CA2092559C - Detergent compositions containing polyhydroxy fatty acid amide and alkyl alkoxylated sulfate - Google Patents

Abstract

Detergent compositions are disclosed containing alkyl alkoxylated sulfate and certain polyhydroxy fatty acid amide surfactants in combination with suds suppressors or auxiliary surfactant component, or in select ratios of alkyl alkoxylated sulfate to polyhydroxy fatty acid amide, and combinations thereof.

Description

2092~5~
W O 92/06158 -1- P7~T/7~Sg1/~702 DETERGENT COMPOSITIONS CONTAIl'lING POLYHYDROXY

~ F ~!'lr?! l1~'7 This 1~v~1tion ~r~ ; 'J~----,-.-';~J
alkyl alkoxylated sulfate and polyhydrox~ ,-at7~y acid amide surfactants.

1~ o~7~ 7~;iu ~i ;ic ;J-~
The ability of detergent con7Oositions ~o c7e-7n a 7arge ~/ariety of so;ls and stains from th3 numerous ~pes o; f3brics present in the typical load of laundry, as well as cleaning of other surfaces (e.g., hard surfaces, hair, etc.) is of high importance in the evaluation of detergent performance. One type of surfactant which has been of value due to lts good overall cleaning ability, particularly its excellent particulate soil cleaning performance, encompasses the alkyl alkoxylated sulfate surfactants. Whereas these surfactant systems have perfor~ed admirably, it is desirable to provide surfactant systems for a variety of cleaning pur?oses with enhanced grease and oil cleaning performance. One of the most common types of surfactants combined with alkyl alkoxylated surfactants to improve greasc/oil cleaning ability is the class known as alkyl benzene sulfonates, particula7rly the linear al~yl benzene sulfonates. These surfactants can provide excellent grease/oil cleaning, ov~r a wid7e range of temperature and conditions. However, alkyl benzene sulfonates are typically derived largely from petroleum-based raw materials, and, recently, ther~ has arisen substantial interest in r~duc,ng consumption of petroleum.
Therefore, it would be desirable to provide alkyl alkoxylate~
sulfate detergent compositions which could provide comparabl3 13~Jels of overall cleaning performance *7ith r~7ducPd, or etJen elimin-7teh7, amounts of alkyl benzene sulfonate, and by substlt7ting in its place surfactant which could largely or entirely be derived from natural renewable, non-petroleum resources.

w o 92/06158 PCT/US~1/0702, 2 0 9 2 ~ ~ 9 - 2 -Conventional nonionic surfactants in combination with alkyl alkoxylated sulfates, such as alkyl ethoxylates, can provide acceptable cleaning, but typically require relatively long wash times, ;llgh ~asf/ temperatllros, and high surfactant concentration to 5 achie~!q ~r-;~c ~V? 9~ S~?/oi~ a~in3.
~,'''. -.--.::'~.~, ,-.; ;-'',n p.~r~',?~ ' surfactant systems having excollent grPase and oil cleaning performance across a range of wa~ ~r t,e.~e?ra''~!r?C .rd w~sh ccncqnt aticns through the combina-tion o,~ al(yl al~oAylat2d sul,ates and certain polyhydroxy fatty ac'i m ;~a s~; ~-c'~- . ~ r h. ;~mo,~a, 'he polyhydroxy ;atty acid a~ldq~ ".?'~i'~ r ?~ti,q~/ fro~ n~tllr~, rc~ne~bl~J
rt r ~
~ ?.-! ~'?~
,', -;_;',_~, _, ~O,j'..J'".-aX;', i~:j ac,~ a""~a~ ave been described in t-~e 'f;. :J-ac~l, .'I-me~,hyl glucam,des, for example, are disclosed by J. ~ oodby, ,~ arcus, E. Chin, and P. L. Finn in ~The Thermotropic Liquid-Crystalline Properties of Some Straight Chain Carbohydrate Amphiphiles," Liquid Crystals, 1988, Volume 3, No. li, pp 1569-1581, and by A. Muller-Fahrnow, V. Zabel, M. Steifa, and R.
Hilgenfeld in "Molecular and Crystal Structure of a Nonionic Detergent: Nonanoyl-N-methylglucamide,~ J. Chem. Soc. Chem. Commun., 1986, pp 1573-1574. The use of N-alkyl polyhydroxyamide surfactants has been of substantial interest recently for use in biochemistry, for example in the dissociation of ~iological membranes. See, for example, the journal article ~N-D-Gluco-N-methyl-alkanamide Compounds, a New Class of Non-Ionic Detergents For Membrane 8iochemistry," Biochem. J. (i982), Vol. 207, pp 363-366, by J. E. K.
Hildreth.
The use of N-alkyl glucamides in detergent compositions has also been discussed. U.S. Patent 2,965,576, issued December 20, 1960 to E. R. Wilson, and G.8. Patent 809,060, published February 18, 1959, assigned to Thomas Hedley & Co., Ltd. relate to detergent compositions containing anionic surfactants and certain amide surfaciants, which can include N-me hyl glucamide, added as a low temperature suds enhancing agent. These compounds include an N-acyl radical of a higher straight chain ratty acid having 10-14 carbon atoms. These compositions may also contain auxiliary materials such as alkali metal phosphates, alkali metal silicates, sulfates, and w 0 92/06158 2 ~ 3 2 ~ ~ 3 P ~ /US91/07~27 carbonates. It is also generally indicated that additional con-stituents to impart desirable properties to 'ne composition c1n aiso be included in the compositions, such as fluorescent dyes, bleacning agents, perfumes, etc.
U.S. Patent 2,703,798, issued ,~arch ~, i9i~ to A. ~ Sch~arfz, relates to aqueous detPrger" compcsi-cit~.., cv.t~i,,ing ".e C~nG_,..a-tion reaction j~roduct of N-alkyl glucamine and an aliphatic ester of a fatty acid. The produc, o,~ ,hi, raat-tit," ,, ;t-,id t" 't,e t~;e"~
aqueous detergent compositions .~ithou' ~ur.he- -~ri r lcation. Tt iS
also kno~Yn to preparo ~ ;ulfur~c a ta- ~ c disclosed in U.S. ~aten-, 2 "~ iV~7~ J-d ~ " 'V ~.
M. Schwartz.
PCT International Application ~0 3~/C;;~Z, publisiled Dec~mber 22, 1983, by J. ~ildreth, relates ~.o -~hl,;~ ;c c~m~ounds contain-ing polyhydroxyl aliphatic groups said to ~e uc~ful .or a ~/a iety o;purposes including use as surfactants in cosmetics, drugs, shampoos, lotions, and eye ointments, as emulsifiers and dispensing agents for medicines, and in biochemistry for solubilizing membranes, whole cells, or other tissue samples, and for preparation of liposomes.
Included in this disclosure are compounds of the formula R'CON(R)CH2R" and RnCON(R)R' wherein R is hydrogen or an organic grouping, R' is an aliphatic hydrocarbon group of at least three carbon atoms, and R" is the residue of an aldose.
European Patent 0 285 768, published October 12, 1988, H.
Kelkenberg, et al., relates to the use of N-polyhydroxy alkyl fatty acid amides as thickening agents in aqueous detergent systems.
Included are amides of the formula ~1C(O)N(X)R2 wherein ~- is a C1-C17 (preferably C7-C17) alkyl, R2 is hydrogen, a C1-C1g (preferably C1-C6) alkyl, or an alkylene oxide, and X is a polyhydroxy alkyl having four to seven carbon atoms, e.g., N-methyl, coconut fatty acid glucamide. The thickening properties of the amides are indicated as being of particular use in liquid surfzctant systems containing paraffin sulfonate, allhough the aqueous surfactant systems can contain other anionic surfactants, such as 3~ alkylaryl sulfonates, olefin sulfonate, sulfosuccinic acid half ester salts, and fatty alcohol ether sulfonatee, nd nonionic surfactants such as fatty alcohol polyglycol ether, alkylpnenol polyglycol ether, fatty acid polyglycol ester, polypropylene WO 92/06158 PCr/US91/0702/
9,~,. 5~
oxide-polyethylene oxide mixed polymers, etc. Paraffin sulfonate/'l-m~t,'t~l ccccnut -.~atty acid glucamide/nonionic surfactant sham~oo For~l~laf.ions aro evem~l fied. In addition to thic~ening attribucos, ,.he ;~I-polyhydrox~ al'~yl Fatty acid amides are said to have su~rior s'~,n 'ol~r~nc~ attribut.~s.
U.S. ia~ n~ ~,3~ l, isju~d ;iay 2, l~ol, to ~oettner, et al., relates t~ ~.2rg~n+ h~r~ ~~nt?~ini~n nr~a, sodium lauryl sulrate anionic su -:~cclnc~ ~nc n ;~i-al;cyiglucamide nonionic surlFactant W,t .. l 5 ~~' .~~ d '~ -'-~ "~ J~~~"lide ~nd ~-~ttethyl, utner 3ieelll7~ta ~ur~';3CC-~.lCS are discios2G, ;or example, in D~
2,2~ ;;r.. ' -.' n '~, ..j ~, ;i. .i. . ~rc, 2c al., ~hich relaies co ~.Yasning composicions comDrising on~ or more surfactants ~nd ~ ?~,?~ ''~?~; ~ -h~S,.~ S J s~n~_st~ring as~r.t;, a"d i sr,m.,5 il'~il,s, ,i"p;o~d 'y th~ addition of an N-acylpolyhydroxy-alkyl-amine of the formula R1C(O)N(R2)CH2(CHOH)n-CH20H, wherein R1 is a C1-C3 al'~yl, R2 is a C1o-C22 alkyl, and n is 3 or 4. The N-acylpolyhydroxyalkyl-amine is added as a soil sus-pending agent.
U.S. Patent 3,654,166, issued April 4, 1972, to H. W. Eckert, et al., relates to detergent compositions comprising at least one surfactant selected from the group of anionic, zwitterionic, and nonionic surfactants and, as a text;le softener, an N-acyl, N-alkyl polyhydro~y7al~yl co~pound o; tne formula R1N(Z)C(OjR2 wherein R1 is a C10-c22 alkyl, R2 is a C7-C21 alkyl, Rl and R2 total from 23 to 3g carbon atoms, and Z is a polyhydroxyalkyl which can be ~ -CH2(CHOH'~CH20H whero ~ is 3 or 4.
U.S. Patent 4,021,53g, issued May 3, 1977, to H. Moller, et al., relates to skin treating cosmetic compositions containing N-polyhydroxylalkyl-amines which include compounds of the formula R1N(R)CH(CHOH)mR2 wherein R1 is H, lower alkyl, hydroxy-lower alkyl, or aminoalkyl, as well as het2roc~clic aminoal~yl, R is the same as Rl but both cannot be H, and R2 is CH20H or COOH.
French Patent 1,360,01a, April 26, 1963, assigned to Commercial Solvents Corporat,on, r~lat s to ,olut,Gns of formaldehyde stabil-ized against pv'ym~rization with th2 additior, of amides of the formula RC(O)~J(R1)G wherein 2 is a carboxylic acid functionality w o 92/061s8 2 0 9 2 ~ ~ 9 P CT/~is~1/0702- - 5 -having at least seven carbon atoms, R1 is hydrogen or a lower alkyl group, and G is a glycitol radical with at l-ea~ ~ c3rbon at3m~, German Patent 1,261,861, February 29, 1968, A. ~e;nC, reliltos to glucamine derivatives useful as wetting ~nd dlspersing ag nt- Gr the formula N(R)(R1)(R2) wherein R is a ;uq-r re.,idu~ o. q.uc--.mine, R1 is a C10-c2o alkyl radical, and R2 i; a v~ d.-~l naGi;~l.
G.B. Patent 745,036, published Febr~ r~ lar~ ~~-gn~d ~~
Atlas Powder Company, relates ~o heL~rOC~ 1jC ~1;,N ~ nb c~ box,~iic esters thereof that are said to ~ie . e,~.' emulsifiers, wetting and di~pier7'~
sorteners, etc. The compounds dre ~;vr?~ n~
N(R) (R1)C(O)R2 wherein R is t;le - s pentol or a carboxylic acid ester ~hereot, 21 is a monovalen hydrocarbon radical, and -C(O~R~ ie ti~ a~
acid having from 2 to 25 carbon at~ms.
U.S. Patent 3,312,627, issued April 4, 1967 to D. T. Hooker, discloses solid toilet bars that are substantially free of anionic detergents and alkaline builder materials, and which contain lithium soap of certain fatty acids, a nonionic surfactant selected from certain propylene oxide-ethylenediamine-ethylene oxide condensates, propylene oxide-propylene glycol-ethylene oxide condensates, and polymerized ethylene glycol, and also contain a nonionic lathering component which can include polyhydroxyamide of the formula RC(O)NR1(R2) wherein RC(O) contains from about 10 ~o about 14 carbon atoms, and R1 and R2 each are H or C1-C6 alkyl groups, said alkyl groups containing a total number of carbon atoms of from 2 to about 7 and a total numoer of substituent hydroxyl groups of from 2 to about 6. A substantially similar disclosure is found in U.S. Patent 3,312,626, also issued April 4, 1967 to D. T. Hooker.
SUMMARY OF THE INYENTION
The present invention provides a low sudsing detergent composition comprising, in general, pol~hydrox~ fatty acid amide surfactant of the formula:
O Rl wherein R1 is H, C1-C4 hydrocarb~l, 2-h~droxy et,yl 7 Gr 2-hydroxy propyl, R2 is Cs-C31 hydrocarbyl, and Z is polyhydroxy nydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly W O 92/06158 PCT/US~1/0702-2 0 9 2 ~ 6 -connected to said chain, or alkoxylated derivatives thereof; alkyl alkoxylated sul-Fate surf,ctant; and a suds suppressing amount of a suds suppressor pr?f.?r~ s?lecrod from the grou? cons~istin~ of monocarboxylic ratt~ acids and salt, ther?of, silicone suds sup-pressors, and monostea~~~l ci-al'~3li ",etal phos~rtates or phosohate esters, and iliyil mOieCUia~ ci~ byarocaroon suds suppressors, and mixtur?s th?raof. ~1h~ ?i~ s~id cnllpnsi..lo~ s ?r?f?r-~bl" ch rac~.?r-ized oy an al.~yl aikoxyiac d sui.~a~:ooiyn;~r,Ay fa~y acid amide weight rat-o 31~ f-;~~,m '~'OJ'I 7 ~. ',0 -~0'~0,~? ?-~er3r2bly from 10 about ~ .o ':30U;. ~ ; ,' ~~ ;'E;~ 0 a~OUI '':I.
I he preTerl ed a ~ i a i .~ox'J I i b G s;~ a -.url~c~an~s are alkyl etho~yla ed ju a--as ~ .o" ~~a.. 3".g '~ro~
about 0.5 and aoouc ~.
Tn :I?!o~.h2r ?.~ ? i ~ n,~ q~ n ~ 5 detergent ccmnosl~l~ns rrmprising a',1~ ~1 e h~xyl:tad ~'ul ,a~e ;urfact-ants and polyhydroxy fatty acid amide, as described above, wherein R1 is methyl, R2 is Cg-Cl7 alk~l or alkenyl, Z is glycityl derived from a reducing sugar, or alkoxylated derivative thereof, and the ratio of alkyl ethoxylated sulfate:polyhydroxy fatty acid amide is from about l:l to about 4:1, preferably about 3:1.
In yet another aspect of this invention, provided are detergent compositions polyhydroxy fatty acid amide and alkyl alkoxylated (preferably ethoxylated) sulfate surfactants, as described above, further comprisins an auviliary s~rfactant cGm~Gnent selected from alkyl sulfates, alkyl ester sulfonates, alky phenol alkoxylates, alkyl benzene sulfonates, alkyl ethoxylates, paraffin sulfonates, and alkyl polyglycosides, and mixtures thereof. Preferably, the auxiliary surfactant ccmponent co".prises from about lX to about 25%, by weight, of the detergent composition. Other auxiliary surfact-ants may additionally be present in the detergent compositionshereof, as well as optional detergent adjuncts and other ingredients known in the art or otherwise desirable for inclusion in detergent compositions.
DETAILED DESCRIPTION OF THE INVENTION
As discussed above, this inv-ntion provides a lo~-sudsing laundry detergent composition com?r sing polyhydroxy fatty acid amide surfactant of the folmmula W O 92/06158 2 0 9 2 ~ ~ 9 Pcr/us~1/n~02 O Rl wherein R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, or 2-hydroxy propyl, R2 is Cs-C31 hydrocarbyl, and Z is polyhydroxyhydrocarD~l having a linear hydrocarbyl chain with at least 3 h~droxyls direcflJ
connected to the chain, or alkoxylated deri~/a~ s ~hzreo.~; ~,~y, alkoxylated sulfate surfactant; and a suds suDpressing ~mqunt or a suds suppressor, preferably selected from tne ~rGup oons~ J 'Jl' monocarboxylic fatty acids and sal+s thqrqof, sil c~n~ ~ud-10 suppressors, and hydrocarbon suds suppr~s,o.s, -J mvn~jS~
di-alkali metal phosphates or pnosphaie esc~rs, dnd m,~c~n~
thereof;
Preferably, the weight ratio of alkyl alkoxylated sul-race ~o polyhydrovy fatty amide is from about 1:10 to ?boUt ~ .or~
preferably from about 1:5 to about 5~ en morq prqfqrably o-about 4:1 to about 1:1. Also preferably, the alkyl alkoxylated sulfate comprises an alkyl ethoxylated sulfate surfactant having a degree of ethoxylation greater than 0.5 typically from about 0.5 to about 6, preferably from about 0.5 to abcut 3.
In an especially preferred embodiment, Rl is methyl, R2 is C11-C17 alkyl or alkenyl, and Z is glycityl derived from reducing sugar, or alkoxylated derivative thereof, and the ratio of alkyl ethoxylated sulfate surfactant to polyhydroxy fatty acid amide is from about 4:1 to about 1:1.
The individual components are described in more detail below.
PolYhvdroxY FattY Acid Amide Surfactant The compositions hereof will comprise at least about 1%, typically from about 3% to about 50'~, preferably from aboui 3YO to about 30~., of the polyhydroxy fatty acid amide surfactant described below.
The polyhydroxy fatty acid amide surfactant component of the present invention comprises compounds of the structural farmula:
O Rl (I) R2 - C - N - z wherein: R1 is H, C1-C4 hydrocarbyl, 2-hydrox~ ethyl, 2-hydrc~y propyl, or a mixture thereof, preferably C1-C4 alk~l, mor-preferably C1 or C2 alkyl, most preferably Cl alkyl (i.e., methyl);
and R2 is a Cs-C31 hydrocarbyl, preferably straight chain C7-C1g W O 92/06158 PCT/US()1/0702-2 ~ 9 2 ~ ~ 9 - 8 -alkyl or alkenyl, more preferably straight chain Cg-CI7 al~yl or alkenyl, most preferably straight chain Cii-ri7 al~yl or alken~l, or mixture thereof; and Z is a ~olyhydro~h~r~carby7 ha/ ng a lin2ar hydrocarbyl chain s~ith 3~ least 3 hJ~drox~ s directl~ connec~ed to the chain, or an alkox,~ d ~i~ri/a;1;~ ~r?;e,-.bl~ etho~Jl3.-d ~r propoxylated) ther~-o;. ? ~-ia~ iii o- ~ieri~/ed rrom a reaucing sugar in a reducti~/e aminJtion r?art~or -~-? ~-?~?ra~ly 7 ',~-glycityl. vuitable ~ ui ~n~ ns i,c ide ~m~cose~ ,ructose, maltose, lactose, gal .lC'.a:,e. -.~.0;', sa ~~d ' ~ n ~a~
l~ high dext,ose cv,, sy.~~ ;.~ m , 0 5 ~
corn syrup can be U~ eU ~ la ~ OI:al ~!lgar~, ''tst?d above. Ihese corn s~ . . ;n .~~a~ ;Jmlad~i nl;s ~'Gr Z~
It should be understood tna~ ii is o~/ no me2ns intend2d to e:<clude other suit2ble r~ .'?~i~'". . '~?'?--.~1'' '' ~~ ~- ____ ,, ,", I5 the group consist~ns v,~ ~ ) ;i r ~ r~ -; lc;~) n ~ ~ -CH20H, -CH2-(CHOH)2(CHOR')(CHOH)-CH~OH, ~here n is an integer from 3 to 5, inclusive, and R' is ~ or a cyclic or aliphatic monosacchar-ide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH20H.
In Formula (I), Rl can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
R2-C0-N~ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallo~2mide, etc.
Z can be l-deoxyglucityl, 2-deoxyfructityl, l-deoxymaltityl, 1-deoxylactityl, l-deoxygalactityl, I-deoxymannityl, l-deoxymalto-triotityl, etc.
Methods for making polyhydroxy fatty acid amides are known in the art. In general, they can be made by reacting an alkyl amine with a reducing sùgar in a reductiYe amination reaction to form a corresponding N-alkyl polyhydroxyamine, and then reacting the N-alkyl polyhydroxyamine ~ith a ~att~ aliphatic ester or triglyceride in a condensation/amidalion step to form the N-alkyl, N-polyhydroxy fatty acid amide product. Processes for making compositions containing polyhydrv~y 6atty acid amides are disclosed, for example, in G.B. P~tQnt S~ecls-,catiGn ~03,060, published February 18, 1959, by Thomas ~edley & Co., Ltd., U.S. Patent 2,965,576, issued December 20, 1960 to E. ~. Wilson, and U.S. Patent WO 92/06158 }~CI'/US~ )/02-2 0 ~ 2 ~ 5 ~
2,703,798, Anthony M. Schwartz, issued March 8, 1955, and U.S.
Patent 1,985,424, issued December 25, 1934 to Piggott, each o' wh-,ch is incorporated herein by reference.
In a preferred process for producing N-alkyl or N-hydroxyal'~y~, N-deoxyglycityl fatty acid amides wherein the glycityl compnnen~
deriYed from glucose and the N-alkyl or N-hydroxyal~yl ,unc~iona,.~
is N-methyl, N-ethyl, N-propyl, N-butyl, N-hydroxyethyl, or N-hydroxy-propyl, the product is made by reacting ii-d~ - Jr N-hydroxyalkyl-glucamine with a fatty ester sel2ct2d f.,"
methyl esters, fatty ethyl esters, and fa-Lty 'n,gl~c?~~1d~
presence of a catalyst selected from the group consis-~i"o ;~
trili~nium phosphate, trisodium phospha~e, tripo~ass-iu,~ p"~~
tetrasodium pyrophosphate, pentapotassium tripolyphospnate, lit,hiuln hydroxide, sodium hydroxide, pot~ssium hydroxide, C~ ~.?, lithium carbonate, sodium carbonate, potassium carbonate, di,~d,u, tartrate, dipotassium tartrate, sodium potassium tartrate, trisodium citrate, tripotassium citrate, sodium basic silicates, potassium basic silicates, sodium basic aluminosilicates, and potassium basic aluminosilicates, and mixtures thereof. The amount of catalyst is preferably from about 0.5 mole X to about 50 mole %, more preferably from about 2.0 mole Y, to about 10 mole %, on an N-alkyl or N-hydroxyalkyl-glucamine molar basis. The reaction is preferably carried out at from about 138-C to about 170-C for typically from about 20 to about 90 minutes. When triglycerides are utilized in the reaction mixture as the fatty ester source, the reaction is also preferably carried out using from about 1 to about 10 weight % of a phase transfer agent, calculated on a weight percent basis of total reaction mixture, selected from saturated fatty alcohol polyethoxylates, alkylpolyglycosides, linear glycamide surfactant, and mixtures thereof.
Preferably, this process is carried out as follows:
(a) preheating the fatty ester to about 138'C to about 170-C;
(b) adding the N-alkyl or N-hydroxyalkyl glucamine to the heated fatty acid ester and mixing to the extent needed to form a two-phase liquid/liquid mixture;
(c) mixing the catalyst into the reaction mixture; and (d) stirring for the specified reaction time.

W O 92/06158 f~Cr/US(~1/07~J2~

2 0 9 2 ~ 5 Also preferably, from about 2% to about 20% of preformed linear N-alkyl/N-hydroxyalkyl, N-linear glucosyl fat'y acid amide prriduc~
is added to the reaction mixture, by weight of tne reactants, a5 the phase transfer agent if the fatt~ es~3r s t,-isl~c~rid~i. ,his seeds the reaction, thereby increasi,3 r-~c i~ na~ . i di~ d experimental procedur~ is p.c~-.d-J ' The po1yhydroxy "fatty acid" amide materials used her3~n 21so offer the advant2ges to the de~e ~en~ -~~r~
prepared wholly or primarily ,rom natural, r?l~:Ya~î3. ron-petrochemical feedstocks and dr? i'_i9, ~-:da~-i -.. , ~-: ' - ;.; -.';, - -~ i toxicity to a~uatic lif~.

acid amideis or Form.ula (I), thei j~.o_e .~ u.~ , ,r,~ii,c- '.';_!'; ~.'1 also typically pi~cduc3 ~uanti;,cii ul liVn'~J;~l~l ;i_ v,~ ' 'CVe~ Cii -esteramides and cyclic polyhydroxy ,a~y acid a"lide. "he l-~el o,~
these by-products will vary depending upon the p2rticul2r r~ ctant;
and process conditions. Preferably, the polyhydroxy fatiy acid amide incor40rated into the detergent compositions hereof will be provided in a form such that the polyhydroxy fatty acid amide-containing composition added to the detergent contains less thanabout 10%, preferably less than about 4%, of cyclic polyhydroxy fatty acid amide. The preferred processes described above are advantageous in that they can yield rather low levels of by-products, including such cyclic amide b~~?roduct.
Alkvl AlkoxYlated Sulfates The alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula R0(A)mS03M wherein R is an unsubstituted Clo-C~4 alkyl or hydroxyalkyl group having ~ S~0-~24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C14-Clg alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation ~e.g., sodium.
potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation. Thus, alkyl othox~lated sulfates as well as alkyl propoxylated sulfates are contemplated herein, ~ith the former being preferred. Speclfic examples of subs~itut~d ammonium cations include methyl-, dimethyl-, trimethyl-ammonium, and w o 92/06158 2 0 9 2 ~ ~ 9 PCT/US~I/0702 quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperdinium, and cations derived from alkanolamines, e.g monoetha-nolamine, diethanolamine, and triethanolamine, and mixtures ther or.
E~emplary surfactants are C12-C18 alkyl polyethoxylate (1.0) sul-5 fate, C12-C1g alkyl polyethoxylate (2.25) sulfate, C12-C1g al'~
pol~2~noxylate (3.0) sulfate, and C12-C1g al'yl polyethoxylate (7.~J
sulfatP wherein M is conveniently selected from sodiu~ and potassium.
The compositions hereof ~ill typicall~ comprise a~ lea;~ ~b~JiA~
!0 1~, b,~ ~ueight, al~yl al~oxylated sulfate, t~pically from ab~u'.
abou-L 3~~,0, prererably ,~rom about 5/0 LO about 20Yo.
Suds juo~ressors Compounds ~nown, or which become kno~n, for reducing or supDressing the formation of suds can be incorporated i-~ ~h?
15 compositions of the present invention. The incorporation o, such materials, hereinafter "suds suppressors," can be desirable because the polyhydroxy fatty acid amide surfactants hereof can increase suds stability of the detergent compositions. Suds suppression can be of particular importance when the detergent cômpositions include 20 a relatively high sudsing surfactant in combination with the polyhydroxy fatty acid amide surfactant. Suds suppression is particularly desirable for compositions intended for use in front loading automatic washing machines. These machines are typically characterized by having drums for contain;ng the laundry and wash 25 water, which have a horizontal axis and rotary action about the axis. This type of agitation can resLlt in high suds formation and, consequently, in reduced cleaning performance. The use of suds suppressors can also be of particular importance under hot water washing conditions and under high surfactant concentration conditions-A wide variety of materials may be used as suds suppressors in the compositions hereof. Suds suppressors are well known to those skilled in the art. They are generally described, for example, in Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, 'Jolume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category of suds suppressor of particular interest ~ncompas;es monocarboxylic fatty acids and soluble salts thereof. These materials are discussed in U.S. Patent 2,954,347, issued September W O 92/06158 PCT/US~1/0702-2 0 9 2 5 ~ 9 - 12 -27, 1960 to Wayne St. John, said patent being incorporated herein by reference. The monocarboxylic fatty acids, and salts thqrqo', for use as suds suppressor typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 13 C.rJO~I ;',O...S. _u.tabl_ salts include the al~ali metal salts ;ucn ~S ~O'','i,~ u~ od lithium salts, and ammoniu,-. ~nd materials are a preferred category of suds suppressor .-or dPter~2r.
compositions.
The detergent compositions may also con~ain non-su, i-'C-.:lnl', .,"ds suppressors. These include, for ~:~amp weight h~drocarbons such as paraf~ n, acid L ~ iglyc~rides), ,a aliphatic C13-O~o ~etones (~.9. ,'~ o~
inhibitors include N-alky7aceu amino Lriazin~j ~uc~ lS '~ 0 hexa-alkylmelamines or di- to tetra-al~yldiamino cnlor-criazinqs formed as products of cyanuric chloride with t~.~o or ~hre2 mol2s of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester, and monosteary di-alkali metal (e.g., Na, K, Li) phosphates and phosphate esters. The hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form. The liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the rang~ of about -40-C and about 5-C, and a minimum boiling point not less than about 110-C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferrably having a melting point below about 100-C. The hydrocarbons constitute a preferr~d cat2sor~ of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo, et al., incorporated herein by reference. Tne hydrocarbons, thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. Tho torm "paraffin,n ~s used ., this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
Another preferred category of non-surfactant suds comprises silicone suds suppressors. This catogor~ includes ~he use o polyorganosiloxane oils, such as polydimethylsiloxane, dispersions w o 92/06158 2 0 9 2 5 ~ 9 Pcr/~is4l/070~-or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorgano-siloxane is chemisorbed of fused onto the silica. Silicone suds suppr~ssors are well known in the art and are, for example, dis-closed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. and European Patent Application No. 89307851.9, pU'Dl is~ed February 7, 1990, by Starch, M. S., both incorporated herein by reference.
Other silicone suds suppressors are disclosed in U.S. Patent 3,~55,~3~ which relates to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of polydi-meth~/lsi~o~ane fluids.
~ ures of silicone and silanated sllica are described, for ins~alc~, ia Ger",an ~atent Application COS 2,12¢,~25. Silicon2 l~ defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al., and in U.S. Patent 4,652,392, Baginski et al., issued March 24, 1987.
An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:
(i) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about lSOO cs. at 25-C;
(ii) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxane resin composed of (CH3)3 SiOl/2 units of SiO2 units in a ratio of from (CH3)3 SiOl/2 units and to SiO2 units of from about 0.6:1 to about 1.2:1; and (iii) from about 1 to about 20 parts per lOO parts by weight of (i) of a solid silica gel;
For any detergent compositions to be used in automatic laundry washing machines, suds should not form to the extent that they overflow the washing machine. Suds suppressors, when utilized, are preferably present in a "suds suppressing amount." By "suds suppressing amount" is meant that the formulator of the composition 3~ can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines. The amount of suds control will vary with the detergent surfactants selected.

W O 92/06158 pcr/~s~1/n7o2 2 0 ~ 2 ~ 14 -For example, with high sudsing surfactants, relatively more of the suds controlling agent is used to achieve the desir?d _ud~ -3n~rûl than with lesser foaming surfactants. In ~eneral, ~ su, f;r,~en~, amount of suds suppressor should be incorporated ln }o~ sLoS'ir.9 detergent compositions so that the suds that -rorm dur ng -ih5 'i cycle of the automatic washing machine ~i.e., u?on a5. a~,oil o.~
detergent in aqueous solution under the intended ~ash ~e-~e,-f~!re and concentration condit-,ons) do no~ exce d ~bù~
volume of washing machine's containmont d u~, ?r~ ~r~~
not exceed about 50~O of said void volum?, ~i, r-~ '? :0'~ . _. .-determined as the dirrerence be-~ween ~o~al voiur,le o~ ,e ;n ~ n~
drum and the volume or the water plus ~he l- n-ry.
When utilized as suds suppressors, monocarboxylic ratt~/ acids.
and salts thereof, ~ill be ~rosent typical~ e~
s~, by weight, of the detergent composi~ion. ' ~m -.b,u ~ J ','J
about 3% of fatty monocarboxylate suds suppressor are typically utilized. Silicone suds suppressors are typically utilized in amounts up to about 2.0%, by weight, of the detergent composition, although higher amounts may 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 .01% to about 1% of silicone suds suppressor is used, more preferably from about 0.25% to about 0.5X. As used herein, these weight percenta~e values include any siiica tnat may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized.
Hydrocarbon suds suppressors are typically utilized in mounts ranging from about .01% to about 5.0%, although nigner levels can be used. The monostearyl phosphate suds suppressors are typically utilized in amounts ranging from about 0.1% to about 2,., by weight, of the compositions.
In another aspect of the invention, this ir.ventizn provid ;
detergent compositions comprising alkyl ethoxylated sulfate surfactants and polyhydroxy fatty acid amide, as described above, wherein Rl is methyl, R2 is Cg-C17 al~yl or alk2nyl, prerc~~ably Cll-C17 alkyl or alkenyl, Z is glycityl derived .rcm a reuuc1,~
sugar, or alkoxylated derivative thereof, and the ratio of alkyl ethoxylated sulfate to polyhydroxy fatty acid amide is from about w o 92/06158 2 0 ~ 2 ~ 5 9 PCT/US(J1/07~27 1.25:1 to about 1:4, preferably from about 1.25:1 to about 1:1.25.
The most preferred of the polyhydroxy fatty acid amides are described above are likewise most preferred hereof.
In yet another aspect of this invention, provided are detergent compositicr,s polyhydroxy fatty acid amide and alkyl alkoxylated ~p~ r~b,y ethoxylated sulfate) surfactants, as describ~d acoYe, further comprising an auxiliary surfactant component selected from an ,dd1tional nonionic surfactant selected from the group consisting of ~ yl ethoxylates, alkyl phenol-alkoxylates (preferably ethoxyl-~ a;;~s~! and alkyl polyglycosides (preferably alkyl polyglucosides.
The ~;t~o of the oolyhydroxy fatty acid amide to the additional ; a" "c su '~c ~nt .s ,r~m ~bout !:10 to about 10:1, ?reforahly a~o;i~ l~ ; to about 5:1. Other auxili~ry surfactants can also be added. Ihê more commonly usPd of thes2 include, but are not limit2d to, alkyl sulfates, alkyl ester sulfonates, alkyl benzene sulfon-atPs, paraffin sulfonates, and mixtures thereof. Preferably, the auxiliary surfactant component comprises from about 1X to about 25X~
by weight, of the detergent composition. Other auxiliary surfact-ants may additionally be present in the detergent compositions hereof, as well as optional detergent adjuncts and other ingredients known in the art or otherwise desirable for inclusion in detergent compositions. The preferred polyhydroxy fatty acid amides, alkyl alkoxylated sulfates, and surfactant ratios described above are preferred in each aspect of the invention.
Anionic AuxiliarY Surfactants Auxiliary anionic surfactants useful for detersive purposes can also be included in the compositions hereof. These can include salts ~including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as r,lono-, di- and triethanolamine salts) of soap, Cg-C20 linear alkylbenzenesulphonates, primary or secondary alkanesulphonates, Cg-C24 olefinsulphonates, sulphonated polycarboxylic acids prepared by sulphonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No. 1,082,179, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfon3tes, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, w o 92/06158 PCl/US41/~7~2-o 9 2'~ 5 9 - 16 -alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C12-C1g monoester;), dis~t~r of sulfosuccinate (especially saturated and unsaturated C~-C1d diesters), N-acyl sarcosinates, sulfates of alkylpolysac-;lar,d ~
such as the sulfates of alkylpolyglucoside (the nonionic "onsu~--a~d compounds being described below), branch~d prima,-~ al~y.
alkyl polyethoxy carboxylates such as those of the ;sr~ul~
R0(CH2CH20)kCH2C00-~ wherein 2 is a Cg-C22 alky " k i, a" ;~
from 0 to 10, and M is a soluble salt-fcrmins ca~on, and ~a acids esterified with isethionic acid and nnutr3' 7-' ;-. ;~
hydroxide. Resin acids and hydroge,laL~d resin a~-,a~ .oo suitable, such as rosin, nydrosenac~d rosin, ;no ,e, ~ - - : -hydrogenated resin acids present in Dr derived froin tdil oii.
Further examples are described in "SurfacP ~ct7vo ~n?a~-~ -.?~
Detergents" (Vol. I and II by Schwartz, Perry and ~erch). A v-.-.~t;~
of such surfactants are also generally disclosed in U.S. Pa-c2n~
3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).
Alkyl sulfate surfactants hereof are water soluble salts or acids of the formula ROS03M wherein R preferably is a Clo-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a Clo-C20 alkyl component, more preferably a C12-Clg alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium,, potassium, lithium), substituted or unsubstituted ammonium cations such as methyl-, dimethyl-, and trimethyl ammonium, and quaternary ammonium cations, e.g., tetramethyl-ammonium and dimethyl piper-dinium, and cations derived from alkanolamines such as ethanolamine, diethanolamine, triethanolamine, and mixtures thereof, and the like.
Typically, alkyl chains of C12 16 are preferred for lower wash temperatures (e.g., below about 50-C) and Cl6 18 alkyl chains are preferred for higher wash temperatures (e.g., above about ~O'C).
The alkyl benzene sulfonate surfactants hereor are well known in the art. These surfactants typically have Cg and higher alkyl groups, preferably linear alkyl groups, to provide th~ linear alk~l benzene sulfonate (nLAS~) class of commerical surfactants. Theso surfactants can be used in either the acid or soluble salt form, w o 92/06158 2 ~ 9 2 5 ~ ~ P~/USgl/07027 with the soluble salt form being preferred. Suitable salts include metal salts (e.g., sodium, potasssium, and lithium) as well as substituted and unsubstituted ammonium salts such as those described abo~le ~ich r~spect to al~ylsulfate salts.
Alkyl Pster sulfonate surfactants hereof include linear esters of C~-~~2u can~ovylic cids (i.e., fatty acids) which are sulfonated ~ith gaseous S03 according to "The Journal of the American Oil C,lc~ s;; So~ ty," 62 (197i), pp. 323-329. Suitable starting matrrials ~ould include natural fatty substances as deri~ed from l's:/! a '~, and coconut oils, etc.
'_ iJ.~~- ;'_;''~"_(i al ~ es Ler sul fonate ,urractan L, Pspeciaily ,or ~ jon~ comprise al~yl ester sulfonate surfactan~s of Lh~ ~,L~LU,a, 'ormula: ;
o ~3 - CH - C - oR4 wherein R3 is a Cg-C20 hydrocarbyl, preferably an alkyl, or combination thereof, R4 is a C1-C6 hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate. Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as methyl-, dimethyl, -trimethyl, and quaternary ammonium cations, e.g.
tetramethy'-ammonium and dimethyl piperd;nium, and cations deriYed from alkanolamines, e.g. monoethanolamine, diethanolamine, and triethanolamine. Preferably, R3 is C10-cl6 alkyl, and R4 is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein R3 is C14-C16 alkyl.
In addition to anionic surfactants, additional nonionic surfactants and other surfactants can be included in the compositions.
Noniûnic AuxiliarY Deterqent Surfactants Suitable nonionic detergent surfactants are generally disclosed in U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1975, at column !3, line 14 through column 16, line 6, incorporated herein by reforonco. Exemplary, non-limiting classes of useful nonionic surfactants are listed below.

WO 92/06158 PCf'/US(J1/0702-2~9?~559 - 18-1. The polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols (re., alkylphenol alkoxylates, such as alkylphenol ethoxylate). In general, the pol~thyleno oxide condensates are preferred. These compounds include the condensation products of alkyl phenols having an alkyl group conta~n.r- f- m about 6 to about 12 carbon atoms in either a strai~ht chain or branched chain configuration with the alk~leno o~id . ,. a preferred embodiment, the ethylene oxide is prosont in an a-.ounL
equal to from about 5 to about 25 moles of ethyl2ne oxid3 ~er i:o -of 2lkyl phenol. Commercially availab7e nonionic ,ur,~art n .~
this type include Igepall~ C0-630, marketod by the GAF Co,por.L -~;
and ~riionTM X-45~ X-1l4, X-lO0~ and ~-102, all mar'ceteà oY ,ho Jo?m & Haas Company. These surfactants are commonl~/ usod as a~ heno' alkoxyletos, e.g., all~yl phenol ethcxylat~~s.
2. The condensation products of aliphatic alcohols with -.ro,n about 1 to about 25 moles of ethylene oxide. The al~yl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 10 to about 20 carbon atoms with from about 2 to about 18 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include TergitolTM 15-S-9 (the condensation product of C11-C1s linear secondary alcohol with 9 moles ethylene oxide), TergitolTM 24-L-6 NMW (the condensation product of C12-C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both mar~eted by Union Carbide Corporation;
NeodolTM 45-9 (the condensation product of C14-C1s linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-6.5 (the condensation product of C12-C13 linear alcohol with 6.5 moles of ethylene oxide), NeodolTM 45-7 (the condensation product of C14-C1s linear alcohol with 7 moles of ethylene oxide), NeodolTM 45-4 (the condensation product of C14-C1s linear alcohol with 4 moles of ethylene oxide), marketed by Shell Chemical Company, and KyroTM EOB (the condensation product of C13-C1s alcohol with 9 moles ethylene oxide), marketod by The Procter & Gamble Company. These are nonionic surfactants are commonly referred to as "alkyl ethoxylates".

WO 92/06158 2 0 9 ~ 5 ~ 9 PCr/US91/0702-3. The condensation products of ethylene oxide with a hy~rophobic b~s2 formed by the condensation of propylene oxide ~ith propylene glycol. The hydrophobic portion of these compounds pf~.-ani~ly ha, a ";olecular weight of from about 1500 to about 1800 an~ axdlioics .~2~er insolubility. The addition of polyoxyethylene o -j . ~h,s ;yGro,;,cbic ,ort,on tends to increase the water solubility o,~ the molecule as a whole, and the 11quid character of ;~a .no~l~rt ~S reta-ne'rl U'p to the point ~here the polyoxyethylsne con~ nt ls about 50~ of the total ~eight of the condensâticQ
'~ ;' '? ~r~ (is ~0 condensation ~.~ith up to about 40 moles ~ x-~irl~s .f sn~ unds ~f this t,~ includ~
'_,', ,', ,'' ' m ~ ;lI'!l'a1'.'~ /a; 1able ~1 uronic~ sur,~actar,."

~~. ine conaensa-cion products of elhylene oxide ~i~h the lj product resulting from the reaction of propylene oxide and et,lyl2nediamine. The hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000. This hydrophobic moiety is condensed with ethylene 20 oxide to the extent that the condensation ploJu~t contains from about 40% to about 80Y. by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. Examples of this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed.by 3ASF.
5. Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atcms and 2 moioties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; watsr-soluble phosphine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and ~ater-soluble sulfoxides containing one alkyl moiety of from about lq to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydrox~alk~l moieties of from about 1 to about 3 carbon atoms.

WO 92/0615X PCI/USg1/0702,~
~,o9~9 - 20-Semi-polar nonionic detergent surfactants include the amine oxida surfactants having the formula o R3(oR4)xN(R~)2 wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mlx~uros thereo-F containing from about 8 to about 22 carbon atoms;
R4 is an alkylenP or hydroxyalkylene group containing from about 2 ~o about 3 carbon atoms or mixtures thereof; x is from O to about 3;
and ~;ch ~5 is an alkyl or hydroxyalkyl group containing rrom about , ~ù :lù~U~ 3 carbon atoms or a polyethylene o~ide group containing ; rrom aoou. 1 io about 3 ethylene oxide groups. The R~ groups can be aL'_C.led 'O '2ch other, e.g., through an oxygen or nitrogen atom, ~o form a ring siructure.
Thase amina oxid~ surfactants in pariicular .nclude SlU-Oi~
alkyl dim2thyl amjne oxides and Cg-C12 alkoxy ethyl dihydroxy ethyl amine oxides.
6. Alkylpolysaccharides disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units. Any reducing saccharide containing S or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties. (Optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giYing a glucose or galactose as opposed to a glucoside or galactoside.) The intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
Optionally, and less desirably, there can be a polyalkylene-oxide chain joining the hydrophobic moiety and the polysaccharide moiety. The preferred alkyleneoxide is ethylene oxide. Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from about 8 to about 18, preTerably from about 10 to about 16, carbon atoms. Preferably, the alkyl group is a straight chain saturated alkyl group. The W 0 92/06158 2 ~ 3 2 ~ 5 ~ P~/USg1/0702 alkyl group can contain up to about 3 hydroxy groups and/or the polyal kylen20xide chain can co.~ain up to about 10, preferably less than 5, al!<yleneoxide moieties. Suitable alkyl polysaccharides are octyl, nonyldecyl, undec~ldodec~l, tridPcyl, tPtradecyl, pentadecyl, hexad~c~l, heptadec~l, and octad2cyl, di-, tri-, tetra-, penta-, and hexaglucos;des, galactosides, lacLosides, glucoses, fructosides, fruc~ QSeS a"d/or galactosos. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, ani pencaglucosides and ~allow alkyl tetr~ -n,~ d 'l~x~ cosides.
lG ~ 3 ~ r~ J~ a,~s ;,~ o~mula n~)t ~ Cos~ l )X
whe~~ain ,~ .s ,ela ~u .nom ~n~ ~rou~ o~nsia~ y of alkyl, alkyl-phenyl h~Jdroxyalkyl, hydroxya7kylphenyl, and mixtures thereof in .~hi~ ? -. ' '~!1 g~o p~ c~t?;l c~O~ ~bo!lt 10 to ~bout l8, pref~rabl~
frcm a~out 12 ~o a~out 14, carbon atums; n ,s 2 3r 3, preferably 2;
t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the l-position).
The additional glycosyl units can then be attached between their l-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, pref2rably predominately the Z-position.
7. Fatty acid amide surfactants having the formula:
o ~6 - C - N(R7)2 wherein R6 is an alkyl group containing from about 7 to about 21 (preferably from about 9 to about 17) carbon atoms and each R7 is selected from the group consisting of hydrogen, Cl-C4 alkyl, Cl-C4 hydroxyalkyl, and -(C2H40)XH where x varies from about 1 to about 3.
Preferred amides are C8-C20 ar~onia amides, monoethanolamides, diethanolamides, and isopropanolamides.
Cationic Surfactants Cationic detersive surfactants can also be included as auxiliary surfactant in det2rgent compositions of the present invention. Cationic surfactants include the ammonium surfactants W O 92/06158 PCT/US91/0702, ~9~3 22 -such as alkyldimethylammonium halogenides, and those surfactants hav,ng t,le formula:
[R2(~R3)y] [R4(0R3)y]2RSN+X~
wherein ~ is an al~yl or alkyl benzyl group having from about 8 to about 13 c~rkon a~oms in the alkyl chain, each R3 is selected frsm the group consisting ot -CH2CH2-, -CH2CH(CH3)-, -CH2CH(CH20H)-, -C~r'~2r~2-, and mi ~tures ther30f; Pach R4 is selected from the grou? consis~lng or C1-C~ alkyl, Cl-C4 hydroxyalkyl, benzyl, ring st'ruc'uras ~ ,o.~l by ~oining the t~o R~ groups, -~S~ Oi-~ ;u.-i'Hc~2ûH ~.~Jherein R6 is any hexose or hexose pol~me~ ila~/-irtl ~ !nolecular ~eight less than about 1000, and hydrogen j;, a, ~ ,, ,;o~ O; i~j is t;le same as R~ or is an alkyl chain ~herein the total number of carbon atoms of R2 ~1 US R5 is not more thzn -~3-~', ',?; ~ C~ L3 ~û~t 10 a~d ~ m ûf the ~ Jâlue, iS ~.'0.1~ 3 'O d''OU~ 15; and ~ is any compatible anion.
Other cationic surfactants useful herein are also described in U.S. Patent 4,228,044, Cambre, issued October 14, 1980, incorporated herein by reference.
Other AuxiliarY Surfactants Ampholytic surfactants can be incorporated into the detergent compositions hereof. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched. One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anlonic water-solubilizing group, e.g., carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, lines 18-35 (herein incorporated by reference) for examples of ampholytic surfactants.
Zwitterionic surfactants can also be incorporated into the detergent compositions hereof. These surfactants can be broadly described as derivatiYes of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or deri~/ativ~s or quaternary ammonium, quaternary phosphonium or tertia-ry sulronium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, line 38 W O 92/06158 2 0 ~ ~ 5 ~ 9 PCT/~S~1/0702/

through column 22, line 48 (herein incorporated by reference~ for examples of zwitterionic surfactants.
Amphol~tic and zwitterionic sur.-~?ictail'; are generatl~ used in combination with one or mor2 anionic and~or nonionic surfactants.
Builders Detergent compositions nf tho prosoin- in~ ntion can coi~prise inorganic or or~ani. d_Lii~g nt bui.d-;-i ~o assi,t in min2rdl hardness control.
The level of bull~ier cin ~ai~J ~iiua;~ e~ ing ~u~on ;ne -end use 10 of tile ccmposi~ion ~ini ~ii's ;' ;.n~ i; i 31 -o~i. Li~uid formulations typicall~ c~mi,r ;e at 1 st : s : '~;', mc,~- ';a. all~
from about 5% to about 5l~%. ~re-rorabm~ !r ~, to about ~iO%, by .Yeight Of d~terno~ . h~ r ~-~n~l ?~ t~ t' Compri~? d~ l~as' ~iiu~ r~ Li~Ui; i'~o ~ a~ou~
80%, preferably from about 1j~ ~o a~oui ~0% by weight o; the detergent builder. Lower or higher levels of builder, howeYer, are not meant to be excluded.
Inorganic detergent builders include, but are not limited to, the alkali metal, ammonium and alktnolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
Examples of silicate builders are the alkali metal silicates, particularly those having a SiO2:Na20 ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium sili~ates described in U.S.-Patent 4,664,839, issued May 12, 1987 to H. P.
Rieck, incorporated herein by reference. HoweYer, other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
Examples of carbonate builders are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesquicarbonate and mixtures thereof ~.~ith ultra-rin~ calcium carbonate as disclosed in German Patent A~plication ,~lo. 2,321,001 published on November 15, 1973, the disclosure of which is incorporated herein by reference.

w o 92/06I58 Pcr/us(31/o7o2~
~9~ J3 - 24 -Aluminosilicate builders are especially useful in the present in~Jentlon. Aluminosilic~Lo builders are of great importance in most currontl~/ ~ar'~e~ed heavy duty ~ranular detergent compositions, and can also ûe ~ signiTicanc builder ingredient in liquid detergent form~ ons Aluminosll1c3~- builders include those haYing the emp~ lUI~-Alû2 '/SiO~) ~nereiil ;i is souium, pocassium, ammonium or substituted ammonium, z jS ,~'~~~ ,0'!' '1.~ ', a'J~ it q; ~~nd ,~ is l; this material haYing a 13 iila4 1~L i 3 S ~ ~bout 50 .~i11igra;n eqUilia' ~' ,a~J~~ 'lar~inA-sâ ~r gram of anhydrous aluminosilicate.
?r n~1; s c~ ~ ~ a ecl,~a builders .~hich have the formu1a:
~I- r~ S ~q~ qO
15 ~here " - .,~ .r~ j_,1 5~,~; .-,~ ;~ 1a~SL ~, Lhe molar ratio of z to y is in the range from 1 0 to about 0.5, and x is an integer from about I5 to about 2~4.
Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al., issued October 12, 1976, incorporated herein- by reference.
Pre;erred synthetic crysta71ine aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:
Nal2[(Alo2)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 aluminosilicate has a particlc size of about O.l-I~ micrGns in diameter.
Specific examples of polyphosphates are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and ?otassium and aru~onium pyrophosphate, sodium and potas,,um orthophosphate, ;odium ~olymeta phosphate in which the degree of polymerization ranges from about 6 to about 21, and salts of phytic acid.

W 0 92/06158 2 0 9 2 ~ 5 9 Pcr/~s~1/0702-Examples of phosphonate builder salts are the water-soluble salts of ethane 1-hydroxy-1, 1-diphosphonate parcicularly 'cne sodium and potassium salts, the water-soluble salts of methylene diphosphonic ac;d e.g. the trisodium and tripotassium salts and the water-soluble salts of substituted meLh~lene di?nospnonic acids, such as the trisodium and tripotasaium c"~ den2, iâ~?yl Opyii~eT12 benzylmethylidene and halo methylideno Dhosohonates. Phos~honate builder salts of the aforemen-~ionèd ~j?aà i~~e diàciOii d in v.~.
Patent Nos. 3,159,581 and 3,213~030 i~ued ~camber 1. 195-~ and October 19, 1965, to Diehl; U.S. ?aLa ~ ''a. ~ s;~~~ a ua~, 14, 1969, to Roy; and U.S. ~a~n~ "~i. 3,.~u~i~8 a"d 3,~ 2,i , issued September 3, 19S8, and Jai,uary ;~ u; : ~ s~
disclosures being incorporated nerein by raFèrencê.
Or~anic detergent builders snltah!e Sor ~e pl!rpos s rf ~he present invention include, but are not res~~ oted t~, a w1de ~a-1ety of polycarboxylate compounds. As used herein, 'polycarboxylate~
refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium salts, especially sodium salts, or ammonium and substituted ammonium (e.g., alkanolammonium) salts are referred.
Included among the polycarboxylate builders are a variety of categories of useful materials. One important category of polycarboxylate builders encompasses the ether polycarboxyl2tes. A
number of ether polycarboxylates have been disclosed for use as detergent builders. Examples of useful ether polycarboxylates include oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al., U.S. Patent 3,635,830, issued January 18, 1972, both ~ which are incorporated herein by reference.
A specific type of ether polycarboxylates useful as builders in the present invention also include those having the general formula:
CH(A)(COOX)-CH(COOX)-O-CH(COOX)-CH(COOX)(8~
wherein A is H or OH; B is H or -O-CH(COOX)-CH2(COOX); and X is H or a salt-forming cation. for example, if in the above general formula w o 92/06~58 Pcr/us~)l/o7o2- ~
209~ 26 -A and B are both H, then the compound is oxydissuccinic acid and its water-soluble salts. I, A la ~ an~ 3 is '~, ~nen the compound is tartrate monosuccinic ~c d ',~ nd its ~a'-r-soluble sal~s. ~f A
is H and ~ is -u- .~ û;~ ;, ;~.?n ~;la cvmpound is tar~rate disuccinic acid ~ . ; ia-~.~-;.iu~,- sal s. .~ix~ures o~
thesq ~ r~ "" ?-,~
larly preferrcd arC ~i~,ur?s ~ S ind ,uS in a ~.~eia'nt r~tio of TMS
to ,DS ~ - ;J~ V_'~ ~ ' 1 C
disclos~?d in IJ.S. ~ ? '.... -1?~; ~ 'u~h qt t.~ n ~2y ~i, 10 lg87.

pa~ic~
ac~"~, ~,J~ ,/ J ~ 'r ~ ;1 u r ~ ~ u 2 all or '.~hiCn arq i:'_3'.~':!n~;:?(~ a, ?.~
Other ~IS~ ~. '' ? '~-~ ? r ~ r ~ ? -~ f .~ ~ r hydroxypolycarboxyla-Les re~ ;an;~d by th2 s;ructur~:
~0-[C(R)(500,~)-C(~)(COO~I)-O]n-H
wherein M is hydrogen or a cation wherein the resultant salt is water-soluble, preferably an alkali metal, ammonium or substituted ammonium cation, n is from about 2 to about 15 (preferably n is from about 2 to about 10, more preferably n averages from about 2 to about 4) and each R is the same or different and selected from hydrogen, Cl 4 al~yl or Cl ~ substituted alkyl (preferably R is hydrogen).
Still other ether polycarboxylates include copolymers of maleic anhydride with ethylene or Yinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid.
Organic polycarboxylate builders also include the various alkali metal, ammonium and substituted ammonium sal;s of polyacetic acids. Examples of polyacetic acid builder salts are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine Letraacetic acid and nit~~ilotriacecic acid.
Also included are polycarbox~lates such as mellitic acid, succinic acid, polym~leic acid, :,enzene 1,3,5-tr1carbovylir acid, benezene pentacarboxylic acid, and carho~ymethylox,~surrinlc acid, and soluble salts thereo w 0 92/06158 2 ~ 9 2 ~ ~ ~ Pcr/Us~ o2 Citric builders, e.g., citric acid and soluble salts thereof, is a polycarboxylat~ ~Jilder of particular importance for hea/y d~uty liquid detergent formulations, but can also be used in granular compositions. Suitable salts include the metal salt; s.ic;. 3;
sodium, lithium, and potassium salts, as well a~ a,emsnis m and substituted ammonium salts.
Other carboxylate builders include the carboxylated carbohydrates disclosed in U.S. Patent 3,7~3,3~7, ~ ?hl, ~- -d March 28, 1973, incorporated herein by reference.
10Also suitable in the detergent compositicns o; ;~
inventicn are the 3,3-dicarbox~-4-ox~-1, -heva~e~ie~
related compounds disclosed in U.S. ~a.e~
January 28, 1986, incorporated herein by reFe~,~e~c-. Ui-;u, ,u-.-",;
acid builders include the Cs-C20 al~yl succinic acius a,ld al ~S
thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Alkyl succinic acids typically are of the general formula R-CH(COOH)CH2(COOH) i.e., derivatives of succinic acid, wherein R is hydrocarbon, e.g., Clo-C20 alkyl or alkenyi, preferably C12-C16 or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all as described in the above-mentioned patents.
The succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanolammonium salts.
25Specific examples of succinate builders include: laurylsuccin-ate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccin-ates are the preferred builders of this group, and are dPscribed in European Patent Application 86200690.5/0,200,263, published November 305, 1986.
Examples of useful builders also include sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclo-hexane-hexacarboxylate, cis-cyclopentane-tetracarboxylate, water-soluble polyacrylates (these polyacrylates having molecular weights to above about 2,000 can also be effectively utilized as dispers-ants), and the copolymers of maleic anhydride with vinyl methyl ether or ethylene.

w o 92/06158 PCr/US')1/~702, 2 0 9 2 5 5 Other suitable polycarboxylates are the polyacetal carboxylates disclosed in U.S. Patent ~ 4,'2i" Cru~.rn,-i~ld ~t ~l., issuod March 13, 1979, incorporat~d her?in b~ refer?ii,ce. These polyacetal carboxylates can oe propar?. b~ bringiils ;~~?~h?r, unaer pol~meriza-tion conditions, an ~i -~ o, giyn;~ cio~ ~r~l a polymorizztion initiator. ~ h3 ra~ ly __;~, _'._v,~,,..~' ~s~er i- ~hen attached to chemically stable ?nd groups ~o s1abi,i~a the polyacetal carboxyl2t4 2S2iq~ v;,;~ ,v; -; -~ ;v~ un , converted to the correspo~ g ;al , and C~?C' ~ sur-act o. .
0 PO l yc arbo ~ a r ?
3,3cv~,as7, pilrhl ~ iJ;'lJC ~ h; ~ di h .-~ ib~
rerL~nc~. auc~ ;, - .,, ? ; ~ O~
and copo,ymers cf ailp"a~ c ~a,~v;; ,; aC-,5; ;UC~I as ma,eic acid, itaconic acid, mesacon c .c~d. -Um~riC aO~,'I. ~C,~
citraconic acid and methylenem?.lonic arid.
Other organic builders ~no~n in t,he art can also be used. For example, monocarboxylic acids, and solubl4 salts thereor, having long chain hydrocarbyls can be utilized. These would include materials generally referred to as "soaps." Chain lengths of Clo-C20 are typically utilized. The hydrocarbyls can be saturated or unsaturated.
Enzvmes Enzymes can be included in the detergent formulations for a variety of purposes includ.rg rem~oval o, prGt2;n-based, carbohy-drate-based, or triglyceride-based stains, for example, and prevention of refugee dye transfer. The enzymes to be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures ther20f. They may be of any su,table origin, such as vegetable, animal, bacterial, fungal and yeast origin.
llo.1~ver, their choice is goYerned by several factcrs sucn as pH-activity and/or stability optima, thermostability, stability versus active detergents, builders and so on. In this respect bacterial or fungal enzymes are ~re;erred, such as oacterial amylases and proteases, and fungal c llulases.
Suitable examples of pro~eases are the subtilisins ~.~hich are obtained from particular strains of 8.s1Jbtilis and ~.lich4niforms.
Another suitable protease i; obta,n5d ~rom a ;train or~ 3acillus, W O 92/06158 2 ~ ~ 2 ~ ~ 9 PCT/~S~1/07~2 having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade name Esperase~. The preparation of this enzyme and analogous enz~mes is described in British patent specification No. 1,243,78~ or .~oJo.
Proteolytic enzymes suitable for removing protein-based stains ~ha~
are commercially available include those sold under the -c. 2d2~ ie~
ALCALASE~M and SAVINASETM by Novo Industries A/S (Denmar~) and MAXATASETM by International Bio-Synthetics, Inc. (~he 'lethe,la..ds,.
Of interest in the category of proteolytic enzymes, espcci-llv for liquid detergent compositions, are en~ymes referrod '.o herein ~-Protease A and Protease 8. Protease A and me~nods ,or preparation are described in European Patent Applicac,on O,i~v, published January 9, 1985, incorporated herein ~y refercnce.
Prote~se ~ is a proteolytic enzyme ~hich differs from Protease ~ n that it has a leucine substituted for tyrosine in position 217 in its amino acid sequence. Protease B is described in European Patent Application Serial No. 87303761.8, filed April 28, 1987, incorporated herein by reference. Methods for preparation of Protease B are also disclosed in European Patent Application 130,756, Bott et al., published January 9, 1985, incorporated herein by reference.
Amyases include, for example, ~-amylases obtained from a special strain of B.licheniforms, described in more detail in British patent specification No. 1,296,839 (Novo), previously incorporated herein by reference. Amylolytic proteins include, for example, RAPIDASETM, International Bio-Synthetics, Inc. and TERMAMYLTM, Novo Industries.
The cellulases usable tn the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH
optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al., issued March 6, 1984, incorporated herein by reference, which discloses fungal cellulase produced from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800, and cellulases produced by a fungus of Bacillus N or a cellulase 212-producing fungus belonging to the W O 92/06158 PCT/USlJl/0702 genus Aeromonas, and cellulase extracted from the hepatopancreas of 9 a marine mollusc (Dolabella Auricula Solande,~).
Suitable lipase enzymes for detergent usano ;nclude thrise produced by microorganisms of the ~saudc"onas 3rouy, uch as Pseudomonas stutzeri ATCC 19.15~, as disc~oc~d i,i 3rit--t P1~-n' lo 1,372,034, incorporated her2i,t by r--,-n~"o . ~u j~rb~ ;ases include those which show a positivP ;mmunol ~ .~n~ -ct~o, with the antibody of the lipase, oro~uc AO ~J ;h~ mio, o~rgan~sm Pseudomonas f1uor.~scens !AM 1~57. Thi-, 1 purification have been deAsc,ibed it la?a s~
53-20~8J, laid open .o pub1ic ins~ecLion ~a ,-;,; r~ hls lipase is availabl~ rrom ~ma,to Pha-imc- ~ 5~
Japan, under ~he trade name Lipase P !'Amano,~ h-reina,~tor reTerr2d to as "Amano-P." Such lir.tases of the ?rCi~,?~e ''~ s''~
a positive immunological cross r~action mth 'h-~ ,;-' m :,.o';, using the standard and well-known immunodiffusion procedure according to Ouchterlony (Acta. Med. Scan., 133, pages 7~-79 (1950)). These lipases, and a method for their immunological cross-reaction with Amano-P, are also described in U.S. Patent 4,707,291, Thom et al., issued November 17, 1987, incorporated herein by reference. Typical examples thereof are the Amano-P
lipase, the lipase ex Pseudomonas fragi FERM P 1339 (available under the trade name Amano-B), lipase ex Psuedomonas nitroreducens Yar.
7ipo7yticvm FERM P 1338 (available under th2 trade name Amano-CES), lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
7ipo7yticum NRRIB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter YiSCOSUm li~ases from U.S.
8iochemical Corp., U.S.A. and Disoynth Co., The Neiherlands, and lipases ex Pseudomonas g7adio7i.
Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc.
They are used for "solution blezching," i.~. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution. Peroxidase enzymes are known in the art, and include, for example, hors~radish peroAidase, ligninase, and haloperoxidase such as chloro- and ~ omû-?e~~oA.dai2.
Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published 2~25~9 W O 92/06158 PCT/US91/0702?

October 19, 1989, by O. Kirk, assigned to Novo Industries A/S, incorporated herein by reference.
A wide range of enzyme mater1als and means for their incorporation into synthetic detergent granules is also disclosed in U.S. Patent 3,553,139, issued January 5, 1971 to McCarty et ~l.
(inc3r ?orated herein by reference). Enzymes are rurther disclcsed in U.S. Patent No. 4,101,457, Place et al., issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued ~arch 26, l985, ~oth incorporated herein by reference. Enzyme materials useful for li~u~d detergent formulations, and their incorporation into such r-3ri..U''~'.On;, are disclosed in U.S. Patent 4,261,868, Hora et al., issu~d Aplii i4, 138i, a7so incorporated hPrain by rPferenc~.
nzy~as are normally incorporated at leYels su;ficient ~o pro~ibe up to about 5 mg by weight, more typical7y about 0.0~ mg to about 3 mg, of active enzyme per gram of the composition.
For granular detergents, the enzymes are preferably coated or prilled with additives inert toward the enzymes to minimize dust formation and improve storage stability. Techniques ior accomplishing this are well known in the art. In liquid formulations, an enzyme stabilization system is preferably utilized.
Enzyme stabilization techniques for aqueous detergent compositions are well known in the art. For example, one technique for enzyme stab;lization in aqueous solutions involves the use of free calcium ions from sources such as calcium acetate, calcium formate, and calcium propionate. Calcium ions can be used in combination with short chain carboxylic acid salts, perferably formates. See, for - example, U.S. Patent 4,318,818, Letton, et al., issued March 9, 1~82, incorporated herein by reference. It has also been proposed to use polyols like glycerol and sorbitol. Alkoxy-alcohols, dialkylglycoethers, mixtures of polyvalent alcohols with polyfunctional aliphatic amines (e.g., alkanolamines such as diethanolamine, triethanolamine, di-isopropanolamine, etc.), and boric acid or alkali metal borate. Enzyme stabilization techniques are additionally disclosed and exemplified in U.S. Patent 4,261,868, issued April 14, 1981 to Horn, et al., U. S. Patent 3,600,319, issued August 17, 1971 to Gedge, et al., both incorporated herein by re~er~nce, and European Patent Application Publication No. 0 199 405, Application No. 86200586.5, published October 29, 1986, W O 92/06158 PcT/us~J1/~7n~~

9 ~ ~ Venegas. Non-boric acid and borate stabilizers are preferred.
Enzyme stabilization systems are also described, for examp7a, -n U.S. Patents 4,261,868, 3,600,319, and 3,519,570.
Bleachinq ComPounds - Bleachinq Aaents and Bleacn ~c,i~aror, The detergent compositions hereof may con-cain b~eac;o~.,g ~en s or bleaching compositions containing bl~ac,ii.,g 352n~ ~n_ n ~n ..,sr bleach activators. When present bleaching comsounds ~ill t~oioal be present at levels of from about lAi~ to auou; C,'" i"o~
from about lYo to about 10%, of the det~rgan -ameos;'ion .n general, bleaching compounds are opti~nal ~emn_ne~v_ ''n ,~;n'- ~'v.
formulations, e.g., granulaf de~ergcnLs ;, pr-~,c;iL, ~;ie m;~
bleach activators ~.~ill t~pic~ e ,-rcm l ac~.~; ''..., :' :~~:; ','.
more typically from about C.5~~o t~ abOUL ~o 0~ Lne b~eac;l;ng composition.
The bleaching agents used herein can be any ~f the l-ac- n-agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that aro no~ bno~n or become known. These include oxygen bleaches as well as other bleaching agents. For wash conditions below about 50-C, especially below about 40-C, it is preferred that the compositions hereof not contain borate or material which can form borate in situ (i.e.
borate-forming material) under detergent storage or wash conditions.
Thus it is preferred under these conditions that a non-borate, non-borate-forming bleaching agent is used. Pre,erably, det3rgenLs to be used at these temperatures are substantially free of borate and borate-forming material. As used herein, "substantially free of borate and borate-forming material n shall mean that the composition contains not more than about 2% by weight of borate-containing and borate-forming material of any type, preferably, no more than 1%, more preferably 07O.
One category of bleaching agent that can be used encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxy-phthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and dipProx~dod2ca,n~diuic acid. Such bleaching agents are disclosed in U.S. Patent ~ 83,781, Hartman, issued November 20, 1984, U.S. Patent Applicaiion 7~0,44O, Burns et al., filed June 3, 198~, European Patent Application W 0 92/06158 2 ~ ~ 2 ~ 5 ~ Pcr/usg1/0702-0,133,354, Banks et al., published February 20, 1985, and U.S
Patent 4,412,934, Chung et al., i,sued November 1, 1983, all of which are incorporated by reference herein. Highly preferred ble~chin~ agQnts also include 6-nonylamino-6-oxoperoxycaproic acid as describod in U.S. Patent 4,634,551, issued January 6, 1987 to 3;;~ , incor~orated herain by refQrencQ.
Another category of bleaching agents that can be used enc~as es the halogen bleaching agents. Examples of hypohalite bleaching agents, for Qxample, include trichloro isocyanuric acid '~ an. le ~odiun ~nd ~otassium dichloroisocyanurates and ~-chlcro and n~ su~phonamides. Such matorials are normally added at J ~ r ~ s~d ~-~du~ ~r~f q-~ h~
i~ C ~
.vxy~en ~leac;7.ng asen~s can al,o be usêd. Sui~aulc peroxyg~n bleaching compounds include sodium carbonate peroxy-hydrat~, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
Peroxygen bleaching agents are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator.
Preferred bleach activators incorporated into compositions of the present invention have the general formula:
o R - C - L
wherein R is an alkyl group containing from about 1 to about 18 carbon atoms wherein the longest linear alkyl chain extending from ar.d ir.rluding the carbonyl carbon contains from about 6 to about 10 carbon atoms and L is a leaving group, the conjugate acid of which has a pKa in the range of from about 4 to about 13. These bleach activators are described in U.S. Patent 4,915,854, issued April 10, 1990 to Mao, et al., incorporated herein by reference, and U.S.
P~tent 4,412,934, which was previously incorporated herein by reference.
~leaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein. One type of non-oxygen bloaching ~gent of particular interest includes photoactivated bleaching agents such as sulfonated zinc and aluminum w o 92/06158 PCT/~S(31/0~02 g ~ ~ ~ 9 phthalocyanine. These materials can be deposited upon the substrateduring the washing process. Upon irradiation ~ith light, in the presence of oxygen, such as by hanging clothes out to dry in the daylight, the sulfonated zinc phthaloc~anine is activatcd },id~
consequently, the substrate is blezched. Preferl-~d --n phthalocyanines and a photoactiYated bleaching prcce,i f~ e -;~
in U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al., incorporated herein by reference. Typically, ~eters.n~. C5mP,..~
will contain about 0.025% to about 1.25%, by ~eight, of suiro" --d zinc phthalocyanine.
Polvmeric Soil Release Aaent ~ ny rolymeric soil rele2se asent, I~,o:i" ~a ~ho ~- s'.;. . . :--art can be emplo~ed in the practice o,~ this ~nvent,vn. ~o ,a-ric soil rel~a,2 ager,t; are characteriz2d vy having OOL;1 ;1YGr0!~ . jC
1~ segments, to hydrophilize the surface of hydrophobic -ribers, sucn as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
Whereas it can be beneficial to utilize polymeric soil release agents in any of the detergent compositions hereof, especially those compositions utilized for laundry or other applications wherein removal of grease and oil from hydrophobic surfaces is needed, the presence of polyhydroxy fatty acid amide in detergent compositions also containing anionic surfactants can enhance performance of many - of the more commonly utili~ed types of polymeric soil release agents. Anionic surfactants interfere with the ability of certain soil release agents to deposit upon and adhere to hydrophobic surfaces. These polymeric soil release agents have nonionic hydrophile segments or hydrophobe segments which are anionic surfactant-interactive.
The compositions hereof for which improved polymeric soil release agent performance can be obtained through the use of polyhydroxy fatty acid amide are those which contain an anionic surfactant system, an anionic surfactant-interactive soil releaso agent and a soil release agent-enhancing amount of the polyhydroxy w o 92/061~8 2 0 9 2 5 ~ 9 PCT/US~1/07027 - 35 - , fatty acid amide ~PFA), wherein: (I) anionic surfactant-interaction between the soil release agent and the anionic surfactant system of the detergent composition can be shown by a comparison or the level of soil release agent (SRA) deposition on hydrophobic -ribers (e.g., polyester) in aqueous solution between (A~
a 'Conc .1 run ~nefein deposition of the SRA of the detergent compos,~ion in aqueous solution, in the absence of the other dctcny2~ i.,5rodionrs, is measured, and (3) an "SRA/Anionic surflct~nt" test run ~.Yherein the same type and amount of the anionic 0 .ur~ac~~.~ stam utilizad in detergent composition is combined in aqueou~ ,o'u~.v,, ;iith he S~, at tho s~me wei~ht ratio of SRA to 'Cl~e 'nnJn C Sl_r'r~C'_an'L sysCPm or cne decergen+ composiLion, ~nereoy reduc ~ aepo-.ttion in ~B) relative to (A) indicates anionic-sur~actant interaction; and (II) whether the decergent com?osition contains a soil release agent-enhancing amount of polyhydroxy fatty acid amide can be determined by a comparison of the SRA deposition of the SRA/Anionic surfactant test run of (B) with soil release agent deposi.tion in (C) an "SRA/Anionic surfactant/PFA test run" wherein the same type and level of polyhydroxy fatty acid amide of the detergent composition is combined with the soil release agent and anionic surfactant system corresponding to said SRA/Anionic surfactant test run, whereby improved deposition of the soil release agent in test run (C) relative to test run (B) indicates that a soil release agent-enhancing amount of polyhydroxy fatty acid amide is present.
For purposes hereof, the tests hereof should be conducted at anionic surfactant concentrations in the a~ueous solution that are above the critical mic21le concentration (CMC) nf the anionic surfactant and preferably above about lO0 ppm. The polymeric soil release agent concentration should be at least 15 ppm. A swatch of polyester fabric should be used for the hydrophobic fiber source. Identical s~atches ~re immersed and agitated in 35-C aqueous solutions for the respective test runs for a period of 12 minutes, then removed, and analyzed. Polymeric soil release agent deposition level can be determined by radiotaggin~ the soil release agent prior to treatment and subse~uently conducting radiochemical analysis, according to techniques '~nown in the art.

W O 92/06158 pcT/~ss1/~7n2 9~9 As an alternat;ve to the radiochemical analytical methodology q~ d;scussed above, so;l release agent deposition can alternately be determined in the above test runs (i.e., test runs A, B, and C) by determination of ultraviolet light (UV) absorbance of the test solutions, according to techniques well known in the art. ~ecreased UY a~scrbanc2 in the t~st solution after removal of th2 h/drs?h~
fiber material corresponds to increased SRA ~eposition. As will be ~ understood by those sk;lled in the art, UY analysis ;hould no ~e ; ut;lized for test solut;ons conta;ning types and levels of materials which cause excessive UY absorbance inter'erence, such ?.5 ~'li9~1 le~!e15 of surfactants w;th aromatic groups (e.y., a,!~;, b~-.i---"
, .. e~.. ~ ~,~ ~ ~
~ ~. " v ~
Thus by "soil release agent-enhancing ~mount" or po ~h~d ox;
fatty acid amide is ,nean'c an amounc or such surfactanl Inat wili enhance deposition of the so;l release agent upon hydrophobic fibers, as described above, or an amount for which enhanced grease/o;l cleaning performance can be obtained for fabrics ~~ashed in the detergent composition hereof in the next subsequent cleaning operation.
The amount of polyhydroxy fatty acid amide needed to enhance deposition will vary with the anionic surfactant selected, the amount of anionic surfactant, the particular soil release agent chosen, as well as the particular polyhydroxy fatty acid amide chosen. G~nerally, compositions w;ll comprise from about 0.01% to about 10%, by weight, of the polymeric soil release agent, typically from about 0.1% to about 5%, and from about 4X to about 50%, more typically from about 5% to about 30~O of anionic surfactant. Such compositions sho~ld generally contain at least about 1%, preferably at least about 3~., by weight, of the polyhydroxy fatty acid am;de, though it is not intended to necessarily be limited thereto.
The polymeric soil release agents for which performance is enhanced by polyhydroxy fatty acid amide in the presence of anionic surfactant include those soil release 'agents having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to 2092~9 WO 92/06~58 PCI-/US91/0702, adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyal'~yl2ne units comprising oxyethylene and from 1 to about 30 oxypropylen2 units ~herein said mixture contains a sufficient amount of 'J,~y~'n~len~ units such that the hydrophile component has hyd op,~ilicicy great onough to increase the hydrophilicity of COi~~'. -n~, n- ! ,~l,J-stei' jyni'"et-c Fiber sur,~aces upon deposit of the soil release agent on such surface, said hydrophile segments pre. e.'.~'' IJl ~ r-;1ng a~ least about 25% oxyethylene units and more pre~?rablv, es~ociall~ for such components having about 20 to 30 O~O ~~~ny~ .? ~.~i s, ~-' loast a~out 50% oxyethylene units; or (b) one or .;.or ~d;~l~hs e ~...rcnent, ~2mpris,ns (i) C3 oxyalbyl2ne ~O ~ , g;~ ;;e~?li~, ir said hydropnobe components also cG."pr.se ~ iene ~erepn-ch21ate, the ratio of oxyethylene ter4~n~.lal ~e:C3 oxyalkylene cerepninalate units is about 2:1 or lo~er (1i) C,t-Cj al~lene or oxy C4-C6 alkylene segments, or mixtures thereof, (iii) poly (vinyl ester) segments, preferably poly(vinyl acetate), having a degree of polymerization of at least 2, or (iv) Cl-C4 alkyl ether or C4 hydroxyalkyl ether substituents, or mixtures thereof, wherein said substituents are present in the form of Cl-C4 alkyl ether or C4 hydroxyalkyl ether cellulose derivatives, or mixtures thereof, and such cellulose derivatives are amphiphilic, whereby they have a sufficient level of Cl-C4 alkyl ether and/or C4 hydroxyalkyl ether units to deposit upon conventiona1 polyester synthetic fiber surfaces and retain a sufficient level of hydroxyls, once adhered to such conventional synthetic fiber surface, to increase fiber surface hydrophilicity, or a combination of (a) and (b).
Typ,cally, the polyoxyethylene segments of (a)(i~ will have a degree of polymerization of from 2 to about 200, although higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100. Suitable oxy C4-C6 alkylene hydrophobe -segments include, but are not limited to, end-caps of polymeric soil relea;e agents such as M03$(CH2)nOCH2CH20-, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, incorporated herein by reference.
~olymeric ;oil release agents useful in the present invention include cellulosic derivatives such as hydroxyether cellulosic W O 92/06l58 PCT/US91/0702 ~9~59 polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate ~ith polyethylene oxide or polypropylene oxide terephthalate, and the like.
Cellulosic derivatives that are functional as soil release agents are commercially available and include hydroxyethers or c~,1u.ose suc,i as ,~ethocel2 (Dow).
Cellulosic soil release agents for use herein also ir,clude LhU~- ielecLed from Lhe group consisting of Cl-C4 alky'i anc 5 h,~dr3~ al~yl cellulose such as methylcel,uloâe, eLh~lcqllul~sa, C ,,_ro~ o~1 ,qthylcellulose, and hydroxybutyl ~e h~lcollul 2.e .
~nia;~ o,~ cel,ulose derivacives useful as soil releaâe pol~mers arq osad -,n U.S. Patent ~,OOO,Og3, issued Dec~moer 28, 137; ;o ~icû1, eL a1., incorporated nerein by reference.
Soi1 rele~se aQen~s ch~r~cteri7qd hy ?oly(~!i"~l a-) !5 hydrQqho~q sqgmPnts include graft copolymers o, poly(~Jinyl ester), e.g., Cl-C6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, sùch as polyethylene oxide backbones. Such materials are known in the art and are described in European Patent Application 0 219 048, published April 22, 1987 by Kud, et al. Suitable commercially available soil release agents of this kind include the SokalanTM type of material, e.g., SokalanTM
HP-22, available from BASF (West Germany).
One type of preferred soil release agent is a copolymer having randûm bloc~s of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. More specifically, these polymers are comprised of repeating units of ethylene terephthalate and PEO terephthalate in a mole ratio of ethylene terephthalate units to pFo ter2phthalate units of from about 25:75 to about 35:65, said PEO terephthalate units containing polyethylene oxide having molecular weights of from about 300 to about 2000. The molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1376, which is incorporated by reference. See also U.S. Patent 3,893,929 to Basadur issued July 8, 1975 (incorporated by reference) which d,scloâas similar copolymers.
~nother prqferred pol~meric soil release agent is a polyester with repeai units of ethylene terephthalate units containing 10-15Y.
by weight of ethylene terephthalate units together with 90-80X by 29925~9 w O 92/061~8 PCT/US91/07027 weight of polyoxyethylene terephthalate units, derived from a polyox~ethylene glycol Or average molecular weight 300-5,000, and the mol~ ratio of ethylene terephthalate units to polyoxyethylene terepntlalac2 uni LS in th~ polymeric compound ;s between 2:1 and 6~ a~,ples ol- this polymer include the commercially available ma-c~rl ~ 7e~n~ f~s;l 3upon-) -nd ilile~se~ T (from ICi). These polymers ~nd methods of their preparat;on are more fully described in U.~. 'a~-n~ ',7~ ssuod ~ctober 27, 19a7 to Gosselink, ~h;ch is inco-~ora,.ed ~ere;n bv reference.
~ ~u~ -e~enred~ mer c soil release agent is a sulfonated ?i~~uU~ v~ l,So~r ;o~pri~d o~ an 0~ j5~ ;'- m ',~ e ~ D'/ 1 and oxyalky7eneoxy repeat uni~s an~ Le~~miilal ",ole;,e; co~a, ntl~ altacned to the bac'~bone, said ~,uil re~ase ~gent ~Qing deri~/ed from allyl alcohol ethoxylate, dimet hyl t erephthalate, and 1,2 propylene diol, wherein after sulronation, the terminal moieties of each oligomer have, on average, a total of from about 1 to about 4 sulfonate groups. These soil release agents are described fully in U.S. Patent 4,968,451, issued November 6, 1990 to J. J. Scheibel and E. P. Gosselink, U.S.
Serial No. 07/474,709, filed January 29, 1990, incorporated herein by reference.
Other suitable polymeric soil release agents include the ethyl-or methyl-capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters of U.S. Pztent 4,711,730, issued December 8, 1987 to Gosselink et al., the anionic end-capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, wnerein the anionic end-caps comprise sulfo-polyethoxy groups derived from polyethylene glyc~l (PEG), th~ block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink, having polyethoxy end-caps of the formula X-(OCH2CH2)n- wherein n is from 12 to about 43 and X is a C1-C4 alkyl, or preferably methyl, all of these patents being incorporated herein oy reference.
Additional polymeric soil release agents include the soil relezce agonts of U.S. Patent 47877,896, issued October 31, 1989 to Maldonado et al.7 which discloses anionic, especially sulfoaroyl, end-capped terephthalate esters, said patent being incorporated herein by reference. The terephthalate esters contain W O 92/06158 PcT/US9l/0702 unsymmetrically substituted oxy~l,2-alkyleneoxy units. Included ' among the soil release polymers of U.S. Patent 4,877,896 are materials ~ith oolyoxyethylene hydrophile components or C3 oxyalkylene terephthalate (propylene terephthalate) repeat units ~ithin the scope of the hydrophobe components of (b)(i~ above. It is tllc ?~ly",~ric soil release agents characterized by either, or both, of thssa criteria that particularly benefit from the inclusion or Li)e pol~hydroxy ra~ty acid amides hereof, in the presence of ~nioR~ ts.
2d~ ;oil release agents ~ill generally comprise from abouc J.Ui,~ ~0 aDOUC ;O.~/o, Dy weight, of the detergent compositions h_'~~_in~ ,,;p~ ~al l~ ,~rcm about 0.1% to about ~0, preferably from about 0.2% to about 3.û%.
Ch l. ~ ~ nts ~,e dA~q gan+ compositions herein may also optionally contain one or more iron and manganese chelating agents as a builder adjunct material. Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally -substituted aromatic chelating agents and mixtures thereof, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
Amino carboxylates useful as optional chelating agents in compositions of the invention can have one or more, preferably at least two, units of the substructure CH2 ~
N - (CH2)X - COOM, wherein M is hydrogen, alkali metal, ammonium or substituted ammonium ~e.g. ethanolamine) and x is from 1 to about 3, preferably 1. Preferably, these amino carboxylates do not contain alkyl or alken~l groups ~ith more than about 6 carbon atoms. Operable amine carboxylates include ethylenediaminetetraacetates, N-hydroxyethyl-ethylenediaminetriacetates, nitrilotriacetates, ethylenediamine 3~ tetrapropr,onat2s, triethylenetetra 2mi nehexaacetates, diethylene-triaminep~n+a2cetates, and ~thanoldiglycines, alkali metal, ammonium, and substituted ammonium salts thereof and mixtures thereof.

W O 92/06158 2 ~ 9 PCT/US91/0702 Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total ~hosDhorus are permitted in detergent compositions.
Compounds Yith one or more, pref2rably at least two, units of the substructure c~2~
~ - (r~ P~M~, wnerein ~hyurùy n, al~ali me;al, ammo"i~m or substituted a~monium -.n~.~m l to ahout 3, proferably 1, are useful and incl~c ; , ~a~ hj~ o- hcn tes), nitrilotris (metnyl~nep,los~ho)a~es; ~nu d,~ ia" ~;~iami"-pe~ia~is (",ethylene-phosphon ~ ;e.~~r j, :"~i a;"llo ~nosv,io,ia~as do not contain alkyl or al~enyi groups with more ~han about ~ carbon atoms.
Al b~yl en~ 9r~'!pS .an h3 s~ared ~y substructures.
15?olyf~n~l onally-cubstitut~ aromatic chel ting agents are also useful in the compositions nerein. These materials can comprise compounds having the general formula OH
R ~ OH
1 ~ l R ~ R
R

wherein at least one R is -S03H or -COOH or soluble salts thereof and mixtures thereof. U.S. ?atent 3,812,044, issued May 21, 1974, to Connor et al., incorporated herein by reference, discloses polyfunctionally-substituted aromatic chelating and sequestering agents. Preferred compounds of this type in acid form are dihy-droxydisulfobenzenes such as 1,2-dihydroxy -3,5-disulfobenzene.
Alkaline detergent compositions can contain these materials in the form of alkali metal, ammonium or substituted ammonium (e.g. mono-or triethanol-amine) salts.
If utilized, these chelating agents ~ill generally comprise from about O.l~o to about 10X by weight of the detergent compositions herein. More preferably chelating agents will comprise from about 0.1~ to about 3.C~. by weight of such compositions.
ClaY Soil ~'~emovzl/Anti-rede~osition Aqents The compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal w o 92/06158 pcT/uss1/o7o2 and anti-redeposition properties. Granular detergent compositions which contain these compounds typically contain from about 0.01% to abou~ iO.~o oy w2ight of the water-soluble ethoxylated amines;
liquid detergent compositions, typically about 0.01% to about 5~.
Th~.o u-' r~ ~~lec'2d pr~ferably ,rom the group consisting ~,:
~i) e~"oAyla~ed i"onoamines having the formula:
L-)-~1-(22)2 ~ 7' ?,;lv~7'~ d dia~i~es having the formula:
~ ,2 ( ~2 ) 2 - N - ~l - N - ( R2 ) 2 L L
.'( ~ X

~ , ,~-,;-,~ " (~ 12 ~3) e,hox~laced polyamines having the formula:

R3-[(Al)q~(R4)t~N-L-X]p (4) ethoxylated amine polymers having the general formula:

[(R2)2-N3W~Rl-N3x~Rl-i~yERl-h-L-x)z and (~) mixtures therPof; wherein Al is 11 "
-NC-, -NCO-, -NCN-, -CN-, -OCN-, R R R R R R

11 ~J "
-CO-, -OCO-, -OC-, -CNC-, R
or -0-; R is H or C1-C4 alkyl or hydroxyalkyl; Rl is C2-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no O-N bonds are formed; each R2 is Cl-C4 or hydrox~alkyl, the moiet~ -L-X, or t~o R2 together form the moiety -~C~.2)r, -A~-(C~2)s-~ wherein A2 is -O- or -CH2-, r is 1 or 2, s is 1 or 2, and r + s is 3 or 4; X is a nonionic group, an anionic group or mixture thereof; R3 is a substituted C3-C12 alkyl, hydroxyalkyl, w o 92/06158 2 0 3 2 ~ ~ 9 PCT/USg1/07027 alkenyl, aryl, or alkaryl group having substitution sites; R4 is Cl-C12 al~yl ne, hydroxyal!<ylene, alkenylene, arylene or alkarylene, or a C~-C3 oxyalkyleni~ moiety having from 2 to about 20 oxyalkylene units provided tha-c no 0-0 or O-N bonds are formed; L is a hydrophilic chain whic,l contains the polyoxyalkylene moiety ~[(R~~)m(C~i2C~2~ini-, ~:lri'rq~ C~ 2~ n~ or h~dro~ yl-ene and m and n are numbers such that the moiety -(CH~CH20)n-comprises at lcqst ~abvut ~C~O bJ' :~ci~ vf ~âi~ ?OlyOAyalkyl2ne moiet~i For said monoam1nes, m is From ~ o a~o~lt 4, and n is at least ~bou' 12; f~:~ s~ -. es, s r-- ~ -o - 3U' 3, and n is at ~as~ aoou~ ~ ~7~ 3 ~ J(~fv~ya~ e,~c~ or all'ienylelle, lnO a~ n-~ ,'; ._ '~'..' ~ m'iln C~-C3 ail~yl-ene, hydroxyal~yl2ne o,~ al';2r,y,er,c; ,or said polyamines and amine polymers. m is from n to ;bout lO and n is at least about 3; p is from 3 to 8; q jc 1 or ~; t is 1 or ~, ?rovid4d that t is 1 whon q is l; w is 1 or 0; x + y + z is at least 2; and y + z is at least 2.
The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986, incorporated herein by reference. Another group of preferred clay soil remoYal/anti-redeposition agents are the cati-onic compounds disclosed in European Patent Application 111,965, Oh and 60sselink, published 3une 27, 1984, incorporated herein by reference. Other clay soil removal/anti-r~dêposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in Euro~ean Patent Appli-cation 112,592, Gosselin~, pu~lished July ¢, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, ;ssued October 22, 1985, all of which are incorporated herein by reference.
Other clay soil removal and/or anti redeposition agents known in the art can also be utili7ed in the compositions hereof. Another type of preferred anti-redeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art Pol~meric DisDersinq Aqents Polymeric polycarboxylate disper;ing agents can advantageously be utilized in the compositions hereof. These materials can aid in w o 92/06158 PCT/US91/0702 9 calcium and magnesium hardness control. Suitable polymeric dispers-9 ~ ~ 5 ing aa nts include polyrn ric polycarboxylates and polyethylene glycols. althcugh others known in the art can also be used.
P~o ymeric dispers.ng ayents are generally used at levels of about ~ io i~out 5~O~ by ~eight, of the detergent composition, ~Ot~ ,r~ r ~'V~ ~ ab~ut 2.~70.
Tlle ?ol~carboxylate materials ~hich can be employed as the po1J"mc.~-lc ,o~jcarboxj~a; dis~ersiil~ agent cornponent herein are thes? ~ol~m?rs or ~onol~me-s ~hich contain at least about ~07~ Sy ;

L '~ rn0?~1 wherein X, Y, and ~ zre each selected from the group consisting of hydrogen, methyl, carboxy, carboxymethyl, hydroxy and hydroxymethyl;
a salt-forming cation and n is from about 30 to about 400. Prefer-ably, X is h~Jrogen or hydroxy, Y 1s hydrogen or carboxy, Z is hydrogen and M is hyJ~ogen, alkali metal, ammonia or substitutedammonium.
Polymeric polycarboxylate materials of this type can be pre-pared by polymerizing sr copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycar-boxylates include acrylic acid, maleic acid (or maleic anhydride), fumar.c acid, Itaconic ac-id, aconitic acid, mesaconic acid, citra-conic acid and methylenemalonic acid. The presence in the polymeric polycarboxylates herein of monomeric se~ments, containing no car-boxylate radicals such as vinylmethyl ether, styrene, ethylene, etc.is suitable provided that such segments do not constitute more than about ~C~ by ~eight.
Particularl~ suitable pol~meric polycarboxylates can be derived from asr~lic acid. Such ~cr~llc ac-.d-bas2d polymers which are useful herQin are the ~at~r-solublQ salts of pol~meriz2d acrylic acid. The a~/eraye molecular ~eignt or such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably WO 92/06158 2 0 9 2 ~ ~ 9 PCl/US91/0702, . . .

from about 4,000 to 7,000 and most prefereably from about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can include, for example, the alkali m~-cal, am~or.ium and substituted ammonium salts. Soluble polymers of this ~ype arD ';~nswn m3t~rials Use of polyacrylates of t~iâ ~Yr~ J~ S '__C~
disclosed, for example, in Diehl, U.S. Pa kn~ ;lo. 3,3u8,0v7, issu2d March 7, 1967. This patent is incorporac~d nerein oy re-;erenco.
Acrylic/maleic-based copolymers may a7so be used as prerDrrod component of the dispersing/anti-red~nosi~ on 1~. r Suc;1 mare-ial.
include the water-soluble sal's of cop~)ly,~ers o, acr~ a5id and maleic acid. The aYerage molaclllar wD;g~r ~ a ~ in ~?
acid form preferably ranqes ,rv,,, abo;it ~ i~0 to ;00; C,, -ore preferabl~ -,rom abou L 5~ GQ0 to ,5 "9G, ~ ;;e~-.~ a. ~ ~u 7,000 to 65,000. The ratio or acrylace ~o malea~ s~gmen-cs in ~uch copolymers will generally rnage from about 30:1 ~o about 1:1, more preferably from about 10:1 to 2:1. 'Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982, which publication is incorporated herein by reference.
Another polymeric material which can be included is polyethylene glycol (PEG). PEG can exhibit disper~ing agent performance as well as act as a clay soil removal/anti-redeposition agent. Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1,000 to about S0,000, more preferably from about 1,50û to about lû,OûO.
Briqhtener Any optical brighteners or other brightening or whitening agents known in the art can be incorporated into the detergent compositions hereof.
The choice of brightener for use in detergent compositions will depend upon a number of factors, such as the t~pe of detergent, the nature of other components present in the detergent composition, the temperatures of wash water, the degree of agitation, and the ratio of the material washed to tub size.

WO s2/n6158 PCT/US9l/07027 ~9~ The brightener selection ;s a;so dependent upon the type of material to be cleaned, e.g., cottons, synthetics, etc. Since most laundry decerg~nc produc ; are used 'co cle2n a variety of fabrics, the dPtergant c~mD3sltl3ns s~3uld contaln a ~lx'ure of brighteners .which ~ ~s. is ~; course necPssar~ 'hat 'he lnd-iiidu~, cvmpon~nts o; such a brightener mix-~u,~~ ~è ~_ Oii~
Cor~mercial op~ 31 vn,5;1~'n''rj WiliCh ma~ oe useful in the pr2521t in~/el'tin/ll ''-:n ;~ i '.n ~ S" 'a-~t pS which include, buc îr e nGt .l'C_SS-r, . j' ' .~,tiC:d ~, deriv~ es OT SCilDene, pyra,oli~ ; ;. , ,n?,~ln~."n.
d i ben~t ~ r~ êm~r~d ~
h~t~ s, . ~ ~'?~ ,~ s ~; ~UC.~
brigh~ rs a,~ d,s.,,;-~ i" ~ -JuUcLio,l ~na App~icacion Ot Fluoresc-nc ~rigntening ~ents;', I~l. 7ahr2dni~, Published by John W;ley ~ Sons, New tork (1982), -che disclosure of which is incorporated herein by reference.
Stilbene derivatives which may be useful in the present invention include, but are not necessarily limited to, derivatives of bis(triazinyl)amino-stilbene; bisacylamino derivatives of stilbene; triazole derivatives of stilbene; oxadiazole derivatives of stilbene; oxazole derivatives of stilbene; and styryl derivatives of stilbene.
Certain derivatives OT bis~triazinyl)aminostilben~ which may be useful in the present invention may be prepared from 4,4'-diamine-stilbene-2,2'-disulfonic acid.
Coumarin derivatives which may be useful in the present invention include, but are not necessarily limited to, derivatives substituted in the 3-position, in the 7-position, and in the 3- and 7-positions.
Carboxylic acid derivatives which may be useful in the present invention include, but are not necessarily limited to, fumaric acid derivatives; benzoic acid deri~a'cives; p-phenylene-bis-acrylic acid derivatives; naphthalenedicarboxylic acid deri~J3ti~Jes; heteroc~clic acid deriva'ciYes; and cinnamic acid deriva'c-i~Jes.
Cinnamic acid deri~atiY~s wnic1 may be userul in the present invention can be ~urther subclassified in'co groups which include, but are not necessarily limited to, cinnamic acid derivatives, 20925~9 w o 92/06158 PCT/USg1/0702-styrylazoles, styrylbenzofurans, styryloxadiazoles, styryltriazoles, and styrylpolyphenyls, as disclosed on page 77 of t~e Zahradni'~ -reference.
The styrylazoles can be further subclassi,ied into styrylbenzoxazoles, styrylimidazoles and styr~Jlthiazole, as disclosed on page 78 of the Zahradni~ re;erence. lt ~ oe understood that these three identified s!bcl~sses m?.,/ n~' necessarily reflect an exhaustive list o, su~grolJps in o ~nlc~
~styrylazoles may be subclassified.
Another class of optical orighteners :~lhicn ."~'! ~' "i~.''.~ r. b~
present invention are the deriYatiYes o-r ~io?nzo;~ ?ilen3~
dioxide disclosed at page 7~1-749 OT The ';~ir'~-u ~m3~ ;lC/ ~ 'S~' Chemical Technoloav, Volume 3, pages 737-750 (John ~1il3y '~ Son.
Inc., 1962), the disclosure of :ih1c~. i i-~~~-~:~-. ,~-J '-_r--~.n ',-' reference, and include 3,7-diaminodib~onzot3liù~hene-2~-d~sui;onic acid 5,5 dioxide.
Another class of optical brighteners which may be useiul in the present invention include azoles, which are derivatives of 5-membered ring heterocycles. These can be further subcategorized into monoazoles and bisazoles. Examples of monoazoles and bisazoles are disclosed in the Kirk-Othmer reference.
Another class of brighteners which may be useful in the present invention are the derivatives of 6-membered-ring hetero- cycles disclosed in the Kirk-Othmer reference. Examples of such compounds include brighteners derived from pyrazine and brighteners derived from 4-aminonaphthalamide.
In addition to the brighteners already described, miscellaneous agents may also be useful as brighteners. Examples of such miscellaneous agents are disclosed at pages 93-95 of the Zahradnik reference, and include 1-hydroxy-3,6,8-pyrenetri- sulphonic acid;
2,4-dimethoxy-1,3,5-triazin-6-yl-pyrene; 4,5-di- phenylimidazolone-disulphonic acid; and derivatives of pyrazoline- quinoline.
Other specific examples of optical brighteners which may be useful in the present invention are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988, tne disclosurs o;
which is incorporated herein by reference. These brighteners include the PhorwhiteTM series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, w o 92/06158 PCT/US91/0702-9~9 48 -Tinopal CBS and Tinopal 5BM; ava;lable from Ciba-Geigy; Arctic White CC and Artic '~hite C'~D, aYailable from Hilton-Davis, located in Italy; the 2-(~-s~ l-ul7.-il/7J-~'l- naDntnoiEi,2-d triazoles;
4,4'-bis- (l~2~3-triazo~ -sl llbenes; ~ -bis(st~ryl)bis-phenyl.; ~.~d ~ .n ~. ;~ ; o-~ t;1e,e brighteners i7i7cl udê ~1 -."et i,''i-/- di ~'th,; 1 - aii7ii70 coumarin; 1,2-ois-(-benLili7idaZo7-~ 7j ~7y .?ne~ -iio;l?~lohra70lines; 2,5-ois-(benzoxazol-2-yl ) t'i7 i ~i7 ~-il2; '~~ apil~h-;1,5-djoxazole; and 2-(stilbene~ - 3-' ~ .
0 ~t.~''r a,, ~. . C_ . ~ a _i~S ,ni i ~ ia'i J ? Ui;? ~ u i i n ;he oresent ;nVent;O;7 ;,1C1UG? ~ ? .. ;~ ? j1 ~ SSIJ~d February ~'7~ 7;7-'~' ,~ "-.-~;'~'',~:~. ,~e ~;'S;.~_U.-- Jl which -,s lnc~. y~ ~.~ i.-l ,.... ......
0th e r i no reG i ën ~ ~
A ~~jda ~Jariet~ or ocher .r,gr~dienls us2,~ul in detergent compositions can be included i n she co~positions hereof, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, etc.
Liquid detergent compositions can contain water and other solvents as carriers. Low molecular 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 ihose containing from ~ to about-6 carbon atoms and from 2 to about 6 hydro~y groups (e.g., propylene glycol, ethylene glycol, glycerine, and 1,2-propanediol) can also be used.
The detergent compositions hereof will preferably be formulated such that during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about II, preferably between about 7.5 and about 10.5. Liquid product formulations preferably have a pH between about 7.5 and about 9.5, more preferably between about 7.5 and about 9Ø Techniques for controlling pH at recommended usage 1e~/els include the use of buffers, al~alis, acids, etc., and are well known to those skill2d in the art.
This invention ,~urther ~rovides a ~ethod ror cleaning substrates, such as fibers, raorics, hard sur;aces, ;kin, etc., by contacting said substrate with the detergent co~positions of the present inYention in the presence of a sol~ent such as water or 2~925~9 w o 92/06158 pcr/us91/o7o2 water-miscible solvent (e.g., primary and secondary alcohols).
Agitation is preferably provided for enhancing cleaning Suitable means for providing agitation include rubbing by hand or ~;th the a;d of a brush, or other cleaning device, automatic laundry ~ashing machines, automatic dishwashers, etc.
EXPE~I~ENTAL
This exemplifies a process for making a ~-methy7, 1-deoxyglucityl lauram;de surfactant for use herain. ~l'hough a skilled chemist can vary apparatus configuration, cne suitable apparatus for use herein comprises a three-liter f~u, -n~ 2d ~1'_'~
fitted with a motor-driven paddle stirrer ~nd a chorm~me~an o-, lens'~ suffic ent to contact the reaction me~ ~m. h- ---e~
nec~s of the flask are fitted with 2 nitrogen iwee~ ~nd ~ ~1d~
side-arm (caution: a wide-bor~ side-arm is im~O'ntaïl_ ,n e~
very rapid methanol evolution) to which is connected an ef,-ici2nt collecting condenser and vacuum outlet. The latter is connected to a nitrogen bleed and vacuum gauge, then to an aspirator and a trap.
A 500 watt heating mantle with a variable transformer temperature controller (nVariacn) used to heat the reaction is so placed on a lab-jack that it may be readily raised or lowered to further control temperature of the reaction.
N-methylglucamine (195 9., 1.0 mole, Aldrich, M4700-0) and methyl laurate (Procter & Gamble CE 1270, 220.9 9., 1.0 mole) are placed in a flask. The solid/liquid mixture is heated with stirring under a nitrogen sweep to form a melt (approximately 25 minutes).
When the melt temperature reaches 145- C, catalyst (anhydrous powdered sodium carbonate, 10.5 9., 0.1 mole, J. T. Baker) is added.
The nitrogen sweep is shut off and the aspirator and nitrogen bleed are adjusted to give 5 inches (5/31 atm.) Hg. vacuum. From this point on, the reaction temperature is held at 150- C by adjusting the Variac and/or by raising or lowering the mantle.
Within 7 minutes, first methanol bubbles are sighted at the men;scus of the reaction mixture. A vigorous reaction soon follows.
Methanol is distilled over until its rate subsides. The vacuum is adjusted to give about 10 inches Hg. (10/31 atm.) vacuum. The vacuum is increased approximately as follows (in inches Hg. at minutes~: 10 at 3, 20 at 7, 25 at 10. 11 minutes from the onset of methanol evolution, heating and stirring are discontinued W o 92/06158 ~CT/USsl/07027 ~ 50 -~ ~ ~ ~ 9 co-incident with some foaming. ~he product is cooled and solidifies.
The following ox2mp7as ~r~ m~3r.t to 2'~".plif~ c~r"positions of the present invention, ~ut are no~ ner.ossar-lv leant to limit or otherwise define ~,~e ~co~e o,~ ~h~ inY~r..icn, said SCOp2 being determined accordi ng to claims ~nic~ fol 1 o:i.
L,;, ,j These examples sho~ he~ J ~!!t'.~ ~.rl~ r ~.?. ~ont o~-~os ~f,ion, containing poiyhydrox~ ciu ~m,-e, ~ c;yla~ sul.~a~2s, and suds suppr~oss~r.
8ase Granllle _ _ ~
C14-15 Alky7 jul,aL-~ 11.3 C14-15 ~l.cyl ,io;~
N-Methyl N-l-Deoxygiuci~yl Cocoa~ide ii.~ 5.
Zeolite A ~ ?
Sodium Citrate Sodium Carbonate 22.0 22.0 16.9 Sodium Silicate 3.0 3.0 5.6 Sodium Sulfate 8.0 8.0 11.1 Sodium Polyacrylate (4500 MW) 3.5 3.5 2.1 Polyethylene Glycol (8000 MW) 1.1 1.1 1.1 ~allow Fatty Acid 2.1 1.1 1.1 Brightener 0.2. 0.2 0.2 Admix and SDrav-on Suds Suppressor rlake * 1.O 0.5 Protease (1.4% active enzyme) o.g o.g o.g Perfume 0 3 0 3 0 3 C12 13 Alkyl Ethoxylate (6.~ mole) 1.1 1.1 1.1 Water and Miscellaneous 5.2 S.l 5.8 100.0 100.0 100.0 *Suds Suppressor Flake contains approximately 5% of a silica/
silicone oil dispersion encapsulated in a flake containing primarily PEG (8000 M~), at grPater than 80~~, ?rd minor o~tional ~~ater soluble ingredients.
Examples 1-3 are formulations for preferred use of about 1400 ppm, ~ash ~ater ~eight basis, ,~or ~a",peratura, below abouL 5G~C.
~he above examples are mado b~ oomblr,ir~ t~e base granule ingredients as a slurry, and spray arying to about 4-8% residual WO 92/06158 2 0 9 2 ~ ~ 9 PCl /US91/07027 moisture. The remaining dry ingredients are admixed in granular or powder form with the spray dried granule in a rotary mixing drum, and the liquid ingredients (nonionic surfactant and perfume) sprayed on.
Base Granule 4 5 C14 15 Alkyl Sulfate 5.8 C16-l8 Alkyl Ethoxy (2.5) Sulfate 6.0 C16 18 Fatty Acid 2.2 2.2 Zeolite A 7.0 7.0 7.0 Polyacrylate (4500 MW) 3.3 3.3 3.3 Polyethylene Glycol (8000 M~) 1.3 1.3 !.3 Scdiu,., 0a,~onat~ 10.? 10.?
Sodium Sulfate i.0 ;.0 5.~
Sodium Silicate (Si02/Na2C=2) 5.0 5.0 j.0 Miscellaneous 7.1 7.1 7.1 Admix Zeolite A 5.0 5.0 ~.0 N-Methyl N-l-Deoxyglucityl Cocoamide 4.0 6.4 4.4 C14 l5 Alkyl Sulfate 11.8 C12 18 Alkyl Sulfate 13.1 16.1 C12 18 Alkyl Ethoxy (2) Sulfate 5.0 C14 15 Alkyl Ethoxy (2.25) Sulfate 4.0 Suds Suppressor Flake* 1.0 0.5 Miscellaneous (filler salts, brightener, enzyme, buffer, zeolite or other builder, etc) 17.2 17.2 16.5 SpraY-On C12 ~3 Alkyl Ethoxylate (6.5 mole) 2.0 2.0 2.0 Perfume 0.5 0.5 0 5 Water and Miscellaneous 8.2 9.4 8.4 Totals 100.0 100.0 100.0 *Suds Suppressor Flake contains approximately 5% of a silica/
silicone oil dispersion encapsulated in a flake containing pr;marily PEG (8000 MW), at greater than 8~/o~ and minor optional water soluble ingredients.
The compositions of Examples 4-6 represent condensed granular formulations prepared by slurrying and spray drying the base granule ingredients to a moisture of about 5%, and mixing in the additional w o 92/061~8 PCT/USgJ/0702-dry powdered or granular ingredients. The resulting mixture is 9~9 dedusted by spraying on the liquid ingredients. The product is intended for use at about 1000 ppm concentration, zt ~ash temperatures less than about 30 C.

The following exzmples ~qm~~s~ q --~-u; - ~ -. - J, compositions containing polyhydroxy fatt~ z~ ~ zmldes, ~ yl ethoxylate sulfates, and suds supp.~-ss~~s.
Ingredients 7 ~ ~~
N-Methyl N-1-Deoxyglucityl Cocoamide '. 7 ~' ~ ' 5 . ~ -C14 15 Al~yl Ethoxy (2.25) Sulfate i2.3 C12 1~ Alkyl Ethoxy ~2.5 Sul,-~t~
C12 14 Alkyl Sulfaie 3.1 C12 14 Alkyl Ethoxylate 3.4 ~.;
Dodecyl Trimethyl Ammonium Chloride 0.5 0.2 Dodecenyl Succinate 5 0 Sodium Citrate 3.4 15.0 5.0 TMS/TDS (80/20) * 3.4 C12 14 Fatty Acid 3.0 3 0 Oxydisuccinate 20.0 Ethoxylated Tetraethylene Pentamine 1.5 2.0 Polyacrylate (4500 MW) 1.5 1.5 Silicone 0il (suds suppressor) 0.9 0.9 Miscellaneous (enzymes, brighteners, release agents, stabilizers, etc) 15.3 14.0 14.0 16.3 Water 52.7 51.2 51.2 54.0 100.0 100.0 100.0 100.0 - *TMS/TDS is tartrate monosuccinate/tartrate disuccinate Inqredients _11 12 N-Methyl N-1-Deoxyglucityl Cocozmide 5.5 ~.5 C12 13 Alkyl Ethoxylate (6.5 mole) 2.5 2.5 C14 1~ Alkyl Ethoxylate (2.25) Sulfate 17.0 17.0 WO 92/06158 2 ~ ~ 2 5 ~ 9 PCI/US91/0702/

Oleic Acid 3 0 3,0 Dodecyl Trimethyl Ammonium Chloride 0.2 0.2 Citric Acid 1.0 1.0 ~onoethanolamine 2.5 2.5 Ethoxylated Tetraethylenepentamine 1.5 1.5 ?rcte s~ (3.1Yo actiYe) 0.5 0.4 Amylase (11.5% active) 0.2 Silico,l~ ~il o.s ~iscPllaneous and solventsbalance balance 100.0 100.0 'xamples 7-12 are preferably used at about 2000 ppm, wash wztor ~eight basis, for wash temperatures below about 50-C. These ara pre?arod ~y combining non-aqueous solvents, aqueous surfact2nt pa;4es or solutions, melted f~tty ?cids, aqueous solutions of 1~polycarbcxylate builders and other salts, aqueous ~thoxylat d tetraethylenpentamine, buffering agents, caustic, and the remaining water. The pH is adjusted using either an aqueous citric acid solution or sodium hydroxide solution to about pH 8.5. After pH
adjustment the final ingredients, such as soil release agents, 20enzymes, colorants, and perfume, are added and the mixture stirred until a single phase is achieved.

An alternate method for preparing the polyhydroxy fatty acid amides used herein is as follows. A reaction mixture consisting of 2584.879. fatty acid methyl ester (source: Procter ~ Gamble methyl ester CE1270), 759. N-methyl-D-glucamine (source: Aldrich Chemical Company M4700-0), 1.049. sodium methoxide (source: Aldrich Chemical Company 16,499-2), and 68.519. methyl alcohol is used. The reaction vessel comprises a standard reflux set-up fitted with a drying tube, condenser and stir bar. In this procedure, the N-methyl glucamine is combined with methanol with stirring under argon and heating is begun with good mixing (stir bar; reflux). After 15-20 minutes, when the solution has reached the desired temperature, the ester and sodium methoxide catalyst are added. Samples are taken periodically to monitor the course of the reaction, but it is noted that the solution i; completely clear by 63.5 minutes. It is judged that the reaction is, in fact, nearly complete at that point. The reaction mixture is maintained at reflux for 4 hours. After removal of the w o 92/06158 PCT/U~91/0702 g methanol, the recovered crude product weighs 156.16 grams. After 9 ~ ~ ~ vacuum drying and purification, an overall yield of 106 92 grams purified product is recovered. However, percentage yields are not calculated on this basis, inasmuch as regul2r 3m~".9 ~IrvU~vU~
the course of the reaction makes an overall percentago yiqld ~aluq meaningless. The reaction can be carr1ed e~!t a ~~~ ~
reactant concentrations for periods up to 6 hours to y-q d rredu~ ~
- with extremely small b~-product formation.
The following is not intended to limit thq nvent n ~--r-.n, but is simply to further illustrato addit-,o"a, ai~
technology which may be considered ~y th? Jr-.U.a~
manufacture of a ~ide variety of detergent ca~ .o~ a polyhydroxy ratty acid amides.
It will be readily apPreciated that the DolvhYdrnxv ~ v ~id 1; amides are, by virtue of h2,r amidq '~;~d, ~ ; m~
instability under highly basic or highly acidic c~ndi~;v.c. ;.;."2 some decomposition can be tolerated, it is preferred that these materials not be subjected to pH's above about 11, preferably 10, nor below about 3 for unduly extended periods. Final product pH
(liquids) is typically 7.0-9Ø
During the manufacture of the polyhydroxy fatty acid amides it will typically be necessary to at least partially neutralize the base catalyst used to form the amide bond. While any acid can be used for this purpose, the detergent formulator will recognize that it is a simple and convenient matter to use an acid wnich provides an anion that is otherwise useful and desirable in the finished detergent composition. For example, citric acid can be used for purposes of neutralization and the resulting citrate ion (C2. 1%~ be allowed to remain with a ca. 40% polyhydroxy fatty acid amide slurry and be pumped into the later manufacturing stages of the overall detergent-manufacturing process. The acid forms of materials such as oxydisuccinate, nitrilotriacetate, ethylenediaminetetraacetate, tartrate/succinate, and the like, can be used similarly.
The polyhydroxy fatty acid amibes derived from coconut alkyl fatty acids (predominantly C12-C14) are more soluble than their tallow alkyl (predominantly C16-C1a) counterparts. Accordingly, ~he C12-C~ materials are somewhat easier to formulate jn l quid w o 92/06l58 2 ~ ~ 2 ~ 5 9 Pcr/US9l/0702, compositions, and are more soluble in cool-water laundering baths.
However, the C~6-Cl~ materials are also quite useful, especially under circumstances where warm-to-hot wash water is used. Indeed, the Cl~-C~8 materials may be better detersive surfactants than their C~2-C.~ counterparts. Accordingly, the formulator may wish to balarca aa~e-o,-manufacture vs. performance ~hen selecting a par~icular polyhydroxy fatty acid amide for use in a given -formula~ion.
Ic will also ~e appreciated that the solubility of the ~oivh~dro~y fatty acid amides can be increased by having points of unsa.u,~a~ion and!or chain branching in the fatty acid moiety. Thus, r j~l~ ;UCa as the polyhydroxy fatty acid amides derived rrom ole,c ac,d ar,d iso-stearic acid are more soluble than their n-alkyl C v u il, ~,; .1, ~, .
ewi,e, the solubility of polyhydroxy fatty acid amides prepar~d from disaccharides, trisaccharides, etc., will ordinarily be greater than the solubility of their monosaccharide-derived counterpart materials. This higher solubility can be of particular assistance when formulating liquid compositions. Moreover, the polyhydroxy fatty acid amides wherein the polyhydroxy group is derived from maltose appear to function especially well as detergents when used in combination with conventional alkylbenzene sulfonate ("LASn) surfactants. While not intending to be limited by theory, it appears that the combination of LAS with the polyhydroxy fatty acid amides derived from the higher saccharides such as maltose causes a substantial and unexpected lowering of interfacial tension in aqueous media, thereb:~ enhancing net detergency performance. (The manufacture of a polyhydroxy fatty acid amide derived from maltose is described hereinafter.) The polyhydroxy fatty acid amides can be manufactured not only from the purified sugars, but also from hydrolyzed starches, e.g., corn starch, potato starch, or any other convenient plant-derived starch which contains the mono-, di-, etc. saccharide desired by the formulator. This is of particular importance from the economic standpoint. Thus, "high glucose" corn syrup, "high maltose" corn syrup, etc. can conveniently and economically be used.
~e-lignified, hydrolyzed cellulose pulp can also provide a raw material source for the polyhydroxy fatty acid amides.

W O 92/~6158 PCT/US91/0702-9~ 3 As noted above, polyhydroxy fatty acid amides derived from the ~ ~ higher saccharides, such as maltose, lactose, etc., are more soluble - than their glucose counterparts. Moreover, it appears that the more soluble polyhydroxy fatty ac;d amides can help solubilize ~neir less soluble counterparts, to varying degrees. Accordingly. ~,e formulator may elect to use a raw matP,ial comprlslng a , î ~ ~J;-corn syrup, for example, but to select a syrup which con-tains a modicum of maltose (e.g., 1% or more). ~he resulting miv-cure ~,r polyhydroxy fatty acids will, in general, exhibit more pra,er-e~i solubility properties over a broader range of em~ara'ures n~
concentrations than would a "pure' glucose-deriv2d polyn~drvx~ ~~a~
acid amide. Thus, in addition to any economic advanca~es ~~o-sugar mixtures rather than pure sugar reactants, the po fatty acid amidos p,ep2rod frcm mixod suca s c~n orLs~
substantial advantages with r~sp~ct ~o p~r-forma,lca an~ aaac-o,-formulation. In some instances, however, some loss of srease removal performance (dishwashing) may be noted at fatty acid malt-amide levels above about 25% and some loss in sudsing above about 33% (said percentages being the percentage of maltamide-der;ved 20 polyhydroxy fatty acid amide vs. glucose-derived polyhydroxy fatty acid amide in the mixture). This can vary somewhat, depending on the chain length of the fatty acid moiety. Typically, then, the formulator electing to use such mixtures may find it advantageous to select polyhydroxy fatty acid amide mixtures which contain ratios of 2~ monosaccharides (e.g., glucose) to di- and higher saccharides (e.g., maltose) from about 4:1 to about 99:1.
The manufacture of preferred, uncyclized polyhydroxy fatty acid amides from fatty esters and N-alkyl polyols can be carried out in alcohol solvents at temperatures from about 30-C-90-C, preferably about 50-C-80-C. It has now been determined that it may be conven-ient for the formulator of, for example, liquid detergents to conduct such processes in 1,2-propylene glycol solvent, since the glycol solvent need not be completely removed from the reaction product prior to use in the finished detergent formulation. Like-wise, the formulator of, for example, solid, typically granular,detergent compositions may find it convenient to run the process at 30~C-90~C in solvents which comprise ethoxylated alcohols, such as the ethoxylated (E0 3-8) C~2-C14 alcohols, such as those available ~925~
WO 92/06158 PCI~/US91/0702, as NEODOL 23 E06.5 (Shell). When such ethoxylates are used, it is preferred that they not contain substantial amounts of ùnethoxylated alcohol and, most preferably, not contain substantial amounts of mono-e+hovyl~tod alcohol. (nT" designation.) '~hile methods for making polyhydroxy fatty acid amides per se form no ~art of the invention herein, the formulator can also note other syncneses of polyhydroxy fatty acid amides as described herQina ~r Typically, the industrial scale reaction sequence for preparing ~ ?~ ~rred ~cyclic polyhydroxy fatty acid amides will comprise:
~eo ~ - ?,eo2ring ~he N-~lkyl polyhydroxy amine derivative from the desir-~d sugar or sugar mixture by formation of an adduct of the ~'i~aî;iJi i~imiil2 and Lhe sug3r, followed by reaction with hydrogen in the Dresence of a catalyst; followed by SteD 2 - reacting the 1- afer~-s ;~ ,nl h~!d Ov~ amino with, oreferably, a fatty ester to form an a",.de bonJ. '~hile a variety of N-alkyl polyhydroxy amines useful in Step 2 of the reaction sequence can be prepared by various art-disclosed processes, the following process is convenient and makes use of economical sugar syrup as the raw material. It is to be understood that, for best results when using such syrup raw materials, the manufacturer should select syrups that are quite light in color or, preferably, nearly colorless ("water-whiten).
Preparation of N-Alkyl Polyhydroxy Amine From Plant-Derived Sugar Syrup I. ~dduct Formation - The following is a standard process in which about 420 9 of about 55% glucose solution (corn syrup - about 231 9 glucose - about 1.28 moles) having a Gardner Color of less than 1 is reacted with about 119 9 of about 50~X aqueous methylamine (5g.5 g of methylamine - 1.92 moles) solution. The methylamine (MMA) solution is purged and shielded with N2 and cooled to about 10-C, or less. The corn syrup is purged and shielded with N2 at a temperature of about 10--20-C. The corn syrup is added slowly to the MMA solution at the indicated reaction temperature as shown.
The Gardner Color is measured at the indicated approximate times in minutes.

~9 TAB~E I
T;me ;n M;nutes: 10 30 60 120 180 240 React;on Temp. ~C Gardner Color (ADProximate) 0 1 1 1 ~ 1 1 1 1 ~ 2 ~ ;

As can be seen from the abo~e data, the Gardne. Color .~o. '.h~
adduct is much worse as the temperature is raised ~bove abcut 30 C
and at about 50 C, the time that the adduct nas a uardne. ;o.i., belo~.Y 7 is only about 30 minutes. For longer react1On, ~.~/,r holding times, the temperature should be less than about 20 C. Th~
Gardner Color should be less than about 7, and p ererably less ;~an about 4 for good color glucamine.
'.~hen one usDs lo.Yer tom?Qrat res ~or formin~ 'ha d~
time to reach substantia1 equilibrium concentration of the adduct is shortened by the use of higher ratios of amine to sugar. '~ith tho 1.5:1 mole ratio of amine to sugar noted, equilibrium is reached in about two hours at a reaction temperature of about 30-C. At a 1.2:1 mole ratio, under the same conditions, the time is at least about three hours. For good color, the combination of amine:sugar ratio;
reaction temperature; and reaction time is selected to achieve substantially equilibrium conversion, e.g., more than about 90YO, preferably more than about 95%, even more preferably more than about 99%, based upon the sugar, and a color that is less than about 7, preferably less than about 4, more preferably less than about 1, for the adduct.
Using the above process at a reaction temperature of less than about 20-C and corn syrups with different Cardner Colors as 30 indicated, the MMA adduct color (after substantial equilibrium is reached in at least about two hours) is as indicated.

Gardner Color (APproximate) Corn syrup 1 1 1 1+ 0 0 0+
Adduct 3 4/5 7/8 7/8 1 2 As can be seen from the above, the starting sugar material must be very near colorless in order to consistently have adduct that is acceptable. When the sugar has a Gardner Color of about 1, the W o 92/06158 2 a 9 2 ~ 5 9 PCT/US91/0702 adduct ;s sometimes acceptable and sometimes not acceptable. When the Gardner Color is above 1 the resulting adduct is unacceptable.
The better the initial color of the sugar, the better is the color of the adduc~.
II. Hvdrooen Reaction - Adduct from the above having a Gardner Cclor - I ~ les; s hydrogenated according to the following procedur~.
~oou- ;35 9 or adduct in water and about 23.1 9 of United Catalys~ G~SB Ni catalyst are added to a one liter autoclave and purg~d wo i"~s ~ith 200 osig H2 at about 20-C. The H2 pressure is rais d ~ u; ilO0 psi and ~he temperature is raised to about ~o~o ,;~ ;r ss~r ls Lh2n raised to about 1600 psig and the temp~rlt -e s held at ~bout 50-55~C for about three hours. The ?r-d"a'~ '.~' a~~ut 95~,' h~dr~genated at this point. The temporaturo is i~ ~n2n ~ ~ is~ OUL ~s~c for ~bouL 3G minutes and the reaction mixture is decanted and the catalyst is filtered out. The product, after removal of water and MMA by evaporation, is about 95% N-methyl glucamine, a white powder.
The above procedure is repeated with about 23.l 9 of Raney Ni catalyst w1th the following changes. The catalyst is washed three times and the reactor, with the catalyst in the reactor, is purged twice with 200 psig H2 and the reactor is pressurized with H2 at 1600 psig for two hours, the pressure is released at one hour and the reactor is repressurized to 1600 psig. The adduct is then pumped into the reactor which is at 200 psig and 20-C, and the reactor is purged with 200 psig H2, etc., as above.
The resulting product in each case is greater than about 95%
N-methyl glucamine; has less than about lO ppm Ni based upon the glucamine; and has a solution color of less than about Gardner 2.
The crude N-methyl glucamine is color stable to about 140~C for a short exposure time.
It is important to have good adduct that has low sugar content (less than about 5%, preferably less than about l%) and a good color (less than about 7, preferably less than about 4 Gardner, more preferably less than about 1).
In anoiher reaction, adduct is prepared starting with about 159 g ot about 50% methylamine in wate~, which is purged and shielded with N2 at about 10-20~C. About 330 9 of about 70% corn syrup (near water-white) is degassed with N2 at about 50-C and is added slowly WO 92/06158 PCI/US91/0702, ~9~5~ to the methylamine solution at a temperature of less than about 20-C. The solution is mixed for about 30 minutes to give about 95%
adduct that is a very light yellow solution.
About 190 g of adduct in water and about 9 9 of United Catalyst G49B Ni catalyst are added to a 200 ml autoclave and purged three timi~s with '~2 at about 20-C. The ~2 pressur2 is raised ~o abo;~ 2C;, psi and the temperature is raised to about 50-C. The pressure is raised to 250 psi and the temperature is held at about 50-~'C Tor about three hours. The product, which is about 95~0 hydrogenated at this point, is then raised to a temperature of about 85 C ror ~bout 30 minuteâ and the product, after removal Oc water and evaporation, is about 95% N-methyl glucamine, a white ?owder.
It is also important to minimize cont~ct betleen edd ct a"d ca~alys~ wh2n the H~ pressure iâ 12ss than abol;t 10,v p 9 -'o mini~i2e Ni content in t,le glucamine. The nickel con;en~ in che N-methyl glucamine in this reaction is about 100 ppm as compared to the less than 10 ppm in the previous reaction.
The following reactions with H2 are run for direct comparison of reaction temperature effects.
A 200 ml autoclave reactor is used following typical procedures similar to those set forth above to make adduct and to run the hydrogen reaction at various temperatures.
Adduct for use in making glucamine is prepared by combining about 420 9 of about 55% glucose (corn syrup) solution (231 9 glucose; 1.28 moles) (the solution is made using 99DE corn syrup from CarGill, the solution having a color less than Gardner 1) and about 119 9 of 50% methylamine (59.5 9 MMA; 1.92 moles) ~from Air Products).
The reaction procedure is as follows:
1. Add about 119 9 of the 50% methylamine solution to a N2 purged reactor, shield with N2 and cool down to less than about 10-C.
2. Degas and/or purge the SS% corn syrup solution at 10-20-C with N2 to remove oxygen in the solution.
3. Slowly add the corn syrup solution to the methylamine solution and keep the temperature less than about 20-C.
4. Once all corn syrup solution is added in, agitate for about 1-2 nours.

W O 92/061s8 2 ~ 3 PCT/US91/07027 The adduct ;s used for the hydrogen reaction right after making, or is stored at low temperature to prevent further d2sradat10n.
Th~ camine adduct hydrogen reactions are as follows:
i 1. ~dd ~oou~ 134 9 adduct (color less than about Gardner 1) and 350Ut 5.3 9 G4gB Ni to a 200 ml autoclave.
2. ~Ur5~ 2 r'acLion mix Wi Lh about 2C0 psi H2 twice at about 2~-30~~.
3. r_s~r~ h n2 t~ abou~ ~00 psi and raise the temperature to -~'CUt 5noC.
;;~ ~,~;~e '~ t 5~C asi, ,~act for about 3 hours. Keep ",!~J,~ u, ~ u~ 5ù-55'~. Take Sample i.
, r ~re a, i~o~t ~5~C .'or about 3û minutes.
~ can~ and ~ er out the ,~i catalyst. Take Sample 2.
~.~n~ ns -~r const~nt tem~erature reactions:
1. ;'~d .~ t 134 g adduct and about 5.8 9 G49B Ni to a 200 ml autoclave.
2. Purge with about 2ûO psi H2 twice at low temperature.
3. Pressure with H2 to about 400 psi and raise temperature to about 50-C.
4. Raise pressure to about 500 psi, react for about 3.5 hours.
Keep temperature at indicated temperature.
5. Decant and filter out the Ni catalyst. Sample 3 is for about 50-55-C; Sample 4 is for about 75-C; and Sample 5 is for about ~5~C. (The reaction time for about 85-C is about 45 minutes.) All runs give similar purity of N-methyl glucamine (about 94~h);
the Gardner Colors of the runs are similar right after reaction, but only the two-stage heat treatment gives good color stability; and the 85-0 run gi~es margin21 color immêdiately after reaction.

The preparation of the tallow ~hardened) fatty acid amide of N-methyl maltamine for use in detergent compositions according to this inYention is as follows.
SteP 1 - Reactants: Maltose monohydrate (Aldrich, lot 01318KW); methylamine (40 wt% in water) (Aldrich, lot 03325TM);
Raney nic~el, 50% slurry (UAD 52-73D, Aldrich, lot 12921LW).
The reactants are added to 91 2SS liner (250 9 maltose, 428 9 me'hylamtnc ,olution, 1ûO g catalys+ slurry - 50 9 Raney Ni) and ~9~5~ placed ;n 3 L rocking autoclave, which is purged with nitrogen (3X500 psig) and hydrogen (2XS00 psig) and rocked under H2 at room temperature over a weekend at temperatures ranging from 28-C to 50-C. The crude reaction m;xture is vacuum filtered 2X throu~h a S glass microfiber filter with a silica gel plug. The filtrate is concentrated to a viscous material. The final traces of water are azecroped of,~ b~ dissolving the material in methanol and then removing the methanol/water on a rotary evaporator. Final dryina is done nde, .,ish vacuum. The crude product is dissolved in refluxing methanol, filtered, cooled to recrystallize, filt~,ed and the fil'er c~~ke is dried under vacuum at 35~C. This is cut ~ he filtla e is colla n-~na-~2d u,m~il a pnecipi-Late begins to form and is stored in a r -m~~cor4~or avornight. The solid is ,iltcrêd and driod under vacu m. This is cut ~2. The filtrate is again concentrated to ha7f 1~ its Yolume and a recrystallization is perform d. Yery littl3 precipitate forms. A small quantity of ethanol is added and the solution is left in the freezer over a weekend. The solid material is f;ltered and dried under vacuum. The combined solids comprise N-methyl maltamine which is used in Step 2 of the overall synthesis.
SteD 2 - Reactants: N-methyl maltamine (from Step 1); hardened tallow methyl esters; sodium methoxide (25% in methanol); absolute methanol (solvent); mole ratio 1:1 amine:ester; initial catalyst level 10 mole % (w/r maltamine), raised to 20 mole %; solvent level 50% (wt.).
In a sealed bottle, 20.36 9 of the tallow methyl ester is heated to its melting point (water bath) and loaded into a 250 ml 3-neck round-bottom flask with mechanical stirring. The flask is heated to ca. 70 C to prevent the ester from solidifying.
Separately, 25.0 9 of N-methyl maltamine is combined with 45.36 g of methanol, and the resulting slurry is added to the tallow ester with good mixing. 1.~1 9 of 25% sodium methoxide in methanol is added.
After four hours the reaction mixture has not clarified, so an additional 10 mole % of catalyst (to a total of 20 mole %) is added and the reaction is allowed to continue overnight (ca. 68-C) after 3~ which time the mixture is clear. The reaction flask is then modified for distillation. The temperature is increased to 110~C.
Distillation at atmospheric pressure is continued for 60 minutes.
Hi~h ~Jacuum distillation is then begun and continued for 14 minutes, at which time the product is very thick. The product is allowed to w o 92/06~58 2 ~ ~ 2 ~ 5 ~ PCT/USgl/07027 remain in the reaction flask at 110-C (external temperature) for 60 minutes. The product is scraped from the flask and triturated in ethyl ether over a weekend. Ether is removed on a rotary evaporator and the product is stored in an oven overnight, and ground to a powder. Any remaining ~J-methyl maltamine is removed from the produc ~in~ . ;-,. A ;llica ~el , urry in 100% methanol is loaded into a ;unnel and washed several times with 100% methanol. A
concenl,~ced samDIe or ,~-h,~ proauc~ (20 y in 100 ml of 100~h methanol) is loaded onto the silica gel and elu-ted several times using vacuum and seve~~l nethanol ~ashes. ihe collec ed eluant is eYaporated to dryne~s (f~tary eva~o.a~ ,n/ remai,ling ~allow ester is removed by ~ri~ n ~ /or~ ed ~v ,~iltr~tion.
~he ~-~ ~r ca~ .~ o'~-n d, 12d o~/e,ni~ht. The product is the in an al ~ci-ila~c ~~-OGe, j~=p i Ol~ ~n2 ;or~50ing reaction sequence can be conducted using commercial corn s~rup comprising glucose or mixtures of glucose and, t~?ically, 5%, or higher, maltose. The resulting polyhydroxy fatty acid amides and mixtures can be used in any of the detergent compositions herein.
In still another mode, Step 2 of the foregoing reaction sequence can be carried out in 1,2-propylene glycol or NEODOL. At the discretion of the formulator, the propylene glycol or NEODOL
need not be removed from the reaction product prior to its use to formulate detergent compositions. Again, according to the desires of the formulator, the methoxide catalyst can be neutralized by citric acid to provide sodium citrate, which can remain in the polyhydroxy fatty acid amide.
Depending on the desires of the formulator, the compositions herein can optionally contain more or less of various suds control agents. Typically, for dishwashing high sudsing is desirable so no suds control agent will be used. For fabric laundering in top-loading washing machines some control of suds may be desirable, and for front-loaders some considerable degree of suds control may be preferred. A wide variety of suds control agents are known in the art and can be routinely selected for use herein. Indeed, the selection of suds control agent, or mixtures of suds control agents, for any specific detergent composition will depend not only on the presence and amount of polyhydroxy fatty acid amide used therein, W O 92/06~8 PCT/US91/~7027 but also on the other surfactants present in the formulation.
~q ~9 However, it appears that, for use with polyhydroxy fatty acid amides, silicone-based suds control agents of various types are more er,-icienu (i.~., lo~er levels can be used) than various other types of suds control as~nts. The silicone suds control agents availa~le ac ~A'3Jm~ 'Cc~.~ Corn.~g) ~re particularly useful.
ThC ,o,mulator o, .abric laundering compositions which can ad~all~a(i~oui1u -~n~ai,l soil reiease agent has a wide variety of '<no.in ma~rials to choose from (see, for example, U.S. Patents C~ ''J8~; ~,238,~31; 4,702,857; 4,721,580 and l,_ ,,_~;). '~i~.cnal ,oil rel2ase materials useful herein include ~ r~i,oi a ~ "--,lc s~eri,ication product of a reaction mixture com?risin~l ~ ouro~ ~' C~-C, al~o~y-t~rminated polyethoxy units !~,n,,~ ~u,r~ru,ru~l~Q,U~, ~ sol.rc2 Or ~2reDhthalovl ~inits (~.9., .; i ..._' .,, . _.'_;'. ;_ . i'_~; 2 ~OU, C_ of pO ly(oxyeLny7ene~oxy units (e.g., polye;,hyiene glycol 1~00); a source of oxyiso-propyleneoxy units (e.g., 1,2-propylene glycol); and a source of oxyethyleneoxy units (e.g., ethylene glycol) espec;ally where;n the mole ratio of oxyethyleneoxy units:oxyiso-propyleneoxy units is at least about 0.5:1. Such nonionic soil release ag nts are of the general formula O O O O
u ,= \ " 11 /=~ 11 RlO-(CH2CH20)x C- ~ CO-CH-CH2C - C ~ CO(cH2cH20)y R2 m n ~, O
~ ~ r - O (CH2CH2O)x-Rl wherein ~r;s lower (e.g., Cl-C~) alkyl, especially methyl; x and y are each integers from about 6 to about 100; m is an integer of from about 0.7~ LO about 30; n is an integer from about 0.25 to about 20;
and R2 is a mixture of both H and CH3 to provide a mole ratio of oxyethyleneoxy:oxyisopropyleneoxy of at least about 0.5:1.
Another preferred type of soil release agent useful herein is of the general anionic type described in U.S. Patent 4,877,896, but with the condition that such agents be substant;ally free of monomers of the HOROH type wherein R is propylene or h;gher alkyl.
Thus, the soil release agents of U.S. Patent 4,877,896 can comprise, for example, ~ne re2ction product or dimethyl terephthalate, etnylene glycol, ~,2-~ropylene gi~col and 3-sodiosulfobenzoic acid, whereas these additional soil release agents can comprise, for w o 92/06158 2 ~ 9 2 ~ ~ 3 PCT/US91/0702, example, the reaction product of dimethyl terephthalate, ethylene glycol, 5-sodiosulfoisophthalate and 3-sodiosulfobenzoic acid. Such agents are preferr~d for use in ~.-a~ular laundry detergents.
Tho formulator ma~ ~lso detarmino that it is advantageous to include a non-perborate bleach, especially in heavy-duty granular laundry detergents. A ~/arietv oF ~eroxy~en bleaches are available, commercially, and can be used herein, out, o; these, percarbonate is conveniont and eronoml~3l. Thus) th~ c~mpo~i'.cns herein can contain a solid percarbonate ~leacn, normally in the form of the sodium sal~, incorpor~ad ' a 1''!~' of ~.~om ~ ish~, more preforabl~ rrom ~ o i~,i b~ Sh ~nd ~o~ p.~rer3bly ,~rom C%
to 15% by ~,Yeignt or ~he com30si~ion.
Sodium percarbo~ac .~ a, ~d ~ ~, .o,,-~ounu na~ing 3 ,ormula corresponding to 2Na~C0~. 3~0?. and is aYailable commercially as a cr~stalli~ so'id. ~3~ c~r~ bl? ?~ r''l 1~~01u~~a a low level o~ a heav~ .,etal se1uest~~i"~ ,u.h aa 'Ci~ hydroxyethyl-idene 1,1-diphosphonic acid (HEDP) or an amino-phosphonate, that is incorporated during the manufacturing process. For use herein, the percarbonate can be incorporated into detergent compositions without additional protection, but preferred embodiments of the invention utilize a stable form of the material (FMC). Although a variety of coatings can be used, the most economical is sodium silicate of SiO2:Na20 ratio from 1.6:1 to 2.8:1, preferably 2.0:1, applied as an aqueous solution and dried to give a level of from 2% to 10% (norm-ally from 3% to 5%), of silicate solids by weisht of the percarbon-ate. Magnesium silicate can also be used and a chelant such as one of those mentioned above can also be included in the coating.
The particle size range of the crystalline percarbonate is from 350 micrometers to 450 micrometers with a mean of approximately 400 micrometers. When coated, the crystals have a size in the range from 400 to 600 micrometers.
While heavy metals present in the sodium carbonate used to manufacture the percarbonate can be controlled by the inclusion of sequestrants in the reaction mixture, the percarbonate sti~l requires protection from heavy metals present as impurities in other ingredients of the product. It has boon found that the total level of iron, copper and manganese ions in th~ produrt should not exceed WO 92/06158 PCr/US~1/07027 ~9 25 ppm and preferably should be less than 20 ppm in order to avoid an unacceptably adverse effect on percarbonate stability.
A modern, condensed laundry detergent granule is as follows Inar2di~nt Wt %
C~ lkyl alcohol sulfonic acid 13 C. ~ a~kyi polyetnoxy (2.25) sulfonic acid 5.60 C 1 2 -1, ' ~ a~ho~ (6.5) 1.45 C12 1; ,atty acid N-methyl glucamide 2.50 10 S~di~ r~aos,lica~e (a~ h~drat4d Zeolite A) 25.2 ~~~ys~:alli~ re~ icata cuilder; 23.3 C i tri c ac i (~ 1 0 . O
~odl~ al~viia~e To get ~ash pH = 9.90 Sodium Dolyacrylate (m.~. 2000-4500) 3.2 ;~ ? ~n ~?.~?tlr ~d Sav",q~- 2 6-Nonanoylamino-6-oxo-peroxycaproic acid 7.40 Sodium perborate monohydrate 2.10 Nonanoyl oxybenzene sulfonic acid 5.00 20 Brightener 0.10 1Layered silicate builders are known in the art. Preferred are the layered sodium silicates. See, for example, the layered sodium silicate builders of U.S. Patent 4,664,859, issued May 12, 1987 to H. P. Rieck, incorporated herein by reference. A suitable layered silicate builder is available as SKS-6 from Hoechst.
2Available from Novo Nordisk A/S, Copenhagen.
Highly preferred granules of the foregoing types are those which comprise from about 0.0001% to about 2% by weight of active enzyme and at least about 1% by weight of said polyhydroxy fatty acid amide, and, most preferably, wherein the anionic surfactant is not an alkylbenzene sulfonate surfactant.
The following relates to the preparation of a preferred liquid heavy duty laundry detergent according to this invention. It will be appreciated 'chat the scabili'cy of enzymes in such compositions is considerably less than in granular detergents. However, by using typical enzyma stabilizers such as formate and boric acid, lipase and rsllulase enzymes can be protect d from degradation by protease enzymes. ~owever, lipase scability is still relatively poor in the w o 92/06158 2 ~ 9 ~CT/US91/0702-presence of alkylbenzene sulfonate (~LAS~) surfactants. Apparently, LAS partially denatures lipase, and, further, it seems that denatured l;pase is more vulnerabla to att3c'~ by ?rot2ase.
In view of the foregoing considerations, ~hich, as notad, can be particularly troublesome in liquid compositions, it is a challenge to provide liquid detergenc compositions containing lipase, protease and C211UlâSa an~;mmi~S~ ~Ogc~ilcr. ~ ls ?ar~icu-larly challenging to proYide such tert.i~r~ ?n7vm~ s~st?ms in stable liquid detergents together ~ii'n an el~-Pc,i~ b~anu ~r decersi~e surfactants. Additionall~ it s di-r,c,lt -~i "~:3rp~r;~~
peroxidase and/or amylase enzyms.~ ab'~ n C~ O~
It 'nas now been decermin~d ~ild- 'la~~iCU~ i"i;~~eS 0; 1 i?ases, proteases, C21 1 ul âSeS ~ al~lyl aS2~
stable in the presence of certain non-al~ylDenz~ne sulTonate surfactant systems, such that~ ~rf?r~i~ "~! c~ r~ ?~?~
liquid detergents can be tormulatel. T"de d~ ',h2 fOI-IIulâLIvn of stable, liquid, enzyme-containing detergent compositions constitutes a highly advantageous and preferred embodiment afforded by the technology of the present invention.
In particular, prior art liquid detergent compositions typically contain LAS or mixtures of LAS with surfactants of the RO(A)mS03M type (~AES~) noted hereinabove, i.e., LAS/AES mixtures.
By contrast, the liquid detergents herein preferably comprise binary mixtures of the AES and polyhydroxy fatty acid amides of the type disclosed herein. While minimal amounts of LAS can be present, it will be appreciated that the stab;lity of the enzymes will be lessened thereby. Accordingly, it ;s preferred that the liquid compositions be substantially free (i.e., contain less than about 10%, preferably less than about 57O~ mare preferably less than about lXo~ most preferably 0~JO) of LAS.
The present invention provides a liquid detergent composition comprising:
(a) from about 1% to about 50,0, pr~fPrabl~ from about ~% to about 40%~ of anionic surfactant;
(b) from about 0.0001% to about 2% of active detersive enzyme;
(c) an enzyme performance-enhGncing amount (pref2rably from about 0.5% to about 12~o) Of a pol~h~drox~ fatty acid amide material of the formula ~9~ 0 R' wherein R1 is H" C1-C~ hydrocarbyl, 2-hydroxy ethyl, ~ ,~r,;~ p~~5Jjl~ v;~ 2 mi~ture Lh2reo~, 22 is Cs-C3I
,lydrocarbyl~ and Z 1s a polyhydroxylhydrocarbyl having a r ~ rA,r~ Sl~.in '?ith 3~ l~ast ~ hydroxyls ~irect1U connPrrcd to said chain, or an alkoxylated and whr-rPin he c mposi ion jc s~bstanti~ free of al~ylbenzene sulfcna~:a ~ila ~ ;o -- - ~ ;ui~,'ac~ar,~ hersin pre;erably compri 5?5 (1~
,~v~ 3 ;'~
wherein ~ is an unsubstit~ d c A-O~ yl or hydroxyal~yl (C;~ r \ ~ . .~ .n ~ i 'r .,' ;,v~ m i ~n integsr great r ~h n . _ia~ h~dnv9 n or a cation. ~referably, R is an unsubstituted CI2-Cl2 alkyl group, A is an e-thoxy unit, m is from about 0.~ to about 6, and M is a cation. The cation is preferably a metal cation (e.g., sodium-preferred, potassium, lithium, calcium, magnesium, etc.) or an ammonium or substituted ammonium cation.
It is preferred that the ratio of the above surfactant (nAES~) to the polyhydroxy fatty acid amide herein be from about 1:2 to about 8:1, preferably about I:I to about 5:1, most preferably about 1:1 to about 4:1.
The liquid compositions herein may alternatively comprise polyhydroxy fatty acid amide, AES, and from about 0.5% to about 5%
of the condensation product of C8-C22 (preferably C1o-C20) linear alcohol with botweon about 1 and ~bout 25, preferably between about 2 and about 18, moles of etnylene oxide per mole of alcohol.
As described above, the liquid compositions herein preferably have a pH in a 10% solution in water at 20-C of from about 6.5 to about 11.0, preferably from about 7.0 to about 8.5.
The instant compositions pre era,,ly 'urther comprise from about 0.1% ;co aoout 50~/O of detergency Duilder. These compositions preferably comprise from about O.I~~O to about 20% of citric acid, or wzter-soluble salt th2reo r, and rom, 2bou ~ 0 . 1% to about 20% o; a water-soluble ~uccinats t~rt afv~ spcciall~ the sodium salt thereof, and mi~cures chereof, or from about 0.1% to about 20% by ~ v ~
W O 92/06158 PCT/US91/0702, weight of oxydisuccinate or mixtures thereof with the aforesaid builders. 0.1%-50% alkenyl succinate can also be used.
The preferred liquid compositions herein comprise from about 0.0001% to about 2%, preferably about 0.0001% to about 1", most preferably about 0.001% to about 0.5%, on an acti~/Q b2si~, 3f detersive enzyme. These enzym3s are pre-,~er?.bl~ .a e ~-d group consisting of protease (preferred), lipase (preterrea), amylase, cellulase, peroxidase, and mixtures ther30l-. Pref-rr?~ ar3 compositions with two or more classes of enzymes, most p.3feraoly where one is a protease.
While various descriptions of detergent pro e2ses. -ell~lases.
etc., are available in the literatur3, d3ro~0nr ~ ?~
somewhat less familiar. Accordingly, LO a sl;t ,h~ ~a~ r, lipases of interest include Amcno A~G and 3;ci'li ~~
1~ Solvay enzymes). Also, see the lipases described in E? ~ O 35Y ~
published November 28, 1990, EP A 0 218 272, published April 15, 1987 and PCT/DK 88/00177, published May 18, 1989, all incorporated herein by reference.
Suitable fungal lipases include those producible by Humico7a 7anuginos~ and Thermomyces 7anuginosus. Most preferred is the lipase obtained by cloning the gene from Humico7a 7anuginos2 and expressing the gene in Aspergi77us oryzae, as described in European Patent Application 0 258 068, incorporated herein by reference, commercially available under the trade name LIPOLASE.
From about 2 to about 20,000, preferably about 10 to about 6,000, lipase units of lipase per gram (LU/g) of product can be used in these compositions. A lipase unit is that amount of lipase which produces 1 ~mol of titratable butyric acid per minute in a pH stat, where p~ is 7.0, temperature is 30-C, and substrate is an emulsion tributyrin and gum arabic, in the presence of Ca++ and NaCl in phosphate buffer.
The following Example illustrates a preferred heavy duty liquid detergent composition comprising:
(a) an enzyme selected from proteases, cellulases and lipases, or, preferably, a mixture thereof, typically comprising from about 0.01% to about 2% by weight of the total composition, although the amounts used can be adjusted according to the desires of the formulator to provide an ~9~9 "effectiven amount (i.e , soil-removing amount) of said enzyme or enzyme mixture;
(b) a polyhydroxy fatty acid amino .urfactant of the type disclosed herein, typically ccmsrising at least about 2%
by weight of the composi,ion, more -'y3ically from about 3%
to about 15%, preror~ frsm -~5~ut 1~// to ~oout 1.%;
(c) a surfactant ~,~ ,"~ ;~0~;i)m~r3" ~ , ai uiicluicd herein, preferably RO(CH~CH~0 k,S0,~ heroin ~ is C.~-C.; ~2'JC.) and m is 2-3 (av~.), n~ci~ iJ or ~ /a~er-soluole salt-formins catiQr., ~.3.~ !!al~ s~i~ su~~ ,t ~ p;cally comprising f,om ~ s ~ 5 '~ h-composi L ion;
(d) optional1y, a ;~n ~ lC';?~ U'~ .'' ' '.~ ,;,,_, __ ;sc;~ ed herein, ?rr,era31y .i,~rcin i~ ls CI2-Cl, (avg.), said surfactant profera~ ~.om~~isin~ ~nr~m ~o~.~t 1,~ ~0 ~:hout 10% by ~,~eight of th~ oom?osit;ons;
(e) a liquid carrier, especially ~ater or water-alcohol mixtures;
(f) optionally, but most preferably, effective amounts of enzyme stabilizers, typically about 1% to about 10%, by weight of the composition;
(g) optionally, but preferably, water-soluble bu;lders, especially polycarboxylate builders, typically at about 4%
to about 25% by weight of the co..,position;
(h) optionally, the Yarious detersiYe adjunrts, brighteners, etc., noted hereinabove, typically (if used) at about 1%
to about 10% by weight of the composition; and (i) the composition is substantially free from LAS.
EXAMPLE lo 30 Inqred;ents W't.%
C14-15 alkyl polyethoxylate (2.25) sulfonic acid 21.00 C12-14 fatty acid N-methyl glucamide~ 7.00 Sodium tartrate mono- and di-succinate (80:20 mix) 4.00 Citric acid 3.8C
C12-14 fatty acid 3 oo Tetraèthylene pentaamine ethoxyl 3 t3 ( 1 ~ -18) I.50 Ethoxylated copolymer of polyethylene 0.20 - polypropylene terephthalate polysu fonic ~cid W O 92/06158 2 0 9 2 5 5 9 PC~r/US91/07027 Protease B (349/l)2 0.68 Lipase (100KLU/g)3 0.47 Cellulase (5000 cevu/g)~ 0.14 Brightener 365 0.1~
Ethanol 5.20 Monoethanolamine 2.00 Sodium formate 0.32 1,2 propane diol 8 ~o Sodium hydroxide 3.1u Silicone suds suppressor o.n,37s Boric acid ~ G
~ater/misc. Balance ;o i~u ~Prepared as disclosed above.
2~ otease B is a modified bacterial serine protease described in rurc~ean P~tent A?plication Serial No. 87 303761 '11ed ~n~
1987, particularly pages 17, 24 and 98.
3Lipase used herein is the lipase obtained by cloning the gene from Humico7a 7anuginosa and expressing the gene in Aspergi7~us oryzae, as described in European Patent Application 0 258 068, commercially available under the trade name LIPOLASE (ex Novo Nordisk A/S, Copenhagen Denmark).
~Cellulase used herein is sold under the trademark CAREZYME
(Novo Nordisk, A/S, Copenhagen Denmark).
5Brightener 36 is commercially available as TINOPA~ TAS 36.
The brightener is added to the composition as a separate7y prepared pre~mix of brightener (4.5~), monoethanolamine (60%) and water (35.5%).

The following Examples illustrate light duty liquid detergent compositions which are especially adapted for dishwashing and other hard surface cleaning operations. In the Examples A-D, the surfactants comprise various alkyl ethoxy sulfate surfactants which, using standard terminology, are abbreviated to indicate their average degree of ethoxylation; thus C,2 13EO(0.8) sulfate indicates a sulfated mixed C12-C13 alcohol fraction having an average degree of ethoxylation of 0.8. These anionic ethoxy sulfates are preferably used in their Na+ or NH~+ salt form. The C12 ~3 amine oxide is a mixed C12 13 (average) dimethyl amine oxide. The C12 ,~

W O 92/06~58 PCT/US91/070~7 AP betaine is Cl2/l4H2s/29CONH(CH2)3N+(CH3)2CH2C02H~ The Cl2 l~ AP
sultaine ;s Cl2/,~H2s/29CONH(CH2)3N+(CH3)2CH2CH(OH)CH2S03H~ The ~9~ C12-14 DM betaine is Cl2/l~H2s/29N~(CHl)2C:~2C02H~ ~ne 3thcx~1ated nonionic surfactant designated Cg ~E0(8) refers to C~-C.. alconols ethoxylated with an average or 8 molPs o; ~nyl-ne o~ide. ~;~e 02~-and Mg++ cations are conveniently in-trodue d In~o ~ile Co.,l~;i ior,s as CaC12 and ~gC12. T~e Dalance o ne co.l~c ~ r~ -''~ "i' 'a~
and citrate/propylene glycol present in the gluc3mide surl~act~.~t (1-5%) and I-3% cumene sul~cna'e ~r ~Jlc-.- su lo.~i ;,2 n ;~drv. AVp_.
The pH is typically 6.8-7.4 (NH + salts) or 7~ - s-Inaredient ~?~ ~
_ C~2-14 ,i-,~ethyl glucam,de C~2 ,3EO(0.8) sulf2ta ~ v~
15 Cl2 l~E0(3) sulfate li --Cl2 ,3E0(6.5) sulfate -- -- 3 Cl2 l~ AP betaine -- -- 2 Cl2 ,4 AP sultaine -- -- 1.0 Cl2 l3 amine oxide 2.5 - I.0 20 C~2 l~ DM betaine -- 2.0 --Cg lE0(8) 0 5 8 7 Ca+~ -- -- 0.5 1.0 Mg++ 0.9 0.25 -- --Balance Ba1 Bal Bal Bal A liquid laundry detergent composition suitable for use at the relatively high concentrations common to front-loading automatic washing machines, especially in Europe, and oY~. a wide ranse of temperatures is as follows.
30 Inqredient Wt. %
Coconutalkyl (Cl2) N-methyl glucamide 14 Cl4 lsE0(2.25) sulfate, Na salt 10.0 Cl4 1sEO(7) 4.0 Cl 2 -14 alkenylsuccinic anhydride~ ~ ~
35 Cl2-l4 fatty acid* 3 0 Citric acid (anhydrous) ~.5 Protease ~enzyme) 2 2092~9 W O 92/06158 PCT/US91/0702, Termamyl (enzyme) 3 0.12 Lipolase (enzyme)l 0.36 Carezyme (enzyme) 5 0.12 Dequest 2060S6 1.0 NaOH (pH to 7.6) 5 5 1,2 propanediol 4 7 Ethanol 4 o Sodium metaborate 4.0 CaCl 2 0.014 10 Ethoxylated tetraethylene pentamine' 0.4 Brighcener3 0.13 Silane3 0 04 Soil release polymerl~ 0.2 Silicone (suds control)1' 0.4 15 Sjlirone dispersant12 0.2 '~ater and minors Balance As SYNPRAX 3 from ICI or DTSA from Monsanto.
2As Protease B as described in EPO 0342177 November 15, 1989, percentage at 40 g/l.
3Amylase, from NOVO; percentage at 300 KNU/g.
4Lipase, from NOVO; percentage at 100 KLU/g.
5Cellulase from NOVO; percentage at 5000 CEVU/l.
6Available from Monsanto.
'Erom BASF as LUTENSOL P6105.
2~ 8BLANKOPHOR CPG766, Bayer.
9Silane corrosion inhibitor, available as A1130 from Union Carbide or DYNASYLAN TRIAMINO from Huls.
0Polyester, per U.S. Patent 4,711,730.
l'Silicone suds control agent available as Q2-3302 from Dow Corning.
12Dispersant for silicone suds control agent available as DC-3225C from Dow Corning.
*Preferred fatty acid is topped palm kernel, comprising 12%
oleic acid and 2% each of stearic and linoleic.

A granular laundry detergent composition suitable for use at the relativel~ high concentrations common to front-loading automatic wash,ng machines, especially in Europe, and over a wide range of temperatures is as follows.

W O 92/06158 PCT/US91/0~02-9 Inqredient Wt. %
~9~5 SOKALAN CP5 (100~/0 active as Na salt)' 3.52 DEQUEST 2066 (100% as acid)2 o ~
TINOPAL DMS3 o ~o MgSO4 0 ~3 Zeolite A (anhydrous 2-5 ~) 17 CMC (100% active~
Na2CO3 ?, !' Citric acid ~.;
10 Layered Silicate SKS-S ~.
Tallow alkyl sulfate (100% actiYe; Na sa~
C1~-Cls alkyi sulrare (100% active; I~la sal~j 3.i C~2-Cls alkyl EO(3) sulfate ., C~6-Cl8 N-methyl glucamide ~.1 5 DOBANOL C~2-C1~ EO(3) ~ -~
LIPOLASE (100,000 LU/g)5 , .~
SAVINASE (4.0 KNPU)6 1.65 Perfume 0.53 X2-34197 0.22 20 Starch 1.08 Stearyl alcohol 0.35 Sodium percarbonate (coated) 22.3 Tetraacetylethylenediamine (TAED) 5.9 Zinc phthalocyanin 0.02 25 Water (ex zeolite) 3alance lSOKALAN is sodium poly-acrylate/maleate available from Hoechst.
2Monsanto brand of pentaphosphonomethyl diethylenetriamine 30ptical brightener available from Ciba Geigy.
~Trade name FINNFIX ava;table from Metasaliton.
5LIPOLASE lipolytic enzyme from NOYO.
6SAVINASE protease enzyme from NOVO.
7X2-3419 is a s;l;cone suds suppressor available from Do~
Corning.
The procedure for prepar;ng the granules comprises various tower-drying, agglomerating, dry-additions, etc., as follo~s. The percentages are based on the finished composition.

2092~9 W O 92/06158 pcT/uss1/o7o27 A. Crutched and Blown Throuah the Tower Using standard techniques the following components are crutched and to~er-dried.
50KALAN CP5 3.52%
DEQUEST 2066 0.45%
TINOPAL DMS 0.28%
,lagnPsium sulfate 0.49~/0 7EOLITE A as anhydrous 7.1%
~;~C ~.~7%
~. S~rfactant Acalomerates ~ lomeration of Sodiu~ Salt of Tallow Alkvl Sulfate and Sodiu~ ~alr Ot Cl~ l5 E0~3) Sul;ate Pastes - A 50% active paste or .all~ al'~,~l sulrate and a 70% paste OT Cl2-c~s EO(3) sulfate are agglomerated with Zeolite A and sodium carbonate according to the following ,ormula (contribution to the detergent formulation after the dr,~ing of the agglomerate~.
Tallow alkyl sulfate 2 . 82%
C,2 ,s EO(3) sulfate 1.18%
Zeolite A 5.3%
Sodium carbonate 4,5%
B2. Aaglomerate of the C~.-C~5 AlkYl Sulfate, C~-C~s Alkvl Ethoxv Sulfate. ~08ANOL C1 7-Cl ~ EO(3) and C.~-Clp N-methYl qlucose amide - The C16-C1fl glucose amide nonionic material is synthesized with D03ANOL C12 1sEO(3) present during the reaction of methyl ester 2~ and N-methyl glucamine. The C12 1sEO(3) acts as a melting point depressor which allows the reaction to be run without forming cyclic glucose amides which are undesirable.
A surfactant mixture of 2~% DOBANOL C~2 ,5 EO(3) and 80%
C16-C1~ N-methyl glucose amide is obtained and coagglomerated with 10% sodium carbonate.
Second, the above particle is then coagglomerated with a high active paste (70%) of a sodium salt of C1~-C1s alkyl sulfate and C12 1s EO(3) sulfate and Zeolite ~ and extra sodium carbonate. This particle evidences a good dispsrsibility in cold water of the C16-C18 N-methyl glucose amide.
The overall formulation of this particle (contribution to the detersent formulation after the drying of the agglomerate) is:

WO 92/06158 Pcr/uS~1/0702-C~6-C18 N-methyl glucose amide 4 l%
~9~9 DOBANOL CI2 ls EO(3) 0.94%
Sodium carbonate 4~94~~o Zeolite A 5 30/~
Na C1~-C1s alkyl sulfate 3 ~%
Na C12 ~5 EO(3) sulfate o.~~
C. DrY Additives The following ingredients are added.
Percarbonate ~ ;J
TAED (tetraacetylethylenediamine) .~-;
Layered silicate SKS 6 from Hoechst Citric acid 3.~,~
Lipolase ~.
1ou, ûûO Lu'j~
SAYINASE 4.0 KNPU ~ ,?' Zinc phthalocyanin (photobleach) ~.n7~7 D. SPraY on DOBANOL C~2-15 EO(3) 2.60%
Perfume 0 53%
E. Suds SuDDressor The silicone suds suppressor X2-3419 (95%-97% high molecular weight silicone; 3%-5~h hydrophobic silica) ex Dow Corning is coagglomerated with Zeolite A (2-5 ~ size), starch and stearyl alcohol binder. ~his particle has the following formulation:
Zeolite A ~.22~~
Starch 1.08%
X2-3419 0.22%
Stearyl alcohol 0 35,0 The detergent preparation exhibits excellent solubility, superior performance and excellent suds control when used in European washing machine, e.g., using 85 9 detergent in a AES-brand washing machine in 30-C, 40-C, 60-C and 90-C cycles.
E%AMPLE 20 In any of the foregoing examples, the fatty acid glucamid~
surfactant can be replaced by an equivalent amount of the maltamide surfactant, or mixtures of glucamid2/maltamide surfactants derived from plant sugar sources. In the compositions the use of ethanolamides appears to help cold temperature stability of th~

W 0 92/06158 2 0 ~ 2 ~ ~ ~ PCT/US91/07027 finished formulations. Moreover, the use of sulfobetaine (aka "sultaine") surfactants provides superior sudsing.
The following Examples illustrate furrther liquid compositions which ~rP ~especially suitable for "light-duty" use, such as for dishwashing.
~XAMPLE 21 A-D
Incredients Percent (wt.) A B C D
Cl2 1~ a7'(yl ethoxy sulfate (l EO) 16 9 12 --0 C12-?; ?~!C'/I ~tho~y sulfate t3 ~0) -- 14 l1 C1~ à1,~';1 aL~OX~1ate ~3~0) 7 3 7 C. . I-",e~;lvl cluc~mide 8 9 12 6 . . . .
C~J~ hz~ol3~id~ -- -- -- 5 D"m21h!' ~vd~-cyl amine oxi dQ ~ ~ ! ~ ~ 2 i5 Coco~,,"dv?ivpyi nyd,ûxysul~aine -- l 3 --Cocoamidopropyl betaine 2 -- -- --Mg2+ -- --Ca2+ 0.5 1 --Sodium toluene sulfonate 3 3 3 3 20 Ethanol 4 4 4 Water ------ Balance ------In the event that especially high sudsing compositions are desired (e.g., dishwashing), it is preferred that less than about ~~XO~ more preferably less than about 2%, most preferably substan-2~ tially no C,~ or higher fatty acids be present, since these cansuppress sudsing. Accordingly, the formulator of high sudsing compositions will desirably avoid the introduction of suds-suppressing amounts of such fatty acids into high sudsing composi-tions with the polyhydroxy fatty acid amides, and/or avoid the formation of C1~ and higher fatty acids on storage of the finished compositions. One simple means is to use C12 ester reactants to prepare the polyhydroxy fatty acid amides herein. Fortunately, the use of amine oxide or sulfobetaine surfactants can overcome some of the negative sudsing effects caused by the fatty acids.
The formulator wishing to add anionic optical brighteners to liquid dstergents containing rel2tively high concentrations (e.g., 10~~ and gr~2ter) of anionic or polyanionic substituents such as the ~ g~9 polycarboxylate builders may find it useful to pre-mix the bright-ener with water and the polyhydroxy fatty acid amide, and then to add the pre-mix to the final composition.
Polyglutamic acid or polyaspart;c acid dispersants can be usefully employed with zeolite-built detergents. AE fluid or flake and DC-544 (Dow Corning3 are other examples of useful suds con~rol agents herein.
It will be appreciated by those skilled in the chemical arts that the preparation of the polyhydroxy fatty acid amides nerein using the di- and higher saccharides such as maltose will ~sult -n the formation of polyhydroxy fatty acid amides wh2r21l, 1~ 5~A
substituent 2 is "capped" by a polyhydroxy ring struciure. juc, materials are ;ully contemplalPd ;or use herein and do no; ~ - r from the spirit and scope of the invention as dlsclosed and ciaimed.

Claims (21)

WHAT IS CLAIMED IS:

1. A detergent composition comprising at least about 1%, by weight, alkyl alkoxylated sulfate surfactant and optional auxiliary surfactants and adjuncts, wherein the improvement comprises incorporting into said detergent at least about 1%, by weight, polyhydroxy fatty acid amida surfactant of the formula:
wherein R1 is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, or 2-hydroxypropyl, R2 is C7-C31 hydrocarbyl, and Z is polyhydroxyhydrocaroyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to said chain, or alkoxylated derivatives thereof; and wherein said composition further has a polyhydroxy fatty acid amide:alkyl alkoxylated sulfate weight ratio of from about 1:10 to about 10:1, and optionally contains a suds suppressor.

2. A detergent composition as in Claim 1 wherein said detergent composition comprises at least about 3% polyhydroxy fatty acid amide and at least about 3% alkyl ethoxylated sulfate, and said suds suppressor is selected from the group consisting of monocarboxylic fatty acids, and salts thereof, silicone suds suppressors, monostearyl phosphate suds suppressors, and hydrocarbon suds suppressors.

3. A detergent composition as in Claim 2, which further comprises from about 1% to about 25% of an auxiliary surfactant component.

4. A detergent composition as in Claim 3, wherein said auxiliary surfactant comprises alkyl benzene sulfonate surfactant, alkyl sulfate surfactant, alkyl ester sulfonate surfactant, alkyl ethoxylate, alkyl phenol alkoxylated surfactant, alkylpolyglycoside, or paraffin sulfonate, or a mixture thereof.

5. A detergent composition as in Claim 1, wherein said suds suppressor comprises a silicone suds suppressor, a hydrocarbon suds suppressor, or a monostearyl phosphate suds suppressor, or a mixture thereof.

6. A detergent composition as in Claim 1, wherein said suds suppressor comprises at least about 0.5% of monocarboxylic fatty acid, or salt thereof.

7. A detergent composition as in Claim 1, wherein R' is methyl, R2 is C9-C17 alkyl or alkenyl, Z is -CH2(CHOH)nCH2OH, -CH(CH2OH)-(CHOH)n-1-CH2OH, or -CH2-(CHOH)2(CHOR')(CHOH)-CH2OH wherein n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide.

8. A detergent composition as in Claim 7, wherein Z is -CH2(CHOH)4CH2OH.

9. A composition as in Claim 1 wherein, with respect to the polyhydroxy fatty acid amide, Z is derived from glucose or maltose or mixtures thereof.

10. A composition as in Claim 1 wherein Z is derived from a mixture of monosaccharides, disaccharides and, optionally, polysaccharides comprising at least about 1% by weight of disaccharides, said mixture being available from plant sources.

11. A detergent composition as in Claim 1, further comprising at least about 1%, by weight, of a detergent builder.

12. A detergent composition as in Claim 1, wherein said alkyl alkoxylated sulfate surfactant is a C14-C18 alkyl ethoxylated sulfate having an average degree of ethoxylation of from about 0.5 to about 6.

13. A detergent composition comprising:
(a) at least about 1% by weight of a polyhydroxy fatty acid amide compound of the formula:

wherein R1 is methyl, R2 is C11-C17 alkyl or alkenyl, and Z is a glycityl derived from a reducing sugar, or an alkoxylated derivative thereof; and (b) at least about 1% by weight of an alkyl ethoxylated sulfate surfactant having an average degree of ethoxylation of from about 0.5 to about 6;
wherein the weight ratio of (a):(b) is from about 1.25:1 to about 1:4.

14. A composition as in Claim 13 wherein, with respect to the polyhydroxy fatty acid amide, Z is derived from glucose or maltose or mixtures thereof.

15. A composition as in Claim 13 wherein Z is derived from a mixture of monosaccharides, disaccharides and, optionally, polysaccharides comprising at least about 1% by weight of disaccharides, said mixture being available from plant sources.

16. A detergent composition comprising:
(a) at least about 1% of a C14-C18 alkyl ethoxylated sulfate surfactant; having an average degree of ethoxylation of from about 0.5 to about 6;
(b) at least about 1% of polyhydroxy fatty acid amide of the formula wherein R1 is methyl, R2 is C9-C17 alkyl or alkenyl, and Z is a glycityl derived from a reducing sugar, or an alkoxylated derivative thereof; and (c) from about 1% to about 25% of an auxiliary surfactant component selected from the group consisting of alkyl phenol alkoxylates, alkyl polyglycosides, and alkyl ethoxylates, wherein the weight ratio of (a):(b) is from about 1:10 to about 10:1, and the weight ratio of (b):(c) is from about 1:10 to about 10:1.

17. A composition as in Claim 1 wherein, with respect to the polyhydroxy fatty acid amide, Z is derived from glucose or maltose or mixtures thereof.

18. A composition as in Claim 1 wherein Z is derived from a mixture of monosaccharides, disaccharides and, optionally, polysaccharides comprising at least about 1% by weight of disaccharides, said mixture being available from plant sources.

19. A detergent composition as in Claim 16, wherein the ratio of (a):(b) is from about 1:1 to about 4:1 and the ratio of (b):(c) is from about 1:5 to about 5:1.

20. A detergent composition as in Claim 19, further comprising a builder.

21. A detergent composition as in Claim 19, substantially free of suds-suppressing amounts of C14 and higher fatty acids.