CA2187304A1 - Detergents containing a builder and a delayed release peroxyacid bleach source - Google Patents

Abstract

There is provided a detergent composition containing (a) a water-soluble builder, and (b) an organic peroxyacid bleach source, wherein a means is provided for delaying the release to a wash solution of said peroxyacid bleach relative to the release of said water-soluble builder.
A pretreat wash method is also provided.

Description

wo 9s/2s46s 2 ~ 8 7 3 0 4 1 ~IIU~ '91 ' DETERGENTS CONTAINING A BUILDER AND A DELAYED RELEASE PEROXYACID
BLEACH SOURCE
This invention relates to detergent ~ containing a water-soluble builder and a source of peroxyacid bleach, wherein a means is provided for delaying the release to the wash solution of said peroxyaci~ bleach relative to the release of said builder.
The ~Li~ra.,~u.~ removal of bleachable soils/stains such as tea, fruit juice and coloured vegetable soils from soiled/stained substrates is a particular challenge to the formulator of a detergent ~ , for use in a washing rnethod such as a laundry or machine ~ , method.
T~iiti-~n~liy, the removal of such bleachable soils/stains has been enabled by the use of bleach ~ , such as oxygen bleaches, including hydrogen peroxide and organic ~UA~ ;d:~. The organic p~,.UAJa~;d~ are often obtained by the in situ ~hydlul~ re4ction between hydrogen peroxide and an orgaluc peroxyacid bleach precursor.
A problem ' with the use of certain organic peroxyacid bleaches in laundry washing methods is a tendency for these peroxyacid bleaches to affect the colourstability of the fabrics being washed. Effects on fabric colour stability can include fading of coloured dyes on the fabrics or localised areas of "patchv" bleaching.
The detergent formulator thus faces the dual challenge of r ' " ~ a product which maximises bleachable soil/stain removal but minimises the occurrence of any u~-., fabric colour stability effects of the bleach.
The Applicants have found that the occurrence of any, ... ' fabric colour stability effects arising from the use of orgailic peroxyacid bleaches in a washing method can be related to the nature of the organic peroxyacid, and also to both the wo 95/28465 - 2 1 8 7 3 0 ~ 91 rate of release of the peroxyacid bleach to the wash solution and the absolute level of peroxyacid present in the wash solution.
A fast rate of release of the peroxyacid bleach to the wash solution tends to heighten the probability that ~ ull~e fabric colour stability effects will be observed, 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 ameliorate this problem, this can be ' by a negative effect ûn the bleachable stain/soil removal ability.
The Applicants have now however found that where a . containing both a waur-soluble builder and a peroxyacid bleach source is employed, and wherein a means is provided for delaying the release to a wash sûlution of the peroxyacid bleach relative to the release of the water-soluble builder enhanced bleachable stain/soil removal may be obtained.
Additionally, where the ~ is used in a laundry washing method a reductiûn in fabric colour stability problems is also obtained.
The Applicants have in additiûn fûund that bleachable stain/soil removal benefits may be obtained when a soiled substrate is pretreated with a solution containing a water-soluble builder, prior to being washed in a method using a bleach cûntaining detergçnt product.
It is therefore an object of the present invention to provide ~ "c suitable for use in laundry and machine .I;~h.. ' ~ methods having enhanced bleachab~e stain remûval.
It is also an object of the present invention to provide ~ c for use in a laundry washing method wherein said ~ show less propensity to cause negative fabric colour stability effects.
It is a related object of the pr~sent invention to provide a stain/soil l,.e~ .l.~,L
method involving pretreating the soiled substrate with a solution containing a water-soluble builder, prior to washing with a bleach-containing detergent product.

wo ssl2s46s 2 1 ~ 7 3 0 4 r~
Summary of the Invenfinn According to the present invention there is provided a detergent containing (a) a water-soluble builder; and (b) an organic peroxyacid bleach source wherein a means is provided for delaying the release to a wash solution of said peroxyacid bleach relative to the release of said water-soluble builder such that in the T50 test method herein described the time to achieve a I that is 50% of the ultimate --- of said water-soluble builder is less than 120 seconds and the time fO achieve a, that is 50% of the ultimate ~.. , ,.1,~l;.,.l of said peroxyacid bleach is more than 180 seconds.
According to the present invention there is provided a detergent .
containing (a) a waoer-soluble builder; and (b) an organic peroxyacid bleach source wherein a means is provided for delaying the rdease to a wash solution of said peroxyacid bleach relative to the release of said water-soluble builder such that in the T50 test method herein described the time to achieve a that is 50% of the ultirnate, of said water-soluble builder is at least 100 seconds, preferably at least 120 seconds, more preferably at Icast 150 seconds less than the time to acbieve a . that is 50% of the ultimate of said pero~yacid bleach.
Said organic peroxyacid bleach source preferably comprises in c~
(i) a hydrogen peroxide source; and (ii) a peroxyacid bleach precursor compound According to another aspect of the present invention there is provided a washingmethod comprising the steps of:

wo 95/28465 2 1 ~ 7 3 0 4 P~ 11 1,~ ~691 (1) applying a bleach-free solution of a ~ containing a water-soluble .
builder to a soiled substrate;

(2) allowing said solution to remain in contact with said soiled substrate for an effective time interval;

(3) washing said soiled substrate using a washing method involving use of a bleach-containing detergent Water-snlllhlP b~ comyound The detergent ~ of the present invention contain as an essential component a water-soluble builder compound, typically present at a level of from 1% to 80% by weight, preferably from 2% to 60% by weight, most preferably from 2% to 40% by weight of the ~c~
Suitable water-soluble builder ~ , ' include the water soluble monomeric P~l.r~uvA~ or their acid forms, homo or ,v~ uly~uA~yL~, acids or their salts in which the POIY~U~AYI;~ acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, carbonates, l- ~ borates, I ' . ' silicates and mixtures of any of the foregoing.
The l,~llbUAJ- ' or ~IY~UA~' builder can be monomeric or oligomeric in type although monomeric ~ ~UUA~' are generally preferred for reasons of cost and Suitable ~bUAY' containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. rul~uA~' containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, I;UAy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether ~UAy' and the sulfinyl ~I~Ay' roly~l.uA.~' containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and . as well as succinate derivatives such as the ~buAy~ loAy described in British Patent No. 1,379,241, la~uA~ ~ described in British Patent No. 1,389,732, and described in N~h~Luld~ Application 7205873, and the uAy~ly~buA~' materials wo ss/2s46s 2 1 8 7 3 4 Y~
such as 2-oxa-1,1,3-propane ~ UAy' described in British Patent No.
1 ,387,447.
Pul~uuAyla~ containing four carboxy groups include u,.~ disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane t.,..~.~l,uAy' 1,1,3,3-propane L~;tl.l~bUA~' and I,1,2,3-propane L~ uA~L.~. r~ly~buAyl..~containing sulfo c ',~ include the ~llr~ t 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 1~ IU~ uly~,~ubuA~' include e yl ~ c .~,cis,cis-t~ UA~ ~IJUA~ 2,3,4,5; y~ - cis, cis, cis t~Lla~uA~ ~, 2,5 .. L~ - cis - lli~l.uA~ 2,2,5,5-' ~JI~ .~l.UAy' 1,2,3,4,5,6-hexane - ~ u~,~' and l derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic ,uuly~buA~' include mellitic acid, ~.. '- - acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343.
Of the above, the preferred puly~ ~ubuA~' are ~.~dluAy~uA~' containing up to three carboxy groups per molecule, more l,~u~i. ul~ly citrates.
The parent acids of the or oligomeric ~ulywllluA~' chelating agents or mixtures thereof with their salts, e.g. citric acid or '~it.i~, acid mixtures are also . ' ' as useful builder - ~
Borate builders, as well as builders cont~ining 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 4ûC .
Examples of carbonate builders are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesqui-carbonate and mixtures thereof with ultra-fine calcium carbonate as disclosed in Gerrnan Patent Application No. 2,321,001 published on November 15, 1973.
Specific examples of water-soluble phosphate builders are the all~li metal olyl 'I , ' sodium, potassium and arnmonium ~ sodium and wo 9sl2846~ 12 1 8 7 3 0 4 r~ "~ .A '^I

potassium and ammonium ~ ' , sodium and potassium ~.i', ' . ' sodium polymeta/phosphate in which the degree of poly...~ .liull ranges from aboui 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 2.0 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 . in accord with the invention at a level of from 5% to 50% by weight of the, . more preferably from 10% to 40% by weight.
~h The detergent ~ ;.. of the invention contain as an essential component an organic peroxyacid bleach source. The peroxyacid bleach source may be the organic peroxyacid per se, or it may be a peroxyacid bleach precursor compound.
Where the source is a peroxyacid bleach precursor compound, the production of the peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. Suitable sources of hydrogen peroxide include inorganic perhydrate bleaches.
Perox~ri~i h~ rh ~iecursors Peroxyacid bleach precursors (bleach activators) are preferred peroxyacid sources in accord with the invention. Peroxyacid bleach precursors are normally . ' at a level of from 1% to 20% by weight, more preferably from 2% to 5% by weight, most preferably from 3% to 10% by weight of the, ,.,..~ c Suitable peroxyacid bleach precursors typically contain one or more N- or O- acyl groups, which precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides and acylated derivatives of imidazoles and oximes, and examples of useful materials within these classes are disclosed in GB-A-1586789.

wo ssl2846s 2 1 8 7 3 û 4 P~ l~
Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A- 0170386. The acylation products of sorbitol, glucose and all ~qrrh~rj~i~c with b~ .~u~l~v..g agents and acetylating agents are also suitable.
Specific O-acylated precursor ~ I ' include 2,3,3-tri-methyl hexanoyl u~.yl,~ sulfonates, benzoyl u~yb~,.lL~ sulfonates, nonanoyl-6-am. ino caproyl u,.yv. ..~ sulfonahs" ' ,r:hLI~.yl glucose benzoyl peroxide and cationic derivatives of any of the above, including the alkyl ammonium derivatives and pentaacetyl glucose. Phthalic anhydride is a suitable anhydride type precursor.
Specific cationic derivatives of the O-acyl precursor . , ' include 2-(N,N,N-trimethyl ~ ~ ethyl sodium ~ 1 carbonahe chloride, and any of the alkyl ~rr.mnnill~ derivatives of the benzoyl u,~ylv.,..~,..~ sulfonates including the 4-(trimethyl ~m.-nnillm) methyl derivative.
Useful N-acyl r _ I are disclosed in GB-A-855735, 907356 and GB-A-1246338.
Preferred precursor ~ ' of the imide type include N-benzoyl ~ ' hV. Iv~. Lu.~l ethylene diamine, N-benzoyl substituted ureas and the N-,N,NINl tetra acetylated alkylene diamines wherein the alkylene group contains from I to 6 carbûn atoms,, ' '.y those ~ . ' in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is l,~vvu;culy preferred.
N-acylated precursor . , ' of the lactam class are disclosed generally in GB-A-955735. Whilst the broadest aspect of the invention ~ . ' the use of any lactam useful as a peroxyacid precursor, preferred materials comprise the and ~ . . "~
Suitable N-acylated lactam precursors have the formula:
R6--C--N f --C H2~C H2 ln wo ss/2s46s 2 1 8 7-3 0 4 r~l"~ 9~ _ wherein n is from 0 to about 8, preferably from 0 to 2, and R6 is H, an alkyl, aryl, alkoxyaryl or alkaryl group containing from l to 12 carbons, or a substituted phenyl group containing from 6 to 18 carbon atoms Suitable ~,a~lulaulall~ bleach precursors are of the formula:
o Il ll I CH
Rl-- e -- N \ / 2 wherein Rl is H or an alkyl, aryl, alkoxyaryl or aLkaryl group eontaining from I to 12 carbon atoms, preferably from 6 to 12 earbon atoms, most preferably Rl is phenyl.
Suitable valero l~ctams have the formula:
o Il o C CH2 --CH2 Il I
Rl -- e -- N
\ CH2--CH
wherein Rl is H or an alkyl, aryl, alkoxyaryl or aLkaryl group eontaining from I to 12 carbon atoms, preferably from 6 to 12 carbon atoms. In highly preferred Rl is selected from phenyl, heptyl, octyl, nonyl, 2,4,4-i ' ~1~...~1, deeenyl and mixtures thereof.
The most preferred materials are those which are normally solid at < 30C, ~au~;~,ul~uly the phenyl derivatives, ie. benzoyl ~ ula~,kul~, benzoyl ~lulal,ku..

wo ss/2046s 2 1 8 7 3 0 J ~ "~,~ --Al .

and their substituted benzoyl analogues such as chloro, amino alkyl, aLkyl, aryl and alkoxy derivatives.
Caprolactam and ~ k.~ulG~ ku.l precursor materials wherein the Rl moiety contains at least 6, preferably from 6 to 12, carbûn atoms provide p..uA~a~ ;J~ on ~ ydlulJ ~;~
of a lly~lu~ ub;~, character which afford n~ lPnrhili~ and body soil clean-up.
Precursor cnmroll^~l~ wherein Rl comprises from l to 6 carbon atoms provide l~yJlul~llilic bleaching species which are yauLi ~ulauly efficient for bleaching beverage stains. Mixtures of 'I-yJIulJllvbiu' and 'hydrophilic' ualJIulaukull~ and valero lactams, typically at weight ratios of 1:5 to 5:1, preferably 1:1, can be used herein for mixed stain removal benefits.
Highly preferred ~a~JII ' and ~ ula.,kull precursors include benzoyl u a~lula~,kalll, nonanoyl capro-lactam, benzoyl v-' ' nonanoyl ~. ' ula~l U~
3,5,5-i ~IhciAauluyl ~alJIula.,lal-l, 3,5.5~ ~ulauuull~ octanoyl ~_a~lulau alll, octanoyl v~l---'- decanoyl ~,alJIul~kull~ decanoyl . ' ula~,~ull, undecenoyl ~a~Jlula~,ku~ undecenoyl ~. ' ' (6-~U~¦)UA~U_.IL--~-- ~ (6 'r~ uyl)uA,yL , (6~ , u~l)-UA~L. '' and mixtures thereof. Examples of highly preferred substituted benzoyl lactams include l.._llljlh~ Luyl ~ ljlh~ ~LUyl val~ ~ula .ku~
L ~Luyl ~ lL ~ ~LV~ ,IU~:u~,.. LUyl ~
IJlU~ ,_.lLUJl ~ . .,.1- l-- " i~u~.ul,jlh~.. Lu~l La~JlUla~ ialll, i~u!,.ul,~lh_..Lu~l vql~rl IqA~q~n l~ lL~_.. LU.yl ""1 : ,. L .ylh.,.. Lu~ , tert-L ~Ih.,.. LuJI
tert-L ~Ib_~ LU~ yl~. Lu~l "
I,_.. Lu~; vql I._A~lL.. ,.. Lu~ _.. Lu~
ellluAyL~ Lu~ h ~AAyL~
~ ayl~ ~IU~UAyL. . LV~ ~ isV¦JlU¦~UA~U~-LU~I r i~ulJIu~uAyL.~ Lu~l ~, ' ulauku--, L yL... Lu~ " L ~L~ ILU~I
. ' ' tert-L ~b~ LU~I u a~lulauLI, tert-L yb~ ~lLu~l ~ ' ula~,kull, yl~ .. LU~ ylJ_.. LU~I v lPm rn ¦~AUA~ LU~I
.,AUAyL ~.,Lvyl VAI~ .. I_.n 2 4 6--trichlu-ul ~.~ Luyl ~1 - 1~~ - 2,4,6--JU~ ula~kalll~ 1~` ' '-rl----~U~ alJIUla~kalll~ L ' ' ,~1 ~_1- "I 1 - ~, diul-luluLc.. Lu~l ualJIulaukal.. ~ Ji-.. Ll-uA~ Lu~l (,a~JIl , 4--~hl.. .JL, .. yl ua~lulauuull~ 2,4~ ulL.~ILu~ i z diualJlula~kull, L~.ILnuuluL~...Lu~vl l-alJlulauL~ -n~ uJL~ y; v l~ ' ' JL~ Lu~ al~ iilUAy1 ~1LU~1 v- l ~ 1_ _ 4--rhl-- vl- -yl wo ss/2846s 2 1 8 7 3 0 4 valerolactam, 2,4-dichlororbenzoyl Vo~ UI~ terephthaloyl divalerolactam, 4-lli~lUb.".LUyl ,~)IUI.~ l, 4~ ul~ Lu~l Val~.U~ l, and mixtures thereof.
Suitable imidazoles include N-benzoyl imidazole and N-benzoyl b. ,~ andother useful N-acyl group-containing peroxyacid precursors include N-benzoyl ulidone, dibenzoyl taurine and benzoyl ~ ,' acid.
Another preferred class of peroxyacid bleach activator compounds are the amide substituted . . ' of the following general formulae:

Il I 11 1 11 11 L
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 aUkylene, arylene, and 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 carl be essentially any leaving group. Rl preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. R1 may be straight chain or branched aUkyl, substituted aryl or alkylaryl containing branching, ' or both and may be sourced from either synthetic sources or natural sources including for example, taUow fat. Analogous structural variations are ~ for R2. The can imclude 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 bleach activator compounds of this type are described in EP-A-0170386.
The L group must be sufficiently reactive for the reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator wiU be difficult to stabilize for use in a bleaching ~ These ~ are generally paralleled by the pKa of the conjugate acid of the leaving group, although exceptions to this convention are known. Ordinarily, leaving groups that exhibit such behavior are those in which their conjugate acid has a pKa in the range of from 4 to 13, preferably from 6 to 11 and most preferably from 8 to 11.
Preferred bleach precursors are those wherein Rl, R2 and R5 are as defrned for the amide substituted ~-~ ' and L is nlected from the group consisting of:
....... .... ......... . ...... , ... . . . .. . . : .. .... . . . : . . ....

WO95/28465 2 1 87304 ~ u ~ 1 .

--o~, --O~Y, and --0~

13 L= R3 Y
y -O-CH=C--CH=CH2 --O--CH=C--CH=CH2 1l Y 1l -O--C--R~ --N' `NR4 ~C~NR4 O O

--O--C=CHR4 , and ~J 1l CH--R4 R3 o and mixtures thereof, wherein Rl is an alkyl, aryl, or alkaryl group containing from I
to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R4 is H or R3, and Y is H or a y~ group.
The preferred ~ hili7in~ 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 I to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted: cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, l~ h~ ~r ' or acetate anion. It should be noted that woss/2846s ~ 1 87 30~ r~
bleach activators with a leaving group that does not contain a ~..1,.1.;1,,;"~ groups should be well dispersed in the bleaching solution in order to assist in their dissolution.
Preferred examples of bleach activators of the above formulae include (6-Uyl)U~y~ '' (6.~ 1.. uyl)u,~y~l.. r.. -nate, (6-~ ' ~ , uyl)uAyL ' ' and mixtures thereof.
Other preferred precursor compounds include those of the 7U.,~ILU~.a~.. type, having the formula:
DO
~ ~C--R1 including the substituted 'u ---: - of the type R4~ R, wherein Rl is H, alkyl, a'lkaryl, aryl, aryla'kyl, and wherein R2, R3, R4, and R5 Day bc the samc or different ' selected from H, ha ogen, a'~kyl, a'~enyl, aryl, hydroxyl, al3coxyl, amino, alkyl amino, COOR6 (wherein R6 is H or a~.~ aLkyl group) and carbonyl functions.
An especially preferred precursor of the ~._..LU~a~.. type is:
O
[~"C~

WO 9S/2846!i 2 1 8 7 3 ~ 4 Irv~uv ~ 5~1 Ore:~nif reroxyacids The detergent c..",~ may also contain organie ~ u,.~c;Js typieally at a level offrom 1% to 15% byweight, morepreferablyfrom 1% to 10% byweightofthe A preferred class of organic peroxyacid rnn~ nAc are the amide substituted compounds of the following general formulae:

Il l 11 1 11 11 O R5 0 or R5 0 0 wherein Rl is an aryl or alkaryl group with from I to 14 earbon atoms, R2 is an alkylene, arylene, and aLcarylene group eontaining from I to 14 earbon atoms, and RS
is H or an alkyl, aryl, or alkaryl group eontaining I to 10 earbon atoms. Rl preferably contains from 6 to 12 earbon atoms. R2 preferably eûntains from 4 to 8 earbon atoms. Rl may be straight chain or branched alkyl, substituted aryl or aLcylaryl containing branching, ' or both and may be soureed from either synthetie sources or natural sources including for example, tallow fat. Analogous swctural variations are ~ ." ~ for R2. The 1,~ ; can includeaLcyl, aryl, halogen, nitrogen, sulphur and other typieal substituent groups or organie, R5 is preferably H or methyl. Rl and R5 should not eontain more than 18 earbon atoms in total. Amide substituted organie peroxyacid compounds of this type are described in EP-A~170386.
Other organic ~.~ ylL~;d~ include diperoxy d~ acid, diperoxy tetra decanedioc acid, d;p~vA~h ~ "-Y aeid, mono- and ~ 'r acid, mono-and .I;~'vl~Lc acid, . ~.y phthalic acid, perbenzoic acid, and their salts as disclosed in, for example, EP-A-0341 947.
!nnrg~nir ~erhyA~rP hlP~rhP~
The ~ ;-- in aecord with the invention preferably include, as a hydrogen peroxide source, an inorganic perhydrate salt, most especially when the organic peroxyacid souree is a peroxyaeid bleach precursor compound.

wo95/28465 ~ ~ 87304 The inorganic perhydrate salts are normally i~ in the form of the 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 ~
~xamples of inorganic perhydrate salts include perborate, ~., ~ , ~ll ' . , persulfate and persilicate salts. The inorganic perhydrate salts are normally the all~ali metal salts. The inorganic perhydrate salt may be included as the crystalline solid without additional protection. For certain perhydrate salts however, the preferred executions of such granular c. . ~ c utilize a coated form of the material whichprovides better storage stability for the perhydrate salt in the granular product.
Sodium perborate can be in the form of the l..u..~ll-yl- of nominal formula NaB02H202 or the t~ ydl_~ NaB2H22-3H2 Sodium l ~ , which is a preferred perhydrate for inclusion in detergent . in accordance with the invention, is an addition compound having a formula -~~ -q~ to 2Na2C03.3H202, and is available . ;~ as a crystalline solid. The ~.~L is most preferably ~ ' into such in a coated form which provides in product stability.
A suitable coating material providing in product stability comprises mixed salt of a water soluble all~ali metal sulphate and carbonate. This coating however allows for rapid release of the ~.~; bleach to the wash solution and is therefore not a suitable means for providing delayed release of the ~.~ bleach into a wash solution. Such coatings together with coating processes have previously been described in GB-1,466,799, granted to Interox on 9th March 1977. The weight ratio of the mixed salt coating material to ç~ lies in the range from 1: 200 to 1:

4, more preferably from 1: 99 to 1: 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 form 0.1 to 3, preferably n is from0.3 to 1.0 and most preferably n is from 0.2 to 0.5.
Potassium ~IU~ '' is another inorganic perhydrate salt of use in the detergent... ~ herein.
Rl~rh r~t~lySt WO 95/2~465 2 1 ~ 7 3 ~ ~ r~l,u~
.

The invention also ~ r.~."~ contilining a cataiytically effective amount of a bleach catalyst such as a water-soluble manganese salt.
The bleach cataiyst is used in a catalytically effective amount in the c.. "~ and processes herein. By "catalytically effective amount" is meant an amount which is sufficient, under whatever ~ . ve test conditions are employed, to enhance bleaching and removal of the stilin 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 d;all~ ' 1, the target substrate may be, for example, a porcelain cup or plate with tea stain or a pol~.,.l.~l,,.l~ plate stilined with tomato soup. The test conditions will vary, depending on the type of washing appliance used and the habits of the user. Thus, front-loading laundry washing machines of the type employed in Europe generally use less waterand higher detergent ~ - than do top-loading U.S.-style machines. Some machines have ~..".i.1. .~1.l~ longer wash cycles than others. Some users elect to use very hot water; others use warm or even cold water in fabric laundering operations.
Of course, the catalytic ~ f~ of the bleach catalyst will be affected by such and the levels of bleach catalyst used in fully-formulated detergent and bleach C ~ ;.. c can be a~ 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 lest one part per ten million of the active blech cataiyst species in the aqueous washing liquor, and wiil preferably provide from about 1 ppm to about 200 ppm of the cataiyst species in the laundry liquor. To iiiustrate this point further, on the order of 3 ' manganese cataiyst is effective at 40C, pH 10 under Europen conditions using perborate and a blech precursor (e.g., benzoyl ~ 1" ~ .). An increase in . of 3-5 fold may be required under U.S.
conditions to achieve the same results. Conversely, use of a blech precusor and the manganese cataiyst with perborate may ailow the formuiator to achieve eciuivaient bleching at lower perborate usage levels than products without the manganese cataiyst.
The blech cataiyst materiai herein can comprise the free acid or be in the form of any suitable salts.
.

One type of blech cataiyst is a cataiyst system comprising a hevy metili cation of defined blech cataiytic activity, such as copper, iron or manganese cations, an WO95/2846~ 21 873D4 .~
.

auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ~ ' ' acid, ~;LIIJ~ .1. .li,."~;,.. ~ II,.(Ill,~llJ _ -r , ~ acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. Pat. 4,430,243.
Other types of bleach catalysts include the ~ based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include MnIV2(u-0)3(1,4,7-trimethyl-1,4,7-Li~. ' )2-(PF6)2, Mnm2(u O)l(u-OAc)2(1,4,7-trimethyl-1,4,7-~i~y.,lu,~u.l~l~)2 (C104)2, MnIV4(u-0)6(1,4,7-Lfi~ ,lul~ull~ ,)4-(Clo4)2~ MnIIIMnIV4(u-O)I(u-OAc)2 (1,4,7-trimethyl-1,4,7-L~, ' -)2-(CIO4)3. and mixtures thereof. Others are described in European patent application publication no. 549,272. Other ligands suitable for use herein include I ,5,9-trimethyl-1 ,5,9-L~ , 2-methyl-,4,7 Lfi~ 2-methyl-1,4,7-~ ,J.' 1,2,4,7 . -' 1,4,7-~ .lù~ , and mixtures thereof.
The bleach catalysts useful in the , herein may also be selected as ~Y!~I~r for the present invention. For examples of suitable bleach catalysts seeU.S. Pat. 4,246,612 and U.S. Pat. 5,227,084.
See also U.S. Pat. 5,194,416 which teaches ' manganese (IV) complexes such as Mn(1,4,7-trimethyl-1,4,7-l.;~ )(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 which is a non-~LLbUAJ' polyh.~dlui~y compound having at least three . ~, C-OH groups.
Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, meso elyi' 1, meso-inositol, lactose, 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 forrnula:

R1 -N=c-B-c=N-R4 = . _ . . ~

W095/28465 2 1 87304 ~I/i Sl wherein R1, R2, R3, and R4 can each be selected from H, substituted alkyl and aryl groups such that each Rl-N=C-R2 and R3-C=N-R4 form a five or six-membered ring. Said ring can further be substituted. B is a bridging group selected from O, S.
CR5R6, 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. r~Li~ul~ly preferred is the ligand 2~2~~b;al~ylidy- ~ Preferred bleach catalysts include Co, Cu, Mn, Fe,-b;~yy.id~ u.a~ and -I,;~
complexes. Highly preferred catalysts include Co(2,2'~ ,yli-ly )C12, D;("~Ll ic~y4~dtu)1~ hly' --cobalt (II), Lli~d;~yl;dy' - cobalt(II) L - Co(2,2-~ y.idy )202C104, Bis-(2,2'-~;~ylidylall~"~,) copper(II) perchlorate, tris(di-2-~ylidy ) iron(II) perchlorate, and mixtures thereof.
Other examples include Mn gluconate, Mn(CF3S03)2, Co(NH3)sCI, and the binuclear Mn complexed with tetr~ N :' and bi-N-dentate ligands, including N4Mnm(u-0)2MnlVN4)+and [Bipy2MnIII(u-0)2MnIVbipy2]-(C104)3.
The bleach catalysts of the present invention may also be prepared by combining a water-soluble ligand with a water-soluble manganese salt in aqueous media and _ the resulting mixture by ~.a~lvldlion. Any convenient water-soluble salt of manganese can be used herein. Manganese (II), (III), (IV) and/or (V) is readily available on a ' 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 ~d~lyLi~l;~ ~r~ amounts. Thus, the sodium salt of the ligand and a member selected from the group consisting of MnSO4, Mn(C104)2 or MnC12 (least preferred) are dissolved in water at molar ratios of ligand:Mn salt in the range of about 1:4 to 4:1 at neutral or slightly alkaline pH. The water may first be de-oxygenated by boiling and cooled by sparging with nitrogen.
The resulting solution is evaporated (under N2, if desired) and the resulvng solids are used in the bledching and detergent ~ . herein without further ~...; I ;~ 1;....
In an alternate mode, the water-soluble manganese source, such as MnSO4, is added to the bleach/cleaning c~ or to the aqueous bl~.,;,;..6/l ' ~ bath which comprises the ligand. Some type of complex is apparenvy formed in si~u, and improved bleach L~[vl~ i5 secured. In such an in situ process, it is convenient _ . . .. . .....

WO 95128465 '~ ~ 8 7 3 0 4 r ~ fi91 , to use a c ~ f, ~I~lr molar excess of the ligand over the ~ , and mole ratios of ligand:Mn typically are 3:1 to 15:1. The additional ligand also serves to scaveng~
vagrant metal ions such as iron and copper, thereby protecting the bleach from 'If~ N'`;~ One possible such system is described in European patent ~rp~ tirm publication no. 549,271.
While the structures of the bleach-catalyzing, ,, . ' of the present invention have not been elucidated, it may be speculated that they comprise chelates or other hydrated ~ " complexes which result from the interaction of the carboxyl and nitrogen atoms of the ligand with the manganese cation. Likewise, the oxidation state of the manganese cation during the catalytic process is not known with certainty, and may be the (+II), (+III), (+IV) or (+V) valence state. Due to theligands' possible six points of attachment to the manganese cation, it may be reasonably speculated that, ' ' species and/or "cage" structures may exist in the af~ueous bleaching media. Whatever the form of the active Mn~igand species which actually exists, it functions in an apparently catalytic manner to provideimproved bleaching l ~ on stubborn stains such as tea, ketchup, coffee, blood, and the like.
Other bleach catalysts are described, for exampk, in European patent ~rrlir~tinn.
publication no. 408,131 (cobalt complex catalysts), European patent ~l,,.l;. l;... ~, publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455 ligand catalyst), U.S. 4,711,748 and European patent

5~rrlir~tjr~1n, publication no. 224,952, (absorbed manganese on: ' '`
catalyst), U.S. 4,601,845 (a' ' support with manganese and zinc or magnesium salt), U.S. 4,626,373 ( ~ 'ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), German Pat. cl ~ 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 g:tglgtato ~y`t`).

WO 95/28465 2 1 ~ 7 3 0 4 r~l~u~
RPI~tive rPIP~cP kinP~irc In an essential aspect of the invention a means is provided for delaying the release to a wash solution of the peroxyacid bleach relative to the release of the water-soluble builder.
Said means may comprise a means for delaying the release of the peroxyacid bleach to the wash solution.
Alternatively said means may comprise a means for enhancing the rate of release of the water-soluble builder to the solution.
ved rate of r~lP~cP rn~-~nc The means may provide for delayed release of the peroxyacid bleach source itself to the wash solution. Alternatively, where the peroxyacid source is a peroxyacid precursor compound the delayed release means may comprise a means of inhibiting,or preventing the in situ ~l~ydlul~ reaction which releases the 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 peroxide source, to the wash solution.
The delayed release means can include coating any suitable component with a coating designed to provide the delayed rdease. The coating may 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 coaring materials include t~ ;, (e.g. partially) I~ O ' vegetable oil, soy bean oil, cotton seed oil) mono or ~ s"..;.,l~l~lline 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.

WO 95~28465 2 1 8 7 3 0 ~
.

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 r ~ _ silicate can also be included in the coating.
Any inorganic salt coating materials may be combined with organic binder materials to provie composite inorganic salt/organic binder coatings. Suitable binders include the Clo-C20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole of alcohol and more preferably the Cls-C20 primary alcohol ethoxylates containing from 20 - 100 moles of ethylene oxide per mole of alcohol.
Other preferred binders include certain polymeric materials. r~l~v with an average molecular weight of from 12,000 to ~00,000 and pol~ 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, ~ t;,~
ether or I~Lh~ l ylil_ acid, the maleic anhydride ~ at least 20 mole percent of the polymer are further examples of polymeric materials useful as binder agerlts.
These polymeric materials may be used as such or in ' with solvents such as water, propylene glycol and the above mentioned C1o-C20 alcohol ethoxylates 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.
Cellulose derivatives such as ' ,~I~ lulu~, ~uu,.,~ ' " ' and l.~.llu~ ellulose, and homo- or co-polymeric ~I~UAyliC acids or their salts are other examples of binders suitable for use herein.
One method for applying the coating material involves ~c~ ;-- Preferredav~' processes include the use of any of the organic binder materials described l.~ Lvv~. Any ;U~ iUl~ ,. may be used including, but not limted to pan, rotary drum and vertical blender types. Molten coating 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 altering the physical ~ of the bleach to control its solubility and rate of W095128465 21 8 73~34 r~ ).. S~l .

release. Suitable protocols could include con~p ~^ti~n mechanical injection, manual injection, and adjustment of the solubility of the bleach compound by selection of particle size of any particulate: .
Whilst the choice of particle size will depend both on the ~ . of the particulate rn~rm-nr and the desire to meet the desired delayed release kinetics, it is desirable that the particle size should be more than 500 ll.k lu~ hl~, preferably having an average particle diameter of from 800 to 1200 Ulll~tU.~.
Additional protocols for providing the means of delayed release include the suitable choice of any other c~ n ~ of the detergent C~ II matrix such that when the ,~ is introduced to the wash solution the ionic strength ~IIV' therein prsvided enables the required delayed release kinetics to be achieved.
r ~ ~ prl- sf rr~ means All suitable means for enhancing the rate of release of the water-soluble builder to the 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 c rf~ " water soluble material.
Other means of providing the required ddayed release include mechanical means for altering the physical . ~ of the water-soluble builder to enhance its solubility and rate of release.
A suitable protocol could include deliberate selection of the particle size of any water-soluble builder containing . The choice of particle size will depend both on the ~ of the particulate ~ r t, and the desire to meet the desired enhanced release kinetics. It is desirable that the particle size should be less than 1200 u...~L.~, preferably having an average particle diameter of from 1100 to 500 ~ ,lu--.~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 water-soluble builder, such that when the WO 95/28465 2 1 8 i 3 0 4 - .
I i - r~
.

.. ~.u~;l;...l is introduced to the wash solution the ionic strength ~ ull....ll therein provided enables the required enhanced release kinetics to be achieved.
D~l~yed release - kinetic ~arameterS
The release of the peroxyacid bleach component from the peroxyacid bleach sourcerelative to that of the water-soluble builder cûmponent is such that in the T50 test method herein described the time to achieve a ~ - that is 50% of the ultimate ~ ;.... of said water-soluble builder is less than 120 seconds, preferably less than 90 seconds, more preferably less than 60 seconds, and the time to achieve a ~ that is 50% of the ultimate c~ of said peroxyacid bleach is more than 180 seconds, preferably from 180 to 480 seconds, more preferably from 240 to 360 seconds.
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 that 180 seconds, preferably from 180 to 480 seconds, more preferably from 240 to 360 secons. A method for ~ AVO levels is disclosed in European Patent Application No. 93870004.4.
In another preferred aspect of the invention, where the peroxyacid bleach source is a peroxyacid bleach precursor, employed in: ' with a hydrogen peroxide source the kinetics of rdease to the wash solution of the hydrogen peroxide, relative to those of the water-soluble builder component is such that in the T50 test method herein described the time to achieve a that is 50% of the ultimate of said water-soluble builder is less than 120 seconds, preferably less than 90 seconds, more preferably less than 60 seconds, and the time to achieve athat is 50% of the ultimate ~ l;.. of said hydrogen peroxide is more that 180 seconds, preferably from 180 to 480 seconds, more preferably from 240 to 360 seconds.
The ultimate wash of the water-soluble builder is typically from 0.0005% to 0.4%, preferably from 0.005% to 0.35%, more preferably from 0.01%
to 0.3%.

wo 9s/28465 2 1 8 7 3 0 4 r~",J ~~n~rrrl The ultimate wash c~ .l 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 . ,~A ~ ;--'' of any peroxyacid precursor is typically 0.001% to 0.08% by weight, but preferably is from 0.005% to 0.05%, most preferably from 0.015% to 0.05%.
Delayed r~lPAc,~ - test mP~hrl~i The delayed release Icinetics herein are defined with respect to a 'TA test method' which measures the time to achieve A% of the ultimate ~ ;.."/levd of that component when a C~ containing the component is dissoived according to the standard conditions now set out.
The standard conditions involve a 1 litre glass beaker filled with 1000 ml of distilled water at 20C, to which lOg of 1l is added. The contents of the bealcer are agitated using a magnetic stirrer set at 100 rpm. The ultimate ~-----'-- 'level is ta~en to be the ~.." 1, -1;~. ~level attained 10 minutes after addition of the to the water-filled beaker.
Suitable analytical methods are chosen to enable a reliable ~' of the incidental, and ultimate in solution ~ . . . , Al ;. ''' - of the component of concern, subsequent to the addition of the ~ ;.... to the water in the bealcer.
Such analytical methods can include those involving a continuous monitoring of the level of; of the - r t, including for example I ' and methods.
Alternatively, methods involving removing titres from the solution at set time intervals, stopping the ~ ;- process by an ~ means such as by rapidly reducing the t~ ~ld~U.~i 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 d~r,~ r ' , to enable calculation of the the TA vaLue from raw analytical results.

Wo s5t2s46~ -2 1 8 7 3 0 4 r~
The patticular analytical method selected for d~ l; the . ~ i..ll of the - r t~ will depend on the nature of that cnmrn~nt and of the nature of the C~J~ II containing that Com~nl n-iti~nql deter~ent ~u ~ 5 The detergent ~ - sr ~ of the invention may also contain additional detergent t~ The precise nature of these additional . and leYels of thereof will depend on the physical form of the ~ - 1 c-~ and the nature of the cleaning operation for which it is ho be used.
The ~ of the invention may for example, be formulated as hand and machine laundry detergent ~ u~ including laundry additive . and suitable for use in the ~ h of stained fabrics and machime When formulated as . . suitable for use in a machine washing method, eg:
machine laundry and machine ~ methods, the ~ l;.. of the invention preferably contain one or more additional detergent . . selected from cl~rfqrtqntc water-insoluble builders, heavy metal ion . , organic polymeric . ' additional enzymes, suds .. , lime soap d.~ . soil suspension and anti-.~ agents and corrosion inhibitors. Laundry C can also contain, as additional detergent , softening agents.
The detergent . ` of the invention may contain as an additional detergent component a surfactant selected from anionic, cationic, nonionic ampholytic, amphoteric and L~i~t~,liU...~, surfactants and mixtures thereof.
The surfactant is typically present at a level of from 0.1% to 60% by weight. More preferred levels of illWl~JUL LliUII 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 with any enzyme r present in the . In liquid or g~l . the surfactant is most wo 95/28465 2 ~ 8 7 3 0 4 r~
preferably formulated such that it promotes, or at least does not degrade, the stability of any enzyme in these ~ ,u~
A typical listing of anionic, nonionic, ampholytic, and ~wil~.iu..;c classes, and species of these cllrf~t~ntc is given in U.S.P. 3,929,678 issued to Laughlin andHeuring 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 suihble cationic surfactants is given in U.S.P. 4,259,217 issued to Murphy on March 31, 1981.
Where present, ampholytic, amphoteric and zwitteronic surfachnts are generally used in . ~. h, -~;.,.. with one or more anionic and/or nonionic cllrf~rt~ntc Aninnir surf~t~
Essentially any anionic surfactants useful for detersive purposes can be included in the These can include salts (including, for example, sodium, pohssium, and substituted a salts such as mono-, di- and, ' salts) of the anionic sulfate, sulfonate, ~ubv,~' and sarcosinate Other anionic surfactants include the ' such as the acyl ' N-acyl taurates, fatty acid amides of methyl huride, al~yl succinates and s '~
rnn~ct~rc of r ' ' (especially saturated and, ' C12-C18 ..... ~. .~) diesters of r ' ' (especially saturated and ' C6-C14 diesters), N-acyl Resin acids and h~,- v ' resin acids are also suihble, such as rosin, I.~J.", ' rosin, and resin acids and 11,~ ' resin acids present in or derived from tallow oil.
Anin~ c~lfate surfachnt Anionic sulfate surfactants suihble for use herein include the linear and branched primary alkyl sulfates, alkyl ~;LI.u-~ r ' , fatty oleyl glycerol sulfates, aL~yl phenol ethylene oxide ether sulfates, the Cs-C17 acyl-N-(CI-C4 alkyl) and -N-(CI-c2 I..~,v-u,~ lh~l) glucamine sulfates, and sulfates of alk~lpu~ ; l, such as the sulfates of alk.~l~ul~;lu~u~ (the nonionic rmnclll~ ' being described herein).

WO 95/28465 2 1 8 7 3 0 p~"~
YI ~ UAY '' surfactants are preferably selected from the group consisting of ~he C6-C1g alkyl sulfates which have been ~ oA~ ' with from about 0.5 to about 20 moles of ethylene oxide per molecule. More preferably, the alkyl elL~JA~
surfactant is a C6 C18 alkyl sulfate which has been ~IIIUA~ ' with from about 0.5 to about 20, preferably from about 0.5 to about 5, moles of ethylene oxide per molecule.

WO 95128465 2 i 8 7 3 0 4 P~

Anionic sulfnn ~ rf~nt~nt Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonatod ,uuly~uuuAylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
Aninni~ UA~ ~ 5 '~
Anionic ~U~UA~' surfactants suitable for use herein include the alkyl ethoxy ~UA~ tw~ the alkyl polyethoxy POI~bUA~ surfactants and the soaps ('alkyl carboxyls'), especially certain secondar,v soaps as described herein.
Preferred alkyl ethoxy ~ubuA~' for use herein include those with the formula RO(CH2CH20)X CH2C00-M+ wherein R is a C6 to Clg alkyl group, x ranges from O tû 10, and the ethoxylate ~' b~ is such that, on a weight basis, the amount ofmaterial where x is 0 is less than about 20 %, and the amount of material where x is gr~ater tban 7, is less than about 25 %, the average x is from about 2 to 4 when the aYerage 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 magnesium ions. The preferred alkyl ethoxy ~uA~ldt~,~ are those where R is a C12 to C1g alkyl group.
Alkyl polyethoxy ~UIy~u~UA~' ' surfactants suitable for use herein include thosehaving the formula RO-(CHRI-CHR2-O)-R3 wherein R is a C6 to C1g alkyl group, x is from I to 25, Rl and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, ;I~JIUA~;~U~C;II;., acid radical, and mixtures thereof, wherein at least one Rl or R2 is a succinic acid radical or II~YdIUA~ ~U~;II;C acid radical, and R3 is selected from the group consisting of hydrogen, substituted or ' ' h~JIu~bù~ having betwen I and 8 carbon atoms, and mixtures thereof.

W095128465 ;;2:~ 87304 ~ .,1,~. .1 Aninnir :c/Y~nnrl~ n~ surf~rt~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 benzoic acid, or as in alkyl-substituted cyclohexyl ~UAy' 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 (~nnrhinhilir portion). The secondary soap surfactants usually contilin 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.
B. Another preferred class of secondary soaps comprises those carboxyl compounds wherein the carboxyl substituent is on a ring l,~d.~u~l unit, i.e., secondary soaps of the formula R5-R6-CooM, wherein R5 is C7-C1O, preferably C8-C9, alkyl or alkenyl and R6 is a ring structure, such as benzene, and ~ (Note: R5 can be in the ortho, rneta or para position relative to the carboxyl on the ring.) . Still another preferred class of secondary soaps comprises secondary carboxyl ' of the formula CH3(cHR)k(cH2)m-(cHR)n-CH(COOM)(CHR)o~(CH2)p~(CHR)q~CH3~ wherein each R is Cl-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 ~buAy' ) is in the range of 10 to 18.
In each of the above formulas A, B and C, the species M can be any suitable, especially water-Y.l..l.,l;,~- ~, counterion.
Especially preferred secondary soap surf~ctants for use herein are water-soluble woss~2846s 21 a 7304 r~l"~ 92 members 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- I-heptanoic acid.
All~li m~t~l sarcosinate surf~rt~nt Other suitable anionic surfactants are the alkali metal s~ ~ of formula R-CON
(Rl) CH2 COOM, wherein R is a Cs-C17 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 ~ul in the form of their sodium salts.
Nonionic ~llrf~rt~nt Essentially any anionic surfactants useful for detersive purposes can be included in the ;" Exemplary, non-limiting classes of useful nonionic surfact~nts are listed below.
yhyJ,uAy fatty acid amide ~llrf~rtS~nt r~lJ~ydluAy fatty acid amides suitable for use herein are those having the structural formula R2CONRIZ wherein: Rl is H, Cl-C4 h~ u~ubyl~ 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 C5-C31 l~ydlu~ubrl~
preferably straight-chain Cs-Clg alkyl or alkenyl, more preferably straight-chain Cg-C17 alkyl or alkenyl, most preferably straight-chain Cll-C17 alkyl or alkenyl, or mixture thereof; and Z is a ~Jul~;lydluAyll.~l~u~ubyl having a linear l~ydlu~ul)jl chain with at least 3 hydroxyls directly connected to the chain, or an al~u~y' ' derivative (preferably ell,uA~' ' or ~IUyU~.y' ` i) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
~nninnir,.. 1~ of ~ikylvhenols The pol~,.l.yh...~, PUIYIJIU~I .l." and IJulybu~yl~ , oxide ' of alkyl phenols are suitable for use herein. In general, the pUIy~hJlU~. oxide, are preferred. These ~ -r - ~ include the ~ products of alkyl phenols having an alkyl group containing from about 6 to about 18 carbon atoms in either a str~ught chain or branched chain ~ ;.. with the alkylene oxide.

W0 95/2~i465 2 18 7 3 0 4 r~ 69l ' hloninnir ~thn~' ' aicohol surf~rt~nt The alkyl ethoxylate c.~ products of aliphatic alcohols with from about I 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 generally contains from 6 to 22 carbon atoms. P~uh~ul~uly preferreci are the products of alcohols having 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.
hn~yl~rPr~ f~ti,y ~irnhnl c~ rt~nt The ethoxylated C6-C18 fatty alcohols and C6-CI8 mixeci CLhUA~ IU~UAY' fatty alcohols are suitable surfactants for use herein, ~UL~l~u~ y where water soluble.
Preferably the chhvA~' ' fatty alcohols are the Clo-CIg cLI.uA~' ' fatty alcohols with a degree of eillUA~Idi~UII of from 3 to 50, most preferably these are the C12-CIg CIIIUA~Y~ ' fatty alcohols with a degree of eLiluA~L.Liull from 3 to 40. Preferably the mixed chluA,r' '/~IU~VA~' ' fatty alccihols have an alkyl chain length of from 10 to 18 carbon atoms, a degree of LlhVA~IdLiùl~ of from 3 to 30 and a degree of ~IUIJVA~;dLiUI~ of from 1 to 10.
Nonionic EO/PO rnnriPn ia~es vith vro~ylene ~Iycol The ' products of ethylene oxide with a l.~d,i.u~l.vl,;~. base formed by the ~. ' of propylene oxide with propylene glycol are suitable for use herein.
The h~.ll.r' ' portion of these compounds preferably has a mûlecular weight of from about 1500 to about 1800 and exhibits water insolubility. EAamples of compounds of this type include cerhain of the ~.OII~-avaiiiable PluronicTM
surfactants, marketed by BASF.
N ~nirnjr EO ~ roducts with pro~ylene UAi~iU/~ rAinP ~ ucts The ... " ,,i... .1 ;..., products of ethylene oxide with hhe product resulting from the reacion of propylene oxide and ~hh~' . " are suitable for use herein. The ll~dl~ r moiety of these products consists of the reaction product of ch~l~r't " and excess propylene oxide, and generally has a molecular weight of wo ssl~s465 2 1 g 7 3 ~ 4 T ~l/lJ~ ~ 4l from about 2500 to about 3000. Examples of this type of nonionic surfactant include certain of the :u--l"~ ,hllly available TetronicTM cnmrollntlC marketed by BASF.
Nonionic alkyl~uly~ surf~r~n-Suitable alhyl,uuly~- .1, ;.1. ~ for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a ll~llu~ Jb;c group containing from about

6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a I,ul~ , e.g., a ~IJ~;IY~U~;d~ hycllu~llilic 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 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties. (Optionally the ll~ group is attached at the 2-, 3-, 4-, etc.positions thus giving a glucose or galactose as opposed to a glucoside or g~
The;"t . ~ .. . 1. .. ;.1~ 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 al~ uul~E;ly~ùs;~u, have the formula R20(CnH2nO)t(glYCsyl)x wherein R2 is selected from the group consisting of alhyl, alhylphenyl, l~d~u~ lhyl, hydroxyalhylphenyl, and mixtures thereof in which the alhyl 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.
~nninnir f~t~y acid amide surfqrtqn' 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 l~dlu~kyl, and -(C2H40)XH, where x is in the range of from I to 3.
A ' surfact,ag~

WO 95f28465 1, 2 1 8 7 3 0 ~

Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the aihyl ~ acids.
A suitable example of an alicyl ~ r~ ylic acid for use hexin is Miranol(TM) C2M Conc. I..cU..,r~ulcd by Miranol, Inc., Dayton, NJ.
Ar~:n- Oxide s~ rt^^~
Amine oxides useful herein include those compounds haYing the formula R3(oR4)XN0f~R5)2 wherein R3 is selected from an aih,YI, h,Ydroxyaii~,Yl, a.,~, --, 1..~.. u~7uyl and aik,YI phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms, preferably 8 to 18 carbon atoms; R4 is an aihylene or ilUJ~ , group containing from 2 to 3 carbon atoms, preferably 2 carbon atoms, or mixtures thereof; x is from 0 to ~, preferably from 0 to 3; and each R5 is an alkyl or i~f~iylu~lhyl group containing from I to 3, preferably from I to 2 carbon atoms, or a pol~L~ 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 C1o-Clg alkyl dimethyl amineoxides and Cg-C1g aiicoxy ethyl r iluA~ l amine oxides. Examples of such materials include iiIII~L~IU~ - oxide, di~,~h~ - oxide, bis-(2-ilu~ fl)dodc~"y- oxide, d;...~ fl~iodc~"~' oxide, i;ylu~i~tl~i~J' oxide, I~ Lil~ ;hjlh~ oxide, ~iUil~.~ ' ' oxide, cetyl " ~' oxide, stearyl .I.... L~ oxide, taf.iow lilll~ r' - oxide and dimethyl-2-ilu~u~,lad~1' - oxide. Preferred are C1U C18 aikyl ~' ~' - oxide, and C1~1g acyiamido aiicyl ," .~' - oxide.
~Witt~ mir 5 ~'-Z~ilt~liu~;c surfactants can aiso be -- r ' ~ into the detergent c - ~
hereof. These surfactants can be broadly desc~ribed as derivatives of secondary and tertiary amines, derivatives of h~t~u~ secondary and tertiary amines, or derivatives of quaternary quaternary ~ ' or tertiary sulfonium WO 95/28465 r~
cn~u~c Betiline and sultaine surfactants are exemplary ~W;~t~liOIl;c surfactants for use herein.
RPt~in~ surfrrt~n~
The betaines useful herein are those . ' having the formula R(R')2N+R2COO- wherein R is a C6-Clg l~ydl~byl group, preferably a C10-C16 alkyl group or C10-l6 acylamido alkyl group, each Rl is typically Cl-C3 alkyl, preferably methyl,m and R2 is a Cl-Cs llydlu~yl group, preferably a Cl-C3 alkylene group, more preferably a Cl-C2 alkylene group. Examples of sui,table betilines include coconut a.,y' ' . u~yldilll~lhyl beti~ine; hexadecyl dimethyl betaine; C12 14 a~y' ' r uyy ' Cg 14 a~y' ~ ~ yld;~ yl betaine;
4[C14-16 ll~y~ ly~ ] 1 I,alLluAyL ~ C16-18 ~,~,y ' yL~.L~ C12-16 a~y' ' yl-betaine; tC12-16 a.~ ,l;.y' ' ' ' y" Preferred betaines are C12 18 dimethyl-ammonio hexanoate and the C10-l8 ~y' ' ~ . (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.
~1~ ,.... .
The sultaines useful herein are those r - ~ having the formula (R(RI)2N+R2S03- wherein R is a C6-CIg 1~1d~byl 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 h1.1lu~jl group, preferably a Cl-C3 alkylene or, preferably, hydroxyalkylene group.
A ~ rt~--Ampholytic surfactants can be il.w.r ' into the detergent ~ , herein.
These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of l.~,~.u~,y~,lic secondary and ter~tiary amines in which the aliphatic radical can be straight chain or branched.
('~tinni~
Cationic surfactants can also be used in the detergent ~ . herein. Suitable cationic surfactants include the quatemary r surfactants selected from mono WO 95/28465 ~ `2 1: 8 7 3 ~ 4 r~l~u~ ~, .

C6-C16, preferably C6-CIo N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, II~YdIUA~ or llydlu groups.
pqrtiqlly 5~ hl~ or in~ lhl~ builder ~ ' The detergent ~o~ of the present invention may contain a partially soluble or insoluble builder compound, typically present at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight, mûst preferably from 20% to 60%
weight of the cc,~
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 nulnber from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclûsed in DE-A-3417649 and DE-A-3742043. For the purpose of the present invention, x in the general formula above has a value of 2, 3 or 4 and is preferably 2. The most preferred material is ~-Na2Si20s, available from Hoechst AG as NaSKS-6.
The crystalline layered sodium silicate material is preferably present in granular detergent, , as a particulate in intimate admixture with a solid, water-soluble ionisable material. The solid, water-soluble ionisable material is selected from organic acids, organic and inorganic acid salts and mixtures thereof.
Suitable ' ' 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. Therl ' material are in hydrated form and are preferably crystalline, cont~uning from 10% to 28%, more preferably from 18% to 22% water in bound form.

w0ssl2846s 2 1 8 17304 3s The ~ minnci1il~tP ion exchange materials can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline ~ minnc~ tP ion exchange materials are available under the ~Pci~n~tinn~ Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeoilte MAP, Zeolite HS and mixtures thereof. Zeolite A has the formula Na 12 LA102) 12 (sio2)l2] xH20 wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na86 [(Alo2)86(sio2) 106] . 276 H20.
Heavy mPt~l ion ~PcllPc~rant The detergent ~ n~ -,lc of the invention may contain as a preferred optional component a heavy metal ion ~PqllPctr~nt By heavy metal ion sequestrant it is meant herein . n"\l"~ which act to sequester (chelate) heavy metal ions. These .,."I,n". . 1~ may also have calcium and magnesium chelation capacity, but I,I;dlly they show selectivity to binding hcavy metal ions such as iron, manganese and copper.
Heavy metal ion ~r~ are generally present at a level of from 0.005% to 20%, preferably from 0.1% to 10%, more preferably from 0.25% to 7.5% and most preferably from 0.5% to 5% by weight of the c-, -",.~
eavy metal ion ~ , ll,, which are acidic in nature, having for example acid or carboxylic acid r~ ;n~ may be present either in their acid form or as a complex/salt wilh a suitable counter cation such as an alkali or alkaline metal ion, ~mmnni~m or substituted ammonium 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 >r.l.lF~ for use herein include organic I 'ml, ' such as the amino alkylene poly (alkylene 1~ ), alkali metal ethane 1-hydroxy ~ and nitrilo ilil"~ lF,~c I ' , ' referred among the above species are diethylene triamine penta (methylene ethylene diamine tri (methylene r~ r) h~iAdll~ lly~ C diamine tetra (methylene phncrho~tP) and hydroxy-ethylene 1,1 Ll~

WO 95/28465 `2 ~ ~ 7 3 0 4 P
.

Other suitable heavy metal ion scquestrant for use herein include nitrilntri~ tir acid and pol~-";-~ ù~yl;c acids such as ~LI.~ ,r~ acid, ~LIIyl ,- ~ l :"- pentacetic acid, eLl~ disuccinic acid, eLlly' ' diglutaric acid, 2-l~yJlu~ Jlu~uy~l I;- IK:~ - disuccinic acid or any salts thereof.
Especially preferred is 1;~ ' N,N'-disuccinic acid (EDDS) or the all~ali metal, alkaline earth metal,: or substituted: salts thereof, or mixtures thereof. Preferred EDDS compounds are the free acid form and the sodiumor magnesium salt or complex thereof. Examples of such preferred sodium salts ofEDDS include Na2EDDS and Na3EDDS. Examples of such preferred magnesium complexes of EDDS include MgEDDS and Mg2EDDS.
Other suitable heavy metal ion , for use herein are ~ acid derivatives such as 2 ~.~J.u~. .h~l diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133.
The acid-N-2-l.~JIu,~.~,u.u~ l sulfonic acid and aspartic acid N-~bu~ l N-2-l~d~u~,u~uu~1-3-sulfonic acid . described in EP-A-516,102 are also suitable herein. The ~-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid ~ - 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 ' acid 1 Dipicolinic acid and 2-1~2~4-Lli~bu~yli~ acid are alos suitable. Gl~ ' N,N'-disuccinic acid (GADS) is also suitable.
E~
Another optional ingredient useful in the detergent ~ , is one or more additional enzymes.
Preferred additional enzymatic materials include the ~ ,lly available lipases, amylases, neutlal and alkaline proteases, esterases, cellulases, pectinases, lactases and wo 9s/2846~ 2 1 8 7 3 (~J 4 r~

~ Cu~ iu~l~ly il~ UI~ ' into detergent crl ~ Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
Preferred ~,u~ ,;olly available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperag by Novo Industries A/S (Denmark), thog sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor r 1 and thog sold under the tradename Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be .,. ~ ,. ~. .1 into the, ., .~I r.~ in accordance with the invention at a level of from 0.0001% to 4% active enzyme by weight of the .~ ,1...-:';.
Preferred amylases include, for example, c~-amylases obtained from a special strain of B 1 ~ ' 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 incul~ ' into the .
in accordance vith the invention at a level of from 0.0001% to 2% active enzyme by weight of the Lipolytic enzyme (lipase) may be pregnt at levels of active lipolytic enzyme of from 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, most preferably from 0.001% to 0.5 % by weight of the The lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of ~miEQL sp., rn...~l,vll~s sp. or r~ Sp.
including r~ .. 1.. ~.~ ~ -~ ,.. ~r.~7. ,l~ . or pc~ tlnm ~ ~' Lipag from chemica71y or genetica7.1y modified mutants of these stra7ns are a7so useful herein~
A preferred ipag is derived from r~ V~ J~ , which is described in Granted European Patent, EP-B-0218272~
Another preferred ipase herein is obtained by cloning the gene from ~m~QL
an~inQ~ and expressing the gene in ACrrr~ lc oryza, as host, as described in Eurûpean Patent Arrlir~tinn~ EP-A-0258 068, which is 'ly available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolag. This lipag is a so described in U.S~ Patent 4,810,414, IIut,_ J.,ll~.. et a7., issued March 7, 1989~

wo ss/2s46s : ~ I a 7 3 0 4 r~ lliJ~ ''i691 Fn~yme ~ i7inp System Preferred enzyme-containing ~ 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 stabilizing system. The enzyme stabilizing 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 stabilizing systems can also comprise reversible enzyme inhibitors, such as reversible protease inhibitors.
The, , herein may further comprise from 0 to about 10%, preferably fromabout 0.01% to about 6% by weight, of chlorine bleach scavengers, added to prevent chlorine bleach species present in many water supplies from attacking and ina~
the enzymes, especially under al~aline conditions. While chlorine levels in water may be small, typically in the range 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 usua ly large; a~U~ " enzyme stability in-use can be ~
Suitable chlorine scavenger anions are widely avatlable, and are illustrated by salts containing ammonium cations or sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc.
such as carbamate, ascorbate, etc., organic amines such as acid (EDTA) or alkali metal sa.t thereof, (~IEA), and mixtures thereof can .ikewise be used. Other l,U..~ iUi.dl scavengers such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as sodium perborate ' ~....~, sodium perborate ' ~.' and sodium ,~.. L as we.l as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, .actate, ma.ate, tartrate, salicylate, etc. and mixtures thereof can be used if desired.
~olymeric comvound rganic polymeric . , ' are ~a~ preferred r ' of the detergent in accord with the invention. By organic polymeric compound it is meant essential.ly any polymeric organic compound commonly used as !', ', and anti-l~ ,u~;-iu.~ and soi`. suspension agents in detergent c(- I~u~

W095/28465 r~,~lVb~a/U.~691 ~ 21 87304 Organic poiymeric compound i5 typically il~ UlUUIa~ in the detergent ~.. . I.r.~;li. .. ~
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 organic polymeric cûmpounds include the water soluble organic homo-or co-polymeric poly- albu~.yli- acids or their salts in which the IJul~ubu~ylic 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 l~ul~a~ Iy' of MWt 200~5000 and their cu~ol~..u,.~
with maleic anhydride, such ~u~ly~ having a molecular weight of from 20,000 to 100,000, especially 40,000 to 80,000.
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 aul~ .u~ ul,~ having a molecular weight of from 2,000 to 80,000.
The polyamino 1, ' are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
Other organic polymeric compounds suitable for ~Ju-aLiull in the detergent herein include cellulose derivatives such as methylcellulose, _L;I~' " ' and h~l.u,.~_ih~ " ' Further useful organic polymeric , _ ' are the pul~_Lh.~lu..~ gLycols, ~)~uLi~ ulaulr those of molecular weight 1000-10000, more ~ , 2000 to 8000 and most preferably about 4000.
T.- ~ rii~r~ compound The ~ Of the invention may contain a lime soap dispersant compound, which has a lime soap dispersing power (LSDP), as defined hereinafter of no morethan 8, preferably no more than 7, most preferably no more than 6. The lime soapdispersant compound is preferably present at a level of from 0.1% to 40% by weight, more preferably 1% to 20% by weight, most preferably from 2% to 10% by weight of the .

wo ss/2846s - . 2 1~ 7 3 0 4 r I~U.. N ~gl A lime soap dispersant is a material that prevents the ,ulr-,;,u;ldliUIl of alkali metal, ammonium or amine salts of fatty acids by calcium ûr magnesium ions. A numericalmeasure of the 1~ J~ of a lime soap dispersant is given by the lime soap dispersing power (LSDP) which is determined using the lime soap dispersion test as described in an article 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 ~ 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.
Nagarajan, W.F. Masler, Cosmetics and Tûiletries, Volume 104, pages 71-73, (1989). The LSDP is the % weight ratio of dispersing agent to sodium oleate required to dispcrse the lime soap deposits fûrmed by 0.025g ûf sodium oleate in30ml of water ûf 333ppm CaCQ3 (Ca:Mg=3:2) equivalent hardness.
Surfactants having good lime soap dispersant capability will include certain amine oxides, betaines, ~ '' ' alkyl ~LI~u~ ' and ethûxylated alcohûls.
Exemplary surfactants haYing a LSDP of no mûre than 8 fûr use in accord with theinvention include C16-C1g dimethyl amine ûxide, C12-C1g alkyl CLIIUA,~ r with an average degree of cLllu~ L;u-- of from 1-5, 1 ' '~ Cl2-cls alkyl eLllu~ r surfactant with a degree of cLllu~ ldliu~ ûf about 3 (LSDP=4), and the C13-C1s cLllu~ ' alcohols with an average degree of ctllu-~h~Liu-- of either 12 (LSDP=6) or 30, sold under the trade names Lutensol A012 and Lutensol A030 .~Li~ , 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 ,u~ulyll~ of acrylic acid, ~ Lh~ acid or mixtures thereof, and an acrylamide or substituted a~ ' ' ', where such polymers typically hav~ a molecular weight of from 5,000 to 20,000.
r-~ system The detergent ~u..,~ ;.- - ûf the invention, when formulated for use in machine washing . preferably comprise a suds , . r, ' ~ system present at a level of from 0.01% to 15%, preferably from 0.05% to 10%, mostpreferably from 0.1% to 5% by weight of the . .. ~
Suitable suds ~U~yl~J~ systems for use herein may comprise essentially any knownantifoam compound, including, for example silicone antifoam - , ' 2-alkyl and alcanol antifoam Comro~ c By antifoam compound it is meant herein any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent ~ uLuly in the presence of agitation of that solution.
P~L~u~ly preferred antifoam compounds for use herein are silicone antifoam ' defined herein as any antifoam compound including a silicone Such silicone antifoam -- - r-- ' also typically contain a silica r , The term "silicone" as used her~in, and in general throughout the industry, . . a variety of relatively high molecular weight polymers containing siloxane units and l~ydl~b~l group of various types. Preferred silicone antifoam ~nmrOI~n~ic are the siloxanes, ~ , the pol~.' ' yl~ u~ having ~ l end blocking units.
Other suitable antifoam c~ro~n~lC include the ' yl;~, 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 -. ~ yllh~ fatty acids, and salts thereof, for use as suds suppressor typically have l..r.l.~l,yl 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 . ' include, for example, high molecular weighî fatty esters (e.g. fatty acid lli~ly~.i~cs), fatty acid esters of . ' alcohols, aliphatic C1g-C40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexa-aL~y' ' or di- to tetra alkyldiamine 11- ~ formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing I to 24 carbon atoms, propylene oxide, bis stearic acid amide and yl di-alkali metal (e.g. =dium, potassium, lithium) phosphates and phosp~ate esters.

w0 ss/2s46~ 2 18 7 3 ~4 r~ 91 Copolymers of ethylene oxide and propylene oxide, ~ .ul~uly the mixed ~ UAY~ ul~uAyl~l~d fatty alcohols with an allcyl chain length of from 10 to 16 carbon atoms, a degree of ~LI.UAyl~iul. of from 3 to 30 and a degree of IJIulJuAylaLi of from I 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-allcyl-alcanols can be used in the c~ c according to the present invention.
A preferred suds ~UL~ g system comprises (a) antifoam compound, preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in, (i) ~JUIydil~ yl siloxane, at a level of from 50% to 99%, preferably 75%
to 95% by weight of the silicone andfoam compound; and (ii) silica, at a level of from 1% to 50%, preferably 5% to 25% by weight of the siLcul.J~iL~ antifoam compound;
wherein said silica/silicone antifoam compound is i..~u.l ' at a level of from 5% to 50%, preferably 10% to 40% by weight;
(b) a dispersant compound, most preferably comprising a silicone glycol ralce copolymer with a ~IYUAYOI~ content of 72-78% and an ethylene oxide to propyleneoxideratiooffrom 1:0.9to l:l.l,ataleYeloffrom0.5% to 10%, preferably 1% to 10% by weight; ? p~uLi,ul~uly preferred silicone glycol rake copolymer of this type is DCO544, "y available from DOW
Corning under the tradename DCO544;
(c) an inert carrier fluid compound, most preferably comprising a C16-cl8 ethoxylated alcohol with a degree of ~,uAyl~tiul, of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;

Wo 95128465 2 1 ~ 7 3 0 4 r~l/Lv ~ 691 A preferred particulate suds suppressor system useful herein comprises a mixture of an alkylated siloxane of the type h~ vuve disclosed and solid silica.
The solid silica can be a fumed silica, a l ~ ' silica or a silica, made by the gel for~nation technique. The silica particles suitable have an average particle size of from 0.1 to 50 Ul~lvh~ preferably from I to 20 ~ and a surface area of at least SOm2/g. These silica particles can be rendered l,~Jl.r' ' - by treating them with dialkylsilyl groups and/or trialkylsilyl groups either bonded directdy onto tbe silica or by means of a silicone resin. It is preferred to employ a silica the particles of which have been rendered ~l~Jlu~hv~ic with dimethyl and/or trimethyl silyl groups. A preferred particulate antifoam compound for inclusion in the detergent ~ u~ in accordance with the invention suitably contain an amount of 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 ~ v system is Irl~lr~ ~t i by a l~.yJIu~ ub;vsilanated (mûst preferably trimethyl-silanated) silica having a particle size in the range from 10 to 201 and a specific surface area above S0m2/g, intimately admixed with dimethyl silicone fluid haYing 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 ., _ system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material haYing a melting point in the range 50C to 85C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid haYing a carbon chain containing from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particula~e suds systems wherein the organic catrier 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 ~ v 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 particulate suds . . v systems comprising silicone antifoam W0 95/28465 r~
~1 ~7304 compound, a carrier material, an organic coating material and crystalline or amorphous ~ min~cil ' at a weight ratio of ~ n~ ciii~tl~ 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.
An exemplary particulate suds ~ system for use herein is a particulate ~,,' c~ t, made by an a, ~ process, comprising in c~ ' ' `
(i) from 5% to 30%, preferably from 8% to 15% by weight of the component of silicone antifoam compound, preferably comprising in .. 1.;.- ~';n .
~Iydi~ l siloxane and silica;
(ii) from 50% to 90%, preferably from 60% to 80% by weight of the . t, of carrier material, preferably starch;
(iii) from 5% to 30%, preferably from 10% to 20% by weight of the component of vv binder compound, where herein such compound can be any compound, or mixtures thereof typically employed as binders for ~v~ most preferably said vv binder compound comprises a C16-C1g clhur.y' ' alcohol with a degree of ~ u~ iiùn of from 50 to 100;
and (iv) from 2% to 15%, preferably from 3% to 10%, by weight of C12-C22 h~.l., ., ' fatty acid.
pnlymr rir dye tr~nC~r ~ ntc l~e detergent i . 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, cuuuly of N ~ ulido..~ and N .;..)' ' '~, ~ulyv;~y ~ ulhlu.._~uly~ or ' thereof.
a) Polyamine N-oxide polymers W0 95128465 2 1 ~ 7 3 0 4 F~
1 , 4s Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula:
(I) AX
R

wherein P is a pol~...~.i~i,l~ unit, whereto the R-N-O group can be attached to, or wherein the R-N-O group forms part of the ~I~ unit or a ~ ", of both.

Il 11 11 A jS NC, CO, C, -O-, -S-, -N-; x is O or 1;
R are aliphatic, c Ih~ y' ' aliphatics, aromatic, I., tc.v~ .li. or alicyclic groups or any ~- 1. - -';.~ 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 1 ' by the following general structures:
O
(R~ ) X -N-(R2)Y
(R3)Z or --1 (R, )X
wherein Rl, R2, and R3 are aliphatic groups, aromatic, h~t~ or alicyclic groups or ' thereof, x orland y or/and z is O or I and wherein the nitrogen 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 ~I~.. i~le 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 ~1~.. ;~1,~., unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, WO 95/28465 2 1 8 7 3 a 4 PCT/I~S95103691 alicyclic or II~ t~ liC groups. One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group. Preferred polyamine N-oxides are those wherein R is a h~L~u~ Lc 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 pol~ l;~Llc unit.
Preferred class of these polyamine N-oxides are the polyamine N-oxides having the general formula (I) wherein R is an arrm -tir I ~ l;l, or alicyclic groups wherein the nitrogen of the N-0 functional group is part of said R group. Examples of these classes are polyatnine oxides wherein R is a h~ ;C compound such as pyrridirle, pyrrole, imidazole and deriYatives thereof.
Another preferred class of polyamine N-oxides are the polyamine oxides having the general formula (I) wherein R are aromatic, I~L.~L~ or alicyclic groups wherein the nitrogen of the N-0 functional group is attached to said R groups. Examples 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, polyimides, pol~. y' and mixtures thereof.
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 appropriate W~JUI,~lll.,li~ll.iOn or by ~l~ul 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 1:1000000, most preferably from 1:7 to 1:1000000. The polymers of the present invention actually encompass random or block ~.~,I,vl.y..l_~ where one monomer type is an amine N-oxide and the other monomer type is either an amine N-oxlde or not.

WO 95128465 2 1 g 7 3 0 4 PC~/US95J03691 The amine oxide unit of the polyamine N-oxides has a PKa < 10, preferably PKa <

7, more preferred PKa < 6.
The polyamine oxides can be obtained in almost any degree of pulyll..,.i~iull. The degree of ~uly~ i~Liol~ is not critical provided the material has the desired water-solubility and dye-suspending 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) Covolymers of N-vi~ ulidu~ i N-v;.~
Preferred polymers for use herein may comprise a polymer selected from N-v ~ ;d~ul~ N .;~ ulido~ cu~,ul~ wherein said polymer has an average molecular 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 .;11.~" ' ' N-p~ U~Iy~ haYe a molar ratio of N .;.,.~' ' ' to N-v .~1~ " ' from 1 to 0.2, more preferably from 0.8 to 0.3, most preferably 6omO.6m~

.

wo gsl~6s - 2 1 ~ ~ 3 0 4 P~ i91 .

c) Pol~lvi.,yl~ lulidu~
The detergent co ~ herein may also utilize ~Iyv;llyllJyllulidu". ("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 pol~v;..yluyllulidull~ are ~ u;oll~ vailable from ISP
Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000). PVP K-15 is also available from ISP Clllr~tirln Other suitable ~I~v;..~ ' ' which are . u.~....".~;~ll~ available from BASF
~'crûp~ n include Sol~alan HP 165 and Sokalan HP 12.
r~l~v~ ul;Jù~, may be ;.._u.l ' in the detergent ~ herein at a level of from 0.01% to 5% by weight of the detergent, preferably from 0.05% tû 3%
by weight, and more preferably from 0.1% to 2% by weight. The amount of l ul~ v;~ ul;du~. 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~l~v;..~
The detergent ~c~ herein may also utilize ~ul~v ,~i~ -,, ,l;l-... ~ as polymeric dye transfer inhibiting agents. Said pol~v ~ ' ' have an average molecular weight of from 2,500 to 400,000, preferably from 5,000 tc) 200,000, more preferably from 5,000 to 50,000, and most preferably from 5,000 to 15,000.
The amount of ~ v ~ ' in the detergent ~ ." 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~v ~ ' ' 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) Pul~ v ~ I ,. ,lr The detergent ~ '; - herein may also utilize polyv ~ - ' as polymericd~e transfer inhibiting agent. Said pul~v;,,~' ' ' preferably have an average WO 9S/28465 2 1 8 7 3 0 4 r~~ IA jl~91 .

molecular weight of from 2,500 to 400,000, more preferably from 5,000 to 50,000,and most preferably from 5,000 to l5,000.
The amount of poly~ ;daLUl~ u~,uu~J in the detergent ~ may be from 0.01% to 5% by weight, preferably from 0.05% to 3% by weight, and more preferablyfromO.1% to2% byweight. Theamountofpol~v;,.~ ~ul~delivered in the wash solution is from 0.5 ppm to 250 ppm, preferably from 2.5 ppm to l50 ppm, more prefer~bly from 5 ppm to 100 ppm.
O~tical bri,~htener The detergent c.,..,~ herein may also optionally contain from about 0.005% to 5 9 i by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the c~. ~,c,-:~ herein will preferably comprise from about 0.01% to 1% by weight of such optical ~n~htPnPr~
The l-~d-u,uh;l;C optical brighteners useful in the present invention are those having the structural formula:
Rl R2 N~ ~C=C~NH~NN~N
R~ SO3M SO3M R
wherein Rl is selected from anilino, N-2-1,;~ h~J~uA.~ i and NH-2-l~d~u R2 is selected from N-2~ . h,~JlUA,~ h,~l, N-2 ~.~dlUA~
- , chloro and amino; and M is a salt-fo~n~ing cation such as sodium or potassium.
When in the above formula, Rl is anilino, R2 is N-2-bis-l.yd.uA~ I and M is a cation such as sodium, the brightener is 4,4',-bist(4-anilino-~(N-2-bis-1.~-1-uA.~.JI)-s-triazine-2-yl)amino]-2,2'- -'L l r ' acid and disodium salt. This particular brightener species is ~ 'ly marketed under the tradename Tinopal-UNPA-GX
by Ciba-Geigy C~tr~ti~n Tinopal-UNPA-GX is the preferred 1~ optical brightener useful in the detergent ~ herein.
. ~ . . ~

WO95/28465 21 87304 P~ 691 .

When in the above formula, Rl is anilino, R2 is N-2-l.~d-uA~ N-2 ..,_.lly' and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-l~ydlw~y.,.llyl N .,.. tllyla.,~ o)-s-triazine-2-yl)amino]2~2~ r~ acid disodium salt. This particular brightener species is, I,;ally marketed under thetradename Tinopal SBM-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 . ' ' - s triazine-2-yl)amino]2,2'-still.. ~ r .. : acid, sodium salt. This particular brightener species is I,;ally marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
The specific optical brightener species selected for use in the present invention provide especially effective dye transfer inhibition ~ ft benefits when used i~
\ with the selected polymeric dye transfer inhibiting agents i ~: ~. f G
described. The ~ ;.... of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) provides _ ~ 'y better dye transfer inhibition in aqueous wash solutions than does either of these two detergent when used alone. 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 ~ ~ ". The exhaustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightener in the wash Liquor. r` _- with relatively high exhaustion '' are the most suitable for inhibiting dye transfer in the context ûf the present invention.
Of course, it will be a~,.G ' that other, ~ u~ tiù.,al optical brightener types of compounds can optionally be used in the present .~ to provide ~u,.~.
fabric "I~ ,h~.~" benefits, rather than a true dye transfer inhibiting effect. Such usage is cu..~.,...iu~u~l and weLl-known to detergent ' ft-~nin~

wo gs/2846~ 2 1 ~ 7 3 0 4 P~.,.J~ -1~ .1 Fabric softening agents can also be ill~,Ul~JUl~ i into laundry detergent ~
in accordance with the present invention. These agents may be inorganic or organic in type. Inorganic softening agents are . ~ by the smectite clays disclosed in GB-A-l 4W 898. Organic fabric softening agents include the water insoluble tertiary amines as disclosed in GB-A-1514 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"wll ' at levels of from 0.5% to 5% by weight, normally from 1% to 3% by weight, whilst the high molecular weight pol~ L ... oxide materials and the water soluble cationic materials are added at levels of from 0.1% to 2%, normally from 0.15% to 1.5% byweight.
OthPr oDtional ineredients Other optional ingredients suitable for inclusion in the .u ~ of the invention include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.
Form of the . , ~;
The detergent ~ of the invention can be formulated in any desirable form such as powders, granulates, pastes, liquids, tablets and gels.
r;~in~l~
The detergent ~ of the present invention may be formulated as liquid detergent . Such liquid detergent . . typically comprise from 94% to 35% by weight, preferably from 90% to 40% by weight, most preferably from 80% to 50% by weight of a liquid carrier, e.g., water, preferably a mixture of water and organic solvent.
~PI ct",. u,;liu ,, wo 95l28465 2 1 8 7 3 0 4 r~ .,~ ~691 The detergent ~ of the present invention may also be in the form of gels.
Such ~ are typically formulated with polyakenyl polyether having a molecular weight of from about 750,000 to about 4,000,000.

wo ss/2s46s 2 1 8 7 3 0 4 r.". . - .1 Solid l,u~
The detergent ~ 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 ~ in accordance with the presentinvention typically have a bulk density of at least 450 g/litre, more usually at least 600 gllitre and more preferably from 650 g/litre to 1200 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 extremity to allow the contents of the fuMel 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 CALII "' It is mounted so that the lower extremity is140 mm above the upper surface of the base. The cup has an overa'l height of 90 mm, an intemal height of 87 mm and an intemal diameter of 84 mm. Its nominal volume is 500 ml.
To carry out a t, the funnd is filled with powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup. The filled cup is removed from the frame and excess powder removed from the cup by passing a straight edged implement e.g. a knife, across its upper edge. The flled cup is then weighed and the va ue obtained for the weight of powder doubled to provide the bulk densit~v in g/litre. ~eplicate ,~ are made as required.
r~l~Cc~ mllar~ r'~
In genera'l, granular detergent ~ - in accordance with the present invention can be made via a variety of methods including dry mixing, spray drying, iK~ 'i;"" and "

Wo ss~2s46s 2 1 8 7 3 0 4 1 ~-~1 1 s4 W~chin~ methods ~
The .u. l.v~;l;..,.~ of the invention may be used in essentially any washing or cleaning method, including machine laundry and d;~ a~h;llg methods.
~rhin~ waall;lle method A preferred machine d;,l., ' ~, method comprises treating soiled articles selected from croclcery, glassware, llollv.. w uc and cutlery and mixtures thereof, with an aqueous liquid having dissolved or dispensed therein an effective amount of a machine ~;~I,wa,l,;l.g ~ in accord with the inevntion. By an effective amount of the machine d~ w~h;l~6 . .. ~ it is 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 Wll~. '' ' machine a,;ullg methods.
~rhin~ I lry methods Machine laundry methods herein comprise treatulg soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detcrgent ~ in accord with the invention. The detergent can be added to the wash solution either via the dispcnser drawer of the washing machine or by a dispensing device. By an effective amount of the deter6ent it is 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 in w..~. ' machine laundry methods.
In a preferred washing method herein a dispensing device cont~uning an effectiveamount of detergent product is introduced into the drum of a front-loading washing machine before the ~-~ r -... ~ .: 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.

W0 95128465 i2 1 8 7 3 0 4 r~ 69l ss 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 responæ 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 posæss a number of openings through which the product may pass. Alternatively, the device may be made of a material which is permeable to liquid but . ' ' to the solid product, which will allow release of dissolved product. Preferably, the detergent product will be rapidly released at the start of the wash cycle thereby providing transient localised high c~ of product in the drum of the washing machine at this stage of the wash cycle.
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 uæ 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 a~ticle by J.Bland published in Chemist, November 1989, pages 41~6 also describes especially preferred dispensing devices for uæ with granular laundry products which are of a type commonly know as the ~granulette".
Especially preferred dispensing devices are discloæd 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 pasæs outwardly through the orifice into the washing medium. The support ring is provided with a masking: ~ to prevent egress of wetted, ~ d, product, this typically comprising radially extending walls extending from a central boss in a spoked wheel ~ or a similar structure in which the walls have a helical form.

wo gs/28465 ~2 1 8 7 3 0 4 P~ 69l Plr~ ~ method In a ~JIrtl~ wash method aspect of the invention a soiled/stained substrate is treated with an effective amount of a 1.. . I l r~ l solution containing a water-soluble builder, but no bleach ~ - r The solution might optionally contain other non-bleach detergent, . such as s~rt~^tc builders, heavy metal ion enzymes and detergent polymers.
The level of the water-soluble builder in said ~...1. ,r-l~.-- - solution is typically from 0.05% to 80%, and preferably is more than 1%.
The I solution is allowed to remain in contact with the soiled substrate for an effective time interval. Said time interval will typically be from 10 seconds to 1800 seconds, more preferably from 60 seconds to 600 seconds.
îhe soiled substrate is then washed using a suitable washing method wherein a bleach-containing detergent product is employed. The washing method may for exatnple, be any of the machine .li~h. _ or machine laundry washing methods described heleill.

wo 95l2846s 2 1 8 7 3 0 4 P ~ ~ ~ ~ . 69 1 In the detergent ~ .u~ the alJl,~ ' component i ~ iri ~i.. have the following meanings:
XYAS : Sodium C1x - Cly alkyl sulfate 25EY : A C12 15 IJl~ , linear 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 : Clx - Cly sodium alkyl sulfate condensed with an aYerage of Z moles of ethylene oxide per mole TFAA : Cl6-CIg alkyl N-methyl glùcamide.
Silicate : Amorphous Sodium Silicate (SiO2:Na20 ratio = 2.0) NaSKS-6 : Crystalline layered silicate of formula o-Na2Si2Os Carbonate : Anhydrous sodium caroonate rvl~ vA~ Copolymer of 1:4, ' /~lyl;c acid, average molecular weight aoout 80,000 Zeolite A : Hydrated Sodium Al ' of formula Na12(AlO2SiO2)12. 2;'H20 having a primary particle size in the range from 1 to 10 Citrate : Tri-sodium citrate dihydrate woss/2s46s ~ 37304 P~
sa r~.~; (fast release : Anhydrous sodium p~wL bleach of empirical panicle) formula 2Na2CO3.3H2O2 coated with a mixed salt of formula Na2SO4.n Na2CO3 where n is 0.29 and where the weight ratio of ~., ~ to mixed salt is 39: 1 r~ (slow release : Anhydrous sodium I ~ bleach coated with a particle) coating of sodium silicate (Si2O:Na2O ratio = 2:1) at a weight ratio of I ~ to sodium silicate of 39:1 TAED : Tetraacetyl ethylene diamine TAED (slow release : Particle formed by ~g~ , TAED with citric particle) acid and ~I~ .. , glycol (PEG) of Mw=4,000 with a weight ratio of: . of TAED:citric acid:PEG of 75:10:15, coated with an external coating of citric acid at a weight ratio of ~,_ citric acid coating of 95:5.
Benzoyl Caprolactam (slow : Particle formed by "~ benzoyl ~u.~
release particle) (BzCI) with citric acid and p.~ glycol (PEG) of Mw=4,000, with a weight ratio of r ' of BzCl:citric acid:PEG of 63:21:16, coated with an e-Aternal coating of citric acid at a weight ratio of ~ acid coating of 95:5 TAED (fast release : Particle formed by ~ TAED with par~ally particle) neutralised poly~buA~,' at a ratio of TAED.~ul~buA~' of 93:7, coated with an external coating of PUIY~IJUA.Y at a weight ratio of __ _ of 96:4 EDDS (fast release : Particle formed by spray-drying EDDS with MgSO4 at particle) a weight ratio of 26:74 woss/2s46~ 21 8 7304 r~ 91 Protease : Proteolytic enzyme sold under the tradename SaYinase by Novo Industries A/S with an activity of 13 KNPU/g.
Amylase : Amylolytic enzyme sold under the tradename Termamyl 60T by Novo Industries A/S with an activity of 300 KNU/g Cellulase : Cdlulosic enzyme sold by Novo Industries A/S with an activity of 100û 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~ yl cellulose HEDP : 1,1 S.~d~u~ ' .' acid EDDS : I~ N, N'- disuccinic acid, [S,S] isomer in the form of the sodium salt.
PVNO : Poly (4 . jl~ " ) N oxidecopolymerof v .r' ' and ~;..~1~ " ' ranular Suds Suppressor : 12% .C ~ ~;li~, 18% stearyl alcohol,70% starch in granular form WO 95/28465 2 i ~ 7 3 0 4 P~,IIL~.. 5~1 Exarn~le I
The following laundry detergent ~ were prepared values being expressedas p~,..,.,..~ by weight of the ~ u ';~ Citric acid and pol~ ,u.~' are both water-soluble builders. Comrr;~inn A is a prior art ~ u~ . . B
to D are in accord with the invention:
A B C D
45AS/25AS (3:1) 9.1 9.1 9.1 9.1 35AE3S 2.3 2.3 2.3 2.3 24E54.5 4.5 4.5 4.5 TFAA2.0 2.0 2.0 2.0 Zeolite A 13.2 13.2 13.2 13.2 Na SKS-6/citric acid (79:21) 15.6 15.6 15.6 15.6 Carbonate 7.6 7.6 7.6 7.6 TAED (fast release particle) 6.3 TAED (slow release particle) - 5.0 - 2.3 Benzoyl ('~rrnl~r~rn (slow - - 5.0 2.7 release particle) ~t L(fastrelease 22.5 - - 22.5 rarticle) r~., I (slow release - 22.5 22.5 particle) .

Wo ssl2s46s 2 ~ ~3 7 3 0 4 r~v~

DETPMP 0.5 0.8 - -EDDS (fast release particle) - - 0.3 0.75 Protease 0.55 1.27 0.55 1.27 Lipase 0.15 0.15 0.15 0.15 Cellulase 0.28 0.28 0.2g 0.28 Amylase 0.27 0.27 0.27 0.27 r~,ly~ ' 5.1 5.1 5.1 5.1 CMC 0.4 0.4 0.4 0.4 PVNO 0.03 0.03 0.03 0.03 Granular suds suppressor 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:

Peroxyacid 130 190 205 240 Builder(citric) 90 60 60 60 WO 95/2846!i ~ ~ 1 8 7 3 0 4 Lr ~ 691 ~mpl~e 2 Pre-stained cotton swatches were prepared by immersing the swatches in a , ' tea solution. Tea stains contain high levels of , and are recognised to be difficult to remove from soiled/stained substrates.
The pre-stained swatches were pretreated with approx 10 ml of a solution containing 5% by weight of sodium citrate solution. The solution was allowed to remain in contact wth the swatches for a period of 10 mirlutes. The swatches were then washed in a laundry washing method comprising a main wash in a Miele washing machine at40C using soft water. The detergent product employed in this washing method hadfast release of bleach, and had the ~ of r ~ A of Example 1.

Claims (10)

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

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

3. A detergent composition according to either one of Claims 1 or 2 wherein said organic peroxyacid bleach source comprises in combination (i) a hydrogen peroxide source; and (ii) a peroxyacid bleach precursor compound

4. A detergent composition according to Claim 3 wherein said peroxyacid bleach source is a perbenzoic acid precursor compound.

5. A detergent composition according to Claim 3 wherein said peroxyacid bleach precursor compound has a cationic charge.

6. A detergent composition according to Claim 5 wherein said peroxy acid bleach precursor is 2(N,N,N-trimethyl ammonium) ethyl sodium 4-sulphophenyl carbonate chloride or 4 (trimethyl ammonium) methyl benzoyl oxybenzene sulphonate.

7. A detergent composition according to Claim 3 wherein said peroxyacid bleach precursor compound is selected from a) an amide substituted bleach precursor of the general formula:
, or mixtures thereof,wherein R1 is an alkyl, aryl, or alkaryl group containing from abouf 1 to about 14 carbon atoms, R2 is an alkylene, arylene or alkarylene group containing from about 1 to about 14 carbon atoms, R5 is H or an alkyl, aryl, or alkaryl group containing from about 1 to about 10 carbon atoms, and L is a leaving group;
b) a benzoxazin-type bleach precursor of the formula:
wherein R1 is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R4, and R5 may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkylamino, -COOR6, wherein R6 is H or an alkyl group and carbonyl functions;

c) an N-acylated lactam bleach precursor of the formula:
wherein n is from 0 to about 8, preferably from 0 to about 2, and R6 is H, an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbons, or a substituted phenyl group containing from about 6 to about 18 carbon atoms;
and any mixtures of a), b) and c).

8. A detergent composition according to any of Claims 1 - 7 additionally containing a bleach catalyst.

9. A detergent composition according to Claim 8 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(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.

10. A washing method comprising the steps of:
(1) applying a bleach-free solution of a composition containing a water-soluble builder to a soiled substrate:
(2) allowing said solution to remain in contact with said soiled substrate for an effective time interval;

(3) washing said soiled substrate using a washing method involving use of a bleach-containing detergent composition.