CA2148099A1 - Detergent compositions with calcium ions and polyhydroxy fatty acid amide nonionic/selected anionic/soap surfactant mixture - Google Patents

Abstract

Mixed nonionic/anionic surfactants which comprise polyhydroxy fatty acid amides and anionic surfactants of the .alpha.-sulfonated fatty acid esters, alkyl ethoxylated sulfate, alkyl ethoxylated carboxylate, alkyl sulfate or sulfated alkyl polyglycoside types are used in various cleaning functions. Thus, C10-C22 fatty acid N-alkyl glucamides are combined with such anionic surfactants, a soap and a source of calcium ions. The resulting mixtures exhibit exceptionally low interfacial tension, especially in the presence of calcium ions. Mixtures of such nonionic/anionic/soap/calcium systems surfactants with conventional ethoxylated alcohol surfactants provide excellent removal of cosmetic stains from fabrics.

Description

wo 94/12609 2 1~ ~3 0 9 9 PCTruss3lll4s3 DETERGENT COMPOSITIONS ~ITH CALCIUM IONS AND POLYHYDROXY FATTY
ACID AMIDE NONIONIC/SELECTED ANIONIC/SOAP SURFACTANT MIXTURE

FIELD OE T~_INVENTlON
The present invention relates to fully-fornulated detergent compositions containing a polyhydroxy fatty acid amide surfactantt a ~ember of a specially seleoted class of aslionic surfactants, together with a soap. The r~sulting compositions yield extremely low interfacial tensions in aqueous media9 especially in the presence of cakium ions, and are thus useful for cl~aning operations .
~QY`~
Most conventional de~ergent compositions contain mixtures of various detersive surfac~ants in order ko remove a wide variety of soil s and stains from surfaces. For example, various anionic surfactants, especially ~he alkyl benzen~ sulfonates, are useful for removin~ particulate soil s, and various nonionic surfactants, such as the al kyl ethoxyl ates and al kyl phenol ethoxyl ates are useful for removing greasy soils. Accordingly, m~xtures of anionic and nonionic surfactants are used in ~any modern det@rgent compositions .
While a review of ltlhe literature wsuld seem to suggest that a wide selection o~ surfactants is availlable to the detergent manu~acturer, the rea,l ~ ~ s that many such materi al s are specialty chemica~s which are not suitable for routine use in low unit cost items such as home laundering c3mpos~tions. The fact remains that most hs~me-use detergents still comprise one or ~ore of the conventional ethoxy~ated n:onionic a,nd sulfated or sulfon-ated anionic surfactants, pr~su~ably due to the econ~mic and perfonnanse ~onsiderations noted below.
Unfortun~tely, many modern detersive xurfac~ants are availa-ble mainly from nonrenewable resou~cs, such as petroche~3icals.
,: Soaps, i.e~, the salts of fatty acids, comprise tr~ditional and time~hono~ed c~ ass of surface-active agents . Soaps have the advantage that they are available via the hydrolysis of renewable resources such as p~ant and animal oils and fats~ Unfortunately, soaps are quite susceptible to the fonnatiQn of ncurd" in the presence of water hardness. Moreover, soaps are not as effective for lowering solution interfacial tensions across conditions of pH

WO 94tl260~ ` PCT/US~3111453 and water hardness as are their counterpart synthetic surfactants, and are 1 ess effecti ve cl eaners, especi al ly for grease and oi l deposits ~
Considerable attention has lately been d~rected to nonionie surfactants which c?n be prepared using mainly renewable resources, such as fatty acid esters and sugars. One such class of surfactants includes the polyhydroxy fatty acid am~des.
Moreover, the combination of such nonion~c surfactants with oonventional an~onic surfactants such ~s the alkyl sulfates, alkyl benzene sulfonates~ alkyl ether sul~ates, ~nd the like, has also been studied. Attention is now b@ing given to the improvRment of ;~
such combinations o~ nonionic/ani~nk surfactants, espec~ally w~th regard to their abil ~ty to reduee interfacial tensions and to provide improved grease,/oil removal from a variety of substances.
To achiev~ this goal t esp~cially in the abs~nce of phosphate builders, is a substantial ohallenge to the detergent fonDulator.
BACK6ROUNU ART~
A method for preparing crude polyhydroxy fattx ac~d amides (glucamides) is described in ll.S. :Patsnt 1,985,424, P~ggott, and in U.S. Patent 2,703,798, Sehwartz. ~The usg of such glucamides ~-with various synthetie anionic surfactants is descr~bed in U.S.
Patent 2,965,576, corresponding to G.B. Patent 8099060. The sulfuric esters of acylated glucamines . are disclos~d in U.S.
Patent 2,717,8~4, SchwartzO :: -5~.E~Y~
The present inYent~on : encompasses detergent compos~tions ~:; : which provide an extrem~ly ?ow interfac:~al t~ns~on, compr~sing a:
mixed nonionictanionic/soap surfactant syste~ whi~h comprises:
(a) a polyhydroxy fatty acid amide ~f the fo~rmula i ~I
o ~1 R2 - c ~ 6 ~
: : wherein :RI is H, Cl^C3 hydrocarbyl, 2-hydroxyethyl, 2-hydroxyp~opyl, or a ~ixture therein, R2 is ~5 C32 hydrocarbyl, and ~:is a polyhydroxyhydrosarbyl mo~ety having a l~tnear hydrocanbyl chain w~th`at:léast two (in the case of glyceraldQhyde), preferably at lea t three (in the case of other reducing sugars) hydroxyls : : directly:connect~d to the ehain~

.~

WO 94/12609 21~ 8 0 9 9 PCT/U593/11453 (b) an anionic surfactant whkh is a ~ember selected ~rom thQ group consisting of alpha-slllfonated fatty acid esters ~also known as alkyl ester sulfonates~
especi al ly ~athyl esters ( ~MES~ ), al kyl al koxyl ated sulfates, ~specially alkyl ethoxylated sulfates (YAES~), al kyl ethoxyl ated carboxyl ates ( I'AEC~ ~, al kyl and alkenyl sulfates ('?AS"), and sulfated alkyl polygtueosides (aSAP"); at a weight ratio of (a):~b) of from about 10:1 to about 1:10;
(f~) a soap; and ~d) a source of cal~ium ions.
The ~anionic surfactants~ enlployed herein are all well-knGwn to detergent ~orlnulators. The C~ alp~a-sulfonated fatty acid methyl esters, the f:l2-18 alkyl ethoxylated (EO 1-7, preferably 3) 1~ sulfates, the C12~1~ alkyl ethoxylated ~(EO 1-7, preferably 3-4) carboxylates, the C12 1~ primary and secondary alkyl and alkenyl ~e.g., oleyl) sulfates and the sulfated C1~ 18 alkyl po~yglyco-sides are all fully described ~n the extensiYe patent and general literature on surfactants.
The terrfl ~soaps" herein is intend~d to encompass the classlc, conventional water-soluble salts of Clo-C18 linear satura~ed and unsaturated fatty acids. Comp~sitions accord~ng to the present invention containiFIg such soaps @xh~b~t qu~$e low ~nterfacial tensions and good yrease remos~al properties, eYen ~lt pllrs near neutral ity, i .e~, in the range of ca~ 6.~' 11.09 and are thus qu~t~
useful for fabr~c lallnderiag~ As a yeneral proposi~on, the improved qualit~es of the compos~tiorls herein appea~ to peak with soaps of about C12, and lto decre~se somewhat ~th soaps whieh are longer than~abollt C13 and shorte~ than a~oul~ spec~ally~lw~th re~pect lto spontaneous emuls~fication of greasy so~ls. Accord-ingly, the C12 soaps are preferred herein, The asoaps~ can be employed: in any ~ water-so1uble sal~ form, e.g., alkali metal, alkaline e~rth ~metals, a~oniunl, alkanQl~n~nonium~ di- or tri-alkanolam~onium?, Cl ~ alkyl amnon~um, basic a~ino acid groups~ and 35 ~ the l~ike; all o1 which are well-known to manufacturers. The sodium salt ~o~n: is convenlent, cheap and effect~v~. The ~at~y acid fn~n can also be used, btlt w111 usllally be conv~rted ~ntQ the ionic forn by pH ~d3ustm~nts which are made during processing of :: :

WO 94/12609 21~ 8 0 9 9 PCT/V593tll453 the compositions. Since water-soluble soaps are generally easier to work with, it is preferred that they be used, rather than the fatty acid form.
Nonli~ting examples of s~aps useful herein include: deca-noate; undecanoate; laurate; undecyleneate; tridecanoate;
2-dodec*noate; and mixtures thereof.
The :soaps typically comprise at least abo~t 1% by weight of the compositions herein and preferably cumprise ~rom about 4% to about lOX by weight of the total oompos~tions her~in. Stated otherwise, the weight rat~o of soap (c) to the co~bined mixture nonionic/anionic (a + b) is in the range c:(a + b) fro~ about 1:20 to about 1:2, preferably about 1:9 to abo ffl 1:3.
Preferred eompositions herein contain at least about lOX, preferably from about 25X to about 65X, by weight of said mixed nonionic/anionic/soap surfactant system. Such composttions typi~alty co~pr~se from abou~ 5X to about 50% of the nonionic sur~actant and from about 5% to about 50% of the an~onie surfact-ant. Highly preferred are compos~tions whieh add~t~onally oontain fro~ about 2X to about 40% by weight o~ an add~t~onal detersive surfactant, as well as other optional deters~ve adjuncts as di sl osed herei nafter . Al koxyl ated al cohol s or al koxyl ated al kyl phenol s at 1 evel s of at ~ east about lX, pref~rably about 2% to about 6%, are espec~ally preferred.
The invention thus ~ncompasses co~positions which comprise from abo~t 1~ ~o about 65% b~y ~eight of said m~xed nonioni~ani-onie/soap surfactant system, fro~ about 1% to about 15% by w~ight o~ an ethoxylated Cg-C24 ~alcohol, and ~ptional builders and ~eters~v~ enzymes. Such compositions exh~b~t espsci al ly good removal of cqs~et~c stains from fab~ics. : i I
The compos~tions herein will also contain from about 0.5X to about 2X~ pref~rably from about lX to about 1.5%, by w~ight, of calcium ions. High sudsing compositions will also cont;ain from about 0. 5Y~ to about 2%, preferably about 1%9 by weight of : magnesium i~ons... Sources o~: cal`c~u~ and magnes~um can be any convenient water-so~uble and toxic~logically aeceptable salt, including but not limited to9 caleium formate, Ca~12, ~gCl~, Ca(OH)~ (OH)~, CaBr2, M~Br2, C~ mal~te, Mg ~alate; Ca ~aleate9 : Mg maleate, or :the calcium and/or magnesium salts of anion k WO 94/12609 , 21,~8D99 PCT/U593/11453 surfactan~s or hydrotropes. CaC12 and MgC12 are convenient and preferr~d herein .
If builders are used in the compositions, it is preferred that ~hey be non-phosphate bu~lders sueh as s1trate, zeol ite or layered silicate. This allows a residuum of ca1cium ions to advantageously eo-act will;h the surfactant system to help lower interfaci~l tension.
~he invention also encompasses a method for redllcing the interfacial tension (IFT; oil/water interface) in a system comprlsing water (e.g., a washing liquorJ and o~l (e.g., a stain or soil on solid sur~aces, fabrtcs, dishware, and the. like~ to a level of about O.lS dynes/cm at the oil/wa~er interface9 whe~reby spontaneous emulsification can occur, thereby cleansing said sDlid surface . In general, usage l evel s of at l e~st about ~00 ppm, typically from about 300 ppm to about 3,000 ppm, of the composi-tions of this invention in water achieve this desirable resultO
The invention also encompasses an i~proved m~thod for removing greasy sta;ns such as cos~etic stains from fabrics, comprising contacting the fabrks thus sta~ned w~th an aqusous bath containing at least abaut 0.02~ by we~ght of a -composition which c~mpr~ses sa:id mixed nonionicjanionic surfact3nt system and said Cg-~24 alkoxylated (preferably ethoxylated) alcohol or al k~xyl ated C~-C24 al kyl. phenol (pre~erably ethoxyl atedj .
All percentages, ratios and proportionc herein are by we~ght, 2~ unless otherdise specified. All documents c~ted are incorporated herei n by reference .

~hile the polyhydroxy fa$ty acid ami~es ~Ised herein ean be prepared, for ~example, by the ~ethods di Glos~d ~n thel Schwart~
`~ 3b 1 references~ above, this invention most preferably employs higt) quality polyhydroxy ~atty aeid amide surfactants which are substantta11y free:of cycl ked by-produsts.
: As an overall proposition, the preparative methods described : in ~0-9,206,154:and ~0-9,206,984 will afford h~gh qual~ty poly-: hydroxy ~atty acid amides. The methods comprise reacting N-alkylamino~polyols with, pre~erably, fagty acid ~ethyl esters in : a solvent using an~alkoxide catalyst at temperatures of about 85~C
~: to provide high yields (90-98%) of polyhydroxy fatty acid amides ~ ~
:

having desirable low levels (typically, less than about 1.0X) of sub-optimally degradable cyclized by-products and also with improved color and impro~ed color stability, e.g., 6ardner Colors ~ below about 4, pre~erably between 0 and 2. For high sudsing 3j ~ co~positions, the N-methyl and N-hydroxyalkyl amine compounds are 3 preferred. For low sudsers, the C2-C3 alkyl, preferably the N-C3 t alkyl amine compounds 3 are used. (~ith so~e of the low sudsers, the methanol introduced via the catalyst or generated during the reaction provides sufficient fluidization that the use of additional reaction solven~ may be optional.) If desired, any unreacted N-alkylamino polyol remaining in the product can be acylated with an acid anhydride, e.g., acetic anhydr~de, maleic anhydride, or the like, to minimtze the overall level of amines in the product.
By ~cyclized by-productsa herein is ~ant the undesirable reaction by^products of the primary reaction wherein ~t appears that the multiple hydroxyl groups in the pDlyhy~roxy fatty acid `~ a~ides an form r~ng structures whlch may not be readilybiodegradable. It w~ll be appreciated by those skilled in the chemical arts that the~preparation of the polyhydroxy fatty acid : amid~s herein ~sing the di-:and higher sacchar~de such as ~altosewill result :in the formation~of polyhydroxy fatty acid `amides ~: where~n linear: substituent ~Z-(wh~ch c~ntains multiple hydroxy substituents): is naturally~ ~sapped4 by a polyhydroxy ring structure~. ~Such: ~aterials are not cy l~zed by-products9 as : defined~herein.~
More generally, the processes and compositions her~in employ polyhydroxy ~atty acid ami~e surfactants o~ the formula: :: :

(I) R2 - C - h - z wherein~ R1 ~is~ H, C1-C3 ~hydrocarbyl ~ (Cl-C2 is pre~rred for d~shwashing; :C3 is~ ~preférred~ for ~abric ~laundering), 2-hydrnxy-ethyl, ~ ~ydroxypropyl,:: or: a mixture thereof, preferably ~ C4 alkyl, more preferably Cl or C2:alkyl,: most preferably Cl alkyl : :(iOe~ yl); and R~ is a Cs-~3l :hydrocarbyl moiety9 preferably straight ~chain C7-~1g alkyl~: or ~alkenyl, ~re pre~erably straight :chaln Cg-C17~ alkyl :or alkenyl, most preferably straight chain ~ , WO 94/12609 ` ` : PCT/US93/11453 7 S 0 9 ~
Cll-Clg alkyl or alkenyl~ or mixture thereof; and Z is a poly-hydroxyhydrocarbyl moiety having a 11near hydrocarbyl chain with at lcast 2 ~in ~he case of glyceraldehyde) or 3 hydroxyls (in the ease of other reducing sugars~ d~rectly eonnected to the ehain, or an alkoxylated derivative ~preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glyc~tyl moiety. Suitable reducing sugars include glucose, fruetos~, maltose, lactose, galactose, mannose, and xylose, as well as glyceraldehyde. As raw materials, high dextrose corn syrup, high fructose corn syrupt and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar eo0ponents for Z. It should be under-stood that lt is by no m~ans intended to iexclude other suitable raw materials. Z preferabïy will be selected from the ~roup consisting of -CH2- ~CHOH)n-CH20H, ~CH(CH~OH)- (CHOH~n~l-CH20H, -CH2-(cHOH)2(cHoR~)(cHQH)-cH2oH~ where n is a~ integer from 1 to 5, inclusive, and R' is H or a cycl~c mono- or poly- saccharid2, and alkoxylated derivat~ves thereof. Most preferred are glycityls whereln n is 4, particularly -CH2-(CHOH)~-CH20H.
Xn Formula (I), Rl can be, for exa~ple, N-methyl9 N-ethyl, N-propyl and N-2-hydroxy ethyl.:
R2-Cû-Nc can be, for example, ~ocamide, stearamide, oleamide, . lauramide, myristamide, eapricamide, palmitamide, tallowa~ide, ete.
Z can be l-deoxyglucityl~ 2-deoxyfruc~tyl~ l-deoxyxyl~tyl~
l-deoxymalt~tyl, l-deoxylactityl, l-deoxygalact~tyl, l-deoxyman-nityl, l-deox~altotriot~tyl, 2,3-dihydroxypropyl ~from glyceral-de~yde~, e~tc.~
1~ will be appreciated that the polyhydroxy fatty acid a~ide surfactants used herein as the noniontc surfactant component can be mixtures of materials having various subs~ituents Rl and R2.
Various ~detersive adjunet~ materials will preferably be used in fully-fo:~mulated detergent compositions containing the surfact-ant/soap~calcium ~ixtures of the present invention. The following arQ intended only to be nonl~miting ~llustrations of sueh adjuncts, more examples of whieh will readily come to mind of the skilled ~ormulator.
, WO 94/12609 21~ 8 0 9 9 PCT/US93/11453 .

En2~mes - Detersive enzymes tan optionally be included in the detergent formula~ions for a wide variety of purposes, especially ~or fabric laundering, including remoYàl of protein based, carbohydrate~based? or triglycRr~de-based stains" for example, and prevention of refugee dye transfer. The enzymes to be incorpor-ated include prote~ses, amylases, lipases, oellulases, and per-oxidases, as well as mixtures thereof. Oth~r typ~s o~ enzymes may also be included. They ~ay be of any suitable origin, sueh as vegetable, animal, bacterial, ~ungal and yeast ortgin. However~
lû their choice is governed by several factors such as pH-aotivity and/ur stabil;ty optima, thermostability, stability v~sus active detergents, builders and xo on. In this respect bacterial or fungal enzymes are preferr0d, such as bact~ri al amyl ases and proteases, and fungal cel l ul ases . ~ .
1~ Enzymes are normally incorpqrated at le~ets sufficient to provide up to about 5 mg by weight, more typically about 0.05 mg to about 3 mg, of active enzyme per gra~ of the compos~tion.
~u~table examples of proteases :are ~he subt~l~s1ns wh~ch are obta~ned from partiolJlar s~rains of ~.subtil~s and B~liohenifo~ns.
~nother su~able protease is obtain~d from a stra~n of Bacillus, having maximum aoti~ty throughout the pH range of 8-129 deYalope~
and sold by Novo Industries A/S under the r~gistered trade name SPERASF. The preparation o~ th~s enzyme and ana~ogous enz ~ s is descrlbed in British Patent Specl~ication No. 1,243,784 of Novo.
Proteolytic enzymes su~table for removing protein-based sta~ns : that are commercially aval7:able include those sold und~r the tradenames ALGALASE and SAVINASE by Novo Industrl~s ~/S (Denmsrkj and PAXATASE by Internat~ional B10-Synthe~ics, ~ Inc. ~he Netherjlands). Other proteases includR Prot~ase~lA (sqe European Patent Applic:ation 130,756, published January 9, 198~) and Protease B:~see~European Patent Applicagion Serial No.~87303761.8, filed April 28, 1987, and European Patent: ~pplication 130,756, : Batt et:al:, published:January 9, 1985).
~: Amylases includes :for example, ~-amylases descr~bed in : : 35 British Patent Spe~ification No. 1,296,839 (H3vo), RAPIDASE, lnternational Bio-Synthe~ics~ Inc. and:TE ~ YL, Novo Industries.
: : The cellulases usable~in the present lnvention include both bacterial or ~ungal cellulase. Preferably? they will have a pH

WO 94/12609 ~ 8 0 9 9 PCTNS93/11453 _ g _ optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Paten~ 4,435,307, Barbesgoard et al, issued Mareh 6, 1984, which discloses fungal cellulase produced from Humicola ~nsolens and Xumicola strain DSM1800 or a cellulas~ 212-produciny fungus belonying to the genus Aeromonas, and eallulase extracted from the hepatopancreas of a mari ne mol 1 usk ~Dol abel 1 a Auri cul a Sol ander~ .
Suitab~e cellulases are also dtsclosed in GB-A-2.075.028;
GB-A-2.095.275 and DE-OS-2.247.832.
Suitable lipase enzy~es for d~tergent usage include those produced by microorgan~s~s of the Ps~udomonas group, sueh as Pseudomonas stutzeri ATCC 19.154, as disclosed in Bri~ish Patent 1,372,034. See also lipases in Japanese Patent Appl~cation 53-20487, laid open to public inspectton on February 249 1978.
This lipase is available ~rom Amano Pharmaceutical Co. Ltd., Nagoya, Japan, unde~ the trade na~e Lipase P ~Amano,U here~nafter referred to as ~Amano-P.~ Other co~mere~al l~pases ~nelude Amano-CFS, 1 ipases ex Chromobacter viscosu~, e.9~ Chro~b~cter , vl'scosum var. 7ipo7ytic~m NRRLB 3673, commercially a~atlab7e from i Toyo Jozo Co., Tagata, Japan; and further Chromobacter ~iscosum ~I 20 lipases from U.S. 3iochemical Corp., U.S.A. and Uisoynth Co~, The ¦ Netherlands, and lipases ex Pseudomonas ~7adio7i.
Peroxidase enzymes are used in combination with oxygen sources, c.g., percarbonate, perborate, persulfate, hydrogen :~1 peroxide, etc. They are used for ~solution ~leaching,~ i.e. to 25 prevent transfer of dyes or pig~ents removed from substrates dur~ng wash operations to ~ther subs~rates in the wash solu~ion.
Perox~dase enzymes are known in the art, and ~nclude, for example, horseradish perox~dase, ligninase7 and halop~rox~dase such as Dro- and~ bro~o-peroxidase. Peroxidase-containing I dete~gent 3~ compasitions are disclosed, for example, in PCT International Appl~catl~n WO 89/099813, published October 19, 1989, by 0, Kirk~
assigned to Novo Industries A/S~
A wid~ range o~ enzyme ~aterials and means for their incorp-oration into synthetie detergent granules is also disclosed in 35 U.S. Patent 3,553,1399 issued January 5, 1971 to McCarty et 21 (3.
: : Enzymes are ~urther disclosed in U.S. Patent 4~101,~57, Place et : al, issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, : issued March 26, 1985, both. En~yme materials useful for liquid :

WO 94/1260~ 214 ~ 0 9 ~ PCT/US93111453 detergen~ formula~ions, and their incorporation into such formula-tions, are disclos~d in U.S~ Patent 4,26}~8689 Hora et al, issued April 14, 1981. Enzymes ~or use in detergents can be stabili~ed by various techni~ues. Enzyme stabilization teohnlques are disclosed and exemplified in U.S. Patent 4,261~868, issued April 14, 1981 to Horn, et al, U.S. Patent 3,600,319~ iesued August 177 1971 to Ged~e, et al, and European Patent Application Publioation No. 0 199 405, Application No. 86200586.5, published OctobeP 29, 1986, Venegas. Enzyme stabili ation systems are also described, for example, in U.S. Patents 4,261,868, 3,600,319, and 3,519,570.
In addition to enzymes, the composigions herein an option-ally include one or more other detergent adjunct materials or other materials for assisting or enhancing cleaning perfo~mance, treatment of the substrate ~o be cleaned, or to modify the lS aesthetics of the detergent composition (e.g., perfu~es, oolor~
ants, dyes, etc.~
Bujlders - Det~rgent builders can optionally be included in ~ the compositlons herein to assjst;in controlling m~neral hardness.
; ~ Inorganic::as well as organic bu~lders can be used. Builders are typically used in fabric laundering composigions to assist ~n the removal of p~rticulate soils.~
: The level o~ builder can vary w~dely d~pending upon the end : use of the composition and ~ts desir~d physical form. When present, the comp~sitions will typically compr~se at:least about ~` ~ 25 lX bu~lder. Liquid formulation:s typically compri:se from about 5%~
~: to about 5~%,~more typically about:5% to about 3~X7 ~y wei9h~$ of : : detergent ~uilder. 6ranular fo m ulations typically comprisg from about 1~% to about 80%, more typical1y f~o~ about 15~ to about 50X
` by weight~ of the ~eterg~Dt builder. .Lower or, higher l~vels of builder, how~ver, are not meant to be excluded. ~
Inorganic deterg~nt builders include,~but are not li~it~d to~
;: the alkal:i:meta1, ammonium and alkanolammonium salt of polyphos-phates (ex~mplified: by the tripolyphosp~ates, pyrophosphates, and :glassy :polymeric: meta-phosphatas),~ phosphonates, phyti~ acid, : 35 ~ :s~licates~ c~rbonates (including;bicarbonates and ~:esqui~carbon-: ates), sulphates, and::aluminosilicates. However, non-phosphate builders;are required~in some locales. Importan~ly, the composi-tions~ herein funct~on surprisingly ~ell even in the presence of : ~: ~ :;; ' WO ~4/12609 . i .~ 8 0 9 9 P~Trusg3/l~453 3 the so-called ~weak" builders (~s eompared with phosphates) such as cîtrate, or in the so-called ~underbuilt~ situation that may ~, occur with zeolite or layered silicate builders.
Examples of silicate builders are the alkali metal silicates, ~ 5 particularl~ those having a SiO2:~Na20 ratio in the range 1.6:1 to ¦ 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,6&4,839, issued May 12, 1987 to H. P.
I Riec~. However~ other silicates maX also be useful such as for ¦ example magnesium silieate, which can serve as a crispening agent in granular formulations, as a st~billz~ng agent for oxy~en bleaches, and as a component of suds contral systems.
Examples of carbonate bu~lders are the alkaline earth and alkali metal carbonates as disclosed in 6erman Patent Application No. 2,321,001 published on November 15, 1973.
Aluminosilicate builders are especially useful in the present lnvention. Aluminosi7i~ate builders are of great importanca in most currently m~rketed heavy duty granular detergent co~pos~-tions, and can also be a sign~ficant bu~lder ingre~ient in liquid detergent formulation~. Aluminosilicate builders include those having the empir~cal formula:
:` Mz~ZA102 YS~02) wherein M is sodium, potassium, am~oniu~ or subst~uted a~onium, z is from about 0.5 to about 2; and y is 1; this ma~erial having a magnesium ion exchange capacity o~ at least about S0 ~illigram equiYalents o~ CaC03 hardness per gram of anhydrous aluminosili-cate. Preferred aluminosilicates are zgol~te builders which have the formula:
: Naz[(Alo2)z ~Sio2)y]-xH2o wherein z and y are integers of at least 6, ~he ~olarlratioiof z to y is in the range ~rom 1.0 to about 0.5t and x is an integer ~ from about 15 to about 264.
: ~ : Useful aluminosilica~e ion exchang~ materials are commer-: cially available. The~e aluminosilicates can be crystalline or amorphous in structure and can be naturally occurring a7uminosili-: 35 ~ates or synthetically derived. A method for producing alumino-;~ silicate ion exchange mat@rials is dis~losed in U.S. Patent 3,985,669, Krummel, et al~ issued Octvber 12~ 1976. Preferred , WO 94/12609 2 i 4 8 0 9 9 PCTfUS93/11453 synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeoltte P (B), and Zeoltte X. ~n an aspecially preferred embodi-ment, the crystal7ine aluminosilicate ion exchange material has the formula:
Nal2[ (~lo2)l2(sio2)l2~ XH20 wherein x is from about 20 to about 30, especially about 27. This material is known as Zeolite A. Preferably, the aluminosilieate has a particle:size of about 0.1-10 microns in diameter.
Organic detergent builders suitabl~ for the pur~oses of the present invention include, but are not restricted ~07 a wide variety of polycarboxylate compounds. As used herein, ~polycar-boxylate" re * rs to~compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builder can generally bs added to the compos~tion in acid form~
but can also b~ added:in:th~ ~form of a neutral~zed s~lt. When ut~l~zed in salt form9 ~lkali metals, such as sodiu~, potassium, and li~hium, or alkanolammonium:sal~s are pre~erred. ~ :
; Included among the polycsrbo%ylate builders are a variety of categories of useful materials. One important category of poly-I ~ carboxylat~ bu~lders enco~passes the e~her polycarbo%ylates, including oxydisucc~inate, as~ disclosed in Ber~ U.S. P~tent 3,128,287, issued April 7, 1964,~and Lamb~rti et al, U.S. Patent 3,635,830, issued January 18, 1972~ ~See also ~TMS/TDS~ buil~ers ` ~ 25 of U.S. Patent ~,663,071, iss~ued to Bush et al, on May S, 1987.
Suitable :ether polycarboxylates~ also~include eyclic compounds, particulàrly :alicyclic compounds, such a~ those described in U.S.
Patents 3,923,679; 3,835,163; 4,1589635; 4,1%0,874 and 4t102.903~
O,ther;useful deterg~acy builders include the ~ther hydroxy-: ~ 30 polycarboxylates, copolyme~s~o~ ~aleic~anhydride with ethylene or inyl methyl~-ether, l,:3,~ 5-trihydroxy ~b~nz~ne-2, 4, 6 trisu~-phonic:aci;d5 and carb~xym~thyloxysuccinic acid, the v~rious alkali met~al~, an~non~um ~and ~sùbst~tuted~ an~nonium; salts of polyacetic acids :~ :: such as~::ethylenediamine` te~raac~tk :acid: and nltrilotriacetic 35~ acid, as well as;polycarboxylates such as:me1litic~acid9 succinic acid, oxydisuccinic acid9~polymaleic~acidg benzene 1,3~5-tricar-boxylic acid, :carboxymethyloxysucc;nic:-acid~ and soluble sa~ts :thereof.

WO 94/17,609 ;. ,; 21 ~ 8 o 99 PCT/US93/11453 Citrate builders, e.g., ~itric acid and soluble salts thereof ~particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulat~ons due to their avai~abil ~ty from renewable resources and their biodegradability. Cltrates can also be used in granular composi-tions, especially in combination w~th zeolite and/or layered s~licate ~uildersO
Also suitable in the det~rg~nt compositions of the present invent~on: are the ~,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U~SO Patent ~,566,984, Bush, ~ssued Januar~ 28, I986. Useful succinic acid bu~lders include the Cs-C20 alkyl and alkenyl succinic acids and salts thereof. A
p~rticularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuc-cinate, myristylsuccinate9 palmitylsucci~ate~ 2-dodecenylsuccinate (preferredJ, 2-pentadecenylsuccinate, and ~he l~ke. Laurylsuccin-ates are the pr~ferred bu~lders of this group, and ar~ descri~ed - in European Patent Appl~catlon 86200690.S~0,200,263, publlshed Nove~ber 5, 1986.
Other su~table polycarboxylates are diselosed in U.S. Patent 4,144,226, Crutchfield et al, issued March 13, 1979 and in U.S~
Patent 3,308,067? D~ehl, issued March 7, 1967. See also D~ehl U.S. Patent 3,723,322.
In situation where phosphorus ~bu~lders can be used, ~he various alkal1 metal phosphates such as the well-known sod~um tripolyphosphatesl sodium pyrophosphates and sodium orthophosphates can be used. Phosphate bu~lders such as ethane~
hydroxy~ diphosphonate and other known phosphonates ~see, for example, U.~S.~ Patents 3,159,581, 3,213,û90:; 3,~42~021; 3~4007,!148;
and 3,422,137) can also be llsed.

- The detergent compositioils :herein Inay opt~onally eolltain bleach~ny agents or bleaching conlpos~ti3ns containing a blea~hing .: ~ agent and one or more bleach~activators. When present9 bleach~ng agents ~ill typically ~e at leYels of from about lX to about 20X, more typi cal ly ~rom about :1% to about 10%~ of the deter~ent compos~tion, especially ~or fabric laundering. If present, the amount of bleach activators will typically be from about 0.1% to : -' WO 94/12609 . 214 8 0 9 9 PCT/U~i93111453 `-about 60~, more typi cal ty from about O . 5% to about 40% of the bleaching co~position comprising the bleaching a~ent-plus-bleach activator .
The bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in tgxtile cleaning, hard stlrface cleanin~, or other cleaning purpsses that ar~ now known or becon e known . These i ncl ude oxygen bl eaches as w~l 1 as other bleaching agents. Perborate bleaches, e.g. ~ sodiu~ perborate (e.gO~ mono- or tetra-hydrate) can be used herein, but~ under son~
conditions, may undesirably int~ract with the polyol nonionic surfactant.
One category of bl eachi ng agent that can be llsed wi thout restrictinn encompasses percarboxylic ~percarbonate") ac~d bleaching agents and salts therein. Suitable ex~mples of this lS class of agents include magnes~um monoperoxyphthalatQ hexahydrate, the magnesium salt :of meta-chloro perbenzoic acid, 4-nonylaml7lo~4-oxoperoxybutyric ac~d and diperoxydodecan~d~olc acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, ~lartman, issued November 2Q, 1984, IJ.S. Patent Appl~oa1;~on 740,446~ IBurns et al, filed Juns 3, 1985, European Pa~ent Application Q,1339354, Banks ~t al, publ~shed February 20, 1985, and UOS. P~tent 4,412,934? Chung e~ al, issued November 1, 1983. Highly preferred bleaching agents also include 6-nonylamillo~6-oxoperoxycaprolc acid as described ~n U:.S. Patent 4,634,551, issu~d January 6, 1987 to Burns et alt Peroxygen bleaching agents can also be u ed. Su~table : ~ peroxy~en bleaching compounds include s~d~um carbonate p~roxy-hydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide~. Pe~sulfate blea~h ~.9~, OXONE, manufac~u~ed 3û con~nercially by DuPontJ can also be used.
Mixt~res of bl~aching agents can also be used.
Peroxygen bl~aching ag~nts~and 1;he p~irborates ,are prefeirab~y ~: combine~ with bleach a~tivators, which lead to the in situ produo-tion in aqueous solution (~.e., during: th~ washing pro~Qiss) of the p~raxy acid :: eorresponding to the bleach act~vator. Yarious :: nonl imiting examples of :act~vators are di closed in U.S. Patent 4,915,854, issued April lû, 1990 to Mao ~t al, and U.S. Patent 4,412,934. The : nonanoyloxybenzene sullFonate (NOBS) and WO ~4/12609 ; , ~ . 21 ~ 8 0 9 9 PCT/USg3/11453 tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can als~ be ussd. See also U.S. 4,634,551 for other typical bleaehes and activators useful herein.
Bl~aching agents other than oxygen bleaohing agents are also known in the art and ~an be ut~ ed herein. One type of non-oxygen bleaching agent of particular interest includes photo-activated bleaching agents such as the sulfonated zinc and/or aluminu~ phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. Typically, detergent co~positions will con~ain about 0.025~ to about 1.25%~ by weight, of sulfonated zinc phthal ocyani ne .
Po~meri~ ~ Soil Relea$e Agent - Any polymeric soil release agent known to those skil~ed in the art can optionally be employed in the compositlions and processes of this invention. Polymeric soil release agents are character~zed by having both hydroph~l ic segments, to hydrophilize the surface of hydrophobio fibers, such as polyester and nylon, and hydrophobic s~gments, to deposit upon hydrophobic f~bers and remain adhered thereto through completion o~ washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic s~gments. Th~s can enable stains occurring subsequent t~ treat~ent wi th the soi 1 rel eas~ agent to be more easily cleaned in later washing procedures.
The polymeri c soi 1 rel ease agents for ~hl ch per~ormance i s enhanced herei n especi al ly i ncl ude those soi 1 rel ease agents havîng: (a) one or more nonionic hydrophile compo~ents c~nsisting essentially of (i) polyoxyethylene segments w1th a degree of polymer~zation of at least 2, or (ii~ oxypro~ylene or polyoxy-propyl~ne segments wtth a degree of polynerization of fron~ 2 to 0~ wherein;; said hydrophile segm~nt does not, encompass ~ any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages~ or ~ a mixture Qf oxyalkylene units comprising oxyethylene and ~rom 1 to about 30 oxypropy7ene units wherein said mixtur~ contains a sufficient amount of oxyethylene units such that the hydr2phile component has hydrophil icity great enough to increase the hydrophil icity of conventional polyester synthetic fiber surface~ upon deposit of the soil release agent on such surface~ said hydrophile segments preferably comprising at least about 25X oxyethylene units and WO 94/12609 21`4 8 O 9 9 PCT~S93/11453 more preferably, especially for such compon~nts having about Z0 to 30 oxypropyl~ne units, at least about 50% oxyethylene units; or (b) one or more hydrophobe components comprising (i) C3 sxyalkyl-ene terephthalate segments, wher~in, if said hydrophobe components also co~npr~se oxyethylene t~rephthala~e, the ratio of oxyethylene terephthal ate: C3 oxyal kyl ene terephthal ate un~ ts i s about 2 :1 or lower9 (ii) C4-C6 alkyl~ne or oxy C4-C6 alkylene s~gments, or mixtures therein, (iii) poly (vinyl ester~ segments, preferably poly(vinyl acetate), haYing a degree of polymerization of at least 2, or (iv) Cl-C4 alkyl ether or C4 hydroxyalkyl ether substitu-ents, or mixtures therein, wherein said substituents are present in the fonn of Cl-C4 alkyl ether or C4 hydroxyalkyl eth~r cellu-lose der~vatives, or mixtures therein, and such cellulose deriva-tives are amphiphil ic, whereby they have a sufficient level of Cl-C4 alkyl ether and/or C4 hydroxyalkyl ether units to deposit upon conventional polyester synthetk fîber surfaces and retatn a suffic~ent level of hydroxyls, once adhered to such comentional synthetic ~iber surface, to increàse fiber surface hydroph~lic~ty, or a combination of (a) and (b). `~
~0 Typically, the polyoxyethylen~ segments of (~ w~ll have a degree of polymerization of from 2 to about 200, although higher levels can be used, preferably from 3 to about 15~, more prefer-ably from 6 t~ about 100.: Suttable oxy C4-C~ alkylene hydrophobe s~gmen~s include, but are not l~mi~ed to, ~nd~caps of po~ymeric so~l release :agents such as M03S(CH2)~0CH2CH20-, where M ts sodium and n is an integer from 4-~, as disclosed ~n U.S. Paten~
4,721,580~ ~ssusd 3an~ary 26, 1988 to GosselinkO
Polyn~ric soi7 release ag~nts useful in the p~esent invention . ! " i also include cellulosic deriYatives ~ such as~ ~hyd~cxyet~er cellu-3û losic polymers, copolymeric blocks of ethylene terephthalate or propylene terephtha7ate w~th polyethylene oxide ~r polypropylene oxide terephthalate, and the~ like. Such agents ar~ com7~ercially a~ailable and inc~ude~ hydroxyethers of celllllose such as METHOCEL
(Dow). Cellulosic soil rel~ase agents fo~ use herein alss include those selected from the group consisting of Cl~C4 alkyl and C4 hydroxyalkyl cellulose; see UOS. Patent 4,000~93, issu~d December 28, 1976 to Nicol, et al.

wo 94/12609 2~ 8;0 9 9 PCT/US93/11453 Soil release agents charaeterized by poly~Yinyl ester) hydrophobe s~gments include graf~ copolyners of poly(Yinyl ester)~
e.g., C1-C6 vinyl esters, preferably poly(vinyl acetate) gra~ted onto polyalkylene oxide backbones, such as polyethylzne oxide backbones. See European Patent Application ~ 219 û48, published April 22, 1987 by Kud~ et al. Commercially avai7able soil release agents of this kind includ2 the 50KALAN type of matsrial, e.g., SûKALAN HP-22, available from BASF (West 6emany).
One type of preferred soil release agent is a copolymer having random blocks of ethylene t~rephthalate and polyethylene oxide ~PEû) terephthalate. The mulecular weight of this polymeric soil release agent is in the range o~ from about 25,000 to about 55,000. See U.S~ Patent 3,9597230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur is~ued July 8" 1975.
lS Another preferred polymerie soil rel~ase agent is a polyester wi th repeat uni ts of ethyl ene terephthal ate un~ ts contai ni ng 10-1~Z by weight of ethyl~ne ter~phthalate un~ts together w~th -90~80Z by wei~hl; of polyoxy~thylene terephthalate un~ts, der~ved from a polyoxyethylene glycol of aYerage molecular w~ight 300-5,000. Examples of -this polymer include the con~nercially availabl~ ma~erial ZELCON 5126 (from DupontJ and MILEASE T (from IC1). See also U.S. Patenl: 4,~02,Q57, issued October 27, 1987 to Gos~el ink.
Another ,oreferred polymeric so~l release agent is a sulfonated product of a substantially linear ester oligomer comprised of an ol igomeric ester backbone of terephthaloyl and cxyal kyleneoxy repeat ` units and teminal moieties covalently attached to the backbone. These soil release agents are described futly jn U.S. Patent 4,9689451, issued Novenlb~r 6~ 1990i to J. ~.
Scheibel and E. P. GosseliQk.
, :~ Other suitable polymeric :soil r~lease agents include the `~ terephl;halate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gossel~ink e~ al, the anionic end-eapped ol igQmeric esters o~: U.S. Patent 4,72I,580, issued January 26, 1988 to ~: 35 Gosselink9 and the block potyester oligo~ric eompounds of U.S.
Patent 4,702,857, issued October 27, 1987 to 60ssetink.
PreFerred polymeric soil rel-ease agents also inclllde the soil release agents o~ U.S~ Patent 4,8779896, isslled October 31, 1989 WO ~4/12609 214 8 0 9 9 PCT/US93/11453 to Maldonado et al, whioh discloses anionic, especially sulfo-aroyl, endcapped terephthalate esters.
If utili~ed, soil release agents will ~enerally comprise from ~bout 0.01% to about lO.OX, by weight, of the detergent composi-tions herein, typically from about 0.1X to about 5X, preferably from about 0.2% to about 3.0%.
~h~lat ~ Aqen~ - The det~rgent eompos~tions herein may also optionally contain one or more iron and/or manganese chelating agents. Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunc~ionally-substituted aromatio chelating agents and mixtures therein, all as hereina~ter defined. Without intending to be bound by theor~, it is believed that the benefit of thess materials is due in part to their exceptional abil~ty to remove j 15 iron and manganes~ ions ~rom washing so~utions by formation of ! soluble chelates.
Amino carboxylates :useful as optional chelating agents ` include ethylened~aminetetraacetates, N-hydroxyethylethylened~
aminetriacetates, nitrilotriacetates, ethylenediamine tetrapropri-onates, ~r~e~hylenetetraam~nehexaaceta~es, diethylenet~iamine-pentaac~tates, and ethanoldiglycines9 alkali ~etal, ammoniu~, and substituted ~mmonium salts therein and mixtures therein.
Amino phosphonates are a1SQ suitable for use as ch~lating agents in the compos~tions of the invention when at teast low levels o~ total phosphorus are penmitted in de~er~ent compos~tions, and ~nclude ethyl~ned~ami~etetrakis (methylen~phos-phonates), nitrilotris ~methylenephosphonates~ and diethxlenetri-aminepentaki$ (~ethyl~nephasphonates). Preferably, these amino phosphonates do not;cootain alkyl or alkenyl g;roups wit~ ~ore,than about 6 carbon atoms.
Poly~unctionalty-substituted aro~atic chelating agents are also useful in the composttions herein. See UOS. Patent 3,812,044, issued May: 21a: 1974~ to Connor et al~ Preferred : cQmpounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy -3 9 S-di sul fobenzene.
A preferred biodegradable chelator for U5e herein is e~hyl-enediamine disuocinate (fEDDS~), as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.

W094/12609 ` ? ~ 180.99 PCI'IUS93/114~3 If utilized, tlflese chelating ~gents will generally cofmprise from about 0.1% to about l~X by weight of the detergent fcomposi-tions herein. More preferably, i~ utili~ed, the chelating agents will comprise from about 0.1% to alfDffofut 3-f~X by weight of such co~pos~tions.
~l~v Soil Removalf/Anti- _de~fosi~ion Agents - The compos1tions o~ the present invention can also optional1y contaifnf water-soluble ethfoxylated amines havingf clay soil remr~fval and anti-redeposition pruperties. Granular detsrgent compositions which contain these compounds typically contain from about 0.01X to about 10.~ by weight of the water-solulbl~ ethoxylated amines; liquirff detergent compositions typically contain about 0.01X tD about S~.
The most preferred soil release and anti-redepofsitiDn agent is ethoxylated tet~aethylenepentamine. Exemplary ethoxylatfsd af~ines arf~ further desrribed in U.S. Patent 4,597,898, Yander~fffeer, ~ssued July 1,~ 1986.: ~Ansther~ group~ of preff~rreff fff cl ay so~ l removal/ant~fredeposition agents are the cationic compounds dis-closed in Europ~an Patent:Application 111,965, Oh and Gosselink, published June 27, 1984. Other clay soil removal/antiredeposition 0 agents which can be usfff~d include the ethoxylatfed amlnfe pol~ers tsfclosed in European Patent Application 1117984, 6Osselink, published June :27~ 1984; thef zwitterionic `polymers disclosedff in Ifurfopean Patent:Applif~ation 112,592, 6ossel:lnfft~ publ1shed July 4, : . 1984; and the amine oxides disclosed in U.S. Patent 4,548,7449 Connor, Ifssued: Ofçtober 22, 1985. Other clay soil: removal and/or .
: anti redepos~tion agents known ~n the art can also be utllizefd in the compos:it~on¢ herein. Anotlff~fer type ~of preferred anti-redeposition agent includes the carboxy methyl cellulose (CMC~
~ faterl ?ls- ~hese:ma~erials are~w:ell ~known i;n tnfe afrt. f ~ ~
:: 3~ el~ Is_niso~ss~ng~:se~ Polymerit dispersing agents can advantageously be utiltfzed: at levels~frfDm affbout O.lX to about 7%, ~: : by we~ght, in the compositlons herein. These materials can also ~ . ~
aid in calcium and: ~agnesiu~ ~hardness control . Suit~b~e polymeric dispersing : age:nts include; ~polymeric: :polycarboxylates and : 35 polyethylene glycols, althQugh others kn~wn in the art can also be used. It: is believed, though it is not int~nded to be limited by theory~:~ that polymeric dispersing a~ents enbance overall det~rgent build2r per~o~mance, when used in ~ombin~tion wlth other builders WO ~4/12609 21~ 8 0 9 9 PCT~JS93/114~;3 (including lower molecular ~eight polycarboxylates) by cry~al growth inhibition~ particulate soil release pept1zation, and anti-red2pos~t~0n.
Polymeric polycarboxylate materials ean be prepared. by polymerizlng or copolymer~z~ng su1table unsaturated monomers, preferably in their actd form. Unsaturated monomeric ae~ds that can be polymer~zed to form su~table polymeric polycarboxylates include aeryllc aeid, maleic acid (or male~c anhydP~de), fumaric acid, ~taconic acid, aconlt k ac~d9 mesacon~c acid, c~tracon~c acid and methylenemalonic acid. The pres~nce in the polym~ric polycarboxylates herein of monomeric segments, eontain~ng no carboxylate radicals such as vinyl~e~hyl ether? styrene, ethylene, etc. is suitable provided that such segments do not constltute more than about 40% by weight.
. 15 Particularly suttable polymeric polyc~rboxylates can be derived from acrylic acid. Such ac~ylic acid-based polymers ~h~ch are useful herein are the water-soluble salts of polymerized acrylic acidO The aYerage molecular we~ght oP such polymers in the acid form prefQrably ranges from about 2,000 to 1090nO, more preferably ~rom a~out 4,000 to 7,000 and most preferably from I about 49000 to 5,000. ~ater~soluble salts of such acrylic acid polymers can include, for example, the alkal~ metal, ammon1um and substituted ~msnium salts. S~luble poly~ers of this type are known materials. Use of polya~rylates of this type in detQrgent compostt~ons has been disclosed, for example, in Diehl, U.S.
Patent 3,308,057, ~ssued March 7, 1967.
Acryl~c/~aleic-based copolymers may also be used as a pr~ferred component of the disp~rsingOanti-redeposition agent~
' Such materials include the water~soluble salts of sopolymers ofacrylic acid and maleic ~ido The average ~ol~cular weigh~ of such copolymers in: the acid form pref~rably ranges from about 2,000 to 100,0~0, more preferab~y from about 59000 to 753000, most preferably~fro~ abaut 7,000 to 65,000. The ratio of acrylate to maleate segmenks in such copolymers will generally range from about 30:1 to about 1:1, more pref@rably from about lO:l to 2:1.
Water-sol~bl~ salts of such aerylic acid~maleic acid copoly~ers can include, for example, the alkal~ ~etal~ ammon~um and substituted ammonium salts. Soluble acrylate/maleate copolymers .~w o 94/12609 2 1 ~ 8 ~ ~ ~ PcTruss3/11~s3 of this type are known materials which are deseribed in European Patent Application No. 66915, published December 15, 1982.
Another polymeric material which can be included is poly-ethylene glycol (PEG). PEG can exhibit dispersing agent psrform-ance as well as act as a clay soil removal/antired~position agsnt.
Typtcal molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1,000 to about 50900G7 ~ore preferably fro~ about l,S00 to about 10,000.
Polyaspartate and-polyglutamate dispersing agents may also be used, especially in conjunction w~th zeol~te builders.
~I~g~ n~ - Any opti~al brighteners or other brightening or whitening ag~nts known in the art can be incorporated at levels typically from about 0.05X to about 1.2%, by weight, into the detergent compositions herein. Co~mercial optical brighteners which may be useful in the pres~nt invention can be class~f~ed into subgroups which include, b~t are not necessar~ly limited to, derivatives of st~lbene, pyrazaline, coumar~n, carboxylic acid, methinecyanines,: dibenzothiphene-5,5-d~oxid@, azol~s~ S- and 6-~embered-ring het~rocycles, and other missellaneous agents.
Examples of such brighteners are disclosed in ~The Product~on and Application of Fluorescent Brightening Agents~, M. Zahradnik, Publish~d by John ~iley & Sons, New York (1982~.
Speeific examples of optical brighteners which are useful in the present oompos~tions are those ~dentified in U.S. Patent 4,790,856, issued to ~ixon on December 13t 1988. Thes~
brighteners lnclude the ~HORWHITE series of bri~hteners from Yerona. Other brighteners disc~osed in this re~arence ~nclude~
Ttnopal U~PA, Tinopal ~BS and ~Tinopal 5BM; available fro~ Ctba-Geigy;i~rc~ic White CC and Artic Whit~ CWD, availa~le fro~ `H~lton-Davis, located in Italy; the 2-~4-styryl-phenyl)-2H- naphthol~l,2-d]triazoles; 4,4'-bis- ~1,2~3-triazol2-yl)-st~1 benes; 4,4'-bis-(styryl~bisphenyls; and the y-aminocoumarins. Specific exa~p~es of these brighteners include 4-methyl-7-diethyl- amino coumarin;
1,2-bis~-~enzim~da201-2-yl)~thylene; 1,3-diphenylphrazolines;
2~5-b1s(benzoxazol-2-yl)thiophene; 2-styryl^naphth-~1,2-d~sxazole;
:~ : and 2-(stilbene-4-yi3-2~ naphtho- [1,2-d]triazQle. See also U.S.
: Patent 3j646,015, issued February 29, 1972 to Hamilt~n.

wo 94/12609 2 1 4 8 0 9 9 PCT/IJ593/11453 S~ ~ ompounds for reducing or suppressing the forlnation of suds can be incorporated into the co~pos1tions of the present invention. The incorporation of such mal;erials, herein-afte~ ~suds suppressors~U in laundry or hard surface cleaning 3 5 appl icat~ons, can be desirable to further reduce the suds~ng of the mixed nonionic/anionic surfactants herein. Additional s~Jds suppression can be of particular importance when the detsrgent con~positions herein optionally include a relatively high sudsing surfactant in combination with the low-suds~ng ~nixed non~onic/ani-on~c surfac~ants of this in~tention.
A wide variety of mal;erials may be used as suds suppressors~
and suds suppressors are well known to those skilled in the art.
See, for exampl e, Ki rk Othmer Encycl opedi a of Chemi cal Technol ogy, Third Ed~tisn, VolumQ 7, pages 430-447 ~John ~liley ~ Sons, Inc., 1979). One category o~ suds suppressor of particu~ar interest encompasses monocarboxyllc fatty acids and oluble salts thgrein.
See U.S. Pat~nt 2,954,34J, issued September 27, 1960 to ~ayne St.
1~ John. The monocarboxyl ic fatty acids and salts th@reof used ~s J j suds suppressor typically have hydrocarbyl chains of lO to about2~ 24 ~arbon atoms, preferably 12 to l8 carbon atoms. Su~table salt~
include the alkali metal salts such as sodium, potassium, and lithium salts, and amnonium and alkanolanllnonium salts.
The detergent compos1tions herein may also contain non-surfactant suds suppressors. These include, fol^ example: high molecular ~eight hydrocarbons such as paraffin, fatty acid esters (e.gO~ fatty ac1d tr~glyeerides), fatty acid esters of monoYalent :~ alcohols, aliphatic Cl8-C40 l~etones (e.g. stearone), etc. Othersuds inhib~tors include N-alkylalted amino triazines such as tri-to hexa-alkylmelamines or di- to tetra-alkyldiamine rhlortriaz~nes formed as products of cyanuric chloride wil;h two or three moles o~
a primary~ or seeondary amine containing 1 to 24 carbon atOmS?
propylene oxide, and monostearyl phosphates such as monostsaryl alcohol :phosphate ester and~ monostearyl di-alkali m~tal ~e.g, K, Na, and Li ) phosphates and p~osphate esters. The hydrocarbons such as paraffin and halopara~fin ctn be utilized in li~uid forn.
The 1 iquid hydrocarbons will be 1 i~uid at room tempPrature and atmospheric pressur~, and will hav.e a pour point in the rallge of about -40-C and about 5-C, and a minimusn boiling point not less ~ O ~4/12609 ~1 ~ 8 0 g 9 PCT~Sg3/11453 than about 110'C ~atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferrably having a melting po~nt b~low about 100-C. The hydrocarbons constitute a preferred category of suds suppressor for detergent compos~tions. Hydrocar-bon suds suppressors are descr1bed~ for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. The hydrocar-bons, thus, incl~de aliphatic, alicyclic, aromatic, and hetero-cyclic saturated or ~nsaturated hydroc~rbons having from about 12 to about 70 carbon atoms. The term ~para~fin,~ as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and eyclic hydrocarbons.
Another preferred category of non-surfactant suds comprises silicone suds suppressors. This category includes the use of polyorganosiloxan~ oils~ such as p~lydimethylsiloxane, dispersions or emulsions of polyorganosilo%ane oils or resins, and combina-tions of polyorganosiloxane with~ stlica particles wherein the polyorganosiloxane is chemisorbed of fused onto the si~l ica.
Silicvne suds suppressors are well known in the art and are, ~or ; ~xample9 disclosed in U.S. :Patent 4,265,779, issued May 5, 1981 to Gandolfo ~ al and European Pat~nt Application No. 89307851.9, published Febrllary 7, 1990, by Starch, M. S.
Other: s~licone suds suppressors are disclosed in U.S. Patent 3,455,83~ which relates to composit~ons and processes for dè~oam-. ing aqueous ~solutions by incorporati~g therein small amounts of : 25~ polydimethyl si l oxane fl ui ds . ~
M~xtures of s~licone and s~lanated s~l~ca are described, fo:r nstance, in German Patent Application DOS 2,124,526. Siticone defoamers and: suds controlling agents in granular detergenl;
compos~itionslare disclosed ln U.S-!Patent..3!,9339672, Bantolot~a e~
al, and ln U.S. Patent 4,65~,392, Baginsk~ et al9 issued March 24, : 1987.
An exemplary s;licone based suds suppressor for use here~n is a suds suppressing amount of~a suds controlling agent c~nsisting : essentialty o~
: (i) polydimethylsiloxane: fluid ~ having a viscosity of from about 20 ~s.::to:about 1500:cs. at 25-C;
ii) from about 5 to:about 50 parts per 100 parts by weight of;(ij of siloxane resin composed of (CH3)3 SiO1/~ units :, WO 94/lZ609 214 8 0 9 9 PCT/IJ593/11453 of SiO2 units in a ratio of from (CH~)3 SiOl/2 units and to SiO2 units o~ froln about 0.6:1 to about 1.2:1; and ~iii) from about 1 to about 20 p~rts per I00 parts by ~eight of (i~ of a solid silica gel;
In the preferred sil icone suds suppressor used herein, the solvent for a continuDus p~ase ~s 0ade up of oertain poly~thylene glycols or polyethyl0n~-polyprQpylene glycol copolymers or mixtures thereof (pr~ferred), and not polypropylene glycol. The prîmary s~lisone suds suppressor is brallched/crosslinked and not I0 1 ~near.
To illustrat@ this point further, typical liq~id la~mdry detergent compos~tions with controlled suds will optionally comprise from about 0.001 to about I, preferably from ab~ut û.01 to about Q.7~ most preferably from abut 0.05 to about 0.5, ~eight IS % of said stlicone suds suppressor, which comprises (1) a nonaqueous emulsion o~ a primary antifoa~ agent which is a mixl;ure of (a) a polyorganosiloxanet tb) a resinolls siloxane or a s~l~cone resin-producing s~licone compoundl (c~ a finely divided filler j material, and (d) a catalyst to promote lthe react~on of mixture 20 components ~a), (b) and (c3, to for~ s~lanolates7 (2) at least one nonionic `sil icone surfac~ant; and (3) polyethylene glycol or a copolymer ~f polyethylene-polypropylene glycol having a solubility in wat~r at roonl ~mperature of more ~han about 2 we~ght X; and withsut polypropyl~ne glycol. Similar amounts can be used in 25 granular compos~tions, gels~ etc. See also U.S. Pate~ts 49978,471, Starch, issued D~cember 18, 1990, anid 4~983,316, Starch, isslled January 8, 1991, and U.S. Pat~nts 4,639,485 and 4,749.740, Aizawa et a~ at columll 1, line 46 through column 4, : ' !~ . ` ' i line 35-The silicone sllds suppr~ssor herein pref~rably cQIllprises polyethyl~ne glycol and a copolymer of polyethylene glycol/poly-propylen~ glycol, all having :an av~rage molectllar weight of less than about 1,000, pre~rably betw~en ~bout 100 and 800. The ~; ~ polyethylene; glycol and ~ polyethylene~polypropylene copolymers ~: herein have a solubi1lity in:~:water at room temperature oF more than :~ about 2 weight X, preferably mo~e than about S welght %.
The:~p~eferr0d sol~/ent herein is polyethylene glycol having an average molecular weight af less t~an about 19000, more preferably WO 94/12609 21~ 8 ~ 9 ~ PCT/US93/114~3 between about 100 and 800, most preferably between 200 and 400, and a copolymer of polyethyl ene glycol/polypropyl ene glycol, ¦ preferably PPG 200/PE6 300. Preferred ~s a weight ratto of betw~en about 1:1 and 1:10~ st preferably between 1:3 ~nd 1:6, of polyethylene glyeol :copol3rlner of polyethylene-polypropylene glycol .
The preferred sil icone suds suppressors used herein do not contain polypropylene glycol, part~cularly of 49001) molecular weight. They also preferably do not conta~n blook copolysners of ethylene oxide and propylene oxide, l~ke PLURONIC L1û1.
Other su~s suppressors: useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols):: and:m~xtures of such alcohols with sil icone oil s, such. as the si1 icones disclosed in U.S .
4,798,679, 4,075,118 and EP: 150,872. ~ The secondary alcohols include the ~6-C16 alkyl alcohols ha~ving a C~ 6 chain. A
preferred alcohol is 2-butyl octanol, wh~ch is a~allable ~rom Condea under the trademark ISO~OL 12. M~xtures of secondary alcohols are available under the trademark ISALCHEM 123 fro~
: . Enichem. Mixed suds suppresç:ors typ~cally comprise mixtures of : : 20 alcohol ~ s~licone at a~weight ratio~of 1:5 to 5:1.
:~ ~ For any detergent compositions to be used in automatic laundry washing ~achines, suds should not hnm to: the extent that thèy over~low the washing mach~ne. Suds suppressors, when:
: . utilized, are pre~ferably~present in a :~suds suppressing amount.X
25: By ~suds suppressing amounta is~meant that the~formulator of the composition can select an amoun~ of th~is~ suds:controlling agent~
that will sufficiently control the:suds to result in a low-sudsîng laundry detergent for use in auto~atic laundry washins machines.
` ' 1, i , ` ` ! `~ i 'i ` .The low~sudsing ~omposi~tions ~here~n,iwill~ generally comprise 3~ from OX: to about 5% of s:uds suppressor. ~When utll~zed as suds : suppr~ssor~, monocarboxyl k~ fatty acids,~and salts:therein,~ will be:present~typically in~ amouDts~up to about 5X~ by~ weigh~, of the detergent composition. ~Preferably, fro~about O.~S% to~about 3% of f~ty monocarboxylate~suds~suppressor~is utilized. Silicone:suds : suppressors are typic~a~l:ly:utilized in amounts up to about 2~X, by weight, of the detergent ~ompos~tion, although higher a~ounts may be used.~ Thi:s~ upper li~it~is practical~1n:na~ure, due-primarly to : concern ~w~lth~:~keeping costs:minimized and ~effectiveness of lower : a~oun~s for effectively controlling sudsing. Preferably from about 0.01X to about 1% of silicone suds suppressor is used9 more preferably from about 0.25~ to about 0.5%. As used herein, $hese weight percentage values include any silica that may be ut~lized in combination with polyorganosiloxane, as well as any adjunct ~aterials that may be utilized. Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from about 0.1% ts about 2%, by weight, of the composition. Hydrocarbon suds suppressors are typically util~zed in amounts ranging from about 0.01X to about 5.0X, althoug~ higher levels can be used.
In addition to the foregoing ingredients whieh ar~ gencrally employed in fabric laundry, dishwashing and hard surface cleaners for cleansing and sanitizing purposes, the surfactant compos~tions herein can also be used with a variety of oth~r adjunct ingredi-ents which provide still other benefits in various compos~tlons within the scope of this invention. Th@ follo~ing illustrates a variety of such ad~unet ingredients~ but ~s not intended to be .l limit~ng therein.
E3L 5 ener~ - Various thr3ugh-the-wash fabric softeners, especially the ~mpalpable s~ect~te clays of U.S. Patent 4,062,647, Storm and Nirschl, issued Dec~mber 13, 19779 as well as oth~r softener clays known in the art, can be us~d typically at leYels . of from about 0.5% to about 1~ by weight in the pr~sent co~posi-¦ t~ons to pro~ide fabric softener benefits concurrently w~th fabri ' 25 cleaning. The polyhydroxy fatty ac~d am~des of the present : ~n~ent~on cause less int~rfQrence w~th the soften~ng performance of t~e clay ~han do the co~on poly~thylene oxide n~nionic sur-factants of the art. Clay softeners can be used ~n c~bination with amine and c~:ionic softeners~ as disclosed, Por iexample, in U.S. Patent 4,375,416, Crisp et al, March 1, 1~83 and U.S. Patent 4,291,071~ Harris et al, issued September 22, 1981.
5_~ ~oC_lC9~:dl~D~ - Shampoo compos~tions fo~ulated in the ~anner of this invention can contain from about 0.05% tQ about l~X by weight of various agents sueh as: conditioners, e.g., siliconcs (see, for examplP, U.S. Patents 4,152,416 and 4,36478~7); ~antidandruff agents such as ~he pyridinethiones, especially zinc pyridinethione ~see U.S. Patents 4,379,7S3 and 4,34570B0~, selenium compounds such as selenium sulfide and .

~/O ~4/Z2609 ` 2 1 ~' ` PCT/U593/11453 OCTOPIROX; hair styl ing pol~ers (see U.S. Patents 4,D12,501 and 4~272,511); and pediculic;~es ~anti-lice agents3 such as LINDANE
and various pyrethrins (see British Patent 17593,601 and U.S.
~ j Patent 4,668~666j-¦ I . 5 Other Inqredients - A wide `variety of other ingr~di~nts useful in detergent compositions can be included in the somposi-tions herein, including uther active ingredients9 carriers, hydrotropes, processing ~ids, dyes or pigments, solvents for I ~ liquid formulatiuns, etc.
I 10 ~arious detersi~e ingredients employed in the present compo-j sitions advantageously oan be stabilized by absorbin3 said I ingredients onto a porous hydrophobie substrate,: then coating said substrate w~th a hydrophobic coating. Pre~erably, the detersive in~redient is admixed with a surfactant before being absorbed into I j 15 the porous substrate. In use, the~:detersive ingredie~t is ¦~ ' rel~ased from the substrate into the aqueous washing liquor, where ~' it performs ~ts intended detersive functlon.
: To illustrate this technique;in more detail, a porous hydro-phobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a ~:~ 20 proteolytic ~nzyme solution co~taining 3%-5% of C13 15 ethoxylat~d alcohol E0(7) nonionic surfactant.~ Typically, the enzyme/surfact-ant solutinn is 2.~ X the weight of sil icaO The resulting powd~r is dispersed~with stirring in silicone oil (Yarious silicone oil ;~ viscos~ties in the range o~ 500-12,500 ~an be used~. The result-ing silicone oil dispersion is emulsi~ied or otherwise a~ded to the final detergent matr~x. By thts means, ingredients such as the aforementioned enzym~s, bleaches, bleach ~acttvators, bleaeh : catalysts9 photoact~vators, dyes, fluores~ers, ~abric c~nd~tioners and h~drolyzable surfactants can be ~prot~cted~ fo~ usel in d~ter-30: ~gents~ including liquid laundry detergent:compos~tions.
L1quid:~detergent~ co~positions:can cont~in water and other solvents as ~carriers. Low molecular weight primary or secondary : alcohols exemplified~ by methanol, etban~l, : propanol,: and ; isopropanol are suitable. Monohydric alcohols are pre~erred for sol:ubil king sur~actant~, ;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-propanediol,~ ethylene glycol, glycerine, and 1,2-propanediol~ ean a~lso be used.

WO 94tl2609 214 8 0 9 9 PCT/US93/11453 !

~i~ - The formulation of effective, modern detergent compositions poses a considerable ohallenge, especially in the absence o~ phasphate builders. For fabric laundering, the fo~nu-lator is required to address the removal of a wide varlety of soils and stains, many of wh~eh are termed ~greasy/oily~ soils, such as foods, cosm~tics, Inotor o~l~ and $he l~ke, from a wide vari ety of fabri c surfaces and under a spectrum of usage condi -tions, rang~ng from boil wash temper~tures preferred by some users to 1 aunder~ng temperatures as cold as 5YC preferred by others .
Local factors, especially water hardness leYels and the presence or absence of metal cati~ns: such as iron in loeal wash water suppl ies, can dramatically impact detergency performance. Like-wise, the formulator of hand dishwash~ng compos~tions must provide compositions which s~emoYe high loads of greasy food residues, but ~5 which do so und~r cond~tions which are not irrltating to the user's skin nor damaging to the arti~les being ~ashed. It ~s especially difficult to provide good g~ease removal at n~ar-neutral pH' s .
It w~ l 1 be appreci ated by the ~onoul ators of detergent compositions that, at sufficientl~ low interfacial tensions, it is theoretically possible to provide what might be termed "spontane-ous emulsification" of greasy/oily soil. I~ such spontaneous emulsification were to be secured~ 1t would very consid@rably enhance grease/ui 1 remoYal from substrates sueh as fabri cs, : ~ 25 d~shware, ~nvironmental hard sur~aces, and the llke. &Ihile extremely low lnterfacial tens~ons and, presumably, spontaneous :~ emulsification9 have possi~bly been achievable with specialized surfactants such as the fluorinated surfactants known in the art, n j ~I tha pres~nt inYention proYides a new, nlild surfactan~ system to ~0 ~chieve this desirable result. Mos~eover, spontaneou~ emulsifica-tion may b~ achievable w~th ;some specia~ized sur~actants only at relativel~ high pHis in ~he range of 10-11~ whereas this desirable result is also achieYable :w~th the present compositions even in the n~ar-neutral pH range of about 6.5-8. This is particularly important for hand-washing operatiQns9 for exa~nple, hand dishwash-~:: ing, where skin mildness is of concern to the user.
While the polyhydroxy fatty. acid amides employed in the : ~ practice of this invention are, structural~y, nonionie-type . . WO 94112609 2 1 ~ 8 D g g PCT/US93/11453 surfaetants and are referred to herein as nn~nionics~. It now also appears that the conformation of the polyhydroxy fatty acid am~des may be changed due: to interaction betwe~n water hardness ions, especially caleiu~ cat~ons,~ and the s~ap or ~nionic surfact-ant. Th~s may increase th~ moleeular packing of the polyhydro%y fatty acid amides at the air/water ~interface. Uhatever the explanation at the molecular level, the net result ~s the lower interfacial tensions and improved ~eleaning benefits assooiated with the compositions of this :in~ention9 especially with respect :
to greasy/o~ly stains.
;:; INJERFAC~AL T~EI9~ ~ ;
By "interfacial tensi~n~ IfT~) herein is ~eant the tension : measured at:the oil/wa~er interfacs. IFT measurements using the ' ' spinning drop techni'que, are d~sclosed by Cayias, Sehe~hter and Wade, ~The Msasure~ent of Low ~Interfacial Tension ~i~ the Spinning Drop:Techni~que~ :AC5~Symposium~:Series~No. 8 gl975) ADSQRPTIOH A~
NTERFACES,~beginning~at~ page 234. ::~Equipment for running IFT
measurements:~i:s~curren~ly ~available from:~W. H. :~ade, Depts. of :
Chem;stry`::~and;'Chemical~Engineering,~ The~ University of Texas at `~ ``20 ' Austin,~Austin,~Texas~78712.;~
'~ By ~low~ nterfaci~al:;tensi:on~herein~is meant an IFT which is~:
`~ suffi:c~'ently~l'ow:~:th~t ~sp~ntaneous;~e~ sification~, i:.e., rapid `'~ emuls~f1cation~wi~th l~ttle~:~or~no:~mee~hanical ag~tation, can occur.~
;~ For~ exàmplé,~;~using~ a`~ gypi~ca~ fatty~cid N-methyl' gluc~mide;
25 ~ nonionic~surfactant,~at~concentrations in water ranging~;from~about~
~ 300 pp~to~ a~ut~600~ppm~and~:a~::water~ hardness:(t~+~ co~centra~
': '~ tions~of~;2 grai'n:s/gallon~(l4~ppm), 7~gr/gal~48~'ppm)~and l5 gr~gal:~
'~ (IQ3 ppm) :one~notes~`a range~of~:~IFT~ from about O.25~ dynes/cm ~to ~ :
'`~ abou~0~`.4 dynes/cm.~Under such conditiQns,~'~spontane4us~emulsifi-~
:30: cation~ of grease/oil~soi~ if~:any, is~minima~ u~
;contràst,~w n~the~:a resa~d~ non'on'c ~:surfa :e~pl:oyed:~wi~h~:~an~:':anionic surfactant and~a soap:in~the~manner o~
:thi~s:~;inventi~o'n, espec~a;lly`~;n~the~presence~of;calcium ions, the IFT~ s~'redù'ced to~O.:l5~ dynes/~ or~ ess~ and spontaneous~oil 5~ emul~si:fi;cation~ s~not~d~

7he~nspontan~ous'~@mulsi:~icati:on~n of :g~easy~/~oily~:soils pro-;'~ : vided:~:by: the~:compo~s'ition~s herein -~an be~ simply~but cDnvincingly~

WO g4/12609 ` ~ ` PCT/US93/11453 2 1 ~ 8 0 9 9 ', demonstrated by admixing a detergent composition in accordance wîth the invention containing the specially selected soap with water. After dissolution of the detergent, a few drops of oil to which a colored oil-soluble dye has been added are added to the detergent solution. With minimal agitation, the entire system appears to take on the col or of the dye, due to the dyed oi l having been finely dispersed by the spontaneous emulsification effect. This dispersion remains for a considerable length of ~ ti~e, typically 30 minutes to several hours, even whan agitation !~ 10 has stopped. By contrast, with surfactant systems which fail to ~¦ provide spontaneous emulsification, the dyed oil dropl~ts produced during agitation rapidly coalesce to form one or more relatively large oil globules at the air/water interface.
More specifically, this de~onstration of sporltanqous emulsi-fication can be run as follows.
A consumer relevant test soi~ is dyed with 0.5% Oil Red EGN.
A 100 ml sample of the detergent composition being tested is prepared at the desired cDnc~ntration (typically, about ~00 ppm) and temperature in water which is "pre-hardened" to any desired concentration o~ cilcium ions (typically, about 48 ppm), a~d contained in an 8 oz. capped jar. The sample pH is adjusted tc-the intended end-use pH (typically in the range o~ 6.5 to 8~ and i 0.2 g of the test soil is added. The Jar is shaken 4 ti~es and : the sa~ple graded. Alt~rnatively~ the sample is placed in a beaker and stirred with a stir bar for 15 seconds, The sample is : graded~as follows:
0 - Clear solution with large red oil drople~s in it (0.1-5 mm diameter), i.e., no smulsification;
. Solution has a defini~e pink~ appearance w~th red oil ~roplets in it (0.1-1 mm), i.e., slight emulsification;
~ ~ 2 ~ Solution is dark;pink with small red droplets in it9 ;~ : i.e., moderate emulsification;
3 ~ Solution is red w:ith small red d~oplets in it (1-200~m), e., emulsification is subst~ntial;
4:= Solution is dark red with little or no visible droplets : ~ SO~m), i.e., emulsification is complete.
; :~ Note: The grading can also be done spectrophotometrically (based :~; : on tight transmittance).

WO94/1~609 _ 3~ _ og9 PC'r/U593/11453 It will further be appreciated that, while the calcium and/or optional magnesium ions ~ay be incorporated into the compositions herein, the formulator may determine that it is acceptable prac-tice to rely on natural water hardness to provide such ions to the compositions under in-use situatiolls. This may be a reasonable expedient, since as little as 2 gr/gal calcium hardness can provid~ substantial benef~ts. However, the formulator will most likely decide to add the calcium and/or optional magnesium ions directly to the compositions, thereby assu~ing their presence in the in-use situation. Under such oircumstances, and especially when formulating liquid products wherein the presence ~f precipi-tates may be un~esirable, it is preferred to add the calcium and/or magnesium to the compositions in the form of a lightly complexed chelate, such as cakium malate or maleate, ~agnesium malate or maleate, or the like.
he detergent compositions herein will preferably be fonmu-lated such that duri~ng use~in aqueous cleaning operations, the : wash water will have a pH of between about 6.5 and about ll, ¦ preferably between about 7.5 and: about la.s. Liquid product formulations~preferably have à pH ~etween about 7.5 and about 9.5, ; ~ morB preferably between~:~about 7.5 and about 9Ø Techniques for :~ controlling~ pH at reeo0nended~ usage levels :inclu~e the use of :~ ~ bu~fers, alkal:is, acids,~etc., and are well kn~wn to tho:se skilled :: ` ~ i~n the art.
~: 25 ~: The ~ollow~ng are ~ypi:cal,:nonlimi~ing examples which ill;us-trate the use~;of the;~ ~ixed ~nonionic/anionic:surfactant:systems provided:bylthis invention~to prepare~fully-formu1ated detergent composltions which can achieve the desired low IFT's and spoRtane ous~emul`silficati~on (~rades 3-4) no~ed above.
~ ; ~eZL
A ~ liquid detergent ~ composition herein ~comprises th~
;~ f~l~lowi:og.:~
~ ln~edlent ;~ Nonionic/anionic* ; .035: ~I Sodium citrate : ~ : 1.0 ~ : ;C~o alcohol::~ethoxylate~(3)~ :: :13.
::~ : Monoethanolamine ~ . .
n : :: Ca maleate WO 94/1260~ 21~ 8 0 9 9 PCT/US931114~3 ~ater/propylene glycol/ethanol ~lOO: l :1) Bal ance *1:1 mixture of coconutalkyl N-methyl glucamide: Cl~-C14 ~EO)3 carboxyl ate.

A granular detergent herein comprises the following.
% ~Wt. !
Nonion~c/anionic* lO.O
Zeolite A (l-10 micrometer) 3000 Sodi um c~ trate 10 . O
Sodium carbonate 20,0 Opti cal brightener O . l Detersive enzy~e** l.O
Cl2 14 alkyl sulfate, Na 5.0 Sodium sulfate 1500 CaC12 1.2 Water and minors Balance *1:1 mixture of tallowalkyl: N-methyl glucam~d~ and sul~ated C10 l4 polyglucoside.
: **Lipolytic enzyslle preparat~on (LIPOLASE).
: 20 ~
:~ The compositions of Example I and II are mod~fted by including 0.5~ o~ a conanerc~al proteolytic enz~yme preparation : ~ ~ESPERASE) therein. Optionally, 0.5X ~f a co~ereial amylase ~: preparation (TE~MYL) and 0.5% of a con~nercial l~polytic enzyn~e 25 preparation (LIPOLASE~ can be ca-incorporated in such l iqu~d and ~: solid deterg~nt compositions.
~PlE~
A dishwashing composition with high grease re~oval prop~rties i s as' fol l ows . .
3û Inqredient Noni oni c/ani oni c* ~ ~ ~o ~ o C~2 sulfobetaine** ~ 5.0 ~: Ca ~ mal eate 1 , 0 : ;` Coconut monoethanolamine 1.0 Water; : Bal ance *C12-C14 fatty acid a~ide o~ N-nlethyl glu mine or N-ethyl - : fructamine: and secondary C12 ~6 alkyl s~lfate as a 3:1 nonionic:anionic mixture and neutralized partly with MgS04 and ~w o 94/126Q~ ",;~ 099 partly with NaOH to provide an overall Mg content in finished detergent compositions of 1.6X.
**Suds: boosting surfactant aka ~sultaine~.
E~A,MPLE l!
A shampoo composition is prepared according to Example IV by dal2ting the:magnesium ions.
It has now been ~et~rmined that the present compositions are especially use~ul for removing cosmetic stains from fabrics. This is an especially important technical improvement in detergency performance. Cosmetics, or facial Rmake-up~ pstick and the like, typically comprise a complex m~xture of finely-ground, highly colored~ particulate material which is int~mately admixed with a greasy :or waxy carrier. Cosmetics are specifically fo~mulated to remaîn on the sur~ace to wh kh they are applied, and for this reaso~ their carriers are water-insoluble and/or water : repellent. As i:s w~ known~, on~e a l~pst~ck or other cosm@t~c: smear is establi~shed ~on a fabric, :its removal can pro~e extremaly di~fi~ult. By comparison, the removal o~ cosmet k sta~ns from fabrics ~s~substantial~ly moi~: difficult than ~s the re~val of -~ ~ommon greasy stains~such as~lard. Compos~tions according to the presen~:tnvention~ wh~ch~ additionally~;comp~i~se from abol~t 1% to about 20%~:~by~ weight~ of an:~ethoxylated (EO 1-7; preferably 2-3) C12-C1g ~al~cohol~or~ alkyl phenol are preferablY :used :~n ~such formul:at:ions~t~further~boost per~onm~nGeo:
;25: :: The~ foregoing~dlsclosu~e~and~xamples i:llustrate the~pract~ce of th~s~inveot~on::in considerabl~e:detall.~ It ~;s to~ be appreci-ate~d, ;~however,~:that ~;thc~advantages afforded by the compvsitions:~
and processes of~th~s invention are ~roadly useful w~th a variety ,~ . ;:; ofiother t~chnQlogies: which~have been~develop~dlfor~use lnjla~wide : variety ~of;~mode~n,~fully-fo~mulatQd cleaning c~mpositions, es~e-:cially :laundry:~detergen~s~ :The compos:itions herein w~ typically `~ be~ u~sed i~n a~ueous~med;ia:~at~concentrations of at least~ ~bout 200 ppm, eOg.9~for l~ightly-soiled~fabrics~and/or hand~;dishwashing.
High:er~usàge conc~ntrations~in~;the~rang~ of; 1,000:~ppm ta 8,000:
~ ~ ppm, and;:~higher,:~ are~used~for heavi~ly-so;led: fabrics.~ However, :~ usage levels;~ can va:ry9 depend:ing on the desires of the user,:soil ~ loads,:soi:l types, and the~like. Wash:temperatures can range from :~ 5-~ to the boil~

WO 94112609 2 I ~ ~ 0 9 9 PCT/US93111453 It will be further appreciated that the invention encompasses a method for lowering IFT's of oil/grease (especially triglyceride fats and oils) in the presence of water~ comprising admixing in said water at least about 200 ppm of the compositions herein.
Such lowering of IFT also provides a means for achieving spontane-ous emulsification which is useful not only in fabric and hard surface cleaning, but also in any circumstance where it is impor$-ant to render oily materials more fluid, e.g.9 petroleurn recovery and transnlission, eosmetic formulations, and the like.

~ ~0 ~`

: :

:: ::

Claims (6)

WHAT IS CLAIMED IS:

1. A detergent composition comprising a nonionic/anionic/soap surfactant system which comprises:
(a) a polyhydroxy fatty acid amide of the formula wherein R1 is H, C1-C3 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, 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;
(b) an anionic surfactant which is a member selected from the group consisting of alpha-sulfonated fatty acids, alkyl alkoxylated sulfates, alkyl ethoxylated carboxylates, alkyl and alkenyl sulfates and sulfated alkyl polyglycosides, at a weight ratio of (a):(b) of from about 10:1 to about 1:10;
(c) a soap; and (d) a source of calcium ions.

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

6. A method for lowering the interfacial tension of an oil/water system to 0.15 dynes/cm, or less, by dissolving in said system at least about 200 ppm of a composition according to Claim 1.