CA2187303A1 - Detergents containing an enzyme and a delayed release peroxyacid bleaching system - Google Patents

Abstract

There is provided a detergent composition containing (a) an enzyme; and (b) an organic peroxyacid bleaching system, wherein a means is provided for delaying the release to a wash solution of said peroxyacid bleach relative to the release of said enzyme.

Description

21 ~7303 WO 95/284G7 P.l/la.,_. /ul DETERGENTS CONTAINING AN ENZYME AND A DELAYED RELEASE PEROXYACID
BLEACHING SYSTEM
This invention relates to detergent , containing an enzyme, preferably an amylase enzyme, and an organic peroxyacid bleaching system, wherein a means is provided for delaying the release to the wash solution of the organic peroxyacidbleach relative to the release of the ~nzyme.
The s~L,r~ul~ removal of coloured naturally derived soils/stains such as blood, egg, chocolate, gravy from soiled/stau~ed substrates is a particular challenge to theformulator of a detergent ~ ... for use in a washing method such as a laundry or machine di;.l.w~ , method.
Tr~iitinn~lly, the removal of such coloured soils/stains has been enabled by the use of bleach . such as oxygen bleaches, including hydrogen peroxide and organic u~ids, and also by enzyme ~ The organic peroxyacids are often obtained by the in situ p. Il~yd~ ,;, reaction between hydrogen peroxide and an organic peroxyacid bleach precursor.
A problem ~ ~ with the use of certain organic peroxyacid bleaches in laundry washing methods is a tendency for these organic peroxyacid bleaches to affect the colour stability of the fabrics being washed. Types of fabric damage can includefading of coloured dyes on the fabrics or localised areas of "patchy" colour bleaching.
A problem ~ J with the use of enzymes as ~ . of detergents is that enzyme activity in the wash may be affected by the presence of other detergent in the wash solution. Degradation of enzymes by bleach c- . has been found to be a particular problem. Also ~ of the enzyme substrates by the bleach has been found to reduce the activity of the enzyme, p~Li. uld.l~ amylase.

WO95/284i67 1'.~ vl 22~7~a3 The detergent formulator thus faces the dual challenge of r.."~ , a product which maximises soillstain remoYal but minimises the occurrence of any . ~ enzyme " or fabric colour stability effects of the bleach.
The Applicants have found that the occurrence of any . ~. ' fabric colour stability or enzyme ~ l effects arising from the use of organic peroxyacid bleaches in a washing method can be related to the rate of release of the peroA-yacid bleach to the wash solution and also to the absolute level of peroA~yacid present in the wash solution.
A fast rate of release of the peroxyacid bleach to the wash solution tends to heighten the probability that u~ u~ fabric colour stability effects and enzyme ~
effects will occur, as does a high absolute level of the bleach in the wash solution.
Whilst reducing either the rate of release of the peroxyacid bleach, or the absolute level of the bleach employed in the wash tends to arneliorate these problems, this can be a~ by a negative effect on the bleachable stain/soil removal ability.
The Applicants have now however found that where a ~ A containing both an enzyme and a pero~yacid bleach source is employed, and wherein a means is provided for delaying the release to a wash solution of the peroxyacid bleach relative to the release of the enzyme enhanced stain/soil removal, I ' 'y on coloured naturally occurring stains/soils, may be obtained. The invention is lu~ut; ' 'y useful forcontaining proteases, lipases and most ~li ' ly amylases, cellulases and pe~
Additionally, where the . ~ is used in a laundry washing method a reduction in the propensity for negative fabric colour stability effects to be observed is also obtained.
It is therefore an object of the present invention to provide CI~ suitable for use in laundry and machine ~ h... ' ~ methods having enhanced stain removal.
It is also an object of the present invention to provide ~ u ~ for use in a laundry washing rnethod wherein said ~ show less propensity to cause negative fabric colour stability effects.

W0 9S128467 2 l 8 73 0 3 ~ u~

Summary of the Invention According to one aspect of the present invention there is provided a detergent r~ ,- ';r..\ containing (a) an enzyme; and ~b) an organic peroxyacid bleaching system wherein a means is provided for delaying the release to a wash solution of said organic peroxyacid relatiYe to the release of said enzyme such that in the T50 test method herein described the time to achieve a . that is 50% of the ultimate C~. ~f .,~ ;"" of the enzyme is less than 120 seconds and the time to achieve a c~ I;r n that is 50% of the ultimate ~n~~f 1~ of the organic peroxyacid is more than 180 seconds.
According to another aspect of the present invention there is provided a detergent ~ . containing (a) a enzyme; and ~b) an organic peroxyacid bleaching system wherein a means is provided for delaying the release to a wash solution of said organic peroxyacid relative to the release of said enzyme such that in the T50 test method herein described the time to achieve a that is 50% of the ultimate r~ of said enzyme is at least 100 seconds, preferably at least 120 seconds, more preferably at least 150 seconds less than the time to achieve a that is 50~ of the ultimate - - ~ of said organic peroxyacid.
The organic peroxyacid bleaching system preferably comprises in .
(i) a hydrogen peroxide source; and (ii) an organic peroxyacid bleach precursor compound An essential component of the detergent , is an enzyme.

wo 95/28467 ' 2 1 8 7 3 ~ 3 ~ 707 Suitable enzymes include the: "y available lipases, amylases, neutral and alkaline proteases, cellulases, pectinases, lactases and ~.u d~, that is enzymeshaving lipolytic, amylolytic, proteolytic, cellulolytic, pectolytic, lactolytic and .hk/ly~ic activity lc*)~~ cu..~.lliu,.,lly ;.I.,ul~uldt~ into detergent C Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
Protease enzymes are especially preferred as the enzyme f rm~ nPn~ Preferred commercially available protease enzymes include those sold under the t ~
Alcalase, Savinase, Primase, Durazym, and Esper,se by Novo Industries A/S
~'Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor r ~ and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be ' into the ~ in accordance with the invention at a level of from 0.0001% to 4% active enzyme by weight of the ~ ~p~
Preferred amylases include, for example, a-amylases obtained from a special strain of B ' ' ~ , described in more detail in GB-1,269,839 ~'Novo). Preferred .,;"lly available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl and BAN
by Novo Industries A/S. Amylase enzyme may be i~l~ul; ' into the ~
in accordance with the invention at a level of from 0.0001% to 4% active enzyme by weight of the ~
Lipolytic enzyme (!ipase) may be present at levels of active lipolytic enzyme of from 0.0001% to 4% by weight, preferably 0.001% to 1% by weight, most preferably from 0.C101% to 0.5 % by weight of the ~ C
The lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Tl.~ sp. or ~"v~lO u. ~. sp.
including F~rJd~ J ~ f~ - -; or pSfll~if~ C fluorPc~n~ Lipase from chemically or genetically modified mutants of these strains are also useful herein.
A preferred lipase is derived from r~ ~'JOI ~IV l~tS ~ ,Ju~ d i ~- A~ ~ . which is described in Granted European Patent, EP-B~218272.

WO 95/28467 ~ 1 ~ 7 3 ~ 3 ~ u~
s Another preferred lipase herein is obtained by cloning the gene from Humicola lanu~inosa and expressing the gene in ACnpre~ c orvza, as host, as described in Eu~opean Patent ArF~ EP-A-0258 068, which is, ~ly available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Hu~_ J~ .l et al, issued March 7, 1989.
r~ni~ reroxy~ hlP~hir(~ system An essential feature of the invention is an organic peroxyacid bleaching system. In one preferred execution the bleaching system contains a hydrogen peroxide sour_e Dd an organic peroxyacid bleach precursor compound. The production of the organic peroxyacid occurs by an in situ reaction of the pre_ursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In an alternative preferred execution a preformed organic peroxyacid is -, I directly into the: . (' nl containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in ' with a preformed organic peroxyacid are also envisaged.
lnor~anic perhydrate bleaches Inorganic Ferhydrate salts are a preferred source of hydrogen peroxide. These salts are normally lJUI~ in the form of the alkali metal, preferably sodium salt at a level of from 1% to 40% by weight, more preferably from 2% to 30% by weight and most preferably from 5 % to 25 % by weight of the c. . .~
Examples of suitable inorganic perhydrate salts include Ferborate, ~ uL~, ' . ' , persulfate and persilicate salts and mixtures thereof. The inorganic Ferhydrate salts are normally the all~i metal salts. The inorganic perhydrate salt may be included as the cryst lline solid without additional protection. For certain perhydrate salts however, the preferred executions of such granular utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product.
Sodium perborate can be in the form of the l~u~ul~yl' ' of nominal formula NaBO2H2O2 orthe i j NaB2H22 3H2 wo ss/2s467 2 1 8 7 3 0 3 r~ 707 lkali metal p~ u~ u li~ul~uly sodium ~ ul ~ are preferred for inclusion in ~ in accordance with the invention.
C~ c containing p~l~bùllal~ have been found to have a reduced tendency to form I ' ' ' gels in the presence of surfactants and water than similar ~" '1'"- ';"'`' which contain perborate. It is belieYed that this is because typicaLly has a lower surface area and lower porosity than perborate l~u~ul~
This low surface area and low porosity acts to prevent the co-gelLing with fine particles of surfactant ~ll . n~ and is therefore not ~tri~ r~l to dispensing.
Sodium p~u~ is an addition compound having a formula ~ ~ r e to 2Na2C03.3H202, and is available ~ "y as a crystalline solid. The y.,.~ is most preferably il~ ' into such ~ u. . .l~ . c in a coated form which provides in product stabiLity.
A suitable coating material providing in product stability comprises mixed salt of a water soluble allcali metal sulphate and carbonate. Such coatings together with coating processes have previously been described in GB-1,466,79g, granted to Interox on 9th March 1977. The weight ratio of the mixed salt coating material to .,,~u~ lies in the range from 1: 200 to 1: 4, more preferably from 1: 99 to I
: 9, and most preferably from 1: 49 to 1: 19. Preferably, the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na2SO4.n.Na2CO3 wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.
Other coatings which contain silicate (alone or with borate salts or boric acids or other inorganics), waxes, oils, fatty soaps can also be used ad~. _ 1y within the present invention.
Potassium ~,u,~y ~ '' is another inorganic perhydrate salt of use in the detergent ~ ;. - herein.
pf roxyacid bleach ~recursor Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a ~l~ydlul~ reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be ~r ' as WosS/28467 2~ ~7303 P~./l,~ /v7 X - C -L
where L is a leaving group and X is essentially any ru~ iùllalily, such that on Pe~ YdIUIU.~5;D the structure of the peroxyacid produced is 1l X-C-OOH
Peroxyacid bleach precursor ~ . ' are preferably . ' at a level ûf from0.5% to 20% by weight, mûre preferably frûm 1% tû 15% by weight, most preferably from 1.5% to 10% by weight of the detergent ~ ;. ,A ~
Suitable peroxyacid bleach precursor . , ' typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide r^Dnge of classes.
Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798,1147871, 2143231 and EP-A-0170386.
The Applicants have found that 'patchy' danAage can be ~ ul~uly associav-d with peroxyacid bleach precursor r which on ~h~lly.llUl~D;D provides a peroxyacid which is (i) a perbenzoic acid, or non-cationic substituted derivative thereof; or (ii) a cationic peroxyacid.
n .,,... -,: precursors have also been found to be p~ ul~ul~ susceptible to the problem.
Leavin~ ~roups The leaving group, hereinafter L group, must be ~ reactive for the p~lllJJIUl.~D;s reaction to occur within the optimum time frame (e.g., a wash cycle).

wo ssns467 F~ . Iul ~1 87303 However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching ~
Preferred L groups are selected from the group consisting of:
--o~ --O~Y and --0~ Y

l3 ~ R3 Y
y .

-O-CH=C--CH=CH2 --O--CH=C--CH=CH2 -O--C--R1 CH2-C --~j /NR4 O O
R3 g Y
--O--C=CHR4 , and --N-- --C,H--R4 R3 o and mi~tures thereof, wherein Rl is an alkyl, aryl, or alkaryl group containing from I
to 14 carbon atoms, R3 is an alkyl chain containing from I to 8 carbon atoms, R4 is H or R3, and Y is H or a: ' ' `1i7in~ 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 ammonium or alkyl - - groups The preferred ~ l;,;,.g groups are -SO3 M+, -CO2 M+, -SO4 M+, -N+~R3)4X- and o<--N(R3)3 and most preferably -S03-M+ and -C02 M+
wherein R is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation , . _ W095/28467 ~1 8~3~3 P~ U
which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali metal, or substituted ~ n- cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, mell.y'~ '' or acetate anion.
perhPn71lin ~ nri ~priv~tives thereof ~rPrllr~rc Perbenzoic acid precursor: . ' provide perbenzoic acid on ~ vlul~
Suitable O-acylated perbenzoic acid precursor . ' include the substituted and ' benzoyl u,~y~ sulfonates, including for exarnple benzoyl u~ nc sulfonate:
o ~o~S03-Also suitable are the ~ V,~;dl.iUII products of sorbitol, glucose, and all with b~ v~ agents, including for example:
OAc AcO~o /~,OAc OBz Ac = COCH3; Bz = Benzoyl Perbenzoic acid precursor ~ ~ ' of the imide type include N-benzoyl ', t~ Lvyl ethylene diamine and the N-benzoyl substituted ureds.
Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl b. ..,; - 1 .~..lr and other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl ~~ O, dibenzoyl taurine and benzoyl y~lu~ lu~ acid.
_ _ _ .. .. .

w0 95/28467 P~ "1 ., _. Iu I

Other perbenzoic acid precursors include the benzoyl diacyl peroxides, the benzoyl tetraacyl peroxides, and the compound having the formula:
~0~ O~COOH
Phthalic anhydride is another suitable perbenzoic acid precursor compound herein:
o ~0 Suitable N-acylated lactam perbenzoic acid precursors have the formula:

~C H2~C H2 ]n wherein n is from O to 8, preferably from O to 2, and R6 is an aryl, alkoxyaryl or aL~ryl group containing from I to 12 carbon atoms, or a substituted phenyl groupcontaining from 6 to 1~ carbon atoms, preferably a benzoyl group.
Perbenzoic ~rifi derivative ~recursors Perbenzoic acid derivative precursors provide substituted perbenzoic acids on ~uitable substituted perbenzoic acid derivative precursors include any of the herein disclosed perbenzoic precursors in which the benzoyl group is substituted by essentially any non-positively charged (ie; non-cationic) functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl and amide groups.
... . . . .. . ..

W095l28467 2~73~3 P~ U~

A preferred class of substituted perbenzoic acid precursor cv-, ' are the amide substituted . . ' of the following general formulae:

Il 1 11 1 11 11 .
O R5 0 or R5 0 0 wherein Rl is an aryl or alkaryl group with from I to 14 carbon atoms, R2 is an arylene, or alkarylene group containing from I to 14 carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group containing I to 10 carbon atoms and L can be essentially any leaving group. Rl preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. Rl may be aryl, substituted aryl or alkylarylcontaining branching, ' or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are p~ for R2. The ..~ 1 can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic ~ 1, ' R5 is preferably H or methyl. Rl and RS should not contain more than 18 carbon atoms in total. Amide substituted bleach activator ~ . ' of this type are described in EP-A-0170386.
('~fjn.lir peroxyacid precllrcnrs Cationic peroxyacid precursor cu..,r ' produce cationic ~IU,~.Ci.l~ on Typically, cationic peroxyacid precursors are formed by ' ~ the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an: or alkyl _ group, preferably an ethyl or methyl group. Cationic peroxyacid precursors are typically present in the solid detergent .~ ;,. c as a salt with a suitable anion, such as a halide ion.
The peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described 1., .~ :,.1.. f~,.~ ~1 "\..,1~, the peroxyacid precursor compound may be an alkyl ~ bu~ acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter .. _ . , ... . . .. _ _ _ . . . .

wog~ 67 r~ . '/Q'707 221 87303 ~
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.K.
1,382,594; EP 47S,512, 458,396 and 284,292; and in JP 87-318,332.
Examples of preferred cationic peroxyacid precursors are described in UK Patent Application No. 9407944.9 ard US Patent Application Nos. 08/298903, 08/298650, 08/298904 and 08/298906.
uitable cationic peroxyacid precursors include any of the or alkyl substituted alkyl or benzoyl UA~b~,llL~,I.., sulfonates, N-acylated ~,G~ 1,7 ' S, and ' ~' ~I glucose benwyl peroxides.
A preferred cationically substituted benzoyl UA,~lb~.l~ll~, sulfonate is the 4-(trimethyl ^~m~ ) methyl derivative of benzoyl UA~b.,~ sulfonate:
o ~40~S03-~+
A preferred cationically substituted allcyl UA~b~.ll~.ll., sulfonate has the formula:
J~/ 3 Preferred cationic peroxyacid precursors of the N-acylated ,a~ ' class include the trialkyl: methylene benzoyl ~G~lUla~kU~ GIIi~.U lUl~ trimethyl mOylene benzoyl ~,G~Iula~uul~.

w0 95128467 ~ 1 ~3 7 3 ~ ui \ ~ ~ N
Otha preferred cationic peroxyacid precursors of the N-acy~ated wlJIula~ uml class includethetrialkyl methylenealkyl,~.",l, I A
O O
)lN
/N+ ~ (CH2)n where n is from O to 12.
Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl ethyl sodium 4 s li ' . ' yl carbonâte chloride.
Alkyl ~ uAylic ~rill h1r~rh ~\rlorllrcnrc A~yl pclw-~u~ ;c acid bleach precursors form ~.wlbu~ylic âcids on ~llyJIul~
Preferred precursors of this type provide peracetic acid on ~.I.~JIul~
Preferred alkyl ~~ JU~lic precursor: of the imide type iAclude the N-,N,NINl tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, I,all;!_ulally those: . in which the alkylene group contains 1, 2 and 6 carbon atoms. T~llaac~lylu;llJ ' (TA~D) is p~~ l~ly preferred.
Other preferred alkyl ~.w lJu~lic acid precursors include sodium 3,5,5-tri-methyl lu ~ u~luAylJ. .I~.l~ sulfonate (iso-NOBS), sodium rlulla~lu~lu~yl~ c sulfonate (NOBS), sodium àc~ tu~yl~ sulfonate (ABS) and pentaacetyl glucose -woss/2s467 2 ~ ~ 73~3 ~ u~

Amide substituted alkyl perox~q~ rPr~sorS
Amide substituted alkyl peroxyacid precursor ~ E ' are also suitable, including those of the following general formulae:

O R5 0 or R5 0 0 wherein Rl is an alkyl group vith from I to 14 carbon atoms, R2 is an alkylene group containing from I to 14 carbon atoms, and RS is H or an alkyl group containing I to 10 carbon atoms and L can be essentially any leaving group. Rl preferably contains from 6 to 12 c^qrbon atoms. R2 preferably contains from 4 to 8 carbon atoms. Rl may be straight chain or branched alkyl containing branching, or both and may be sourced from either synthetic sources or natural sources including for ex~mple, tallow fat. Analogous structural valiations are ;I,lr for R2. The ~ can include alkyl, halogen, nitrogen, sulphur and other typical substituent groups or organic cnn~pol~n~lc R5 is preferably H or methyl. Rl and R5 should not contain more than 18 carbon atoms in total. Amide substituted bleach activator ~ of this type are described in EP-A-0170386.
r ~ ~erox~q~ precursors Also suitable are precursor com~ C of the b~..~u~i,~ type, as disclosed for example in EP-A-332,294 and EP-A482,807, ~ i.,uLl~ those having the formula:
o ~ ~o Wos5/28467 21873~3 r~l,, 9,1 ,~"
including the substituted ~ of the type R2 S' R3~ - R
Rs wherein Rl is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R4, and my be the same or different ` ~ f` selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR6 (wherein R6 is H or an alkyl group) and carbonyl functions.
An especially preferred precursor of the benzoxazin-type is:
1l ~ "C~
Preforn~ ero~y~
The organic peroxyacid bleaching system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid, typically at a level of from 1% to 15% by weight, more preferably from 1% to 10% by weight of the ~'J'"l~'` ';""
A preferred class of organic peroxyacid ' are the amide substituted ' of the following general for~nulae:
R1--C--N--R2--Cl--OOH R1--I--C--R2--Cl--OOH
O R5 0 or R5 o wherein Rl is an allyl, aryl or alkaryl group with from I to 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms, and RS is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. Rl W0 95/28467 2 1 ~ ~ 3 ~ ~ P.~ 707 preferably contains from 6 to 12 carbon atoms. R2 preferably eontains from 4 to 8 carbon atoms. Rl may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, ~ ,." or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are ~ Ir for R2. The ' can inelude alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic r R5 is preferably H or methyl. Rl and R5 should not contain more than 18 carbon atoms in total. Amide substituted organic peroxyacid . ' of this type are described in EP-A-0170386.
Other organic p~.u~ ,ids indude diacyl and t~ u/L~, especially dilJ~,.u~yJo-~ c acid, Ji~u~.y~ r. ~ c acid and J;~.u,~ acid. Mono- and ~ acid, mono- and ~;~wb~ iC
acid and N-l ' ' 'C.~' r U~ U;C acid are also suitable herein.
('hl~lrinP hlP~lrh The cu",~ herein are preferably free of chlûnne bleach.
nlr~rh r~t~¦ySt The invention also ~ ,- containing a catalytically effective amount of a bleach catalyst such as a water-soluble manganese salt.
The ~leac~ ~a~alyst is ~5P~l in a c~talytically effP tive am..o~JDt in. th5 ~
herein. By "~61~L~lly effective amount" is meant an amount which is suffieient, under whatever ~,ul~.pcudLv~ test eonditions are employed, to enhanee bleaehing and removal of the stain or stains of interest from the target substrate. Thus, in a fabric laundering operation, the target substrate will typically be a fabric stained with, for example, various food stains. For automatic di Ih.. ' ~, the target substrate may be, for example, a porcelain cup or plate v~ith tea stain or a ~ul~ ..., plate stained with tomato soup. The test eonditions will vary, depending on the type ûf washing appliance used and the habits of the user. Thus, front-loading laundry washing maehines of the type employed in Europe generally use less water and higher detergent, - than do top-loading U.S.-style machines. Some maehines have ~.U~Ji~ bly longer vash cycles than others. Some users eleet to use very hot water; others use warm or even cold water in fabric laundering opera~ions. Of ~ Wos~2s467 2 ~ 3 ~ u~

course, the catalytic ~lr~ of the bleach catalyst will be affected by such , and the levels of bleach catalyst used in fully-formulated detergent and bleach ~ can be a~lul '~/ adjusted. As a practical matter, and not by way of limitation, the ....~ and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about I ppm to about 200 ppm of the catalyst species in the laundry liquor. To illustrate this point further, on the order of 3 ~ ol~ manganese catalyst is effective at 40C, pH 10 under European conditions using perborate and a bleach precursor (e.g., benzoyl ~lula~ ). An increase in ~ "~ of 3-5 fold may be required under U.S.
conditions to achieve the same results. Conversely, use of a bleach precusor and the manganese catalyst with perborate may allow the formulator to achieve equivalentbleaching at lower perborate usage levels than products without the manganese catalyst.
The bleach catalyst material herein can comprise the free acid or be in the form of any suitable salts.
One type of bleach catalyst is a catalyst system comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron or manganese cations, anauxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, ~l;~,,,l,..ly, Lll~' " - acid, 'Il..,lh~k . ' ~' acid) and water-soluble salts thereof Such catalysts are disclosed in U.S. Pat. 4,430,243.
Other types of bleach catalysts include the ~ based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts includeMnlV2(u-0)3(1,4,7-trimethyl-1,4,7-~;~,' e)2-(PF6)2, Mnm2(U-O)l(u-OAc)2(1,4,7-trimethyl-1,4,7-Lli~ (C104)2, MnIV4(u-0)6(1,4,7-Ll~."r. 1( )4-(C1O4)2, MnmMnIv4(u-o)l(u-oAc)2-(l~4~7-trimethyl-1,4,7-L~. ' )2-(C104)3. and mixtures thereof. Others are described in European patent application publication no. 549,272. Other ligands - suitable for use herein include l~5~9-trimethyl-l~s~9-Ll;~ ,YIO,1~ - .. , 2-methyl-1,4,7-LI;~ , 2-methyl-1,4,7-L~ ,' , 1,2,4,7 '~ L-IIIY
1,4,7-LI;~, , and mixtures thereof.
.

w0 ssns467 2 18 7 3 0 3 r~ /vl ~

For examples of suitable bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat.
5,227,084. See also U.S. Pat. 5,194,416 which teaches ,~ ..", 1. ~, manganese (IV) complexes such as Mn(1,4,7-trimethyl-1,4,7-L i~y. ' )(OCH3)3 (PF6). Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is a water-soluble complex of manganese (II), (III), and/or (IV) with a ligand wbich is a non-~UAy' ~ulyhydluAy compound having at least three . vt; C-OH groups.
Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, meso ~1~;' 1, meso-inositol, ]actose, and mixtures thereof.
U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of transitionmetals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand. Said ligands are of the formula:

R1 -N=C-B-C=N-R4 wherein Rl, R2, R3, and R4 can each be selected from H, substituted alkyl and aryl groups such that each Rl-N=C-R2 and R3-C=N-R4 form a five or six-membered ring. Said ring can further be ' ' B is a bridging group selected from O, S.
CRSR6, NR7 and C=O, wherein R5, R6, and R7 can each be H, alkyl, or aryl groups, including substituted or ~ ' ' groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings.
Optionally, said rings may be substituted with ' such as alkyl, aryl, alkoxy, halide, and nitro. lF ' 'y preferred is the ligand 2,2'-b;*~ylily' Preferred bleach catalysts include Co, Cu, Mn, Fe,-1;~y.idyl...~LI.~.~ and -I,;~ylidyl~lficomplexes. Higbly preferred catalysts include Co(2,2 -~ ylidy ,C12.
D (;~v~l~iu~,y )b; .t~yliuJ' cobalt (II), i 'i ylidy' cobaltaI) , Co(2,2-~;~y.i~y' )?02CI04, Bis-(2,2'-~i~y.idy' ~.) copper(II) tris(di-2-~yli.lyl.ll..;..~) iron(lI) I ' ' , and mixtures thereof.
Other examples include Mn gluconate, Mn(CF3S03)2, Co(NH3)sCI, and the binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including N4MnIII(u-0)2MnIVN4)+and [Bipy2Mnm(u-0)2MnIVbipy2]-(C104)3.
The bleach catalysts may also be prepared by combining a water-soluble ligand with a water-soluble manganese salt in aqueous media and ~ I ~, ,. _. .1~ ,~1'. .~, the resulting ~095/28467 2 1 87 3~3 1~

mixture by e~ ,u~ iul,. Any cûnvenient water-sûluble salt ûf manganese can be used herein. Manganese (II), (III), (IV) and/or (V) is readily available on a rr~ rri~1 scale. In some instances, sufficient manganese may be present in the wash liquor, but, in general, it is preferred to add Mn cations in the . . - to ensure its presence in ~~ y-effective amounts. Thus, the sodium salt of the ligand and a member selected from the group consisting of MnS04, Mn(C104)2 or MnC12 (least preferred) are dissolved in water at molar ratios of ligand:Mn salt in the range ûf about 1:4 to 4:1 at neutral or slightly alkaline pH. The water may first be de-UA,~ ~ ' ' by boiling and cooled by sparging with nitrogen. The resulting solution is evaporated (under N2, if desired) and the resulting solids are used in the bleaching and detergent ~ u ~ herein without further 1~
In an alternate mode, a water-soluble manganese source, such as MnS04, is added to the bleach/cleaning ~ U ~ n or to the aqueous bleaching/cleaning bath which comprises the ligand. Some type of complex is apparently formed in situ, and improved bleach ~ rul ~ ul~ is secured. In such an in situ process, it is convenient to use a cu ~ molar excess of the ligand over the ~ , and mole ratios of ligand:Mn typically are 3:1 to 15:1. The additiûnal ligand also serves to scavenge vagrant metal ions such as iron and copper, thereby protecting the bleach from One possible such system is described in European patent ~rrli~ti~m publication no. 549,211.
While the structures of some of the bleach-catalyzing ..,~ .,. c~ c described herein have not been elucidated, it may be speculated that they comprise chelates or other hydrated ~UIdil~ iUII complexes which result from the interaction of the carboxyl and nitrogen atoms of the ligand with the manganese cation. Lilcewise, the oxidation state of the manganese cation during the catalytic prc~cess is not known with certainty, and may be the (+II), (+III), (+IV) or (+V) valence state. Due to theligands' possible six points of attachment to the manganese cation, it may be reasonably speculated that multi-nuclear species and/or "cage" structures may exist in the aqueous bleaching media. Whatever the form of the active Mn~igand species which actually exists, it functions in an apparently catalytic manner to provideimproved bleaching ~. . r.." - ~ on stubborn stains such as tea, ketchup, coffee, blood, and the like.
Other bleach catalysts are described, for example, in Europe~n patent ~rr1ir~-inn publication no. 408,131 (cobalt complex catalysts), European patent ~

wo ss/2s467 2 ublication nos. 384,503~ and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455 ligand catalyst), U.S. 4,711,748 and ~uropean patent :Ir~lir~tir~n publication no. 224,952, (absorbed manganese on -' ' catalyst), U.S. 4,601,845 (~' 1 support with manganese and zinc or salt), U.S. 4,626,373 ( _ 'ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), German Pat. ~ 2,054,019 (cobalt chelant catalyst) Canadian 866,191 (transition metal-containing salts), U.S. 4,430,243 (chelants with manganese cations and non-catalytic metal cations), and U.S. 4,728,455 (manganese gluconate catalysts).
l~tive release kinetics In an essential aspect of the inYention a means is provided for delaying the release to a wash solution of the organic peroxyacid bleach relative to the release of the enzyme.
Said means may comprise a means for delaying the release of the organic peroxyacid bleach to the wash solution.
Alternatively said means may comprise a means for enhancing the rate of release of the enzyme to tbe solution.
A most preferred way is to delay the release of both the peroxyacid bleach and the release of H22 I)elay~d r~t~ of release - rn.o~c The means may provide for delayed release of an organic peroxyacid bleach sourceitself to the wash solution. Alternatively, where the organic peroxyacid source is a peroxyacid precursor compound the delayed release means may comprise a means of inhibiting, or preventing the in situ ~.I,~J~ reaction which releases the organic peroxyacid into the solution. Such means could, for example, include delaying release of the hydrogen peroxide source to the wash solution, by for example, delaying release of any inorganic perhydrate salt, acting as a hydrogen peroxidesource, to the wash solution.
The delayed release means can include coating any suitable component with a coating or mixture of coatings designed to provide the delayed release. The coating may wo 95~w67 . ~l/L.__ _. IU7

2~ 873~3 therefore, for example, comprise a poorly water soluble material, or be a coating of sufficient thickness that the kinetics of dissolution of the thick coating provide the controlled rate of release.
The coating material may be applied using various methods. Any coating material is typically present at a weight ratio of coating material to bleach of from 1:99 to 1:2, preferably from 1:49 to 1:9.
Suitable coating materials include L~ ;dW (e.g. partially) ~ ,. ' vegetable oil, soy bean oil, cotton seed oil) mono or ~;~ly~.i~,s, .~ alline waxes, gelatin, cellulose, fatty acids and any mixtures thereof.
Other suitable coating materials can comprise the alkali and alkaline earth metal sulphates, silicates and carbonates, including calcium carbonate.
Preferred coating material is sodium silicate of SiO2: Na2O ratio from 1.6: 1 to 3.4 : 1, preferably 2. 8: 1, applied as an aqueous solution to give a level of from 2 % to 10%, (normally from 3% to 5%) of silicate solids by weight of the p~L
silicate can also be included in the coating.
Any inorganic salt coating materials may be combined with organic binder materials to provide composite inorganic adl;/l ~ binder coatings. Suitable binders include the C1o-C20 alcohol CilL-~A.~' ' containing from 5 - 100 moles of ethylene oxide per mole of alcohol and more preferably the C1s-C20 primary alcohol ethoxylatw containing from 20 - 100 moles of ethylene oxide per mole of alcohol.
Other preferred binders include certain polymeric materials. r~
with an average molecular weight of from 12,000 to 700,000 and ~ hjl.,a~ glycols(PEG) with an average molecular weight of from 600 to 10,000 are examples of such polymeric materials. Copolymers of maleic anhydride with ethylene, .r;t;llyl ether or ,II~ lic acid, the maleic anhydride ~ ~ at least 20 mole percent of the polymer are further examples of polymeric materials useful as binder agents.
These polymeric materials may be used as such or in . ' with solvents such as water, propylene glycol and the above mentioned Clo-C20 alcohol ethoxylatws containing from 5 - 100 moles of ethylene oxide per mole. Further examples of binders include the Clo-C20 mono- and diglycerol ethers and also the Clo-C20 fatty acids.

woss/2s467 21 87 303 ~ r~ u/ ~

Cellulose derivatives such as ~ ,LI~ lu~ Ll.~l~cllulose, ethyl h~J~uA~Lll.ylcellulose and l~J~ .,Ll.~ llulose, and homo- or co-polymeric ub~ yl;c acids or their salts are other examples of binders suitable for use herein.
One method for applying the coating material involves ~ Preferred ~ ;. . processes include the use of any of the organic binder materials described h~ll bove. Any w.. ~. I `LE~""'' ' ' ~' / ' may be used including, but not limted to pan, rotary drum and vertical blender types. Molhen coating c.. ~ c may also be applied either by being poured onto, or spray atomized onto a moving bed of bleaching agent.
Other means of providing the required delayed release include mechanical means for alhering the physical ~ h ;~ of the bleach to control its solubility and rate ofrelease. Suitable protocols could include cnnnp~ rinn mechanical injection, manual injection, and adjustment of the solubility of the bleach compound by selection of particle size of any particu~ate ~ , Whilst the choice of particle size will depend both on the c~ of the particulate, . t, and the desire to meet the desired delayed release kinetics, it is desirable that the particle size should be more than 500 I...~.,,,,,~h~,~, preferably having an average particle diameter of from 800 to 1200 Additional protocols for providing the means of delayed release include the suitable choice of any other ~ . of the detergent ~ ll ll l matrix such that when the ~ , is introduced to the wash solution the ionic strength ~..~;..
therein provided enables the required delayed release kinetics to be achieved.
Fnh~lr~ of release - means All suitable means for enhancing the rate of release of the enzyme to ~he solution are envisaged.
The enhanced release means can include coating any suitable component with a coating designed to provide the enhanced release. The coating may therefore, forexample, comprise a highly, or even ~rr~ , water soluble material.

W095128467 2~ ~73~3 P~l/u~ JP~707 Other means of providing the required delayed release include mechanical means for altering the physical ~ c of the enzyme to enhance its solubility and rate of - release.
A suitable protocol could include deliberate selection of the particle size of any enzyme containing . The choice of particle size will depend both on the cc ~ of the particulate r t, and the desire to meet the desired enhanced release kinetics. It is desirable that Lhe particle size should be less than 1200 ~fi~lu~ t~ , preferably having an average particle diameter of from 1100 to 500 Il.;~IUI~l~L~
Additional protocols for providing the means of delayed release include the suitable choice of any other . of the detergent ~ matrix, or of any particulate component containing the enzyme, such that when the . ~ is introduced to the wash solution the ionic strength ~..vilu...l.~,-L therein provided enables the required enhanced release kinetics to be achieved.
D,~l~yed r~lP~ kin~tir F~rPrn~t-~rS
The release of the organic peroxyacid bleach component from the peroxyacid bleaching system relative to that of the enzyme component is such that in the T50 test method herein described the time to achieve a ~u ~ ;.. that is 50% of the ultimate ~a~ of said enzyme is less than 120 seconds, preferably less than 90 seconds, more preferably less than 60 seconds, and thG time o ac~hisve a that is 50% of the ultimate ~ l of said peroxyacid bleach is more than 180 seconds, preferably from 180 to 480 seconds, more preferably from 240 to 360 seconds. In another aspect, the T50 for the enzyme component is at least 100 seconds less than the T50 for the peroxyacid bleach.
In a highly preferred aspect of the invention the release of bleach is such that in the T50 test method herein described the time to achieve a level of total available oxygen (AvO) that is 50% of the ultimate level is more than 180 seconds, preferably from 180 to 480 seconds, more preferably from 240 to 360 seconds. A method for AvO levels is disclosed in European Patent Application No. g3870004.4.

.
WO gS/28~67 P~ . IU I
21 87303 ~

In another preferred aspect of the invention, where the peroxyacid bleach source is a peroxyacid bleach precursor, employed in ~ ;o,- with a hydrogen peroxide source the kinetics of release to the wash solution of the hydrogen peroxide, relative to those of the enzyme component is such that in the T50 test method herein described the time to achieve a, that is 50% of the ultimate .~ ;..,. of said enzyme is less than 120 seconds, preferably less than 90 seconds, more preferably less tban 60 seconds, and the time to achieve a that is 50% of the ultimate of said hydrogen peroxide and said peroxyacid bleach precursor is more that 180 seconds, preferably from 180 to 480 seconds, more preferably from 240 to 360 seconds.
Where the enzyme is a protease, the ultimate amount in a typical wash solution is from 0.1 to 100 KNPU, but preferably is from 0.5 to 50 ~PNU, more preferably from 3 to 30 KNPU and most preferably from 6 to 30 KPNU.
Where the enzyme is an amylase, the ultimate amount in a typical wash solution is from I to 200 KNU, but preferably is from 10 to 100 KNU, more preferably from 40to 80 KNU.
Where the enzyme is a lipase, the ultimate amount in a typical wash solution is from I
to 300 KLU, but preferably is from 10 to 200 KLU, more preferably from 10 to 100E~U.
Where the enzyme is a cellulase, the ultimate amount in the wash is typically from 10 to 1200 CEVU, but preferably is from 50 to 1000 CEVU, more preferably from 80 to500 CEVU.
The ultimate wash, of any inorganic perhydrate bleach is ,typically from 0.005% to 0.25% by weight, but preferably is more than 0.05%, more preferably more than 0.075%-The ultimate wash ~ of any peroxyacid precursor is typically 0.001% to0.08% by weight, but preferably is from 0.005% to 0.05%, most preferably from 0.015 % to 0.05 % .
yed r~ test m~th~l wo ssl28467 2 1 87 3 ~ 3 ~ u~
The delayed release kinetics herein are defined with respect to a 'TA test method' which measures the time to achieve A% of the ultimate ~ /level of that component when a . , " containing the component is dissolved according to the standard conditions now set out.
The standard conditions involve a I litre glass beaker filled with 1000 ml of distilled water at 20C, to which lOg of , "' is added. The contents of the beaker are agitated using a magnetic stirrer set at 100 rpm. The magnetic stirrer is pealovule-shaped having a maximum dimension of l.5cm and a minimum dimension of O.Scm.
The ultimate ~ f ' ~ level is taken to be the c . ~ /level attained 10 minutes after addition of the nl ''' to the water-filled bealcer.
Suitable analytical methods are chosen to enable a reliable ~ ! of the incidental, and ultimate in solution ,~ of the component of concern, subsequent to the addition of the ~ , ' to the water in the beaLfer.
Such analytical methods can include those involving a continuous monitoring of the level of . ~ ' of the ~ , t, including for example ~': .( ' and methods.
Altematively, methods involving removing titres from the solution at set time intervals, stopping the ~" ' ' process by an ~Yl ~ means such as by rapidly reducing the; , of the titre, and then ~' ' ' ' _ the ' of the component in the titre by any means such as chemical titrimetric methods, can beemployed.
Suitable graphical methods, including curve fitting methods, can be employed, where ~, , ' to enable calculation of the the TA value from raw analytical results.
The particular analytical method selected for ~ the . ' of the ---- r t~ will depend on the nature of that: . t, and of the nature of the N~ containing that cnnlpnn~n~
- Addi~ion~ tf~pnt ~-r~ ,~.. ,, ,.t~
The detergent ~- . . ,1~ ,- ;. A C of the invention may also contain additional detergent The precise nature of these additional . , and levels of .
WO 95/28467 P~ u /
~1 87~Q3 ~

f. thereof will depend on the physical form of the ~ , and the nature of the cleaning operation for which it is to be used.
The ~ , ~ of the invention may for example, be formulated as hand and machine laundry detergent ~u~ u~ , including laundry additive ~ . - and ;-- suitable for use in the ~ of stained fabrics and machine Ji l;-WCL~I-;-~, "
When formulated as ~ suitable for use in a machine washing method, eg:
machine laundry and machine J;~ methods, the ..- ~ of the invention preferably contain one or more additional detergent ~ r ' selected from c~ rt~r~tc builders, heavy metal ion --I organic polymeric Comro~n~lc, suds :~U~IQ~UI:~ lime soap ~'-r ', soil suspension and anti~ u~;i;u,. agents and corrosion inhibitors. Laundry: . can also contain, as additional detergent . r - softening agents.
The detergent . - of the invention may contain as an optional detergentcomponent a surfactant selected from anionic, cationic, nonionic ampholytic, ~mrhf~tf nf and ~w;~t~.;u..;~ surfactants and mixtures thereof.
The surfactant is typically present at a level of from 0.1% to 60% by weight. More preferred levels of; ..~ of surfactant are from 1% to 35% by weight, most preferably from 1~ to 20% by weight.
The surfactant is preferably formulated to be compatible w~th any enzyme cu~
present in the, . In liquid or gel ~ , the surfactant is most preferably formulated such that it promotes, or at least does not degrade, the stability of any enzyme in thQe < .... ,l.. ,- ~ ;.. ~
A typical listing of anionic, nonionic, ampholytic, and ~W;~t~l;Ul~;~, classes, and speciQ of these 5~rf~r~ntc, is given in U.S.P. 3,929,678 issued to Laughlin and Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A list of suitable cationic surfactants is given in U.S.P. 4,259,217 issued to Murphy on March 31, 1981.

w09s~W67 ~ ~ ~73~3 P~ 707 Where present, ampholytic,: ~ ' and zwitteronic surfactant are generally used in ~ ' with one or more anionic and/or nonionic c.. ~-~voss/2s467 21873~3 ~ u~ ~
Anionic surfactant ~
~ssentially any anionic surfactants useful for detersive purposes can be included in the ~r,."~ ;.... These can include salts (including, for example, sodium, potassium,and substituted ammonium salts such as mono-, di- and;
salts) of the anionic sulfate, sulfonate, ~bu~y' and sarcosinate 51. fqrtq~tc Other anionic surfactants include the ' such as the acyl ' N-acyl taurates, fatty acid amides of methyl tauride, llcyl succinates and '' monoesters of ,'( (especially saturated and i ' C12-C18 ) diesters of ' (especially saturated and, ~ C6-C14 diesters), N-acyl ~, Resin acids and ;.ydl~ O ' resin acids are also suitable, such as rosin, I.y.ll~ O ' rosin, and resin acids and l~y; O ' resin acids present in or derived from tallow oil.
Anionic sulfate surfactant Anionic sulfate surfactants suitable for use herein include the linear and branched primary alhyl sulfates, alkyl ~ u~.y r ' , fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the Cs-C17 acyl-N-(cl-c4 alkyl) amd -N-(C1-C2 I~y~lu~y~lhyl) glucamine sulfates, and sulfates of alk~ùly~ such as the sulfates of alhyl~lyol~l~ùs;dl: (the nonionic r ' ~ r I being described herein).
Alkyl t~tllu~y Ir surfactants are preferably selected from the group consisting of the C6-C1g alkyl sulfates which have been c~.u..y' ' with from about 0.5 to about 20 moles of etbylene oxide per molecule. More preferably, tne alkyl t;~l~w~y r surfactant is a C6-C1g alkyl sulfate which has been t;Lllu~y' ' with from about 0.5 to about 20, preferably from about 0.5 to about 5, moles of ethylene oxide per molecule.
Anirmi~ sulfonate cl~rfq~tqrlt Anionic sulfonate surfactants suitable for use herein include the salts of Cs-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated poly~l,ù7.yli,, acids, alkyl _ _ _ . .... . . _ .. .. . _ .. ... . . . .

wog5n8467 2 1 87303 1 11. . ~u~
glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
A ~ ~I t~ S~f~
~nionic w~u,-.~' surfactants suitable for use herein include the alkyl ethoxy wbu,~' , the alkyl polyethoxy ~ul~wbu~ t~ surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.
Preferred alkyl ethoxy w~u~y' for use herein include those with the formula RO(CH2CH20)x CH2COO-M+ wherein R is a C6 to Clg alkyl group, x ranges from O to 10, and the ethoxylate J;~ ;n is such that, on a weight basis, the amount of material where x is O is less than about 20 %, and the amount of material where x is greater than 7, is less than about 25 %, the average x is from about 2 to 4 when the average R is C13 or less, and the average x is from about 3 to 10 when the average R
is greater than C13, and M is a cation, preferably chosen from alkali metal, alkaline earth metal,: . mono-, di-, and tri-; ' ~' ~ . most preferably from sodium, potassium, and mixtures thereof with I I ions. The preferred alkyl ethoxy wI,u,.~' are those where R is a C12 to C1g alkyl group, Alkyl PUI~ UAY l~uly~b~J~' surfactants suitable for use herein include those having the formula RO-(CHRl-CHR2-0)-R3 wherein R is a C6 to C1g alkyl group, x is from I to 25, Rl and R2 are sdected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, llyJlU~ DUC~;.,iC acid radical, and mixtures thereof, wherein at least one Rl or R2 is a succinic acid radical or I~JIu~
acid radical, and R3 is selected from the group consisting of hydrogen, substituted or d~uwbu~ having between I and 8 carbon atoms, and mixtures thereof.
~!!ninnir 5.~nn~ n~ ~lm'qnt~nt Preferred soap surfactants are secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon. The secondary carbon can be in a ring structure, e.g. as in p-octyl benwic acid, or as in alkyl-substituted cyclohexylc~l,u,.~Lt~D. The secondary soap surfactants should preferably contain no ether linkages, no ester linkages and no hydroxyl groups. There should preferably be no nitrogen atoms in the head-group ~ portion). The secondary soap W095/28467 2 ~ ~7~D3 surfactants usually contain 11-15 total carbon atoms, although slightly more (e.g., up to 16) can be tolerated, e.g. p-octyl benzoic acid.
The following general structures further illustrate some of the preferred secondary soap surfactants:
A. A highly preferred class of secondary soaps comprises the secondary carboxyl materials of the formula R3 CH(R4)CooM, wherein R3 is CH3(CH2)x and R4 is CH3(CH2)y, wherein y can be O or an integer from I to 4, x is an integer from 4 to 10 and the sum of (x + y) is 6-10, preferably 7-9, most preferably 8.
. Another preferred class of secondary soaps comprises those carboxyl r ~ wherein the carboxyl substituent is on a ring II~YdIV~b~I unit, i.e., secondary soaps of the formula R5-R6-CooM, wherein R5 is C7-C10, preferably C8-C9, alkyl or alkenyl and R6 is a ring structure, such as benzene, and ~J~ 1~ ' - (Note: R5 can be in the ortho, meta or para position relative to the carboxyl on the ring.) C. Still another preferred class of secondary soaps comprises secondary carboxyl --r-- ' of the formula CH3(CHR)k-(CH2)m-(CHR)n-CH(COOM)(CHR)o~(CH2)p~(CHR)q~CH3~ wherein each R is C1-C4 alkyl, wherein k, n, o, q are integers in the range of 0-8, provided that the total number of carbon atoms (including the ~bv~y' ) is in the range of 10 to 18.
In each of the above forrnulas A, B and C, the species M can be any suitable, especially water- ' ' ' ~ counterion.
Especially preferred secondary soap surfactants for use herein are water-solublemembers selected from the group consisting of the water-soluble salts of 2-methyl- 1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid.
Al~li mPr~l sarcosinate surfactant w0 9s/28467 2 ~ ~ 7 3 ~ ~ r~l,u~ ~u~

Other suitable anionic surfactants are the alkali metal ~, of formula R-CON
~Rl) CH2 COOM, wherein R is a Cs-Cl7 linear or branched alkyl or alkenyl group, Rl is a Cl-C4 alkyl group and M is an alkali metal ion. Preferred examples are the myristyl and oleyl methyl in the form of their sodium salts.
Nonionic surfacta~t Essentially any anionic surfactants useful for detersive purposes can be included in the Exemplary, non-limiting classes of useful nonionic surfactants are listed below.
Nonionic ~ol~ dluAy fatty acid amide c~rfact~Lt Pol~hydlu~.y fatty acid amides suitable for use herein are those having the structural formula R2CONRlZ wherein: Rl is H, C1-C4 h~dlu~l~l~ 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferable Cl-C4 alkyl, more preferably Cl or C2 alkyl, most preferably Cl alkyl (i-e., methyl); and R2 is a Cs-C31 II.YdIU~IJI~
preferably straight-chain Cs-C1g alkyl or alkenyl, more preferably straight-chain Cg-C17 alkyl or alkenyl, most preferably straight-chain C 1 1-Cl7 alkyl or alkenyl, or mixture thereof; and Z is a polyh~dlu~-yh~Jlu~ll.yl having a linear II.rdlU~llb.~l chain with at least 3 hydroxyls directly connected to the chain, or an " ~' ' derivative (preferably uLI.u,~' ' or ~u.u~ ' ' I) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
Nonionic ~u ~ , of alkyl ~henols The pol~ llyl~ , pclyl,lu~Jyl~n~, and polybuL~ oxide ' of alkyl phenols are suitable for use herein. In general, the ,uul~ yl~ , oxide .
are preferred. These . . ' include the c~ products of alkyl phenols having an alkyl group containing from about 6 to about 18 carbon atoms in either a straight chain or branched chain, '., with the alkylene oxide.
lr~hr~l The alkyl ethoxylate ~ ' products of aliphatic alcohols with from about l to about 25 moles of ethylene oxide are suitable for use herein. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and ::
woss/2s467 21~733~3 r~l,u.. lu/ ~
enerally contains from 6 to 22 carbon atoms. Pal ' 'y preferred are the products of alcohols haYing an alkyl group containing from 8 to 20 carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of alcohol.
Nonionic ell~u~ /yluyv~.y~ J fatty alcohol surf~ t~nt The cLl,u,.~' ' C6-C1g fatty alcohols and C6-CIg mixed eLllu~ Uyu~y' fatty alcohols are suitable surfactants for use herein, ~ali ' ~y where water soluble.
Preferably the eLllu~ Lui fatty alcohols are the C1o-C1g ellluA~' ' faKy alcohols with a degree of eLllu~ylaLion of from 3 to 50, most preferably these are the C12-C1g ;Ll~u~' ' fatty alcohols with a degree of eLllu~.~laLiull from 3 to 40. Preferably the mixed l;Lllu~ lUIJV7~y' ' ' fatty alcohols haYe an alkyl chain length of from 10to 18 carbon atoms, a degree of eLIlu~laLiull of from 3 to 30 and a degree of uyu~laLiu.. of from 1 to 10.
Nonionic EO/PO . ~ with pro~ylene ~lycol The: ' products of ethylene oxide with a l~ydiuyllvb;c base formed by Khe ~.,..~1. ..- -';--.. of propylene oxide with propylene glycol are suitable for use herein.
The l~.ydluyllvlJic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility. Examples of ' of this t,Ype include certain of Khe ~ 'ly-available PluronicTM
s rf~r~-~c marketed by BASF.
Nonionic E~O ~ roducts with proyylene u~d.~ h,.~ diamine adducts The; ' products of ethylene oxide with the product resulting from the reaction of propylene oxide and eL~ ' ' ' are suitable for use herein. The , ' ' - moiety of these products consists of the reaction product of eLII~ ' ~ and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000. Examples of this type of nonionic surfactant include certain of the Ily available TetronicTM ~ . marketed by BASF.
Nonionic alh~l~,ol~ 8 surfactant Suitable alkylyvly - ~ for use herein are disclosed in U.S. Patent 4,565,647, Ilenado, issued January 21, 1986, having a llyd~ ' group containing from about W095128467 2187303 r~l~u..

6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a pol~.,.,halidc, e.g., a pù1.~61y~0~id~ yd~uyllilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units. Any reducing saccharide containing S or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties. (Optionally the l~dl.,' ' ~ group is attached at the 2-, 3-, 4-, etc.
positions thus giving a glucose or galactose as opposed to a glucoside or ~qlqrh~
The ' '~ bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
The preferred alk~ 61~siJ~ have the formula R20(CnH2nO)t(glycosyl)x wherein R2 is selected from the group consisting of alkyl, alLylphenyl, l~d~u~lL~I, hydroxyalL-ylphenyl, and mixtures thereof in which the alLyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3; t is from 0 to 10, preferably 0, and X is from 1.3 to 8, preferably from 1.3 to 3, most preferably from 1.3 to 2.7. The glycosyl is preferably derived from glucose.
~nni~mir. fqtty qrir! ' ' ~llrfqr~
Fatty acid amide surfactants suitable for use herein are those having the formula:
R6CoN(R7)2 wherein R6 is an alkyl group containing from 7 to 21, preferably from9 to 17 carbon atoms and each R7 is selected from the group consisting of hydrogen, Cl-C4 alkyl, Cl-C4 hydroxyalL-yl, and -(C2H40)XH, where x is in the range of from I to3.
Am~hoteric ~llrfq,~tqnt Suitable , ' - surfactants for use herein include the amine oxide surfactants and the alkyl ~lph~bu~lic acids.
A suitable example of an alLyl ~ li. acid for use herein is Miranol(TM)C2M Conc. ' J by Miranol, Inc., Dayton, NJ.
..... . ...... . .

wos~28467 2~ ~3~3 r~l,Ov

3~
A Oxide ~ r~
Amine oxides useful herein include those compounds having the formula R3(oR4)XNO(R5)2 wherein R3 is selected from an alhyl, hydroxyalkyl, ~,y' ' ' ~ ulJuyl and alhyl phenyl group, or mixtures thereof, containing from ~ to 26 carbon atoms, preferably 8 to 18 carbon atoms; R4 is an alhylene or l~JIIu~y~hyl~llc group containing from 2 to 3 carbon atoms, preferably 2 carbon atoms, or mixtures thereof; x is from O to 5, preferably from O to 3; and each R5 is an alhyl or hydyroxyalkyl group containing from I to 3, preferably from I to 2 carbon atoms, or a ~ol~l,yl~l~c oxide group containing from 1 to 3, preferable 1, ethylene oxide groups. The R5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
These amine oxide surfactants in particular include Clo-CIg aLkyl dimethyl amineoxides and Cg-CIg alkoxy ethyl ~"' ydlu~J~Lilyl amine oxides. Examples of such materials include d;~ ylu~,Ly' - oxide, d;~,L;.jld~' oxide, bis-(2-lly~lu~y~ l)dOd~.~' - oxide, ~ Idhle~y' ~ oxide, yl.~ ' oxide, ' yl~_Lllylh~,A~l~Cy' oxide, dod~y' ', u~Jyl dilY.~,Llly' o~ide, cetyl ~" ' y' oxide, stearyl d;l~illylL~ c oxide, tallow ~;IIl.,Llly' oxide and dimethyl-2-IIY(IIU~YU~L~C~YI~ ,c oxide. Preferred are Clo-CIg alhyl ~" ' yLIIIu~ oxide, andC10-l8 acylamido alhyl ~" ' y' oxide.
ZwilL~Iiull;c surfactant Zwitterionic surfactants can also be i..cùl~ul.l~d into the detergent ~ C
hereof. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of h~,t~u~ secondary and tertiary amines, or derivatives of quatemary: quaternary 1' . ' or tertiary sulfonium Betaine and sultaine surfactants are exemplary Lw;~t~ n;~ surfactants for use herein.
R~ surf~r~rl~ , The betaines useful herein are those compounds having the formula R(R')2N+R2COO- wherein R is a C6-CIg I~Y'IIU~U~JI group, preferably a C10-C16 alhyl group or C10 16 acylamido aLlcyl group, each Rl is typically Cl-C3 alkyl, . . .

W095128467 21873~3 preferably methyl,m and R2 is a Cl-Cs llyJ-uwbyl group, preferably a Cl-C3 alkylene group, more preferably a Cl-C2 alkylene group. Examples of suitable betaines include coconut a~' ' r U~' ~- " yl betaine; hexadecyl dimethyl betaine; C12 14 a.,yl~ u~.u~ ." Cg 14 a~ -,idùl.~,~yldiethyl betaule;
4tC14-16 ~ '7]-I~ JU~ C16-18 a~ ' ' Jl~ Cl2-l6 a~ J r ' ' yl betaine; tC12-16 a4~' ' ~' '( ' ' ~II",.,f...c. Preferred betaines are C12 18 ~
hexanoate and the C10-l8 a~' ~ . ~ r ~ (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.
Sultaine surf~t~.~t The sultaines useful herein are those: , ' having the formula (R(RI)2N+R2SO3- wherein R is a C6-Clg l~ydluwbyl group, preferably a C10-C16 alkyl group, more preferably a C12-C13 alkyl group, each Rl is typically Cl-C3 alkyl, preferably methyl, and R2 is a Cl-C6 llydluw~yl group, preferably a Cl-C3aLkylene or, prefera~71y, hydroxyalkylene group.
Am~holytic surfacta~
Ampholytic surfactants can be i~.~u.l ' irlto the detergent , herein.
These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of h~t~u~ ,lic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched.
('~tirmir 51'rf~rtallL
Cationic surfactants can also be used in the detergent , herein. Suitable cationic surfactants include the quaternary surfactants selected from mono C6-C16, preferably C6-CIo N-alkyl or alkenyl surfactants wherein the remaining N positions are substituted by methyl, h~.l.u7.~ 1 or l~,~d~u7~ JIu~
groups.
W~tl-r-soluble h~ r com~ound The detergent c~ of the present invention contain as a preferred optional component a water-soluble builder compound, typically present at a level of from 1%

W095/2~'467 2187303 P~ u to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight of the ~
Suitable water-soluble builder compounds include the water soluble IllullUlll~,liC
~ JUA~- or their acid forms, homo or ~U~I~ .;C ,~uly~bvAJli~ acids or their salts in which the puly~,~ul7uA~lic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, carbonates, , borates, I ' ~. ' silicates amd mixtures of any of the foregoing.
Thel,~IJUA~' orPOIY~UAY ~ buildercanbel u~ .- oroligomericintype although monomeric POIY~UA~ are generally preferred for reasons of cost and r Suitable C~UA.Y' containing one carboxy group include the water soluble salts oflactic acid, glycolic acid and ether derivatives thereof. rul.y~l.uAy' containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, Ay) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether ~7UA~' and the sulfinyl ~I.UA~' ' roly~..uA~' contairling three carboxy groups include, in particular, water-soluble citrates, aconitrates and c - as well as succinate derivatives such as the uA~ ,tllyluAy ' described in British Patent No. 1,379,241, IdcluA~ described in British Patent No. 1,389,732, and:
described in ~1~ ' ' ' Application 7205873, and the UA~JUI~.UI7UA~ materials such as 2-oxa-1,1,3-propame ~li~7UUA~' described in British Patent No.
1,387,447.
rùl~l,uAy' containing four carboAy groups include UAy~ disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane t~t7~7JUAyl~t~,.7, 1,1,3,3-propane ~ buA~' and 1,1,2,3-propane ~t7~wbuA~' r~ly~uAJ' containing sulfo ~ include the c--l~ ' derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000.
Alicyclic and ~.~t~..u."~.,li., ~ UI~17uA~' include ~ ' r ~ cis,cis,cis-t~t7~ 7UAy ~ ~;J~ r ~ y ' , 2,3,4,5~ urul~ - cis, cis, cis-l~tl.,~ul.uAy 2,5 ~tl~.J~IIur...a.. - cis - d;~u~uA~ 2,2,5,5-~,dlurul~. - h~l~.~l.uA~' 1,2,3,4,5,6-heAane - II~A~UIJ~7~ and ... ... . _ . . .. .. . . .. .. ... .. .. .. . _ _ . _ . . . .

w0951~8467 2 1 8730~
~ubu~ derivatives ûf polyhydric alcûhols such as sorbitol, mannitol and Aylitol. Aromatic L~ul~uL,v~l~ include mellitic acid, ~ylu,n~llili., acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343.
Of the above, the preferred L~ul~ubuAy' are lI,~dIUA~ )U~ ' ' containing up to three carboAy groups per molecule, more ~i.,ulGll~ citrates.
The parent acids of the or oligomeric ~uly~ubuA~ldt~, chdating agents or mixtures thereof with thei~ salts, e.g. citric acid or, ~ acid miAtures are also. ' ' as useful builder .
Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions can also be used but are not preferred at wash conditions less that about 50C, especially less than about 40C.
Examples of carbonate builders are the alkaline earth and all~ali metal ~uL
including sodium carbonate and sesqui-carbonate and miAtures thereof with ultra-fine calcium carbonate as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
Specific examples of water-soluble phosphate builders are the alkali metal L-iL~l~L , , sodium, potassium and ~ r ~ ', sodiumand potassium and a ~ .' , sodium and potassium Ul~
sodium polymeta~phosphate in which the degree of pol~.,.~,,i~liu.. ranges from about 6 to 21, and salts of phytic acid.
Suitable silicates include the water soluble sodium silicates with an SiO2: Na20 ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.4 being preferred, and 2.û ratio being most preferred. The silicates may be in the form of either the anhydrous salt or a hydrated salt. Sodium silicate with an SiO2: Na20 ratio of 2.0 is the most preferred silicate.
Silicates are preferably present in the detergent 1 in accord with the invention at a level of from 5% to 50% by weight of the ~J-~ , more preferably from 10% to 40% by weight.

wo g5n8467 . ~ 1 ~8 1 3 û 3 r~l,u~

p~rt~ y soluble or insoluble builder com~ound The detergent ~ ;.., of the present invention may contain a partially soluble orinsoluble builder compound, typically preænt at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60%
weight of the ~ ~
Examples of partially water soluble builders include the crystalline layered silicates.
Examples of largely water insoluble builders include the sodium Crystalline layered sodium silicates have the general formula NaMSix02x+1 YH20 wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their ~ are disclosed in DE-A-3417649 and DE-A-3742043. For the purpose of the preænt invention, x in the general formula above has a value of 2, 3 or 4 and is preferably 2. The most preferred material is o-Na2Si20s, available from Hoechst AG as NaSKS-6.
The crystalline layered sodium silicate material is preferably present in granular detergent 1, as a particulate in intimate admixture with a solid, water-soluble ionisable material. The solid, water-soluble ionisable material is ælected from organic acids, organic and inorganic acid salts and mixtures thereof.
Suitable -' ~ 1 zeolites have the unit cell formula Naz[(A102)z(SiO2)y].
XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. Theli material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% wa~er in bound form.
The -' 1 ion exchange materials can be naturally occurring materials, but are preferably synthetically derived. Synthetic cr~vstalline r' ' ''' ' ion exchange materials are available under the ~ .. - Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeoilte MAP, Zeolite HS and mixtures thereof. Zeolite A has the formula ~v0 95/28467 ~ ~1 8 7 ~ u~

Na 12 [AIO2) 12 (si2)12] xH2O
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na86 t(Alo2)86(sio2)lo6]- 276 H2O.
Heavy metal ion se~uestrant The detergent . , of the invention may contain as a preferred optional component a heavy metal ion , By heavy metal ion sequestrant it is meant herein ~ . which act to se~uester (chelate) heavy metal ions. These C') ~ t` may also have calcium and v chelation capacity, but ,f~ lly they show selectivity to binding heavy metal ions such as irnvn, manganese and copper.
Heavy metal ion ~ are generally present at a level of from 0.005% to 20%, preferably from 0.1% to 10%, morepreferably from 0.25% to 7.5% and most preferably from 0.5 % to 5 % by weight of the Heavy metal ion . which are acidic in nature, having for example 1 ' ~ ' acid or carboxylic acid ' ' may be present either in their acid form or as a complex/salt with a suitable counter cation such as an alkali or aLkaline metal ion,: or substituted: ion, or any mixtures thereof.
Preferably any salts/complexes are water soluble. The molar ratio of said counter cation to the heavy metal ion sequestrant is preferably at least 1:1.
Suitable heavy metal ion ~ for use herein include organic L
such as the amino alkylene poly (alkylene I " ' ), alkali metal ethane 1-hydroxy ~", ' . ' and nitrilo i ' jl.,..~ I ' . ' Preferred among the above species are diethylene triainine penta (methylene I ' . ' ), ethylene diamine tri (methylene I ' . ' ) I ' yl~ diamine tetra (methylene ~ ) and hydroxy-ethylene 1,1 ~'ip~ . ' Other suitable heavy metal ion se~uestrant for use herein include ~ l; acid and ~ li., acids such as ~,li.~' ' - acid, W09s/28467 ' 21 ~î'3~3 p ", ,~, yl~ pentacetic acid, ~ disuccinic acid, eL~I.y' ~ ' diglutaric acid, 2-llydluAy~lul~y' " ~ disuccinic acid or any salts thereof.
Especially preferred is t~ N,N'-disuccinic acid (EDDS) or the aLkalimetal, alkaline earth metal,: - or substituted ammonium salts thereof, or mi-Atures thereof. Preferred EDDS: . ' are the free acid form and the sodium or _ salt or complex thereof. E-Aamples of such preferred sodium salts of EDDS include Na2EDDS and Na3EDDS. Examples of such preferred complexes of EDDS include MgEDDS and Mg2EDDS.
Other suitable heavy metal ion ~- lu .~ for use herein are ,, ~ 1;. acid derivatives such as 2-~ JIUA~ l diacetic acid or glyceryl iminû diacetic acid, described in EP-A-317,542 and EP-A-399,133.
The - ' - acid-N-2-l-ydluAy~,lu~Jl sulfonic acid and aspartic acid N-~I)UA~ N-2-ll~d~uA.~ 1-3-sulfonic acid:, described in EP-A-516,102 are also suitable herein. The 3-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid N ~ - acid and ' ~ acid described in EP-A-509,382 are also suitable.
EP-A-476,257 describes suitable amino based ~, EP-A-510,331 describes suitable ~ ~ derived from collagen, keratin or casein. EP-A-528,859 describes a suitable alkyl; . . . - ~1 -. . I ;. acid ~ ~ Dipicolinic acid and 2-, 1,2,4-~.;wlbu~lic acid are alos suitable. Gl~, ' N,N'-disuccimic acid (GADS) is also suitable.
Fnz~vme Shbilizing, System Preferred enzyme-conhining ~J .~ nc herein may comprise from about 0.001%
to about 10%, preferably from about 0.005% to about 8%,most preferably from about 0.01% to about 6%, by weight of an enzyme shbilizing system. The enzyme shbilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such stabilizing systems can comprise calcium ion, boric acid, propyleneglycol, short chain carboxylic acid, boronic acid, and mixtures thereof. Such shbilizing systems can also comprise reversible enzyme inhibitors, such as reversible protease inhibitors.

wo ss~28467 2 1 8 7 3 0 3 r~ /u7 The (,u~ herein may further comprise from 0 to about 10%, preferably from about 0.01% to about 6% by weight, of chlorine bleach scavengers, added to prevent chlorine species present in many water supplies from attacking and ~ the enzymes, especially un~ ~kaline conditions. While chlorine levels in water may be small, typically in the 1.~ ~ from about 0.5 ppm to about 1.75 ppm, the available chlorine in the total volume of water that comes in contact with the enzyme during washing is usually large; acc~ld;..~ly, enzyme stability in-use can be ~
Suitable chlorine seavenger anions are widely available, and are illustrated by salts containing cations or sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc.such as carbamate, ascorbate, etc., organic amines such as yl~ ~`A~ ;' acid (EDTA) or alkali metal salt thereof"
(MEA), and mixtures thereof can likewise be used. Other . u,.~,.iiu,.al scavengers such as bisulfate, nitrate, chloride, souroes of hydrogen peroxide such as sodium perborate Lt~ y,' , sodium perborate ' ~' and sodium p~L as well as phosphate, condensed phosphate, aoetate, benzoate, citrate, formate, laetate, malate, tartrate, salicylate, etc. and mixtures thereof can be used if desired.
C~ ~olvr~n~
rganic polymeric . . ' are ~ / preferred ;--~r of the detergent in aceord with the invention. By organie polymerie eompound it is meant essentially any polymerie organie compound eommonly used as rii~rPr~ c and anti-lr~ and soil suspension agents in detergent ~ u Organic polymeric compound is typically r ' in the detergent c~
of the invention at a level of from 0.1% to 30%, preferably from 0.5% to 15%, most preferably from 1% to 10% by weight of the ~ . -Examples of organie polymerie ~ . ' inelude the water soluble organie homo-or co-polymeric ~UIr~UAyliC acids or their salts in which the ~l~ubuA~lic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756.
Examples of such salts are pol~ ' of MWt 2000-5000 and their col,ul~
with maleic anhydride, sueh ~,u~l~ having a molecular weight of from 20,000 to 100,000, especially 40,000 to 80,000.
. . .

~vvoss/2s467 ~18~3~3 r~ /ul ~

Other suitable organic polymeric compounds include the polymers of acrylamide and acrylate having a molecular weight of from 3,000 to 100,000, and the acrylatetfumarate copolymers having a molecular weight of from 2,000 to 80,0û0.
The polyamino ~ r- are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
Terpolymers containing monomer units selected from maleic acid, acrylic acid, ul~ ic acid and vinyl alcohol, l~dli ' ~.y those having an average molecular weight of from 5,000 to 10,000 are also suitable herein.
ther organic polymeric cnmro -~lv suitable for ,UUld~iUI~ in the detergent herein include cellulose derivatives such as methylcellulose, ~bu-~yl..~ l~llulu~ and l~llw~ h.y' Further useful organic polymeric . are the ~JUI~ ..c glycols, ~ ulall~
those of molecular weight 1000-10000, more ~ ly 2000 to 8000 and most preferably about 4000.
Tirn-~ ~n~ r~ nt compound The ~ u~ of the invention may contain a lime soap dispersant compound, which has a lime soap dispersing power (LSDP), as deflned hereinafter of no morethan 8, preferably no more than 7, most preferdbly no more than 6. The lime soapdispersant compound is preferably present at a level ûf from 0.1% to 40% by weight, more preferably 1% to 20% by weight, most preferably from 2% to 10% by weight of the u~
lime soap dispersant is a material that prevents the ~ l ;.... of allcali metal, or amine salts of fatty acids by calcium or magnesium ions. A numerical measure of the ~rf~tiv~ of a lime soap dispersant is given by the lime soap disrersing power (LSDP) which is determined using the lime soap dispersion test as described in an aTticle by H.C. Borghetty and C.A. Bergman, J. Am. Oil. Chem.
Soc., volume 27, pages 88-90, (1950). This lime soap dispersion test method is widely used by r~ in this art field being referred to, for example, in the following review articles; W.N. Linfield, Surfactant Science Series, Volume 7, p3;
W.N. Linfield, Tenside Surf. Det., Volume 27, pagesl59-161, (1990); and M.K.
. _ . . . . . _ .. . .. . .. .. .

Wogs/28467 ~ ~73~ P ~ u~

Nagarajan, W.F. Masler, Cosmetics and Toilet~ies, Volume 104, pages 71-73, (1989). The LSDP is the % weight ratio of dispersing agent to sodium oleate required to disperse the lime soap deposits formed by 0.025g of sodium oleate in30ml of water of 333ppm CaCO3 (Ca:Mg=3:2) equivalent hardness.
Surfactants having good lime soap dispersant capability will include certain amine oxides, betaines, ~ . alkyl eLIlu~ '' and eLI-u~.y` ' alcohols.
Exemplary surfactants having a LSDP of no more than 8 for use in accord with theinvention include C16-C18 dimethyl amine oxide, C12-CIg alkyl ~Ll~u~y '' with an average degree of ~Lllu~yl~Liull of from 1-5, p~Li~..l~l.y C12-Cls alkyl ~LIIu~ '' surfactant with a degree of ~ u~yl~LiOn of about 3 (LSDP=4), and the C13-Cls eLllu~' ' alcohols with an average degree of eLllu~yl~Lio.~ of either 12(LSDP=6) or 30, sold under the trade names Lutensol A012 and Lutensol A030 `~t~Li~.,-y, by BASF GmbH.
Polymeric lime soap dispersants suitable for use herein are described in the article by M.K. Nagarajan and W.F. Masler, to be found in Cosmetics and Toiletries, Volume 104, pages 71-73, (1989). Examples of such polymeric lime soap dispersants include certain water-soluble salts of w~ly~ . . of acrylic acid"~..,lh~lyL~, acid or mixtures thereûf, and an acrylamide or substituted ~.,ly' ' ~ where such polymers typically have a molecular weight of from 5,000 to 20,000.
Suds suVvressing system The detergent c~ c of the invention, when formulated for use in machinewashing , - . preferably comprise a suds . ~ system present at a level of from 0.01% to 15%, preferably from 0.05% to 10%, most preferably from 0.1% to 5% by weight of the ~
Suitable suds ~ ; systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam . ', 2-alkyl and alcanol antifoam, By antifoam compound it is meant herein any compound or mixtures of ~omro~ c which act such as to depress the foaming or sudsing produced by a solution of a detergent cc~ ~rc~ ~Li-,ul~uly in the presence of agitation of that solution.
_ . . . ... . . .. _ _ ... _ _ _ _ _ . . .

W095/28467 2:~ ~7~3 r~ ~707 P~iuuLuly preferred antifoam compounds for use herein are silicone antifoam cnmro~ defined herein as any antifoam compound including a silicone Such silicone antifoam . ~. ' also typically contain a silica r ' The term "silicone" as used herein, and in general throughout the industry, ~ u~ a variety of relatively high molecular weight polymers containing siloxane units and l~ydlu~,~ul/yl group of various eypeS. Preferred silicone antifoam: , ' are the siloxanes, p uLi~ul.uly the ~Iyd;~ ylsiloxanes having Llilnc~ ;lyl end blocking units.
Other suitable antifoam compounds include the ~ ~u~u~yli~ fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The - b~J~.ylic fatty acids, and salts thereof, for use as suds suppressor typically have llydlu~lJ~I chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the aLkali metal salts such as sodium, potassium, and lithium salts, and: and salts.
Other suitable antifoam ~----r ' include, for example, high molecular weight fatty esters (e.g. fatty acid Ll;61y~.;~), fatty acid esters of monovalent a~cohols, aliphatic Clg-C40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to he~ca-alky ' or di- to tetra alkyldiamine ' ' forrned as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and l..~JIIolt~yl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.
Copolymers of ethylene oxide and propylene oxide, ~,~ui ' 'y the mixed ~ u~.y' '/~llu~ y' ' fatty alcohols with an alkyl chain length of from 10 to 16 carbon atoms, a degree of ~ u~yl,~iiull of from 3 to 30 and a degree of ~u~-~yl~liul.
of from 1 to 10, are also suitable antifoam ~ , ' for use herein.
Suitable 2-alky-alcanols antifoam ~ . ' for use herein have been described in DE 40 21 265. The 2-alkyl-alcanols suitable for use herein consist of a C6 to C16 alkyl chain carrying a terminal hydroxy group, and said alkyl chain is substituted in the a position by a Cl to Clo alkyl chain. Mixtures of 2-alkyl-alcanols can be used in the ~ according to the present invention.
. , _ _ _ _ wo 95/28467 ~ 8,7,3,,~3 r~ u~
A preferred suds ~u~ ;..6 system comprises (a) antifoam compound, preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in (i) poly~" ' yl siloxane, at a level of from 50% to 99%, preferably 75%to 95 % by weight of the silicone antifoam compound; and (ii) silica, at a level of from 1% to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound;
wherein said silicalsilicone antifoam compound is . ' at a level of from 5%
to 50%, preferably 10% to 40% by weight;
(b) a dispersant compound, most preferably comprising a silicone glycol ra~e copolymer with a polyu/~y~lLyl~ . content of 72-78% and an ethylene oxide to propylene oxide ratio of from 1:0.9 to 1:1.1, at a level of from 0.5% to 10%, preferably 1% to 10% by weight; a ~ ,uLul~ preferred silicone glycol rake copolymer of this type is DCO544, 'Iy available from DOW
Corning under the tradename DCO544;
(c) an inert ca~ier fluid compound, most preferably comprising a C16-CIg ~II.v,.~' ' alcohol with a degree of ~ u~ Liv.l of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;
A preferred particulate suds suppressor system useful herein comprises a mixture of an alkylated siloxane of the type h~ ùv~ disclosed and solid silica.
The solid silica can be a fumed silica, a I . ' silica or a silica, made by the gel formation technique. The silica patticles suitable have an average particle siæ of from 0.1 to 50 .";.,.u...~t~.~, preferably from l to 20 .-~ and a surface atea of at least 50m2/g. These silica particles can be rendered I~Jd~u~hvb;~, by treating them with dialkylsilyl groups and/or ~ l groups either bonded directly onto the silica or by means of a silicone resin. It is preferred to employ a silica the particles of which have been rendered h.~dlu~l~vb;c with dimethyl and/or trimethyl silyl groups. A preferred patticulate antifoam compound for inclusion in the detergent, . in accordance with the invention suitably contain an amount of woss/2s467 ~ 7~13 ~ u~

silica such that the weight ratio of silica to silicone lies in the range from 1:100 to 3:10, preferably from 1:50 to 1:7.
Another suitable particulate suds ~u~ c~;..6 system is ~ I~ by a lly~
silanated (most preferably trimethyl-silanated) silica having a particle size in the range from 10 1 to 20, and a specific surface area above 50m2/g, intimately admixed with dimethyl silicone fluid having a molecular weight in therange from about 500 to about 200,000 at a weight ratio of silicone to silanated silica of from about 1:1 to about 1:2.
A highly preferred particulate suds ~ g system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50C to 85C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate suds ~u~ , systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45C to 80C.
Other highly preferred particulate suds ~ g systems are described in copending European Application 91870007.1 in the name of the Procter and Gamble Company which systems comprise silicone antifoam compound, a carrier material, an organic coating material and glycerol at a weight ratio of glycerol: silicone antifoam compound of 1:2 to 3:1. Copending European Application 91201342.0 also discloseshighly preferred ~ticulate suds , r ' 1~ systems comprising silicone antifoam compound, a carrier material, an organic coating material and crystalline or amorphous s ~ t~ at a weight ratio of ~ silicone antifoam compound of 1:3 to 3:1. The preferred carrrier material in both of the above described highly preferred granular suds controlling agents is starch.
n exemplary particulate suds ~ g system for use herein is a particulate -~ r t, made by an ~ process, comprising in ,, ,.. ,1 .; .... ;....
(i) from 5% to 30%, preferably from 8% to 15% by weight of the component of silicone antifoam compound, preferably comprising in ~,O
poly~' ' yl siloxane and silica;
..... .. _ . _ . ..... . ......... ... ... .........

w095/28467 21 873~3 ~ u~ u~

(ii) from 50% to 90%, preferably from 60% to 80% by weight of the ~ r t~
of carrier material, preferably starch;
(iii) from 5% to 30%, preferably from 10% to 20% by weight of the component of lgg' binder compound, where herein such compound can be any compound, or mixtures thereof typically employed as binders for __' most preferably said ~g' binder compound comprises a C16-C1g ~ UAy' ' alcohol with a degree of ell.uA~ll,ion of from 50 to 100;
and (iv) from 2% to 15%, preferably from 3% to 10%, by weight of C12-C22 I~J~u~ ~ fatty acid.
Polymeric dye transfer inhibitin~ a~ents The detergent ~ -- "~ herein may also comprise from 0.01% to 10 %, preferably from 0.05% to 0.5 % by weight of polymeric dye transfer inhibiting agents.
The polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, ~u~ulylll. ., of N .;~yl~yllulidO.I~ and N-v ylill.;J~I~, polyv;..yl~,ylluliJo.~,ly...~l~ or ~ ' thereof.
a) Polyamine N-oxide volymers Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula:

(I) I
R
wherein P is a poly ' ' unit, whereto the R-N-O group can be attached to, or wherein the R-N-O group forms part of the ~71yIll~li~bl~ unit or a ~ of both.

WO95/28467 7 1 873Q3 P~

Il 11 11 A is NC, CO, C, -O-, -S-, -N-; x is O or1;
R are aliphatic, ~LI,v,~' ' aliphatics, aromaùc, I.~ .,lic or alicyclic groups or any . ' thereof whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group is part of these groups.
The N-O group can be ,c, ' by the following general structures:
o O
(R~) X-N-tR2)Y
IR3)Z or --N-(R1)x wherein Rl, R2, and R3 are aliphatic groups, aromatic, l~,t~u,~ or alicyclic groups or ' thereof, x or/and y or/and z is 0 or I and wherein the rlitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups~ The N-O group can be part of the pol~ ' ' unit (P) or can be attached to the polymeric backbone or a .~ ;.... of both~
Suitable polyamine N-oxides wherein the N-O group forms part of the pol~ l;~lc unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic,alicyclic or l,~ ,lic groups~ One class of said polyamine N-oxides comprises thegroup of polyamine N-oxldes wherein the nitrogen of the N-O group forms part of the R-group~ Preferred polyarnine N-oxides are those wherein R is a l~ ,lic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
Another class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group is attached to the R-group~
Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O groupis attached to the ~uly ' '~ unit.
,,, ,, , _ . , ,, . _ . _ ,, .. . , . ... ,,, . , . . ,, ,, , _ _ _ W095128467 21~3~ r~ ,u, Preferrcd class of these polyamine N-oxides are the polyamine N-oxides having the general formula (I) wherein R is an arn~ ir ll ~ u~,y~,lic or alicyclic groups wherein the nitrogen of the N-0 functional group is part of said R group. Examples of these classes are polyamine oxides wherein R is a ~..,t~,u."~.,li~. compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
Another preferred class of polyamine N-oxides are the polyamine oxides having the general formula (I) wherein R are aromatic, h~,t~lu~ , or alicyclic groups wherein the nitrogen of the N-0 functional group is attached to said R groups. ~xamples of these classes are polyamine oxides wherein R groups can be aromatic such as phenyl.
Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, puly ' pul,~a~ ' ' and mixturesthereof.
The amine N-oxide polymers of the present invention typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1000000. However the amount of amine oxide groups present in the polyamine oxide polymer can be varied by 4~
Cu~l~ a~h~ll or by au~l~, degree of N-oxidation. Preferably, the ratio of amine to amine N-oxide is from 2:3 to 1:1000000. More preferably from 1:4 to l:lOOOOOO,mostpreferablyfroml:7tol:1000000.Thepolymersoftheprcsent invention actually encompass random or block ~u~l~ where one monomer type is an amine N-oxide and the other monomer type is either an amine N-oxide or not.
Tne amine oxide unit of the polyamine N-oxides has a PKa < lû, preferably PKa <
~, more preferred PKa < 6.
The polyamine o~ides can be obtained in almost any degree of ~Ig The degree of pol.~ a~iùn is not critical provided the material has the desired water-solubility and ~, , ' , power. Typically, the average molecular weight is within the range of 500 to 1000,000; preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.
b) Co~olyr-rs of N-vi~ v~ r ' N-vinylim~zQ~

Wo9sl2846~ 73~3 ~ u~
so Preferred polymers for use herein may comprise a polymer selected from N-vinylimidazole N-v...~ ..ulidu~,~, cu~ul,y~ wherein said polymer has an average molccular weight range from 5,000 to 50,000 more preferably from 8,000 to 30,000, most preferably from 10,000 to 20,000. The preferred N ~;.,~' ' '- N-V;~ cu~l~ have a molar stio of N--v ~I;...;JdLul~ to N-vil~ ulidu~c from I to 0.2, more preferably from 0.8 to 0.3, most preferably fromO.6toO.4 .
c~ rVI~v;..Jl~yllul;du....
The detergent ~ herein may also utilize ~ul~v;~ PVP"
having an average molecular weight of from 2,500 to 400,000, preferably from 5,000 to 200,000, more preferably from 5,000 to 50,000, and most preferably from 5,000to 15,000. Suitable ~ v;~ ,y.-, "' are ~ .,;ally vailable from ISP
ion New York, NY and Montrcal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molccular wPight of40,000), PVP K-60 (average molccular weight of 160,000), and PVP K-90 (average molecular weight of 360,000). PVP K-15 is also available from ISP l'~ n Other suitable ~ulJv...~ ..ul;du.1~ which are . ly available from BASF
CoopP~inn include Sokalan HP 165 and Sokalan HP 12.
r~ ulid~ may be r ' ~ in the detergent ~ . herein at a level of from 0.01% to 5% by weight of the detergent, preferably from 0.05% to 3%
by weight, and more preferably from 0.1% to 2% by weight. The amount of POI~V;I~ I ' ' delivered in the wash solution is preferably from 0.5 ppm to 250 ppm, preferably from 2.5 ppm to 150 ppm, more preferably from 5 ppm to 100 ppm.
d) r~ lu-~ ul;du--~
The detergent ~ - herein may also utilize ~1~ v;ll,~l- .~ ~ ,- .li~l- - - - as polymeric dye transfer inhibiting agents. Said polyvi~lv~ . have an average molecular weight of from 2,500 to 400,000, preferably from 5,000 to 200,000, more preferably from 5,000 to 50,000, and most preferably from 5,000 to 15,000.
The amount of ~ol~ v ;l. ~1~ ' '( ~ldt~ in the detergent ~ c may be from 0.01% to 5% by weight, preferably from 0.05% to 3% by weight, and more preferably from 0.1% to 2% by weight. The amount of pul~
.. . . . _ . .. .. .. . ~ . .. _ _ wossi28467 ~1 8~73~ /u~ ~u~

delivered in the wash solution is typically from 0.5 ppm to 250 ppm, preferably from 2.5 ppm to 150 ppm, more preferably from 5 ppm to 100 ppm.
e) r~lyv;llylilllid~ul~
The detergent ~ , herein may also utili2e ~Iy v;~ylil~;d~l~ as polymeric dye transfer inhibiting agent. Said polyv;ll.~' ' ' preferably have an average molecular weight of from 2,500 to 400,000, more preferably from 5,000 to 50,000,and most preferably from 5,000 to 15,000.
The amount of polyi yli~lid~l~ i..~.~t~ in the detergent cc~ may be from 0.01% to 5% by weight, preferably from 0.05% to 3% by weight, and more preferably from 0.1% to 2% by weight. The amount of ~Iyvi~ id~ delivered in the wash solution is from 0.5 ppm to 250 ppm, preferably from 2.5 ppm to 150 ppm, more preferably from 5 ppm to 100 ppm.
Optical bripb~
The detergent: . herein may also optionally cont~in from about 0.005% to 5% by weight of certain typPs of l~yJI~ optical brighteners which also provide adye transfer inhibition action. If used, the ~ c herein will preferably comprise from about 0.01% to 1% by weight of such optical bri~ht~nprc The hydrophilic optical brighteners useful in the present invention are those having the structural formula:
Rl R2 ~ON~ IN~C=C~NI ~N

wherein Rl is selected from anilino, N-2-bis-l-ydlu/~ hJl and NH-2-l~ydlu~
R2 is selected from N-2-bis-l.yd.u~"Li.yl, N-2-l~ydl~ yl N ' y' ~, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.

Wo9!7/28467 ` ~ 3 P~ u~
~3 When in the above formula, Rl is anilino, R2 is N-2-7~;~ h~d~u~_L.~yl and M is acation such as sodium, the brightener is 4,4' ,-bis[(4-anilino-6-7~N-2-7J;s ~ u~ L.~yl)-s-t7~iazine-2-yl)amino]-2,2'-~till ~ -- 7~ r.",:~ acid and disodium salt. Tbis particular brightener species is ~,;ally marketed under the tradename Tinopa7i-UNPA-GX
by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred l,~_.u~,l.;lic optical brightener useful in the detergent; , herein.
When in the above formula, Rl is anilino, R2 is N-2-1,~_1u,~ l N 2~
and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-IlyLlv~vLll~l-N-ll~ ;llv)-s-t7iazine-2-yl)amino]2~2~-cti~ lrll :~acid disodium sa7~t. This particular brightener species is ~ ~;ally mar~eted under the tradename 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-6-.1,ùll ' " s triazine-2-yl)amino]2,2'-:till ... ,. ~7, ~, .l r~ ..., acid, sodium salt. This particular brightener species is~o..,..~ lly marketec under the tradename Tinopa7i AMS-GX by Ciba Geigy Corporation.
The specific optica7i brightener species selected for use in the present invention provide especially effective dye transfer inhibition pe.rullll~l.,_ benefits when used in with the selected polymeric dye transfer inhibiting agents I ` r e described. The .~ ;-... of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal SBM-GX and/or Tinopal AMS-GX) provides - _ ~ -ly better dye transfer inhibition in aqueous wash solutions than does either of these two detergent when used alûne. Without being bound by theory, it is believed that such brighteners work this way because they have high affinity forfabrics in the wash solution and therefore deposit relatively quick on these fabrics.
The extent to which brighteners deposit on fabrics in the wash solution can be defined by a parameter called the "exhaustion ~rrlc;.,.,L . The exhaustion coef~lcient is in general as the ratio of a) the bri~htener materiaL deposited on fabric to b) the initial brightener in the wash liquor. r v~ with relatively high exhaustion . ~ -~ are the mo$ suitable for inhibiting dye transfer in the context of the present invention.
. _ . .. . _ . .

wo95/28467 21873~3 r~ ul s3 f course, it will be ~ ' that other, cu~ optical brightener types of can optionally be used in the present ~ I to provide . u..~. I
fabric ~ benefits, rather than a true dye transfer inhibiting effect. Such usage is c~..v~.-Liu.lal and well-known to detergent r ~ -Sof~
Fabric softening agents can also be i~lcull ' into laundry detergentin accordance with the present invention. These agents may be inorganic or organic in type. Inorganic softening agents are ~.... jll;ri.~.i by the smectite clays disclosed in GB-A-I 400 898. Organic fabric softening agents include the water insoluble tertiary amines as disclosed in GB-A-I 514 276 and EP-B-0 011 340.
Levels of smectite clay are normally in the range from 5 % to 15 %, more preferably from 8% to 12% by weight, with the material being added as a dry mixed componentto the remainder of the & ' Organic fabric softening agents such as the water-insoluble tertiary amines or dilong chain amide materials are i .,,lu ,.. ~ l at levels of from 0.5% to 5% by weight, normally from 1% to 3% by weight, whilst the high molecular weight pUl.~Ll.~- .lc oxide materials and the water soluble cationic materialsareaddedatlevelsoffromO.1% to2%, normallyfromO.15% to 1.5% by weight.
OthP-o~ on~l inpr~
Other optional ingredients suitable for inclusion in the ~ of the invention include perfumes, colours and filler salts, with sodium sulfate being a preferred filler woss/28467 2187303 r~ ul s4 FQrm of the ~u~ v~,7 The detergent c~ ; "-c of the invention can be formulated in any desirable form such as powders, granulates, pastes, liquids and gels. The ~v ~ are preferably not in tablet-form. Most preferably, the .u ~lr.~ . are in granular form.
T. ' ~v.r~vva l;v ~
The detergent ~v ~ c of the present invention may be formulated as liquid detergent f ~ '- ' ;"" ` Such liquid detergent . typically cQmprise from 94% to 35% by weight, preferably from 90% to 40% by weight, most preferably from 80% to 50% by weight of a liquid catrier, e.g., water, preferably a mixture of water and organic solvent.
Gel .
The detergent ... ~ ;.--, of the present invention may also be in the forrn of gels.
Such ~ c are typically formulated with polyakenyl polyether having a molecular weight of from about 750,000 to about 4,^00,000.
Solid Sv~ cn;~ivl~i _ The detergent .v~ ;.., of the invention are preferably in the form of solids, such as powders and granules.
The particle size of the . . of granular ~ in accordance with the invention should preferably 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.
The bulk density of granular detergent ""--~i - ';" - in accordance with the present invention typically have a bulk density of at least 450 g/litre, more usually at least 600 g/litre and more preferably from 650 g/litre to 12vO g/litre.
Bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel moulded rigidly on a base and provided with a flap valve at its lower _ . .. . . .. . .. . . . _ wo gs/28467 2 1 8 7 3 0 3 r~l"~ ~u~
ss extremity to allow the contents of the funnel to be emptied into an axially aligned cylindrial cup disposed below the funnel. The funnel is 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base. The cup has an overa,l height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.
To carry out a t, the funnel is filled with powder by hand pouring, theflap valve is opened and powder allowed to overf~ll the cup. The filled cup is removed from the frame and excess powder removed from the cup by passing a straight edged implement e.g. a knife, across its upper edge. The filled cup is then weighed and the value obt~ined for the weight of powder doubled to provide the bulk density in g/litre. Replicate I are made a required.
prn~pccpc e~u~ com~Si~QPs Ln general, granular detergent ~ - in accordance with the present invention can be made via a variety of methods including dry mixing, spray drying, -~ccln~r ~ and W;lchin~ Pth~l~lc The ~ of the invention may be used in essentially any washing or cleaning method, including machine laundry and d;,llwa,l~ methods.
',.._ h "~ P~h~
A preferr~d machine .li~hw~h...~ method comprises treating soiled articles selected from crocker,v, glassware, hollowware and cutlery and mixtures thereof, with an aqueous liquid having dissolved or dispensed therein an effective amount of a machine .1;,1.... ' ~ . , in accord with the invention. By an effective amount of the machine d;,h~ it is typically meant from 8g to 60g of product dissolved or dispersed in a wash solution of volume from 3 to 10 litres, as are typical product dosages and wash solution volumes commonly employed in ~u machine di,l... ' _ methods.
~hine I ~rY methods wo sSr2s467 2 7 ~ ?3 r~ 07 s6 Machine laundry methods herein wmprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent c~ in accord with the invention. The detergent can be adderl to the wash solution either via the dispenser drawer of the washing machine or by a dispensing device. By an effective arnount of the detergent ,.... it is typically meant from 40g to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed im w~ ...iu~l~l machine laundry methods.
In a preferred washing method herein a dispensing device wntaining an effective amount of detergent product is introduced into the drum of a, preferably front-loading, washing machine before the: of the wash cycle.
The dispensing device is a container for the detergent product which is used to deliver the product directly into the drum of the washing machine. Its volume capacity should be such as to be able to contain sufficient detergent product as would normally be used in the washing method.
Once the washing machine has been loaded with laundry the dispensing device containing the detergent product is placed inside the drum. At the . of the wash cycle of the washing machine water is introduced into the drum and the drum periodically rotates. The design of the dispensing device should be such that it permits of the dry detergent product but then allows release of this product during the wash cycle in response to its agitation as the drum rotates and also as a result of its immersion in the wash water.
To allow for release of the detergent product during the wash the device may possess a number of openings through which the product may pass. Alternatively, the device may be made of a material which is permeable tû liquid but ,~ lr to the solid product, which wiU allow release of dissolved product. Preferably, the detergentproduct will be rapidly released at the start of the wash cycle thereby providing transient localised high ~ of: . such as water-soluble builder and heavy metal ion sequestrant ~ . in the drum of the washing machine at this stage of the wash cycle.
. .

woss/2s467 21 8~3~
s7 Preferred dispensing devices are reusable and are designed in such a way that container integrity is maintained in both the dry state and during the wash cycle.
Especially preferred dispensing devices for use in accord with the invention have been described in the following patents; GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345 and EP-A-0288346. An article by J.Bland published in r~ Chemist, November 1989, pages 41-46 also describes especially preferred dispensing devices for use with granular laundry products which are of a type commonly know as the agranulette~.
Especially preferred dispensing devices are disclosed in European Patent Application Publication Nos. 0343069 & 0343070. The latter Application discloses a device comprising a flexible sheath in the form of a bag extending from a support ring defining an orifice, the orifice being adapted to admit to the bag sufficient product for one washing cycle in a washing process. A portion of the washing medium flows through the orifice into the bag, dissolves the product, and the solution then passes outwardly through the orifice into the washing medium. The support ring is provided with a masking: ~ to prevent egress of wetted, u~J;~ l, product, this typically comprising radially extending walls extending from a central boss in ~ spoked wheel . '1, or a similar structure in which the walls have a helical form.
In the detergent ~ . the ~u~ ' component i~lf liri. ~ have the following meanings:
XYAS : Sodium Clx - Cly alkyl sulfate 24EY : A C12 14 l~ lly Iinear primary alcohol condensed with an average of Y moles of ethylene oxide XYEZ : A Clx - Cly ~ , linear primary alcohol condensed with an average of Z moles of ethylene oxide XYEZS : C1x - C1y sodium alkyl sulfate condensed with an average of Z moles of ethylene oxide per mole 2 ~ 87303 WO 95/28467 P~ u TFAA : C16-CIg alkyl N-methyl glucamide.
Silicate : Amorphous Scdium Silicate (SiO2:Na2O ratio = 2.0) NaSKS-6 : Crystalline layered silicate of formula ~-Na2Si2Os Carbonate : ADhydrous sodium carboDate roly~L~uA~' : Copolymer of 1:4 ~ ;c/a.,.~Lc acid, average molecular weight about ~0,000 Zeolite A : Hydrated Sodium ~1 1 ' of formula Nal2(AlO2SiO2)12. 27H20 having a primary particle size in the raDge from I to 10 ~ ,lu-ll.,t~.a Citrate : Tri-sodium citrate dihydrate r~,l~L (fastrelease : Anhydrous sodium ~ . L bleach of empirical particle) formula 2Na2CO3.3H2O2 coated with a mixed salt of formula Na2SO4.n.Na2CO3 where n is 0.29 and where the weight ratio of p~.~L to mixed salt is 39: 1 r~ (slow release : Anhydrous sodium ~.~L bleach coatcd with a particle) coating of sodium silicate (Si2O:Na2O ratio = 2:1) at a weight ratio of ~l~uL to sodium silicate of 39:1 TAED : T~h~e~yl~
TAED (slow release : Particle formed by s",L;I~ g TAED with citric particle) acid amd ~I~ ,.. , glycol (PEG) of Mw=4,000 with a wdght ratio of . of TAED:citric acid:P~G of 75:10:15, coated with an exterDal coating of citric acid at a weight ratio of ~g~lr-- citric acid coating of 95:5.
, . . .

w095/28467 2~873~3 ~ u~
ss Benzoyl Caprolactam (slow : Particle formed by ~ g benzoyl ~lul~uul-release particle) (BzCI) with citric acid and ~I~ yl~ n~ glycol (PEG) of Mw=4,000, with a weight ratio of ~ ~i of BzCl:citric acid:PEG of 63:21:16, coated with an external coating of citric acid at a weight ratio of acid coating of 95:5 TAED (fast release : Particle formed by a~ TAED with partially particle) neutralised l uly~bw~y' at a ratiû of TAED.pf~ly~ubu~yl~ of 93:7, coated with an external coating of poly~u,.~' at a weight ratio of "~, . of 96:4 EDDS (fast release : Particle formed by spray-drying EDDS with MgS04 at particle) a weight ratio of 26:74 Protease : Proteolytic enzyme sold under the tradename Savinase by Novo Industries A/S with an activity of 13 KNPU/g.
Amylase : Amylolytic enzyme sold under the tradename Termamyl 6ûT by Novo Industries A/S with an activity of 300 KNU/g Cellulase : Cellulosic enzyme sold by Novo Industries A/S with an activity of 1000 CEVU/g Lipase : Lipolytic enzyme sold under the tradename Lipolase by Novo Industries A/S with an activity of 165 KLU/g CMC : Sodium ~bu~ l cellulose HEDP : 1,1 I~,~dlW~ ' ' acid LDDS : ~ ' -N, N'- disuccinicacid, [S,S] isomer in the form of the sodium salt.

wo ss/2s467 2 ~ ~ 7 3 ~ 3 ~ u~

pVNO : Poly (4~ G) N-oxide copolymerof vi.~ ..;JdAul~ and v;~ ul;du.,~ having an average molecular weight of 10,000.
ranular Suds Suppressor : 12% .~ ;li~, 18% stearyl alcohol,70% starch in granular form Nonionic C13-C1s mixed.,ll-u,~ u~y' ' fatty alcohol with an average degree of G~huA~ldi~ of 3.8 and an average degrGe of ,ululJu~laLiua of 4.5 sold under the tradename Plurafac LF404 by BASF Gmbh (low foaming) ~: I : Sodium ' (SiO2:Na2Oratio = 1.0) Phosphate : Sodium Lli~JUI~
480N : Random copolymer of 3:7 dc. ylic/l.l~ L., aeid, average molecular weight about 3,500 PBl : Anydrous sodium perborate ' ~, - in eompacted particulate form to retard release of hydrogen peroxide Cationie laetam . : Cationie peroxyacid bleaeh precursor salt of trialkyl ammonium methylene Cs-alkyl c~ ul~.)) with tosylate DETPMP : Diethylene triamine penta (methylene .~' . ' acid), marketed by Monsanto under tae tradename Dequest 2060 Bismuth nitrate : Bismuth nitrate salt Paraffin : Paraffln oil sold under the tradename Winog 70 by ~.. . ..

woss/2s467 21 ~7303 P~ u~

BSA : Amylolytic enzyme sold under the tradename LE~17 by Novo Industries A/S (approx 1% enzyme activity) Sulphate : Anhydrous sodium sulphate.
pH : Measured as a 1% solution in distilled water at 20C.

wo 95/28467 ~ 1 8 7 3 ~ 3 r~l,~J ' , F ' 1 The following laundry detergent ~ Y.~ were prepared values being expressed as ~..... ~ by weight of the ~ .llc ~ , ' A is a W~ Jalali~
B to E are in accord with the invention:
A B C D E
45AS/25AS (3:1) 9.1 9.1 9.1 9.1 7.0 35AE3S 2.3 2.3 2.3 2.3 4.0 24E5 4.5 4.5 4.5 4.5 3.0 TFAA 2.0 2.0 2.0 2.0 2.0 Zeolite A 13.2 13.2 13.2 13.2 15.0 Na SKS-61citric acid 15.6 15.6 15.6 15.6 13.0 (79:21) Carbonate 7.6 7.6 7.6 7.6 8.0 TAED (fast release 6.3 - - - -particle) TAED (slow release - 5.0 - 2.3 5.0 particle) Benzoyl Caprolactarn - - 5.0 2.7 (slow release particle) re.~l,o.. a~ (fast 22.5 - - 22.5 release particle) WO 95/28467 ~ ~ -~ ~73D3 ~ ~u~

r~ ut (slow - 22.5 22.5 release particle) PBI - - - - 16.0 DETPMP 0.5 0.8 - - -EDDS (fastrelease - - 0.3 0.75 0.5 particle) Protease 0.55 1.27 0.55 1.27 1.3 Lipase 0.15 0.15 0.15 0.15 0.2 Cellulase 0.28 0.28 0.28 0.28 0.3 Amylase 0.27 0.27 0.27 0.27 0.3 r~ y 5.1 5.1 5.1 5.1 5.1 CMC 0.4 0.4 0.4 0 4 0.4 PVNO 0.03 0.03 0.03 0.03 0.03 Granular suds suppressor 1.5 1.5 1.5 1.5 1.5 Minors/misc to 100%
The following T50 values (in seconds) were obtained for each of products A to D:

Protease < 60 < 60 < 60 < 60 Peroxyacid 130 190 205 240 W0 9S/28467 2 1 8 7 3 0 3 P~ ul AVO 95 ¦ 225 ¦ 230 ¦ 115 CL dti.~ testin~
T~ method - stain removal S ' pre~aration Three white cotton sheets were prewashed in a non-biological bleachfree heavy duty detergent. Sets of six test swatches of si_e ocm x ocm were cut from each sheet.Stains were evenly painted onto each swatch set.
Additionally, pre-prepared swatches obtained from the EMPA institute were also employed.
In summary, the following sets of swatches were employed:
Fn7vmatic stains Grass;
F- C'~
EMPA Blood;
~MPA Blood Milk and Ink;
GrPqcv stair~s Milky coffee;
Lipstick;

WO 95128467 r~ A /u7 6~l ~73o3 The sets of fabric swatches were subjected to one wash cycle in an automatic washing machine. The swatches were then assessed for removal of the stains by an ~xpert panel using a four point Scheffe scale. The combined averaged paired results of each of the sets of 1 are as set out below, with prior art cc, y~ A being used as the common reference.
In more detail, a Miele 698 WM automatic washing machine was employed, and the 40C short cycle ~ILo selected. Water of 12 German hardness ( Ca: Mg = 3 : 1) was used. 75g of detergent, dispensed from a granulette dispensing device placed in the middle of the load was employed. One swatch of each type was washed alongwith a ballast load of 2.7 Kg of lightly soiled sheets (I weeks domestic usage).
;Ye ~ct;no - St~;p remoYal The above stain removal test method was followed in comparing the efficiency of Cn~r ;tinn B with the reference prior art r-- .,~ A in removing different type of stains.
The results obtained were as follows:
Stain type Stain remoYsl benerlt ~PSIJ) EMPA blood +2.8~
EMPA BMl + 1.6#
Grass + 1.0 Milly coffee + I .1 Lipstick +0.8 ~slO~.ir~ at 95 % confidence limit Exann~le 2 The following bleach-contsining machine Lli~h.... ~ . . were prepared (parts by weight) in accord with the invention.

w095/28467 2 1 87303 ~"~

A B C D E F G
Citrate 15.0 15.0 15.0 15.0 15.0 15.0 480N 6.0 6.0 6.0 6.0 6.0 6.0 Carbonate 17.5 17.5 17.5 17.5 17.5 17.5 Phosphate - - - - - - 38.0 Silicate (as 8.0 8.0 8.0 8.0 ~.0 8.0 14.0 sio~) MPr~C;I 1.2 1.2 1.2 1.2 1.2 1.2 2.5 (as SiO2) PBI1.2 1.2 1.5 1.5 1.5 2.2 1.2 TAED (slow 2.2 2.2 2.2 3.5 - 2.2 2.2 release particle) Cationic lactam - - - - 3.3 Paraffin 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Bismuth - 0.2 0.2 0.2 0.3 0.4 0.2 nitrate Protease 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Amylase 1.5 1.5 1.5 1.5 1.5 1.5 BSA - - - 1.5 DETPMP 0.13 0.13 0.13 0.13 0.13 0.13 HEDP 1.0 l.0 1.0 l.0 1.0 1.0 w0 ssn8467 2 1 8 7 3 ~ 3 F~ ul 67 ~f Nonionic 2.0 2.0 2.0 2.0 2.0 2.0 1.5 Sulphate 23.0 22.8 22.4 22.7 22.2 21.5 0.3 misc inc moisture to balance pH (1% 10.7 10.7 10.7 10.7 10.7 10.7 11.0 solution)

Claims (15)

68

1. A detergent composition containing (a) an enzyme; and (b) an organic peroxyacid bleaching system wherein a means is provided for delaying the release to a wash solution of said organic peroxyacid relative to the release of said enzyme such that in the T50 test method herein described the time to achieve a concentration that is 50% of the ultimate concentration of the enzyme is less than 120 seconds and the time to achieve a concentration that is 50% of the ultimate concentration of the organic peroxyacid is more than 180 seconds.

2. A detergent composition according to Claim 1 wherein the time to achieve a concentration that is 50% of the ultimate concentration of the organic peroxyacid is from 180 to 480 seconds.

3. A detergent composition containing (a) an enzyme; and (b) an organic peroxyacid bleaching system wherein a means is provided for delaying the release to a wash solution of said organic peroxyacid relative to the release of said enzyme such that in the T50 test method herein described the time to achieve a concentration that is 50% of the ultimate concentration of said enzyme is at least 100 seconds less than the time to achieve a concentration that is 50% of the ultimate concentration of said organic peroxyacid.

4. A detergent composition according to any of Claims 1 - 3 wherein said organicperoxyacid bleaching system comprises in combination (i) a hydrogen peroxide source; and (ii) an organic peroxyacid bleach precursor compound

5. A detergent composition according to Claim 4 wherin said peroxyacid bleach precursor compound is selected from a peroxyacid bleach precursor compound which on perhydrolysis provides a peroxyacid which is (i) a perzbenzoic acid, or non-cationic substituted derivative thereof;
or (ii) a cationic peroxyacid

6. A detergent according to Claim 5 wherein said peroxyacid bleach precursor compound is selected from the group consisting of a) an amide substituted bleach precursor of the general formula:
, wherein R1 is an aryl, or alkaryl group containing from 1 to 14 carbon atoms, R is an arylene or alkarylene group containing from 1 to 14 carbon atoms, R5 is H or an alkyl, aryl, or alkaryl group containing from 1 to 10 carbon atoms, and L is a leaving group; or b) an N-acylated lactam bleach precursor of the formula:
wherein n is from 0 to 8, preferably from 0 to 2, and R6 is an aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbons, or a substituted phenyl group containing from 6 to 18 carbon atoms;
and mixtures of a) and b).

7. A detergent composition according to Claim 4 wherein said peroxyacid bleach precursor compound is wherein R1 is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R4, and R5 may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkylamino, -COOR6, wherein R6 is H or an alkyl group and carbonyl functions;

8. A detergent composition according to Claim 4 wherein said peroxyacid bleach precursor compared is tetraacetylethylenediamine.

9. A detergent composition according to Claim 4 wherein said hydrogen peroxide source is an inorganic perhydrate salt.

10. A detergent composition according to Claim 9 wherein said inorganic perhydrate salt is an alkali metal percarbonate.

11. A detergent composition according to any of Claims 1-10 additionally containing a bleach catalyst.

12. A detergent composition according to Claim 11 wherein said bleach catalyst is selected from the group consisting of MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(PF6)2, MnIII2(u-O)1(u-OAc)2(1,4,7-tri-methyl-1,4,7-triazacyclononane)2-(ClO4)2; MnIV4(u-O)6(1,4,7-triazacy-clononane)4-(ClO4)2; MnIIIMnIV4(u-O)1(u-OAc)2 (1,4,7-tri-methyl-1,4,7-triazacyclononane)2 (ClO4)3; Mn(1,4,7-trimethyl-1,4,7-triaza-cyclononane(OCH3)3-(PF6); Co(2,2'-bispyridyl-amine)Cl2; Di-(isothio-cyanato)bispyridylamine-cobalt (II); trisdipyridylamine-cobalt (II) per-chlorate;
Co(2,2-bispyridylamine)2-O2ClO4; Bis-(2,2'-bispyridylamine) copper(II) per-chlorate; tris(di-2-pyridylamine) iron (II) perchlorate; Mn gluconate;
Mn(CF3SO3)2; Co(NH3)5Cl; binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including N4MnIII(u-O)2MnIVN4)+and [Bipy2MnIII(u-O)2MnIVbipy2]-(ClO4)3 and mixtures thereof.

13. A detergent composition according to any of Claims 1 to 12 which is free of chlorine bleach.

14. A detergent composition according to any of Claims 1 to 13 which is in non- tablet form.

15. The use of a detergent composition according to any of Claims 1 to 14 in a laundry washing method wherein the detergent composition is delivered to the wash solution by means of a dispensing device introduced into the drum of a washing machine before the commencement of the wash.