CA2187169A1 - Bleach compositions comprising metal-containing bleach catalysts - Google Patents

Abstract

Laundry bleaching compositions having reduced metal-containing bleach catalyst-induced fabric damage comprising a peroxy compound selected from the group consisting of preformed organic percarboxylic acids bleaching mixtures containing a bleaching agent that is a source of hydrogen peroxide and one or more bleach activators, and mixtures thereof present in an effective amount to cause bleaching; a metal-containing bleach catalyst (preferably a manganese bleach catalyst) present in an effective amount to activate the peroxy compound: and wherein further the molar ratio of hydrogen peroxide to peracid, from the preformed organic percarboxylic acids or the bleach activator, is less than about 4:1.

Description

~8~I 69 BLEACH COMPOSITIONS CO~RISING METAL-CONTAINING BLEACH
CATALYSTS

TECHNICAL F~F.T n The present invention relates to bleaching ~.u .~ (e.g., granular detergent c~.~n~ , iiquid bleach additive ~r~ -) useful for laundering fabrics comprising a metai bleach cataiyst and a peroxy compound, wherein the molar ratio of hydrogen peroxide to peracids is less than about 4:1.
BA-'T~ OUND OF T~F INVF.~TION
Metai-containing cataiysts have been described in bleach ~
including _ -containing catalysts such as those described in EP 549,271; EP
549,272; EP 458,397; US 5,244,594; US 5,246,621; EP 458,398; US 5,194,416; and US 5,114,611. These bleach cataiysts are described as being active for cataiyzing the 20 bleaching action of peroxy: . ' against various stains. Several of these bleaching systems are said to be effective fûr use in washing and blcaching of substrates, including laundry and hard surfaces (such as machine li;ai~. '' g, general cleaning) and in the textile, paper and wood pulp industries.
It has been discovered that these metal-containing bleach catalysts, especially 25 the ~ containing cataiysts, have the particularly undesirable property, when us~d with textiies, of damaging the fabric resulting in loss of tensile strength of the fibers and/or producing color damage to the fabric. Obviously, such properties for is a Breat drawback to the general use of these ~ , in the laundry area.
It has now been SU~ ;a;l~ y discovered that controiing the ratio of the bleaching agent that is a source of hydrogen peroxide to the bleach activator in such laundry ~ comprising metal-containing bleach catalysts reduces the fabric damage resulting from these cataiysts in the laundry process.
These and other objects are secured herein, as will be seen from the following disclosures.
BACKGROUr~D ART

wo ss/2777s 2 1 8 7 1 6 9 ; ~ 2 ~ P~
The use of amido-derived bleach activators in laundry detergents is described in U.S. Patent 4,634,551. Arlother. class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990. The use of manganese vvith various complex ligands to enhance bleaching is reported in the following United States Patents: 4,430,243; 4,728,455;
5,246,621; 5,244,594; 5,284,944; 5,194,416; 5,246,612; 5,256,779; 5,280,1 17;
5,274,147; 5,153,161; 5,227,084; 5,114,606; 5,114,611. Seealso: EP 549,271 Al;
EP 544,490 Al; EP 549,272 Al; and EP 544,440 A2.
SUMMARY OF THE INVENTION
The present invention relates to laundry bleaching ~1.. ,l,,,~;l;,.. ~ having reduced metal-containirlg bleach catalyst-induced fabric damage, said ~ 1'~
comprising:
(a) a peroxy compound selected from the group consisting of preformed organic p_.~,albu~li_ acids, bleaching mixtures coMaining a bleaching agent that is a source of hydrogen peroxide and one or more bleach activators, and mixtures thereof present in an effective amount to cause bleaching;
(b) a metal-containing bleach catalyst (preferably a manganese bleach catalyst) present in an effective amount to activate the peroxy compound; and wherein further the molar ratio of hydrogen peroxide to peracid, from the preformed organic p~ llbU~I;~. acids or the bleach activator, is less than about 4:1.
All ~ CIIlL~ , ratios and IJl u~ul ~;ull~ herein are by weight, unless other vise specified. All documents cited are, in relevant part, ;Il~,ullJola~td herein by reference.
DET~rr Fn DESCRIPTION OF THF. INVENTION
Metal-C, Rl~zlrh (`~t~lyst One type of bleach catalyst is a catalyst system comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron or manganese cations, an auxiliary 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 auxi~iary metal cations, particularly e~ t ~ acid, elhJ~ ' '.,.e~ acid) and water-soluble salts thereof.
Such catalysts are disclosed 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-O)3(1,4,7-trimethyl-1,4,7-~-;a,a~, 't )2-(PF6)2, Mnm2(u-0)1(u-OAc)2(1,4,7-trimethyl-1,4,7-ll;a~a~Y~lvlll~ )2(clo4)2~
MlllV4(U-0)6(1,4,7-~ A y~Iù"'-lf)4(C104)4~ MnlllMnlV4(u-)l(u-OAC)2-(l~4~7-trimethyl-l~4~ l;a~al~y~lullu~ -)2(clo4)3~ and mixtures thereûf Others are WO951~7775 ~ ,I/U~,; ,r described in European patent application publication no. 549,272. Other ligands suitable for use herein include l,5,9-trimethyl-1,5,9~ ,y.'c~d~ , 2-methyl-1,4,?-Lli~.,y,' 2-methyl-1,4,7-l.i~,y,' ~, 1,2,4,7-tetramethyl-1,4,7-~l;~,' , and mixtures thereo Also included are the . ~
S manganese (IV) complexes suçh as MnIV(1,4,7-trimethyl-1.4,7-.;~,lo~o.. ~)(OCH3)3(PF6) as described in U.S. Pat. 5,194,416.
Still another type of bleach catalyst, as disclosed in U.S. Pat. 5, 114,606, is a water-soluble complex of manganese (Il), (m), andlor (IV) with a ligand which is a non-carboxylate pGlyh~.l.u~y compound having at least three Cu...,~ ive C-OH
groups. Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, meso-erythritol, ' 1, 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 of the forrnula:

Rl-N=C-B-CSN-R4 wherein Rl, R2, R3, and R4 can each be selected from H, substituted alkyl and aryl groups such that each Rl-N=C-R2 and R3-C=N-R4 form a five or six-membered ring. Said ring can further be substituted. B is a bridging group selected from 0, S.
CR5R6, NR7 and CsO, wherein R5, R6, and R7 can each be H, alkyl, or aryl groups, including substituted or llncllhstitllt~ groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings.
Optionally, said rings may be substituted with ~u~ such as alkyl, aryl, alkoxy, halide, and nitro. Particularly preferred is the ligand 2,2'-b;~ .;Jy' Preferredbleach cahlysts mclude Co, Cu, Mn, Fe,-b;~ .i.ly' ' and -b;a~ hl~' ' complexes. Highly preferred catalysts include C0(2,2-~;atJ~l;.l~ )C12, Di(- ~, )b;a~ cobalt (II), ~,ia.l;l,~l;J~lalll;..e-cobalt(II) perchlorate, Co(2,2-b;a~J~.hlyl~ll...l.~)202C104, Bis-(2,2'-~;a~,~.id~h...,i.l~) copper(lI) ~.,.1 ' ' ', tris(di-2-~,J.id~' -) iron(II) perchlorate, and mixtures thereof Other examples include Mn gluconate, Mn(CF3S03)2, Co(NH3)sCI, and the binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including N4Mnm(u-0)2MnlVN4)+and [Bipy2Mnlll(u-0)2MnlVbipy2]-(C104)3 The bleach catalysts of the present invention may also be prepared by combining a water-soluble ligand with a water-soluble manganese salt in aqueous media and ~u,. l.~ the resulting mixture by evaporation Any convenient water-soluble salt of manganese can be used herein. Manganese (II), (III), (IV) and/or (V) is readily available on a commercial scale. In some instances, sufficient ,,,, ... ,, .. ,, , .. , .. .. _, , , _ wo 9s/27775 2 1 8 7 1 6 9 ,~
manganese may be present in the wash liquor. but, in general, it is preferred to add Mn cations in the c- i~u~;f~ to ensure its presence in ~d~dlyliL..') cffective amounts. Thus, the sodium salt of the ligand and a member selected from the group consisting of MnSO4, Mn(ClO4)2 or MnC12 (least preferred) are dissolved in water5 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 resulting solution is evaporated (under N2, if desired) and the resulting solids are used in the bleaching and detergent f ,J".~ c herein without further p~-rifif ~iinn In an alternate mode, the water-soluble manganese source, such as MnSO4, is added to the bll,a~ or to the aqueous Ih~c;u~ bath which comprises the ligand. Some type of complex is apparently formed in sltu, and improved bleach p, ~ is secured. In such an in situ process, it is convenient to use a ~ . .-- - -l ,-l ~lt molar excess of the ligand over the manganese, and mole ratios 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 ,l~ ,- One possible such system is described in European patent application, publication no 549,271.
While the structures of the bleach-catalyzing Illàll,~;a~ ,ul~ L".~ of the present invention have not been elucidated, it may be speculated that they comprise chelates or other hydrated l,uuld;l,aL;ul, 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.
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 bleaching media Whatever the form of the active Mn-ligand species which actually exists, it functions in an âpparently catalytic manner to provide improved bleaching ~"fu. on stubborn stains such as tea, ketchup, coffee, blood, and the like.
Other bleach catalysts are described, for example, in Eurûpean patent application, publication no. 408,131 (cobalt complex catalysts), European patent1" ' , publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455 (1llL~ 5all1)l~ Uf Iigand catalyst), U.S 4,711,748 and European patent application, publication no. 224,952, (absorbed manganese on catalyst), U.S 4,601,845 (:' " support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S
.. .. _ _ _ _ 1 6 ~
~ wo s5l2777s 4,119,557 (ferric complex catalyst), German Pat ~ ;.". 2,054,019 (cobalt chelant catalyst) Canadian 866,191 . ~transition metai-containing salts), U.S.
4,430,243 (chelants with manganese cations and non-catalytic metal cations), and U.S. 4,728,455 (manganese gluconate catalysts).
The bleach catalyst is used in a catalyticaUy effective amount in the and processes herein By '`~al~ , effective amount" is meant an amount which is sufficient, under whatever comparative test conditions are employed, to enhance bleaching and removal of the stain or stains of interest from the target substrate. Thus, in a fabric laundering operation, the target substrate will typicaily be a fabric stained with, for example, various food stains. The test conditions wiU vary, depending on the type 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 detergent uull.,c,~ Liu..., than do top-loading U.S.-style machines. Some machines have l,ù....i~,.al~ longer wash cycles 15 than others. Some users elect to use very hot water; others use warm or even cold water in fabric laundering operations. Of course, the catalytic p.,.ru,.,.a..~,~ of the bleach cataiyst will be affected by such cc,,...:~c.~,lU~...., and the ievels of bleach cataiyst used in fully-formulated detergent and bleach .,~ ,.. can be 4~ lû~J~;at~,lJ adjusted. As a practical matter, and not by way of limitation, the 20 r.u ~ and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 0.1 ppm to about 700 ppm, more preferably from about I ppm to about 500 ppm, of the catalyst species in the laundry liquor. To illustrate this point &rther7 on the order of 3 I.u~,lulllOlal manganese 25 catalyst is effective at 40C, pH 10 under European conditions using perborate and a bleach activator (e.g., benzoyl .,~.~,. ula.,~ ). An increase in of 3-5 fold may be required under U.S. conditions to achieve the same results. Conversely, use of a bleach activator and the manganese catalyst with perborate may allow the formulator to achieve equivalent bleaching at lower perborate usage levels than 30 products without the manganese catalyst.
The, , herein will therefore typically comprise from about I ppm to about 1200 ppm of the metal-containing bleach catalyst, preferably from about 5 ppm to about 800 ppm, and more preferably from about 10 ppm to about 600 ppm.
Most preferred ~ ` comprise the bleach catalyst MnlV2(u-O)3(1,4,7-35 trimethyl-1,4,7-LI;~.,lu.. ull~ulc~)2-(PF6)2 in a ~.ull~ iull of from about 30 ppm to about 1000 ppm, preferably from about 50 ppm to about 650 ppm. more ... ......... ....... , _ . . .

wo95/27775 r~".,. .
6~ 6 .~, preferably from about 50 ppm to about SoO ppm, and most preferably from about 120 ppm to about 400 ppm.
Peroxv l~nnlpm-n,~c It is to be appreciated that the bleach catalyst does not function as a bleach by 5 itself. Rather, it is used as a catalyst to enhance the p~r bleaches and~ in particular, oxygen bleaching agents such as perborate, P~ JUII~persulfate, and the like, especially in the presence of bleach activators. Accordingly, the ~ herein also contain peroxy compounds which as used herein includes bleaching agents and bleaching mixtures containing a bleaching agent and 10 one or more bleach activators, in an amount sufficient to provide bleaching oF the stain or stains of interest (e.g., tea stains; wine stains).
However, for purposes of the present invention, the peroxy compound must be selected from the group consisting of preformed organic ~ .,bu~lk, acids, bleaching mixtures containing a bleaching agent that is a source of hydrogen peroxide 15 and one or more bleach activators, and mixtures thereo Further, when a bleaching agent that is a source of hydrogen peroxide is present in the ~ u ~ of the present invention, said ru .~ further have a molar ratio of hydrogen peroxide to bleach activator is less than about 4 :1.
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 .. ~,.. 1.~,~;1;.,, especially for fabric laundering. Bleach and pre-soak ~ may comprise from 'i% 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 bleaching mixture comprising the bleaching agent-plus-bleach activator.
1. ~ srrntc The bleaching agents used herein can be any of the bleaching agents useful for detergent or bleaching, . in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known, and are useful for bleaching f~ -h~;l;h as used in the present invention to treat fabrics. These include oxygen bleaches as well as other bleaching agents. Perborate bleaches, e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
a. Rl~srhi~ nt thgt iS a Source of Hvdro~en Peroxide:
Peroxygen bleaching agents that are a source of hydrogen peroxide may be used in the c.~. p .~:l;...,~ Suitable peroxygen bleaching compounds include sodium 5 carbonate ~ u~yhJd~ and equivalent "p~ ,al~ull~l~e" bleaches, sodium u~ lla~, urea p.,.U~.ylly.ll~ , and sodium peroxide. Persulfate bleach (e.g., OXONE, ~ td l;ul~ lly by DuPont) can also be used.
. _ _ . _ _ _ ., : , ,,,, _, , ~ , .. ............ ...... .... . . . ........

WO ss/2777s ~ 6 g 7 P ~ S/A~ ~
A preferred ~ IJOI~ bleach comprises dry particles having an average particle size in the range from about 500 ilf~ ulll~ to about 1,0û0 ..u~,.u...~t~
not more than about 10% by weight of said particles being smaller than about 200llf~.,lu~lLt~ and not more than about l00~A by weight of said particles being larger 5 than about 1,250 ~u~ . Optional~y, the ~.,,.,~,.I,o..~ can be coated with silicate, bûrate or water-soluble surfactants. Ftll,albûll~lL~ is available from varjous commercial sources such as FMC7 Solvay and Tokai Denka.
b. Preforrn~l OrFA~nirE~tl~ vA~il;c Ari~c As used herei4 bleaching agents also comprise preformed organic 10 ~ ul,u~l;c acids. Such bleaching agents that can be used without restriction encompass ~ I,albu~lic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium r- u~y~l-LIl~ h~ L~dldL~
(INTEROX), the msgnesium salt of metachloro perbenzoic acid, 4-~1ull~' 1 UAU~J~IU~LIt,~l;U acid and d;~ IUA~ ' . acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S.
Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent Application û,l33,354, Banks et al, published February 20, 1985, and U.S. Patent4,412,934, Chung et al, issued November 1, 1983. Highly preferred bleaching agents also include 6-.-o..,' - 6-UAU~ .U~aIJIU;I~ acid (NAPAA) as described in U.S.
20 Patent 4,634,551, issued January 6, 1987 to Burns et al.
Such materials nûrmally have a general formula:
HO-O-C(O)-R-Y
25 wherein R is an alky~ene or substituted alkylene group containing from I to about 22 carbon atoms or a phenylene ûr substituted phenylene group, and Y is hydrogen, halogen, alkyl, aryl or -C(O)-OH or -C(O)-O-OH
The organic p~,.,,c.l~UA~, acids usable in the present invention can contain either one or two perûxy groups and can be either aliphatic or aromatic. When the organic p~ UA.~, acid is aliphatic, the ~ J acid has the general formula:

HO-O-C(O)-(CH2)n~Y

WO 95127M5 21 g 716 ~ `
where Y can be, for example, X CH3, CH2CI, COOH, or COOOH; and n is an integer from I to 20.
When the organic p~,~UO,~l/UA,~, acid is aromatic, the ~ lrrl acid has the genera5 formula:

HO-O-C(O)-C6H4-Y
wherein Y is hydrogen, alkyl, ~ lv~, .., halogen, or COOH or COOOH.
Typical ~ P~.U~IIIJUA~5;- acids useful herein include alkyl 10 p.,~w~bu~l;., acids and aryl p.lu~hbuAyL acids such as:
(i) p.,.UA~.,.~v;., acid and ring-substituted ~J~,.UA~,.LViC acids, e.g., peroAy-o-naphthoic acid;
(ii) aliphatic, substituted.aliphatic and arylalkyl nlvl.u~,.uAy acids, e.g.
p~..UAyl..,,.i., acid, p~.uA~al~u;., acid, and N~N-~l~Ll~aluJ~ r UA~ U;C acid I S (PAP).
Typical diperoxy ~ u~l;~, acids useful herein include alkyl diperoAy acids and luyldl;~J.,.uAy acids, such as:
(iii) 1,12-J;~,.,.vA.yJ~ i;v;~ acid;
(iv) 1,9-.5;1,~,.u~ ' - acid;
(v) d;~,.uA~ aa~ ;., acid; .I;IJ~U~D~ C;C acid and .I;".,,UA~ , ' ' ' acid;
(Vi) 2-d~ ..,,UA~ -1,4-dioic acid;
(vii) 4,4-aul~.l~l/;alJ.,.uA~,.~u;~, acid.
The present invention may further encompass bleaching ~.~, 1...':;., 25 comprising an effective amount of a ' ' '1~, insoluble organic p~ ,lbv acid bleaching agent having the general formula:
O O O O
Il 11 11 11 R~C--N--R2-C--OOH, R~N--C--R2-C--OOH
Rs Rs wherein Rl is an alkyl, aryl, or alkaryl group containing from about I to about 14 carbon atoms, R2 j5 an alkylene, arylene or alkarylene group containing from about 30 I to about 14 carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group containing from about I to about 10 carbon atoms.
Peroxygen bleaching agents, the perborates, the p~ lll)u~ ta, etc., are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) of the ~.,.w~lJuA~l;c acid 35 ~,u~ u...l;.,~ to the bleach activator.

~ wogsm77s ~ 8~9

2. RlP~i~h Activ~tnrc B1each activators are known and amply described in literature, such as in the GB Patents 836,988; 864,798; 907,356; 1,003,310 and 1,519,351; Gemman Patent

3,337,921; EP-A-0185522; EP-A-0174132i EP-A-0120591; and U.S. Pat. Nos.
1,246,339; 3,332,882; 4,128,494; 4,412,934 and 4,675,393.
A class of bleach activators is that of the quatemary ammonium substituted peroxyacid activators as disclosed in U.S. Pat. Nos. 4,751,015 and 4,397,757, inEP-A-284292, EP-A-331,229 and EP-A-03520. Examples of peroxyacid bleach activators of this class are:
2-(N,N,N-trimethyl ~n~n-; ~nn) ethyl-4~ carbonate--(SPCC), N-octyl,N,N-dimethyl-N 10-cali,u~ uAy decyl ammonium chloride--(ODC);
3-(N,N,N-trimethyl: ) propyl sodium4 ~l ~r yl ~aliJuAyla and N,N,N-trimethyl ammonium toluyloxy benzene sulphonate.
Other activators include sodium-4-benzoyloxy benzene sulphonate;
N,N,N',N'-tetracetyl ethylene diamine; sodium-l-methyl-2-benzoyloxy benzene-4-sulphonate; 50~ 1 'YI-3-~ UYIUAY benzoate; sodium nonanoyluAy~
sulphonate; sodium 3,5,5,-trimethyl h~AGl~ loAyl/~ e sulphonate; glucose ~ and tetraacetyl xylose.
Bleach activators of also useful 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 or mixtures thereof, wherein Rl is an alkyl, aryl, or alkaryl group containing îrom 25 about I to about 14 carbon atoms, R2 ;5 an alkylene, arylene or alkarylene group contairiing from about I to about 14 carbon atoms, R5 is H or an alkyl, aryl, oraikaryl group containing from about I to about 10 carbon atoms, and L can be essentiaily any suitable leaving group. A leaving group is any group that is displaced i-rom the bleaching activator as a rnnCPqllpn~e of the l~ attack 30 on the bleach activator by the p~" IIJ ~ii uAide anion. This, the p.,. Ilyiil ul,~;a reaction, results in the formation of the p~uAyuGlbuA~lh, acid. Generally, for a group to be a suitable leaving group it must exert an electron attracting effect. It should also fomm a stable entity so that the rate of the back reaction is negligible. This faci~iitates the ., .~ attack by the ~ lUAi~i., anion.

wo ss/2777s ~ 6 9 ~ P ~ A ~ ~
The L group must be sufficiently reactive for the reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching ~ 9~ These ,L~ L;.,~ are generally paralleled by the pKa of the conjugate acid of the 5 leaving group, although exceptions to this convention are known. Ordinarily, leaving groups that exhibit such behavior are those in which their conjugate acid 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 l l.
Preferred bleach activators are those of the above general formula wherein 10 Rl, R2 and R5 are as defned for the peroxyacid and L is selected from the group consisting of:
--o~, --O~Y, and --0~5 --N--C--R1 --N N 1l R3. Y
-O-CH=C--CH=CH2 --O--CH=C--CH=CH2 -O--C--R1 _N~ NR4 , ~C~NR4 O O

--O--C=CHR4 , and O
and mixtures thereof, wherein Rl is an alkyl, aryl, or alkaryl group containing from about I to about 14 carbon atoms, R3 is an alkyl chain containing from I to about 8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing group.
The preferred solubilizing groups are -SO3-M , -CO2-M+, -SO4-M+, 20 -N (R3)4X- and O<--N(R3)3 and most preferably -SO3-M and -CO2-M

, t ~ .
wo ss/2777s ~ ~ ~ 7 ~ ~ g I ~ l, u~ sir~ -wherein R3 is an alkyl chain containing from about I to about 4 carbon atoms, M is a cation which provides solubility to the bleach acti~ator and X is an anion which provides solubLiity to the bleach activator. Preferably, M is an aikali metal, ammonium or substituted ammonium cation, with sodium and potassium being 5 most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion. It should be noted that bleach activators with a leaving group that does not contain a 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 generai formula wherein L
10 is selected from the group consisting of:
~ O~Y , and --0~
wherein R3 is as defined above and Y is -SO3 M or -CO2 M wherein M is as defined above.
Preferred examples of bleach activators of the above formulae include (6-, U~ Ay~ , (6--~ r.~ U;¦)UAy~ ~r nate, (6-~ . uyl)u~yb. ~1 r , and mixtures thereof.
Another important class of bleach activators provide organic peracids as described herein by ring-opening as a c.,... 1 ~ ~ of the, ~ pi.il ~ attack on the carbonyl carbon of the cyclic ring by the perhydroxide anion. For instance, thisring-opening reaction in certain activators involves attack at the lactam ring carbonyl by hydro~en peroxide or its anion. Since attack of an acyl lactam by hydrogen peroxide or its anion occurs preferably at the exocyclic carbonyl, obtairling a significant fraction of ring-opening may require a catalyst. Another example of ring-opening bleach activators can be found in other activators, such as those disclosed in U.S. Patent 4,966,723, Hodge et al, issued Oct. 30, 1990.
Such activator ro~rol~n~i~ disclosed by Hodge include the activators of the type, having the formula:
o ~N~8 R1 including the substituted 1,.. ,... A~ ~ of the type W0 95/27775 ,~
2~8rt~6g '~2 ~--R4J~ ;
wherein Rl is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R4, and R5may be the same or different ~ selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR6 (wherein R6 iS H or an alkyl S group) and carbonyl functions.
A preferred activator of the benzoxazin-type is:
1l "C~
When the activators are used, optimum surface bleaching p~,.rOI is obtained with washing solutions wherein the pH of such solution is between about8.5 and 10.5 and preferably between 9.5 and 10.5 in order to facilitate the ~ hJd~ul~ reaction. Such pH can be obtained with substances commonly known as buffering agents, which are optional cu,l.r of the bleaching systems herein.
Still another class of preferred bleach activators includes the acyl lactam 5 activators, especially acyl ~,~"" ul,,~l,.ll.~ and acyl valerolactams of the formulae:
O O

`CH2--CH2~ 2 `CH2--CH2 wherein R6 ;5 H, an alkyl, aryl, alkoxyaryl, or alkaryl group containing from I to about 12 carbon atoms, or a substituted phenyl group containjng from about 6 to about 18 carbons. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 20 1985, il~cul~ led herein by reference, which discloses acyl L~ luk.cL~ s, including benzoyl ~ ' , adsorbed into sodium perborate.
Various nonlimiting examples of additional activators which may comprise the bleach ~....1,,,~:l;.,..~ 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. The ~ ,.~.".c sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) wossl2777s ~ 9 `; `~ P~l/u~

activators are typical, and mixtures thereof can also be used. See also U.S.

4,634,551 for other typical bleaches and .activators useful herein.
The superior blc~luu~l.,D~ullg action of the present ~ is also preferably achieved with safety to natural rubber machine parts and other natural S rubber articles, including fabrics Cu..h;lu~ .,f Lul~l rubber and natural rubber elastic materials. The bleaching mechanism and, in particular, the surface bleaching mechanism are not completely understûod However, it is generally believed that the bleach activator undergoes, ' . ' ' attack by a I~.l.rJ~u~dc anion, which is generated from the hydrogen peroxide evolved by the peroxygen bleach, to formlû a p~.u~.,~ul.u~.~lh, acid. This reaction is commonly referred to as perhydrolysis.
The amido-derived and lactam bleach activators herein can also be used in ' with preferably rubber-safe, enzyme-safe, hydrophilic activators such as TAED, typically at weight ratios of amido-derived or .,~
activators:TAED in the range of 1:5 to 5:1, preferably about 1:1.
15 R ~tinc Of (~, ~
For purposes of the present invention, it is important to control the molar ratio of hydrogen peroxide to peracids (preformed or from bleach activators) is less than about 4:1 and preferably is within a specified limit, in order to obtain the desired reduction in fabric damage from the metal-containing bleach catalyst. It is further 20 preferred that the molar ratio of hydrogen peroxide to heavy metal ions from the bleach catalyst be controlled.
The molar ratio of hydrogen peroxide to peracid is defined herein to be the molar ~,n~ of hydrogen peroxide obtained from the bleaching agent that is a source of hydrogen peroxide ([H202]) to the theoretical molar ,u..~ lalion of peracids generated by the bleach activator plus any preformed peracid compounds present in the cv ~ u~ ([Peracid]). For example, one mole of p~,l a.l,u~ , will provide 1.5 moles of hydrogen peroxide and one mole of perborate viill generate one mole of hydrogen peroxide; the FI202] from such sources are therefore calculatedbased on these values and the molar Cull~ lliu~ of the bleaching agent that is asource of hydrogen peroxide being used. Similarly, for the bleach activators used in the f,., .~ u~ the [Peracid] is calculated l~,urlu~ ; that, for example, one mole of TAED ll.~,u.~ will provide two peracids; thus the [Peracid] is 2 times the molar ~ . f I ~ of TAED.
The molar ratio of [H202]:1Peracid] is therefore less than about 4:1, preferably between 1:1 and 3 :1, and most preferably between I .û2: 1 and 2.5 :1.
Also preferred for the present c....~ , when the ~ contain more than about 20 ppm heavy metal ions sourced by the bleach catalyst (therefore, , .. . ..... . ..

W0 95127775 ~1 ~ 7 1 ~ 9! ~

does not include non-cataiytic heavy metal ions in the rn~rocitir~nc or heavy metal ions fortuitously present in the wash solution), is controlling the molar ratio of hydrogen peroxide to heavy metal ions sourced by the bleach catalyst (i-H202]:[E~]) to be less than about 1200 1.
Aiso preferred is controlling the molar ratio of peracid to heavy metal ions from the bleach cataiyst (~Peracid]:i~IMI]) to be more than about 350:1, preferably greater than about 500:1, and most preferably greater than about 700:1. The molar rl~ IIAI;~I of the heavy metai ions from the bleach catalyst ([HMI]) is obtainedfrom the molar, of the bleach catalyst times the number of heavy metai ions per catalyst. For example, the preferred catalyst ~inIv2(u-O)3(1,4,7-trimethyl-1,4,7-~ ,y~lu~u~ e)2-(pF6)2 provides 2 moles of Mn per mole of cataiyst, thus the i~] for the Mn sourced by this catalyst equals 2 times the molar of the cataiyst.
Finaiiy, it is further preferred for the present invention that ~
comprise less than about 50 ppm of heavy metai ions sourced by the catalyst, andmost preferably iess than about 40 ppm.
Adjunct In~rPrliPntc The ~ :l;,. - herein can optionally include one or more other detergent adjunct materials or other materials for assisting or enhancing cleaning p~,.ru.,....,,~.c, 20 treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent (e.g., perfumes, colorants, dyes, etc.). Preferably, the adjunct ingredients should have good stability with the bleaches employed herein. Preferably, the detergent ~ ;"--- herein should be boron-free and phosphate-free.
Additionaily, dishcare f( ' are preferably chlorine-free. The following are 25 iiiustrative examples of such adjunct materials.
Free Radical r~r~ven~ing Antioxidant Iviaterials:
"Free radicai scaYenging antioxidant materials", as used herein, means those materiais which act to prevent oxidation in products by functioning as free radical scavengers. Examples of A..l;.,~ that can be added to the ur~ of this 30 invention include a mixture of ascorbic acid, ascorbic palmitate, propyl gallate, available from Eastman Chemical Products, Inc., under the trade names TenoxR PG
and Tenox S-1; a mixture of BHT (butylated l~y~i~u~yluh~.,.lc), BHA (butylated h~i-UA~ ~ ), propyl gailate, and citric acid, available from Eastman Chemical Products, Inc., under the trade name Tenox-6; butylated hydlu~y~ulu.,.~." available 35 from UOP Process Division under the trade name SustaneR BHT; tertiary L~ , e, Eastman Chemical Products, Inc., as Tenox TBHQ; natural ~o,,oph~,.uls, Eastman Chemicai Products, Inc., as Tenox GT-1/GT-2; and butylated wO 95/2777~ 6 ~3 ~ ` ~ ` . IIU~,SlO~ .
h~ u~. -'e, Eastman Chemical Products, Inc., as BHA; long chain esterS (C8-C22) of gallic 2cid, e.g., dodecyl gallate; lrganoxR 1010; IrganoxR 1035; IrganoxR
B 1171; IrganoxR 1425; IrganoxR 3114; IrganoxR 3125; mono-tert-butyl hr~ ~ (MTBHQ); benzoic acid and salts thereof; toluic acids and salts

5 thereof; t-butyl catechol; l, I ,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl) butane (Topanol CA available from ICI); monoalkyl ethers of Iydl~, ~ (e.g., 4-' ~, ' '); and mixtures thereof.
Preferred are BHT, BHA, TBHQ, propyl gallate, ascorbic acid, and mixtures thereo It is to be recognized that for purposes of the present invention, materiais othervvise useful as ' which do not act as free radical scavengers, such as those materials which function solely by chelating metais which can initiate oxidation reactions are not "free radical scavenging antioxidant materials" herein, but are preferred optional material to be used with the free radical scavenging antioxidant materiais.
The term " ' effective amount", as used herein, means an amount of a free radical scavenging antioxidant material effective for reducing, under whatever ~,u~ alaliv~ test conditions are employed, the extent of any fabric damage (including, for example, tensile strength loss and/or color damage) observed by the presence of the metal-containing bleach catalyst in the l_UllllJV~ iUII. Such fabric damage may be evaluated under any typical wash conditions, including the greater than 40 C wash conditions common in Eurûpe. Levels of free radical scavenging antioxidant materiais to be used in products are therefore easily ~f t~rrnin~i and are typicaily present in the ~ , according to the present invention within the range of from about I ppm to about 2%, preferably from about 20 ppm to about 6000 ppm, and most preferably from about 50 ppm to about 2000ppm. Further, in a powder ~ ' , the antioxidant may be introduced into the ~ - as a powder or through d~ oln~aliull or granulation or any other process to keep the catdlyst and dntioxidant close to each other and thereby allow quick interaction in the wash.
Buiiders - Detergent buiiders can optionally be included in the ~ ;n..c herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering ~ .o~ to assist in the removal of particulate soils.
The level of builder can vary widely depending upon the end use of the .,., 1 1 o~ and its desired physical forrn When present, the ~ulllpoa;iiolls will typically comprise at least about 1% builder. Liquid rullllul~Liul~a typically comprise ... . . .
_ _ ... .. . .

woss/2777~ 218~69 ~ P ~
from about 5% to about 50%, more typically about 5% to about 30%, by weight, of detergent builder. Granular ~ "~ typically comprise from about 10% to about 80%, more typically from about 15% to about 50% by weight, of the deter8ent builder. Lower or higher levels of builder, however, are not meant to be excluded.
Examples of silicate builders are the alkali metal silicates, particularly thosehaving a SiO2:Na2O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na2SiOs lllul~ lu~ form of Isyered silicate. It can be prepared by methods such as those described 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 those having the general formula NaMSixO2x+l yH2O wherein M is sodium or hydrogen, 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 layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-I 1, 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 silicate, which can serve as a crispening agent in granular ru~ ulaLiull~, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
~l ' builders are useful in the present invention. ~l "
builders are of great importance in most currently marketed heavy duty granular detergent ~ , and can also be a significant builder ingredient in liquid detergent 1;- -~ - - ' builders include those having the empirical forrnula:
Mz(zAlO2)y] xH2O
wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
Useful ' " ion exchange materials are cu"",.~, "y available.
These ' ' can be crystalline or amorphous in structure and can be naturally-occurring ~ ' - ' or synthetically derived. A method for producing ' ' ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline WO9~J27775 ~ 9 ` P~ JJI~71 ' " ion exchange materials useful herein are available under the A~ :;c,r~ Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especialiy preferred el,.l,u ' t, the crystailine ' - ' ion exchange material has the formula:
Nal2[(Alo2)l2(sio2)l2] xH2o wherein x is from about 20 to about 30, especially about 27. This material is known as Zeûlite A. Dehydrated zeoiites (x = 0 - 10) may also be used herein. Preferably, the l ' ' has a particle size of about 0.1-10 microns in diameter.
Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of pGly.~ uAyl~ v~ As used herein, "l~ul~ GAy6~" refers to compounds having a plurality of ~ bUA.~h. ~, groups, preferably at least 3 c.llbùA~ld~ . PulyL~liJuAyLIle builder can generally be added to the ~ u~ in acid form, but can also be added in the form of a neutralized sait. When utilized in salt form, alkali metals, such as sodium, potassium, and iithium, or " ' salts are preferred.
Included among the pc~ uiJuAyL~ builders are a variety of categories of useful materiais. One important category of ~.,lJ~IbuAyl~Le builders; n~
the ether pGl~ uAjk~, including UAr; :, as disclosed in Berg, U.S.
Patent 3,128,287, issued April 7, 1964, and Lamberti et ai, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,û71, issued to Bush.et al, on May 5, 1987. Suitable ether pOly..,ll,uArl.lLcs aiso include cyciic . . ', particularly alicyclic .u...,. 's, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
Citrate builders, e.g., citric acid and soluble salts thereof ~particularly sodium sait), are ~ul.~ iJuAy' builders of particular importance for detergent ru~ lllul.Lu~s due to their availability from renewable resources and their l);1~1F~ .'l' y, Citrates . can be used in liquids or in granular ~ ., especially in ~ with aeolite and/or layered silicate builders. Ar~ are also especially useful in such c~ and ~
Fatty acids, e.g., C12-CIg ll~ollûL~l~uA.ylic acids, can also be ~u~dl~d into the ~ aione, or in ~.u~ with the aforesaid builders, especially citrate and/or the succinate builders, to provide additional buiider 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 pllu~ lu~-based builders can be used, and especially in the r.., . ,~ of bars used for hand-laundering operations, the vanous alkali metal .. . ... ... . . . .

WO95/27775 2~8~ 18 phosphates such as the well-known sodium L. ;IJùly~ n~ , sodium 1..~.~ . ' . ' and sodium U~ PI '`1~ can be used.
('hPl~ino A ~o~ntc - Although builders can be used. the detergent ~,.J~
herein preferably do not contain those manganese chelating agents which abstract the 5 manganese from the bleach catalyst cpmplex. In particular, I,I..~l,I,n ~ ,, l ' , ' , and the ~r' . ' chelating agents such as DEQUEST are preferably not used in the .,u ~l.ù,;l;....~ However, nitrogen-based manganese chelating agents, such as ~ J' ' N,N'-disuccinate (EDDS), are useful.
Detersive Surfactants - ~ ' ~ examples of surfactants useful herein 10 typically at levels from about 1% to about 55%, by weight, include the Cv.l._l.L;ù..~l Cll-CIg alkyl benzene sulfonates ("LAS") and primary, branched-chain and random Clo-C20 alkyl sulfates ("ASn), the Clo-CIg secondary (2,3) alkyl sulfates of theformula CH3(CH2)X(CHOSO3-M+)CH3 and CH3(CH2)y(CHOS03~M+) CH2CH3 where x and (y + I) are integers of at least about 7, preferably at least about 9, and 15 M is a water-solubilizing cation, especially sodium7 ....~ 1 sulfates such as oleyl sulfate, the Clo-CIg alkyl alkoxy sulfates ("AExS"; especially EO 1-7 ethoxy subfates), Clo-CIg alkyl alkoxy ~ buAyLIle~ (especially the EO 1-5 ~ UA~ IJUAYL~S)~ the ClO I8 glycerol ethers, the CIO CI8 alkyl pvl~dl~,u~id~,,.
and their ~ulle~ul~d;~lg sulfated poly~ .,u~;d~,~, and C12-CIg alpha-sulfûnated fatty 20 acid esters. If desired, the ~u...~iiun~l nonionic and amphoteric surfactants such as the C12-CIg alkyl ethoxylates ("AE") including the so-called narrow peaked alkylethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ~LIIUA~I~JIUYUAY), C12-CIg betaines and c~lfobPt~inps ("sultaines"), CI0 CI8 amine oxides, and the like, can also be included in the overall ~,....l..~:l;.- ~ The C10-C18 25 N-alkyl pGl~ UA~ fatty acid amides can also be used. Typical c-Aamples include the C12-C18 N-~ h~'~' ' See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhyd,uAy fatty acid amides, such as Clo-CIg N-(3 ' ~IU~I) glucamide. The N-propyl through N-hexyl Cl2-CI8 glucamides can be used for low sudsing. Cl o-c20 conventional soaps may also be used. If high 30 sudsing is desired, the branched-chain Clo-cl6 sûaps may be used. Mixtures ofanionic and nonionic surfactants are especially useful. Other cu,.~ ..iu,.~l useful surfactants are listed in standard texts.
Suitable nonionic surfactants particularly suitable for dishcare are the low-foaming or non-foaming ethoxylated straight-chain alcohûls such as PlurafacTM RA35 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 Cû.

wo gsl27775 Clav sOa RemovaVAnti-lcd~ o~ ull Aoents - The ~ , of the present invention ean aiso optionally. contain water-soluble ethoxylated amines having elay soil re--moval and ~ , properties. Granular detergent which eontain these romrolln~ic typically contain from about 0.01% to 5 about 10.0% by weight of the water-soluble ethoxylates amines; liquid detergent c-- I-c~ typieaiiy eontain about 0.01% to about 5%.
The most preferred soil release and anti--r~ agent is ethoxylated tLt~ LI~I r~ ' ' Exemplary ethoxylated amines are further deseribed in U.S.
Patent 4,597,898, VailLi.l~i`.., issued July 1, 1986. Another group of preferred elay 10 soii removal-ài,Li,e i~ua;~iu,, agents are the cationic ~r~mrol.n~ic disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984.
Other elay soil ICI~IUV ~ tilCi~iL,jJU~ iUII agents whieh ean be used inelude the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the ~;.LLI;OIUC polymers disclosed in ~uropean Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, CoMOr, issued October 22, 1985. Other clay soil removai and/or anti .ed~uiiLio" agents known in the art can aiso be utilized in the, . ~ herein. Another type of preferred ~L.l.ilrri ~ ... agent includes the carboxy methyl cellulose (CMC) materials. These materials are well icnown in20 the art.
Polvmeric l~ic~nprcin~ A~ents - polymeric dispersing agents can a i.. _ '~/ be utiiized at levels from about 0.1% to about 7%, by weight, in ther~-lF- herein, especially in the presence of zeolite and/or layered silicate builders. Suitable polymeric dispersing agents include polymeric p and pGI~ Li~!L~lL glycols, although others known in the art can also be used. it is beiieved, though it is not intended to be limited by theory, that poly--m-eric dispersing agents eMance overall detergent builder p.,.ru~ allLe, when used in ~.r~
with other buiiders (including lower molecular weight j'JUI~iliJU~l~LLL.~) by crystal growthiMibition,particulatesoilreleasepPrti7~tirn, andanti-,ei~,.u~:l;.~
Polyrneric ~ul~ bu~.yld~ materials can be prepared by pLJlyll~ iLillg or Cu~jJU~ , suitable I _ ' monomers, preferably in their acid form.
- TT ' monomeric acids that can be pcl~.. ,.. ,i~.;i to form suitable polymeric pUIyLaibU~ ' include acrylic acid, maleic acid (or maleie anhydride), fumaric aeid, itaeonie aeid, aeonitic aeid, mesaconic acid, citraconic acid and lil.~l.y~. .~. ~,.. :
35 acid. The presence in the polymei-ic pOl,yLal bù~ LI:a herein or monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is , .. . .... . ... .. . .. . _ .

wossl2777s ~ ~711ig ~ ,1IL..,~'^'~ ~
suitable provided that such segments do not constitute more than about 40% by weight.
Particularly suitable polymeric puly~ bu~ can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water-soluble 5 saits of pul~....,.i~ acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from about 2,00û to 10,000, more preferably fromabout 4,000 to 7,000 and most preferably from about 4,000 to 5,00û Water-solublesaits of such acrylic acid polymers can include, for example, the aikali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are 10 known materiais. Use of POI~ G;~ of this type in detergent ~ J~ has been disclosed, for example, in Diehi, U.S. Patent 3,308,067, issued march 7, 1967.
A~,lyl;~/ ' -based copolymers may also be used as a preferred component of the ~ c~ u~;l;ull agent. Such materials include the water-soluble saits 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, more preferably 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 30:1 to about 1:1, more preferably from about 10:1 to 2:1. Water-soluble saits of such acrylic acid/maleic acid copolymers can inciude, for example, the 20 aikaii metal, ammonium and substituted ammonium saits. Soluble a~,~' ! ' copolymers ofthis type are icnown materials which are described in European Patent Application No. 66915, published December 15, 1982.
Another polymeric materiai which can be included is polyethylene glycol (PEG). PEG can exhibit dispersing agent i,~,ru,."~l"..c as weii as act as a clay soil removai-a.,~ilt i~p~ ;u" agent. Typical molecular weight ranges for these purposes range from about 500 to about 100,00~, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.
rul~ ui and pGI~,,' ' ' dispersing agents may also be used, especially in conjunction with zeolite builders. Dispersing agents such as pc,l~ preferably have a molecular weight (avg.) of about 10,000.
Enzvmes - Enzymes can be included in the r~ herein for a wide variety of fabric laundering purposes, including removal of protein-based, .,~bu~ Llc-based, or ~ ,;d. -based stains, for example, and for the prevention of refugee dye transfer, and for fabric restoration The enzymes to be il~cullJO.~led include proteases, amylases, lipases, cellulases, and ~J."u~i~Lls~, as well as mixtures thereo Other types of enzymes may also be included. They may be of any suitableorigin, such as vegetable, animal, bacterial, 1ngai and yeast origin. However, their _ . . _ . _ . _ _ ~ woss/27775 ,~7~f~9 choice is governed by several factors such as pH-activity and/or stability optima, ib ' ' ~, 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.
5 Enzymes are normally il.. ,ù.po.dLed at levels sufficient to provide up to about 5 mg by weight, more typically about 0.01 mg to about 3 mg, of active en2yme pergram of the ~ .. Stated otherwise, the "r. ~ ;...,c herein will typically comprise from about 0.001% to about 5%, preferably 0.01%-1% by weight of a commercial enzyme preparation. Protease enzymes are usually present in such 10 commercial l~lC,Ud~dLiU.... at leve]s sufficient to provide from 0.005 to 0.1 Anson urlits (AU) of activity per gram of ~ ;rn~
Suitable examples of proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. l,. l.. ,;~.., ~ Another suitable protease is obtaincd from a strain of Bacillus, having maximum activity throughout the pH range 15 of 8-12, developed and sold by Novo Industries A/S under the registered trade name ESPERASE. The preparation of this enzyme and analogous enymes is described in British Patent Sp~rifir~ n No. 1,243 ,784 of Novo. Proteolytic enzymes suitable for removing protein-based stains that are ~,~.,..,~., "y available include those sold under the tradenames ALCALASE and SAVINASE by Novo Industries AtS
(Denmark) and MAXATASE by IllLel~ u~ldl Bio-Syn'thetics, Inc (The N ' ~ ~ ). Other proteases include Protease A (see European Patent Application 130,756, published ~anuary 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).
Amylases include, for example, o-amylases described in British Patent S~ t;.... No. 1,296,839 (Novo), RAPIDASE, I..L~ , L;o..,,l Bio-Synthetics, Inc.
and TERMA~L, Novo Industries.
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 lipase enzymes for detergent usage include those produced by ....-uulL of the r~ ~ g~oup, such as r~v lu~ c stutzeri ATCC
19.154, as disclosed in British Patent 1,372,034. See also lipases in Japanese Patent Application 53,20487, laid open to public inspection on February 24, 1978. This - lipase is available from Amano rl.,,.,.,,~ L;.,dl 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 Cl"u.l.ul,~ - viscosum, e.g.
Chromobacter viscosum var. Iipolyticum NRRLB 3673, Cul}~ ,y available from , , , , , ., . .. . _ , .. . ., . _ . _ _ , _ wo gs/27775 2 1 8 7 1 6 ~1 22 P
Toyo Jozo Co., Tagata, Japan; and further Cluu~ub~ el viscosum lipases from U.S.Fn~ Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex r ~ ~adioli. The LIPOLASE enzyme derived from Humicola lanuginosa and , ".~, available from Novo (see also EPO 341,947) is a preferred lipase 5 for use herein.
Peroxidase enzymes are used in .~...,1, ~;.,.. with oxygen sources, e.g., p~ ,al~ , perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
10 Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and llâlu~ uAidà~e such as chloro- and bromo-peroxidase.
Peroxidase-containing detergent ~ c;~ are disclosed, for example, in PCT
l,.t~ --'1 Application WO 89/099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries AIS.
A wide range of enzyme materials and means for their ;.. ~,ul~Ju,~liu.~ into synthetic detergent ~ :l;u -- are also disclosed in U.S Patent 3,553,139, issuedJanuary 5, 1971 to McCarty et al Enzymes are fiurther disclosed in U.S. Patent 4,101,457, Place et al, issued July 18, 1978, and in U.S. Patent 4,5û7,219, Hughes, issued March 26, 1985, both. Enzyme materials usefiul for liquid detergent r.. ~ and their I,u,.. liu.. into such ru~ ulaL;ull~, 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. 8~7no586 ~, published October 29, 1986, Venegas. Enzyme ' ' systems are also described, for example, in U.S. Patent 3,519,570.
Enzvme Stabilizers - The enzymes employed herein may be stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished which provide such iûns to the enzymes. (Calcium ions are generally somewhat more effective than magnesium ions and are preferred herein if only onetype of cation is being used.) Additionâl 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 about I toabout 30, preferably from about 2 to about 20, more preferably from about 5 to about 15, and most preferably from about 8 tû about 12, millimoles of calcium ion per liter of finished ~ .., This can vary somewhat, depending on the amount of enzyme present and its response to the calcium or magnesium ions. The level of wo ss~2777~ 2 ~ ~ 7 1 ~9 23 - ~
calcium or magnesium ions should be selected so that there is always some minimum level available for the enzyme, aAer allowing for ~..,,..i,!..~l;~., with builders, fatty acids, ete., in the ~ ) Any water-soluble calcium or magnesium salt can be used as the source of calcium or magnesium ions, including, but not limited to, 5 calcium chloride, calcium sulfate, caleium malate, calcium maleate, calcium hydroxide, ealcium formate, and calcium acetate, and the cu..c~.ùl.l;.,~ magnesium salts. A smaD amount ûf calcium ion, generally from about û.û5 to about 0.4 miDimoles per liter, is oAen also present in the c~ Q- l;r~A due to calcium in the enzyme slurry and formula water. In solid detergent . , - the lù.~..uL.lio~l may include a suffieient quantity of a water-soluble calcium ion source to provide such amounts in the laundry liquor. In the alternative, natural water hardness may sufiice.
It is to be understood that the foregoing levels of caleium and/or magnesium ions are sufficient to provide enzyme stability. More calcium and/or magnesium ions can be added to the ~ to provide an additional measure of grease removal ~. ~ Aeeordingly, as a general proposition the .,. .~ - herein will typicaDy eomprise from about 0.05% to about 2% by weight of a water-soluble source of caleium or magnesium ions, or both. The amount can vary, of course, with the amount and type of enyme employed in the ~ ~p~
The r -- herein may also optionally, but preferably, contain various additional stabilizers, especially borate-type stabilizers. Typically, such stabilizers will be used at levels in the ~ ..c from about 0.25% to about 10%, preferably from about 0.5% to about 5%, more preferably from about û.75% to about 3%, by weight of boric acid or other borate eompound capable of forming boric acid in the , , - (calculated on the basis of boric acid). Boric acid is preferred, althoughothet ~ , ' such as boric oxide, borax and other alkali metal borates (e.g., sodium ortho-, meta- and pyroborate, and sodium ~ r) are suitable.
Substituted boric acids (e.g.,, ' rlbolu"h acid, butane boronic acid, and p-bromo pl~ bu~u~u~, acid) can also be used in place of boric acid.
~gh~ - Any optical brighteners or other brightening or whitening agents known in the art can be ;II~,UIIJUl~ d at levels typically from about 0.05% to about - 1.2%, by weight, into the detergent c.. ~ herein. Commercial optical brighteners which may be useful in the present invention can be classified into - subgroups, which include, but are not necessarily limited to, derivatives of stilbene, 35 pyrazoline, coumarin, carboxylic acid, I".,;h;...,.,~.,.f"l.,~, ' l ', ' ~-5,5-dioxide, azoles, 5- and 6-membered-ring ll~ u~ , and other 1~ llc agents.
Examples of such brighteners are disclosed in "The Production and Application of , , ,, ,, . . . . _ .. .. . . . . .

wo 95/27775 2187 ~ ~ 9 24 ~ 7 ' -Fluorescent ~righ~l~nin~ Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982).
Specific examples of opticai brighteners which are useful in the present c.. ~ are those identified in U.S. Patent 4,790,856, issued to Wixon on S December 13, 1988. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners disclosed in this reference include:
Tinopai UiiPA, Tinopai CBS and Tinopal SBM; available from Ciba-Geigy; Artic White CC and Artic White CWD, available from Hilton-Davis, located in Italy; the 2-(4-stryi-phenyl)-2H-napthol[1,2-d]triazoles; 4,4'-bis- (1,2,3-triazol-2-yl)-stilbenes;
4,4'-bis(stryl)bisphenyls; and the ~ -cu~ Specific examples of these brighteners include 4-methyl-7-diethyl- amino coumarin; 1,2-bis(.- ~ -2-yl)ethylene; 1,3-diphenyl-,' " 2,5-bis(bexazol-2-yl)thiophene; 2-stryl-napth-[1,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho- [1,2-d]tria_ole. See aiso U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton. Anionic brightenersare preferred herein.
~--Ac Suppressors - Cnn~rollnr c for reducing or su~",-c~ the formation of suds can be i~l~,ul~Jula~e~i into the , of the present invention. Suds DU~ ~ J~ can be of particular importance in the so-called "high, cleaning process" and in front-loading E.ll r ~ style washing machines.
2û A wide variety of materials may be used as suds ~u~ vl~, and suds ~u~y.c:.~ul~ are well known to those skilled in the art. See, for example, Kirk Othmer ~ y~ - of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John ~ley & Sons, Inc., 1979). One category of suds suppressor of particular interest c ~ JAyliC fatty acid and soluble salts therein. See U.S.
Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The ~!k, fatty acids and salts thereof used as suds suppressor typicaily have il~J.U~ l chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable saits include the alkali metal salts such as sodium, potassium, and iithiumsaits, and ammonium and " ' salts.
The detergent ~.~. l.. ~; ;.. ~ herein may also contain non-surfactant suds~U~,~..,~Vl~. These include, for example: high molecular weight lly~ilu~ liJull~ such as paraffin, fatty acid esters (e.g., fatty acid ~ .cl;d~ ), fatty acid esters of v ' aicohols, aliphatic Clg-C40 ketones (e.g., stearone), etc. Other suds inhibitors include N-alkylated amino triazines such as tri- to hexa-~ yll...,la..~i...,s or 35 di- to tetra . " yl~ ll...lG ~,I iu. formed as products of cyanuric chioride with two or three moles of a primary or secondary amine containing I to 24 carbon atoms, propylene oxide, and l..vllostG~.yl phosphates such as lllvllù~è~llyl alcohol phosphate . ., ,! ' . .!
W095127775 ~71 ~9 ~ _~11....~1P7 ester and ~I di-alkali metai (e.g., K, Na, and Li) phosphates and phosphate esters. The h~ ùcallJvll~ such as paraffin and I ~ald~ l can be utilized in liquid form. The liquid IIJJlu~,al~ will be liquid at room ttllly~"dLulc and All...~l/~. .;~, pressure, and wiii have a pour point in the range of about -40C and about 50CC, and 5 a minimum boiiing point not less than about 110OC (AI~ pressure). It is also known to utiiize waxy h~ iluuali~ulla, preferably having a melting point below about lû0C. The ll.~J~u~,aliJu..~ constitute a preferred category of suds suppressor for detergent ~ .,c 1IrJ~vc~lJoll suds su,u~ avla are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. The i~ ilvcalbv~10 thus, include aliphatic, aiicyclic, aromatic, and l.~Ltlu~,yl,l;C saturated or, hyJIul,albu..~ having from about 12 to about 70 carbon atoms. The term "paraffin,"
as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic i~J~ilu~,al~
Another preferred category of non-surfactant suds aU,UlJIe:~ùl~ comprises 15 siiicone suds auylJI'e~ a. This category includes the use of pulyu-~,- ,- ~a l ~ - ' oils, such as p~l~." ' ,' ' , dispersions or emulsions of pvlyul~;r~ - ûils or resins, and ~ ' of pvlyu,~ --- with silica particles wherein the pvl,v,~ - l( ~ is ch~ "i,.,d or fused onto the silica. Silicone suds ~Uy~Jlcv~.vlS are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandûlfo et al and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M. S.
Other siiicone suds auyyl~,vl~ are disclosed in U.S. Patent 3,455,839 which relates to ~...,, I .- ~;-,~-c and processes for defoaming aqueous solutions by ~ ,, therein smaii amounts of p~lyd;..l~,lh~' ' - fluids.
Mixtures of silicone and silanated silica are described, for instance, in GermanPatent Application DOS 2,124,526 Silicone defoamers and suds controlling agents in granular detergent, , f~n~ are disclosed in U.S. Patent 3,933,6?2, Bartolottaet ai, 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 30 auyyl~ ~ amount of a suds contrûlling a8ent consisting essentially o (i) pul.~.' ' ,' ' ~ fluid having a viscosity of from about 20 cs. to about 1,500 cs. at 25C;
(ii) from about 5 to about 50 parts per 10û parts by weight of (i) of siloxane resin composed of (CH3)3SiO112 units of SiO2 units in a ratio of from (CH3)3 SiO112 units and to SiO2 units of from about 0.6:1 to about 1.2:1; and . .

wo ss/2777s 2 1 ~ 7 1 6 g 26 (iii~ from 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 certain pG~ . glycols or polyelhylene-5 pol~,.ul.J!~ e giycol copolymers or mixtures thereof (preferred), or polyl,.u~"l~,.,~,giycol. The primary silicone suds suppressor is branchedU,,Iu~;.lil~c~ and preferably not linear.
To iDustrate this point further, typical liquid laundry detergent 40.~ ..C I;....
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 0.05 to about 0.5, weight % of said silicone suds suppressor, which comprises (I) a l~u, ~y ...~ emulsion of a primary antifoam agent which is a mixture of (a) a pol~v~ ..r, (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: , (a), (b) 15 and (c), to form silanolates; (2) at least one nonionic silicone surfactant; and (3) p~ "!~,.le giycol or a copolymer of pOI~ -pulJ~Jlu~ , glycol having a solubility in water at room L~ ,.dlul c: of more than about 2 weight %; and without PU~ UIJJ!~ giycol. Similar amounts can be used in granular ..J...r~ -., gels, etc. See aiso U.S. Patents 4,978,471, Starch, issued December 18, 1990, and 4,983,316, Starch, issued January 8, 1991, 5,288,431, Huber et al., issued February 22, 1994, and U.S. Patents 4,G39,489 and 4,749,740, Aizawa et al at columr. 1, line 46 through column 4, line 35.
The siiicone suds suppressor herein preferably comprises p.,l~lhyl~ , glycol and a copolymer of PUIJ~Ih~ glycoUpvl~u.u~ , glycol, all having an average molecular weight of less than about 1,000, preferably between about 100 and 800.The p~l~.,ih~!~,..., glycol and pvl~ J!~ p~ lu~ e copolymers herein have a solubility in water at room ~ J."alul~ of more than about 2 weight %, preferablymore than about 5 weight %.
The preferred solvent herein is pGI~LI.~!.,"~, glycol having an average moiecular weight of less than about 1,000, more preferably between about 100 and800, most preferably between 200 and 400, and a copolymer of PUIJ~;IIJI~
giyCoUI,ul~,lulJJ~ c glycol, preferably PPG 2001PEG 300. Preferred is a weight ratio of between about 1:1 and 1:10, most preferably between 1:3 and 1:6, of pvl~,h~ glycol:copolymer of pcl~ ,,l.".e-polypropylene glycol.
The preferred silicone suds suppressors used herein do not contain JIU~JJ~ C glycol, particularly of 4,000 molecular weight. They also preferably woss/27775 2~ 69 ; ,~

do not contain bloek copolymers of ethylene oxide and propylene oxide, like PLURONIC L101.
Other suds ~u~ ula useful hetein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,198,679, 4,075,118 and EP 150,872. The secondary alcohols 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 ~u~ ~aul~ typically comprise mixtures of alcohol +
silicone at a weight ratio of 1:5 to 5:1.
For any detergent c~ ;nr~ to be used in automatic laundry washing machines, suds should not form to the extent that they overfiow the washing macbine. Suds ~u~ S, when utilized, are preferably present in a Usuds ,.. ,, amount. By "suds ~Up~..l,~S;llg amount" is meant that the formulator of 15 the ~ , can select an amount of this suds controlling agent that will sufticiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.
The c~ herein will generally comprise from 0% to about 5% of suds suppressor. When utilized as suds ~u~ u.~ lul~ llbu~yl;~, fatty acids, and 20 salts therein, will be present typically in amounts up to about 5%, by weight, of the detergent ~ml~o :1;~ Preferably, from about 0.5% to about 3% of fatty 1JUA.J` suds suppressor is utilized. Silicûne suds ~uy~lc~ùl~ are typiwlly utilized in amounts up to about 2.0%, by weight, of the detergent c.. ~
although higher amounts may be used. This upper limit is practical in nature, due 25 primarily to concern with keeping costs minimized and c~,L;~ of lower amounts for effectively controlling sudsing. Preferably from about 0.01% to about 1% of silieone 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 .u ~ with pOIyul~ Y.- c, as well as any adjunct materials that 30 may be utilized. M~llcia~ yl phosphate suds :~UyUlC~.~Ul~ are generally utilized in amounts ranging from about 0.1% to about 2%, by weight, of the ~
II~dluwlbu~, suds :iUIJlJlC:~:>Ul:> are typically utilized in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used. The alcohol suds 1~u~ ul ~ are typically used at O.2%-3% by weight of the finished c.~.. .1 ~.~ l ;. . -Fabric S~ n~s - Various through-the-wash fabric softeners, especially the impalpable smectite clays of U.S. Patent 4,û62,647, Storm and Nirschl, issued December 13, 1977, as well as other softener clays known in the art, can optionally ,, . . , ., . , .. . _, . .. . . . . . . . . .

wo ss/2777s 2 ~ 8 rt 1 ~ ~1 28 ~
be used typically at levels offrom about 0.5/0 to about 10% by weight in the present .. l.. ~:l;.. --- to provide fabric sofiener benefits concurrently with fabric cleaning.
Clay sof~eners can be used in ' with amine and cationic softens 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 22, 1981.
Dve Transfer Inhibitin~ A~ntc - The ~ 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 polyvinyl U,~ ' ' polymers, polyamine N-oxide10 polymers, copolymers of N .;~ ,., '' ' and N ~ c, manganese 1' ' ' _,. , p.~UAl~aSe~, and mixtures thereof. If used, these agents typically comprise from about 0.01% to about 10% by weight of the . ~ .", preferably from 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 pu~ .iLabl. unit to which an N-O group can be attached or the N-O group can form part of the POI~ ~abl~ unit or the N-O group can be attached to both units; A
is one of the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=; x is 0 or 1; and R is aliphatic, ethoxylated aliphatics, aromatics, Il~ uc~ . or alicyclic groups or any . ' ' 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 h.,,elu~ , group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereo The N-O group can be represented by the following general structures:
1 o (R~)X--I--(R2)y ; =N--(R~)x (R3)z wherein Rl, R2, R3 are aliphatic, aromatic, ..~c.u."y.,l;., or alicyclic groups or thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be attached or form part of any of the d['Ul c~ ;u~,d groups. The amine oxide unit of the polyamine N-oxides has a pKa <10, preferably pKa <7, more preferred pKa <6.
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, polyalkylenes, polyesters, polyethers, polyamide, polyimides, pul~a~,l~l..`~,., and mixtures thaeof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the i 2777~ g 29 r~"~
other monomer type is an N-oxide. The amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate cupu~ ..i~liu.. or by an appropriate degree of N-oxidation. The S polyamine oxides can be obtained in almos~ 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.
The most preferred polyamine N-oxide useful in the detergent ~.r...~l.,.- l;., herein is poly(~ Ih " -N-oxide) which as an average molecular weight of 10 about 50,000 and an amine to amine N-oxide ratio of about 1:4.
Copolymers of N . Jl~oJI~ ~ and N ~ .r' ' ' polymers (referred to as a class as "PVPVI") are also preferred for use herein. Preferably the PVPVI has an aversge molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average 15 molecular weight range is determined by light scattering as described in Barth, et al., Vol 113. "ModernMethodsofPolymer ('h ~ r~ the disclosures of which are ~ i,u.~ herein by reference ) The PVPVI LUP;)I~
typically have a molar ratio of N-~ to N ~ J.I~ ' ~ ~ from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1.20 These copolymers can be either linear or branched.
The present invention ,,.. I.. ,;l;.,.. c also may employ a pGly~ rolidone ("PVP") having an average molecular weight of from about 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, ~,u. ~d herein by reference.
C.. ~ -- containing PVP can also contain pGl~.hrl...., glycol (~PEG~) having an average molecular weight from about 500 to about 100,000, preferably from about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2:1 to about 50:1, and more preferably from about 30 3:1 toabout 10:1.
The detergent ~ I.ù~ 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 ru,..l ~ herein will preferably comprise from about 0.01% tO 1% by weight of such optical l,. _' The hydrophilic optical brighteners useful in the present invention are those having the structural formula:
.. ... .. . . ... . . .. ..

WOg5/27775 ~8 30 p~~ 9r N~ ~H~ I ~NI ~ON
R2 SO3M SO3M Rl wherein Rl is selected from anilino, N-2-bis-llyJ.u~.,ll,yl and NH-2-l~yJ.u~.~ .h~l;
R2 is selected from N-2-bi~ JJIu~.,Ll~l, N-2-llyJIu~.Lllyl-N-l~l~.Lh~lallullO~
morphilino, chloro and amino; and M is a salt-forming cation such as sodium or 5 potassium.
When in the above formula, Rl is anilino, R2 is N-2-bis-llyJluA~ ' and M
is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-llyJ~u~lyl)-s-triazine-2-yl)amino]-2,2'- 'L ~ r ' acid and disodium salt.
This particular brightener species is l~UI~U~ / marketed under the tradename 10 Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent ~ herein.
When in the above forrnula, Rl is anilino, R2 is N-2.~rJ~u~.~..llyl-N-2-....,.hJ' ' and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-l-~Jlu~,lllyl-N ' ylc~u~u)-s-triazine-2-yl)amino]Z~2~ ''` acid 15 disodium salt. This particular brightener species is cullull~ ,;allr marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corpûration.
When in the above formula, Rl is anilino, R2 iS morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-...u.l ~ ~ r triazine-2-yl)amino]2,2'-cti'' ~ - ' "` acid, sodium salt. This particular brightener species is 20 cu~u...,.l,;.~ 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 p.,. f~ benefits when used in with the selected polymeric dye transfer inhibiting agents l..,lL;.Ib.,f~
25 described. The ~ ' of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX Tinopal 5BM-GX and/or Tinopal AMS-GX) provides s;~;.uL.,zu.ily better dye transfer inhibition in aqueous wash solutions than does either of these two detergent "J` I""' fU"'I""' 'I` when used alone. Without being bound by theory, il is 30 believed that such brighteners work this way because they have high affnity for fabrics in the wash solution and therefore deposit relatively quick on these fabrics.
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 ~, wogsl2777/C ~8~1fi~ 31 generaA as the ratio of a) the brightener material deposited on fabric to b) the initial brightener ~ in the wash. Iiquor. Brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention.
Of course, it will be appreciated that other, CU~ ;OII~AI optical brightener types of ~ , ' can optionaAly be used in the present r~ u~:l;ù c to provide cu..~ iol~l fabric "I,liollLl.~,.a" benefits, rather than a true dye transfer inhibiting effect. Such usage is cu~ tiUll~l and well-known to detergent rul Illul. liulla.Other ~ ntc - A wide variety of other ingredients useful in detergent lu~ can be included in the ~ , herein, including other active ~, ' , carriers, ~IrJ~u~lu~.~, processing aids, dyes or pigments, solvents for liquid 1~ ., solid fillers for bar cu~ , etc. If high sudsing is desired, suds boosters such as the Clo-C16 " ' ~ can be i~l.,u~u~cd into the V~ , typically at 1%-10% levels. The C10-C14 . .~ ,l and diethanol amides illustrate a typicaA 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 aAso ad~ LO~,uua. If desired, soluble magnesium salts such as MgC12, MgSO4, arAd the like, can be added at levels of, typically, 0.1%-2%, to provide additionaA suds and to enhance grease removal ~, '`
Various detersive ingredients employed in the present ~.,J ~
optionaAly can.be fiurther stabilized by absorbing said ingredients onto a porous }l~J~u~ u~i~, substrate, then coating said substrate with a ~.~J.u~lllul,ic coating.
Preferably, the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate. In use, the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive fiunction.
To illustrate this technique in more detail, a porous llydl~r'~': silica (trademark S~ERNAT D10, Degussa) is admixed with a proteolytic enzyme solution containing 3%-5% of C13 1s ethoxylated aAcohol (EO 7) nonionic 30 surfactant. TypicaAly, the ~ u-r~ AL solution is 2.5 X the weight of silica.
The resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used). The resulting silicone oil dispersion is emulsified or other~vise added to the final detergent matrix. By this means, ingredients such as the ~ru~c~ Liul~d enzymes, bleaches, bleach activators, 35 bleach catalysts, photoactivators, dyes, fluorescers, fabric ' ~ and ~IyJluly~l~ surfactants can be "protected" for use in detergents, including liquid laundry detergent ~
... ... _ . _ _ _ _ _ . .. . .. . . .

' ~ _ P ~ r7~-woss/2777s ~ 6~ 32`
Liquid detergent ~ can contain water and other solvents as carriers. Low molecular weight primary or secondary aicohols exemplified by methanol, ethanol, propanol, and i u~lvpGl~ol are suitable Monohydric alcohols are 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-~,v, ' 1, ethylene glycoi, giycerine, and 1,2~ ' ') can also be used. The ~ o~
may contain from 5% to 90%, typically 10% to 50% of such carriers.
The detergent r(~ v~ herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 11, preferably between about 7.5 and 10.5. Automatic ~' ' Gi L...~ product r ~ '' preferably have a pH between about 8 and about I l. Laundry products are typicaiiy at pH 9-11. Techniques for controlling pH atusage levels include the use of buffers, alkalis, acids, etC., and are well known to those skilled in the art.
The following examples illustrate ~.,~,...... l-,,,,l;,. ~ according to the invention, but are not intended to be iimiting thereo The following detergent ~.,,,,,l,"~ l;,~..c are prepared (parts by weight).
MPr.F I
Wei~2ht %
Zeolite 38.0%
Silicate 2.0R 6.0%
Carbonate (Sodium) 9.0%
~thylene Diamine Tetra Methylene ~' , ' 0.2%
Brightener 47 (Tirlopai DMS) 0.1%
Brightener 49 (Tinopal CBS) 0.05%
r~ ,G,I, 8.0%
TAED 7.0%
Mn Catalyst~vppm) 350 Savinase (4.0 KNPU/g) 2.0%
Lipolase (100,000 LU/g) 0.22%
C12 14 Aikyl Sulphate 5.6%
C12 14 AE4.2 nonionic 11.6%
Soap 1.0%

~7I6g WO gs/2777~ .'^7 ' ~- " /Moist.
Balance 100%
*Mnlv2(u-o)3(l74~7-trimethy~ 4~7-L~ y~lullull~ )2(pF6)2 ExAMPLF n Weight %
Zeo&te 38.0%
Si&cate 2.0R 6.0%
Carbonate (Sodium) 7.0%
Ethylene Diamine Tetra Methylene r~ , ~ 0.2%
Brightener 47 (Tinopal DMS) 0.1%
Brightener 49 (Tinopal CBS) 0.05%
r~5.0%
TAED 2.0%
Mn Catalyst*(ppm) 350 Savinase (4.0 KNPU/g) 2.0%
Lipolase (100,000 LU/g) O.æ%
C12 14 Alkyl Sulphate 5.6%
C12 14 AE4.2 nonionic 11.6%
Soap 1.0%
Persulfate 1 0.0%
M C., 11 -- - v ~lMoist.
Balance 100 *Mnlv2(u-0)3(1,4,7-trimethyl-1,4,7-Ll;~ )2(PF6)2 S EXAMP~.F 111 Wei~ht %
Zeolite 38.0%
Silicate 2.0R 6.0%
Carbonate (Sodium) 7.0%
Ethylene Diamine Tetra Methylene pl , ' 0.2%
Brightener 47 (Tinopal DMS) 0.1%
Brightener 49 (Tinopal CBS) 0.05%

W095/27775 2~ g 34 r~
rLI ~,c~l 5.0%
TABD 2.0%
Mn Catalyst*(ppm) 350 Savinase (4.0 KNPU/g) 2.0%
Lipolase (100,000 LU/g) 0.22%
C 12 14 Alkyl Sulphate 5.6%
C12 14 AE4.2 nonionic 11.6%
Soap 1.0%
PAP4~ 10.0 ~' " 'Moist. 100 Balance ~MnlV2(u-0)3(1,4,7-trimethyl-1,4,7-~1;c~"~, ' -)2(PF6)2 ~N,N-I' ' ' ,' , u~.y~,c~lu;cacid All of the foregoing granular ~ u~ may be provided as srpay-dried granules or high density (above 600 g/liter) granules or ,.~1.,.. n~ In ~xample III, the PAP may be replaced by 6-llUII~' 6-u~ulJ~U~.y~ u;~, acid (NAPAA).

Claims (9)

WHAT IS CLAIMED IS:

1. Laundry bleaching compositions having reduced metal-containing bleach catalyst-induced fabric damage, said composition comprising:
(a) a peroxy compound selected from the group consisting of preformed organic percarboxylic acids, bleaching mixtures containing a bleaching agent that is a source of hydrogen peroxide and one or more bleach activators, and mixtures thereof present in an effective amount to cause bleaching;
(b) a metal-containing bleach catalyst present in an effective amount to activate the peroxy compound; and wherein further the molar ratio of hydrogen peroxide to peracid, from the preformed organic percarboxylic acids or the bleach activator, is less than 4:1.

2. The laundry bleaching composition according to Claim 1 wherein the peroxy compound is a preformed organic percarboxylic acid.

3. The laundry bleaching composition according to Claim 1 wherein the peroxy compound is a bleaching mixture containing a bleaching agent that is a source of hydrogen peroxide selected from perborate, percarbonate, and mixtures thereof.

4. The laundry bleaching composition according to either of Claims 1 or 3 wherein the bleach activator is TAED.

5. The laundry bleaching composition according to either of Claims 3 or 4 wherein the molar ratio of hydrogen peroxide to peracid is from 1:1 to 3:1

6. The laundry bleaching composition according to any of Claims 3-5 wherein the molar ratio of hydrogen peroxide to heavy metal ions sourced by the bleach catalyst is less than 1200:1.

7. The laundry bleaching composition according to any of Claims 3-6 wherein the molar ratio of peracid to heavy metal ions sourced by the bleach catalyst is more than 350:1.

8. The laundry bleaching composition according to either of Claims 1 or 2 wherein the preformed organic percarboxylic acid is selected from 6-nonylamino-6-oxoperoxycaproic acid, N,N-phthaloylaminoperoxycaproic acid, and mixtures thereof.

9. A method for laundering fabric comprising contacting fabric in need of laundering with a laundry solution of a composition according to any of Claims 1-8 at a concentration such that said laundry solution has a metal-containing bleach catalyst concentration within the range of from 0.1 ppm to 700 ppm.