacting :N-alkylamino polyols wlth, Qreferably, fatty acid methyl esters in a solveDt using an alkox~de catalyst at te~peratures of about 85-C
to proYide high yields (90-98X) of polyhydroxy Patty acid amides having desirable low le~els (typically, less than about 1%) of ~o sub-optimally degradable ~yclized by-products and also with improYed color and improved color stabil~ty9 e.g., Gardner C~lors be~ow about 4, preferably betweer~ O and 2. Use of N-C2-C~
alkylamins pQlyOlS yields low^sudsing compounds o~ the type employed hereill. (With some of the lQW sudsers, e.~., n-butyl, iso-butyl, n-h~xyl, the methanol introdùced via the cata~yst or g~nerated during the reaction provides sufficienk fluidization that the use of additional reaction solYent may be optional.~ If desired, any unreacl:ed N-al bl~mino polyol remaining in the product can be acylated ~ith an:acid anhydride, e.g.~ acetic anhydride, maleic anhydride, ~r ~he llke, to minimize t~e overall : tevel of amines in the~product. ~ ~ ~
;~ : : By ~cycllzed by-products~ herein ~s ~eant the undesirable : reaction:by-products of the primary ~eaction wherein ~t appears that; the mul:tiple hydroxyl:groups in the polyhydroxy fatty acid : 35 amides can form ring stru~tures whieh may not be readily : : biodegradable. It will~be appre~iated by those skilled in the che~ic2l arts that the preparation of the polyhydroxy fatty acid amides here~in using the di- and higher saccharides such as maltose :
: :

WO 94/12598 PCTIU593/11451 _ 21~809r) - 6 - will result in the formation of polyhydroxy fatty acid amides wherein 1 inear subst~tuent Z (which contains multiple hydroxy substituents) is naturally ~cappeda by a polyhydroxy ring structure. Such materials are . no.t~ ~ycltzed by-products, as defined herein. ~
By low sud~ing~ herein is.m~t a suds he~ght or suds volume for the low sudsing detergent compositions herein containing the C3-Cg N~alkyl po7yhydroxy fatty acid amkle surfactant which is substantially less than that which is achieved in csmparable com~ositions containing the N-methyl polyhydroxy fatty acid amide surfactant. Typically, the compos~tions herein proYide sudsin~
which is no grea~er, :on aver~ge, than about 70X, preferably no greater than about 50X~ ~ that prodalced w~ th the H-methyl surfactants. Of course, the sudsing can b~ st~ll further reduced 1~ by ~eans of standard suds control a~ents such as the sil ~cones9 various fatty materials and the l~ke-For the conventence of the fo~ulator, a useful test procedllre for comparing the sudsing of the low-slJds compos~t~ons her~in i s provlided hereinafter. The t~st comprises ag~tating aqueous solutions sontainirlg the daterg~nt be~ng tested in a st~ndardized fashion and comparing sudsirlg aga~nst equivalerlt detergents containing th~ N-methyl polyhydroxy fatty acid amide.
:~ This particular test is run ~t ambient temp~rature (c~. 23~C~ and at 60-C, and st water hardness ~3:1 Ca:Mg~ le~01s cf 10.4 gr/gal 2 tl79 pp~) and 25 gr/~al ~428: ppm) to ~mic 2 wlde Yariety of prospectlve usage cond~t~onsO Of c~urse, the fsrmulator may : ~ mod~fy the test cond~tions to focus on prospectiYe usage cond~t~ons and user habtts and practices throughout the world.

30~ ~ Sltds cylinders~hav~ng the di~ensions 12 inch (30.4 cm) height and 4 inch (~0.16: cm): diameter are releasably ~ttached to a achine ~which rotates the cyliFIders 36Q- ~round a fixed axis. A
typical~ test uses four cylirlders, two for the standard comparison , det~rgen~ product and ~: two for the low su~lsing detergent test product. ~ ~
In the test,: 500 mL of aqueous solwtion of the respectiYe detergents is p~aced in the cylinders. I:onveniently~ the solut~70ns cDmprise 3 9 of the detergent, but other amounts can be used. The temperature of the solutions and their hardness are adjusted as noted above. Typically, CaC~2 and MgCl2 salts are used to supply hardness. ïhe cylinders are sealed and the 5ûO ml leYel ~arked with tape. The cylinders are rotated through ~wo complete revolutions, stopped and ~ented.
After the ~oregoing preparatory matter~ have been completed, the test begins. The cylinde~s are allowed to rotate 360- on the machine at a rate of 30 revolutions per minute. The machine is stopped at one minute intervals~ the suds height fronl the top of the solution to the top of the suds is m~asured, and the machine i s restarted . The test proceeds thusly for lO minut~s . A suds "vo~ume~ is calculated by taking the average suds height over the test time (lQ minutes) and can be expressed as suds volume per minute ~cm), which confornls with: suds Yolu~l~e per minute ~ sum of suds height at each time of measurement di~ided by 1~otal time (lO
mi nutes ) .
Xt i s tn be understood that :the foregQ~ng test prov~des re~ative comparison between low sudsing del~er~ent compos~tions of the type~ provided herein vs. standard comparison products. tated other~se~ absolute Yalues of suds he~ghts are mea~s~n~less, since they can vary widely w~th solution tempee~atllre and w~ter hardness .
~` To illustrate this po~nt ~urtAer, ar~ N-n-propyl polyhydrsxy ~atty ac1d a~de (low sudser~ exhibits~; suds volllmes per minute in the above test of: 0.5 cm at ~ambient, hardness lO.4; 2.1 cm :at `~ ~ 25 f~amb~ent, hardness 25. :In comparison? the resp~ctive ~igures for a tallowalkyl N-aethyl glucamide (high sudser) are I ~cm and 3O3 :~ ~ cm.

More spec~fically, l~he compositions and processes herein use ~: ~ 30 low~sudsing polyhydroxy ~atty~ qcid amide s urfaceants of the formul a ~ O Rl ;

( I ) ~ 2 ~ z : (and~tbeir corresponding su~tated r~actiqn products) wberein: Rl is Cz-Cg: hydrocarbyl, :especit311y ~3-t6 alkyl; and R2 is a C~-C31 :
hydrocarbyl ~moi:~ty, preferably straight ehain C7-Elg alkyl or~
alkenyl,~ more ~preferably straight chain l:g-C17 alkyl or alkenyl, most preférably straigh~ chain Cll-Cl9 alkyl or alkenyl, or WO 94/1259$ ~ 9~ PCT/US93/11451 8 - `
mixtures thereof; and Z is a polyhydroxyhydrocarbyl mniety having a linear hydrocarbyl chain with at least 2 ~in the case of glyceraldehyde which can be considered to be a sug~r for the present purposes) or 3 hydroxyls ~in the oase of other reducing sugars) directly connected t~ ~ e chaint or an alkoxylat~d ~erivative ~preferably ethux~ ed or propoxylated) thereo~
prefarably will be der~ved ~ m a reducing sugar ~n a reductive a~ination reaction; more preferably Z is a glycityl moiety.
Suitable reducing sugars include glucose, fructose, lactose, galactose, mannose, and xylose, as well as glyceraldshyde. As raw materials, high dextrose c~rn syrup, high fructose 'eorn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed aboYe. ~hese corn syrups may yield a mix of susar components for Z. It should be undersl:ood that ~t is by no m~ans lS ~ntended to exclude other suitable raw mater~als/ ~ preferably ~ill be selected from the group consisting of -CH2-(CHOH)n-CH20H~
-CH~CH2OH)-(CHOH)n l-CH2OH, -CH2-(CHOH)2(CHOR')(CHOH~-~H2OH, where n is an int~ger from 1 to 5, inclusive, and R' is H or a cyclie ~ono- or poly- sacchar~de, and alkoxylated derivatives thereof.
Most preferred ~re glycityls wherein n is 49 partic~larly -Cff~ - (CHOH ) 4 -CH20H .
In ~ormula (I), Rl can be, for example, N-n-prspyl, H-iso-propyl, N-n~butyl9 N-isobutyl, N-n-h~xyl, or N~2~ethyl hexyl.
R~-CO-Nc can be, for ~xample, cocamide, stearamide, oleantide, 2S lauramide, myr~staR~de, capricamide, pal~tamide, tall owamide~
etc.
Z ~an be l-deoxyglucityl, 2-deoxyfructltyl, l-deo%yxyl~tyl ~
l-deoxymal~ityl, l-deoxylact~tyl ~ l-deoxygalaetityl, l-deoxyman-n~tyl~ I~deoxymaltatriotityl, 2,3~dihydro3typropyl (from glyceral 30 dehyde), etc.
It will be appreci~ted that the polyhydroxy fatty acid amide surfactants used herein as ths nonianic surfactant co~ponent can be mixtures of mat~rials having various substttuerlts Rl a~sd R2.

It is to be underst~od that th@ ~n~onic sulfation products Us@d herein are b~lieYed to b~ mainly ~ono-sul~ates ~fl the ter-minal ~ydroxyl subst1tuent of the polyhydroxy fatty acid amides.
Ho~ever, s~nce th~ amides do contain ~ultiple hydroxyl groups WO ~4/12598 214 8 0 9 7 PCT/I~S93/11451 .~

where sulfation can occur, the di-, tri-, tetra-, etc. sulfates can be fonmed in varying amounts and be oo-present in the composi tions. Indeed, it appears that using the syntheses disclosed herein, approximately 10% di-sul~ation can routinely occur. The presence of such poly-sul~ated materials does not detract from the perfonmance herein`j and no special purification steps need be used to remove them.
cQeonYt Gluc_seL~ SulEa~e - One mole of coconut N-n-propyl glucose am~de (mainly C11H23~0N(n-C3H7)CH2~CHOH]~CH2OH, made from 95% C12 methyl ester), is;dissolYed in dry chloroform.
(Note: chloroform is passed through silica gel to ~ry and to remove ethanol). :Dry apparatus is used. One mole of chlorosul-fonie acid is dissolved in ohloroform~ and the aoid solution is dripped into the glucose amide solution~at 54-C (15 minutes) with stirring under a nitrogen blanket. The solùtion is stirred an additiona~ 45 minutes with a nitrogen sweep at 50~C to evaporate : off about half:of the chloroform and cooted below 30-C. The acid : solution is slowly poured into a vigorDusly stirred, ice: cooled base solut~on~ ~Thè pH is :monitored tD assure that ~t remains basic at all times~. : A mSxtu`re w~th a~flnal pH of 9.0 is achieved with 1~ sodium hydroxide. The mixture is ev~porated at ambient in a dish in hood-air stream ~or one week w~th occasional stirring to : remove ch~oroform. . ::
: ln an~alternative process, the coconut N-n-propyl glucose 2$ amide sulfa~e is made i~ a multi-step process,~as follows.~
O.S moles of~said glucose amide~ are~dissolved in mzthylene chloride:in a ~reaction ~flask. ~ :- 0.5 ~oles of a 1~ ole : ~ basis)~pyridine/SO3 complex obtained fro~ ~ldrich Chemical tompany : are adde~ to the reaction :flask.~ The reac~ion is al)owed; o 30` pr~ceQd~!at roo~` temperature for three days`(ai ~atter of conveni-: ence; other reaetion times~can be used, depending on:temperature, etc.j.~ Sodium~carbonate is~diss~lved~in water and ~added to::the:~reaction ~lask with ~ixing for four hours.~ - The : crude~reacti~on~mtxture; i~s evap4rateG~ and the~res1due taken up in 35 ~ : me~han~ _E~ :The~methanol ~ s dried over HgSO4~ and the solids~rèmoved ~by Yacwm filtration. ~!e~ The me~banol solution~ decolor~zed wlth char~oal; the charcoal is removed by f:i~ltra~tlon through a~Celite ~bed. ~UL Z - FXcess methanol is WO 94/12598 2 1 4 8 o 9 7 PCT/US93/11451 - 10 - .:
e~ap~rated on a r~tary evaporator (60-C; vacuu~. The residue is slurried with ethyl acetate (slightly warm). SteP 8 - The ethyl acetate slurry is cooled to room temperature and the solids allowed to ~ettle. The ethyl ace~ate containing the desired sulf~ted glucamide surfaetant is d~ec~nted from the solids and the solvent removed by evaporation~ $teD~ The solids remaining after eYaporation of th~ ethyl acetate are ground by mortar and pestle and dried in a vacuum oven (25~C; 20 mm pressure).
The aforesaid sulfated product is mixed w~th the unsulfated CI2-~I4 ~-~n-C3H7~ gluca~ide at any desired ratio to provide the mixed nonionic/an~onic surfac~ants of the inYention. In an alternate mode, the sulfation reaetion uses one-half the stated amount of pyridine/S03 ta pro~id~ a 1:1 mixture of nonionic/ani-onic withuut further work-up.
Tallow (C16-CIg) N-n-hexylgluca~ide, G12-C14 N-iso-propyl 97ucamide C12-C14 N-n-butyl glucam~de, C12-C14 N-isobutyl I glucamide and C12-C14 Nn-hexyl fructamtde are gach sulfated L similarly to the above-noted multi-step proeess, except that pyr~dine is used ~n place of methylene ch~oride as the solYent in the ~irst step. The respQct~ve sulfated produets are used to prepare th~ ~ixed compostt~ons of this inven~on~
The sulfated polyhydroxy:fatty acid amides used herein as the :~ : anionic surfaetant component can also compr1se the sulfated ~ reaction product of polyhydroxy fatty acid a~ides having a mtxture 1 25 of Rl and R2 substituents.

The sulfated polyhydroxy f~tty aeid a~ide surfactants used herein are conventionally prepared in their:acid~ or alkali metal (e.g.9 Na, K) salt fonms9 or as ammonium or alkanolammoniu~ salts, e.g., triethanolammonium. Th`ese counterion~salits are non~ iting exa~ples of typical sulfated detergents. However, in circum-~:~ stances ~here high grease removal per~ormancg is of par~i ular ::: importance, the~f~nmulator may find ~t advantageous to incorporate at:least about 0.5X, preferably from about 0.6~ to about 2X, by ;: 35 we~ght of magnesium ~ons, calcium ions, or mixtures thereof, into the finished~detergent compos1tion. Th1s ean be done by simpty adding Yarious water-soluble sa~ts surh as the chlorides, sul-~: : fat2s, acetates, fonmates, malates, maleates, etc. of magnesium or ~ ~ :

' . : :

calcium to the compositions. (Preferably, if such compositions contain builders, they will be selected from non-phosphat~ -builders, especially citrate, zeolite and layered silicate.) It is also useful to senerate the magnesium and/or calcium salts of the sulfated polyhydroxy ~atty acids ~erein by reacting Mg~OH)2 or A Ca(OH)2 with the acid form of the sulfated polyhydroxy fatty acid amide, and this can convenieRtly be done in sitv during the . formulation of the finished detergent compositions or as a separ-ate step during the manufacture of ~he sulfated surfactant, itself. :
The: a~oresaid nonionic/anionic mixtures ~an be. used with conYentional "detersive adjunct" ~materials to provide fully-formulated de~ergent composltions. The ~de~erslve adjunet~
materials will ~ary, depending on the: intended end-use of the final compositions. : The following are intended only to be nonlimlting illustrations of such adjuncts, more examples o~ which wil1 readily come to mind of the skilled formulator.
- Detersive:enzymQs can optionally be inciuded in the : detergent formulations for a wide variety of purposes, especially for fabric laundering,~ including ~removal ~ o~ protein-based, carbohydrate-based, or trig~lyceride-based stains,~for example, and prevention of refugee:dye:trans~er. ~The anzy~es to be incorpor-; ~ ated include~ proteases, amyl~ases, lipases, cell~ulases, and~per-oxidases,ias well as mi~tures thereof. :Other types of enzymes may 2~5 : also be included.~ They~ may be of any sultable origin, such as vegetable, animal,:~bacterial:, fungal and yeast: origin. ~ However, their choice l5 ~go~erned by several factors such as~pH-activity~
and/or stability optima,~thermostability, ~stability v~ersus actiYe detergents,~ bui:lde~s and~so~ on.~ In: this ræspect bacterial; or~
~30 fung~al en~ymes a~e pre~:erred,; ~suth~ as~ba~terial amylases and prot~ases`,`an~d fungal cel?ul:ases.
En~ymes~ are~:~bo m ally:~incorporated~at levels sufflcient :to provide up~to;~about~S~ g ;by weig~t, ~ore :b pi~oally about 0.05 mg to about~3~mg, of~cti~vè enzyme~:~per~gram of:the :composition.
35 ~ : Suitabl~e~examples of proteases~ar~:the: subtilisins whih are obtain~d~:fro~parti~cular~strains;of;B.subtili:s`~and B.licheni~orms.
Another~:sui:table:~protease is o~tained~from a strain o~:Bacitlus, havln~ max~i~mum~activlty throughout the pH range of 8-l29 developed ~`t WO 94/12598 PCTIIJS93/11451 _ 21480g7 - 12 -and sold by No~o Industries A/S un~sr the reg1stered trade name ESPERASE. The preparation of this er3zyme and ~na~ogous enzymes is described in British Patent Specification No. 1~243,784 of Novo.
Proteolytic enzymes suitable for removing protein-based stains that are con~nercially available ~,include those sold under the ' tradenames ALCALASE and SRVINASE; by Novo Industries A/S ~Denmark) and MAXATASE by International Bi~-Synthetics, Inc. (The N~therlands). Other proteases incllJde Protease A gsee European Patent Appl ication I30,7~6, publ ish~d January 9, 1985) and IO Protease B (SQe European Patent Application S~rial No. 8730376I.8, filed April 289 1987, and Europ~an Patent Application 130,756, Bott et al, published January 9, 1985).
Amyl ases i ncl ude t for ~exampl e, o-anlyl ases descri bed i n British Patent Specification No. 1,296,839 (Novo), RAPI~ASE, I7lternational Bio-Synthetics, Inc. and TERMAMYL, Novo Industries.
The cellu~ases usable in the present invention ~nclude both bacterial or fungal cellul~se. Preferably, they w111 have a plt optimu~ o~ betweerl 5 and 9.S. Su1table cellul:ases are disclosed in U.SO Patent 4,435,307, ~arbesgoard et al, issued ff~rch 6, I9~4, : I : 20 which discloses funQal cellulase produced from Humicola insolens and Humicola strain DSM1800 or a cellulase 2~2-producing fungus belonging to the genus Aeromonas, and cellulase ~xtracted frsm the hepatopancreas oF ~ ~arine m~lusk (Dolabella Aus~kula Sol~nder).
Sui tabl e cel 1 ul ases are ~ al so di scl osed i n GB-A-~ 0 075 . 028;
GB~A-2.Q95.:27~ and D~-OS-202470832.
Suitable lipase enzynes :for detergent usage include those ps~oduced by microorganisms of the Pseu~omonas group, such~ as Pseudo~onas stut~eri ATCC 19.154, as disclosed in ~ritish Pat~nt ~: 1,372,034. ~ See al50 lipases in .)aRanese ~Pat~n~ ~pplieatio 53~20487~ 1aid vpen to public inspec~ion ~n February ~A~ 1978.
This 1 ipase is availabl:e ~rom ~mann Pharmaoeut1cal ~o. Ltd., Nagoya, Japan,~ under ehe~trade~name Lipase p ~ anQ,~ hersinafter referred to as : ~Amano- P . ": Ogher cQmmerci al l i pases i ncl ude Amano-ES,: l ipases~ sx~ :~Chr~nlob~ter ~ViSCosufl~, e.9. cl7ro~ob?cter - ~ : : 35 vis~osvnJ~var.~ Jrpo1yticJm NRRLB 3673, co~nelcially ava~lable from Toyo ~lo~o ~o.,~ Tagata, Japan;: and further ~ro~obacter viscosum lipases $rom~U~.S,~ Biochemical Corp., ~oS~A~ and Disoynth Co., The Netherlands,~~and lipases ex Pseudomonas g1ddio~i.

WO 94112598 2 1 4 8 0 9 7 P~TIUS93/11451 .;

Peroxidase enzymes are used in combin~tion with oxygen sources, e.g., percarbonite, perborate, persulfate, hydrogen peroxide, etc. They are~ used fnr ~solution bleaching,~ i.e. to prevent transfer of d~es~ or pigm~nts removed from substrates ~uring wash operations to other substra~es in ~he wash solution.
Perox1dase enzymes ar~ kns~n in the art~ and include, for example, hors~radish peroxidase, ligninase9 snd ~ha70peroxidase such as chloro- and bromQ^peroxidase. Perox~dase-containing detergent co~pos~t~ons are dis losed, for exa~ple, in PCT International Application W0 89/099BI3, pub~ished Octob:er 19, 1989, by 0. Kirk, assigned to Novo Industries:A/S.
A:wide range of enzyme ~materials and means~for:their incorp-oration into synthetic detergent granules: is a~so disclosed in U.S~ Patent 3,553~I39, issued January S, 1971 to McCarty et al ().
I 15 Enzymes are further disclosed ln U.S. Patent 4,101t4~7, Place et :1 : al, issued July 18, 1978, and:tn U.S. Patent 4,507,2I9,~ Hughes, ssued March 26, 1~5~ both. Enzyme ~a~er~als useful for ttquid ~ : detergent formulattons, and~ their :incorporat~on ~nto such ;~; ~ formulations:?~;are discl:osed~in U.S.: Paten~ 4~,261,868, ~ora et al7 issued~pril~ 14,~;1981.~ Enzymes~ for~use in det~rgent:s~ can be~
sta~ zed~by~vario~s techniques~. Enzyme stab~ltzation techniques ~: ~ are ~d~sclosed~and: exemplif~ed~;ln U~S. Patent 4,26i,868,~ lssued ~, April ~14,:~1981 to Horn, et ~al~i U.S. :P~tent 3~6O0~319D issued:
August~l7,~;:197~1:to~Gedge,~et~al, and European Patent ~ppli:cation ~9~ ` 25Publ:i~ation ~No.::0 199 4Q5:~ Application NOD~86200586.~9 published :: ;October~29,~;19~6,~ Venegas.~:~ Enz~me~stabil:~z~t~on ~systems~arè~?1so deser~bed~ for~example,~in~U.S.:P~tents 4,261,868~, 3,600,3~ and 19 ~70 :m /: ;ln`~addition to enzymes, t~e :compos:ltions~herei~n ca~ option-30 : :~:ly include ~ne~ or -~ore~other~de~erge~nt~adjunct: ~aterials~ or bther~materials~for~:ass~lstll7g~or~enhaneiflg~cle~ning~per~ormance~,: ::
;`` treatmèn~t:~ of~the ~substrt~é::to:~be cl~aned,; or~to modi~y :the aesthet:i~ts~of the:;~detergent compos1t~Dn~ (~.g~., perfumes, ` colora~s~ dyes~,~et~
35:~Detergent;~builders ean optionally be included in the~com~osi~ions ~erein~to assist in controll~ing mineril hardness.
lnorganlc: as:~well::as organic builders:can be used. :Builders ~re WO 94/12~98 . PCT/US93/11451 214809~ - 14-typically used in fabric laundering compos~tions to assist in the removal of particulate soils.
The level of builder can vary widely depending upon the end use of the composition and its~desired physieal form. ~hen present, the compositions will ~jpically comprise at least about lX bu~lder. Liquld formulatic~l; typically ~omprise from about 5%
to about 5~%, more typically~`about 5X to about 3~X, by weight, of detergent builder. Granular formulati~ns typically comprise from about I~% to about 80X, more typieally from about 15X to about 5~X
I0 by weight, of the detergent builder. Lower or higher leYels of bwilder, however~ are not meant to be excluded.
Inorganio detergent builders 7nclude, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphos-phates (exemplified by the trtpolyphosphates, pyrophosphates, and glassy polymeric meta~phosphates), phosphonates, phytlic acid, sil~oates, carbonates (inelllding bicarbonates and sesquicarbon-ates~, sulphates, and alum~nosilicates, However, non^phosphate builders are requ~red in some locales. lmportant7y, the compos~-tions herein funct~on surprisingly well even in the presenee of the so-called ~weak~ builders (as c~mpared wlth phosphates) suc~
as e~trate, ~r in the so-called: ~underbu11t~ situation that may occur with zeolite or layered silicate builders. MoreDY~r, the polyhydroxy fatty ~cid am~des herein actually s~em to perform best in the presence of w~ak, nonphosp~ate bui~ders wherein some free : 25 Ca++ or Mg+~ is present.
Examples of silîcate bu~lders are the alkali ~etal s~licates, particularly those having a SiO2:Na20 ratto in the range 106:1 t9 ~ 3.2:1 and layered sil~cates, such as the:layered sodium s~l~ca~es : described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P.
i !3~ Rieck.; !However, other sil kates may also be usefu1 such as for example ma~nesium sili:cate, which can serve as a crispening agent :~ : in granular formu7ations, as a st~bilizing a~ent for oxygen ~:: bl~aches, and as a component o~ suds control systems.
~: Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2~32l,0aI publis~ed on November I5,. I973.
Aluminosilicate bui~ders are espeoial~y useful in the~pr@sent invention. Aluminosilicate builders are of great i~portance in : ~ :

WO 94/12598 21~ 8 0 9 7 PCT/US93/11451 .

most currently marketed heavy duty granular detergent composi ~
tions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical fonmula:
MZ(zAlo2-ysio2) wherein M is sodium, potassium, ammonium or substituted ammoniumS
z is from about O.5~to about 2; an~ y is 1; this material haYing a magnesium ion exchange capacity of: at least about 50 milligram equivalents of CaC03 hardness per gram ~of~anhydrous aluminosili-IO cate. Preferred aluminosilicates are~ zeolite builders which have ~.
the formula:
Na~E(AlO2~)z (s1o2~yi xH2~
wherein z and y~are integèrs of at';least 6, the molar ratio of z to y is in the range from l.0 to about 0.59 and x i:5 an integer fro~ about 15 to abou~ 264.
Useful alu~in~silicate ion' exchange mater~als are ~ommer-cial1y~vailable..~These ;aluminosilicates can be cs~ystall~ne or a~orphous~in~structure and~can be~na~turally-occurring aluminos;li-cates~;or ~syntheticaily derived~. ;A method ~or producing alumino-20~ ' sil1cate~ on~exchange~mat;erials ~is disclosed in~ U.S. Patent 3,985,6~g,~Krummëlt ~et 'al,~ issùed~Oetober 12, l976. Pre~erred synthetic~ erys~alline al~uminosilicate ion ~exchaDge mater;i~ats useful~ herein~are~aYailabl~e~under~the designa~ians~Zeolite A, ; Zeol~lte~ P~(B), ~nd ~Zeoli~te~X. ~ In ~an~ especially preferred ~ embod1mént,~the crysta11~1ne;alum1nos~;1icate~1On~exchange;~mater1al has t~e~f~rmul~
N~12t~(Al:o2)l2(sio2)l2]-xH~o:; :~
whereln~-x~ s~from about~20~to;about 30,~espeei211y about~27.~Th1s material is known as ~eolite;~A. Preferably, the ~aluminosilicate ; has~a' p`art~cl~e s~ize o~ ibout 0~ 10~microns ln~di~ameter.' Organic~detergent;~bui;lders suitable for the~purposes of the present~ i~nvent~ion~ ncl~de~ but~ are~ not restrlcted~to,~a wide variety~ of~ pol~ycarboxyl~ate~ ompounds~ As~ ~us~d~ here' po~yG~arboxylate~ r~fers~ tD~ co~pounds~having~ a ~plurality of 35~ carb ~ laté~ g ps~ prefer'bly;~ ~at ~least~ 3~ carbox lates.
Polycar 1 ;~bu11der can~g~` r~l1y be~ added to~the~composition n~ acid~fo' ,~ but can~also~;be ~d ed~in the~;fo ~ of a~neutralized~

wo 9q,l259~ 1 g 8 0 9 ~ PCT/US93/11451 salt. When utilized in salt fonm, alkali ~etals, such as sodium, potassium5 and lithium, or alkanolammonium salts are preferred.
Included amQng the polycarboxylate builders are a variety of categories of useful materials. One important categury of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate,~ as disclosed in Berg9 U.S. Patent 3,128,2879 issued April ~ 1964, and Lamberti et al, U.S. Paten~
3,635,830, issued Jan~ ~ 18, 1972. See also ~TMS/TDS~ builders of U.S. Patent 4,663~071, issued to Bush et al, on May 5, 1987.
Suitable ether polycarboxylates also include cyclic compolJnds, pa~ticularly alicyclic compounds, such as those described in U.S.
Paten~s 3,923,679; 3,835,16~; 4,158,635; 4,120,874 and 4,102,903~ ~
Other useful detergency builders include the ether hydroxy- :
polycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trtsul-phonic acid, and carbo%ymethyloxysuccinic a~id, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine :tetraacetic acid and nitrllotriacetic acid, as well as po~yc?rboxylates such as ~ellitic acid, succinic acid, oxydisuccinic acid~ pol ~ aleic acid, benzene 1,3~5-tricar-boxylic acid, carboxymethyloxysuccinif acid, and soluble salts thereof .
Citrate bu~lders, e.g., citric acid and soluble salts there~f (particsllarly sod~um ~ saltj, are polycarboxylate builders of particular i~portance for heavy duty liquid detergent formulatlons due to their: availab~lity from renewable~ resources and their biodegradability. Cltrates can a)so: be ~sed in granular eompasi-tions, especially ~n eo~blnation with zeol~te andtor layered silicate builders.
Also~ sulta~le in the detergent composit~ons olf the present in~ention are the 393-dicarboxy-4-oxa-1,6-hexanedioates and the :~ related co~pou~ds disclosed in U.S. Patent 4,~66,9~4, Bush, issued anuary 28,~ 1986. ~ Use:ful succinic aeid builders include the : ~: : Cs C20 alkyl and alkenyl succinic acids and ~alts thereof. A
3 5 particularly preferred compound of this ky~e is dode~enylsuecinic acîd. Specific examples of succinate builders inclllde: laurylsuc-cinat2,: myristylsuccina~e, palm~tylsuccinate, 2-dodecenylsuccinate ~ ' ~

::` :~ :

(preferred), 2-pentadecenylsuccinate, and the lik~. Laurylsuccin-ates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,26~, published Nove~ber 5, 1986.
Other suitable polycarboxylates are diselosed ifl U.S. Patent 4,144,226, Crutehfield et al, issued March 13, 1979 and in U.S.
Patent 3,308,067, Diehl, issued Mareh 7, 1967. See also Diehl U.S. Patent 3,723,322.
Fatty acids, e.g., C12-C1g mono~arboxylic acids, can also be incorporated into the compos~tions alone, or in cQmbination w~th the aforQsaid~builders, e:specially: citrate and/or thQ succinate ~uilders, to provide add~tio~al builder activ~ty. Such use of fatty acids will generally result in a diminution of sudsing, which should be taken int~ account by the formulator.
In situations wh~re phosphorus-based builders can be used;
the various alkali metal phosphates ch as the well known sodium ~ripolyphosphates, ~sod~um pyrophosphate ~nd sod~u~ orthophosphate can be used; Phosphonate bui~ders sueh:as ethane-l-hydroxy~
diphcsphonate and other known phosphonates (see, for example, U.S.
Patents 3,159,~81; 3,213t030; 3,4Z2,021; 3?4DO,148 and 3,422,137 can also be used.`~
.
: The detergent co0pos~tions herein may: op~ionally contain bleaching agents or bleaching co~pos~tions containing a bleaching agent and one or more:bleach actiYators. ~hen present,~ bleaching agents~wi~ typically be at leYels o~ from about lX t~ about~ 20X, ~more ~ypically from ~bout 1% to about: ~ , of the detergent compos~tion, e~special:iy ~for :~abric laundering. If: present, ths amount of bleach activators ~i~ll` typlcally be fro~ ab~out 0.1% to : a~out ~60Z, more typicàlly from:about 0.5Z to; about 40~ of the : bleachi~g: composit~lon comprising the bleaching agent-plus-bleach : a~ a~or.
:The b~eaching agents used~;herein~:can be any o~ the bleaching agen~s:use~ul f~ det~rgent~compos~tions in~textile ~leaning,:hard surface~cl~eanlng, or ot~er:cleaning purpo~es that are:now known or become known. These~;~include ~xygen bl~aches as we~l as other bleachi:ng:~agents. Per~orate bleaches, e.~., sodium:: ~erborate .g;.,~mono- o~tetra-hydrate) can:be used herein, but~ under some WC) 94/12~5g8 21~8g~ PCTJUS93/11451 conditions, may u~desirably interact with the polyol nonionic surfactant.
. ~ne cat~gory of bleachin~ agent that can be used without restriction encompasses perca~boxylic (~percarbonate~) acid I S bleaching agents and salts there~n. Suitable examples of this ¦ class of agents inc~ude magnesi`um monoper~xyphthalate hexahydrate, the magnesiu~ salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyr~c acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Patent 4,483t781, Hartman, jcsued November 20, 1984, U.S. Patent Appl~cation 740,446, Burns et al, filed June 3, 19~5, Eu~Qpean Patent Applicatio~ 0~133,354, Banks et al, published Februa~y 20, 1985, and U.S. Pagent 49412,934, Chung et al, issued Nove~ber 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in IJ.S. Patellt 4,634,551, ~ssued January 6, 19B7 to Burns et al. ~ ~
Peroxygen bleach~ng agents can also be used. Sllitable . peroxygen bleaching colnpounds include sod~um carbonate peroxy-hydrate, sodium pyrophosphate ~ peroxyhydrate, urea peroxyhydrate, and sodium perox1de. ~ Pers~llfate bleach te.g., OXONE~ manufactured 1 con~nerci:ally by DuP~nt) can also be used.
: ~ : M~xt~r~s of bleaching ag~nts can also be us~d.
eFoxygen bleach~ng agents and the p~rbor~tes are preferably I combined with bleach acti~ators9~ which l~ad to the in s~u prodo~e-; 25 tion in ~queous solu~on ~t.e.~ during the washing process) of the ; peroxy ac~d corresponding to :the ~ bleach act~atnr. Various nonlimit~ng examples o f activators :a~e d~sclosed in U.S. Patent : 4,~15,854, issued Apri1 lO~ l990 to Mao et al, and ll.S. Patent 4,4129934. The nonanoyloxybenzene sul~fonage ~NOB5) and tetraacetyl ethylene diamine (TAED) activators are typ~cal~ and mixtures thereof can a~so: be ussd. ~Se~ also U~S~ 4,634,551 ~or : other~typica1 bleaehes:and~activators~use~l herein.
Bleaching agents other than oxygen bl~aching agents are also `: : known in the~ art and can be utilized herein. One type of non-oxygen bleach:ing agent ~of~parti wlar interest inclu~es photo-actiYa~ed ~bleaching agents such as the sulfonated zinc and/or alum:inum ph~thatocyanines. See U.SO Patent 4,033,718, issued 3uly 5, 1977 ~to~Holco~be et al. Typicalty, det~rgent compositions will ~.
j ~ ~

, WO 94/12~93 214 8 0 9 7 PCTflJS~3/11451 contain about 0.~25X to abollt 1.25Z., by weight, of sulfonated zinc phthal ocyani ne .
Pol~eric Soil Re~e Aqent - Any polymeric soil release agent known to those skilled in the art can optionally be employed S in the compos~tions and processes of this invention. Polymerio soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobi c f i bers and re~ai n adhered thereto through compl eti on of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment wi th the so; l rel ease agent to be more easily cleaned in later washing p:roce~ures.
The amount of n~ixed nQnionic/anisnic surlFactant needed to enhance deposition will Yary w~th the particular soil release agen~ chosen, the optional presence or absence of other aniontc surfactants, and ~heir type, as well as the particlJlar - ~ nonionic/an~onic chosen. Generally, sompositions will compr~se from about 0.01% to about 1~%, by wetght, of thc polymeric soil release a~rt, typically from ~ abaut O~lX ~o about ~%, and from : about 4X to about 50X, more typically from about 5%to about 30 of anion~ic surfactarlt~ Such compositions shollld generally contain at least: about lX, preferably at least about 3%, by weight, o~ the mixed nonionic/anionic surfactant of this invention, though it is not intended to necessarily~ be linlited thereto.
The polymeric soil release agents for which perf~rmance lS
enhanced ~ herein especially inc1:ude those ~ soil~ release ~agents ` having: ~a) one or more nolliollic hydrophile componQnts c~nsisting essentially of (i) polyoxyethylene segments with a degree of `pdlynJerization of at least 2, ~or (iii) oxypropylebe or polyoxy-:: ~ propy~ene ~se~ments with a :degree: of pol~n7erization: of from 2 to 10, wherein said~ hydroph~l:e segment does ~not :eneolnpass any oatypropylene ;unit unless i~ is bonded to adja~ent moie~ies at each end by eth:er l i nkag~s, or ~ i i i j a :mi xture ~f oxyal kyl en~
: ~ :
35: units comprisillg oxyethylene: and from 1 to :about 30 oxypropylene units wherein sai~ I nixture oontains a suff~cierlt amount of oxyethylene llnits such that the hydrophile compoRent has hydro-philicity great enough to increase the hydrophilicity of WO 9411~598 PCl'/U~i93/11451 21~8g~ ~0-conventional polyester synthetic fiber surfaces upon deposit of the soil release agent on such surface, said hydrophile segments preferably comprising at least about 25% ~xyethy~ene units and more preferably, especially ~or such components haYing about 20 to 30 oxypropy~ene units, a~; ~east about 50X oxyethylen~ units; or (b) one or ~ore hydrophobe components comprising (i) ~3 oxyalkyl-ene terephthalate segments~ wherein, ~f said hydrophobe components also comprise oxyethylene terephthalate, the ratio of oxyethylene ~erephthalate:C3 oxyalk~lene terephthalate units is about 2:1 or lower, (ii) C4-~6 alkylene or oxy C4-C6 alkylene segments, or mixtures therein,~ ~iii) poly (vinyl ester) segments,. preferably poly(vinyl acetate)9 having a degree of polymerization of at least 2, or (iv) Cl-C4 alkyl ether or ~4 hy~rnxyalkyl ether substitu-ents, or mixtures therein, wherein said substituents are present in the fonm~of Cl-C4 alkyl ether or C4 hydroxyalkyl ether cellu-: lose deriYatives, or m~xtures therein, and such c~llulose der~va-tiYes are amphiphilic, whereby they have a suff~cient leve~ of . Gl-C4 alkyl ~ther andfor C4 hyd~oxyalkyl ether units to deposlt ; upon conventional polyester~synthetic fiber surfaces and r~tain a ` 20 sufficient le~el of hydroxyls, once adhered to such conventionalsynthetic fiber surface, to increase fiber surface hydrophilic~ty, or a combination nf (a) and:(b).
~ Typ ka~ly, the polyoxyethylene seg~en~,s of (a)(~) w~ll ha~e a : ! degree of polymerization of from 2 to about 200, although higher 2S lev~ls can be used, preferably from 3 to about ~150, more prefer-ably f~om 6 ~o ~bout 100.~ Suitable oxy C4-C6~alkyl~ne hydrophobe s~gments include, but ar~ not limited to, end-caps of polymer k soil release agents such as M03S(CH2~nOCH~CH2~-, where M is sodium and n is an int~ger~ from `4-6, as disclosed in U.S. P:atent ~ 4,721,580, i;ssued January 26,~198Q to`Gosseli~k. I ~
~: Polymeric soil release agents useful in the present invention also include cellulosic derivatives such ~s hydroxyether cellu-losic polymers~ c~polymeric blocks of ethylene tereph~halate or propylene terephthalate with~ polye~hyl~ne oxide or po~ypropylene : 35 :~ oxide te~phthalate,~and the~ e. Such agents are co~mercially av~ilable~and include hydroxyethers of cellulose sueh as METHOCEL
(Dow).~ Cellulosic soil release agents for uso hereio also include those selected from the gr~up consisting of Cl-C~ alkyl and C4 WO 94112598 21 ~ ~ O 9 7 PCT/US93J11451 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al.
Soil release agents characterized by polylvinyl ester) hydrophobe s~gments include graft copolymers of poly(vinyl ester), e.g., Cl-C6 vinyl esters, preferably poly~vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones. See European Patent Appl k ation 0 219 048, published April 22, 1987 by ~ud, et al. Con~nercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKhLAN HP-22~ available from BASF (West Germany~.
One type of preferred soil release agent is a copoly~er having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weiyht of this polymeri~
soil release agent is in the range of from about ~5,~00 to about ~5,000. See U.S. Patent 39959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 ~o Basadur issued July 89 1975.
Another preferred polymeric soil release agent is a polyester - with repeat unl~s of ethylene terephthalate units containing 10-15% by weight of ethylene terephthalate units together with 90-80X by weight of polyoxyethylene terephth~late units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000. Examples of this polymer inc~ude the commerc~ally a~ailable material ZELC~N 5126 ~fro~ Dupont) and MILEASE T (from ICI). Sea also U.S. Patent 4,7C2~857, issued October 27, 1937 to Gosselink.
Another preferred polymeric soil rel~ase agent is sulfonated product of a substantially linear est~r oli~omer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently ' ` 30 attached to the ba~kbone. These soil re~ease agents are described fully in U.S. Patent 4,96B,451, i~sued Hovember 6, 1990 to J. J.
Scheibel and E. P. Gosselink.
Other suitable poly~eric soi~ release ag~nts include the terephthalate polyesters of U.S. Patent 4,7119730, issued December 8, 19~7 to Gosselink et al, the anionic end-capped oligomeric esters of U.5. Patent 4,721,580, issued ~anuary 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S.
Patent 4,702,857, issued October 27, 1g87 to Gosselink.

2~ 097 - 22 -Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which discloses anionic, especially sulfo-aroyl9 end-capped terephthalate esters.
If util~zed9 soil release~agents will generally comprise from about 0.01X to about 10.0%,~by,~we~ght, of the detergent compssi^
tions herein, typically f~ about O.1X to about 5%, preferably from about 0.2X to about~ %.
Chelatinq Aqe~s - The detergent compositions herein may also optionally contain one or more iron andtor manganese chelating agents. Such chelating agents can be selected fro~ the group consisting of amino carboxylates, amino phosphonates, polyfunctionally substituted aromatic ehelating agents and mixtures therein, all as hereinafter defined. Withou~ intending t~ be bound by theory, ~t is believed that the ben`efit of these materials is due in part to their exceptional abil~ty to re~ove iron and manganese ~ons from washing solutions by fo m ation of soluble ~helates.
~mino carboxylates useful~ as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyeth~lethylenedi-aminetriacetates, nitrilotriacetates, ethylenediamine tetrapropr1-onates, ~riethyl~netetraaminehexaacetatas, diethylenetriamine pentaacetates, and ethanold~glyciRes, alkal~ metal, ammonium, and : substituted a m onium salts therein and m~xtures th~rein.
~mino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at teast low levels of total phQsphorus are perm~tt~d in det@rge~t compositions, and incl~de ethylenedia~inetetrakis ~methylenephos-phonates ), ni tri l otri s ~methyl enephosphortates) ar,d di ethyl enetri -, !30 aminepentakis ~methylenephosphona~es). preferafbly~l ~hese amino phosphofnates do not feontain alkyl or alkenyl groups with f~ore than :~ about 6 carbon atoms.
:; Polyfunctionally-subst~tuted ~romatic chelating agents are also useful in the compositions herein~ See U.S. Patent 3,~12,044~ issued May 21, 1g74, to Connnr et al. Preferred compounds nf this :type ifl acid ~orm are dihydrDxydisulfobenzenes such as 1~2-dihydroxy -3,5-disulfobenzene.

:

WO ~4/1~$98 21 4 8 o 9 7 PcTlus93lll45l A preferred biodegradable chelator for use ~erein is ethyl-enediamine disuccinate (nEDDS~), as described in U.S. Patent 4,704,233, November ~9 1987, to Hartman and Perkins.
If utilized, these chelating agents will generally comprise from about 0.1~ to about 10~ by weight of the detPrgent composi-tions herein. More preferably, if utilized, the chelating agents will comprise from about 0.1% ~o ab~ut 3.~ by weight of such compositions.
~ - The compositions of the present invention can also optionally eontain water-soluble ethoxylated amines:having clay soil removal and anti-r.edeposition properties. Granular detergent compositions which contain these compounds typically contain from about O.OlX to about 10.0~ by weight of the water-soluble ethoxylated amines; li~uid detergent compositions typically contain about 0.01% to about 5X.
The most preferred:ssil rclease and anti~redeposition agent ¦ is ethoxylated tetraethylenepentam~ne. Exemplary ethoxylated $ - amines are further described in U.S. Patent 4,597,898, ~anderMeer, ~ issued July 1, 1986. Another yroup of preferred clay soil ¦ 20 remo~al/antiredeposition agents are the cationic compounds dis-closed in European Patent Application 111,965, Oh an~ Gosselink, published ~une 27, 1984. Other claj soil removal/afltiredeposition agents which can be used inc?~de the etho%ylated amine polymers diselosed in European Patent Application 111,984, ~osselink, ~5 published 3une 27, 1984; the zwitterionic polymers disclosed in European Patent~Application }12,592, GQssel1nk, published July 4, : 1984; and the amine oxides disclosed in U.S~ Patent 4,548,744, Connor, issued October ~2, 1985. Other clay soil removal and/or anti redeposition agents known in the art ca~ also be utilized in the' compositions here1n. Another type of preferre~ anti-redeposition agent includes the carboxy methyl cellulose ~CMC~
: ~ mater~ials. ~These materials are well known in the art.
: ~ - Polymeric dispers~ng agents can advantageously be utilized at levels from about 0.1% ~o about 7X, ~5 by weight, in the composition~ herein. These materials can also aid in ealcium and magnesium hardness control. Suitable polymeric ; dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art ean also be t ~, WO 94/1259S 21 ~ 8 0 9 ~ PCT/US93/11451 used. It is believed, though it is not intended to be limit~d by theory, ~hat polymerie dispersiny a~ents enhance overall detergent bui)der performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release peptization, and anti-redeposition.
Polymeric polycarboxyla~e .<materials can be prepared by polymerizing or copolymeri~ g suitable unsaturated m~nomers, j p~eferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable potymeric polycarboxylates include acryl ic acid, maleic acid (or maleic anhydrid~), fumaric acid, itaconic acid, acon~tic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the polymeric polycarboxylates herein of monomeric se~ments, eontaining no carboxylate radicals such as vinyl~ethyl ether, styrene7 ethylene, etc. is suitable provided that sueh segments do not constltu~e more than about 4~% by:~e~ght.
Particularly suitable polymerie polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers wh~ch ; tO are useful herein are the~water-soluble salts of polymer~zed acryliG acid. The aYerage molecular weight of such polymers in.
. the acid ~orm pre~erably ranges from about 2,0no to 1~,000, more preferably from about 4,0ao to 7,0Q0 and most preferably from ¦; : about 4,000~to 5,000. ~ater-soluble salts of such acrylic acid z5 po~ymers can include, for example, the alkali metal, ammoni~m and substituted ammonium salts. So~uble pGlymers of this type are known ~ater~a!s. Use of palyacrylates of this type in detergent compos~tions has ~een disclosed, for example, in Diehl~ U~S.
Patent 3,3089067, issued March 7, 1967.
Acrylic/maleic-based co~olymers~ ~ay also be used as a preferred component of the dispersing/~nti-redepositinn agent.
Such materials incl~de the water-soluble salts of copolymer~ of :` acrylic acid and maleie acid. The average ~ol@cular weight of such eopolymers in the acid form preferably ranges from about 2,00a to 100,000, more preferably ~rom absut 5~000 to 75,000, most preferably from: about 7,000 to 65tO00. The ratio of acrylate to : maleate segments in such copolymers will generally range from a~out 30:1 to about 1:1, more preferably from about 10:1 to 2:1.
:: .

WO 94/12598 ~CT/US93/11451 ~ 219L8097 ~later-soluble salts of such acrylic acid/maleic acid copolymers can i nc~ ude, for exampl e 9 the al kal i metal, an~noni um and substituted an~nonium salts. Soluble acrylate/maleate copolyners o~ this type are known materials which are described in ElJropean Patent Application No. 66915, published December 15, 1982.
Another polymeric material whkh can be included is poly-ethyl ene glycol ( PE6) . PEG can exhi bi t di spersi ng agent perform-ance as well as:act as a clay soil removal/antiredeposition agent.
Typical ~olecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1,000 -to about 50,000, more preferably from about 1,500 to about 1090~0.
Polyaspartate an~ polyglutamate dispersing agents may also be used, especially in conjunc~ion with zeolite builders.
Bri~Ltener - Any optioal brighteners or oth@r brightening or whitening agents known in the art can be incorpo~ated at levels typically from about 0.05% to ab~ut 102%, by weight, into the detergent compos~tions here~n. Commerc~al opt~cal brighteners which may be useful in the present invention can be classified into subgroups which include, but are not necessarily limited to, derlvatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecy~nine~,; dibenzothiphene-5,5-dio%ide, azoles, 5~ and 6-membered-ring heterocyc~es, and other miscellaneous agents.
Examples of such brighteners are disclosed in ~The Production and Application of Fluorescent Brightening Agents", M. ~ahradnik, Published by John ~iley ~ Sons, New York (1982).
Specific examples of optical brighteners wh~ch are useful in the present compssitions are those~identi~ied in UOS. Patent 4,790,856, issued to ~ixon on D~cember 13, 1988. These brighteners include the PHOR~HITE series of brighteners from . l l 30 Verona. Other br~ghteners disclosed in this reference' include:
Tinopal UNPA, Tinopal cas and Tinopal 5BM; available from Ciba-~ Geigy; ~rctic ~hite CC and Artic ~hite CWD, available from Hilton-: Davis, located in Italy; the 2-(4-styryl-phenyl)-2H- naphthol[~,2-d]triazoles; 4,4'-bis- (1,2?3-triazol-2-yl~-stil- benes, 4,4'-bis-(styryl)bisphenyls; and the y-aminocoumarins. Specific examples of these brighteners inc)ude 4-methyl-7-diethyl- amino coumarin;
1,2: bis(-ben~imidazol-2-yl)ethylene; 1~3-diphenylphrazolin~s;
2,5-bis(benzoxazol-2-yl)thiophene9 2-styryl-naphth-Elq2-d~oxazole;

WO 94/12598 o 9 ~ PCT/US93/11451 and 2-~stilbene-~ yl)-2H-naphtho- [1,2-dJtriazole. See also U.S.
Patent 3,646,015, issued February 29, 1972 to Hamilton.
Suds SuDp_e~s~ Compounds for reducing or suppressing the furmation of suds can be incnrporated into the compos~tions o~ the present invention. The incorporation of such ~aterials, herein-after ~uds suppressors,~ ca ~be desirable to further reduce the already-low sudsing of t4~:'mixed nonionic/anionic surfactants h~rein. Add~tional su`~s ` suppression can be of particular importance when the detergent compositi~ns herein optionally include a relatiYely high sudsing surfactant in combinatinn w~th the low-su~sing mixed nonionic/anionic surfactants o~ th~s invention.
A wide variety of materi:als ~ay be used as suds suppressors, and suds suppressors are well known to those skilled in the art.
See, for example, Kirk Othmer Encyclopedia oP Chemical Technology, Third Edition, V~lume 7, pages 430-447 (John ~iley & Sons, Inc., : 1979J. One category of suds suppressor of part~cular interest : encompasses monocarboxylic fatty acids and soluble salts there~n.
See U.S. Patent 29954,347, issued September 27, 1960 to Wayne St.
John. The monoearboxylie ~atty acids and salts th~reof used: as suds suppressor typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon ato~s. Su~table salts i~clude the alkal~ metal salts such as sod1um, potassium, and lithium salts,:a~d ammonium and alkanolammon~um salts.
The detergent co~pos~tions ~herein may al~so contain non-I s~rfactant suds suppressors. These include, P~r example: h~gh molecular weight: hydrocarbons ~uch as paraffin, ~atty ~cid esters (e.g., fatty acid trig~ycerides),: ~atty ac~d `este~s of monovalent alcohols, aliphatic Clg-~4~ ketoncs (e.~. stearone~, e~c. Other ~:: ~ ` 30 s~ds;inhlbitors include N-alkylated amino triazines sùch as tri-to hexa-3lkylmelamines or di- to tetra-alkyldia~i~e chlortriazines I fonmed as products of cyanuric chloride with two or three ~oles of a primary or sec~ndary a~ine containing 1 to 24 carbon atoms, propylene oxide, ~nd monostearyl phosphates such as ~onostearyl ~lcohol phosphate ester and monostearyl di-alkali metal (e.g. K~
Na~ :and Li) phospha~es and ph~sphate esters. The hydrocarbons such ~as paraffin and haloparaffin can be utilized in liquid form.
~; The liquid hydrocarbons will be liquid at r~om temperature and ~WO ~4/12598 214 8 o 9 17 P(::TtUS93/11451 atmospheric pressure, and will have a pour point in the range of about -40-C and abnut 5 C, and a minimum boiling point not less khan about 110-C (atm~spheric pressure), It is also known to utilize waxy hydrocarbons, preferrably having a melting point below about 100'C. The hydrocarbons constitute a preferred - category of suds suppressor for detergent oompositions.
Hydrocarbon suds suppressors are described, for example, in U.S0 Patent 4~265,779, iss~ed May 5, 1981 to GandolFo et al. The hydrocarbons, thus, include atiphatic, alicyclic9 aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 74 carbon atoms. The term "paraf~in,~ as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
Another preferred categ~y of non-surfactant suds suppressors comprises silicone suds supprsssors. This category includes the l~se of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of po~yorganosiloxane oils or resins, and combinations of polyorganosiloxane ~ith silica particles wherein the po~yorganosiloxane is chemisorbed of fused onto the silica.
~o Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779, is6ued May 5, 1981 to Gandolfo et al and urop~an Patent Application No. 89307851.9, published Febr~ary 79 19.909 by Starch~ M. S.
Other s~licone s~ds suppressors are disclosed i~ U.S, Patent 3,455,839 which re~ates to compositions and prooesses for def~aming aqueous solutions by incorporating therein small amounts of polydi~ethylslloxane fluids.
Mixtures of siliGone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526. 5ilicone de~foamers and suds conl;rolling agents in granular detergent compositi;ons are disclosed in U.S. Patent 3~933,672, ~artolotta et al, an~ in U.S. Patent 4,652,3929 Baginski et al7 issued March 24, 1987.
An exemplary sîlicone based suds suppressor for use herein is a ~uds ~suppressing amount of a suds controlling agent consisting essenti al ly of:
(i ) polydi~ethylsiloxane fluid having a ViSt:DSity of ~rom about 20 cs. to about 1500 cs. at ~5C;

:

wo s4/l2sg8 2 1 ~ 8 0 9 'l PCTIU593/ll4;

- 2~ -ti i ) from about 5 tD about ~û parts per 100 parts by weight of ~i) of siloxane resin composed of (CH3)3 SiO1t2 units of SiO2 units in a ratio of from (CH3)3 SiO1~2 units and to SiO2 unlts of from about 0.6:1 to about 1.2:1; and (iii) from about 1 to about 20 parts per 10û pants by weight of (i~ of a solid ~i~l`ica gel;
In the preferred sil i~cone suds sup~ressor used herein, the solvent for a ~ontinuolls phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copol~yTners or mixtures :the~enf (prefs~red~, and not polypropyl~ne glycol. The primary silicone suds suppressor is branched/cro~slinked and not ` l i near . ~ : ~
To illustrate this point further, typical liquid laundry detergent composttions with controlled suds will optionally comprise fronl about 0.001 to aboul; 1, preferably from about û~01 to about 0.7, most preferably frcm abut 0.05 to about 0.5, w~ight % of said s11icone ~ suds suppre~sor, wh~ct~ comprises (1) a .
` nonaqueous emulsion of a primary antifoaln agent which is a mix~alre of (a) a polyorganosiloxalle, (b) a resinous siloxane or a silicone resin-prod~cing sil~cone compound, (c1 a finely divided filler material, and (d) a catalyst to :promote the reaction of mixture componants ~8~, (b~ and (c~, to fora~ silanolates; (2) at least one ~ nonionic sil~cone surfact~nt; and (3) polyethyl~ne glycol or a : ~ copolymer of polyethylene-polyproFylene glycol haYing a salubility in water at :room temperature of more than about 2 weight X; and ~: ~ withuut polypropylene glycol. Similar a~ounts~ can be used in ::~: ; ~ granular compos~tions, gels,~ e~c.; See a~so U.S. Patents 4,~78,471, ~tarch, issued December 18, ~99û, and 4~9B3~31Ç, Starch, issued January 8, 1991, and U.S. Patents 4,63~,489 and 4i,749.740,::Aiiawa et al at ~olumn~ 1, line 46 through~ol~n 4, : line 35.:
The; silicone suds: ~suppressor herein pre~e~ably comprises pol~yethylene glycol and~a~opolymer~ of polyethylene glycol/poly-: propylene g~ycol, all having an average m~lecular weight of l~ss : than about l,OOO, pre~erably between about lOO and 800. ~he : : polyethylene glycol~ ~and polyethylene/polypropyJene copolymers herein~have~:a~solubili~y in ~ater at room temperature of mDre than ; about 2 weigh~X, preferably ~ore than about 5 weig~t X.

WO 94/12598 2 ~ 4 8 1~ 9 7 PCT/US93/11GiSl - 2g -The preferred solvent herein is pol~yethylene glyool having an average ~olecular weight of less than about 1,000~ more preferably between about lûO and 800, most pre~erably between 200 and 4û0, and a copolymer of polyethylene glycol/polypropylen~ glycol 7 preferably PPG 200/PEG 300. Preferred is a we~ght ratio of between about 1:1 and 1: lû, most preferably between 1:3 and 1:6, of polyethylene glycol :copolymer of po7yethylene-polypropylene glyc~l .
The preferred sil icone suds suppressors wsed herein do not con~ain polypropylene glycol ~ particular`ly of 4,00û mslecular we~ght. They also preferably do not contain block c~polymers of ethylene oxide andl propylene oxide, like PLllP~ONIC L101.
Other suds suppressors useful herein compri se the secondary alcohols (e.9., 2-alkyl alkanols~ and mixtures of such alcohols i5 with silkone oils, such as the silicon~s d1sclosed in U.S.
4,798,679, 4,07~,118 and EP 150,872. The secondary alcohols include the C6-C~6 alkyl alcohols having a C~-C16 c31ain. A
preferred alcohol is 2-butyl octanol g which is available from Condea under the trademark ~SOFOL 12~ Mixtures of secondary alcohols are available under the trademark ISALCHEPl 123 from Enichem. Mixed suds suppressors typically comprise mixtures of alcohol ~ silicone at a weight ratio of 1:5 to 5:1.
For any detergent co~pos~tions to be used in auto~at~c laundry washing rrachines, suds should not form ~o ~he extent that they overflow the w~shin~ ~achine. Suds suppressors, when util ~zed9 are preferably presgnt in a "suds suppressing a~ounl~. ~
By asuds suppressing amount~ is meant that the formulator of the compos~tion can select an amoun~ of this sud controlling agent ,! that will suff:kiently control the suds tv result in a low-sudsing laundry detergeTIt for use in automatic laundry washing~machilles.
.1 The compositions herein will generally eomprise fr~ 0% to abnut 5X of suds supp~essor. ~Ihen utilizes~ as suts suppressors~
monocarboxylic fatty acids~ and salts therein, will be present typically in amounts up to about 5%, by we19hl;9 of the detergent :~ 3s composition. Preferably, froln about 0.~ to about 3% of fatty monocarboxylate suds suppressor is utili~ed. Silicone suds suppressors are typical~y utilized in amounts up to about 2.O%, by weight~ of the detergent composition, although higher amourl~s may .
~, WO ~4/12598 . PCTIUS93/11451 21~8097 be used. This upper limit is practical in nature, due primarly to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing. Preferably from about 0.01~ to about 1% of sil kone suds suppressor is used, more preferably from about 0.25% to about 0.5%. As used herein, these weight percentage values include any silica tha~ may be uti7ized in combination with polyorganosiloxane, as well as any adjunct materials that may ~e util~zed. Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from about 0.1% to about 2%, by weight, of the composition. Hydrocarbon suds suppressors are typically utilized in amounts rangin~ from about 0.01X to about 5.0X, al~hough higher lev~ls can be used.
In addition to the foregoing ingredients, the surfactant compositions herein can also be used with a variety af other adjunct ingredients which provide st~ll other bene~ts in Yarious compos~tions within the scope ~f this inYention. The following illustrates a var~ety of such adjunct ingredienks, but is not intended to b~ lim~ting there~n.
~ E~e~1:JS~ n~r~ ~ Various through-the-wash fabric softeners, :1 20 especially the impalpable smectite clays of U.S. Patent 4,062,647, 1 Storm and Nirschl, issued December 13, 1977, as well aj other : I softener clays known in the art, can opt~onally be used typically at levels of fro~ about:O.S% to about ~OX by weight in the present tompos~tions to provide fabric softener beneflts eoncurrently with ~5 fabric cleaning. The polyhydroxy:fatty ~cid amides of the:present invent~on cause less inter~erence with the softening perfonmance of the clay than do the common polyethylene oxide nonionic surfactants o~ the art. Clay softeners can be used in combination ~ith amine and cationic softeners, as disclosed, for example, in n ! 30 U.S~ Patent 4,375,416, Crisp et~al, March 1~ 1983 ~nd U.g. Patent 4,291,071, Harris et al, issued Septe~ber Z2, 1981.
he c~post~ions herein are : des1gned to provide good c~ea~ing with quite low:sudsing. Accord-ingly~ if the fo~mulator wishes to incorporate sdditional high 3$ sudsing surfactants into: the compositions to provide var~ous auxiliary cleaning benefits, it is pre~rred that such surfa~tants be used at levels less than about 1~% by weight. If levels up to ~:m3~X ~y: weight~are used, then it is- preferable to also employ one .

_WO 94/12598 2 1~ PCT/US93111451 or more of the suds suppressors noted above to help maintain low sudsing.
Nonlimiting examples of optional (albeit high sudsing) surfactants useful herein include the conYentional C11-C1i6 alkyl benzene sulfonates, the C12-C1g primary and secondary alkyl sulfates and C12-C18 unsaturated (alkenyl~ sulfates such as oleyl sulfate, the C10-cl8 alkyl alkoxy sulfates (especially ethoxy sulfatesl9 the Clo-cl8 alkyl polyglycosides and their correspond-ing sulfated polyglycosides, C12-C1g alpha-sulfonated fatty acid esters, ~12-Clg alkyl and alkyl phenol alkoxylates ~especially ethoxylates and mixed ethoxy/propoxy), C12-C1g b~taines and sulfobetaines, C1~-C18 amine oxides, and the like, having due regard for the effects on sudsing noted above. Polyhydroxy fatty acid amides wherein R1 is methyl can also be used. Other conven-tional useful surfactants are listed in standard texts.
O~t~r~ kLe~ A wide variety of other i~gredients useful in detergent co~pos~tions can be included in the composi-- t~ons herein, including other artive ingredients, carriers, hydrotropes, p~ocess~ng aids, dyes or pigments, solvents for liquid ~ormulations~ etc.
Various detersive ingredients employed in the present co~po-sitions advantageously can be stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic ~Dating. Preferably, the de~ersive ingredient is admixed with a .ur~actant before bein~ absorbed into ~ the porous substrate. In use, the detersive ingredient is : released from the substrate lnto the aqueous washing liquor, where it perfo~ms its intended detersive function~
~ To illustrate this technique in ~ore detail9 a porous hydr~-`I ' 30 phoblc silica ~trade~ark SIPERNAT D1~, DeGuss`a) isiadmixed with a : proteolytic enzy~z solution containing 3%~5% of C13 15 ethoxylated ~ alcohol EO(7) noniontc surfactant. Typically, $he enzyme/surfact-: ant solution is 2.5 X the weight o~ silica~ ~he resultin~ powder : is dispersed with stirring in silicone oil (various silieone oil : 35 viscosities in the range of 50~-12,~00 can be used). The result-; ing silicone oil dispersion is emulsified or othe~wise added ta the final d~tergent matrix. By this means, ingredients such ~s ` ,~

WO 94/12~98 PCT/~S93tll4~
2~4~9't - 32 - ' the aforementioned enzymes, b~eaches, bleach actiYators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfact2nts can be "protected" for use in deter-gents, including liquid laundry detergent compas~tions.
L~quid detergent comp~s1t~ons can contain water and oth~r solvents as carr~ers. Low r~ol.ecular weight primary or secondary alcohols exemplified by ~~.methanol, ethanol~ propanol, and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those conta~ning from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propan~d~ol, ethylene glycol, glycerine~ and l,2-propanediol) can also be used.:
The detergent compositions herein will pref2rably be formulated s~ch that during use in aque~us cleaning operations, the wash water will haYe a pH of between about 6.5 and abaut ll, preferably between: about 7.5 and about 10.5. Liguid product formulat~ons preferably have a pH between about 7.5 and a~out 9.5, : more preferably betwcen about 7.5 and about 9Ø Techniques for controlltng pH at recDmmended usage levels include the:use of buffers, alkalis, ac~ds, etc., and are well known to those skilled in the art. : ~
The following are typt~ai, nonlimlt~ng examples wh k h lllustrate the use of the m~xed nonion~c/anionic surfactant ~ systems provided by this ~nvention to prepare fully-formulated `~ 25 detergent compos~t~ons. ~ ~

A liquid detergent compositlon herein comprises the ~: fot~owing.
Inqredient 30~ Nonioni~/aniontc~ i5!0 `Sodium ci~rate : 1.0 ~ ; Clo alcohol ethoxytate ~3)~ :~ 13.0 ;~ ~ Monoethanolamine : ~ ~ ~ : 2.5 atertpropylene glycol/ethanol (:100:1:1) Balaace : 3s ~ : ~*l:l~ mixtura:o~ ~coconutalkyl N-n-propyl glucam~de and its : sulfated counterp~art~surfactant, Na sal~. ~

~ 0 94/12598 21 4 ~ O 9 7 PiCT/US93/11451 ~EL~LL
A granular detergent herein comprises ~he following.

Nonionic/anionic* 10.0 S Zeolite A (1^10 micrometer)30.0 Sodium citrate 10.0 Sodium carbon:ate 20.0 Optical brightener 0.1 Deters~ve enzyme** 1.0 C~4 16 Fatty acid 5.0 Sodiu~ sulfate ~5.Q
~ater and minors ~ Balance ~1:1 mixture of tallowalkyl N-n-hexyl glucamide and its ~sul-~ated counterpart surfactant, Na salt.
~Lipolytic enzyme preparation (LIPOLASE).
~: :EXAM~E~
~he compos~tions of Example II and III are modified by including 0.5% of a commerc~a~ proteolytic enzyme preparation (ESPERASE) therein. Optionally, 0.5% of a commercial a~ylase preparati:on ~TERMAMYL) and 0.5% of a commerei:al lipoly~ic enzyme preparation (LIPOLASE) can be co-incorporated in such detergent compos~tions.
: E~l!!
~ A washing composition with high grease re~oYa~ properties is : 25 as follows.

Nonionic/anionic* : 20.0 Coconut monoethanolamine 1.0 Water : ~ Balan~ce ~C12-C14:fatty aci~ afflide ~f N-n-propyl g~ucamine or N ethyl fructamine, sulfated to provîde ~a 3:1 nonionic:sulfated anioflie mixture and neu~ralized partly~ w~th MgSO~ and partly w1th NaOH to provide a Mg content in finished detergent compos~tions of 1.6%.
`:

A ~stable, clear, transparent liquid he~vy duty laundry detergent suitable for use in European-style front-loading washing : machines is~as follows.

WO 94112598 Pl:: T/US93/11451 ?.,~ 4~09~ 34 -Inqredient % (wt,.1 C12 14 N-n-prqpyl glucamide 8.0 C12-14 N-n-propyl glucamide sulfate ~.o ~12-14 ethoxylated alcohol (E07) 7.5 Pal~ kernel fa~ty acids ~~ ~ 6.0 Citric acid (as anhydrous]; 3.0 Ethanol .`~` 3,0 1,2-propanediol 4.0 Monoethanolamine/NaOH to 7.8-8.0 Water and minors ~ Balance PL~
A heavy duty laundry granule suitable for use in a European washing machine is as follows. :
lnqredient % lwt.
~12-18 N-n-propyl glucamide sulfate g,o ~12-18 N-n-propyl glucamide: 6.0 ~eolite A (1-10 microns) ~ : 20.0 Sodium s~licate : : ~ 4.Q
Sodium carbonate ~ }0.0 Polyacryl:ate~ma~eate copolymer* 4.0 ~ Diethyl0ne triamine pentakis ~methylene : pho~sphonic acid) ~ 0.4 Tetraacetylethglenédiamine ~ 5.0 So~ium cit~ate Sodium~perborate1H20 ~ 16.0 ~ater and minors : ~ ~ ~ Balance *Available from BASF Corp. under the trade na~e 50KALAN CP5.

; The compositions of Exa~ples V and VI are, respectively, modified by replacing the nonionic and anionilc N-n!propyl polyhy-droxy~ fatty acid amides with their ~espe~tive~ :N-n-butyl, ` N-isobutyl: and N-n-hexyl counterpart compounds~ to secure ~ow-~ ~ : sudsing~ompos:iti:ons. : ~ ~ ~
:: : The~ forego1ng dislosure and Examp~es illus~rate the practice ~f this invent1~on ~n cons~erablè detail. It :is to be appreci-ated,~ however, that the:advantag~s a~forded by the ~om~ositions and proeesses of this~ invention are broadly use~ul with a variety : of other technologies wh~ch have been developed for use in a wide .~WO 94/12598 2 1 4 8 o 9 7 PC~/US93/11451 variety of modern, fully-formulated cleaning compositions, espe-cially laundry detergents. The compositions herein will typically be used i n aqueous medi a at concentrati ons o~ at l east about 200 ppm, e.g., for lightly-soiled fabrics and/or hand dishwashing.
Higher usage concentrations in the range of l,ûO0 ppm to 8,0û0 ppm, and higher, are used for heavily-soiled fabrics. However, usage levels can vary, depending on the desires of the user9 soil p loads, soil types~ and the like. Wash temperatures can range from 5C to the boil.
As disclvsed hereinabove, the mixed nonionic/anion k composi-tions herein can also comprise mixtures of nonionic compounds of formula I:, wherein Rl is C2-Cg a~kyl with their anionic, sulfated counterpart compounds wherein R1 is methyl. Likewise, the mi~ed nonionic compositions can eomprise mixtures of nonionic ccmpounds of formula I wherein Rl is methyl and their anionic, sulfated co~paunds wherein Rl are C2-Cg alkyl. In such mixtures, the weight ratio o~ .~he nonionic:anionic compounds typically ranges - from about 10:1 to about 1:10.

' . 20 :
:

, ~5 :~; , :

Claims (14)

1. A method for cleaning surfaces with low sudsing, character-ized in that it comprises contacting the surface to be cleaned with an aqueous medium containing a mixed nonionic/anionic sur-factant system which comprises a polyhydroxy fatty acid amide (a) of the formula:
wherein R1 is C2-C8 hydrocarbyl, R2 is C5-C32 hydrocarbyl, and 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 10:1 to 1:19.

2. a method according to Claim 1 which comprises laundering fabrics.

3. A method according to Claim 1 wherein a secondary (2,3) alkyl sulfate is also present in the aqueous medium.

4. A method according to Claim 1 which comprises washing eating utensils or other hard surfaces.

5. A method according to Claim 1 which comprises cleansing skin or shampooing hair.

6. A method according to Claim 1 wherein R1 is n-propyly n-butyl, isobutyl or n-hexyl, whereby cleaning is achieved with low sudsing.

7. A method for laundering fabrics in an automatic washing machine according to Claim 6.

8. A method for washing eating utensils in an automatic dish-washer according to Claim 6.

9. A method for cleaning hard surfaces according to Claim 6.

10. A composition of matter which is especially adapted for use as the surfactant mixture in a detergent composition, character-ized in that it comprises (a) a polyhydroxy fatty acid amide of the formula:
wherein R1 is C2-C8 hydrocarbyl, or a mixture thereof, R2 is C5-C32 hydrocarbyl, and 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 10:1 to 1:10.

11. A low sudsing composition according to Claim 10 wherein R1 is selected from n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl and n-hexyl, and wherein R2 is C12-C18 hydrocarbyl.

12. A low-sudsing composition according to Claim 10 wherein R1 is C3-C8 hydrocarbyl and the combination of R1 and R2 comprises a total of no more than 20 carbon atoms.

13. A composition of matter, characterized in that it comprises:
(a) a polyhydroxy fatty acid amide of the formula:
wherein R1 is C2-C8 hydrocarbyl, or mixture thereof, R2 is C5-C32 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least two hydroxyls directly connected to the chain; and (b) a sulfated reaction product of the foregoing polyhydroxy acid amide having R1 as methyl;
at a weight ratio of (a):(b) of from 1:10 to 10:1.

14. A composition of matter, characterized in that it comprises:
(a) a polyhydroxy fatty acid amide of the formula:
wherein R1 is methyl, R2 is C5-C32 hydrocarbyl and Z is a polyhydroxyhydrocarbyl moiety having a linear hydro-carbyl chain with at least two hydroxyls directly connected to the chain; and (b) a sulfated reaction product of the foregoing polyhydroxy fatty acid amide having R1 as C2-C8 alkyl;
at a weight ratio (a):(b) of from 1:10 to 10:1.