CA2214397A1 - Detergent composition comprising source of hydrogen peroxide and protease enzyme - Google Patents

Abstract

There is provided a non-phosphate builder-containing detergent composition comprising a surfactant, and a) at least 0.5 % by weight of a source of hydrogen peroxide; b) from 0.01 % to 10 % by weight of an organic peroxyacid bleach precursor; c) from 0.001 % to 5%
by weight of a proteolytic enzyme; d) an alkalinity source having the capacity to deliver alkalinity to a wash solution as measured by the alkalinity release test described herein, such that the % weight NaOH equivalent of the composition is greater than 10.6 % by weight of the composition, and wherein the detergent composition has a Hydrogen peroxide Precursor Proteolytic enzyme (HPP) Index of at least 0.35 as defined by the formula HPP - (% weight of precursor x % weight of proteolytic enzyme)/(%AvO2)2, wherein the % weight of proteolytic enzyme in the formulation is based on an enzyme activity of 13 knpu/g of the enzyme particle, and wherein the %AvO2 is the total amount of available oxygen present in the composition.

Description

W 096/28534 PCTnUS96/02337 Detergent Composition Comprising Source of Hydrogen Peroxide and Protease Enzyme Technical field The pr~sent invention reiates to non-phosphate builder-containing detergent compositions. More particularly, the invention relates to non-phosphate detergent compositions, comprising a SL" ra~;tal ,t, a source of hydrogen peroxide, an organic peroxyacid precursor, a proteolytic enzyme and an alkalinity source, which provide effective soil/stain removal.

Back~round of the invention The salisrdclGfy removal of soils/stains is a particular challenge to the formulator of a deler~~e"1 co,nposition for use in a washing process such as laundry or machine dishwashing process.

Traditionally, the removal of soils/stains has been achieved by the use of bleach co",po,)ents such as oxygen bleaches, including hydrogen peroxide and o~ ganic peroxyacids, and also by enzyme components.

Oxygen bleaches are known to effectively decolourise pigments from soiled/s~ai"~d subsl,dles.

Enzymes are also known as effective soil/stain removal agents, for example, in the removal of proteinaceous stains/soils such as blood, egg, chocolate, gravy and the like.

rl,os~ l,oius containing compounds such as sodium tripolyphospl,~te have effective builder properties; however environmental concems have made the use of phosphorus containing compounds less attractive in detergent compositions.

A problem encountered with the use of high levels of oxygen bleaches is the propensity of these oxygen bleaches to lead to stain fixing and/or darkening.
FLII ll ,e", lOf'a, high levels of oxygen bleaches increase the cost of the delergents to the consumer. On the other hand low levels of oxygen W O 9G128S34 PCT/u~ 23~/

bleaches can lead to poor stain/soil removal ~.e,fo"-~ance especially when used in a non-phos~,l ,ate builder containing co" ,position.

A problem encou,)lered with the use of peroxyacids in ",acl,ine dishwashing methods is the ta,.,isl~ing/corrosion of any silverware co",~onel,ls of the washload. Such a problem, ~liscl~sed in GB Patent Application No 9407533.0 is known in the art. Oxygen bleaches tend to give rise to more of a problem of tamishing than chlorine bleaches. The level of tamishing observed can range from slight r~iscolcralio, I of the silverware to the formation of a dense black codli"g on the surface of the silverware.

A problem encountered with the use of enzymes as components of d~ter~enls is that enzyme activity in the wash may be arrecled by the presence of other deterge"l co,npo,)~nls in the wash solution. GB Patent plic~tion No 9407533.0 discloses that enzymes may be degraded by bleach COIll~Gl)e~nlS.

The detergenl formulator thus faces the challenge of formulating an enviro,)",enlally friendly product which ",~in,ises soil/stain removal without fixing and/or darkening stains/soils which avoids degradation of the detergent cor"pG"el ,ts and which is also inex~,ensive.

Pending GB Patent Application No 9407536.3 that forms part of the state of the art under Article ~4(3) EPC disclQses the use of a bleach containing deterge, n col-lposilio-, which con~ains low levels of bleach and bleach activator with higher levels of chelant and enzyme and defines a specific Biological Bleach Index which provides stain removal p~,ror..,a,.ce. Specific ki.lelics of bleach delivery are not disclosed nor are the means to achieve such kinetics.

Pending GB Patent Application No 9407533.0 that forms part of the state of the art under Article 54(3) EPC discloses the use of an enzyme together with a source of peroxyacid bleach wherein a means is provided for delaying the release to the wash solution of said peroxyacid bleach relative to the release of said enzyme. The delayed release is provided by coali,-g the source of peroxyacid bleach. The coating may occur on the hyd~oge"

-W 096/28534 P~l/~;5.~2J37 peroxide source itself and/or the peroxyacid bleach precursor itself. Specific ratios of hydrogen peru,cide: precursor: pr~,lease are not ~isclose~

The Appli~rlts have found that the occurrence of soil/stain fixing and/or darkening effects arising from use of peroxyacid bleaches in a washing Illelhod is related to the rate of release of the hydluye~ peroxide source. A
fast rate of release of the hyd,oyeil peruxido source to the wash solution ~ tends to exac~rbale soil/stain fixing and/or darkening problems. Whilst reducing the rate of release of the hyd~og~l"~eroxicJe source employed in the wash tends to ameliorate these problems this is acco",pa"i l by a marked negative effect on the bleachable stains/soil removal ability.

The Ar~plir~nts have now surprisingly found that the provision of an alkalinity source which prorl~ces a speciric minimum amount of alkaline salts into the wash solution ameliorate these problems when low rate of release of the h~dlogen peroxide source to the wash sol~tion is used in combination with organic peroxyacid bleach precursors and proteolytic enzymes.

The Ap,ulical lls have also found that where a non-,c hosphate builder-containing deterye"t composition containing a source of hyd~ oyen peroxide an organic peroxyacid bleach precursor and a proteolytic enzyme defined in term of an H~dloyell pe,oxide Precursor Proteolytic enzyme (HPP) index which relates to the ratios of Hyd~oye,) peroxide precursor and proteolytic enzyme togetl,er with a high level of an alkalinity source is employed an o nl ,a"ced stain/soil removal may be obtained.

The ~pplic~lts have also found that the total available oxygen (Av02) cGIltellt in the cGi"position should preferably be less than 1.5% by weight of the composition.

The Applicants have also found that the the further addition of co,npounds e~lhances the overall stain/soil removal performance. Such compounds may be selected from amylases water-soluble oryanic polymeric polycarboxylic c~""~ounds chelants and mixtures thereof W 096/t8534 PCTrUS96/02337 It is thererore an object of the present invention to provide cG""~osilions suitable for use in laundry and machine dishwashing " ,ell ,ods having e, Ihanced stain removal.

It is a further object of the invention to provide co",positions for use in laundry and machine dishwashing methods wherein said cG""~ositions show less propensity to cause stains fixing and/or darkening as well as ~eterge"l CC~ )G~ llS de~~(adalion.

Summalv of the invention Accordi,)~a to the present invention there is provided a non-phosphate builder- containing deterge, ll composition CG" ,prising a surfactant, and a)- at least 0.5% by weight of a source of hydrogen peroxide, b)- from 0.01% to 10% by weight of an organic peroxyacid bleach precursor, c)- from 0.001% to 5% by weight of a proteolytic enzyme, and d)- an alkalinity source having the capacity to deliver alkalinity to a wash solution as measured by the alkalinity release test des~ibed herein, such that the % weight NaOH equivalent of the composition is greater than 10.6%
by weight of the con"~osilion, and wherein the detergen~ composition has an Hydrogen peroxide Precursor Proteolytic enzyme (HPP) Index of at least 0.35 as defined by the formula (%weight of precursor x %weight of proteolytic enzyme) HPP =
(%AVO2)2 wherein the %weight of proteolytic enzyme in the formulation is based on an enzyme activity of 13 knpu/g of the enzyme particle, and wherein the %AvO2 is the total amount of available oxygen present in the co"~osi(ion.

If the actual activities of these proteolytic enzymes in the detergent cor,~position are dirrtren~ from their 13 knpu/g standard activities, the level of proteolytic enzyme will be adjusted accordingly. The level of proteolytic enzyme is defined as the actual level of the prill/granulate on a 13 knpu/g Savinase particle.

W 096/28534 PCTrUS96/02337 Non limiting examples of enzymes other than Savinase which can also be used for the purpose of the invention include enzyme of the Bacillus Lentus type L,achl,ol ,e such as M~x~c~l, Opticlean, Durazym and r, operase, enzyme of the Bacillus Licheniformis type backbone such as Al~'~se and .al~se and enzyme of the Bacillus Amyloliquefaciens type backbone such as Pli",ase.
For example, if a protease is used having an activity of 26 knpu, the amount of ~rolease will be red~ ~ced by a factor 2 to con ",e, .sale for the extra activity of the protease.
For the purpose of the invention, proteases which are in other units of activity should be converted according to the following steps:
1 conversion of the level of proteolytic enzyme used into the level of pure enzyme, and 2-conversion from the level of pure enzyme to a 13 knpu/g Savinase particle basis according to the following equation:
13 knpu/g = 33 mg pure enzyme/g of enzyme particle It is to be un.lersloo~ that total amount of available oxygen present in the co""~,osition includes available oxygen provided by the source of hydrogen peroxide with or without peroxyacid bleach precursors.

Preferably the total available oxygen (Av02) content in the composition is less than 1.5% by weight.

Alkalinity is the co"~Li.,ing power of a base measured by the maximum number of equivalents of an acid with which it can react to form a salt. In soll ~tion, it represents the carbonates and silicates in the water and is determined by titration with standard datum points.

For the purpose of the invention, alkalinity is defined as the weight equivalent of sodium hydroxide (NaOH) needed to be delivered into the wash to neutralise an equivalent amount of hydrochloric acid.

Detailed descriPtion of the invention W 096/28534 PCTnUS96/02337 HPP index The ~,ese,ll invention relates to the discovery of a Hydloge" peruxiJe Precursor r~oteolytic enzyme (HPP) Index which de~ines a formula which relates speciric ratios of hy-JI ogen peroxide: precursor: ~ oteolytic enzyme.

Accordi. ,g to this is provided a non-phospl ,ale builder~G, ~lai"ing detergent CGI I .posiliol I having a Hydl uge n perùxicle Precursor Proteolytic enzyme (HPP) Index of at least 0.35 as defi"e.l by the formula (%weight of precursor x C6woi~1)l of proteolytic enzyme) HPP =
(%AYO2)2 wherein the %weight of proteolytic enzyme in the formulation is based on an enzyme activity of 13 knpu/g of the enzyme particle, and wherein the %AvO2 is the total amount of available oxygen ~resel,l in the CGrl l~oSiliGI~.

r, eren ~bly the HPP Index is of at least 0.40 and most pre~erably 0.50.

rl-erer;3bly the total available oxygen (Av02) content in the cûlnposition is less than 1.5% by weight.

Source of hvdu~c~en oeroxide An essential co""~onei ,L of the det~rgei ,l cGI",~osilion is a source of hy.hog~n peroxide. The source of hyd,ogen , eroxide is normally i,.co"~rdled at a level of at least 0.5% by weight, more plererdbly from 4%
to 15% by weight and most prefe,ably from 4% to 10% by weight of the cû,, ~l ~osili~i ..
Said source of hyd,oyen peroxide is a slow releasing source. The slow release of hydl o~ei, peroxide source relative to that of the protease is such that the time to achieve a concenl, alio,) that is 50% of the ultimate co"cenlralicji, of said enzyme is less than 120 secor,ds, prl3fe,ably less than 90 seconds, more p,e~rably less than 60 secol ,Js, and the time to achieve a ~..~nl.alion that is 50% of the ultimate concel~lldliGIl of said hydrogen peroxide source is more than 180 seconds, ~,,erefably from 180 to 480 seconds, more preferably from 240 to 360 secG"Js. rlefer~bly the time to W 096/28534 PCTnUS96102337 achieve a coi~ce"l,dlion that is 50~/0 of the Lllli",ale cGncenl,ation of said enyme is at least 100 secc "ds less than the time to achieve a co"cer,l,alion that is 50% of the ulli",ate concel1lralion for the hyd~ugen peroxide source.
Such slow release kinetic is more particularly des~il)ed in pe"di-,g GB
~ppli~Ption No. 9407533 0 In this respect, a preferred source of hyd,oyel~ peroxide is an i"organic perhydrate. A ~,refel,ed perhydrate is pelLorate tetrahydrate of nominal formula NaB02H202.3H2 0. The inorganic perhydrate will normally be in the form of the sodium salt. More prererably, the source of hydl oge peroxide consisls of at least 90% by weight of a pe, L,orale tetrahydrate.

Alle",dli-/ely, other perhydrate co",pounds may be used in addition or in place of the pe,l,orale tetrahydrate togell,er with approp,iate means such as ~ati"y or co~gglo" ,eralion, to obtain a slow release of hydrogen ,varoxide. Such COI "~unds can include pe, L.ol ale " ,onol ,ydrate percd, 1~1 ,ale, pe" hospl ,ate persilicate salts and mixtures thereof.
Of these cGI~pounds a prerel,ed perhydrate is percarbonate. Coarse per~s, L,onate materials of average particle size greater than 600 ",icro",eters and preferdL,ly yl~dler than 750 micrometers may be used rleferably, these perca,Li~"ale materials are coated with s~hsPnces which are s~s,i,)gly soluble in water. Water insoluble codli"g materials may be selected from fatty acid polymers hydl o~ L i c silicas, waxes and magnesium silicates and mixtures thereof. Perca.bonate materials whicn are ~xcl- ~sively coated with water-soluble s~ ~~ ~sl~nces such as citrates borosili~tes borate derivatives sodium c8~bonale or sodium/magnesium sulphate are not preferred.
When ~,erca, bo. ,ate is used the source of hydrogen peroxide consists of at least 90% by weight of a perca,bonate having a particle size of at least 600 micrometers and coated with water-insoluble materials.

Mixtures of any of the herein before described perhydrate col~,pounds can also be used.

In a p(erelled embodiment of the invention the level of total available oxygen (Av02) in the ccl"posilion is less than 1.5% by weight. A method for W 096/28534 PCT/U~r5~2337 det~l " ,ining AvO2 levels is disclosed in European Patent ~pplir~tion No.93870004.4.

Oraanic Peroxvacid bleach Drecursor Peroxyacid bleach precursors are co",~ounds which react with hycJ,ogen peroxide in a perhydrolysis reactioo to produce a peroxyacid. Generally pero~yacid bleach precursors may be ,eprese,)led as o X-e-L

where L is a leaving group and X is essentially any fu..ctionalil~ such that on perhydrolysis the structure of the peroxyacid produced is o X-e-OOH

Peroxyacid bleach precursor co""~ounds are ~referably i.,cG,~oraled at a level of from 0.01% to 10% by weight more prereral,ly from 3% to 10% by weight, most ~.referably from 5% to 9% by weight of the precursor cc " I~osilio,~.

Leavina arouPs The leaving group, hereindrler L group, must be sufficiently reactive for the perhydrolysis Fes~ lion 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 composition.

Prt7fe, led L groups are selected from the group consisting of:

W 096/28534 PCTrUS96/02337 --0~, --O~Y, and --(~R3Y

--N C--R1 --NL~ --N--C--CH--R4 lR3 r --0--C H=C--C H=C H2--0--C H=C--C H=C H2 -O--C--R1 CH~ Y11 O O

--0--C--CHR4 , and N S--CH--R4 and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R4 is H or R3, and Y is H or a sclubili~ing group. Any of R1, R3 and R4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and a,r,r"c)i,ium or alkyl ammmonium groups The prefe" ed solubilizing groups are -S03-M+, -C02-M+, -S04-M+, -N+(R3)4X- and 0~--N(R3)3 and most preferably -S03-M+ and -C02-M+
wherein R3 is an alkyl chain ~"taining from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. F,eferably, M is an alkali metal, arn" ,ol ,ium or substituted ammonium cation, with sodium and W 096128534 PCTrUS9~33'/

pot~ssi~ln being most ~,refer,ed, and X is a halide, h~,dloxicle, methylsulfate or ~c~ 1e anion.

Suitable peroxyacid bleach precursor materials are co, npounds which com~rise at least one acyl group fo""iny the peroxyacid moiety bonded to a leaving group through an -O- or-N- linkage.
These can be selecled from a wide range of cl~sses that include anhydrides, esters, imides, laclar"s and acylated derivatives of imid~oles and o~i",es. Examples of useful nlaterials within these c~~sses are disclosed in GB-A-1586789. Suitable esters are disclose~i in GB-A-83l;9~, 864798, 1147871, 2143231 and EP-A-0170386.
A preferred class of bleach precursor is the class of N-acylated precursors of which TAED is the prerel, e-J one.

Peroxyacid precursor ~" ,positions containing mixtures of any of the precursors hereir,drler disrlosed are also contemplated by the present invention.

relber.~ acid Drecursor re.be., -i~ acid precursor ~",pounds provide pelL,e"~oic acid on perhydrolysis.

Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, including for example benzoyl oxybel ,~ene sulfonate:
o (~O~SO3-Also suitable are the benzoylation products of sorbitol, glucose, and all sa~:ha, ides with benzoylating agents, including for example:

W 096128S34 PCTrUS96/02337 OAc AcO--~o ~,OAc OAc~
OBz Ac = COCH3; Bz = Benzoyl Perbenzoic acid precursor co""~ounds of the imide type include N-benzoyl succi,-i."ide tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas. Suitable i,nid~ole type perbenzoic acid precursors include N-benzoyl imid~ole and N-benzoyl be"~i",id~ole and other useful N-acyl group-containing pe,b~"~oic acid precursors include N-benzoyl pyrrolidone dibenzoyl taurine and benzoyl pyroglutamic acid.

Other perl3en~oic acid precursors include the benzoyl diacyl peroxides the benzoyl tet,dacyl peroxides and the cor"pound having the formula:
O O
~O' O~COOH

Phthalic anhydride is anotl,er suitable perb6",0ic acid precursor compound herein:
o ~0 Suitable N-acylated precursor compounds of the lactam class are disclosed generally in GB-A~55735. Whilst the broadest aspect of the invention CGI llel I ,plates the use of any lactam useful as a peroxyacid precursor prefe"ed materials co",~rise the caprolactams and valerolactams.

W 096/28534 PCTnUS96102337 t~le caprolacld", bleach precursors are of the formula:

o Il .

Il I \

R C - N

wherein R6 is H or an alkyl, aryl, alkoxyaryl or alkaryl group cc,nlaining from 1 to 12 ~, L,o" atoms, pref~,ably from 6 to 12 cal L,on atoms.
Suitable valero lacta",s have the formula:

Il I

CH CH

wherein R6 is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbon atoms, ~,rererably from 6 to 12 ~Ibol~ atoms. In highly ,uref~"~d elllbodime~ls, R6 is selected from phenyl, heptyl, octyl, nonyl, 2,4,4-trimethylpentyl, decenyl and mixtures thereof.

The most prefel,ed materials are those which are normally solid at ~30~C, particularly the phenyl derivatives, ie. benzoyl valerolactam, benzoyl caprolactam and their substituted benzoyl a"alogues such as chloro, amino alkyl, alkyl, aryl and alkyloxy derivatives.

Caprolactam and valerolactam precursor ",alerials wherein the R6 moietyconlai"s at least 6, p,eferdbly from 6 to about 12, carbon atoms provide peroxyacids on perhydrolysis of a hydro~ hobic character which afford -W 096/28534 PCTrUS96/02337 n~ philic and body soil clean-up. Precursor cG""~ounds wherein R6 col"~,rises from 1 to 6 carbon atoms provide hydrophilic bleaching species which are particularly efficient for bleacl,iny beverage stains. Mixtures of 'hydro~hobic' and 'hydrophilic' caprolactar,~s and valero l~c~a",s, typically atweight ratios of 1:5 to 5:1, preferably 1:1, can be used herein for mixed stain removal ben~ils.

Perbenzoic acid derivative Drecursors Pell,e"~oic acid derivative precursors provide substituted p~,L,e"~oic acids on perhydrolysis.

.SuiPhlQ substituted perbenzoic acid derivative precursors include any of the herein dis-,losed pelLell ~ic precursors in which the benzoyl group is s~ ~hstit~ed by essentially any non-positively chargecl (ie; non-cationic) fu, I-,lio"al group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl and amide groups.

A preferred class of substituted perl,e" oic acid precursor co"~,ounds are the amide substituted compounds of the following general formulae:

Il l 11 1 11 11 .
O R5 O or R5 O O

wherein R1 is an aryl or alkaryl group with from 1 to 14 calLGn atoms, R2 is an arylene, or alkarylene group ccnlai"ing from 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be ~ssel ,lially any leaving group. R1 p, ~f~rably contains from 6 to 12 carbon atoms. R2 prererdbly contains from 4 to 8 carbon atoms. R1 may be aryl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for e,~am~,le, tallow fat. Analogous structural variations are permissible for R2. The substitution can include alkyl, aryl, halogen, nil, oge", sulphur and other typical substituent groups or organic co"",ounds. R5 is preferably H or methyl. R1 and R5 should not contain more than 18 carbon atoms in total. Amide s~hstituted bleach activator cc mpounds of this type are des~ ibed in EP-A4170386.

W 096/28S34 PCTrUS96/02337 _ Cationic Deroxvacid Precursors Cationic peroxyacid precursor coh,pounds produce c liGl.ic peroxyacids on perhydrolysis.

Typically, calio"i~ peroxyacid precursors are fo""e.l by substituting the peroxyacid part of a suitable peroxyacid precursor co" ,~ound with a positively charged ful .ctio"al group, such as an ammo"ium or alkyl a" ,l "" ,onium group, I,, ererably an ethyl or methyl a" " "o"ium group.
Cationic peroxyacid precursors are typically present in the solid deterge"l cG""~osilions as a salt with a suitable anion such as a halide ion.

The peroxyacid precursor cGI"pound to be so calionically substituted may be a p61 6erlcoic acid, or s~ Ihstit~ Ited derivative thereof precursor compoundas described I ,erei. I6erore. Allel "ali-/ely the peroxyacid precursor ~,npound may be an alkyl per~r6Oxylic acid precursor cor"pound or an amide substituted alkyl peroxyacid precursor as des~ ibed hereinafter Cationic peroxyacid precursors are described in U.S. Patents 4,904 406;
4 751,015; 4,988,451; 4 397 757; 5 269 962; 5 127 852; 5 093 022;
5 106 528; U.~ 1 382 594; EP 475 512 458 396 and 284 292; and in JP
87-31 8 332.

Exa."ples of prefer,ed calioni~ peroxyacid precursors are described in UK
Patent Application No. 9407944.9 and US Patent Application Nos.
08/298903 08/298650 08/298904 and 08/298906.

Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybe"~e"e sulrl,nales N-acylated caprolactams and monobenzoyltetraacetyl glucose benzoyl peroxides.

A prer~"ed calionically substituted benzoyl oxybe,-~ene sulfonate is the 4-(trimethyl a-"monium) methyl derivative of benzoyl oxybenzene sulfonate:
.

CA 022l4397 l997-08-29 W 096128534 PCTrUS96/02337 O

\N+

A prere, ~ ~d cationically substituted alkyl oxyL,er,~e"e sulrondle has the formula:
.

O ~ S~3 rl efer, ~ad ~lionic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl a,nl~,Gnium methylene benzoyl caprolactams particularly t i,netl,yl a""nG"ium methylene benzoyl caprolactam:

o ~o / N ~

Other pr~fel, ecl cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl al "" ,onium methylene alkyl caprolacta, ns.
O O

(CH2)n ~) where n is from O to 12.

Another prerel,~d cationic peroxyacid precursor is 2-(N N N-trimethyl a" " "o"ium) ethyl sodium 4-sulphophenyl ~a, L ol ,ate chloride.

CA 022l4397 l997-08-29 W 096/28534 PCTrU~3. ~23~/

Be,~-o~;n G19dniC peroxyacid precursors Also suitable are precursor co,~,pounds of the ~,e,~o),;A~;n-type, as ~:li5c~ seti for example in EP-A-3~ 94 and EP-A482,807, particularly those having the formula:
1~l ~C--R1 including the s~ Ihstit~ ~ted ben7ox~ s of the type wherein R1 is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R4, and R5 may be the same or clifrerent substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR6 (wherein R6 is H or an alkyl group) and carbonyl fiJn~,liGIls.

An especi-"y prefei red precursor of the bel ~,o.~ ;. ,-type is:

1~l ~N~C~

Alkvl ~er~, L,oxYlic acid bleach precursors Alkyl per~a, I,oxylic acid bleach precursors form perca, boxylic acids on perhydrolysis. r,efe~ d precursors of this type provide peracetic acid on perhydrolysis.

W 096t28534 PCTrUS96/02337 r~e~,.ed alkyl perc;3r60xylic precursor ~,npounds of the imide type include the N N-N' N' tetra acetylated alkylene diar"ines wherein the alkylene group cGntains from 1 to 6 Cal~GIl atoms particularly those con,pounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tel,aacelyl ethylene diamine (TAED) is particularly pre~

Other prefe..ed alkyl per~,boxylic acid precursors include sodium 3,5,5-tri-methyl I ,exanoyloxyL.el .~e ne sulro,)ale (ISONOBS), sodium nonanoyloxyL,e.,~ene sulro"ale (NOBS) sodium acetoxyl~e,)~ene sulr(,"ate (ABS) and pe"taacelyl glucose.

Amide substituted alkYI Peroxyacid Precursors Amide s~hstit~tecl alkyl peroxyacid precursor cGm~ounds are also suitable including those of the following general formulae Il l 11 1 11 11 O R5 0 or R5 0 0 ,erein R1 is an alkyl group with from 1 to 14 carbon atoms R2 is an alkylene group col,tai--i,)g from 1 to 14 carbon atoms and R5 is H or an alkyl group co.,laining 1 to 10 carbon atoms and L can be essentially any leaving group. R1 prl3rerably contains from 6 to 12 c~,L,o" atoms. R2 prererably co,llai.-s from 4 to 8 carbon atoms. R1 may be sl.ai$~hl chain or bral ,~ .ed alkyl containing branching substitution or both and may be sourced from either synthetic sources or natural sources including for ex;~.."~le, tallow fat. Analogous structural variations are permissible for R2.
The s~hstih~tion can include alkyl halogen nitrogen sulphur and other typical s~hstituent groups or organic ~""~ounds. R5 is prefetably H or methyl. R1 and R5 should not contain more than 18 carbon atoms in total.
Amide substituted bleach activator compounds of this type are described in EP-A-01 70386.
r, efe" ed amide substituted alkyl peroxyacid precursor compounds are (6~cldl ,a",ido-caproyl)oxybe"~, lesulfonate (6-, IG"a"ar"ido~proyl)oxy be"~e"e sulfonate and (6-decanamido~aproyl)oxyLe"~ene sulronale and mixture thereof.

W 096r28534 PCTrUS96/02337 More p,er~ d peroxyacid bleach precursors co",pounds for use in the invention are selected from N,N-N',N' tetra acetyl ethylene diamine, 3,5,5-tri-methyl l,exa"oyl oxybe.-~e"e sulrondle".onanoyl oxyL.en~ane s--lronale, amide s~ ~hstitute~ e. ~, ~~oic acid precursor cGr"pounds, amide substituted alkyl peroxyacid precursors and mixtures ll.ereor.
A most p,ef~ d peroxyacid bleach precursor is N,N-N',N' tetra acetyl ethylene diar"i"e:When used TAED will ~,r~rerably be at a level of from 0.5% to 2.5% by weight.

Bleachi"g agents other than oxygen bleachin~ agents are also known in the art and can Gptionally be utili~ed herein. One type of non-oxygen bleaching agent of particular interest incl~des pholo~ctivated bleaching agents such as the sulrc,nal~d zinc andlor aluminum phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, delergent co"~po~itio- ,s will typically contain from 0.025% to 1.25%, by weight, of such bleaches, especially sulronate zinc phthalocyanine.
r"~teolvtic enzYme An essenlial ~~ GI ,6nl of the deterger,l co",~osition is an enzyme showing proteolytic activity.
For the purpose of the invention, the level of proleolytic enzyme in the formulation is based on an enzyme activity of 13 knpu/g of the enzyme ~dl licla.
The cc,l"~osilions herein will typically comprise from 0.001% to 5% active ~rotease by weight of the composition.

Non limiting examples of enzymes other than Savinase which can also be used for the purpose of the invention include enzyme of the Bacillus Lentus type backbone such as M~ c~l, Opticlean, Durazym and Properase, enzyme of the Bacillus Licheniformis type backbone such as AlG~'-se and M~ se and enzyme of the Bacillus Amyloliquefaciens type backbone such as r, i"~ase. Of these, M~Y~C~I jS a prere, .ed one.

Preferred co, . ,n ,el ~ially available ~,l v~ease enzymes include those sold under the i.dda,-s",es Al~ se, Savinase, Pli,),ase, Durazym, and Es,uerase by Novo Industries A/S (Der" "a, k), those sold under the l~a~e~ar"e M~ 5e, M~Y~C~I and Maxapem by Gist-Broc~des, those sold CA 022l4397 l997-08-29 W 096/28534 PCTrU~ 23 by Genencor Intemational, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Mixture of the herein before des~ibed proteases may be used.
A most pref~r~d ~rol~asl3 is Savinase.

Alkalinitv source An essential cGIllpoll~l)l of the delerger,l composition is an alkalinity source.

For the purpose of the invention, alkalinity is defined as the weight equivalent of sodium hydroxide (NaOH) needed to be delivered into the wash to neutralise an equivalent amount of hydrochloric acid.

To enable practical colllpalisGn of the relative capacily of composilions coi ,~ai,)ing dirrer~nl alkaline co",pGnents to deliver alkalinity to a wash solution it is useful to e~ress the alkalinity released on addition of the co""~osilions to the wash solution in terms of % weight equivalent of NaOH.
That is, in terms of the % weight of NaOH which would have equivalent 'alkaline effect', e. 9. in neutralising acid species, to that of the alkalinityspecies actually released when the co""~osition is added to the wash. For uniform co""~a~ison it is also then useful to define standard wash solution characleristics. Thus, the capacity to deliver alkalinity to a wash solution is herein ~;haracteri~ed by rererei ,ce to a representative test method now described.

Alkalinitv release test method A 19 sample of detergent co,nposition is added to 100 ml of distilled water at a temperature of 30~C with stirring at 150 rpm using a magnetic stirrer of size 2cm, thus providing a 1% detergent solution, as would be a typical concentration of a laundry wash solution. The solution is titrated against a slandald HCI solution using any suitable titration method. Commonly known acid-base titration methods employing colorimetric end-point dete""ination methods, for example using chemical end-point indicalor:, are particularly suitable. Thus, the number of moles of HCI which the detergent solution is ca~atl of neutralising is obtained. For the avcidance of doubt, 'neutralising' in this context is defined to mean lilldling to pH 7. This numberwill be equivalent to the number of moles of alkalinity, expressed as NaOH

W 096/28534 PCTrUS96/02337 equivalent prese.,l in the detergent solution. Thus the % weight equivalent NaOH present in the sample of the delerge"l co- "posilion may be c--~c~ ~I~'ed as:

% weight equivalent NaOH =

100 x number of moles NaOH equivalent in solution x Mw of NaOH

Theoretical maximum alkalinitv Where the cG,npositional make up of a detergent product is known it is rossibls to ~Ic~Jl~e the ll,eorelical ,.,axi-..um alkalinity eApressed as %
weight equivalent of NaOH which the product could provide to a solution as the sum over each alkaline species of:

% weight (alkaline species) . Mw (NaOH . n / Mw(alkaline species) where n is the formal negative charge carried by the alkaline species.

As an exa."pl a col.,posilion containing 15% sodium carbonate is equivalent to a theoretical ma~ m of 11.32% NaOH obtained as (15 x 40 x 2)/106, since this amount of NaOH in the ~""~osition would theoretically neutralise the same amount of acid as the 15% sodium carbonate alkaline com~,onenl.

Alkalinitv reauirement In accord with the present invention the alkalinity source is present in the detergent ~mposilio., such that the capacity to deliver alkalinity to a wash solution measured by the given test ~.,ethGd is such that the % weight NaOH
equivalent of the ~l~position is g,~dler than 10.6% ,c,rererably at least 14.6% by weight of the composition.

The alkalinity source is p,ererably selected from alkali metal carbonate alkali metal silicate and mixture thereof.

-CA 022l4397 l997-08-29 W 096/28534 PCTrUS96/02337 Suitable alkali metal ca,bGnales include the alkaline earth and alkali metal carbonates, including sodium carbonate and sesqui~a,L.G"ale and mixtures ll,~reor with ultra-fine calcium ca,l,onale as cJisclosed in German Patent Application No. 2,321,001 published on Nov~r"ber 15, 1973.

Suitable silicates include the alkali metal siliçat~ SiO2:Na20 with a ratio of from 1.0 to 2.8 and 1.6:1 ratio being more pr~fer-~d. The silicates may be in the form of either the anhydrous salt or a hydrated salt. Sodium silicate with an SiO2:Na2O ratio of 1.6:1 is the most prere"~d silic~te.

Other cG",pounds which provide free alkalinity in ~ eo~ ~s solution may also be used. Such cGl"pounds include the crystalline layered silicate and/or alu",inosilic~te c~""~ounds as clesuil,e.l herein after, but also the bicarbonates, hydroxides, borates and ~l ,osphales.

Addilional CG~ onents The ~leterg~"l co",position of the invention will, of course cGntain one or more su,r~tanls and ad-Jilional con~pounds for er,ha"ci,.y the soil removal p61 r~""a, Ice.
Such cc"..~Jounds include the water-soluble organic polymeric pol~ca,L,oxylic oo" ,pounds, chelants, amylases, builders and con~enliG"al detersive adjuncts.

Detersive Su, rac,tants The total amount of su,ractants will be generally up to 70%, typically 1 to 55%, l~referal,ly 1 to 30%, more preferably 5 to 25% and especially 10 to 20% by weight of the total composition.
~J~nli.l~ililly examples of su,ra-,ta"ts useful herein include the conventional C11-C1g alkyl benzene sulronates ("LAS") and primary, branched-chain and randon, C10-C20 alkyl sulfates ("AS"), the C10-C1g seco"da,y (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 inteyers of at least 7, ~,ref~rably at least 9, and M is a water-solubilizing cation, especially sodium,unsaturated sulfates such as oleyl sulfate, the C10-C1g alkyl alkoxy sulfates ("AExS"; esreci~lly EO 1-7 ethoxy sulfates), C1 0-C1 8 alkyl alkoxy ca, L,oxylates (especially the EO 1-5 ethoxy~, L oxylates), the C1 0-18 glycerol ethers, the C10-c18 alkyl polyglycosides and their co"esponding W 096/28534 PCTrUS9'~2~37 sulfated polyglycosicles and C12-C1g alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and an~pl)oleric su,rc-,ctanls such as the C12-C18 alkyl ethoxylates ("AE"), including the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especi 'Iy ethoxylates and mixed ethoxy/l.r~o~y) C12-C18 betaines and sulroL,etaines ("sultaines"), C10-C18 amine oxides, and the like, can also be included in the overall coi.,posilions. The C10-C18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical exd""~les include the C12-C18 N-methylglucal.,ides. See WO 9 206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C10-C1g N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C12-C1g gluca,nicJes can be used for low sudsing. C10-C20 convenlional soaps may also be used. If high sudsing is desired the b,ancl)ed-chain C10-C16 soaps may be used.
Other suitable sulrci-td,,ls suitable for the purpose of the invention are the anionic alkali metal sarcosil~dles of formula:
R-CON(R1 )CH2COOM
wherein R is a Cg-C17 linear or branched alkyl or alkenyl group R1 is a C1-C4 alkyl group and M is an alkali metal ion. Prerer,ed examples are the lauroyl cocoyl (C12-C14) myristyl and oleyl methyl sarcosinates in the form of their sodium salts.
Still another class of su, ra~;ta"t which may be suitable for the purpose of theinvention are the ~3lionic su~ractanL Suitable cationic su,rac~ar,l~ include the quate")a,y a,nn,onium surfactants selected from mono C6-C16.
pr~3ferably C6-C10 N-alkyl or alkenyl a"""onium surfactants wherein the r~l ~ ,aining N positions are substituted by methyl hydroxyethyl or hydroxypropyl groups.

Mixtures of anionic and nonionic surfactants are especially useful. Other conve, ItiGnal useful surractanls are listed in sta"dard texts.

Water-soluble oraanic Polvmeric polvca, L,oxvlic compounds Suitable polymeric polycarboxylate co" "~ounds are the water-soluble organic polymeric polycalLoxylic compounds. r~ferc,bly these co",pounds are homo- or co-polymeric polycalrboxylic compounds and most pre~erably co-polymeric polycalL-)~ylic compounds in which the acid monomer of said polycarboxylic col"pound comprises at least two calL,oxyl groups separaled _ W 096/28534 PCTrUS96/02337 by not more than two carbon atoms. Salts of these polycarboxylic co""~ounds are also considered herein.

Polymeric polyca~L,oxylate coi,.pounds can advant~geously be utilized at levels from 0.1% to 7%, pr~rerably less than 3% and more prererably less than 1 % by weight, in the CGIllpOSiliollS herein, especially in the pfesence ofzeolite and/or layered silicate builders and diphosphonate chelants.

Polymeric polycalL,oxylate materials can be p,epared by poly",eri~ing or copoly" ,eri~i"g suitable unsaturated rl lGI IOI I lel s, p, ~rerably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polyca,boxylates are selected from acrylic acid, maleic acid (or maleic anhydride), fumaric acid, ilacGnic acid, aconitic acid, ",~s~n,ic acid, cil,aconic acid and methylenemalonic acid. The presence in the polymeric polycarboxylates herein of monomeric segments, containi,)y no ca. L,oxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such seg,nents do not conslilute more than 40% by weight.

Polymeric polyc~rboxylate materials can also optionally include further monomeric units such as nonionic spacing units. For example, suitable nonionic spacing units may include vinyl alcohol or vinyl acetate.

Particularly prer~, . ed polymeric polycarboxylates are co-polymers derived from monomers of acrylic acid and maleic acid. The average mol~'-~ weight of such polymers in the acid form ~,refelably ranges from 2,000 to 10,000, more prererdbly from 4,000 to 7,000 and most preferably from 4,000 to 5,000. Water-soluble salts of such acrylic/maleic acid polymers can include, for example, the alkali metal, arr,mG"ium and substituted ammonium salts. Soluble polymers of this type are known ",dlerials. Use of polyacrylates of this type in detergent compositions has - been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued march 7, 1967. The ratio of acrylate to maleate segments in such copolymers will gel,erally range from 30:1 to 1:1, more prererdbly from 10:1 to 2:1. Soluble acrylate/maleate copolymers of this type are known ",alerials which are cles~iLed in European Patent Application No. 66915, published Dece",ber 15, 1982, as well as in EP 193,360, published Septe,nber 3, 1986, which CA 022l4397 l997-08-29 W 096/2853~ PCTnUS96/02337 also des~-ibes such polymers comprising hydroxypropylacrylate. Of these acrylic/maleic-based copolymers, the water-soluble salts of copolymers of acrylic acid and maleic acid are prere, I,ad.

Another class of polymeric pol~ca,boxylic acid co""~ounds suitable for the purpose of the invention are the homo-polymeric polycarboxylic acid cc ""~ounds derived from acrylic acid. The average mole~ ~ weight of such homo-polymers in the acid form preferably ra"5~es from 2,000 to 100,000, more preferably from 3,000 to 75,000, most prl3f~rably from 4,000 to 65,000.

A further example of polymeric polycarboxylic compounds suitable for the purpose of the invention include the malciclac. ~lic/vinyl alcohol terpolymers.
Such materials are also ~lisclose~ in EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.

Another example of polymeric polycarboxylic cG",pounds suitable for the purpose of the invention include the biodegradable polyaspa,lic acid and polyglutamic acid ~mpounds.

Chelants Chelating agents generally comprise from 0.1% to 10% by weight of the ~mpositions herein. More preferably, if utilized, the chelating agents will comprise from 0.1% to 3.0% by weight of such cGmpositions.

A chelating agent can be selected from amino ca, Loxylate, organic pl ,osphol)ale, polyfunctionally-substituted aromatic co,~ "~ound, nitriloaceticacid and mixture II,ereor. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceplionalability to remove l.a"sition metal ions such as iron and ."anga,.ese ions from washing solutions by formation of soluble chel~tes Amino carboxylates useful as optional chelating agents include ethylenedia..,i.,etel.acetales, ethylenediamine dis~cc;nale, N-hydroxyethylethylenediaminetria~lates, 2-hydroxypropylene diamine dis! ~cc;,)aLe, nitrilotriacetates, ethylenediamine tel. apro~rionates, triethylenetetraamineh~x~cet~les, ethylene triamine pentaacetate, diethylenetriamifie~,enlaaceta~es, and ethanoldiglycines, alkali metal, a...,nonium, and substituted ammonium salts therein and mixtures therein.

W 096/28534 PCT/U~.,GJ~.233~

rlefei,ed amino carboxylates chelants for use herein are ethylanedia,nine succindle ("EDDS"), especially the [S S] isomer as described in U.S.
Patent 4 704,233, ethylene.Jia",ine-N,N'-digll,~a",ate (EDDG) and 2-hydroxypropylene-dia~ ~ ~ine-N N'~lisucc inale (HPDDS) cc " "~ounds.
A most prefer~ed amino cs,L,oxylate chelant is ethylenediamine ~isucc:inate.
Organic phospl-onates are also suitable for use as chelating agents in the col ~ .posiliGns of the invention when at least low levels of total P hOS~hOI IJS are ,c,el ")illed in detergent c~"~posilions, and include ethylenedia,ninetetralcis (methylenephospl .onates) available under the l.aclel.,a,k DEQUEST from Mor.sal.lo diethylene triamine penta (methylene phos~l ,Gnate), ethylene diamine tri (methylene ~l ,OS~JI ,o"ate) he,~a")elhylene diamine tetra (methylene phosphol .ale), a-hydroxy-2 phenyl ethyl diphosphondle, methylene di,c)hospl)GI late, hydroxy 1,1 -hexylidene vinylidene 1 1 diphospl,Gnate 12 dihydroxyethane 1 1 diphosphonate and hydroxy-ethylene 1,1 diphosphonale.
r, efe. ably, these amino phospho,)ates do not contain alkyl or alkenyl groups with more than 6 carbon atoms.
rl efe. . ~d chelants are the diphosphooate derivatives selected from a-hydroxy-2 phenyl ethyl di~Jhosphonate methylene diphospl.G,.ale hydroxy 1,1-hexylidene vinylidene 1 1 dipl,os~Jl,o,)ale, 12 dihydroxyethane 1 1 di~l,os,vl,ol,ate and hydroxy-ethylene 1 1 cli~l,osphol)ate. A most preferred is hydroxy-ethylene 1 1 diphosphonate.
Polyfunctionally-substituted arc,l"alic chelating agents are also useful in the compositions herein. See U.S. Patent 3 812 044. rrefei,ed cGill~ounds of this type in acid form are dihydroxydisulfobenzenes such as 1 2-dihydroxy-3 ~disulfob~i~ei)e.

Amvlases ~, efe" ed amylases include for example a-amylases obtained from a special strain of B licheniformis described in more detail in GB-1 269 839 (Novo). P,~fer,ed ccl"l"ercially available amylases include for example those sold under the tradename Rapidase by Gist-Brocades and those sold under the l,cdename Te,,,,c,nyl and BAN by Novo Industries A/S. Amylase enzyme may be inco,po,aled into the col"position in accords,)ce with the invention at a level of from 0.001% to 5% active enzyme by weight of the composition.

W 096/28534 PCTrUS96/02337 Builders Detergent builders can oplio"ally be incl~ded in the c~""~osilions herein to assist in controlling mineral I ,ardness. Inor~dnic as well as organic builders can be used. Builders are typically used in fabric lau"deri"~ co",posilions to assist in the removal of particulate soils.
The level of builder can vary widely depel,d;ng upon the end use of the composition and its desired physical form. When present, the cGIll~osiliol~s will typically cor"p,ise at least 1% builder. Granular formulations typically cci""crise from 10% to 80%, more typically from 15%
to 50% by weight, of the ~eleryel~l builder. Lower or higher levels of builder, however, are not meant to be excluded.
These can include, but are not resl, ic~ed to phytic acid, silicates, alkali metal cal Llonates (including 6ica, l,Gnales and ses~Jic --- L,o,~ales), sul,vhates, aluminosilicates, monomeric polycal L,oxylates, homo or copolymeric poly~, l oxylic acids or their salts in which the polyca, L,oxylic acid COI "~, ises at least two ca, L oxylic r~ic~s separaled from each other by not more than two carbon atoms. Examples of silicate builders are the crystalline layered sili-~tes, such as the layered sodium silicates described in U.S. Patent 4,664,839. NaSKS-6 is the ll ade,na, k for a crystalline layered silicate ~"a,l~ted by lloeol,sl (commo"ly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum.
NaSKS-6 has the delta-Na2Si2Os morphology form of layered silicate. It can be l~repa,ecJ by methods sucn as those described in German DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly prefe"ed layered silicate for use herein, but other such layered silic~tes, such as those having the ~el ~rdl formula NaMSix02x+1 .yH20 wherein M is sodium or hyd,ogell, x is a number from 1.9 to 4, pre~rably 2, and y is a number from 0 to 20, pref~raL ly 0 can be used herein. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and ga""~a forms. As noted above, the delta-Na2Si2Os (NaSKS-6 form) is most preferred for use herein. Other silicates may also be useful sucn as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilising agent for oxygen bleaches, and as a component of suds control systems.
Aluminosilicate builders are especially useful in the present invention. Aluminosilicate builders are of great i""~o, lance in most currently marketed heavy duty granular deteryellt compositions, and can also be a W O 96t28534 PCTnUS96/02337 significant builder ingredient in liquid deter9e"l formulations.
Aluminosilicate builders inciude those having the empirical formula:
NaZ[(A102)Z(SiO2)y] XH20 ~ whsrein z and y are illlegeis of at least 6, the molar ratio of z to y is in the range from 1.0 to 0.5, and x is an inleyer from 15 to 264.
Useful aluminosilicate ion exchange r,al6,ials are cGi~"nercially available. These aluminosilicates can be crystalline or a",or~,l ,ous in structure and can be naturally-occurring aluminosilicates or sy,.ll,elically derived. A method for producing aluminosilicAte ion exchange materials is disclosed in U.S. Patent 3,985,669. r, efen ed synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the desiy--aliGi-s Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especi ~'ly pre~, ~ eJ ei nbocJi, nent, the crystalline aluminosilicate ion exchange ,..dl~.ial has the formula:
Na12[(Alo2)12(sio2)12] XH20 wherein x is from 20 to 30, especi-'ly 27. This material is known as Zeolite A. Dehydlaled zeolites (x = O - 10) may also be used herein. Pleferably, the aluminosilicate has a particle size of 0.1-10 microns in diameter.
Organic cJetergenl builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polyca,Lo~ylate compounds. As used herein, "polycarboxylate" refers to compounds having a plurality of ca, l,o..ylate groups, ~,referdbly at least 3 carboxylates.
Polycarboxylate builder can gei)erally be added to the c~lllposilio,) in acid form, but can also be added in the form of a neutralised salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanola""..oni ~m salts are prefer.ed.
Inc~uded among the polyca, boxylate builders are a variety of ~lego,ies of useful materials. One important category of polycarboxylate builders encGI~p~-sses the ether polycarboxylates, including oxydisuccinate, as disclosed in U.S. Patent 3,128,287 and U.S. Patent 3,635,830. See also '~MS/TDS" builders of U.S. Patent 4,663,071. Suitable ether polyc~, L,o,sylates also include cyclic co"~pounds, particularly alicyclic col."~ounds, such as those described in U.S. Patents 3,923,679; 3,835,163;
4,158,635; 4,120,874 and 4,102,903.
Other useful detergency builders include the ether hydroxypolyca,boxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, or acrylic acid, 1, 3, 5-trihydroxy benzene-2, 4, 6-W 096/28534 PCTnUS96/02337 trisulphonic acid, and ca~ boxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted a"""onium salts of polyacetic acids such as ethyle"ecJia. nine tet. ~Ac~lic acid and nitrilotriacetic acid, as well as polyca.-,oxylates such as mellitic acid, succinic acid, oxy~is~ccinic acid, polymaleic acid, L el ~ e"e 1 ,3,5-l, ica, L,oxylic acid, ca, L,oxymethyloxysuccinic acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and scl Ihl~ salts thereof (particularly sodium salt), are polyca,L,oxylate builders of particular i"" GIla"ce for heavy duty liquid detergel)t formulations due to their availability from renewable resouroes and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxy~isuocinales are also especially useful in such co""~osilions and co"lbi,-ations.
Also suitable in the cor.~.osilions conlair.ing the present invention are the 3,3~ic~,l,oxy-4-oxa-1,6-hexanedioates and the related compounds dicclQsed in U.S. Patent 4,566,984. Useful succinic acid builders include the Cs-C20 alkyl and alkenyl succinic acids and salts thereof. A particularly prefe u ed CGI I "~ound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuccinale, myristylsuccinate, palmitylsucci"ate, 2- lodece"ylsucci"ale (preferred), 2-pent~de~n nate, and the like. Laurylsuccinates are the pr~fe, led builders of this group, and are described in EP 0,200,263.
Other suitable poly~rL,oxylates are disclosed in U.S. Patent 4,144,226 and in U.S. Patent 3,308,067. See also U.S. Pat. 3,723,322.
Fatty acids, e.g., C12-C18 monocarboxylic acids, can also be inc~"~oraled into the col~"~ositions alone, or in co",binalion with the aforesaid builders, espsci~'ly citrate and/or the succinale 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.

Conventional dete,~ive adiuncts The compositions herein can optionally include one or more other detergent adjunct materials or other materials for assisting or enhancing cleaning pe,ror",a"ce, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergel ,l composition (e.g., perfumes, colorants, dyes, etc.). The following are illustrative examples of such adjunct materials.

W 096128534 PCTnUS96102337 EnzYmes Other enzymes than proteases and amylases may be used. These include cPll~ ses lirAses l~eroxidase endoglu~naseand mixturesthereof.

These enzymes may be incorporated into the con"~osition in acccrdance with the invention at a level of from 0.001% to 5% active enzyme by weight of the composition.

The cellulases 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 cell~ ses are disclosed in U.S. Patent 4435 307 which discloses fungal cellulase prod~ced from Humicola insolens and Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aerc."lo"as, and cell~ se extracted from the hep~top~ncreas of a marine mollusk (Dolabella Auricula Solander). Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
ENDO A CAREZYME both from Novo Industries A/S are especially useful.
Suitable lipase enzymes for dete.ge"l usage include those produced by ,.,icrool-ganis,ns of the Pseudomonas group such as Pseudomonas stutzeri ATCC 19.154 as disclosed in GB 1 372 034. See also lipases in Japanese Patent Application ~3 20487 laid open to public inspection on February 24, 1978. This lipase is available from Amano Pha""aceutical Co.
Ltd. Nagoya Japan under the trade name Lipase P "Amano" hereinafter referred to as "Amano-P." Other ~,~""ercial lip~ses include Amano-CES
I jPASeS ex Chromob~ctP~r viscosum e.g. Cl ,ru,,,o!~cter viscosum var.
Iipolyticum NRRLB 3S73 co",r"ercially available from Toyo Jozo Co.
Tagata Japan; and further Cl-,or"obacter viscosum lipases from U.S.
Biochemical Corp. U.S.A. and Disoynth Co. The Netherlands and lipases ex Pseudomonas gladioli. The LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo (see also EP 341 947) is a preferred lipase for use herein.
Peruxidase enzymes are used in ~i.~b;,.ation with oxygen sources e.g. ,cerca,L,o,)ate ~,e,L,orale persulfate hydrogen peroxide etc. They are used for "solution bleaching" i.e. to prevent l-dnsfer of dyes or pigments removed from su6sl,ales during wash operations to other suLsl,dles in the wash solution. Peroxidase enzymes are known in the art and include for -W 096/28534 PCT/U~3~ 23s' example, I,orser~dish peroxidase, ligninase, and haloperoxid~se such as chloro- and bromo-pernxid~se. Pero.~ddA-se~"lai"i"y deterye- ,t c~lllposiliGns are ~isclose~l, for exarr" l~, in EP-A~,424,398.
A wide range of enzyme ",alerials and means for their incG".~ralion into synthetic deterge,)l compositions are also discls~se~l in U.S. Patent 3,553,139. Enzymes are further ~isclos6cl in U.S. Patent 4,101,457 and in U.S. Patent 4,507,219. Enzyme n,alerials useful for liquid deteryent formulations, and their i"cGIpGrdlion into such formulations, are riicclQse~l inU.S. Patent 4,261,868. Enzymes for use in ~lele,yenls can be stabilized by various techniques. Enzyme stabilisation te.ih,.i~ues are ~isclQsed and e~e""~lified in U.S. Patent 3,600,319 and EP 0 199 405. Enzyme stabilisalio" systems are also desc. ibed, for e~ample, in U.S. Patent 3,519,570.

EnzYme Stabilizers - The enzymes employed herein are stabilized by the ~,rese"ce of water-soluble sources of calcium and/or magnesium ions in the finishe-J cc,l, "~osiliGns which provide such ions to the enzymes.
(Calcium ions are yenerally somewhat more effective than maynesium ions and are prefe,.ed herein if only one type of cation is being used.) Additional stability can be provided by the presence of various other art~isclosed stabilizers, especi~"y borate species: see Severson, U.S. 4,537,706.
Typical deterge-,ls, especially liquids, will comprise from 1 to 30, ~rererably from 2 to 20, more ~referdbly from 5 to 15, and most pre~erably from 8 to 12, millimoles of calcium ion per liter of r~ Shed composili~n. This can vary somewhat, ~e~ e ndi~ ~y on the amount of enzyme p, esenl and its response to the calcium or magnesium ions. The level of calcium or magnesium ions should be selected so that there is always some minimum level availabie for the enzyme, after allowing for complexation with builders, fatty acids, etc., inthe cGn"~osilion. Any water-soluble calcium or ,naynesium salt can be used as the source of calcium or magnesium ions, including, but not limited to, calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, calcium fc~,."ale, and calcium ~cet~l~, and the ~,(espG"ding magnesium salts. A small amount of calcium ion, generally from 0.05 to 0.4 millimoles per liter, is often also present in the cc,mposilion due to calcium in the enzyme slurry and formula water. In solid deterge"l ~mposilions the formulation may include a sufficient quantity of a water-soluble calcium ion W 096128534 PCTrUS96/02337 source to provide such amounts in the laundry liquor. In the alle,.,ali-/e natural water I ,a, dl ,ess may suffice.
It is to be understood that the foreyoin9 levels of calcium and/or magnesium ions are sufficient to provide enzyme stability. More calcium and/or ",agnesium ions can be added to the co""~osilions to provide an ~W;lioi)al measure of grease removal pe,ru"..a"ce.
The cGm~-osiliu"s herein may also opliG"ally, but pre~rably, contain ~ various ~J-Iilio,~al stabilizers especially borate-type stabilizers. Typically such stabilizers will be used at levels in ths co,-.posiliûns from 0.25% to 10% prereldbly from 0.5% to 5%, more ,,referably from 0.75% to 3% by weight of boric acid or other borate compound capable of forming boric acid in the cG.,.posi~ion (~IG~ ted on the basis of boric acid). Boric acid is pnafel,ed although other co",pounds such as boric oxide borax and other alkali metal borales (e.g., sodium ortho-, meta- and pyroborate, and sodium pel~tabor~le) are suitable. Substituted boric acids (e.g. phenylLoro"ic acid butane i~oronic acid, and p-bromo phenyl~orol ,ic acid) can also be used in place of boric acid.

Polvmeric DisPersin~ Aqents - Polymeric dispersing agents can be utilized at levels from 0.1% to 7% by weight in the compûsilions herein.
A polymeric material which can be included is polyethylene glycol (PEG).
PEG can exhibit d;spersi"g agent performance as well as act as a clay soil removal-a,)ti.~le~Josilion agent. Typical molecular weight ranges for these pu. poses range from 500 to 100 000 preferably from 1 000 to 50 000 more p. eferably from 1 500 to 10 000.
Polyaspa. lale and polyglula- "ate dispersing agents may also be used esp~ri?'ly in conjunction with zeolite builders. Dispersing agents such as polyaspal late p, efe, ably have a molecul~r weight (avg.) of 10 000.

Clav Soil Removal/Anti-redePosition Aaents - The c~mposiliGns of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition properties. Granular deterger,l cG",positions which co"lain these cc",pounds typically contain from 0.01% to 10.0% by weight of the water-soluble ethoxylates amines;
liquid deterge"t co,-"~ositions typically contain 0.01% to 5%.
The most pl e~ ~ ed soil release and anti-redeposition agent is ethoxylated tel- d~lhylenepentamine. Exemplary ethoxylated amines are W O 96/28534 PC~rrUS96/02337 further desc il,ed in U.S. Patent 4,597,898 VanderMeer, issued July 1 1986. Another group of prefer,ed clay soil removal-antire-~eposiliGi. agents are the cationic co.-.pounds ~lisclosecl in Eu-opea.. Patent A~lj~t;GII
111,965 Oh and Gosselink, published June 27, 1984. Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111 984 ~;osselink, published June 27 1984; the zwitterionic polymers disclosed in European Patent Application 112,592 Gosselink published July 4 1984 and the amine oxides disclose~J in U.S. Patent 4,548,744 Connor, issued October 22 1985. Other clay soil removal and/or anti re-le~osiliGn agents known in the art can also be utili7ed in the colllposiliG"s herein. Another type of prefer, ed antire~leposition agent includes the ca, ~,oxy methyl cellulose (CMC) materials. These materials are well known in the art.

Polvmeric Soil Release Aqent - Any polymeric soil release agent known to those skilled in the art can oplionally be employed in the compositions and ~,n~c~sses of this invention. Polymeric soil release agents are characterized by having both hydrophilic segments to hydrophilize the surface of hydl c pl ,ol~ic fibers such as polyester and nylon and hydrophobic sey",enla, to depos;l upon hydlophoLic fibers and remain adhered thereto through completion of washing and rinsing cycles and thus serve as an a,)cl,or for the hydrophilic segments. This can enable stains occurring sl~hse~uent to treatment with the soil release agent to be more easily cleaned in laterwasl.iny proce.Jures.
J The polymeric soil release agents useful herein especially include those soil release agents having: (a) one or more "o"io"ic hydrophile ~m~otl6nla consisting essentially of (i) polyoxyethylene segments with a das~. ee of poly"~eri~dlion of at least 2 or (ii) oxypropylene or polyoxypropylene segments with a degree of poly",eri~alion of from 2 to 10 wherein said hydrophile segment does not e"~r"pass any oxypropylene unit unless it is bonded to ~j~c~nt moieties at each end by ether linkages or (iii) a mixture of oxyalkylene units cc""~risi,lg oxyethylene and from 1 to 30 oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units such that the hydrophile ccmponent has hydrophilicity great enough to increase the hydrophilicity of con~,enlio"al polyester sy"ll,etic fiber surfaces upon deposit of the soil release agent on such surface said hydrophile segments preferably ccl",~,risi"g at least 25%

W 096/28534 PCTnUS96102337 oxyethylene units and more p,er~rably, especially for such co",poi,enls having 20 to 30 oxypropylene units, at least 50% oxyethylene units; or (b) one or more hyd~u~l-ol,e cG",po"ents co,.~prising (i) C3 oxyalkylene terephll ~alate segments, wherein, if said hydl uphobe co, - .ponents also cG..,prise oxyethylene tere~ hll.alate, the ratio of oxyethylene terepl.ll)aldte:C3 oxyalkylene telepl,lllalate units is 2:1 or lower, (ii) C4-C6alkylene or oxy C4-C6 alkylene se~lllents, or mixtures therein, (iii) poly (vinyl ester) seg..-e--ls, prefer~bly polyvinyl ~c~t~te), having a degree of polymeri~dtiG.. of at least 2, or (iv) C1-C4 alkyl ether or C4 hydroxyalkyl ether substituents, or mixtures ll .ere;, ., wherein said substituents are ~,resenl in the form of C1-C4 alkyl ether or C4 hydroxyalkyl ether cellulose derivatives, or mixtures therein, and such cellulose derivatives are amphiphilic, whereby they have a sufficient level of C1-C4 alkyl ether and/or C4 hydroxyalkyl ether units to deposil upon conventional polyester synthetic fiber surfaces and retain a sufficient level of hydroxyls, once adhered to such convei)tior-al synthetic fiber surface, to increase fiber surface hycll opl ~ilicil~, or a corrh:nalio. . of (a) and (b).
Typically, the polyoxyethylene seS~",ents of (a)(i) will have a degree of polymerization of from 200, although higher levels can be used, preferaLIly from 3 to 150, more preferably from 6 to 100. Suitable oxy C4-C6 alkylene hydlophobe segments include, but are not limited to, end~aps 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 4,7211~80, issued January 26, 1988 to Gosselink.
Polymeric soil release agents useful in the present invention also include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terepl,tl,alate or propylene tereplltl,alate with polyethylene oxide or polypropylene oxide tereplltl,alate, and the like.
Such agents are co"""ercially available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C1-C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued Decer"ber 28, 1976 to Nicol, et al.
Soil release agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., C1-C6 vinyl esters, preferably poly(vinyl ~cePtP) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones. See European Patent CA 022l4397 l997-08-29 W 096/28534 PCT/U~ 233/

~pplic~tion 0219048, published April 22,1987 by Kud, et al. Co"""e~ially available soil release agents of this kind include the SOKALAN type of ",alerial, e.g., SOKALAN HP-22, available from BASF (West Germany).
One type of prefe" ~d soil release agent is a copolymer having r~nclon, blocks of ethylene tere~Jl)l~ ,alate and polyethylene oxide (PEO) tereplltl,alate. The molec~ weight of this polymeric soil release agent is in the range of from 25,000 to 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25,1976 and U.S. Patent 3,893,929 to R~s~d~Jr issued July 8, 1975.
Another prerel,ed polymeric soil ,elease agent is a polyester with repeat units of ethylene tert~cl,l~,alate units contains 10-15% by weight of ethylene tere~htl ,alate units together with 90-80% by weight of polyoxyethylene tere,c,l,lllalate units, derived from a polyoxyethylene giycol of average molec~ r weight 300-5,000. EXdlllpleS of this polymer include the co",.nercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857, issued October 27, 1987 to t~;osselink.
Another ~rerel . e.J polymeric soil release agent is a sulrona~ed product of a s~ -lially linear ester oligomer comprised of an oligomeric ester ~acl~l,one of terephll .aloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone. These soil release agents are described fully in U.S. Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Other suitable polymeric soil release agents include the terephll ,alate polyesters of U.S. Patent 4,711,730, issued Decei"ber 8,1987 to ~osselink et al, the anionic end-capped oligomeric esters of U.S. Patent 4,721,580, issued January 26,1988 to ~osselirlk, and the block polyester oli~o,.,eric compounds of U.S. Patent 4,702,857, issued October 27,1987 to Gosselink.
P,ere,.ed 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~a~"~ed terq~l,ll,alate esters.
If ~-til;~g~l, soil release agents will generally comprise from 0.01% to 10.0%, by weight, of the deterge"l ccmposilions herein, typically from 0.1%
to 5 %, preferably from 0.2 % to 3.0%.
Still another prere"ed soil release agent is an oligomer with repeat units of tere~l-ll,aloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and W 096/28534 PCTrU~3Gl~23~/

oxy-1,2-propylene units. The repeat units form the backboi)e of the oligomer and are ,creferably te,."i.,ated with modified isetl,iondle end-caps.
A particularly prefe" ed soil release agent of this type CGI I ",rises one sulfoisGphll,aloyl unit, 5 terq~lltl,aloyl units oxyethyle"eoxy and oxy-1,2-propyleneoxy units in a ratio of from 1.7 to 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)~ll,anesulro"ate. Said soil r~lea-~.e agent also co,oprises from 0.5% to 20% by weight of the oligomer of a crystalline-reducing st~hili~er, ,~ refera~ly ~ le-l from the group collsisliny of xylene sulro"dte, cumene sulrol ,ale, toluene sulfonate and mixtures ll ,ereof.

DYe Tral ,~rer Inhibitina Aqents - The cor"positions of the ,c resenl invention may also include one or more materials effective for inhibiting the l,ansrer of dyes from one fabric to another during the cleaning ~,ocess. Generally such dye l,an~rer iullitlilillg agents include polyvinyl pyrrolidone polymers polyamine N-oxide polymers, copolymers of N-vinylp)", olidone and N-vinylimid~ole manganese phthalocyanine peroxidases and mixtures ll,ereof. If used, these agents typically col"~rise from 0.01% to 10% by weight of the cGlnposilion~ prererably from 0.01% to 5% and more preferably from 0.05% to 2%.
More specifically, the polyamine N-oxide polymers prerel,ed for use herein contai.- units having the following structural formula: R-AX-P; wherein P is a poly",eri~able unit to which an N-O group can be attached or the N-O
group can form part of the pol~",e,i~able unit or the N-0 group can be allacl)~i 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 ali~l ,alic ethoxylated aliphatics aro",alics l,eterc~clic or alicyclic groups or any cG",bi"alion thereof to which the rlilloyell of the N-O group can be alla~;l,ed or the N-O group is part of these groups. Prere"ed 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:
O O
2~; = N ~ 1 ~3~

W O9G128534 PCTrUS96/02337 wherein R1, R2, R3 are aliphatic, aro",alic, I,ete,ucyclic or alicyclic groups or cc,-~ lio,~s thereof; x, y and z are 0 or 1; and the ~-ilr~gen of the N-0 group can be aUacl.ed or form part of any of the arorer..e.,llo.-ed groups.
The amine oxide unit of the polyamine N-oxides has a pKa <10, ~referably pKa ~7, more prer~ pKa c6.
Any polymer l,ac~L,one can be used as long as the amine oxide polymer ~I~ed is water-sol~hlo and has dye l,an:irer inhibiting ptopellies.
Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures ll,~r~or. These polymers include random or block copolymers where one .nono--,er type is an amine N-oxide and the other ..,o.,or..er 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 ~resenl in the polyamine oxide polymer can be varied by appro~,riale copoly. . .eri~alio., or by an a~.p. o~l iate degree of N~xiddliGn. The polyamine oxides can be obtained in almost any degree of polymerization.
Typically, the average m ~l ec~ weight is within the range of 500 to 1,000,000; more prefel . ed 1,000 to 500,000; most ~,re~rre~ 5,000 to 100,000. This ,c,ref~..ed class of ...dterials can be referred to as "PVNO".
The most ~,refe(. ed polyamine N-oxide useful in the detergent ccm~sitions herein is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of 50,000 and an amine to amine N-oxide ratio of 1:4.
Copolymers of N-vinylpyrrolidone and N-vinyli, niJa~ole polymers (referred to as a class as "PVPVI") are also prer~l . ed for use herein.
r~eferdbly the PVPVI has an average molsall~r 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 molecular weight range is determined by light sc~lleri--y as desc ibed in Barth, et al., Cl,elnical AnalYsis, Vol 113.
"Modern Methods of Polymer Ch~ra-;leri alion", the disclosures of which are incorporated herein by reference.) The PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more pfererably from 0.8:1 to 0.3:1, most p.ererdbly from 0.6:1 to 0.4:1. These copolymers can be either linear or brdnd~ed.
The presel.l invention compositions also may employ a polyvinyl-pyrrolidone ("PVP") having an average molec~ weight of from 5,000 to 400,000, p,efer,ably from 5,000 to 200,000, and more prefelably from S,000 to 50,000. PVP's are known to persons skilled in the detergent field; see, for exa",l~le, EP-A-262,897 and EP-A-256,696. Co",posilions containi"g PVP can also conW,) polyethylene glycol ("PEG") having an average moleu~ weight from 500 to 100,000, prererably from 1,000 to 10,000.
r,ef~rably, the ratio of PEG to PVP on a ppm basis delivered in wash sol ~tions is from 2:1 to 50:1, and more ~r~f~rdbly from 3:1 to 10:1.
The datergent compositions herein may also optionally contain from 0.005% to 5% by weight of certain types of hydrophilic optical b,i~l,le-)ers which also provide a dye l,ansrer inhibition action. If used, the ccmposilions herein will prefer~bly comprise from 0.01% to 1% by weight of such optical b. i~l .lel ,ers.
The hydrophilic optical bri~JI .leners useful in the p, ese, ll invention are those having the structural formula:
Rl R2 N O~NI ~NI ~N
~N H H N~
R2' SO3M SO3M R
wherein R1 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, r"o"~l,ilino, chloro and amino; and M is a salt-forming cation such as sodium or poPssi~ Im.
When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino~-(N-2-bis-hydroxyethyl)-s-l, ia~ine-2-yl)amino]-2,2'-stilL,enedisulfonic acid and disodium salt. This particular b,i~hlener species is commercially marketed under the l,adena",e Tinopal-UNPA-GX by Ciba-Geigy Corporation.
Tinopal-UNPA-GX is the pr3re"ed hydrophilic optical brightener useful in the detergel)l compositions herein.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4,4'-bisl(4-anilino~-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid ~lisorliuln salt. This particular brigl.tel,er species is commercially marketed under the l,ade,-a...e Tinopal 5BM-GX by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino~-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular W 096/28534 PCTrUS96/02337 briyl ,lener species is coi - "~ ,ercially marketed under the lralJe, .a, . ,e Tinopal AMS-GX by Ciba Geigy CGI ,UOr;~I;G~ 1.
The s~e~ iric optical brigl ,te, .er specias sele~e- I for use in the present invention provide especi~y effective dye l(dn~rer inhibition pelrol-"dnce benefits when used in comb.. ~atiGn with the sele~1e-J polymeric dye lr~l ,srer inl ,ibiling agents hereinberore desc, il,ed~ The combination of such selected polymeric materials (e~g~, PVN0 and/or PVPVI) with such selected optical b,i!Jl,leners (e~g. Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) provides significantly better dye l-ansrer inhibition in ~ eous wash sol~tions than does either of these two delergent c~l..posilion cG",pGnents when used alone. Without being bound by theory it is believed that such briyl Itel ~ers work this way be~use they have high affinity for fabrics in the wash solution and tl,ererore ~leposil relatively quick on these fabrics~ The extent to which L,ri!Jl.te,)era cJe~sil on fabrics in the wash solution can be d~ine~l by a para.,.eter called the "exh~ustion coefficient"~ The exhaustion cG~rricie.,l is in general as the ratio of a) the brightener material de~osiled on fabric to b) the initial brightener concenl, dlion in the wash liquor.
B- iyl ~lel)ers with relatively high exh~ Istion coefric;e. ,ts are the most suitable for inhibiting dye transfer in the context of the present invention~ _ Of course, it will be appre~ ted that other conventional optical briyl ,tener types of co""~ounds can optionally be used in the present coi n~osilions to provide conventional fabric "bri~l ,l"ess" benefits rather than a true dye t-d"arer inhibiting effect. Such usage is conventional and well-known to deter~e"t formulations.

Conventiol,al optical brigl,lenera or other brightening or whitening agents known in the art can be i"c~l~,o(aled at levels typically from 0.005% to 5%
pre~r~bly from 0.01% to 1.2% and most prefe,ably from 0.05% to 1.2% by weight into the d-3terge,lt compositions herein. Coi "" ,ercial optical bri5Jl,tenerà which may be useful in the present invention can be classified into subgroups which include but are not necess--- ily limited to derivatives of stilbene, pyrazoline coumarin ca,Loxylic acid ."ell,inecyanines dibel- otl,io~,l,e"e-55~ioxide azoles 5- and 6~ner,bered-ring heterocycles and other miscellaneous agents. Examples of such brigl ,te"era are ~isclosed in '~he Production and Application of Fluorescent Brightening Agents", M. Zah-adl,ik Published by John Wiley & Sons New York (1982). Further optical brigl,Lener which may also be used in the W 096/28534 ' PCTnUS96/~2337 present invention include naphthlimide, ben,o~ol3, benzofuran, bell~illlid~No and any mixtures thereof.
Specific examples of optical L ri$~1,le, .ers which are useful in the present cG"~posiliGns are those identified in U.S. Patent 4,790,856. These brighle"efs include the PHORWHITE series of ~riyl,leners from Verona.
~ Other L.righl6l ,er~ ~lisclosed in this rerer~nce include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artic White CC
and Artic White CWD; the 2~4-styryl-phenyl)-2H-I ,apl1 lo[1,2-d]tri~olcs;
4,4'-bis(1,2,3-triazol-2-yl)-stilbenes; 4,4'-bis(styryl)bisphenyls; and the aminocou",arins. Specific e~a",,~ s of these bri~l ,teners include 4-methyl-7-diethyl- amino coumarin; 1,2-bis(-benzimidazol-2-yl)ethylene; 1,3-diphenyl-pyr~olines; 2,5-bis(ben7Ox~ol-2-yl)thiophene; 2-styryl-naptho-~1,2-d'o.~-l~; and 2-(stilbene4-yl)-2H~)apl,lho[1,2-d]tri~ole. See also U.S. Patent 3,646,015.

Suds SuPDressors - Compounds for reducing or suppressing the formation of suds can be i,.ccl~.oraled into the composilions of the pr~senl invention.
Suds su~.r~ssiGn can be of particular i""~olla"ce in the so-called "high concel-l, dlion cleaning ~,rc,cess" and in front-loading EUI upeal ,-style ~ashing ma~ ,i"es.
A wide variety of materials may be used as suds suppressors, and suds su~ressGra are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430 447 (John Wiley 8 Sons, Inc., 1979). One category of suds su~",r~ssor of particular interest enco"-p~sses monoca,Loxylic fatty acid and sohlhle salts therein. See U.S. Patent 2,954,347, issued Sept~",ber 27, 1960 to Wayne St. John. The monoca,L,oxylic fatty acids and salts thereof used as suds suppressor typically have hydl oczi, byl chains of 10 to 24 carbon atoms, preferdbly 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and a",mGnium and alkanol~n""onium salts.
The deterge"t cGillpositions herein may also contain non-surfactant suds suppressor~. These include, for example: high molecular weight hyclruca, L,ons such as pararri", fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C1g-C40 ketones (e.g., stearone), etc. Other suds inhibitors include N-alkylated amino ll i~i"es such as tri- to hexa-alkylmelamines or di- to tetra-W 096/2853~ PCTnUS96/02337 alkyldia,ni.le chlo,l,ia~ines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine conlaininy 1 to 24 carbon atoms, propylene oxide, and ",Gnoslearyl phosphates such as ",o"ostea(yl alcohol phosphate ester and ~nG.,oslea"~l di . ~k~li metal (e.g., K Na and Li) pl,ospl,dtes and pl,ospl,ale esters. The hydn~calL,o,)s such as pa,~fin and halGpararfin can be utilized in liquid form. The liquid hydloca,~Gns will be liquid at room le",per~l-Jre and at",os~l,eric pressure, and will have a pour ~ point in the range of 40~C and 50-C and a minimum boiling point not less than 110~C (al",ospl,~ric pressure). It is also known to utilize waxy hyd~oca. L,ons, ,~,referably having a melting point below 1 00~C. The hy.l~ o~. L,ons CGI ,slilute a preferred c~tegory of suds suppressor for detergent cGmposili~lls. Hyd~oca,L,on suds supprdssGrs are des~i~ed for exd""~le in U.S. Patent 4 265 779, issued May 5, 1981 to Gandolfo et al.
The h~d~oc ILolls, thus, include aliphatic, alicyclic arc"-,alic and hetero~clic saturated or unsaturated hyd~o~,bons having from 12 to 70 ca, L,on atoms. The term pa, arfin," as used in this suds suppressor ~is~ ~ssion, is in~e, Ided to include mixtures of true pardfi"s and cyclic hy~ GI)S.
Another p. er~l ~ ed c~tegory of non-su- ra~a"t suds suppressors cGmp~ises silicG"e suds suppressors. This calegG,y inrl-~des the use of pol~,orya,)osiloxa~le oils such as polydi"~ll)ylsiloxane dispersions or emulsions of polyorga"osilo)~ne oils or resins and combinations of polyorganosiluxa"e with silica particles wherein the polyorganosiloY~ne is che",isG,bed or fused onto the silica. Silicone suds sup~ressors are well known in the art and are for example ~isclosed in U.S. Patent 4 265 779 issued May 5, 1981 to GanJolro et al and Europea,) Patent Applicdlion No 89307851.9 published February 7 1990 by Starch M. S.
Other silicone suds suppressor~ are disclosed in U.S. Patent 3 455 839 which relales to compositions and processes for defoaming eous solutions by incorporating Ll ,erei.l small amounts of polydi"~ell)ylsiloxane fluids.
Mixtures of silicone and silanated silica are described for insta"ce in German Patent Application DOS 2124 526. Silicone defoa"~e,a and suds controlling agents in granular de~ergenl col"posilions 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.

W 096/28534 ' PCTrUS96/02337 An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent c~nsisling esser,lially of:
(i) polydimethylsiloxane fluid having a viscosily of from 20 cs. to 1,500 cs. at 25~C;
(ii) from 5 to 50 parts per 100 parts by weight of (i) of siloxane resin cc,."posed of (CH3)3SiO1t2 units of SiO2 units in a ratio of from (CH3)3 SiO1/2 units and to si02 units of from 0.6:1 to 1.2:1; and (iii) from 1 to 20 parts per 100 parts by weight of (i) of a solid silica gel.
In the prefe"ed silicone suds suppressor used herein, the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof .ere,.~d), or polypropylene glycol. The primary silicone suds suppressor is ~ranel .edtcrossli. ,kec~ and prerer~bly not linear.
To illustrate this point further, typical liquid laundry detergent co~ osilio..s with controlled suds will optionally c~,.,p,ise from 0.001 to 1, ~,ere,ably from 0.01 to 0.7, most preferably from 0.05 to 0.5, weight % of said silicone suds suppressor, which comprises (1) a non~ eo~s emulsion of a ~ri",a,y anliroan, agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to proi"ote the reaction ofmixture cc"--~oneuls (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone su.ra.;ta.lt, and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than 2 weight %; and without polypropylene glycol Similar amounts can be used in granular cc,i."~ositions, gels, etc. See also 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 4,639,489 and 4,749,740, Aizawa et al at column 1, line 46 through column 4, line 35.
The silicone suds suppressor herein prereraL,ly comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular weight of less than 1,000, preferably between 100 and 800. The polyethylene glycol and polyethylene/polypropylene copolymers herein have a sol~hility in water at room te--"~erdlure of more than 2 weight %, preferably more than 5 weight %.

W 096/28534 PCTrUS96/02337 The p, efer, ed solvent herein is polyethylene glycol having an average molecular weight of less than 1,000, more preren31,1y between 100 and 800, most pref~rably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300.
r, ere" ad is a weight ratio of between 1:1 and 1 :10, most prerer~L ly between 1:3 and 1:6, of polyethylene glycol:copolymer of polyethylene-polypropylene glycol.
The prefe"~d silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molec~ weight. They also ,.,rere,ably do not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC L101.
Other suds suppressor:, useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones (I;sclosed in U.S. 4,798,679, 4,075,118 and EP
150,872. The seconda(y al~hols include the C6-C16 alkyl alcohols having a C1-C16 chain. A prere"ecl alcohol is 2-butyl octanol, which is available from Condea under the l(ade,.,a,k ISOFOL 12. Mixtures of secondaly alcohols are available under the trademark ISALCHEM 123 from Enichem.
Mixed suds su~.pressGrs typically comprise mixtures of alcohol + silicone at a weight ratio of 1:5 to 5:1.
For any detergenl CGI I ,positions to be used in automatic laundry washing machines, suds should not form to the extent that they overflow the washing ",ac~,ine. Suds suppressors, when utilized, are prefe,ably present in a "suds sL"~"~ressinSJ amount. By"suds s~"~pressing amount" is meant that the formulator of the ccmposilion can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry clelergenl for use in automatic laundry washing machines.
The compositions herein will generally comprise from 0% to 5% of suds s~.~pressor. When ~tili~ed as suds suppressors, monoca,boxylic fatty acids, and salts ll,erGi.), will be present typically in amounts up to 5%, by weight, of the deteryent composition. P,ererably, from 0.5% to 3% of fatty monoca,L,oxylate suds suppressor is utilized. Silicone suds suppressors are typically utilized in amounts up to 2.0%, by weight, of the detergent ~mposiliGn, although higher amounts may be used. This upper limit is practical in nature, due primarily to cGnce,n with ke~ping costs minimized and effectiveness of lower amounts for effectively controlling sudsing.
P,~rerably from 0.01% to 1% of silicone suds suppressor is used, more -W 096/28534 PCTrUS96/02337 prererably from 0.25% to 0.5%. As used herein, these weight percentage values include any silica that may be utilized in COIllbi- IdliUn with polyoryanosiloxane~ as well as any adjunct ",alerials that may be utili~e~
Monostearyl phospl,ale suds suppressGrs are ge"erally utili~ed in amounts rang;. ,y from 0.1 % to 2%, by weight, of the co" ~ ~osilion. Hydl uca, bon sudssup,c"~ssor~ are typically utili~e~ in amounts ranging from 0.01% to 5.0%, although higher levels can be used. The alcohol suds s~ ,essor:j are typically used at 0.2%-3% by weight of the finished co" I~. osiliG~ ~s.

Fabric Softeners - Various through-the-wash fabric softeners, especially the irnp~lpAble s",ectile clays of U.S. Patent 4,062,647, Storm and Nirschl, issued Dec~,~,ber 13, 1977, as well as other softener clays known in the art, can optionally be used typically at levels of from 0.5% to 10% by weight in the present co",positions to provide fabric sonener benefils concurrently with fabric cleaning. Clay s~flener~ can be used in cG",bi.)dlion with amine and cationic sonenel~ as dis-,lQse~l. 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 Septe" ,ber 22, 1981.

Other Inaredients - A wide variety of other functional ingredients useful in deteryent compositions can be included in the ~" ,~ositions herein, including other active ingredients, carriers, h~ rol,opes, processing aids, dyes or piyn~el)ts~ solvents for liquid formulations, solid fillers for bar compositions, etc. If high sudsing is desired, suds boosters such as the C10-C16 alkanolamides can be incG"~G,aled into the com~siliu,,s, typically at 1%-10% levels. The C10-C14 ",onoettlanol and diethanol amides illustrate a typical class of such suds boosters. Use of such suds boosters with high sudsing adjunct su,ra,,lanls such as the amine oxides, betaines and sultaines noted above is also advantageous. If desired, soluble magnesium salts such as MgCI2, MgS04, and the like, can be added at levels of, typically, 0.1%-2%, to provide additional suds and to enhance grease removal pe,ru""ance.
Liquid detelgent co",posilions can contain water and other solvents as carriers. Low molecular weight primary or secc "da(y alcohols exemplified by methanol, ethanol, pn~panol, and iso~ropanol are suitable.
Mo"ol"~dric alcohols are prere"ed for solubilizing surfactant, but polyols such as those containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy W 096128534 ~CTrUS96/02337 groups (e.g., 1 ,3-1,rol~. ~ediol, ethylene glycol, glycerine, and 1,2-~rG~.a-lediol) can also be used. The comrositions may contain from 5% to 90%, typically 10% to 50% of such ca,.ie,a.
The deter~~enl colllposiliGIls herein will ~,,ererably be formulated such that, during use in :3~UeO! IS cleaning operdlio"s, the wash water will have a pH of between 6.5 and 11, ~ f~rably between 7.5 and 10.5. Liquid dishwashing product formulations ,~referably have a pH between 6.8 and 9Ø Laundry products are typically at pH 9-11. Techniques for controlling pH at reco...,-~er,d~J usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.

Form of the cGi-"~osilions The det~.gel ,l co,..posilions of the invention can be formulated in any deâil able form such as powders, granulates, pastes, liquids, and gels.

Liquid com~ositions The .leler~enl compositions of the prese"l invention may be formulated as liquid del~rgel~t co.nposilions. Such liquid detergent compositions typically ~..-~,,ise from 94% to 35% by weight, preferably from 90% to 40% by weight, most prefefably from 80% to 50% by weight of a liquid carrier, e.g., water, prefe, ably a mixture of water and organic solvent.

Gel co..,i~osilions The de~er~e, It co,."~ositions of the ~,resent invention may also be in the formof gels. Such comrosilions are typically formulated with polyakenyl polyether having a molecular weight of from about 750,000 to about 4,000,000.

Solid co,~"~ositions The Jeteryent cGI~"~osilions of the invention may also be in the form of solids, such as powders and granules.

The mean particle size of the co" ,ponents of granular compositions in accorda"ce with the invention should prererably be such that no more that 5% of particles are greater than 1 .4mm in diameter and not more than 5% of particles are less than 0.15mm in diameter.

W O 96/28534 PCTrUS96/02337 The term mean pa,licle size as defined herein is calc~ te-i by sieving a sample of the c~s",posi~ion into a number of rl~~ions (typically 5 fractions) on a series of Tyler sieves. The weight r,actions thereby obtained are plotted against the aperture size of the sieves. The mean particle size is taken to be the aperture size through which 50% by weight of the sample would pass.

The bulk density of granular delerge,)l cor"posilions in accorda"ce with the prese"l invention are also useful in concenl, dled granular deterge"l composiliol ,s that are cl ,aracterisecJ by a relatively high density in cGmpa~isGn with convenlio"al laundry deterger)l cGIllposilion3. Such high density composilions typically have a bulk density of at least 600 g/litre more p, ererably from 650 g/litre to 1200 g/litre most preferably from 800g/litre to 1 OOOg/litre.

Bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel mo! ~ded rigidly on a base and provided with a flap valve at its lower exl,e",ily to allow the cGnlel)ls of the funnel to be emptied into an axially aligned cylindrical cup disposed below the funnel.
The funnel is 130 mm high and has intemal dia",eters of 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower e~lre",ily is 140 mm above the upper surface of the base. The cup has an overall height of 90 mm an intemal height of 87 mm and an intemal dia",eter of 84 mm. Its nol"inal volume is 500 ml.

To carry out a measure",ellt the funnel is filled with powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup.
The filled cup is removed from the frame and excess powder removed from the cup by passing a straight edged implement eg; a knife across its upper edge. The filled cup is then weighed and the value obtained for the weight of powder doubled to provide a bulk density in g/litre. Replicate measurements are made as required.

Mahil ,q ~rocesses - aranular comPositions - In yel)ernl~ granular detergent compositions in accordal)ce with the present invention can be made via a variety of methods including dry mixing spray drying agylol"eration and granulation.

W 096128534 PCTrUS96/02337 The invention is illustrated in the following non limiting e).a...~les, in whichall pe.c~"lages are on a weight basis unless otherwise stated.

In the bleaching compositions of the invention, the abbreviated ~m~o.-e"~
id6nliri~liGns have the following meanings:
LAS : Sodium linear C12 alkyl be"-ene SU4JI ~C: I .al~
TAS : Sodiumtallowalcohol sulphate C45AS : Sodium C14-C1 5 linear alkyl sulphate C45E7 : A C14 15 predominantly linear primary alcohol cc")de.)sed with an average of 7 moles of ethylene oxide C25 E3 A C12-15 ~rdl)~cl primary alcohol cc ndel ,sed with an average of 3 moles of ethylene oxide C25E5 : A C12 15 branched primary alcohol conde,)sed with an average of 5 moles of ethylene oxide NO.~;GI);C : (hydroxyethyl dimethyl) a""~,onium quatemary Silicate : Amo",l ,ous Sodium Silicate (SiO2:Na20; 1.6 ratio) NaSKS4 : Crystalline layered silicate offormula ~ -Na2Si205 Ca,bol,ate : Anhydrous sodium carbonate with a particle size between 200~m and 9001lm Sulphate : Anhydrous sodium sulphate Zeolite A : Hydrated Sodium Aluminosilicate of formula Na12(A102SiO2)12- 27H2~
having a primary particle size in the range from 0.1 to 10 mi~cnneters MA/AA : Copolymer of 1:4 malciclacrylic acid, average molecular weight about 70,000.
PB4 : Sodium perL,orale tetrahydrate of nominal formula NaBo2~3H2o H2o2 PB1 : Anhydrous sodium perborate bleach of nominal formula NaBo2.H2o2 TAED : Tetraacetyl ethylene diamine ~ AvO2 : Total amount of available oxygen present in the ~ composition Bri-Jhlel ,er 1 : Disodium 4,4'-bis(2-sulphostyryl)biphenyl -W 096/28534 PCT/U~ v~37 Bri~l Itener 2 : Disodium 4,4'-bis(4-anilino~-",o"JI ,olino-1.3.5-triazin-2-yl)amino) stilbene-2:2'-disul,ul ,onale.

HEDP : Hydroxy-ethylene 1 1 di~l ,os~hu. ,dle DTPMP: Diethylene l,ia",;ne penta (methylene phos~Jl,onate) marketed by Mlonsanto under the Trade name st 2060 EDDS : Ethylenediamine -N, N'- dis~ ~ccinic acid, [S S] isomer in the form of the sodium salt.

Silicone a"tiro~" ,; Polydimethylsiloxane foam controller with Siloxane-oxyalkylene copolymer as ~ispe, ~ing agent with a ratio of said foam controller to said ~isper~i,)g agent of 10:1 to 100:1.
Pl ,otû~ ated: Sulpl ,or,aled Zinc Phthalocyanine enc~rsu~ted in bleach dextrin soluble polymer Savinase : proteolytic enzyme of standard activity 1 3KNPU/g Carezyme : cellulytic enzyme of activity 1000 CEVU/g Te,l"a",yl : Amylolytic enzyme of activity 60KNU/g ipol~se : Lipolytic enzyme of activity 1 00kLU/g Endol~se : E:ndoglunaseA
all sold by NOVO Industries A/S

PVNO : Polyvinylpyridine N-oxide PVPVI : Copolymer of polyvinylpyrolidone and vinylimidazole CMC : Sodium carboxymethyl cellulose Metolose : Carboxy methoxyether SRA : Sulfobenzoyl end carped esters with oxyethylene (Soil Release : oxy and lere~ lhaloyl bac~bone t ' Agents) ExamPle 1 -CA 022l4397 l997-08-29 W 096/28534 PCTÇUS96/02337 The following formulations were prepared where A and B are in accord with the invention and 1 and 5 are prior art cc",~positions.
2009 from each formulaliGns A,B and 1 to 5 was taken and subjected each to a full scale was~,i,.y machine test using a Miele autGn)atic w~sh;.,g machine (Model WM W698) set to the short wash cycle at 40~C for each formulation. Water of 12~ German hardl,ess ( = 1.8 mol Ca2+/litre) was used.
Coin~0l~6~1t A B 1 2 3 4 5 (% by weight) LAS -4 ~-4 -4 5-4 4 4 5-4 TAS ~9 ~9 ~9 ~9 9 9 9 C25 E3 ~.0 ~.0 ~.0 ~-.0 ~-.0 ~.0 ~.0 nonionic 0.60 0.60 G.60 C,.60 C,.60 C.60 0.60 Zeol te A 19.1 19.1 5.5 5.5 5.5 5.5 5.5 MA/AA 0.3 0.3 '.8 2.8 '.8 ~.8 7.8 PB4 9.25 9.25 4.1 4.1 4.1 '4.1 4.1 TAED .8 1.4 .6 - .8 . ~ 2.5 Av02 .02 1.93 .43 .53 .87 . ~9 7.11 Carbo~ ~ale '0.5 '0.5 8.6 8.6 8.6 8.6 8.6 silicate 7.8 2.8 ~-.7 ~.7 ~.7 ~.7 .7 Savinase ~.28 ~.33 C .12 0.15 0.19 C .13 0.28 Pl otease Te".ldln~l 0.10 0.10 nil nil nil nil nil ~mylase ~TPMP Q.3 0.3 0 3 0 3 0 3 0 3 0 3 - EDP ~u.2 0.2 nil nil nil nil nil ~linors and miscel ~neoL s to bala ~ce HPP Index ¦ 0.5 0.5 0.1 ¦ 0.0 ¦ 0.1 ¦ 0.05 ¦ 0.16 Two s~hatcl,es dGlllol)slfali.)y dirrering degrees of soil removal pelror",a,)cewere used as slanclard to est~hlish a 4 point scale in which '+' represents a very poor soil removal pe,rc,.,.,allce and '+++' average soil removal performance.
The two slancla,ds are used to define the mid points between the various des~ i~Jtions of soil removal pel ror,nd, lce viz +verypoorsoil removal pelrur"lance ++ poor soil removal pe, rGl Illance +++ average soil removal performance ++++ good soil removal pe,ru"nance Two expert panellists are used and their results are averaged.

=

W 096/28534 PcT/u~ 2337 The results are as follows:

Stain removal ++++ ++++ + + + + ++
pe. rGI ~ .~ance It is seen that Compositions A and B produce ~,II,a-,ced stain removal p~, ru",~ance over the prior art Composilions 1 to 5 ExamPle 2 The following laundry ~eter~e"t ccm~,osilio..s C, D and 6 were prepared where C and D are in accord with the invention and 6 is a prior art COl'llpOSiliGI ~;
Col . "~onent C D 6 (% by .reight) C25E~ 4.0 40 40 . or,ion c 0 65 0 6 f 65 ~eol te A 20 5 20 ~ ~0 5 UAI~A 0 95 0 9;~L 95 PB~- 92 - 92 Av~2 C 94 0 94 0 94 C~, ~"at~ ~0 5 '0 5 ~o 5 silicate ~9 ~9 29 Savinase Plolease ~ :~3 u _3 ~) 0 Tel.. ,al."~l Amylase 0 0 0 0 0 0 DTPMP o~
~EDP
~inors and miscellaneous to ba ance HPP Index 0 67 1 0 671 0 20 It was seen that compositions having an HPP Index over 0 35 produced e~lhanced soil removal ~.elrc,r..,al,ce Said performance is further e~lhanced when the hyd~ u!aen peroxide consisled of at least 90% by weight of PB4 ExamPle 3 w 096/28534 PCTrUS96/02337 The following laundry dele.gelll compositions E, F and 7 were pre~ared, where E and F are in accord with the invention and 7 is a prior art osilio,):
CGII II~GI )~1 ll E F 7 (% by weight) LAS /--AS 5.4 /1.9 5.4 /1.9 5.4 /1.9 C2 E~ 4.0 4.0 4 0 r on on c 0.60 0.60 0.60 eo te A 20.5 "0.5 20.5 VWAA 0.95 q.8 3.7 PB4 ~.6 8.6 ~5.6 TAED ~ .4 ~ .4 .0 Carbonate 20.5 ~0.5 ~ 8.6 silic~t~ -~ g ~ g ~ "
Savinase Protease ~.~3 0.~3 ~.~ 3 T~- .. a.. ,yl Amylase 0. ~ 0 0. ~ 0 DTPMP 0._ 0.~ 0 3 HEDP 0.2 Minors and mis~ll~neous to balance HPP Index ¦ 0.6 10-6 10-05 Compositions E and F with HPP Index of 0.6 produce enhanced soil removal pe-ro----a-,ce over the prior art refere,)ce composition 7 of HPP
Index 0.05.
It was also be seen that combination of polycarboxylic acids and ~I ,os~l ,o"ales c,helarlts further enhanced the soil removal pel rO, . . ,ance,esp~ci~"y when the polyc~,L,oxylic acid is present in low amount (e.g Iess than 1% by weight).

Exal I "~la 4 The following detergent compositions according to the invention were prepared:
CGI 1 II~OneI IlS G H

LAS 8.0 8.0 C25E3 4.10 4.10 Zeolite A 12.0 19.10 Na SKS-6 6.16 W 096/28534 PCTrUS96/02337 MA/AA 1.50 0.30 SRP 0.10 Metolose 0.30 PVNO/PVPVI 0.02 cdlLGndle 20.50 20.5 Silicate - 2.82 PB4 12.0 9.25 AvO--, 1.25 0.96 TAED 1.85 1.85 EDDS 0.19 DTPMP - 0.25 HEDP 0.20 0.22 MgS04 0.30 0.30 Savinase ~ otease 0.50 0.28 Lipolase lipase 0.12 Tel"~a",yl amylase 0.38 0.10 Carezyme Cellulase 0.08 En~ol~se 0.08 CMC - 0.22 Bl i~l ,lener 1 0.12 Brightener 2 - 0.11 Pl-otoactivated bleach 0.003 15ppm Silicone alllirudlll 0.10 0.55 Sulphate 24.0 25.88 Perfume 0.25 0.27 Minors and miscellaneous to balance HPP Index ¦ 0.6 ¦ 0.56 The above formulations were seen to produce effe. tive soil removal p~l rul " ,a, ~
t

Claims (20)

Claims

1- A non-phosphate builder-containing detergent composition comprising a sufactant, and a)- at least 0.5% by weight of a source of hydrogen peroxide, b)- from 0.01 % to 10% by weight of an organic peroxyacid bleach precursor, c)- from 0.001% to 5% by weight of a proteolytic enzyme, d)- an alkalinity source having the capacity to deliver alkalinity to a wash solution as measured by the alkalinity release test described herein, such that the % weight NaOH equivalent of the composition is greater than 10.6%
by weight of the composition, and wherein the detergent composition has an Hydrogen peroxide Precusor Proteolytic enzyme (HPP) Index of at least 0.35 as defined by the formula HPP = Wherein the %weight of proteolytic enzyme in the formulation is based on an enzyme activity of 13 knpu/g of the enzyme particle, and wherein the %AvO2 is the total amount of available oxygen present in the composition.

2-A detergent composition according to Claim 1, wherein the source of hydrogen peroxide is an inorganic perhydrate salt.

3-A detergent composition according to either one of Claim 1 or 2, wherein the source of hydrogen peroxide consists of at least 90% by weight of a perborate tetrahydrate.

4-A detergent composition according to either one of Claim 1 or 2, wherein the source of hydrogen peroxide consists of at least 90% by weight of a percarbonate having a particle size of at least 600 micrometers and coated with water-insoluble materials.

5-A detergent composition according to any one of Claims 1-4, wherein the total available oxygen (AvO2) content in the composition is less than 1.5%
by weight.

6-A detergent composition according to any one of Claims 1-5 wherein said source of alkalinity is selected from alkali metal carbonate, alkali metal silicate and mixture thereof.

7-A detergent composition according to Claim 6, wherein said alkali metal silicate has a ratio of 1.6:1.

8-A detergent composition according to any one of Claim 1-7, wherein said detergent composition further comprises one or more water-soluble organic polymeric polycarboxylic compounds.

9- A detergent composition according to Claim 8, wherein said polycarboxylic compound is a co-polymeric polycarboxylic acid having monomeric unit selected from acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid and mixtures thereof.

10-A detergent composition according to any one of Claims 1-8, wherein said detergent composition further comprises a polycarboxylic compound in amount less than 1% by weight.

11-A detergent composition according to any one of Claims 1-10, wherein said detergent composition comprises a chelant selected from amino carboxylate,organic phosphonate, polyfunctionally-substituted aromatic compound,nitriloacetic acid and mixture thereof.

12-A detergent composition according to Claim 11, wherein said organic phosphate chelant is selected from ethylenediaminetetrakis (methylenephosphonates), diethylene triamine penta (methylene posphonate), ethylene diamine tri (methylene phosphonate), hexamethylene diamine tetra (methylene phosphonate), .alpha.-hydroxy-2 phenyl ethyl diphosphonate, methylene diphosphonate, hydroxy 1,1-hexylidene, vinylidene 1,1 diphosphonate, 1,2 dihydroxyethane 1,1 diphosphonate and hydroxy-ethylene 1,1 diphosphonate.

13-A detergent composition according to either one of Claim 11 or 12, wherein said chelant is hydroxy-ethylene 1,1 diphosphonate.

14-A detergent composition according to Claim 11, wherein said amino carboxylate chelant is selected from ethylenediaminetetracetates, ethylenediamine disuccinate, N-hydroxyethylethylenediaminetriacetates, 2-hydroxypropylene diamine disuccinate, nitrilotricetates, ethylenediamine tetraproprionates, triethylenetettraaminehexacetates, ethylene triamine pentaacetate, diethylenetriaminepentaacetates and ethanoldiglycines, preferably ethylene diamine disuccininate.

15-A detergent composition according to any one of Claims 1-14, wherein said detergent composition comprises an amylase in amount from 0.01% to 5% by weight.

16-A detergent composition according to any one of Claims 1-15, wherein said bleach precursor is selected from bleach precursor compounds which comprise at least one acyl group forming the peroxyacid moiety bonded to a leaving group through an -O- or-N- linkage.

17-A detergent composition according to any one of Claims 1-16, wherein said bleach precursor is N,N-N', N' tetra acetyl ethylene diamine.

18-A detergent composition according to Claims 17, wherein said bleach precursor is in amount from 0.5% to 2.5% by weight.

19-A detergent composition according to any one of Claims 1-18, wherein said proteolytic enzyme is selected from Alcalase, Savinase, Primase, Durazym, Esperase, Maxatase,Maxacal,Maxapem, Opticlean and Optimase and mixture thereof, preferably Savinase.

20-A detergent composition according to any one of Claims 1-19, wherein said detergent composition further comprises builders and conventional detersive adjuncts.