CA2191439A1 - Bleach compositions comprising oleoyl sarcosinate surfactants - Google Patents

Abstract

Bleaching and cleaning compositions comprising a bleaching compound, oleoyl sarcosinate surfactant, and, optionally but preferably, a bleach catalyst and one or more bleach activators are provided. Thus, laundry detergent compositions which comprise perborate, percarbonate and, preferably, activators such as benzoyl caprolactam exhibit improved performance in the presence of the oleoyl sarcosinate surfactant.

Description

~ W095133043 21 91 43q .~.I/U.. r-7q6 BLEACH CO~OSITIONS CO~RISING OLEOYL
SARCOSrNATE STJRFACTANTS
S
TECHNICAT FTFT.n The present invention relates to cleaning and bleaching cnmrositinn~ which employ oleoyl sarcosinate surfactants to boost pciru..l.G..~. Bleaching, fabric 10 laundering, automatic di~l,vl~l.;.lg and sanitizing ru~ o~ with improved oxygen bleach activity are provided.
BACKGROT~ND OF T~F INVENTION
It is common practice for formulators of cleaning . ~,.,11..,,;l;l~..~ to include bleaching agents such as sodium perborate or sodium p~ u~v~Gte in such 15 ~ for their bleach effect. Such bleaches are widely recognized for their ability to remove various stains and soils from fabrics. In like manner, formulators of automatic u;~ c~ have found that various bleaching agents can assist in the removal of tea stains, ,u~u~ v~i soils, and the like, from dishware.
Various fabric bleach and/or pre-soaking ~ u ~ ;ù ~ also comprise ~ L~u~dt~. or 20 perborate bleaches.
TT..~U.lL...,t.l~, many bleaching agents do not function optimally under all usage conditions. As a general proposition. perborate and p."..,.L bleaches are more effective in hot water than in cold. Yet, many consumers now conduct fabnc laundering and other cleaning operations under moderate-to-cold water ~ Lulc:, 25 (below about 60C). To improve the p~ulllldllce of perborate and ~ lbùllcLc bleaches, ~ ul~lulcl~ have turned to the so-called "bleach activators". Such activa~ors typically comprise organic molecules which interact with perborate or ullaLe to release "per-acid" bleaching species. The c~ ;l,l of bleach-plus-activator functions well over a wide range of water ~ y.,~Lulu~ and 30 usage conditions. It is also known that various transition metal cations, such as manganese, have the potential to function as bleach activators, presumably by virtue oftheir catalytic interaction with peroxide or per-acid bleaching species.
~ r ~ iull.lLcly, many peracids, bleach activators and transition metal catalysts can cause fabric damage. Without bein~ limited by theory, it is believed that fabric 35 damage from bleaching compounds is due to the ~ Liu,l of the activators and catalysts onto fabrics which causes fabric damage upon radical formations with hydrogen peroxide. Likewise, the bleaching species may precipitate onto the fabrics ... . ... . . ..... .. , .. .. ...... _ . .... .. .. ~

W095133043 ~1 9 1 439 P~
.

and cause isolated spotting and fabric damage Fabric damage can be particularly dramatic at lower temperatures because many of the peracids. activators and catalysts solubilize more siowly at colder It...~,~.d~ules and, therefore, readily precipitate upon the fabric surfaces.
It has now been discovered that bleach ~ ~ comprising oleoyl sarcosinate surfactant can be used to provide effective, improved bleaching. Further, these ~ c seem to deter fabric damages caused by the peracids, catalysts and bleach activators. Without being limited by theory, it is believed that the oleoyl sarcosinate is partl-cularly effective at solubilizing the bleaching compounds and dispersing it throughout the wash liquor, especially at cooler Ic~ ,.dlulca (less than about 60C). Thus, the p~ dliull of bleaching compounds in the wash liquor is reduced.
Accordingly, it is an object of the present inventiûn to provide improYed cleaning and bleaching ~,...,I,.,~;l;~..,c using bleaching compounds and oleoyl 15 sarcosinate surfactants. It is another object herein to provide a means for removing soils and stains from fabrics and dishware using the bleaching systems and oleoyl âarcosinate of this invention. The ~....~1 ,..c,l ;.... also provide excellent color care for dyed fabrics and excellent sicin mildness for handwash operations. These and other objects are secured herein, as will be seen from the following disclosures.
BACKGROUND ART
Oleoyl sarcosinate is described in the following patents and r ' ~' " U.S.

2,542,385; U.S. 3,402,990; U.S. 3,639,568; U.S. 4,772,424; U.S. 5,186,855;
European Patent Publication 505,129; British Patent Publication 1,211,545; Japanese Patent Publication 59/232194; Japanese Patent Publication 62/295997; Japanese Patent Publication 021180811; and Chemical Abstracts Service abstracts No.s 61:3244q, 70:58865x, and 83:181020p.
The use of manganese with various complex iigands to enhance bleaching is reported in the following United States Patents: 4,430,243; 4,~28,455; 5,246,621;
5,244,594; 5,284,944; 5,194,416; 5,246,612; 5,256,779; 5,280,117; 5,274,147;
5,153,161; 5,227,084; 5,114,606; 5,114,611. See also: EP 549,271 Al; EP 544,490 Al; EP 549,272 Al; and EP 544,440 A2.
The use of amido-derived bleach activators in laundry detergents is described in U.S. Patent 4,686,063 and US. Patent 4,634,551. Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S.
Patent 4,966,~23, issued October 30, 1990.
SUMl~ARY OF THF rNVENTlON

I ~.I/IJJ S 7q6 ~ wo ss/33043 2 1 q 1 ~ 3 9 The present invention r~ bleach ~ ",1.l",~ comprising oleoyl sarcosinate surfactant and a bleaching agent.
The present invention also rl~ UIIIIIA~ bleach ,.~ comprising oleoyl sarcosinate surfactant, a bleaching agent, especially a bleach which is aS member selected from the group consisting Of H22, perborate, p~ ,a~uullaL~, persulfate and peracid bleaches, and one or more selected bleach activators.
Preferred bleaching agents comprise percarbonate or perborate bleach~ or mixtures thereof Preferred bleach activators are selected from acyl lactam-type activators, amido-derived activators, benzoaxin-type activators~ L~Ll aa~eL~ tl~ le-diamine 10 (TAED), alkanoyloxyt~Pn~PnP~ f~nAt~ps~ including ~vAyb~ le-sulfonate (NOBS), and ben~oyloxyt~ .,,. ~"lr,,.. ,r (BOBS), and mixtures thereof. Per4eidsmay also be included in the present ~ o~ Suitable peracids include amido peracids~ cationic peracids, nonylamide of peroxyadipic acid (NAPAA), and mixtures thereof Additionally, the present invention further rll~ bleach ~ L~
comprising oleoyl sarcosinate surfaclant, a bleaching agent, one or more selected bleach activators, and a caldlJi' "J,-efective amount of one or more bleach catalysts, especially metal bleach catalysts Preferred activators which are optionally employed in the present invention 20 inelude ben_oyl ~ ula~la~ nonanoyl l,a!,.ula~,lalll~ benzoyl v-' ula~,lalll, nonanoyl v ' ula~,Lalll, 3~5~5-L-;.~L~ AAIIVYI l,a~JIvl_~,Lalll, 3,5,5-trimethyl-hex-anoyl v~' vla~,L_IIl, octanoyl ~ ula~,L~.,.I, octanoyl v' ,' , decanoyl ~,à~lul_~,Lalll, deeanoyl v:' vlacLa~, undeeenoyl ~.aiJIula~,lalll~ undeeenoyl valerol-aetam, (6-o~ Uyl)uAy~ ~lr.~ ~^, (6-1~ l..uyl)-oxy-25 I; ~ r lr (6-I' ' , UYI)OXY1~ Ir~ e, ~IvAy-ben-LUjlUAyi ', ~:llaàl~e~yl~illyl C~\l.u;_~ and mixtures thereo Examples of highly preferred substituted benzoyl laetams include h~lt~ Lu~ lula~,lalll, Ill~ UJI ~ ' ulA.,Ia~ J ~ 4Uyl caprolac-tam, ~:lh,:5~.~Lu~l vL' UIAA~ IU~ LU~I ~.a~ulA~ ut~ylb.,.~uyl valerol-30 actam, ;~u~JIu~ LUjl l,a~JlUla~lalll~ ;au~lu~ lLuyl v. ' ula.,~alll, i~u~ ."~u~l ~,-A,ulula~,~alll, bu~yll/.,~uyl val~,~ulA.,Lalll, tert-bu~yli~ uyl ~a~lvL,LA~, tert-bu~ylt~ Lu~l ~ ' ula~,~.. , pe~iyll,~Luyl ~.a~lula~,~al~l, pentylbenzoyl ~. ' uL,~alll, .,A.~ tl~UYI l~a~JIUIa~LaIII~ h..A~ ~UYI ~ Ia~LaIII~ ~IIUAYlI--~I~UYI ~aUIUIaI~L~II~
~IIUAY~ ILUYI V ~t uL.Lalll, propoxybenzoyl ~a~lula~,~alll, propoxy-benzoyl 35 ~_' ula~,Lalll, ;~U~IU~UAY~ UYI l~a~lula~alll~ ;~U~IU~JUAY~ UYI valero-laetam, lJUIUAY~ a~IUIa~1aIII~ LULUAY~ UYI ~alu~ula~a~lL~ ten-butoxy-benzoyl ~,a~lulal,Lalll, ten-butoxybenzoyl Y ' ul_~,La~ J~tVAy~ uyl eapro-laetam, pen-Wo gs/33043 2 1 9 1 ~ 3 9 ~ .q6 toxybenzoyl valerolactam, hexoxybenzoyl caprolactam. h~,~u~.yL~ uyl valerolac-tam, 2,4,6-1~i""loloi~ uyl caprolactam, 7,4,6-LIh,~lùlui~ uyl ~,dh,,ula. Ld,...
iJ~I'dnUUIuiJ~ UYI caprolactam, pentafluorobenzoyl valerolactam, dh,l~lului~ uylu~ uldUL~ , dimethoxybenzoyi caprolactam, 3-ul~iùl uiJ.,Il~uyl c~llJI ula~ , 2,4-5 i;~,lllù~u~L~ uyl caprolactam, terephthaloyl dic.l,ululd~,Ld~ Lclc,' ' ' ,yl di-, pentafluorobenzoyl ~ .IUIG~,Ldl,l, u~lldriUUIUiJ~ Uyl v ' ulda~
i..hlo,u~,.l,uyl ~di_lùlduLdlll, i;lll~.llu~yi~ uyi valerolactam. 3-1,hl~ui~ell~u~1 l~luld~L~ . 2,4-dichlorobenzoyl ~ ' uh~ . terephthaloyl i;v '~ ùl~L~,ldlll, 4, Il;llui~ uyl capro-lactam, 4-nitrobenzoyl valerolactam, d;lulluL.,u~u,~
IU ~,d~JlUI. .~ luL~ uyl valerolactam, and mixtures thereof Particularly preferred are bleach activators selected from the group consist-ing of benzoyl ~a,ulula~,ldlll. benzoyl val..uL,Id"l. nonanoyl cd!Jlula~Lalli. nonanoyl .' Ula.,Ldll-. 4-luLluiJ.,.I~uyl ~,diJlula~,LI:lll. 4-~1;LlùL~ uyl ~ ' ul~-,Ldll~, octanoyl uaiJlukl~,Lcull, octanoyl v;il..uk.l,l~.,.., decanoyl ca,u~vla~,L~Ill, decanoyl ~ ' vlo~
15 undecenoyl ~I,uluL.~,Ldlll. undecenoyl v.d~.ul~.,LGIll. 3.5.5-trimethyl i~ u~caprolactam. 3,5.~-Llill.~ lvyl valerolactam, ~ ;L~uL..,.I~u~l capro-lactam, iuu~uL~ uyl val.,.ula.,l,l.,., terephthaioyl d~ ;,ulula~ L~ el~, ' ' ' ~' divalerolac-tam, (6-o ~ uyl)uf.y~ (6 ~ -caproyl)u,.yL. ~ r, (6-1~ u,~l)u,~yL '~ , 2û l~u~ lluylu~.yL~ r.. ;~, L.~UJIU~Y~ r,,, ~el lell~O~,e~ yl-~n~ and mixtureS thereof Preferablyl the molar ratio of hydrogen peroxide yielded by the peroxygen bleaching compound to bleach activator is greater than about l.û, Most preferably the molar ratio of hydrogen peroxide to bleach activator is at least about 1.5 25 Preferred ~.1..... l.. ~;l;.. her~in are those wherein the bleach catalyst is a metai-bOsed catalyst.
The invention also ~ .,.,.1~-. detergent ~ , especiaily laundry detergents, comprising otherwise cull..,l..iull~ll surfactants and other detersive ingredients.
3û The invention also ~ n-~ detergent or bleach .,u l~ comprising oleoyl sarcosinate surfactant, a bleaching agent, and a ~I~ effective amount of a water-soluble manganese salt The invention also _."...,.I.~c a method for improving the bleachin~
~J~..rù~ Oul~e of oxygen or per-acid bleach ~ . comprising adding thereto 35 oleoyl sarcosinate surfactant in the presence of selected ligands and a catalytically effective amount of manganese cations. This provides û method for removing stains 2 1 9 1 4 3 q from fabrics, comprising conlacting said fabrics with an aqueoas medium comprising said ~ o~
Ail pc,.~ .5~j, ratios and proportions herein are by weight, unless otherwise specifed. All documents cited are, in relevant part, i.lcu~Juldle~i herein by reference.
DETALED DESC~IPTION OF THE INVENTION
1. Oleûyl Sarcosinate:
The present invention ~ c.;l;~ comprise oleoyl sarcosinate, in its acid and~or salt form selected as desired for the . u",~ ,, and uses herein, having the following formula: l wherein M is hydrûgen or a cationic moiety. Preferred M are hydrogen and alkaii metal salts, especially sodium and potassium. Oleoyl sarcosinate is . "~
svailable, for example as Hamposyl O supplied by W. R. Grace & Co. Bleaching 15 c~ u~ according to the present inYention comprise at least about 0.1%, typically from about 0.1% to about 55%, preferably from about 1% to about 20%, and most preferably from about 3% tû about 15%, of oleoyl sarcosinate by weight of the ~....,1.~,~;l;l~,, In addition to the ~,ul-u~ a~ f oieoyl sarcosinate, oleoyl 20 sarcosinate useful herein can also preferably be prepared from the ester (preferably the methyl ester) of oleic acid and a sarcosine salt (preferably the sodium salt) under anhydrous reaction conditions in the presence of a base catalyst with a basicity equal to or greater than alkoxide catalyst (preferably sodium methoxide). For example, the reaction may be illustrated by the scheme:

W095/33043 21 9~1 43q r~ '7q6 ~ -o CH O
H,N~QNa NaOCH3 (cat) I

This salt may optionally be neutralized to form the oleoyl sarcosinate in its acid form.
The preferred method for preparing oleoyl sarcosinate is conducted at a temperature from about 80C to about 200C, especially from about 120C to about200C. It is preferred to conduct the reaction without soivent although alcohol solvents which have a boiling point of at least 100C and are stable to the reaction conditions (ie. glycerol is not acceptable) can be used. The reaction may proceed in about 85% yield with a moiar ratio of methyl ester reactant to sarcosine salt reactant to basic catalyst of about 1:1:0.05-0.2.
Methyl ester mixtures derived from high oleic content natural oils ~preferably having at least about 60%, more preferably at least about 75%~ and most preferably at least about 90% oleic content) are especially preferred as starting materials.
Examples include high-oleic sunflower a*d rapeseed/canola oil. In addition, a high-oleic methyl ester fraction derived from either palm kernel oil or tallow is acceptable.
It is to be understood that such oils typically will contain some levels of impurities, including some fatty acid impurities that may be converted to sarcosinate compounds by this synthesis method. For example, commodity ~ .ola~'~p~ ,d oii may comprisea majority of oleic acid, and a mixture of fatty acid impurities such as palmitic, stearic, linoleic, linolenic and/or eicosenoic acid, some or all of which are converted to the sarcosinate by this reaction method. If desired for formulation purposes, some or all of such impurity materials may be excluded from the starting oil before preparing the oleoyl sarcosinate to be used in the present ...."l.n~

WO 9~133043 P._~/U~ r '~')6 21 9l 439 Finally, sarcosine remaining in the reaCtiOn mixture can be converted to an amide by addition of maleic or acetic anhydride to Ihe mixture, thereby minimizing the sarcosine content and any potential for formation of undesired nitrOgen-containing impurities.
The synthesis of oleoyl sarcosinate may be carried out as follows to prepare the sodium oleoyl sarcosinate.
Svnthesis of Oleoyl Amide of Sarcosine Sf~ m ~all A 2 L, 3-neck, round bottom flask is fitted with lI. .."ù.,n,L~" Dean-Stark trap with condenser. mechanical stirring, and a gas inlet adapter through which nitrogen is passed over the reaction mixture The reaction vessel is charged with sarcosine (43.3 5, 0.476 mol), sodium methoxide ''5% in methanol (9~.7 g, 0.452 mol), and methanol (400 mL). The reaction is refluxed 15 min to neutralize the sarcosine and then methyl ester derived from Cargill regular high-oleyl sunflower oil (l48.25 g, 0.5 mol) is added. After the methanol is removed with the Dean-Stark trap, reaction mixture is heated to 170CC
for I hr to drive off any water. The reaction is initiated by the addition of sodium methoxide 25% in methanol (15.4 g, 0.0714 mol). Reaction is kept at 170C for 2.5 hr during which methanol is collected in the Dean-Stark trap. The reaction is allowed to cool slightly and then methanol (200 g) is added. Maieic anhydride (9.43 g, 0.095 mol) is added to the methanol solution and the reaction is stirred at 60C for 0.5 hr. Then most of the methanol is removed by rotary cv~u~ ull and acetone (2 L) is added to precipitate the product. The product is collected by suaion filtration and allowed to air dry to give an off-white solid. Analysis of the reaction mixture by GC indicates the majority of the product is oleoyl sarcosinate, with minor amounts of the foliowing impurities: sarcosine, oleic acid, and the ~al~,ual~ L~a derived firom palmitic acid, stearic acid, and linoleic acid.
Rl-~arhin~ Cvmpollnds and RlParhinY A~ents - In addition to oleoyl sarcosinate surfactant, bleaching ~ herein also contain bleaching agents or bleaching mixtures containing a bleaching agent and one or more bleach activators, in an amount suffcient to provide bleachin~ of the stain or stains of interest. Bleaching agents will typically be at levels of from about 1% to about 80%, more typically from about 5% to about 20%, of the detergent ~, I.c~ , especially for fabric laundering. Bleach and pre-soak ....I l v~ may comprise from 5% to 99% of the bleaching agent. If present, the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the 3 5 bleaching mixture comprising the bleaching agent-plus-bleach activator.
The bleaching agents used herein can be any of the bleaching agents useful for detergent ~'''''I''J`;I;''''` in textile cleaning or other cleaning purposes that are now WO9~/33043 ~ 1 9 ~ 439 r~ 7q6 ~
known or become i~nown. These include oxygen bleaches as well as other bleachingagents. Perborate bleaches, e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
Peroxygen bleaching agents are preferably used in the LUIII,UU~;liU~I~. SuitableS peroxygen bleaching compounds include sodium carbonate i;.,.u~yll~il5l~ and equivaient "iJ~.L51i~Ulldt~" bleaches, sodium pylU,LllU~,Li~.lLC peroxyhydrate, urea IJ~IU~YIIYLiI5L~ and sodium peroxide. Persulfate bleach (e.g., OXONE, .luLLlulcLi Lu~ L;511y by DuPont) can also be used.
A preferred iJ~,L5~i~u~1~lLe bleach comprises dry particies having an average lû particle size in the range from about 500 ~ u.n~t~.~ to about 1,000 .,.,~,,u",.,.~,,, not more than about 10% by weight of said particles being smaller than about 200IlliLlUlll~t~.~ and not more than about 10% by weight of said particles being larger than about 1,250 IlliLlUI~I."CI~. Optionally, the iJ~-GliJU115~e can be coated with silicate, borate or ~ater-soluble surfactants. ~IL51iJVl151c is available from various 15 commercial sources such as FMC, Solvay and Tokai Denka.
The ~ ;.;.. of the present invention may also comprise mixtures of bleaching activators.
Peroxygen bleaching agents. the perborates, the p."LaliJU115LC~, etc., are preferably combined with bleach activators, which lead to the In sltu production in 20 aqueous solution (i.e., during the washing process) of the peroxy acid to the bleach activator, ~ Ik~n~ylv~,yl~ for ~s - Suitable alkanoylu~yiJ ~ r ~- bleach activators which can be employed in the present invention are of the formula:
l A
R1-C-O~SO3M
25 wherein Rl-C(O)- contains from about 8 to about 12, preferably from about 8 to about 11, carbon atoms and M is a suitable cation, such as an alkali metal, ammonium, or substituted ammonium cation, with sodium and potassium being most preferred.
Hi~hiy preferred hydrophobic aikanoylu,.yv ., .. lr., ~ are selected from 3û the group consisting of l~u~5~uylu~yv ~ - Ir~ -~e, 3,5,5-L~ ,ylh~A5,,vjl uJ-,yL . 2-e~ As~vylù~yL , ~ ,~lv~.yi~
fonate, d~5~uylu~. . ,. ~.,lr".. r, dodecanoylu7~y~ ~.,lr.. r, and mixturesthereof.

-WO 95/33043 2 1 9 1 4 3 ~ r -7q6 ~ mirl~ Derived ~leach ~r'iYators - The amido derived bleach activators which can be employed in the present invention are amide substituted compounds of the general formulas O O O O
Il 11 11 11 R1-C--N--R2-C--L, R1--N--C--R2-C--L
Rs Rs 5 or mixtures Ihereof, wherein Rl is an alkyl, arYI, or alkaryl group containing from about I to about 14 carbon atoms, R2 is an alkylene, arylene or alkarylene groupcontaining from about I to about 14 carbon atoms, R~ is H or an alkyl, aryl, or alkaryl group containing from about I to about 10 carbon atoms, and L is essentially any suitable leaving group A leaving group is any group that is 10 displaced from the bleaching activator as a, ~ of the ~ ' -r~ '~' attack on the bleach activator by the perhydroxide anion. This, the ~.,.llydlul~ reaction, results in the formation of the l~,u~y~ bu~ylh, acid. Generally, for a group to be a suitable leaving group it must exert an electron attracting effect. It should also form a stable entity so that the rate of the baek reaetion is negligible. This 15 faeilitates the ' -r ' ' attaek by the perhydroxfi~ on.
The L group must be suffieiently reaetive for the reaetion to oecur within the optimum time frame (eg, a wash eyele). However, if L is too reaetive, this aetivator will be diffieult to stabilize for use in a bleaehing ..~ These eli~Li~,~ are generally paralleled by the pKa of the eonjugate aeid of the 20 leaving group, although exeep~ions to this eonvention are known. Ordinarily, leaving groups that exhibit sueh behavior are those in whieh their conjugate aeid has a pKa in the range of from about 4 to about 13, preferably from about 6 to about 11 and most preferably from about 8 to about 11.
Preferred bleaeh activators are those of the above general formula wherein 25 Rl, R2 and R5 are as defined for the peroxyaeid and L is seleeted from the group consisting of:
_o~, --O~Y, and --(}~R3Y
--N--11--R1 _N N --N--11--CH--R4 ~ c Ll I c I
y WO95/33043 21~1439 r~ .r~q6 ~ ~

-0-CH=C--CH=CH2 --0--CH=C--CH=CH2 -0--C--R~ N~ NR ~ ~C~NR4 il 11 O O

--0--C=CHR4 and --N--S--CH--R4 R3 o and mixtures thereof, wherein Rl is an alkyl, aryi, or alkaryl group containing from 5 about I to about 14 carbon a~oms, R3 is an alkyl chain containing from l to about 8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing group.
The preferred solubiiizing groups are -S03-M , -C02-M , -S04-M , -N+(R3)4X and o~--N(R3)3 and most preferably -S03 M and -C02 M+
wherein R3 is an aikyl chain containing from about I to about 4 carbon atoms, M is 10 a cation which provides solubility to the bleach actiYator and X is an anion which provides solubility to the bleach activator. Preferably, M is an aikali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion. Itshould be noted that bleach activators with a leaving group that does not contain a 15 solubilizing groups should be well dispersed in the bleaching solution in order to assist in their dissolution.
Preferred bleach activators are those of the above general formula wherein L
is selected from the group consisting of:
--0~ --O~Y, and --0~5 wherein R3 is as defined above and Y is -S03-M or -C02-M wherein M is as defined above.
Preferred examples of bleach activators of the above formulae include (6-' ~ "U,y'l)UAyi~ , (6-- ' , u~l)u~ r, nate, (6-'- ' ' , uyl)u~yb. ,,"~ , and mixtures thereof Another important class of bleach activators provide organic peracids as described herein by nng-openin~ as a ~o,~ of the ml 't r~ ~' attack on the CTlusss/062s6 wo ss/33043 P

Il carbonyl carbon of the cyclic ring by the perhydroxide anion. For instance, thisring-opening reaction in lactam activators involves attack at the lactam nng carbonyl by hydrogen peroxide or its anion. Since attack of an acyl lactam by hydrogen peroxide or its anion occurs preferably at the exocyclic carbonyl, 5 obtaining a significant fraction of ring-opening may require a catalyst. Another example of ring-opening bleach activators can be found in activators, such as those disclosed in U.S. Patent 4~966,723, Hodge et al, issued Oct. 30, 1990.
Such activator compounds disclosed by Hodge include the activators of the benzoxa~in-type, having the formula:
o N~C R1 including the substituted b~ of the type 1 5 R~
wherein Rl is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R4, and R5may be the same or different ~llhctitll~nlc selected from X halogen, alkyl, alkenyl, aryl, hydrQxyl, alkoxyl, amino, alkyl amino, COOR6 (wherein R6 iS H or an alkyl BrUP) and carbonyl functions A preferred activator of the benzoxazin-type is:
1l ~N"C~) When the activators are used, optimum surface bleaching p..ru~ t is obtained with washing solutions wherein the pH of such solution is between about8.5 and 10.5 and preferab~y between 9.5 and 10.5 in order to facilitate the 25 ~ rdlulyl;~ reaction. Such pH can be obtained with substances commonly .. , . , . ,, . .. _ . _ . , . ,,,, _ ... .. . . ... .

woss/33043 21 9 l 43~ L~ ~r--q6 known as buffering agen~s, which are oplional ~omrcnpnt~ of the bleaching syslems herein.
Still another class of preferred bleach actlvators includes the acyl lactam activators, especially acyl l,a~/l uld~ldllla and acyl Và:.luld~lJ.l,s of the formulae:
O O

CH2--CH2~ ~CH2--CH2 wherein R6 js H, an alky~, aryl, alkoxyaryl, or alkaryl group containing from I to about 12 carbon atoms, or a substituted phenyl group containing from about 6 to about 18 carbons. See copending U.S. A~ 08/064,562 and 08/082,270, which disclose substituted benzoyl lactams. See also U.S. Patent 4,545,784, issued lû to Sanderson, October 8, 1985, illcu.,uu,dltd herein by reference, which discloses acyH,a~lul~A~,lGlll~, including benzoyN,a~JIula~,Lalll, adsorbed into sodium perborate.
Vanous nonlimiting examples of activators which may also compnse the bleach i..:....l.~,~.li,...~ disclosed herein include those in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934. See also U.S. 4,634,551 for 15 other typical bleaches and activators useful herein.
Rl~.'A~h;~ ~l~nt~ - Another optional, yet preferable, category of bleaching agent that can be used without restriction,, ~ albu~lh~ acid bleaching agents and salts thereof Suitable examples of this class of agents include magnesium l~o~op.,.u~yphthalate h~".ahJ~Idl~: (rNTEROX), the magnesium salt of metachloro 20 perbenzoic acid, 4-nonylamino-4-ù,~uu~,u,.~uLy,;~, acid and dlu",u"y~ln~lr~A .1i,~;.
acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984; U.S. Pat. App. 740,446, Burns et al, filed June 3, 1985;
European Pat. App. 0,133,354, Banks et al, published February 20, 1985; and U.S.Patent 4,412,934, Chung et al, issued November 1, 1983. Highly preferred bleaching 25 agents also include 6-nonylamino-6-u~u,u~.u~.a~,,u.c acid as described in U.S.
Patent 4,634,551, and 4,686,063, both Burns et al., issued January 6, 1987, and August 11, 1987, respectively.
Suitable &..I;Ju~u~"u~aCida are ofthe formula:
O O O O
R1-C--N--R2-C--OOH, R1--N--C--R2-C--OOH
Rs Rs 30 wherein Rl, R2, and R5 are as deflned for the amido-derived type bleach activators described above.

WO 95/33~)43 2 1 9 1 4 3 9 Preferred organic peroxyacids are selected from the group consisting of 4-nonylamino-4-u~u~.~. u~yvu~yric acid, 6-(nonyl-amino)-6-oxoperoxycaproic acid;
dee~.~ulpl,v"~ "u~.;vllh, acid: and heptyl, octyl-, nonyl-, decyl-sulphonyl-perbutyric acid; and mixtures thereof 5 Example I of U.S. Pat. 4,686,063 contains one description of the synthesis fo NAPSA, from col. 8, line 40 to col. 9, line 5, and NAPAA, from col. 9 line 15 to col. 9, line 65 The superior bleaching/cleaning action of the present ....,,,l,v~;l;,...~ is achieved with safety to natural rubber machine parts and other natural rubber 10 articles, including fabrics containing natural rubber and natural rubber elastic malerials The bleaching mechanism and, in particular, the surface bleaching mechanism are not completely understood. However, it is generally believed that the bleach activator undergoes llu~ .uul~ , attack by a ~ u~i i, ar~ion, which is generated from the hydrogen peroxide evolved by the peroxygen bleach, to form15 a ~ u~ycaliJu~ylic acid. This reaction is commonly referred to as v~ ilvlr ~; ~
The amido-derived and lactam bleach activators herein can also be used in .,....I.;,.~.'.~n with rubber-safe. enzyme-safe~ hydrophilic activators such as TAi D, typically at weight ratios of amido-derived or Ca~ v activators:TAi,D in the range of 1:5 to 5:1, preferably about 1:1.
20 Bleach Catalvst The bleach catalyst material used herein can comprise the free acid form, the salts, and the like. It is to be appreciated that the bleach catalyst does not function as a bleach by itself Rather, it is used as a cataiyst to enhance ~he p~ 'ullllall~,c of l,ull~s"lliolldl bleaches and, in particular, oxygen bleaches such as perborate,25 IJ,-,a~VUIIa~c, persulfate, and the like, especially in the presence of bleach activators.
One type of bleach catalyst is a catalyst system comprising a heavy metal cation of defined b~each catalytic activity, such as copper, iron or manganese cations, an auxiiiary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ~l'r.~' ' as~,ciiC acid, eth~ a(lll~,lh,~' ,'~ ,' ' acid) and water-soluble salts thereof Such catalysts are disciosed in U.S. Pat. 4,430,243.
Other types of bleach catalysts include the _ based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include MnlV2(u-0)3(1,4,7-trimethyl-1,4,7-LliaLal,~ 2-(PF6)2, Mnill2(u-O)I(u-oAc)2(l~4~7-trimethyl-l~4~7-~liaLacrl~ )2 (C104)2-MnlV4(u-0)6(1,4,7-lliaLa~ ,lu.lu.. aae)4(Cl04)4, MalllMnlV4(u-O)I(u-oAc) . O~q6 wos~/33043 2~91~39 ~

(I,4,7-trimethyl-1,~ triazacyclononane)~(C104)3,andmixturesthereof Othersare described in European Pat App Pub. No. 549,27''. Other ligands suitable for use herein include l,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triaza-I,y~lunvl~ne, ~-methyl-1,4,7-Lli~c~.lv,~v,,~ne, 1,2,4,7-tetramethyl-1,4,7-triaza-5 ~y~,lorlu~ c, and mixtures thereof The bleach catalysts useful in machine d;~ a lllll~ ~ IJ ~L~ and ~o~ .lL~L~d powder detergent ~..J~ may also be selected as appropriate for the present invention. For examples of suitable bleach catalysts see U.S. Pat.

4,246,612 and U.S. Pat. 5,''27,084.
See also U.S. Pat. ~.194,416 which teaches ml.,.. ~ manganese (IV) complexes such as MnlV( I ,4,7-trimethyl- 1 ,4,7-L~ ;~.y~lvnv..~.,e)- (OCH3)3(PF6).
Still another type of bleach catalys~, as disclosed in U.S, Pat. 5,114,606, is awater-soluble complex of manganese (Il), (111), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH
groups. Preferred ligands include sorbitol. iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof.
U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand.
Said ligands are ofthe formula:

R 1 -N=C-B-C=N-R4 wherein Rl, R2, R3, and R4 can each be selected from H, substituted alkyl and aryl groups such that each R1-N=C-R2 and R3-C=N-R4 form a five or six-member2d ring. Said ring can further be substituted. B is a bridging group selected from O, S.
CR5R6, NR7 and C=O, wherein R5, R6, and R7 can each be H, alkyl, or aryl groups, including substituted or ~ .c~ d groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings.
Optionally, said rings may be substituted with cllh~ti~ n-c such as alkyl, aryl, alkoxy, halide, and nitro. Particularly preferred is the ligand 2~2~ iyh~ . Preferred bleach catalysts include Co, Cu, Mn, Fe,-bisp~.;d~ "L.l. and -b;:",.~,i.l~' ' complexes. Highly preferred catalysts include Co(2,2-~ tJy~ )C12~
Di(;~vLll;v,,~ ....Lv)bispyridylamine-cobalt (Il), trisdipyridylamine-cobalt(II) per-chlorate, Co(2,2-~ yk.. l;,.. )2 02C104, Bis-(2,2'-l,;~.y~;.l~l.. ;,~.,) copper(lI) perchlorate, tris(di-2-pyridyl-amine) iron(II) perchlorate, and mixtures thereofOther examples include Mn gluconate, Mn(CF3SO3)2, Co(NH3)sCI, and the binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including N4MnllI(u-0)2MnlVN4)+and [Bipy2Mnlll(u-0)2MnlVbipy2]-(C104)3.

~ w095/33043 2 1 9 1 4 3 ~

The bleach catalysts of Ihe present invention may also be prepared by combining a water-soluble ligand with a water-soluble manganese sal~ in aqueous media and ~OI~C~ Lillg the resulting mixture by evaporation. Any convenient wa~er-soluble salt of manganese can be used herein Manganese (Il), (III), (IV) 5 andlor (V) is readily avaiiable on a commercial scale. In some instances~ sufficient manganese may be present in the wash liquor, but. in general, it is preferred to add Mn cations in the I u~ o~ to ensure its presence in catalytically-effective amounts. Thus, the sodium salt of the iigand and a member selected from the group consisting of MnS04, Mn(C104)2 or MnCI ~ (least preferred) are dissolved in water 10 at molar ratios of ligand:Mn salt in the range of about 1:4 to 4:1 at neutral or slightly alkaline pH. The water may first be de-oxygenated by boiling and cooled by sparging with nitrogen. The resultin~ solution is evaporated (under N2, if desired) and the resulting solids are used in the bleaching and detergent ~.,,,,1,..~;l;,~ ~ herein without further purification.
In an alternate mode, the water-soluble manganese source, such as MnSO4, is added to the bleachlcieaning ~ l;,.,. or to the aqueous i,L,~,I,;.,~/, ' ' ~ bath which comprises the ligand. Some type of complex is apparently formed in si~u, and improved bleach p~.ru,...a.., . is secured. In such an i~7 si~l process, it is convenient to use a ~.ull~;;L,IaiJl~ molar excess of the ligand over the manganese, and mole ratios 2û of ligand:Mn typically are 3:1 to 15:1. The additional ligand also serves to scavenge vagrant metal ions such as iron and copper, thereby protecting the bleach from ;ol, One possible such system is described in European Pat. App. Pub.
No. 549,271.
While the structures of the bleach-catalyzing Illall~al~ cu",~ of the 25 pr~sent invention have not been elucidated, it may be speculated that they comprise chelates or other hydrated .uulu;llaliul, complexes which result from the interaction of the carboxyl and nitrogen atoms of the ligand with the manganese cation.
Likewise, the oxidation state of the manganese cation during the catalytic process is not known with certainty, and may be the (+II), (+III), (+IV) or (+V) valence state.
30 Due to the ligands' possible six points of attachment to the manganese cation, it may be reasonably speculated that multi-nuclear species and/or "cage" structures mayexist in the aqueous bleachin~ media. Whatever the form of the active Mn-ligand species which actually exists, it functions in an apparently catalytic manner to provide improved bleaching ,u.,ru--"~ on stubborn stains such as tea, ketchup, coffee, 35 blood, and the like.
Other bleach catalysts are described, for example, in European Pat. App. Pub.
Nos. 408,131 (cobalt complex catalysts), 384,503, and 306,089 (metallo-porphyrin WO 9S/33043 P~ f ''~46 219l~39 catalysls), U.S. 4,728,455 (llI.lll~ Jllllllti~i~nt~tf' ligand catalyst), U.S. 4,711,748 and European Pat. App Pub. No. 224,957, (absorbed manganese on ~l ...,:....~;l;.Alr calalyst), U.S. 4,6QI,~45 (~ll"";",.~;l;,Alr support with manganese and zinc or magnesium salt), U.S. 4,626,373 (Ill~ll~.lll~,./li~all~ catalyst), U.S. 4,119,557 (ferric complex catalyst)~ German Pat. ~ " 2,054,019 (cobalt chelant catalyst) Canadian 866,191 (transilion rnelal-containirlg salls), U.S. 4,430,243 (chelants wilh manganese cations and non-catalytic metal cations), and U.S. 4,728,455 (manganese gluconate catalysts).
If employed in the ~,~",I,.,~;lil",~ and processes herein, the bleach catalysl is used in a calalytically effeclive amounl. By ''calalytically effeclive amount" is meant an amounl which is suffcienl, under whalever comparative test conditions are employed, to enhance bleaching and removal of the stain or stains of interest from the target substrale. Thus~ in a fabric laundenng operalion, Ihe largel substrale will Iypically be a fabric slained wilh, for example, various food slains. ~or automatic ~iailwaall;llg, the largel substrale may be, for example, a porcelain cup or plate with tea stain or a pol~.llyl.,.,e plate slained with tomato soup. The test conditions will vary, depending on Ihe Iype of washing appliance used and the habits of the user.
Thus, front-loading laundry washing machines of the type employed in Europe generally use less water and higher detergenl CO~ ...ldLifJlls than do top-loading 20 U S.-style machines. Some machines have l.~Ul~S;d~.dbl,~ longer wash cycles than others. Some users elect IO use very hol water; others use warm or even cold water in fabric laundering operations. Of course, the catalytic ~.rullllàll~c of the bleach catalyst will be affected by such uulla;d~,ldl;ulla, and the levels of bleach catalyst used in fully-formulated detergent and bleach f,-,l,l",~;l;~...~ can be a,utJlu,ul;a~ adjusted.
25 As a practical matter, and not by way of limitation, the r~,,~il~;l;.~~ and processes herein can be adjusled to provide on Ihe order of al leasl one part per len million of the active bleach calalysl species in the aqueous washing liquor, and will preferably provide from aboul 0.1 ppm IO aboul 700 ppm, more preferably from aboul I ppm toabout 500 ppm, of Ihe catalysl species in the laundry liquor. To illustrale this point further, on the order of 3 micromolar manganese catalyst is effective al 40C, pH 10 under European conditions using perborate and a bleach activator (e.g., benzoyl u~,ulula~,Lalll). An increase in uull.~llLIdL;ull of 3-5 fold may be required under U.S.
conditions to achieve the same resulls. Conversely, use of a bleach activator and the manganese calalysl with perborate may allow Ihe formulator to achieve equivalenlbleaching al lower perborale usage levels Ihan products wilhout the man~anese catalysl.
A,djunct In~rediems - P ., l / ~
~11, wos5/33043 2 1 9 l 4 3 9 The . ~ herein can optionally include one or more other detergent adjunct materials or other materials for assisting or enhancing cleaning ~ ru~l.,a"~.
treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent - rC~mroci~ior (e.g., perfumes. colorants, dyes, etc.). The following are illustrative 5 examples of such adjunct materiais.
- Detçrsive Surf~t~lntc - Nonlimiting examples of optional, detersive surfactants useful in detergent ~ u~ herein typically at levels from about 1%
to about 55%, by weight, include the cu.. l.iu1,41 Cl l-CIg alkyl benzene sulfonates ("LAS") and pnmary, branched-chain and random Clo-C20 alkyl sulfates ("AS"), theClo-C18 secondary (2,3) alkyl sulfates of the formula CH3(CH2)X(CHOSO3-M ) CH3 and CH3 (CH2)y(CHOSO3 M ) CH2CH3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation~
especially sodium, unsaturated suifates such as oleyl sulfate, the Clo-CIg alkylalkoxy sulfates (''AEXS'', especially x up to about 7 EO ethoxy sulfates), C10-C18 alkyl alkoxy c~bu~L~ (especially the EO 1-5 ~llu~yl~ u~l4le5), the C10 18 glycerol ethers, the Clo-C18 alkyl poly~;l,y.,o ,;d~,J and their .,u"c~,u., i;".~ sul&ted pù1~5:~,0~id~,J, and C12-CIg alpha-sulfonated fatty acid esters. If desired, theCull~ iUll~l nonionic and amphoteric surfactants such as the C12-C18 aikyl ethûxylates ("Ai~") including the so-called narrow peaked alkyl ethoxylates and C6-20 C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ~LIIu~y/~lu~Ju~y), C12-CIg betaines and clllfrlb~t~ ("sultaines"), Clo-CIg amine oxides, and the like, can also be included in the overall .,.. 1..,~ The Clo-C18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-Clg N-~ yl~ See WO 9,206,154. Other sugar-derived surfactants 25 include the N-alkoxy polyl~y~i,u~cy fatty acid amides, such as Clo-CIg N-(3-.,,~,.llo,~y~,,u~.~l) glucamide. The N-propyl through N-hexyl C12-C18 glucamides can be used for low sudsing. Clo-C20 u"i~.,Liùl~l soaps may also be used. If high sudsing is desired, the branched-chain Clo-Cl6 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful 30 surfactants are listed in standard texts.
Builders - Detergent builders can optionally be included in the ~.u l~c~:l;....-herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering ..u .~ to assist in the removal of particulate soils.
The level of builder can vary widely depending upon the end use of the ~U...I~ and its desired physical form. When present, the ,,l....l",~:l;.~..c will typically comprise at least about 1% builder. Liquid ru.,l,ul41iu.,s typically comprise , , _ ...... . ....... . ....

~ 5. ~J6 _ w0 9~/33043 2 1 9 1 4 3 9 from about 5% to about 50%. more typicall~ about 5% to about 30%. by weight, of detergent builder. G~anular ~ uldL;ulls typically comprise from about 10% to about 80%, more typically from about 15% to about 50% by weight, of the detergent builder Lower or hir~her levels of builder however, are not meant to be excluded.
Inorganic or P-containing detergent bui~ders include, but are not limited to, the alkali metal~ ammonium and ~ nf)l~mmflni~lm salts of IJulylJllua~ tts (exemplified by the Lli,uulyyl~v~ f;Lc~, p~v~ and giassy polymenc meta-phosphates), r~ v~ r~ phytic acid~ silicates~ carbonates (including i~h,~ ul~cte~
and sesquicarbonates)~ sulphates~ and ~ minfl~ilif~rf~i However~ non-phosphate builders are required in some locales. lmportantly~ the ~ ;f,.,~ herein functionsurprisingly well even in the presence of the so-called "weak" builders (as compared with phosphates) such as citrate~ or in the so-called "u~d~.iJuil." situation that may occur with zeolite or layered silicate builders.
Examples of silicate builders are the alkali metal silicates~ particularly thosehaving a SiO2:Na2O ratio in the range 1.0:1 to 3.Z:I and layered silicates, such as the layered sodium silicates described in U.S. Patent 4~664,839~ issued May 12, 1987 to H. P. Rieck. NaSKS-6 is the trademark fûr a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite buiiders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na2SiOs ",o,yl1ùio~y form of layered silicate. It can be prepared by methods such as thûse descnbed in German DE-A-3,417~649 and DE-A-3,742.043. SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as thûse haYing the general formula NaMSixO2x+l yH2O wherein M is sodium or hydrûgen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein. Various other layaed silicates from Hoechst include NaSKS-5~ NaSKS-7 and NaSKS- I I ~ as the alpha, beta and gamma forms. As noted above, the delta-Na2SiOs (NaSKS-6 form) is most preferred for use herein. Other silicates may also be useful such as for example magnesium siiicate, which can serve as a crispening agent in granular ru""uk.liù,ls, as a stabilizing agent for oxygen bleaches, and as a compûnent of suds control systems.
Examples of carbonate builders are the alkaiine earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
~1 ~ builders are useful in the present invention. Al~ fl-'~
builders are of great importance in most currently marketed heavy duty granular detergent ~u~ J~ . and can also be a significant builder ingredient in liquid ~ wo s~/33043 2 1 9 1 4 3 ~ r~
~9 detergent ru~ h~iol~s. Alllminn~ilinAt~ builders include those haYing the empirical formula.
Mz n[(Aio2)z(sio2)yi xH2O
wherein z and y are integers usual~y of at least 6, the molar ratio of z to y is in ~he range from 1.0 to 0, and x is an integer from 0 to about 264, and M is a Group IA or IIA element, e.g., Na, K, Mg, Ca with valence n Useful ~ ion exchange materials are CU~ ;GIIY available.
These Al~ . A~ can be crystalline or amorphous in structure and can be naturally-occurring ~IIlmin~ t~ or synthetically derived. A method for producing A~ ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline Alllminn~ t~- ion exchange materials useful herein are available under the Zeolite A, Zeolite P (B), Zeoiite MAP and Zeolite X. In an especially preferred l~mhodim~nt, the crystalline Al~lmin~ ' ion exchange materia~ has the 1 5 formula:
Nal2[(AiO2)12(siO2)l2] xH2o wherein x is from about 20 to about 30, especially about 2?. This material is known as Zeolite A. Dehydrated zeoiites (x = 0 - 10) may also be used herein. Preferably, the ~11", J~ lr has a panicle si2e of about 0.1-10 microns in diameter.
Organic detergent builders suitable for the purposes of the present invention include, but are not restncted to, a wide variety of pùlr.G,i,uAylate romrmln~ As used herein, "polycarboxylate" refers to compounds having a piurality of carboxylate groups, preferably at least 3 ~,G~iJùAylGI~s. rol~GIiJuAylGlc builder can generally be added to the ~ ù~ l;o.~ 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, or: " ~ ' salts are preferred.
Included among the pUI~.GliJUA~lGie builders are a variety of categories of useful materials. One important category of pUI,r~,Gli~VA~l~le builders . u ~
the ether pcl~,GIi)uA,~lGLes~ including oxydi~r~in~t~ as disclosed in Berg, U.S.Patent 3,128,287, issued April ;t, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued lanuary 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et ai, on May 5, 1987. Suitable ether pOI,~.,GliJUA~lGLcs also include cyclic cnmrolln~ particularly alicyclic nn~nrollnrl~ such as those described in U.S.
Patents 3,923,6~9; 3,835,163 4,158,635 4,120,874 and 4,102,903.
Other useful detergency builders include the ether I~iIUAY~JUI~I~G~iJUA~ , copolymers of maieic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and ~,GliJUA~ lVAysUccinic acid, the _ , , ,, , . . . . .. .. .. .. . .... , ...... _ . . _ .. _ .. .... . _ _ _ , w0 95/33043 2 1 9 1 4 3 ~ J r ~ 796 ~
~o various alkali melal, ammonium and substituted ammonium salts of polyacetic acids such as eth~'~.,.d;a",;"e tetraacetic acid and ";i,;lo~ L;c acid, as well as polyc~,i,u,~ es such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3~5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble 5 salts thereof Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biOd~ iaiJ;!;~y. Citrates can also be used in granular ~ ;n,~, especiaily in 10 I"...I,;",.I;n,l with zeolite and/or layered siiicate builders. O~.y l;~ are also especially useful in such ~u~yO~ iùll~ and ~
Aiso suitable in the detergent cn ..l.o~ of the present invention are the 3,3-dicarboxy-4-oxa-1,6-h~ in`rr~ and the related compounds disclosed in U.S.
Patent 4,566,984, Bush, issued lanuary 28, 1986. Useful succinic acid builders include the Cs-C20 alkyl and alkenyl succinic acids and salts thereof A particuiarly preferred compound of this type is dod~.,c,.j;~J.,.,;,,;c acid. Specific examples of succinate builders include: làul~ial.ll,l,;llalr, ~ l;a~p ' ', palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-y.,,~L~ lyl~ t., and the like.
Laulyl~uL~ al~ are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
Other suitabie puly~lui)uAylai~ are disclosed in U.S. Patent 4,1447226, Crutchfield et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. See also Diehl U.S. Patent 3,723,322, Fatty acids, e.g., C 12-C 18 lllvllvl~ali/uAylic acids such as oleic acid and/or its salts, can also be incu,yuld~cd into the ~.u l o~ - alûne, or in I ~ ; with the aforesaid builders, especially citrate and/or the succinate builders, to provide additional builder activity. Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
In situations where phosphorus-based builders can be used, and especially in the forrnulation of bars used for hand-laundering operations, the various alkali metai phosphates sueh as the well-known sodium il ;yvl,yr l 1 l ' , sodium ~ " ' , ' and sodium ul~ Jlllln~ Alr can be used. PllO~yl~vll~lle builders such as ethane-l-hydroxy-l,l-~lit,l~ .~1,l..,..~l~ and other known 1~ (see, for example, U.S.
Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be 35 used.
~ Ym~ - Enzymes can be included in the ru~ uk~ivlls herein for a wide variety of fabric laundering purposes, including removal of protein-based, ~ woss/33043 21 91 439 r~ s ~1 carbohydrate-based, or Iri~lyceride-based stains, for example, and for the preYention of refugee dye transfer, and for fabric resloration. The enymes to be in.,u~l~ù~dltd include proteases, amylases. Iipases~ cellulases, and peroxidases, as well as mixtures thereof Other types of enzymes may also be inciuded. They may be of any suitable5 origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity and/or stability optima, .,l,uaLdbili~, stability versus active detergents, builders and so on. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
Enymes are normally ia~,u~l~ù~led at levels sufficient to provide up to about 5 mg by weight, more typically about 0.001 mg to about 3 mg, of active enzyme per gram of the c~ Joa;l;ull. Stated otherwise, the ..,. ~ herein will typically comprise from about 0.001% tO about 5%, preferably 0.01%-2% by weight of a commercial enzyme preparation Protease enymes are usually present in such commercial ~,";~.d,dt;o.,s at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of ~ .. ,,, ,1 ~fJ~;I ;u"
Suitable examples ûf proteases are the subtilisins which are obtained from panicular strains of B. subtilis and B. I;Lh~ ;ru~la. Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH r4nge 20 of 8-12, developed and sold by Novo Industries A/S under the registered trade name ESPEi~ASE. The preparation of this enzyme and analogous enzymes is described in British Patent srP. ifi~ ~ifln No. 1.243,784 of Novo. Proleolytic enzymes suitable for removing protein-based stains that are commercially available include those soldunder the tradenames ALCAi_ASE and SAViNASE by Novo Industries A/S
25 (Denmark) and MAXATASE by IlllellldliUlldl Bio-Synthetics, Inc. (The N~ "ld..~is). Other proteases include Protease A (see European Palent Application 130,~56, published lanuary 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130,756, Bott et al, published lanuary ", 1985). Other proteases include Protease A (see European Patent Applicalion 130,756, published lanuary 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130,756, Bott et al, published lanuary 9, 1985) Other proteases include Protease A (see European Patent Application 13û,756, published lanuary 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130,756, Bott et al, published January 9, 1985). Most preferred is what is called herein "Protease C", which is a vanant of an alkaline serine protease from .. .... . .. . . .. _ . _, . . _ . _ . _ _ . . .. . . ..

wo 95/33043 1 ~ 7q6 21 ql 439 Bacillus, particularly Bacillus IPntll~ in which arginine replaced Iysine at position 27, tyrosine replaced valine at position 104~ serine replaced asparagine at position 123, and alanine replaced threonine at position 274. Protease C is described in EP
90915958:4; U.S. Patent No. 5,185,250; and U.S. Patent No. 5,204,015. Aiso preferred are protease which are described in copending application U.S. Serial No.
08/136,797, entitled Protease-containing Cleaning C~ and copending Application U.S. Serial No. 08/136,626, entitled Bleaching C'~"'l"J`;I;""` Comprising Protease Enzymes. which are incorpora~ed herein by reference. Genetically modified variants. particularly of Protease C, are also ;ncluded herein.
Amylases include, for example, a-amylases described in British Patent ~p~PAifiAAtinn No. 1,296,839 (Novo), RAPIDASE, Ill~elllG~ Gl Bio-Synthetics, Inc.
and TERMAMYL, Novo Industnes.
The cellulase usable in 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, which discloses fungal celluiase produced from Humicola insolens and Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the 1~ G~ of a marine mollusk (Dolabeila Auricula Solander). suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.2~5 and DE-OS-2.247.832. CAREZYME ~Novo) is especially useful.
Suitable lipase enzymes for detergent usage include those produced by ";.,, UUI~;GI~ of the p~ A~ group, such as pSP"t~om~nA~ stutzeri ATCC
19.154, as disclosed in British Patent 1,372,034. See also lipases in Japanese Patent Application 53,2048i, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pl,G,,,,A.,~ui;~,Gl Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter referred to as "Amano-P." Other commercial lipases include Amano-CES, lipases ex ClllulllO~ctèl viscosum, e.g.
Cluù~l~u~G~,Iel viscosum var. Iipolyticum NRRLB 3673, ~u,,.,,.~ , available fromToyo Jozo Co., Tagata, Japan; and further Clllullluba.,lel viscosum lipases from U.S.
Bio~AhPmiAAI Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex r, .. l... ,~ ~ gladioli. The LIPOLASE enzyme derived from Humicola lanuginosa and .,u.. ,.~ available from Novo (see also EPO 341,947) is a preferred lipase for use herein.
35 Peroxidase enzymes are used in ~,~.",1,;.. 1;,~.~ with oxygen sources, e.g., u~.uG~bull_le, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from ~ wo g5/33043 2 1 9 1 4 3 9 ~ 96 substrates during wash operations to other substrates in the wash solution.
Peroxidase enzymes are known in the an, and include, for example, horseradish peroxidase, ligninase, and llaloi,~.u~ se such as chloro- and bromo-peroxidase.
Peroxidase-containing detergent ~,u~ o~;~ioll~ are disclosed, for example, in PCT
International Application WO 89/099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A S. It may be desired to use, in . u l.: ~l;.... with these peroxidases, materials viewed as being peroxidase ~ such as .l~ rùll~p and/or p~'f '~ l A';llf' A wide range of enzyme materials and means for their ;II~.UIlJUI~:L;OI~ into synthetic delergem ~u,,,ll~l~;l;nllc are also disclosed in U.S. Patent 3,553,139, issued January 5, 1971 to McCarty et al. Enzymes are funher disclosed in U.S. Patent 4,101,457, Place et al, issued luly 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued March 26, 1985, both. Enzyme materials usefiul for liquid detergent l'ul~ lflL;u~s, and their ;ncùl~.ol~L;u,l into such ;u~..d~Liu~l~, are disclosed in U.S.
Patent 4,261,868, Hora et al, issued April 14, 1981. Enzymes for use in detergents can be stabilized by various techniques. Enzyme ' ' .. techniques are disclosed and exemplified in U.S. Patent 3,600,319, issued August 17, 1971 to Gedge. et al, and European Patent Application Publication No. 0 199 405, Application No. 86200586.5, published October 29, 1986, Venegas. Enzyme ' "' systems are also described, for example, in U.S. Patent 3,519,570.
Enzyme Stabilizers - The enzymes employed herein are stabilized by the presence of water-soluble sources of calcium andffor magnesium ions in the finished c.. l.. ,~:l;~.. ,~ which provide such ions to the enzymes. (Calcium ions are generaily somewhat more effective than magnesium ions and are preferred herein if oniy one25 type of cation is being used.) Additional stability can be provided by the presence of various other art-disclosed stabilizers, especially borate species: see Severson, U.S.
4,537,706. Typical detergents, especially liquids, will comprise from aboul I IOabout 30, preferably firom about 2 to about 20, more preferably from about 5 to about 15, and most preferably from about 8 to about 12, millimoles of calcium ion 30 per liter of finished ,,i,..,l.n~;l ;u~ ~ This can vary somewhat, depending on the amount of enzyme present and its response to the calcium or magnesium ions. The level of calcium or ma~nesium ions should be selected so that there is always some minimum Ievel available for the enzyme, after allowing for ~ I;nl~ wilh builders, fally acids, etc., in the rclmrn~itinn Any water-soluble calcium or magnesium salt can be 35 used as the source of calcium or magnesium ions, including, but not limited to, caicium chloride, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, caicium formale, and caicium acetate, and the UUI~C:~f~Ull~i;ll~ magnesium . 5 ~ ~

219143~

salts A small amount of calcium ion, generally From about 0.05 to about 0.4 millimoles per liter~ is often also present in the composition due to calcium in the enzyme slurry and formula water In solid detergent ~u~ u~;L;OllS the formu~ationmay include a suffcient quantity of a water-soluble calcium ion source to provide 5 such amounts in the laundry liquor. In the alternative, natural water hardness may suffice.
It is to be understood that the foregoing leveis of calcium and/or magnesium ions are suffcient to provide enzyme stability. More calcium and/or magnesium ions can be added to the compositions to provide an additional measure of grease removal 10 p..l`u~ Accordingly, as a general proposition the ro~ c herein will typically comprise from about 0.05% to about 2% by weight of a water-soluble source of calcium or magnesium ions, or both. The amount can vary, of course, with the amount and type of enzyme employed in the c. ,".l ,. ,~
The ~...,..I..I~;I;I~,~c herein may also optionally, but preferably, contain various 15 additional stabilizers, especially borate-type stabilizers. Typically. such stabilizers will be used at levels in the ,:.-.,,,1l,-~;l;~ from about 0.25% to about 10%, preferably from about 0.5% to about 5%, more preferably from about 0.75% to about 3%, by weight of boric acid or other borate compound capable of forming boric acid in the f ~ ;.:," (calculated on the basis of boric acid). Boric acid is preferred, although 20 other compounds such as boric oxide, borax and other alkali metal borates (e.g., sodium ortho-, meta- and pyroborate, and sodium LJ.,.IL~UI~ ) are suitable.
Substituted bonc acids (e.g., ,uh~ bù-u"h, acid, butane boronic acid, and p-bromo ul u..h, acid) can also be used in place of boric acid. It is to be recognized that such materials may also be used in rull"ulaliù.ls as the sole stabilizer as well as being used in ~ l with added calcium and/or magnesium ions.
Finally, it may be desired to add chlorine scavengers, especially to protease-containing ~.'''''I''J`;I;''''~. to protect the enzymes from chlorine typically present in municipai water supplies. Such materials are described, for example, in U.S. Patent 4,810,413 to Pancheri et al.
Polvmeric Soil Release A,~rnt - Any polymeric soil releâse agent known to those skilled in the art can optionally be employed in the ,ùlll~Ju~;Liu..a and processes of this invention. Polymeric soil release agents are cl~ ,L~ by having both hydrophilic segments, to lly ilu,ul~ the surface of l~rJ~u~ ùl);c fibers, such as polyester and nylon, and hyJlu~,l,ub;. segments, to deposit upon I~J~u~ ùb;~, fibers 35 and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for ~he hydrophilic segments. This can enable stains -WO9S/33043 2 1 9 4 3 .~I/1~ ~. .,~
.
~s occurring subsequent to treatment with the soil release asent to be more easily cleaned in later washin~ procedures.
The polymeric soil release agents useful herein especially include those soil release agents having: (a) one or more nonionic hydrophile .u"~ consisting 5 essentially of (i) polyoxyethylene segments with a degree of poly"~ L;u~ of at least 2, or (ii) oxypropylene or polyu,~y,ulup~ e segments with a degree of pu~ -t;oll offrom 2 to lû, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages. or (iii) a mixture of oxyalkylene units compnsing oxyethylene and from I to lû about 30 oxypropylene units wherein said mixture contains a suff~cient amount of oxyethylene units such that the hydrophile component has l~ u~ y great enough to increase the hyilul~ll;l;~;~y of ~ù"~.,.io"~l polyester synthetic fiber surfaces upon deposit of the soil release agent on such surface, said hydrophilesegments preferably comprising at least about 25% oxyethylene units and more 15 preferably, especialiy for such cc."",o,~ having about 20 to 30 oxypropylene units, at least about 50% oxyethylene units; or (b) one or more hydrophobe comprising (i) C3 oxyalkylene ~el~ ' ' segments, wherein, if said l,~.u~l,ul,c also comprise oxyethylene telt,ul~ tc, the ratio of o~y.,.l.,y~
lel~,uh~ d~ .C3 u~ k,..e lele~lltllGldt~ units is about 2:1 or lower, (ii) C4-C620 alkylene or oxy C4-C6 alkylene segments, or mixtures therein, (iii) poly (vinyl ester) segments, preferably polyvinyl acetate), having a degree of pul~ ...~. ;~;u.~ of at least 2, or (iv) Cl-C4 alkyl ether or C4 hydroxyalkyl ether c l,~ , or mixtures therein, wherein said cllhc-itll~ntc are present in the form of Cl-C4 alkyl ether or C4 hydroxyalkyl ether cellulose derivatives, or mixtures therein, and such cellulose 25 derivatives are ;lmrhir~ whereby they have a sufficient level of C l-C4 alkyl ether and/or C4 hydroxyalkyl ether units to deposit upon Cùl;~'~...;ullal polyester synthetic flber surfaces and retain a suffcient level of hydroxyls, once adhered to such Cull~...,;olldl synthe~ic fiber surface, to increase fiber surface hyd,l r'`'` ` y, or a of (a) and (b).
Typically, the pol,~ù~ l.. = segments of (a)(i) will have a degree of pùl~ iul. of from 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 hJd,.r' ': ~ segments include, but are not limited to, end-caps of polymeric soil release agents such as MO3S(CH2)nOCH2CH2O-, 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.

WO 9~/33043 r~ .'t '~6 21~143q Polymeric soil release agents useful in the present invention also include cellulosic denvatives such as hydroxyether cellulosic polymers~ ~ulJuiJ~ ,.h, blocks of ethylene terephthalate or propylene t~ JllL1141~ with polyethylene oxide or polypropylene o.YIde terephthalate~ and the like. Such agents are .. ".. ~.,,;~11 5 available and include hydroxyethers o~` cellulose such as METHOCEL (Dow).
Cellulosic soil release agents for use herein also include those selected from the group consisting of Cl-C4 aikyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4~000,093~ issued December 28, 1976 to Nicol~ et al.
Soil reiease agents .lla..~ ;i by poly(vinyl ester) hydrophobe segments include graft copoiymers of poly(vinyl ester~ e.g.~ Cl-C6 vinyl esters~ preferably poly(vinyl acetate),grafted onto polyalkylene oxide backbones~ such as polyethylene oxide backbones. See European Patent Application 0 219 048. published April 77~
1987 by Kud, et al; CO,,.I.l~ y available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF
(West Germany).
One type of preferred soil release agent is a copolymer having random blocks of ethylene tc, c~ LI~41ilLc and polyethylene oxide (PEO) Ltl C~hLI1~l4LC. The moiecular 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~ 1976 and U.S.
Patent 3,893,929 to Basadur issued luly 8, 1975.
Another preferred polymeric soil release agent is a polyester with repeat units of ethylene ~c,~ l.Lh414Le units contains 10-15% by weight of ethylene ~cle~ l4141è
units together with 90-80% by weight of pol~uA~.l,yl.nc Lel t~,htl,414~c units, derived from a pol) u,~y~h~;.,..~ glycol of average molecular weight 300-5,000. Examples of 25 this polymer include the .u.,i.,.,' "y available material ~:ELCON 5126 (hrom Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
Another preferred polymeric soil release agent is a sulfonated product of a linear ester oligomer comprised of an oligomenc ester backbone of tcl~,' ' ' yl and u~llk.~h,.~ y repeat units and terminai moieties covaiently attached to the backbone. These soil release agents are descnbed fully in U.S. Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Other suitable polymeric soil release agents include the terephthalate polyesters of U.S.
Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic end-capped olisomeric esters of U.S. Patent 4,721,580, issued lanuary 26, 1988 to Gosselink. and the block polyester oligomenc compounds of U.S. Patent 4,702,857,issued October 27~ 1987 to Gosselink.
_ ~ wo ss/33043 2 1 9 1 4 3 9 . ~1/1)~,5~ '746 Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which discloses anionic, especially sulfoarolyl, end-capped terephthalate esters.
Still another preferred soil release a~ent is an oligomer with repeat units of 5 terephthaloyl units, sul~u;auttlt~ Lll~loyl units, oxyethyleneoxy and oxy-1,2-propylene units. The repeat units form Ihe backbone of the oligomer and are preferably terminated with modified isethionate end-caps. A particularly preferred soil release agent of this type comprises about one ~l~lruisu~ Jyl unit, 5 It~tr' ' ' yl units, oxyethyleneoxy and oxy-1,2-~,lu~ units in a ratio offrom lû about 1.7 to about 1 8, and two end-cap units of sodium 2-(2-hy i,u~ll,u,~
p~h~no~lllfi.n~ Said soil release agent also comprises from about û.5% to about 2û%, by weight of the oligomer, of a crystalline-reducing stabilizer, preferablyselected from the group consisting of xylene sulfonate, cumene sulfonate. toluene sulfonate, and mixtures thereof If utilized, soil release agents will generally comprise from about û.ûl% to about 10.0%, by weight, of the detergent ,.u ~ herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0%.
(~hPl~tiT~p ,~Pnr~ - The detergent ~u~ u~ herein may also optionaliy contain one or more iron and/or manganese chelating agents. Such chelating agents 20 can be selected from the group consisting of amino carboxylates, amino u"AIrc polyf r "~ substituted aromatic chelating agents and mixtures therein, 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 exceptionai ability to remove iron and manganese ions from washing solutions by formation of soluble 25 chelates.
Arnino carboxylates useful as optionai chelating agents include cLh~ .,c1~1t~ T ~ u~ ylethy' '' ' i~,e1a~ta, nitrilotri-acetates, eth~ ..r ~ u~ ,lhJI~ ... h. .~ "
diethylene-l~i- ,.;.,. ~.. .".-- ~:~lrs. and clll~l,ol~i;~l,y~.;l,~,O, alkali metal, ammonium, and 30 substituted ammonium salts îherein and mixtures therein.
Amino ~ are also suitable for use as chelating agents in the .,1,l,.,.:l;,...~ of the invention when at lease low levels of total phosphorus are permitted in detergent ~- I.n~;l;.~..: and include c~h,~ is ~ ,til~ ) as DEQUEST. Preferred, these amino ,"1~ to 35 not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
Pol,y5.r ' "~ ~ubstituted aromatic chelating agents are also useful in the herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et WO 95/33043 2 ~ q 1 ~ 3 9 PCT/lJsgS/06296 al. Preferred compounds of Ihis type in acid form are dih~, i. u~y, l;c, ,Ir..~.., ,.... ~ such as 1,2-dihydroxy-3,5-disulfobenzene.
A preferred biodegradable chelator for use herein is ethyl."~i;G"u.,~:
disuccinate ("EDDS''), especially the [S,S~ isomer as described in U.S. Patent 4,704,233. November 3, 1987, to Hartman and Perkins.
If utilized, these chelatinQ agents will generally comprise from about 0.1% to about 10% by weight of the detergent cu~,uo~iùlls herein More preferably, if utilized, the chelating agents wiil comprise from about û. 1% to about 3.0% by weight of such Culll~Jùa;liul1S.
Clav Soil i3~emova~Anti-redeeosition Ar~ents - The ~ of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and GIILilc ii~ u~;liull properties. Granular detergento~ which contain these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylates amines; liquid detergent ~ C typically contain about 0.01% to about 5%.
The most preferred soil reiease and anti-lc i,,~u~;l;o-l agent is ethûxylated h~ r ' ' Exemplary ethoxylated amines are further described in U.S.
Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred c~ay soil removal-G~Ilil c~ ,o~;liù.~ agents are the cationic compounds disclosed in 2û European Patent Application I i 1,9(55, Oh and Gosselink, published lune 27, 1984.
Other clay soil remov~ G..~ d~,po~;liùn agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the ~;.lcl;ol.;~ polymers disclosed in European Patent Application 112,592. Gosselink. published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985. Other clay soil removal and/or anti l~ Jua;l;ùll agents known in the art can also be utilized in the ..~,".r~ r. herein. Another type of preferred Gllli~ U~;.iUIl agent includesthe carboxy methyl cellulose (CMC) materials. These materials are well known in the an.
Polvmeric i~isi~ersin~ A~ents - Polymeric dispersing agents can adY _ )u~ly be utilized at levels from about 0.1% to about 7%, by weight, in theu ~ herein. Suitable polymeric dispersing agents include polymeric i~UIy~.GliJU~.~lGl~s and polyethylene glycols, although others known in the art can also be used.
Polymeric polycarboxylate materials can be prepared by ~Jol~ .iL;.. ~ or cupol~ ;ll3 suitable unsaturated monomers, preferably in their acid form.
Unsaturated monomeric acids that can be pUI~.ll",;L~;i to form suitable polymeric ~IV09s/33043 2191~39 .
~9 poly~4.1,0~k,Lt, include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methyl~ ' ' acid. The presence in the polymeric polycarboxylates herein or monomeric segments, containing no carboxylale radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight Panicularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are usefui herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from about '2,000 to 1~,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and subslituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent ~ o~ has been disclosed, for example, in Diehl~ U.S. Patent 3,308,067, issued March 7, 1967.
Acrylic/maleic-based copolymers may also be used as a preferred component of the dia~J~"a;l~ o~iiiùll agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000. A
preferred copolymer has an average molecular weight of about 2,000 to 15,000, more preferably about 6,000 to about 13,000, and most preferably about 7,000 to about 12,000. Other preferred copolymers have an average molecular weight from about 5,000 to 75,000, most preferably from about 7,000 to 65,000. The ratio of acrylate to maleate segments in such copolymers will generally range from about 3o:ltoaboutl:2~morepreferablyfromaboutlo:ltol:l~andmostpreferablyabout 2,5:1 to 1 1. Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts.Soluble 41_1yl~;1,1/ ' ' copolymers of this type are known materials which are described in European Patent Appiication No. 66915, published December 15, 1982,as well as in EP 193,360, published September 3, 1986, which also describes suchpolymers comprising l-yd~u~ u~Jylacrylate Still other useful dispersing agents include the ' ' '~ yli~/~hlyl alcohol L~ ,. a. Such materials are also disclosed in EP 193,360, including, for example, the 45145~10 terpolymer of G.,.yl;~..~l.h,/~rinyl alcohol.
Panicularly preferred dispersant polymers are low molecular weight modified ~ul~ h ~ copolymers. Such copolymers contain as monomer units: a) from about 90% to about 10%, preferably from about 80% to about 20% by weight acrylic acid w0ss/33043 . r~ J.. Cî-~q6 or its saits and b) from about 10% to abou~ 90%~ preFerably from about 20% to about 80% by weight of a substituted acrylic monomer or its salt and have the general formula -[(C(R2)C(RI)(C(o)oR3)]- wherein the incomplete valencies insidethe square braces are hydrogen and at least one of the substituents Rl, R2 or R3, 5 preferably Rl or R2, is a I to 4 carbon alkyi or hydroxyalkyl group, Rl or R2 can be a hydrogen and R3 can be a hydrogen or alkali metal salt. Most preferred is a substituted acrylic monomer wherein R I is methyl, R2 is hydrogen and R3 is sodium.
The low molecular weight pulya~ly;~lc dispersant polymer preferably has a molecular weight of less than about 15,000, preferably from about 500 to about 10,000, most preferably from about 1,000 to about 5,000. The most preferred polyacrylate copolymer for use herein has a molecular weight of 3500 and is the fiully neutralized form of the polymer comprising about 70% by weight acrylic acid and about 30% by weight methacrylic acid.
Other suitable modified poiyacrylate copolymers include the low molecular 15 weight copolymers of unsaturated aliphatic carboxylic acids disclosed in U.S. Patents 4,530,~66, and 5,084,535, both i,~.,.al~.ol~lltd herein by reference.
Ag~;lOIIl~,alcd forms of the present invention may empioy aqueous solutions of polymer dispersants as iiquid binders for making the a~;lvlll~dlC (particularly when the ~..,,.1,..~;ll.~.l consists of a mixture of sodium citrate and sodium carbonate).
Especially preferred are polyacry~ates with an average molecular weight of from about 1,000 to about 10,000, and a~,~lG~t/,.,~lc~ or acrylate/ fumarate copolymers with an average molecular weight of from about 2,000 to about 80,000 and a ratio of acrylate to maleate or fumarate segments of from about 30:1 to about 1:~. Examples of such copolymers based on a mixture of unsaturated mono- and dh,~ u~.y;
monomers are disclosed in European Patent Application No. 66,915, published December 15, 1982, ir,.,ul~Jul~lt~;i herein by reference.
Other dispersant polymers useful herein include the pol,~ .,c glycols and polypropylene glycols having a molecular weight of from about 950 to about 30,000 which can be obtained from the Dow Chemical Company of Midland, Michigan.
Such compounds for example, having a melting point within the range of firom about 30 to about 100C can be obtained at molecular weights of 1450, 3400, 4500, 6000, 7400, 9500, and 20,00û. Such compounds are formed by the pol~ .u., of ethylene glycol or propylene glycol with the requisite number of moles of ethylene or propyiene oxide to provide the desired molecular weight and melting point of therespective po~."h,~h".~, glycol and pol~,.ul.~L,.It, glycol. The pOlr~h~
pol,~"u~ , and mixed glycols are referred to using the formuia ~ WO 95/33043 2 1 q 1 4 3 9 . ~ ~ M ''96 HO(CH2CH2O)m(CH~CH(CH3)O)n(CH(CH3)CH2O)oH wherein m, n, and o are integers satisfying the molecular weight and temperature requirements given above.
Yet other dispersant polymers useful herein inciude the cellulose sulfate esterssuch as cellulose acetate sulfate~ cellulose sulfate, hydroxyethyl cellulose sulfate~
S methylcelluiose sulfate, and hydroxypropylcellulose sulfate. Sodium cellulose sulfate is Ihe most preferred polymer of this group Other suitable dispersant polymers are the carboxylated poi~,d~ .id~, particulariy starches, celluloses and alginates~ described in U.S. Pat. No. 3,723,322, Diehl, issued Mar. 27, ] 973, the dextrin eslers of polycarboxylic acids disclosed in U.S. Pat. No. 3,929,107, Thompson, issued Nov 11, 1975; the hydroxyalicyl starchethers, starch esters, oxidized starches, dextrins and starch hydrolysates described in U.S. Pat No. 3~803,285~ Jensen, issued Apr. 9~ 1974; the carboxylated starches described in U.S. Pat. No. 3.629,121, Eldib, issued Dec. 21, 1971; and the dextrin starches described in U.S. Pat. No. 4,141,841, Mci1~anaid, issued Feb. 27, 1979; all 15 i,..,u,~u,4ted herein by reference. Preferred cellulose-derived dispersant polymers are the carboxymethyl celluloses.
Yet another sroup of acceptable dispersants are the organic dispersant polymers, such as ~JUi~ I Ld~e.
Another polymeric material which can be included is polyethylene glycol 2û (PEG). PEG can exhibit dispersing agent ~ ru~ an~,~ as well as act as a clay soil removal-~ ;,ed~,o,;L;u" agent. Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.
rOI~ l Idle and polyglutamate dispersing agents may also be used, 25 especially in conjunction with zeolite builders. In ~,~,",~ c containing detergent builders, it is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhanc~ overall detergent builder p~
especially zeolite and/or silicate builders, when used in, I' ' with other builders (including lower mûlecular weight polycarboxylates) by crystal growth 30 inhibition, particulate soil release peptization, and anti-~ ;.." Dispersing agents such as p~ J411dLe preferably have a molecular weight (avg.) of about lû,OOO.
Briithtener - Any optical brighteners or other brightening or whitening agents - icnown in the art can be .. ~.,ul,~oldled at levels typically from about 0.05% to about 35 1.2%, by weight, into the detergent rcmrociti~n~ herein. Commercial optical bri~hteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, .. _ . _ _ . _ _ . ... .. . . . . ... .. ., . .. .... . .. .. _ ........ _ _ woss/33043 2 1 9 1 ~39 P~l~u~'(''~q6 ~
3~
pyrazoline, coumarin, carboxylic acid. methinecyanines, .1ll,. ..,,,11l;1,ll. ,~-5,5-dioxide, azoles, 5- and 6-membered-ring hererocycles, and o~her micr~llAn~r,llc agents.
xamples of such brighteners are disclosed in "The Production and Application ofFluorescent Bnghtening Agents", 1~l. Zahradnik, Published by lohn Wiley & Sons, 5 New York ( 1982).
Specific examples of optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1 9gg. These brighteners include the PHORWHITE senes of bnghteners from Verona Other brighteners disclosed In this reFerence include:
10 Tinopal UNPA~ Tinopal CBS and Tinopal 5BM, available from Ciba-Geigy; Artic White CC and Artic White CWD. available from Hilton-Davis, located in Italy; the 2-(4-stryl-phenyl)-2H-napthol[1,2-d]triazoles; 4,4'-bis- (1,2,3-triazol-2-yl)-stil- benes;
4,4'-bis(stryl)bisphenyls, and the A..~ u,...A i"s. Specific exampies of these brighteners include 4-methyl-7-diethyl- amino coumarin; 1,2-bis(~ ;.,.;Jr,ul-2-yl)ethylene; 1,3-diphenyl-phrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-stryl-napth-[1,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho- [1,2-d]triazole. See also U.S. Patent 3,646,015, issued February 29, 19~2 to Hamilton Anionic brighteners are preferred herein.
,r~llri~ Suvvrr~r~rs - Compounds for reducing or suppressing the formation of 20 suds can be il.cu,~.u._l~d into the .~ of the present invention. Suds suppression can be of particular importance in the so-called ~high Illl _ :lAl;..ll cleaning process" as described in U.S. 4,489,455 and 4,489,574 and in front-loading European-style washin~ machines.
A wide variely of materials may be used as suds suppressors, and suds 25 suppressors are well known to those skilled in the art. See, for example, Kitk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category of suds suppressor of particular interest e ~ Illull.a~,rl~u,.~lic fatty acid and soluble salts therein. See U.S.Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The 30 ,I,onocr~.l,u~l;c fatty acids and salts thereof used as suds suppressor typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms, Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts~ and ammonium and " ' saits, The detergent ~...r.,l.r~;.;....~ herein may also contain non-surfactant suds 35 suppressors. Theseinclude, for example: high molecularweight l~ u~ u,.~ such as paraffin, fatty acid esters (e.g., fatty acid ~ ;d~), fatty acid esters of monovalent alcohols, aliphatic Clg-C40 ketones (e.g., stearone), etc. Other suds W095~33043 ~ ~ 91 4 3 9 .~.,, r'7q6 r inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine ~ lul ~l;a~ formed as products of cyanuric chloride with Iwo or lhree moles of a primary or secondary amine containing I to 24 carbon atoms, propylene oxide, and Illu~lost~yl phosphates such as monostearyl alcohol phosphate 5 ester and monostearyl di-alkali metal (e.g., K~ Na, and Li) phosphates and phosphate esters. The hydrocarbons such as paraffin and l~lu~ dir~ can be utilized in liquid form. The liquid hydrocarbons will be liquid at room temperature and ~LL,..ualul.F.ic pressure~ and will have a pour point in the range of about -40C and about 50C, and a minimum boiling point not less than aboul 110C (d~lllua~ ,i., pressure). It is also 10 known to utilize waxy hydrocarbons, preferably having a melting point below about 100C. The hyd,u~ u.,a constitute a preferred category of suds suppressor for detergent ~ c Hydrocarbon suds au~J~Icaaula are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. The llydlul,~ ulla, thus, include aliphatic~ alicyclic~ aromatic, and heterocyclic saturated or unsaturated 15 hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffn,"
as used in this suds suppressor discussion, is intended to include miYtures of true paraffinsand cyclic l~ uu~ ul-~.
Another preferred cate~ory of non-surfactant suds Su~J,ulcaaula comprises silicone suds suppressors. This category includes the use of pulyu,v-.,r~ oils, 20 such as polyd;ll..,~ lailo~ ..e, dispersions or emulsions of pol,yul~ oils or resins, and ~ c of polyul. ,",.. ~ .F with silica particles wherein the polyu.y,,~ r)Y~n~ is cll~,.ll;auliJFd or fused onto the si~ica. Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No. 89307851.9, published February 7, 199û, by Starch, M. S.
Other silicone suds suppressors are disclosed in U.S. Patent 3,455,839 which relates to .: u l u~ and processes for defoaming aqueous solutions by ill~,ul~Jul a~ therein small amounts of pc,l~l;l.l~,.llyl~ ' fluids.
Mixtures of silicone and silanated silica are described, for instance, in GermanPatent Application DOS 2,124,526. Silicone defoamers and suds controlling agentsin granuiar detergent .. ~ 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 suppressin~ amount of a suds controlling agent consisting essentially of (i) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about 1,500 cs. at 25C;

-WO 95/33043 P~
2191~9 (ii) froni about j to about S0 parts per 100 parts by weight of (i) of siloxane resin composed of (CH3)3SiOI/7 units of SiO7 units in a ratio of from (CH3)3 SiOI/7 uni~s and to SiO2 units of from about 0.6:1 to about 1.7:L, and (iii) froni about I to about 20 parts per 100 parts by weight of(i) of a solid silica gel.
In the preferred silicone suds suppressor used herein, the solvent for a continuous phase is made up of cenain polyethylene glycols or polyethylene-pol~ ",yle..~ glycol copolymers or mixtures thereof (preferred), or polyp,~
10 glycol. The primary silicone suds suppressor is branched/crosslinked and preferably not linear.
To illustrate this point further, typical liquid laundry detergent ~ ; ;ol ~
with controlled suds will optionally comprise from about 0.001 to about 1, preferably from about 0.01 to about 0.7, most preferably from about 0.0S to about 0.5, weight 15 % of said silicone suds suppressor, which comprises (1) a r~ u~ emulsion of aprimary antifoam agent which is a mixture of (a) a pol~u~ ., (b) a resinous siloxane or a silicone resin-producing silicone compound~ (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture c~ (a)~ (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant, and (3) 20 polyethylene glycol or a copolymer of pol~.,,l,yl."~, polyt,,v~ glycol having a solubility in water at room t~ J..aLulc of more than about 2 weight %; and without pol~ glycol. Similar amounts can be used in granular c~ n~ , gels~
etc. See also U.S, Patents 4,978,471, Starch~ issued December 18, 1990, and 4,983,316, Starch, issued lanuary 8, 1991, 5,288,431, Huber et al., issued February 22, 1994, and U,S, Patents 4,639,489 and 4,749,740, Aizawa et al at column 1, line 46 through column 4, line 35.
The silicone suds suppressor herein preferably comprises pol~.l,,yl..,., glycol and a copolymer of polyethylene glycoU~ ""`...e glycol, all having an average molecular weight of less than about 1,000, preferably between about 100 and 800,30 The pc,l~,Lh~ glycol and polyeth~l,lpolyp.u~ h,.l~ copolymers herein have a solubility in water at room temperature of more than about 2 weight %, preferably more than about 5 weight %.
The preferred solvent herein is polyethylene glycol having an average molecular weight of less than about 1,000, more preferably between about 100 and800, most preferably between 200 and 400, and a copolymer of polyethylene glycoL/polypropylene glycol, preferably PPG 200/PEG 300 Preferred is a weight W0 95/33043 2 1 9 1 4 3 9 P~ . r 796 3i ralio of be~ween about I I and 1:10, most preferably between 1:3 and 16, of polyethylene glycoi:copolymer of polyethylene-polypropylene glycol.
The preferred silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4.000 molecular weight. They also preferably 5 do not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC L101.
Other suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disciosed in U.S. 4,798,6~9, 4,0~5,118 and EP 150,8~2. The secondary a~cohols include the C6-C16 alkyl alcohols having a Cl-Cl6 chain A preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12.
Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem. Mixed suds suppressors typicaily comprise mixtures of alcohol silicone at a weight ratio of 1:5 to 5:1.
For any detergent ~u,~ c to be used in automatic laundry washing machines, suds should not form to the extent that they overiiow the washing machine. Suds suppressors. when utilized, are preferably present in a "suds suppressing amount. By "suds suppressing amount" is meant that the formulator ofthe .~ ." can select an amount of this suds controlling agent that will 20 suffciently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.
The ~ ,..t,.,~ herein will generally comprise from 0% to about 5% of suds suppressor. When utilized as suds au~ caaula, Illul~Ol,ali~w~ylh, fatty acids, and salts therein, will be present typically in amounts up to about 5%, by weight, of the 25 detergent ..u~ l u~;l;ù,, Preferably, from about 0.5% to about 3% of fatty ".u..o.,a.i,u~ylate suds suppressor is utilized. Silicone suds suppressors are typically utilized in amounts up to about 2.0%, by weight, of the detergent ..~,...t~.J~;~;U."
although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimized and effectiveness of lower 3û amounts for effectively controlling sudsing. Preferably from about 0.01% to about 1% of silicone suds suppressor is used, more preferably from about 0.25% to about 0.5%. As used herein, these weight percentage values include any silica that may be utilized in ~ with polyu~ , as well as any adjunct materiais that may be utilized. Monostearyl phosphate suds su~u~ulcaaùla are generally utilized in amounts ranging from about 0.1% to about 2%, by weight, of the .. 1.. ~;l,Il,~ ilUUaliJUII suds suppressors are typically utilized in amounts ranging from about WO 95/33043 ~ ,.r ~~~~
2191~3~ --0.01% to about 5:0%, although higher levels can be used. The alcohol suds suppressors are typically used at 0 2%-3% by weight of the finished ~ ~
Fabnc Sofieners - Various through-the-wash fabric softeners. especially the impalpable smectite clays of U.S. Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as other softener clays known in the art, can optionally be used typically at levels of from about 0.5% to about 10% by weight in the present lolll~ to provide fabric softener benefits concurrently with fabric cleaning.
Clay softeners can be used in ~nmhin~iQrl with amine and cationic softeners as disclosed, for example, in U.S. Patent 4,375,416, Crisp et al, March 1, 1983 and U.S.
Patent 4,291,071, Harris et al, issued September 27, 1981.
Dve Transfer Inhibitine ~p~n~C - The ~Qmrncitir,nc of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process. Generally, such dye transfer inhibiting agents include poiyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-v;,~ l.;d~ul~, mangaDese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from about 0.01% to about 10% by weight of the ~ ;n~, preferably frûm about 0.01% to about 5%, and more preferably from about 0.05% to about 2%.
More specifically, the polyamine N-oxide polymers preferred for use herein contain units having the following structural formula: R-AX-P; wherein P is a poly~ iJI~ unit to which an N-O group can be attached or the N-O group can form part of the poly...~ liJI~ unit or the N-O group can be attached to both units; A
is one ofthe following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=; x is 0 or 1; and R is aliphatic, ethoxylated aliphatics, aromatics, I~ u~,y~,lh, or alicyclic groups or 25 any ~ ;o l thereof to which the nitrogen of the N-O group can be attached or the N-O group is part of these groups Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof The N-O group can be represented by the following general structures:
(Rl )x--IN--(R2)y; =N--(Rl)x (R3)z wherein R I, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or~,r.~ h~l~C thereof; x, y and z are 0 or 1; and the nitrogen of the N-0 group can be attached or form part of any of the drul~,.,.",~iul,c~ groups. The amine oxide unit of the poiyamine N-oxides has a pKa ~10, preferably pKa <7, more preferred pKa C6.

~ WO 9SN3043 2 1 9 1 4 3 q . ~ 7q~i Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyls, poiyalkylenes~ polyesters. polyethers, polyamide, polyimides, polyacrylates and miYtures thereof These polymers include5 random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide. The amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of ~ 0:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymeri~alion or by an appropriate degree of N-oxidation. The 10 polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferred 1~000 to 500,000~ most preferred 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO".
The most preferred polyamine N-oxide useful in the detergent ~ p~
15 herein is poly(~ ~;";~!~y~i~l;n~-N-oxide) which as an average molecular weight of about 50~000 and an amine to amine N-oxide ratio of about 1:4.
Copolymers of N-~ lPJ..~" ' and N ~;.,,1';..,;~ule polymers (referred to as a class as "PVPVI") are also preferred for use herein. Preferably the PVPVI has an average molecular weight range from 5,ûO0 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scatterin~ as described in Barth, et al., Ch,m~ l Ar~lysis~ Vol 113. "Modern Methods of Polymer 1`~ the disclosures of which are ill-,Ul,UUl~ ;d herein by reference.) The PVPVI copolymers typically have a molar ratio of N ;...~ d~ to N ;..~',uylll ' ' - from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:~, most preferabiy from 0.6:1 to 0.4:1.These copolymers can be either linear or branched.
The present invention ~,u.,,,uu,;,;o.,~ also may employ a polyvinyl-pyrrolidone ("PVP") having an average molecular weight of from abou~ 5,000 to about 400,000,preferably from about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000. PVP's are known to persons skilled in the detergent field; see, for example, EP-A-262,897 and EP-A-256,696, ;~o~,uo~dLtd herein by reference.
C~ , containing PVP can also contain polyethylene glycol ("PEG~) having an average molecular weight from about 500 to about 100,000, preferably from about l,OOO lo about 10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about ~:1 to about 50:1, and more preferably from about 3:1 to about 10:1.

WO 95133043 P~l~J.,,5,'~''q6 21914~9 3~
The detergent ,u~ Oa;~iu~la herein may also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners whichalso provide a dye transfer inhibition action. If used, the ~ ,o~ herein will preferably comprise from about 0 01% to 1% by weight of such optical brighteners.
The hydrophilic optical brighteners useful in the present invention are those having the structura~ formula:
~N
R~ SO3M SO3M Rl wherein Rl is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl;R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
When in the above formula. Rl is anilino, R2 iS N-2-bis-hydroxyethyl and M
is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-..~J~u~ yl)-s-triazine-2-yl)amino]-2,2'-~ acid and disodium salt.
15 This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GXby Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent . I.,..L~ herein.
When in the above formula, Rl is anilino. R2 is N-2 ~.yJ.u~J~ yl-N-2-lO and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-20 (N-2-lly~llu~ l-N~ Lll.rlr-~ lo)-s-triazine-2-yl)amino]2~2l-ctilh~n~ r acid disodium salt. This particular brightener species is l.UIIIII..,II ' 1~ marketed under the tradename Tinopal SBM-GX by Ciba-Geigy Corporation.
When in the above formula, R I is anilino, R2 iS morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-..,u,l' ' ~ triazine-2-25 yl)amino]2,2'-c~ilhl~n~ir-llfonir acid, sodium salt. This particular brightener species is ~UIll~ lly marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
The specific optical brightener species selected for use in the present invention provide especially effective dye transfer inhibition ~. f~ benefits when used in3û 1 ' ' with the selected polymeric dye transfer inhibiting agents ~..,~.,;..~.,~.
described. The ~ il .l, of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX Tinopal SBM-GX, Tinopal-PLC, and/or Tinopal AMS-GX) provides a;~ll;l;~,rllLly better dye P~ J~5,r-~96 ~ wo gsl33043 2 1 9 1 4 3 9 transfer inhibition in aqueous wash solulions than does either of these two detergent composition cu",~,,a,.~""~ when used alone. Without being bound by theory. it isbelieved that such brighteners work this way because they have high affinity forfabrics in the wash solution and therefore deposit relatively quick on these fabrics.
5 The extent to which brighteners deposit on fabrics in the wash solution can be defined by a parameter called the "exhaustion coefficient". The exhaustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightener ~un~ dLiu,~ in the wash liquor Brighteners with relatively high exhaustion coeffcients are the most suitable for inhibiting dye transfer in the context 10 ofthe present invention Of course~ it will be appreciated that other, ~,unv~".,iu"dl optical brightener types of compounds can op~ionally be used in the present ~u" ~ ;l;u ~ to provideconventional fabric ''brightness" benefits, rather than a true dye transfer inhibiting effect Such usage is conven~ional and well-known to de~ergent ru""ul..li~"a.
Other Inuredients - A wide variety of other ingredients useful in detergent ,u~ can be included in the ~ c;l;~J ~ herein. including other active ingredients. carriers. I~y~ullu~J~,s. processing aids. dyes or pigments. solvents for liquid ru~l~-ulc~liu~a. solid fillers for bar ~.u~ JCa;liu~ . etc. ~f high sudsing is desired, suds boosters such as the Clo-cl6 " -' ' can be ;llcùluulaicd into the ~1 .~\1.. ,~;l;.~.,~ typically at 1%-10% levels The Clo-C14 .. ,.. J~ ,.f.1 and diethanol amides illustrate a typical class of such suds boosters Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides. betaines and sultaines noted above is also advsntageous If desired. soluble magnesium salts such as M~C12, MgSO4, and the like, can be added at levels of, typically, 0.1%-2%, to 25 provide additional suds and to enhance grease removal p~.. L, ,,,,,,,~,c .
Various detersive ingredients employed in the present .~...1.. ,~;l ;, ...~
optionally can be fiunher stabilized by absorbing said ingredients onto a poroushrd," ' ' . substrate, then coating said substrate with a l~ u~ obil, coating Preferably, the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate. In use. the detersive ingredient is reieased from the substrate into the aqueous washing liquor. where it perforrns its intended detersive function.
To illustrate this technique in more detail. a porous ilydlu,uho~;~, silica (trademark SIPERNAT D 10. DeGussa) is admixed with a proteolytic enzyme sOlUtion containing 3%-5% of C13 15 ethoxylated alcohol (EO 7) nonionic surfactant Typically, the c.,~ 'su,r~ ,l solution is 2.5 X the weight of silica.The resulting powder is dispersed with stirrin~ in silicone oil (various silicone oil WO ss/33043 . , ~ ~ 9~
21 91~3q viscosities in the range of 500~ 500 can be used). The resulting silicone oil dispersion is emulsified or olherwise added to the final detergent matrix. By this means, ingredients such as the dru~c~.,"~iu~ l enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and S hydrolyzabie surfactants can be "protected" for use in detergents, including ~iquid laundry detergent n nrnroSjtinnc Liquid detergent comrncitinnc 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 10 preferred for solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and l,~-propanediol) can aiso be used. The ~..,,.1..~;l;..
may contain from 5% to 90%, typically 10% to 50% of such carriers.
Granular detergents can be prepared, for example, by spray-drying (final 15 product density about 52û g/l) or agglomerating (final product density above about 6ûO g/l) the Base Granule. The remaining dry ingredients can then be admixed in granular or powder form with the Base Granule, for example in a rotary mixing drum, and the liquid ingredients (e.g., nonionic surfactant and perfume) can be sprayed on.
The detergent ~ .n~ herein will preferably be formulated such that, 20 dunng use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 11, preferably between about 7.5 and lû.S. Liquid J;~
product formulations preferably have a pH between about 6.8 and about 9Ø
Laundry products are typically at pH 9-11. Techniques for controlling pH at I i~ u.. ,.. "1. ~I usage levels include the use of buffers, alkalis. acids, etc., and are well 25 known to those skilled in the art.
The following examples illustrate ~....1..,,;l,....~ according to the invention,but are not intended to be limiting thereof EXAMPLE I
A dry laundry bleach is as follows:
30~gl~ % (Wt.
Sodium r~l ~.GI L 20 Benzoyl ~.GUI UIGI, Llll ~1 1 O
Citrate l 0 GLGI~ ~ 0.2 35C12-l8 alkyl ethoxy (0.6)sulfate 12 Oleoyl Sarcosinate 12 Water-soluble filler~ ~ Balance ~ W0 95/33043 2 1 9 1 ~} 3 9 T~ u~ 46 ~Mnlv2(u-o)3(l~4~7-trimethy~ 4~7-Llla~ y~lvnvllall~)2(pF6)2. as described in U.S. Pat. Nos. 5,246~621 and 5,244,594.
~Sodium carbonate, sodium silicate mixture (1:1).
In the foregoing ~ "JC;I;"". the sodium L)~-G~I)U~ can be replaced by an 5 equivalent amount of perborate.
Additionally, in the foregoing 1 .l ll ll~ l, the bleach activator can be replaced by an equivalent amount of the following activators benzoyl ~..h,.ula~."", nonanoyl ~ ula~ , nonanoyl ~ Lk,.ulc~,L. Ill, 4-nitro-benzoy~ .,ula.,~",. 4-nitrobenzoyl valero~actam, octanoyl caprolactam, octanoyl lû val.,.uld.,~l,l" decanoyl caprolactam, decanoyl val~.ul~ , undecenoyl ~lnul~ ~Lalll~ undecenoyl ~ ula~ , 3,5,5-trimethylhexanoyl ~ ula~ , 3,5,5-AGIIVyl V ll.,~ ulal,~ l;LI uL . .I~vyl ~.GUI ula~l~,lll, (~i..;~l uL,~ ~u,~:
v~' ul~ ...., terephthaloyl di~Gu~ula~L~ Ltll, ' ' ' -yl divalerolactam, (6-octan-amidocaproyl)oxy~ ..,..,. ~,~lr~ (6-I1~ OI ~uJl)oxy~ ..,..,. ~lllr 15 (6-d. . .~ uyl)oxy~ ;"lr",.-lr, and mixtures lhereof The ..u~ of Example I can be used per 5e as a bleach, or can be added t.. a pre-soak or surfactant-containing detergent ~.c.,~ l .~;l;.,.. to impart a bleaching cenefit thereto.
~ n use for fabric cleaning, the f~ l u, ~ are employed in c~ ...;o.~al 20 manner and at CUIl~ ;ulldl ~ 1...1;.,.. rhus, in a typical mode, the ~u...l,. ~;l;, ~ are placed in an aqueous liquor at levels which may range from about 100 ppm to about 10,000 ppm, dependin~ on soil load and the stained fabrics are agitated therewith.

The following liquid detergent ~, ., ,,1~, .~;l ;. ,.~ are prepared (parts by weight).
ComrJonents Wei~ht %
Oleoyl Sarcosinate 9 C12 18 alkyl ethoxy (0.6)sulfate 12 C12 l4 N-methyl glucamide 6 30 Cg 11 alkyl ethoxylate (eo = 8) 3 C 12-20 fatty acid 4 Citric Acid 0. 5 ~e,~,. ,L 5 Nonanoyl Caprolactam 5 35 Protease 0.5 Lipase 0.2 Amylase 0. 1 W095133043 21 91 439 r~ r ~ ~

Cellualase enzyme o. l Brightener 0 9 Soii release polymer 0.2 Waterand ",;~. ~llAIIrOIIC to balance.
The above, ~ can funher be modified by addinr~ an equivalent amount of a bleach catalysts identified in Example 1.
The above compositions can be modified by replacing the nonanoyl capro-lactam with an equivalent amount of the bleach activators identified in Example 1.
E~ .F 111 10 A bleaching sYstem, useful as a bleach additive, is prepared comprising the following ingredients.
Components Wei,~ht %
Nonanoyl \/dl.. uld~ l 15 Sodium p~ liJo"~ 25 15Ethyl.,.,~d-... ;,.~ disuccinate chelant 10 Oleoyl Sarcosinate 25 Minors, filler** and water 13alance to 100%
*Average panicle size of 400 to 1200 microns.
**Can be selected from convenient materials such as CaC03, talc, clay, silicates, and 20 the like.
The above ~.u l.u~.l;...,~ can be modified by the addition of lipase en_ymes.
The above ,-, I,o~ can also be modified by replacing the nonanoyl valeroiactam bleach activator with an equivalent amount of the bleach activatorsidentified in Example I and/or with the addition of 0.1% metal catalyst.
The above csmrscitin~c can also be modified by replacing the p~ liJull~le with an equiYalent amount of perborate.
EXA~LE IV
A laundry bar with bleach is prepared by standard extrusion processes and comprises Oleoyl Sarcosinate (20%); sodium ~ JOlyp~.oa~ L~ (20%); sodium silicate (7%); sodium perborate Illul~oh~dl~Le (10%); (6-1- '' , u~:)oxy-b~n7Pn~clllfon~t~ (10%), (1.0%), MgS04 or talc filler; and water (5%).
The above romrociti~nc can be modified by the addition of lipase enz,Ymes.
The above ~,u~ u~;.iu~s can also be modified by replacing the (6--L.,u~l)o,~yb. .~ lfon~-e bleach activator with an equiYalent amount of the bleach activators identified in Example I and/or with the addition of 0.1%
metal catalyst.

~ W095/33043 2 l '~1 43(~ r~

The above CUI~uù~lLiull~ can also be modified by replacing the perborale with an equivalent amounl of percarbonate EXAMPLE V
An automatic dishwashing ~Qmr~ititln is as follows.
5 Inr~redient /0 (Wt.) Oleoyl Sarcosinale 6 Trisodium Citrate 15 Sodium Carbonate ~û
Silicate 1 9 10 Nonionic Surfactant2 3 Sodium Polyacrylate (m.w 4000)3 S
Termamyl Enzyme (60T) l l Savinase Enzyme (12T) 3.0 Sodium perborate IrlU.lUII~ 10 15 Benzoyl ~ UIUIG.,~
Mn-catalyst4 0.03 Minors Balance IBRITESIL, PQ Corporation 2Poly.,.hyl~ u,.i.le/pul~,y.uu,~L,,..,o~iu~, low sudser 3ACCUSoL, Rohm and Haas 41:1 mole ratio of Mn cation and ligand to form MnlV2(u-O)3(1,4,7-trimethyl-1,4,7-)2(PF6)2~ insitu In the above ~ , the perborate can be replaced by an equiva~ent amount of ~ . L
In the above ~.~,.,1,,.~;,l,.,,, the bleach catalyst can be replaced by an equivalent amount of preformed bleach catalyst, as identified in Example 1, or with metal cations and Ggands to form the bleach catalysts identified in Example 1.
The above ~1.,..l.~,~;l;.,..~ can also be modified by replacing the benzoyl ~ ,.ul~..,L~.., with an equivalent amount ofthe bleach activators identified in Example 3û 1.
In the above .... l u~ " the surfactant may be replaced by an equivalent amount of any low-foaming, nonionic surfactant. Example include low-foaming or non-foaming ethoxylated straight-chain alcohols such as PlurafacTM RA series, supplied by Eurane Co., LutensolTM LF series, supplied by BASF Co., TritonTM
DF series, supplied by Rohm & Haas Co., and SynperonicTM LF series, supplied by ICI Co.

WO95/33043 2 1 9 ~ 4 3 q r~ l,tJ.. ~r 7q6 Automatic dishwashingcnmp~citinnc may be in granular~ tablet, bar, or rinse aid form Methods of makin~ ~ranules, tablets, bars, or rinse aids are known in the art. See, for instance, U.S. Pat. Serial Nos. 08/106,022, 08/147,22~, 08/147,224, 08/147,219, 08~052,860, 07/867,941 All of the foregoing granu~ar ~mrncitinnC may be provided as spray-dried granules or high density (above 600 g/l) granules or ~ IU~ d~ . If desired, the Mn catalyst may be adsorbed onto and into water-soluble granules IO keep the catalyst separate from the balance of the ~ ..a~ , thus providing additional stability on storage. Such ,ranules (which should not contain oxidizable 10 ~o.~ o~ ) can comprise, for example, water-soluble silicates, carbonates and the like.
Although the fore~oiny ~u",~ are rypical of those useful herein, it is most preferred that: (I) the ~ ;nn; not contain STPP builder; (2) that the ;n.~;~ surfactant ratio be greater than 1:1, preferably at least 1.5:1; and (3) 15 that at least 1% perborate or other chlorine scavenyer be present in the ~.u~ to minimize format;on of MnO2 in use.
While the foregoing examples illustrate the use of the present technology in h;~ n~ designed for use in laundering and dishcare, it will be appreciated by those skilled in the art that the catalyzed bleaching systems herein 20 can be employed under any .,;I.,ulllal..l~ where improved oxygen bleaching isdesired. Thus, the technology of this invention may be used, for exatnple, to bleach paper pulp, to bleach hair, to cleanse and sanitize prosthetic devices such as dentures, in dentifrice ~ to clean teeth and kill oral bacteria, and in any other ~,;II ulll~L~ a where bleaching is advantageous to the user.

Claims (13)

Claims:

1. A bleaching composition comprising a bleaching compound capable of yielding hydrogen peroxide in an aqueous liquor and oleoyl sarcosinate surfactant.

2. A bleaching composition according to Claim 1 wherein said oleoyl sarcosinate surfactant comprises at least 0.1%, by weight, of bleaching composition.

3. A bleaching composition according to Claim 1 further comprising or one or more bleach activators, wherein said bleach activators are members selected from the group consisting of a) alkanoyloxybenzenesulfonate bleach activators;
b) tetraacetylethylenediamine;
c) an amido-derived bleach activator of the general formula:
or mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R2 is an alkylene, arylene or alkarylene group containing from 1 to 14 carbon atoms, R5 is H or an alkyl, aryl, or alkaryl group containing from 1 to 10 carbon atoms, and L is a leaving group;
d) a benzoxazin-type bleach activator of the formula:
wherein R1 is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R4, and R5 may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkylamino, -COOR6, wherein R6 is H or an alkyl group and carbonyl functions;
c) N-acyl lactam bleach activators of the formula:

wherein n is from 0 to 8, preferabiy from 0 to 2, and R6 is H, an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbons, or a substituted phenyl group containing from 6 to 18 carbon atoms; and d) mixtures of a), b) and c).

4. A bleaching composition according to Claim 3 wherein said bleaching compound is percarbonate or perborate, or mixtures thereof, and wherein said bleach activator is selected from the group consisting of benzoyl caprolactam, 4-nitrobenzoyl caprolactam, 4-nitrobenzoyl nonanoyl valerolactam, 4-nitrobenzoyl caprolactam, 4-nitrobenzoyl valerolactam, octanoyl caprolactam, octanoyl valerolactam, decanoyl caprolactam, decanoyl valerolactam, undecenoyl captolactam, unde-cenoyl valerolactam, 3,5,5-trimethyl-hexanoyl caprolactam, 3,5,5-trimethylexanoyl valerolactam, dinitrobenzoyl caprolactam, dinitro-benzoyl valerolactam, terephthaloyl dicaprolactam, terephthaloyl di-valerolactam, (6-octanamidocaproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamido-caproyl)oxybenzenesulfonate, nonanoylozybenzenesulfonate, benzoy-loxybenzenesul-fonate, tetraacetylethylenediamine, and mixtures thereof.

5. A detergent composition according to Claim 1 further comprising a catalytically effective amount of one or more bleach catalysts.

6. A detergent composition according to Claim 4 further comprising a catalytically effective amount of one or more bleach catalysts.

7. A composition according to Claim 5 wherein the bleach cataiyst is selected from the group consisting of MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2, MnmIII2(u-O)1(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2(CIO4)2;MnIV 4(U-O)6(1,4,7 triazacyclononane)4 (ClO4)4; MnIIIMnIV4(u-O)1(u-OAc)2(1,4,7-tri-methyl 1,4,7-triaza-cyclononane)2(ClO4)3; MnIV(1,4,7-trimethyl 1,4,7 triazacyclononane (OCH3)3(PF6); Co(2,2'-bispyridylamine)C12; Di(iso-thiocyanato)bispyridylamine-cobalt (II); trisdipyridylamine-cobalt (II) perchlorate, Co(2,2-bispyridylamine)2O2ClO4; Bis-(2,2'-bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine)iron (II) perchlorate; Mn gluconate; Mn(CF3So3)2; Co(NH3)5CI; binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including N4MnIII(u-O)2-MnIVN4)+and [Bipy2MnIII(u-O)2MnIVbipy2]-(ClO4)3 and mixtures thereof.

8. A laundry detergent composition comprising other, detersive surfactants, other detersive ingredients, and a bleach composition according to Claim 1.

9. A laundry detergent composition comprising other, detersive surfactants, other detersive ingredients, and a bleach composition according to Claim 4.

10. A method for improving the bleaching performance of bleaching composition comprising oxygen or per-acid bleach or a bleaching compound capable of yielding hydrogen peroxide in an aqueous liquor, wherein said improvement comprises adding thereto an effective amount of oleoyl sarcosinate surfactant.

11. A method for removing stains from fabrics or dishes comprising contacting said fabrics or dishes with an aqueous medium comprising a bleach composition according to Claim 1.

12. A method for removing stains from fabrics or dishes comprising contacting said fabrics or dishes with an aqueous medium comprising a bleach composition according to Claim 4.

13. A bleaching composition comprising a preformed peracid bleaching compound and oleoyl sarcosinate surfactant