CA2261944A1 - A detergent composition - Google Patents

Abstract

A detergent composition comprising a detergent surfactant, a dicarboxylic acid source and an alkaline source wherein said dicarboxylic acid source and alkaline source are capable of reacting together to produce a gas; said dicarboxylic acid source has an effervescence optimum index (EOI) of 4.00, where EOI = [MW x HI] x [10.2-pKa1]-1 x [10.2-pKa2]-1; MW = molecular weight of the dicarboxylic acid of the acid source; HI = hydrophobicity index = ratio of the number of carbon atoms in the chemical formula of the dicarboxylic acid of the acid source : number of oxygen atoms in the chemical formula of the dicarboxylic acid of the acid source; pKa1 is the logarithm of the reciprocal of the dissociation constant of one of the carboxylic acid groups; pKa2 is the logarithm of the reciprocal of the dissociation constant of the second carboxylic acid group; and pKa's 10.20 are not taken into consideration; and the mole ratio of the dicarboxylic acid source to the alkaline source is between 0.005 : 1 and 2.00 : 1; with the proviso that the detergent composition does not contain an alkali metal chloroisocyanurate.

Description

WO 98t04667 PCT/US971121~96 A D~lel~elll Composition Technical Field S The present invention relates to a detergent composition which is suitable for use in laundry and dish washing methods. The present invention also relates to a process for ~p~;ng these detergent powders.

Background to the Invention There is a trend amongst commercially available granular del~,.gellls towards higher bulk densities and towards granular del~,rgenl compositions which have a higher content of deter~elll active ingredients. Such detelge~ offer greater convenience to the consumer and at the same time reduce the amount of p~c~ging materials which will, nltjm~t~ly, be 15 disposed of.

Many of the prior art ~ Jt~ to move in this direction have met with problems of poor solubility ~.ope.Lies arising from low rate of dissolution or the formation of gels. A
consequence of this in a typical washing process can be poor dispensing of the product, 20 either from the dispensing drawer of a washing m~hin~, or from a dosing device placed with the laundry inside the m~hint?. This poor dispensing is often caused by gelling of particles, which have high levels of surfactant, upon contact with water. The gel prevents a ~JlOpol lion of the dc;l~lgent powder from being solubilized in the wash water which reduces the effectiveness of the powder. This is a particular problem at low water 25 pressures andlor at lower washing temperatures.

Further, there has been another recent trend towards re~lcing or elimin~ting the use of phosph~te builders, which have generally been replaced with zeolite (crystallinealuminosilicate). D~telgt;nls co..l~inil-g zeolite builders have been found to be poorer dispensers than detergents cont~ining phosphate builders.

EP-A-0 578 871 describes a process which seeks to make a high bulk density detergent composition which dissolves rapidly and ~ispe~es effectively. The process involves formulating a base powder with a particle size distribution between 150 microns and 1700 microns in combination with additional filler ingredients whereby at least 20% by W 098/04667 PCT~US97/12896 weight of the filler particles is less than 150 microns. The filler particles include salts of citrate, sulphate, (bi-)calbol1ate and silicates.

WO95/14767 relates to the poor dispensing of high density, non-spray-dried detergent S powders, and discloses the use of a citric acid salt which has a Rosin Rammler particle size of less than 800 microns.

W094/28098 discloses a non-spray-dried delc-gent powder comprising a combination of an ethoxylated primary C8-18 alcohol, an alkali metal aluminosilicate builder and 5 to 40 10 wt% of a water-soluble salt of a citric acid.

EP-A-0 639 637 discloses the repl~Pment of pe.l,o,~le bleach with an alkali metal percarbonate to improve the dispensing profile and dissolution rate of a d~telgell~. Citrate or mixtures of citrate with sulphate or carbonate can be used to coat the pclcallJorlale 15 bleach. EP-A-0 639 639 contains a similar disclosure in this respect.

Other ways to improve dispensing include the use of an efferv~osc~n~e system. If the detergent contains an effervescence system then the generation of a gas such as carbon dioxide pushes the particles of the detergent apart, and prevents them from gelling.
The use of effervescçn~e to improve the dispersibility of granular materials has been used extensively in ph~ ceutical pl~palalions. The most widely used effervescentsystem in this respect is citric acid in combination with bicarbonate. The use of this simple effervescent system has also been described for improving the dispersibility of 25 pesticidal compositions for controlling water-borne pests, e.g. GB-A-2,184,946.

US-A-4,414,130 discloses the use of a readily ~lisi~le~r~ble builder particle ~,vith a zeolite-based detergent. It also discloses the use of an effervescence material to improve the dissolving and dissolution of the particles. Sodium carbonate or sodium bicarbonate 30 may be combined with the zeolite binder mix and the balance of the del~.gent may include citric acid, monosodium phosphate, boric acid or other suitable acidifying material, preferably enc~rsul~te~ or agglomerated with bicarbonate, for reaction with it to generate carbon dioxide.

W O 9~04667 PCTAUS97/12896 W092/18596 discloses that improved solubility/dispersion for granular detergents can be achieved by admixing sodium carbonate and citric acid in a specified weight ratio of from 2: I to 15: 1.

EP-A-0 534 525 discloses the use of citric acid with a specified particle size range of 350 to 1500 microns.

US-A-5,114,647 discloses a saniti_ing composition in co~ essed form comprising an laklai metai carbonate, an AliphRtic carboxylic acid and an alkali metal chloroisocyanurate to aid dish~ g~alion.

JP-A-1024900 discloses a detergent co.~ ing a water-soluble carbonate powder and a solid acid powder in a bag made of a film of a water-soluble polymer.

EP-A-0 333 223 relates to a bathing ~Ict)aldlion cOtll~3;.. il~g (a) fumaric acid, (b) a carbonate, (c) carboxymethyl cellulose, or an alkali metal slat thereof, and (d) not less than 0.02% by weight and less than 0.1 % by weight, based on fumaric acid, of a nonionic surface active agent having an HLB of 7 or more.

20 The addition of citric acid results in a reduction in alkalinity. Such an ~lkAlin.o pH
promotes cleAning, stain removal and soil sl~spçn~ion, there is th~,.efol~ need to minimi7e the level of citric acid used. Also citric acid is a relatively expensive ingredient which further reinforces the need to keep the level of citric acid very low. We have also surprisingly found that the present invention allows low levels of the acid to be 25 .c~ti~fA-,tQrily used in the detergent composition. More particularly, the present invention specifies more weight effective acids which provide dispensing benefits to d~lelge particularly granular detergents.

All docllm~nt~ cited in the present description are, in relevant part, incorporated herein 30 by reference.

Su~ of the Invention According to the present invention there is provided a dt:lelge"t composition comprising 35 a d~le.genl sllrfAI~t~nt a dicarboxylic acid source and an alkaline source wherein said dicarboxylic acid source and ~Ik~line source are capable of reacting together to produce a ... ..

W O 98104667 PCT~US97112896 gas; said dicarboxylic acid source has an effervescence optimum index (EOI) of < 4.00, where EOI = [MW x HI] x [10.2 - pKal]~l x [10.2 - pKa23~' s MW = molecular weight of the dicarboxylic acid of the acid source;
HI = hydrophobicity index = ratio of the number of carbon atoms in the chemical formula of the dicarboxylic acid of the acid source: number of oxygen atoms in the chemical formula of the dicarboxylic acid of the acid source;
10 pKa~ is the logarithm of the reciprocal of the dissociation con~lt of one of the carboxylic acid groups;
pKa2 is the log~;lhll, of the reciprocal of the dissociation cons~ll of the second carboxylic acid group;
and pKa's 2 10.20 are not taken into consideration;
15 and the mole ratio ofthe dicarboxylic acid source to the ~lk~line source is between 0.005 :1 and 2.00 : 1;
with the proviso that the detergent composition does not contain an alkali metalchloroisocyanurate .

20 Surprisingly we have found that organic acid materials which meet the defined criteria of the present invention provide improved di~el-sing.

More particularly, we have found that the addition of the acid source in accordance with the crtieria of the present invention and an alk~line source to a d~telge,lt composition 25 improves the solubility and/or dispersion of the delelge~l in the laundering solution and elimin~tes or reduces the problems of solid deterg~ particles rem~ining in the washing m~ in~ and on washed clothes. It is believed that the acid reacts rapidly with the alkali in the laundering solution to release the gas. This helps disperse the detergent and minimi7~ the formation of insoluble clumps.

Detailed Description of the Invention The present invention includes a granular dete.~enl composition. Such compositions comprise a base composition co~ e one or more surfactant, and preferably a builder 3s m~t~ri~l The base composition may be prepared by spray-drying and dry-mixing/agglomeration. The base composition may also comprise the ~lk~lin~ source.

W O 98/04667 PCT~US97/12896 s Alternatively the particulate acid source and/or ~lk~line source may be added as separate components to the detergent base composition, preferably in a granular form.

The ingredients of the present invention, including optional ingredients, and processes 5 for making the d~l~,.g. .ll~, are described in detail below.

A. Deter~ent Surfactant This ingredient is plefc.ably present in an amount of from 1%, IJlefi l~lbly to 90%, preferably 3% to 70%, more preferably 5% to 40%, even more preferably 10% to 30%, most preferably 12% to 25% by weight of the detergent composition. Preferably the detergent is selected from anionics, nonionics, zwitterionics, ampholytics, amphoteric, cationics and mixtures thereof. Preferably the surfactant is anionic, nonionic or a mixture thereof. When the composition contains more than one surfactant the additional surfactant is preferably present at a level of from 0.1% to 50%, more preferably from 1%
to 40%, most preferably from 5% to 30% by weight of the total surfactant present. Where present, arnpholytic, arnphoteric and zwitterionic surf~ct~nt~ are generally used in combiantion with one or more anionic and/or nonionic surf~ct~n 20 Anionic s~lrf~rt~nt The surfactant system may include an anionic surfactant. F.ssPnti~lly any anionic surf~rt~nt~ useful for detersive purposes are suitable. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as25 mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surf~ct~ntc. Anionic sulfate surf~rt~ntc are preferred.

Other anionic s..~ct~nt.c include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, 30 monoesters of sulfosuccinate (especially saturated and unsaturated C l 2-C 1 8 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C6-C 14 diesters), N-acyl sarcosin~tes Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.
Anionic sulfate surfactant CA 0226l944 l999-0l-27 W O 98/04667 PCT~US97/12896 Anionic sulfate surf~ctant~ suitable for use herein include the linear and br;a,lched primary and secondary alkyl sl-lfAtes, alkyl ethoxysulfates, fatty oleoyl glycerol s-llfates, alkyl phenol ethylene oxide ether sl~lfates, the Cs-C17 acyl-N-(CI-C4 alkyl) and -N-(Cl-5 C2 hydroxyalkyl) glucamin~ sulfates, and sulfates of alkylpolysaccharides such as thesulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).

Alkyl sulfate surfar,t~nt.e are preferably selected from the linear and bl~lched primary C I o-C 18 alkyl sulfates, more preferably the C I 1 -C 15 branched chain alkyl sulfates a~d the C 1 2-C 14 linear chain alkyl sulfates.

Alkyl ethoxysulfate surf~ct~nt~ are preferably selected from the group consisting of the Clo-C18 alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of 15 ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C I I -C 18~ most pl~f~,.dbly C I 1 -C 15 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from I to 5, moles of ethylene oxide per molecule.

A particularly preferred aspect of the invention employs mixtures of the preferred alkyl 20 sulfate and alkyl ethoxysulfate surf~ct~nt~ Such mixtures have been disclosed in PCT
Patent Application No. WO 93/18124.

Anionic sulfonate surfactant 25 Anionic sulfonate surfart~ntc suitable for use herein include the salts of Cs-C20 linear alkylbel~.,.lc sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
Anionic carboxylate surfactant Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate su~fartant~ and the soaps ('alkyl carboxyls'), especially 35 certain secondary soaps as described herein.

Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH20)X
CH2C00-M+ wherein R is a C6 to C 18 alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the arnount of material where x is 0 is less than 20 % and M is a cation. Suitable alkyl polyethoxy polycarboxylate5 surf~ct~nt~ include those having the formula RO-(CHRl-CHR2-O)X-R3 wherein R is a C6 to Clg alkyl group, x is from I to 25, Rl and R2 are selected from the group con~icting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group coneietin~ of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and 10 mixtures thereof.

Suitable soap surf~çt~nts include the secondary soap surfact~nt~ which contain acarboxyl unit connected to a secolldar~ carbon. Plef~ d secondary soap surf~et~nte for use herein are water-soluble members selected from the group coneicting of the water-soluble salts of 2-methyl-1-1ln~eç~noic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl- 1 -octanoic acid and 2-pentyl- 1 -heptanoic acid. Certain soaps may also be included as suds s~lJre3sol~.

Alkali metal sarcosinate surfactant Other suitable anionic surf~t~nte are the alkali metal sarcosinates of formula R-CON
(R1 ) CH2 COOM, wherein R is a Cs-C 1 7 linear or branched alkyl or alkenyl group, Rl is a C I -C4 alkyl group and M is an alkali metal ion. Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.
Alkoxylated nonionic surfactant F..e~enti~lly any alkoxylated nonionic surf~ t~ntc are suitable herein. The ethoxylated and propoxylated nonionic surfactants are p.~fel,ed.
Preferred alkoxylated surfaçt~nt~ can be selected from the classes of the nonionic con~en~tes of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate con-len~t~
with propylene glycol, and the nonionic ethoxylate cond~n~tion products with propylene 35 oxide/ethylene di~mine adducts.

W O 98/04667 pcTrus97ll2896 Nonionic alkoxYlated alcohol s~ur~ t The conden~tion products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are suitable for use herein. The S alkyl chain of the aliphatic alcohol can either be straight or br~nrh~.l primary or secondary, and generally collLaills from 6 to 22 carbon atoms. Particularly pl~r~ c;d are the condenc~tion products of alcohols having an alkyl group cont~ining from 8 to 2 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.

10 Nonionic polYhvdroxy fatty acid amide surfactant Polyhydroxy fatty acid amides suitable for use herein are those having the structural forrnula R2CONR1Z wherein: R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C 1 -C4 alkyl, more preferably C 1 or C2 alkyl, most preferably C 1 alkyl (i.e., methyl); and R2 is a Cs-C3 1 hydrocarbyl, preferably straight-chain Cs-C1g alkyl or alkenyl, more preferably straight-chain Cg-C17 alkyl or alkenyl, most preferably straight-chain C 1 1 -C 17 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably 20 ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar - in a reductive amination reaction; more preferably Z is a glycityl.

Nonionic fatty acid amide surfactant 25 Suitable fatty acid amide surfactants include those having the forrnula: R6CoN(R7)2 wherein R6 is an alkyl group cont~ining from 7 to 21, preferably from 9 to 17 carbon atoms and each R7 is selected from the group consisting of hydrogen, C 1 -C4 alkyl, C 1-C4 hydroxyalkyl, and -(C2H4O)XH, where x is in the range of from 1 to 3.

30 Nonionic alkylpol~s~cch~ride surfactant Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group co..~ g from 6 to 30 carbon atoms and a polys~rsh~ride, e.g., a polyglycoside, hydrophilic group cont~ininp 35 from 1.3 to 10 saccharide units.

Preferred alkylpolyglycosides have the formula R20(CnH2nO)t(glYC~sYl)x 5 wherein R2 is selected from the group concicting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived from glucose.

10 AmPhoteric surfactant Suitable amphoteric surfactants for use herein include the amine oxide s.lrf~ct~ntc and the alkyl amphocarboxylic acids.

15 Suitable amine oxides include those compounds having the formula R3(oR4)XNO(R5)2 wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, cont~inin~ from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group cor ~ ing from 2 to 3 carbon atoms, or ~ s thereof; x is from 0 to 5, preferably from 0 to 3; and each R5 is an alkyl or hydroxyalkyl group 20 cont~ining from 1 to 3, or a polyethylene oxide group cont~ining from 1 to 3 ethylene oxide groups. Pl~fel,~d are Clo-C1g alkyl dimethylamine oxide, and C10-l8 acylamido alkyl dimethylamine oxide.

A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Conc.
25 m~nnf~ctured by Miranol, Inc., Dayton, NJ.

Zwitterionic surfactant Zwitterionic surfactants can also be incorporated into the detergent compositions hereof.
30 These surfactants can be broadly described as derivatives of secondary and tertiary ~min~c, derivatives of heterocyclic secondary and tertiary amines, or derivatives of q~ y ammonium, ql~t~m~ry phosphonium or tertiary sulfonium compounds.
Betaine and sultaine surf~ct~ntc are exemplary zwitterionic surf~ct~ntc for use herein.

35 Suitable betaines are those compounds having the formula R(R')2N+R2COO- wherein R
is a C6-CIg hydrocarbyl group, each R1 is typically Cl-C3 alkyl, and R2 is a Cl-Cs W O 98/04667 PCT~US97/12896 hydrocarbyl group. P.er~l,ed betaines are C12 18 dimethyl-ammonio hexanoate and the C 10- 18 acylamido~ )ane (or ethane) dimethyl (or diethyl) bet~in~ s Complex betaine surfactants are also suitable for use herein.

5 Cationic surfactants Additional cationic surf~ct~nt~ can also be used in the detergent compositions herein.
Suitable cationic surfAct~nts include the q~ y ammonium surfactants selected from mono C6-C16, preferably C6-C 10 N-alkyl or alkenyl ammonium surf~ct~nt~ wherein the 10 r~m~ining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.

Cationic ester surfactant The surfactant system may include a cationic ester surfactant. That is. a pr~l; Idbly water 15 dispersible compound having surfactant l)r~p~ Lies comprising at least one ester (ie -COO-) linkage and at least one cationically charged group.

Suitable cationic ester surf~ct~nt~, including choline ester surf~. t~nt~, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.
Plefc~ed water dispersible cationic ester surf~t~nt~ are the choline esters having the formula:

Il fH3 wherein Rl is a C 11 -C 19 linear or branched alkyl chain.

Particularly pl~ r~l ied choline esters of this type include the stearoyl choline ester q--~t~rn~ry methylammonium halides (R1=C17 alkyl), palmitoyl choline ester ql-~tern~ry 30 methylammonium halides (Rl=CIs alkyl), myristoyl choline ester qll~
methylammonium halides (R1=C13 alkyl), lauroyl choline ester methylammonium halides (Rl=CI 1 alkyl), cocoyl choline ester ~lu~r ~.~.y methylammonium halides(R1=C11 C13 alkyl), tallowyl choline ester qll~tern~ry methylammonium halides (R1=C 15 C 17 alkyl), and any mixtures thereof.

W O 98/04667 PCT~US97112896 Il .

In a plefelled aspect the cationic ester surf~t~nt is hydrolysable under the conditions of a laundry wash method.

5 B. Source of Alkali In accoldance with the present invention, the alkalinity system is present in the d~le.gen~
co,-,?o~ilion such that it has the capacity to react with the source of acidity to produce a gas. Preferably this gas is carbon dioxide, and therefore the alkali is a carbonate, or a 10 suitable derivative thereof.

The d~Le~gelll composition of the present invention ~ r.,.ably contains from about 2% to about 75%, preferably from about 5% to about 60%, most preferably from about 10% to about 30% by weight of the alkali source. When the alkali source is present in an I S agglomerated det~rg~ particle, the agglomerate preferably contains from about 10% to about 60% of the alkali source.

In a preferred embodiment, the allc~linity source is a carbonate. E~ ,lcs of pl~Ç~ d carbonates are the ~Ik~line earth and alkali metal carbonates, including sodium 20 c~boll~le, bic~ l~or~le and sesqui-c~l.onate and any mixtures thereof with ultra-fine calcium c~l,o,lale such as are disclosed in German Patent Application No. 2,321,001 published on November 15, I973. Alkali metal perc~l,onate salts are also suitable sources of carbonate species and are described in more detail in the section 'inorganic perhydrate salts' herein.
The ~Ik~linity source may also include other co,l")one~ , such as a silicate. Suitable silicates include the water soluble sodium silicates with an SiO2: Na2O ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.0 being preferred, and 2.0 ratio being most pl~f~lled.
The ~ tPs may be in the form of either the anhydrous salt or a hydrated salt. Sodium 30 silicate with an SiO2: Na2O ratio of 2.0 is the most preferred silicate. Alkali metal persilicates are also suitable sources of silicate herein.

Other suitable sources will be known to those skilled in the art.

35 Preferred crystalline layered silicates for use herein have the general formula NaMSix02x+ 1 ~YH20 wherein M is sodiurn or hydrogen, x is a number from l.9 to 4 and y is a number from 0 to 20. Crystalline layered sodiurn silicates of this type are disclosed in EP-A-0164514 and methods for their plcp~d~ion are disclosed in DE-A-3417649 and DE-A-3742043.Herein, x in the general formula above preferably has a value of 2, 3 or 4 and is preferably 2. The most preferred material is o-Na2Si20s, available from Hoechst AG as NaSKS-6.

10 C. Dicarboxylic Acid Source In accordance with the present invention, the dicarboxylic acid source is present in the detergent composition such that the it is capable of reacting with the source of alkali to produce a gas.
The dicarboxylic acid source an effervescence Op~illlUlll index (EOI) of < 4.00, where EOI = [MW x HI] x [10.2 - pKal] ~ x ~10.2 - pKa2]~1 20 MW = molecular weight of the dicarboxylic acid of the acid source;
HI = hydrophobicity index = the ratio of the number of carbon atoms in the chemical formula of the dicarboxylic acid of the acid source: nurnber of oxygen atoms in the chemical formula of the dicarboxylic acid of the acid source;
pKa, is the logarithm of the reciprocal of the dissociation constant of one of the 25 carboxylic acid groups;
pKa2 is the logarithm of the reciprocal of the dissociation constant of the second carboxylic acid group;
and pKa's 2 10.20 are not taken into consideration.

30 Preferably, the EOI is < 3.40, more preferably < 3.10, even more plefelably < 2.80.
According to an especially plcr.,.lcd embodiment of the present invention the EOI is <

2.40.

Preferably the acid source is fumaric acid, malic acid, maleic acid, tartaric acid, malonic 35 acid, or a derivative thereof. Tartaric acid or a derivative thereof is especially preferred.
Preferred derivatives include salts and esters.

W O 98/04667 PCTrUS97/12896 The values used to calculate the EOI will be known to a skilled worker, but, for ease of reference only, the figures used to calculate the EOI for the plerell~d acid sources are shown below in Table 1.

Table I

Acid Formula MW pKal pKat Malonic C3H404 104.1 2.83 5.69 Fumaric C4H404 1 16.1 3.03 4.44 Maleic C4H404 116.1 1.83 6.07 Malic C4H605 134.1 3.40 5.I l Tartaric C4H606 150.1 2.98 4.34 The source of acidity is plefeldbly present at a level of about to about 15% by weight of the composition. Preferably up to about 10%, more preferably up to about 7% by weight.
As previously mentioned it is advantageous to use as little of the source of acidity as possible, we have found that the present invention allows the use of levels as low as about 0.25% to about 5%. In a ~leÇellc;d embodiment of the present invention the source of acidity is present in the range of about 1% to about 3%, most preferably about 3% by weight of the composition.

The mole ratio of the dicarboxylic acid source to the ~Ik~lin~- source is between 0.005: 1 and 2.00: 1. In a ~l~f~,~lcd embodiment the mole ratio is between 0.008: 1 and 1: 1. In a more pi~,r~ d embodiment, the mole ratio is between 0.01: 1 and 0.07: 1. For example, the molecular weight of funaric acid is 1 16.1 and that of sodium carbonate is 106. Hence, in a detergent composition with 2% by weight fumaric acid and 15% by weight sodium carbonate, the acid: carbonate ratio is [2: 116.1]: [15: 106] = 0.12: 1.

Additional dcter~elll col-lpoll~,llts The dt;lelgelll compositions of the invention may also contain additional detergent colllponen~. The precise nature of these additional components, and levels of incorporation thereof will depend on the physical form of the composition, and the precise nature of the washing operation for which it is to be used.

.

W O 98/0~667 PCTrUS97/12896 The compositions of the invention preferably contain one or more additional detergent components selected from additional surfact~ntc, bleaches, builders, organic polymeric compounds, enzymes, suds suppressers, lime soap di~ s, soil suspension and anti-5 redeposition agents and corrosion inhibitors.

Water-soluble builder compound The detergent compositions of the present invention preferably contain a water-soluble 10 builder compound, typically present at a level of from 1% to 80% by weight, pl~Çclably from 10% to 70% by weight, most preferably from 20% to 60% by weight of the composition.

Suitable water-soluble builder compounds include the water soluble monomeric 15 polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals sepaldled from each other by not more that two carbon atoms, borates, phosph~tec, and mixtures of any of the foregoing.

20 The carboxylate or polycarboxylate builder can be monomeric or oligomeric in type although monomeric polycarboxylates are generally ple~lled for reasons of cost and performance.

Suitable carboxylates cont~inin~ one carboxy group include the water soluble salts of 25 lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
Polycarboxylates cont~ining three carboxy groups include, in particular, water-soluble 30 citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccin~tes described in British Patent No. 1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No. 1,387,447.

. I -Polycarboxylates cont~ining four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates Cn~ ;..g sulfo substituents include the sulfosuccinate 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. ~ler~ d polycarboxylates arehydroxycarboxylates con~ ing up to three carboxy groups per molecule, more particularly citrates.

The parent acids of the mono~ ic or oligomeric polycarboxylate ç~ ting agents ormixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also conte,llplated as useful builder coll,pol~llls.

Borate builders, as well as builders cont~ining borate-forming materials that can produce borate under detergent storage or wash conditions are useful water-soluble builders herein.

Suitable examples of water-soluble phosph~te builders are the alkali metal tripolyphosph~tt?s, sodium, potassium and amrnonium pyrophosphate, sodium and potassium and ~mmnnium pyrophosphate, sodium and potassium orthophosph~te sodium polymeta/phosFh~te in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.

PartiallY soluble or insoluble builder compound The det. lg~ compositions of the present invention may contain a partially soluble or insoluble builder col~,pound, typically present at a level of from 1 % to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% weight of the composlhon.
F.Y~mples of largely water insoluble builders include the sodium aluminosilicates.

Suitable aluminosilicate zeolites have the unit cell formula Naz[(AlO2)z(SiO2)y]. xH2O
wh.,,~:in 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. The aluminosilicate , W O 98/04667 PCTnUS97/12896 material are in hydrated form and are preferably crystalline, cont~ining from 10% to 28%, more preferably from 18% to 22% water in bound form.

The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the design~tions Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS
and mixtures thereof. Zeolite A has the formula Na 12 [AIO2) 12 (sio2)l2]~ xH2O
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na86 [(A1o2)86(sio2) 1 06~ 276 H2O.

Organic peroxvacid bleaching sYstem A pler~lled feature of delelgent compositions of the invention is an organic peroxyacid blearhing system. In one prefc,~d execution the ble~rhing system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound. The production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of 20 hydrogen peroxide. ~l~fe.,~,d sources of hydrogen peroxide include inorganic perhydrate bleaches. In an altern~tive ~ ;f~ d execution a preformed organic peroxyacid is incorporated directly into the composition. Compositions co."~;. .ing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.
Inor~anic perhydrate bleaches Inorganic perhydrate salts are a p,eft~ ,d source of hydrogen peroxide. These salts are normally incol~uolal~d in the forrn of the alkali metal, preferably sodium salt at a level of 30 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 compositions.

Examples of illolganic perhydrate salts include p.,ll,ol~te, pe.c~ul,onate, perphosphate, pçrslllf~te and persilicate salts. The inorganic perhydrate salts are normally the alkali 35 metal salts. The inorganic perhydrate salt may be included as the crystalline solid without additional protection. For certain perhydrate salts however, the preferred W O 98/04667 PCTrUS97/12896 executions of such granular compositions utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product. Suitable co~ting~ comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as waxes, oils, or fatty soaps.
s Sodiurn lucll~orate is a preferred perhydrate salt and can be in the form of themonohydrate of nominal formula NaBO2H2O2 or the tetrahydrate NaBO2H2O2.3H2O.

Alkali metal pelc~l,ollales, particularly sodium pe~;~bullat~ are pl~,Ç~ d perhydrates 10 herein. Sodium p~.c~l,ollâte is an addition compound having a formula coll~J~.onding to 2Na2CO3.3H2O2, and is available commercially as a crystalline solid.

Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in the detergent compositions herein.
Peroxyacid bleach precursor Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precu~sors 20 may be represçntPd as X-C-L

where L is a leaving group and X is ec~enti~lly any functionality, such that on 25 perhydroloysis the structure of the peroxyacid produced is o X-C -OOH

Peroxyacid bleach precursor compounds are preferably incûrporated at a level of from 0.5% to 20% by weight, more preferably from 1% to 15% by weight, most preferablyfrom 1.5% to 10% by weight of the detergent compositions.

Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide range of classes. Suitable W O 98/04667 PCT~US97/12896 classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988,864798,1147871, 2143231 and EP-A-0170386.
s Leaving groups The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the o~ time frame (e.g., a wash cycle).
10 However, if L is too reactive, this activator will be difficult to stabilize for use in a ble~ching composition.

Preferred L groups are selected from the group con~i~ting of:

--0~ O~Y and --0 O ~ O
--N--C--R1 _N N --N--C--CH--R4 R3 ' LJ ' R3 Y
y -O--C H=C--C H=C H2 --O--C H=C--C H=C H2 1~l Y 1~l -O--C--Rl _N' ~NR4 ~C~NR4 ~ Il O

--O--C=CHR4 , and R3 o W O 98/04667 PCT~US97/12896 and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group cont~ining from 1 to 14 carbon atoms, R3 is an alkyl chain conS~ining from 1 to 8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing group. Any of Rl, R3 and R4 may be substituted by e~s~nti~l~y any functional group including, for example alkyl, hydroxy, alkoxy, halogen, S amine, nitrosyl, amide and ~mmonium or alkyl ~mmmonium groups The pler.,.led solubilizing groups are -SO~ M , -C02 M, -SO4-M, -N (R3)4X- and o<--N(R3)3 and most preferably -SO3-M and -CO2-M wherein R3 is an alkyl chain cont~ining from 1 to 4 carbon atoms, M is a cation which provides solubility to the 10 bleach activator and X is an anion which provides solubility to the bleach activator.
Preferably, M is an alkali metal, ammonium or substituted ammoniurn cation, withsodium and potassium being most prefel,ed, and X is a halide, hydroxide, methylsulfate or acetate anion.

15 AlkYI pelca- l~oxylic acid bleach precursors Alkyl percarboxylic acid bleach precursors form pelc~boxylic acids on perhydrolysis.
Preferred precursors of this type provide peracetic acid on perhydrolysis.

20 Piefe~l~,d alkyl pe~ oxylic precursor compounds of the imide type include the N-,N,NlNl tetra acetylated alkylene r~iQmines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene ~ mine (TAED) is particularly ~ d.

25 Other preferred alkyl ~,crc~boxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybell~;elle sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.

Amide substituted alkyl peroxvacid ple~;ulao Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:

O R5 0 or R5 0 0 W O 98/W667 PCTnUS97/12896 wherein Rl is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene group cont~ining from 1 to 14 carbon atoms, and RS is H or an alkyl group cont~inin~ 1 to 10 carbon atoms and L can be eCcenti~lly any leaving group. Amide substituted bleach 5 activator compounds of this type are described in EP-A-0 170386.

Ptll,e,.~oic acid Precursor Pe~ ,.-70ic acid precursor compounds provide pc~ oic acid on perhydrolysis. Suitable 10 O-acylated pC,~ .l~uiC acid precursor compounds include the substituted and unsub~iLuled benzoyl ox~l)el~elle sulfonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl sucçinimide, t~LI~sb~ oyl ethylene ~ mine and the N-benzoyl substituted ureas. Suitable imidazole type perbenzoic acid precursors include N-benzoyl 15 imidazole and N-benzoyl benzimidazole. Other useful N-acyl group-co.ll~ini..f~
perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Cationic peroxyacid precursors Cationic peroxyacid ~ or compounds produce cationic peroxyacids on perhydrolysis.

Typically, cationic peroxyacid precursors are formed by substituting the peroxyacid part 25 of a suitable peroxyacid pre~;u,sor compound with a positively charged functional group, such as an ~mmonium or alkyl ammmonium group, preferably an ethyl or methyl ~ olliurn group. Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion.

30 The peroxyacid precursor compound to be so cationically substituted may be a p~ll,e~Goic acid, or substituted derivative thereof, precursor compound as described hereinbefore. ~Itern~tively, the peroxyacid precursor compound may be an alkyl p~lc~l,oxylic acid p~ or compound or an amide substituted alkyl peroxyacid precursor as described hereinafter W O 98/04667 PCT~US97/12896 Cationic peroxyacid precursors are described in U.S. Patents 4,904,406, 4,751,015;
4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594; EP
475,512, 458,396 and 284,292; and in JP 87-318,332.

5 Examples of plefell~d cationic peroxyacid precursors are described in UK Patent Application No. 9407944.9 and US Patent Application Nos. 08/298903, 08/298650, 08/298904 and 08/298906.

Suitable cationic peroxyacid precursors include any of the ammonium or alkyl 10 ammoniurn substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprol~ct~m~, and monobenzoy}tetraacetyl glucose benzoyl peroxides. P~ef~.led cationic peroxyacid precursors of the N-acylated caprolactarn class include the trialkyl arnmoniurn methylene benzoyl caprolactams and the trialkyl amrnoniurn methylene alkyl caprol~rt~rnc Benzoxazin organic peroxYacid precursors Also suitable are precursor compounds of the benzox~in-type, as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the forrnula:

~(N~C R1 wherein Rl is H, alkyl, alkaryl, aryl, or arylalkyl.

25 Preformed or~anic peroxyacid The organic peroxyacid bleaching system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid, typically at a level of from 1 % to 15% by weight, more preferably from 1 %
30 to 10% by weight of the composition.

W O 98/04667 PCTrUS97/12896 A preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:

O R5 O or R5 O O
s wherein Rl is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group cont~inin~ from 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group cont~ining 1 to 10 carbon atoms. Amide s~slilul~:d organic peroxyacid compounds of this type are described in EP-A-0170386.
Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydo~ec~neAioc acid, diperoxytetr~dec~ne~lioc acid and diperoxyhex~ec~n~lioc acid. Mono- and di,oc;l~zelaic acid, mono- and dipe,l,l~s~ylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.
Bleach catalYst The compositions optionally contain a transition metal cont~inin~ bleach catalyst. One suitable type of bleach catalyst is a catalyst system comprising a heavy metal cation of 20 defined bleach catalytic activity, such as copper, iron or m~n~n~se cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or al..minl~m cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylene~ minetetraacetic acid, ethyl.on~ min~tetra(methylenephosphonic acid) and water-soluble salts thereof. Such 2S catalysts are disclosed in U.S. Pat. 4,430,243.

Other types of bleach catalysts include the m~ng~n~se-based complexes disclosed in U.S.
Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples ofthese catalysts include MnIV2(u-0)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(PF6)2, MnIII2(u-0)1(u-OAc)2( 1 ,4,7-trimethyl- 1 ,4,7-triazacyclononane)2-(ClO4)2, MnIV4(u-o)6( 1,4,7-triazacyclononane)4-(ClO4)2, MnIIIMnIV4(u-O) 1 (u-OAc)2 ( l ,4,7-trimethyl- 1,4,7-triazacyclononane)2-(C1O4)3, and mixtures thereof. Others are described in European patent application publication no. 549,272. Other ligands suitable for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-W O 98/04667 PCT~US97/12896 1,4,7-triazacyclononane, 1,2~4~7-tel~ elllyl- 1,4,7-triazacyclononane, and mixtures thereof.

For examples of suitable bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat.
5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear m~ng~n~se (IV)complexes such as Mn(1,4,7-trimethyl-1,4,7-triazacyclononane)(OCH3)3 (PF6). Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is a water-soluble complex of m~n~nese (III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups. Other examples 10 include binuclear Mn complexed with tetra-N-dentate and bi-N-dentate lig~nrls, including N4MnIII(u-O)2MnIVN4)+and [Bipy2MnIII(u-O)2MnIVbipy2~-(clo4)3.

Further suitable bleach catalysts are described, for example, in E~opeall patentapplication No. 408,131 (cobalt complex catalysts), European patent applications, 15 publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455 (m~ng~nPsP/multidentate ligand catalyst), U.S. 4,711,748 and European patent application, publication no. 224,952, (absorbed m~n~nçse on alllrninosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with m~ng~n.ose and zinc or m~gnesium salt), U.S. 4,626,373 (m~n~n~s~/ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), 20 German Pat. specification 2,054,019 (cobalt chelant catalyst) C~n~ n 866~191 (transition metal-ct ~t~in;l~g salts), U.S. 4,430,243 (chelants with ...~l~g~ -f ~e cations and non-catalytic metal cations), and U.S. 4,728,455 (m~ng~n~se gluconate catalysts).

Heavy metal ion sequestrant The detelge.l~ compositions of the invention preferably contain as an optional component a heavy metal ion sequestrant. By heavy metal ion sequestrant it is meant hereincoll~ollents which act to sequester (chelate) heavy metal ions. These components may also have calcium and m~necium chelation capacity, but plefe.e.,lially they show30 selectivity to binding heavy metal ions such as iron, m~n~n~se and copper.

Heavy metal ion sequestrants 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 compositions.

CA 0226l944 l999-0l-27 W 098/04667 PCTrUS97/12896 Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane l-hydroxy disphosphonates and nitrilo trimethylene phosphonates.

P,efe~l~d arnong the above species are diethylene triamine penta (methylene phosphonate), ethylene ~ min~ tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate.

Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and 10 polyaminocarboxylic acids such as ethyle~e~ ninotetracetic acid, ethylenetriamine pe~t~cetiC acid, ethylene~ mine disuccinic acid, ethylene.li~min~ diglutaric acid, 2-hydroxypropylene~ mine disuccinic acid or any salts thereof. Especially preferred is ethylen~ mine-N,N'-disuccinic acid (EDDS) or the alkali metal, ~lk~line earth metal, amrnoniurn, or substituted ammonium salts thereof, or mixtures thereof.
Other suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-20 sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein. The ~-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also suitable.

EP-A-476,257 describes suitable amino based sequestrants. EP-A-510,331 describes25 suitable sequestrants derived from collagen, keratin or casein. EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are alos suitable. Glycinamide-N,N'-disuccinic acid (GADS), ethylenç~ minP-N-N~-diglutaric acid (EDDG) and 2-hydroxypropylen~ mine-N-N'-disuccinic acid (HPDDS) are also suitable.
Enzyme Another l.lefel~d ingredient useful in the detergent compositions is one or moreadditional enzymes.

Preferred additional enzymatic materials include the comrnercially available lipases, cutin~eS~ amylases, neutral and ~Ik~line proteases, esterases, cellulases, pec-linases, lactases and peroxidases conventionally inc~l~Jo~al~d into detergent compositions.
Suitable enzymes are discussed in US Patents 3,519,S70 and 3,533,139.
s Preferred co,~ elcially available protease enzymes include those sold under the tr~den~nn~s Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S
(Demnark), those sold under the tr~den~me ~t~ce, Maxacal and Ma~ape~.l by Gist-Brocades, those sold by G~ c.-cor Intern~tional, and those sold under the tr~ ...c 10 Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001% to 4%
active enzyme by weight of the composition.

Preferred amylases include, for example, a-arnylases obtained from a special strain of B
licheniformis, described in more detail in GB-1,269,839 (Novo). Preferred commlorcially available amylases include for example, those sold under the tr~l~n~me Rapidase by Gist-Brocades, and those sold under the tr~d~ n~me Termamyl and BAN by Novo Industries A/S. Amylase enzyme may be incol~ordled into the composition in accordance with the invention at a level of from 0.0001 % to 2% active enzyme by weight of the composition.

Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001% to 2% by weight, prefelably 0.001% to 1% by weight, most preferably from 0.001% to 0.5% by weight of the compositions.
The lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pse~1do~lcali~eenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mllt~ntc of these strains are also useful herein. A plefelled lipase is derived from Pseudomonas pseudoalcali~enes. which is described in Granted European Patent, EP-B-0218272.

Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and ~l.les~ g the gene in Aspergillus orvza, as host, as described inEuropean Patent Application, EP-A-0258 068, which is commercially available from W 098/04667 PCT~US97/12896 Novo Industri A/S, Bagsvaerd, Denm~rk, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.

Organic polvmeric compound Organic polymeric compounds are p~ d additional co,l~ponents of the d~ gellt compositions in accord with the invention, and are preferably present as components of any particulate components where they may act such as to bind the particulate component together. By organic polymeric compound it is meant herein es~enti~ly any 10 polymeric organic compound commonly used as dispcrs~,ts, and anti-redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein.
Organic polymeric compound is typically incorporated in the delelgellt composilions of the invention at a level of from 0.1 % to 30%, preferably from 0.5% to 15%, mostpreferably from l % to 10% by weight of the compositions.

Examples of organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid 20 comprises at least t~vo carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the }atter type are disclosed in GB-A- 1,596,756. Examples of such salts are polyacrylates of MWt 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 100,000, especially 40,000 to 80,000.
The polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.

Terpolymers co~ g monomer units select~d from maleic acid, acrylic acid, 30 polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.

Other organic polymeric compounds suitable for incul~ol~lion in the d~telgellt compositions herein include cellulose derivatives such as methylcellulose, 35 carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.

WO 98/04667 PCI/US97tl2896 Further useful organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 400~.

Suds suppressin~e svstem The detergent colllposilions of the invention, when form~ ted for use in m~ in.owashing compositions, preferably comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.05% to 10%, most preferably from 0.1% to 5%
10 by weight of the composition.

Suitable suds su~ ,;.sillg systems for use herein may comprise essentially any known antifoarn compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.
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 detelgellt composition, particularly in the presence of agitation of that solution.

20 Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component.
Such silicone antifoam compounds also typically contain a silica col~ponel~l. The term "silicone" as used herein, and in general throughout the industry, encomp~cses a variety of relatively high molecular weight polymers cont~ining siloxane units and hydrocarbyl 25 group of various types. P,ef.,.l~d silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
Other suitable ~llifo~ll compounds include the monocarboxylic fatty acids and soluble salts thereof. These m~tçri~l~ are described in US Patent 2,954,347, issued September 30 27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammoniurn salts.

35 Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic W O 98/04667 PCT~US97112896 C I g-C40 ketones (e.g. stearone) N-alkylated amino tri~ines such as tri- to hexa-alkylmel~min~os or di- to tetra alkyl~i~min~ chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.

A plef~ d suds suppl~s~ g system comprises (a) antifoam compound, preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination (i) polydimethyl siloxane, at a level of from 50% to 99%, preferably 75% to 95% by weight of the silicone antifoam compound; and (ii) silica, at a level of from 1 % to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound;

wherein said silica/silicone antifoam compound is incorporated at a level of from 5% to 50%, preferably 10% to 40% by weight;
(b) a di~Jersallt compound, most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of from 1 :0.9 to 1: 1.1, at a level of from 0.5% to 10%, preferably 1 % to 10% by weight; a particularly preferred silicone glycol rake copolymer of this type is DCO544, commercially available from DOW Corning under the tr~ on~me DCO544;

(c) an inert carrier fluid compound, most preferably comprising a C 16-c 18 ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;

A highly prefclled particulate suds su~ples~ g system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50~C to 85~C, wherein the organic carrier material comprises a 35 monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate suds s~l.ressillg r W O 98/04667 PCT~US97/12896 systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain cont~ining from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45~C to 80~C.

5 CJaY softenin~ sYstem The d~le~g~l~l co.llposilions may contain a clay softening system comprising a clay mineral compound and optionally a clay flocc~ tin~ agent.

10 The clay mineral compound is preferably a smectite clay compound. Smectite clays are disclosed in the US Patents No.s 3,862,058, 3,948,790, 3,954,632 and 4,062,647.
European Patents No.s EP-A-299,57S and EP-A-313,146 in the name of the Procter and Gamble Company describe suitable organic polymeric clay flocculating agents.

I S Polvmeric dye transfer inhibitin~ agents The detergent compositions herein may also comprise from 0.01% to 10 %, preferably from 0.05% to 0.5% by weight of polymeric dye lldll~. inhibiting agents.

20 The polymeric dye transfer inhibiting agents are preferably selecte~l from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimi~1~7O1e, polyvinylpyrrolidonepolymers or combinations thereof.

a) Polyamine N-oxide polYmers Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula:

(I) . Ax R

wherein P is a polymerisable unit, and W 098/04667 PCT~US97/12896 A is NC, CO, C, -O-, -S-, -N-; x is O or1;

R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be ~t~cht?~l or wherein 5 the nitrogen of the N-O group is part of these groups.

The N-O group can be represented by the following general structures:

(R1 ) X -N-(R2)y (R3)z or N.(R1)x wherein Rl, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be ~ h~c~ or wlle~ the nitrogen of the N-O group forms part of these 15 groups. The N-O group can be part of the polymerisable unit (P) or can be ~ rhld to the polymeric backbone or a combination of both.

Suitable polyarnine N-oxides wherein the N-O group forrns part of the polymerisable unit comprise polyarnine N-oxides wherein R is selected from aliphatic, aromatic, 20 alicyclic or heterocyclic 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 heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
Other suitable polyarnine N-oxides are the polyarnine oxides whereto the N-O group is hPd to the polymerisable unit. A ~ f~l~ed class of these polyamine N-oxides comprises the polyamine N-oxides having the general forrnula (I) wherein R is anaromatic,heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional ,. ,. . I , , ~ ... .. , . , .. " .. _ , ...

group is part of said R group. Examples of these classes are polyamine oxides wherein R
is a heterocyc}ic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.

The polyamine N-oxides can be obtained in almost any degree of polymerisation. The degree of polymerisation 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.

b) CopolYmers of N-vinylpyrrolidone and N-vinvlimidazole Suitable herein are coploymers of N-vinylimid~ole and N-vinylpyrrolidone having an average molecular weight range of from 5,000 to 50,000. The plcf~ d copolymers have a molar ratio of N-vinylimida_ole to N-vinylpyrrolidone from 1 to 0.2.
15 c) Polvvinylpyrrolidone The detergent compositions herein may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from 2,500 to 400,000. Suitable polyvinylpyrrolidones are commercially vailable from ISP Corporation, l~lew York, NY and Montreal, Canada 20 under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), 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 Corporation. Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.
d) PolyvinYloxazolidone The delel~ell~ compositions herein may also utilize polyvinylox~olidones as polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an average molecular 30 weight of from 2,500 to 400,000.
e) PolvvinYlimi~7ole The dt;lel~g~ compositions herein may also utilize polyvinylimid~ole as polymeric dye 35 transfer inhibiting agent. Said polyvinylimid~oles preferably have an average molecular weight of from 2,500 to 400,000.

W 098/04667 PCTrUS97tl2896 OPtical brightener The detergent compositions herein also optionally contain from about 0.005% to 5% by 5 weight of certain types of hydrophilic optical brightçners.

Hydrophilic optical brightçners useful herein include those having the structural formula:

~N H~C=C~NH~N

wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.

15 When in the above formula, Rl is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the bright~ner is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tr~-lPn~me Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener 20 useful in the d~ ent compositions herein.

When in the above formula, Rl is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylarnino)-s-tri~ine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt. This 25 particular bri~htenPr species is comrnercially marketed under the tr~den~me Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the above formula, R1 is anilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[~4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-30 stilbenedisulfonic acid, sodium salt. This particular brightener species is comrnerciallymarketed under the tr~-~en~me Tinopal AMS-GX by Ciba Geigy Corporation.

W 098/04667 PCT~US97/12896 33 Cationic fabric softening a~ents Cationic fabric softening agents can also be incorporated into compositions in accordance with the present invention. Suitable cationic fabric softening agents include 5 the water insoluble tertiary amines or dilong chain arnide materials as disclosed in GB-A-1 514 276 and EP-B-0 011 340.

Cationic fabric softening agents are typically incorporated at total levels of from 0.5% to 15% by weight, normally from 1% to 5% by weight.
Other optional in~redients Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes, colours and filler salts, with sodiurn sulfate being a preferred filler salt.
pH of the compositions The present compositions preferably have a pH measured as a 1% solution in distilled water of at least 10.0, preferably from 10.0 to 12.5, most preferably from 10.5 to 12Ø
Form of the compositions The compositions in accordance with the invention can take a variety of physical forms including granular, tablet, bar and liquid forms. The compositions are particularly the so-25 called concentrated granular detergent compositions adapted to be added to a washingm~chine by means of a dispensing device placed in the m~rhin~ drum with the soiled fabric load.

The mean particle size of the base composition of granular compositions in accordance 30 with the invention should preferably be such that no more that 5% of particles are greater than 1 .7mm in ~ rneter and not more than 5% of particles are less than 0.1 Smm in ~i~m-oter.

The term mean particle size as defined herein is calculated by sieving a sample of the 35 composition into a nurnber of fractions (typically 5 fractions) on a series of Tyler sieves.
The weight fractions thereby obtained are plotted against the aperture size of the sieves.

The mean particle size is taken to be the aperture size through which 50% by weight of the sample would pass.

The bulk density of granular detergent compositions in accordance with the present invention typically have a bulk density of at least 600 g/litre, more preferably from 650 g/litre to 1200 g/litre.Bulk density is measured by means of a simple funnel and cup device con~i~ting 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 funnel to be emptied into an axially aligned cylindrical cup disposed below the funnel. The funnel is 130 mm high and has int~ meters of 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower ~L~ y is 140 mm above the upper surface of the base. The cup has an overall height of 90 mm, an intemal height of 87 mm and an intern~l diameter of 84 mm. Its nominal volurne is 500 ml.

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

The composition is preferably soluble in cold or cool water, i.e. the composition readily dissolves/disperses in water at a telllpe~ re between about 0~C and 32.2~C, preferably between about 1 .6~C and 1 0~C.
Surfactant a~glomerate particles The surfactant system herein is preferably present in granular compositions in the forrn of surfactant agglon~ te particles, which may take the form of flakes, prills, marumes, noodles, ribbons, but preferably take the form of granules. The most preferred way to process the particles is by agglomerating powders (e.g. aluminosilicate, c~bonate) with high active surfactant pastes and to control the particle size of the resultant agglomerates within specified limits. Such a process involves mixing an effective amount of powder with a high active surfactant paste in one or more agglomerators such as a pan 3 5 agglomerator, a Z-blade mixer or more preferably an in-line mixer such as those manufactured by Schugi (~Iolland) BV, 29 Chroomstraat 821 1 AS, Lelystad, r W O 98~4667 PCTfUS97tl2896 Netherlands, and Gebruder Lodige ~ hin~nbau GmbH, D-4790 Paderborn 1, Elsenerstrasse 7-9, Postfach 2050, Germany. Most preferably a high shear mixer is used, such as a Lodige CB (Trade Name).

5 A high active surfactant paste comprising from 50% by weight to 95% by weight,preferably 70% by weight to 85% by weight of surfactant is typically used. The paste may be pumped into the agglomerator at a telllp~ldlule high enough to m~int~in apumpable viscosity, but low enough to avoid degradation of the anionic surf~ct~nt~ used.
An op.,lathlg ~elllp~ldlllre of the paste of 50~C to 80~C is typical.
In an especially ple~ d embodiment of the present invention, the dt~ ent composition has a density of greater than about 600 g/l and is in the form of powder or a granulate cont~ining more than about 5% by weight of the alkali source, preferably (bi-)c~bonate or percarbonate. The alkali material is either dry-added or delivered via 15 agglomerates. The addition of acid source(up to 10%) may be introduced into the product as a dry-add, or via a se,.aldte particle.

Laundrv washin~ method 20 Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing m~cllin~ having dissolved or dispensed therein an effective arnount of a m~hine laundry detergent composition in accord with the invention. By an effective amount of the detergent composition it is meant from 40g to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, 25 as are typical product dosages and wash solution volumes commonly employed in conventional m~rhine laundry methods.

In a preferred use aspect a dispensing device is employed in the washing method. The di~y~ ing device is charged with the d~lel~e"t product, and is used to introduce the 30 product directly into the drum of the washing machine before the commencenn~nt of the wash cycle. Its volume capacity should be such as to be able to contain sufficient dele~ l product as would normally be used in the washing method.

Once the washing .llachillc has been loaded with laundry the dispensing device 35 co..~ g the detergent product is placed inside the drum. At the commen~-en~ nt of the wash cycle of the washing m~l~.hine water is introduced into the drum and the drurn . ~ .

W O 98104667 PCT~US97112896 periodically rotates. The design of the dispensing device should be such that it permits containment of the dry detergent product but then allows release of this product during the wash cycle in response to its agitation as the drum rotates and also as a result of its contact with the wash water.
s To allow for release of the detergent product during the wash the device may possess a number of openings through which the product may pass. Alternatively, the device may be made of a material which is permto~ble to liquid but i~ eable to the solid product, which will allow release of dissolved product. Preferably, the d~ rgelll product will be rapidly released at the start of the wash cycle thereby providing transient localised high concentrations of product in the drum of the washing m~rlline at this stage of the wash cycle.

Preferred dispensing devices are reusable and are design~ in such a way that container integrity is m~int~in~d in both the dry state and during the wash cycle. Especially ~ref~"~d dispensing devices for use with the composition of the invention have been described in the following patents; GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345 and EP-A-0288346. An article by J.Bland published in ~nnf~rtllring Chemist, November 1989, pages 41-46 also describes especially preferred ~ p~n~ing devices for use with granular laundry products which are of a type commonly know as the "granulette". Another ~ ;d dispensing device for use with the compositions of this invention is disclosed in PCT Patent Application No. WO94/11562.

Especially preferred di~pton~ing devices are disclosed in European Patent Application Publication Nos. 0343069 & 0343070. The latter Application discloses a device comprising a flexible sheath in the form of a bag exten~ing from a support ring defining an orifice, the orifice being adapted to admit to the bag sufficient product for one washing cycle in a washing process. A portion of the washing medium flows through the orifice into the bag, dissolves the product, and the solution then passes outwardly through the orifice into the washing medium. The support ring is provided with am~cking arrangemnt to prevent egress of wetted, undissolved, product, this arrangement typically comprising radially e~cten~ling walls e~cten~ling from a central boss in a spoked wheel configuration, or a similar structure in which the walls have a helical form.

Alternatively, the dispensing device may be a flexible container, such as a bag or pouch.
The bag may be of fibrous construction coated with a water imperrneable protective r material so as to retain the contents, such as is disclosed in European published Patent Application No. 0018678. Alternatively it may be formed of a water-insoluble synthetic polymeric material provided with an edge seal or closure designed to rupture in a~ueous media as disclosed in European published Patent Application Nos. 0011500, 0011501, 0011502, and 0011968. A convenient form of water frangible closure comprises a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene.

Pac~ginp for the compositions Commercially marketed executions of the ble~çhing compositions can be packaged in any suitable container including those constructed from paper, cardboard, plastic materials and any suitable l~min~tes A preferred p~ ing execution is described in European Application No. 94921505.7. An especially preferred container is a double 15 bag. Preferably any container is water-insoluble.

Example 1 - Colllua,dlive Pc.ro-l,lance Testing The following e~ e,l~ illustrate the benefits of using a formulation of the present 20 invention. More particularly we found that the formulation of the present invention showed a significant improvement at least in terms of the dispensing profile under stressed conditions (i.e. low water pressure and te~peldLu~e) coll,~aled to the same formulation without the source of acidity having the particle size distribution of the present invention.
Test Protocol A Hotpoint automatic washing m~rhin~ was employed, and a 2 minute 20~C cycle selected. 150 g of dt:telgcl,l dispensed via the dispenser drawer was used. The water flow 30 rate into the m~çhine was set at 2.0 Vminute.

The results are shown below in Table 2.

Table 2 W 098/04667 PCT~US97/12896 Dicarboxylic acid % Residues left in EOI
dispensing drawer Fumaric 17 2.8 Malic 20 3.1 Maleic 24 3 4 Tartaric 25 2.4 Malonic 25 2.4 Ascorbic 31 28.9 Aspartic 41 55.5 Adipic 41 7.9 Abbreviations used in following Examples In the detergent compositions, the abbreviated component identifications have the 5 following me~ni~

LAS : Sodium linear C12 alkyl benzene sulfonate TAS : Sodiumtallowalkyl sulfate C45AS : Sodium C l 4-C 15 linear alkyl sulfate CxyEzS : Sodium Clx-Cly branched alkyl sulfate con.len.ced with z moles of ethylene oxide C45E7 : A C 14-15 predominantly linear primary alcohol con~emed with an average of 7 moles of ethylene oxide C25E3 : A C12 15 branched primary alcohol con-~ence~l with an average of 3 moles of ethylene oxide C25E5 : A C12 15 branched primary alcohol con~len~e~ with an average of 5 moles of ethylene oxide CEQ : RlcoocH2cH2 N+(CH3)3 with R1 = C11-C13 QAS : R2.N+(CH3)2(C2H4OH) with R2 = C12 ~ C14 Soap : Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut oils.
TFAA : C 16-C 18 alkyl N-methyl gl~.c~mitl.
TPKFA : C12-C14 topped whole cut fatty acids STPP : Anhydrous sodium tripolyphosphate Zeolite A : Hydrated Sodium Aluminosilicate of formula Nal2(A102SiO2)12. 27H20 having a primary particle size in the range from 0.1 to 10 micrometers NaSKS-6 : Crystalline layered silicate of formula ~ -Na2si2os Citric acid : Anhydrous citric acid Carbonate : Anhydrous sodium carbonate with a particle size between 200 ~m and 900~m Bicarbonate : Anhydrous sodium bicarbonate with a particle size distribution between 400~1m and 1 200~1m Silicate : Arnorphous Sodium Silicate (SiO2:Na20; 2.0 ratio) Sodium sulfate : Anhydrous sodium sulfate Citrate : Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425~m and g50~m MA/AA : Copolymer of 1:4 maleic/acrylic acid, average molecular weight about 70,000.
CMC : Sodiumcarboxymethyl cellulose Protease : Proteolytic enzyme of activity 4KNPU/g sold by NOVO Industries A/S under the traden~me Savinase Alcalase : Proteolytic enzyme of activity 3AU/g sold by NOVO Industries A/S
Cellulase : Cellulytic enzyme of activity 1000 CEVU/g sold by NOVO Industries A/S under the tradçn~me Carezyme Arnylase : Arnylolytic enzyme of activity 60KNU/g sold by NOVO Industries A/S under the tr~dton~me Terrnamyl 60T
Lipase : Lipolytic enzyme of activity 1 00kLU/g sold by NOVO Industries A/S under the tradPn~me Lipolase Endolase : Endoglunase enzyme of activity 3000 CEVU/g sold by NOVO Industries A/S
PB4 : Sodium p~,lbuldl~ tetrahydrate of nominal formula NaB02.3H20 H202 PB 1 : Anhydrous sodium perborate monohydrate bleach of nominal formula NaBO2.H2O2 Percarbonate : Sodium Pelc~l,onate of nominal forrnula W O 98/04667 PCTrUS97tl2896 2Na2Co3-3H2o2 NOBS : Nonanoyloxybenzene sulfonate in the form of the sodium salt.
TAED : Tetraacetylethylene~i~minto DTPMP: Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Trade name Dequest 2060 Photoactivated : Sulfonated Zinc Phthlocyanine enc~ps~ t~d in bleach dextrin soluble polymer Bri~htçn~r I : Disodium4,4'-bis(2-sulphostyryl)biphenyl Bri~hten~or 2 : Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-tri~in-2-yl)amino) stilbene-2:2'-disulfonate.
HEDP : 1, I -hydroxyethane diphosphonic acid PVNO : Polyvinylpyridine N-oxide PVPVI : Copolymer of polyvinylpyrolidone and vinylimid~ole SRP 1 : Sulfobenzoyl end capped esters with oxyethylene oxy and terephtaloyl backbone SRP 2 : Diethoxylated poly (1, 2 propylene terephtalate) short block polymer Silicone antifoam: Polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1.
Alkalinity : % weight equivalent of NaOH, as obtained using the alkalinity release test method described herem.

In the following Examples all levels are quoted as % by weight of the composition:

30 Exarnple I

The following granular laundry d~lcrgelll compositions A and B of bulk density 750 g/litre were prepared in accord with the invention:

A ¦ B

LAS 5.61 4.76 TAS 1.86 1.57 C45AS 2.24 3.89 C25AE3S 0.76 1.18 C45E7 - 5.0 C25E3 5.5 CEQ 2.0 2.0 STPP
Zeolite A 19.5 19.5 NaSKS-6/citric acid (79:21) 10.6 10.6 Carbonate 21.4 21.4 Bicarbonate 2.0 2.0 Silicate Sodium sulfate - 14.3 PB4 12.7 TAED 3.1 DETPMP 0.2 0.2 HEDP 0.3 0.3 W O 98/04667 PCTrUS97/12896 Protease 0.85 0.85 Lipase 0.15 0.15 Cellulase 0.28 0.28 Amylase 0.1 0.1 MA/AA 1.6 1.6 CMC 0.4 o 4 Photoactivated bleach (ppm)27 ppm 27 ppm Brighten~r 1 0.19 O.lg Brightener 2 0.04 0.04 Perfùme 0.3 0.3 Silicone antifoarn 2.4 2.4 Tartaric acid 1.5 2.0 Minors/misc to 100%

Example 3 The following detergent formulations, according to the present invention were prep~red, S where C is a phosphorus-cont~ining detergent composition, E~ is a zeolite-cont~ining detergent composition and E is a compact detergent composition:

C D E

Blown Powder STPP 14.0 - 14.0 Zeolite A - 20.0 C45AS 9.0 6.0 8.0 MA/AA 2.0 4.0 2.0 LAS 6.0 8.0 9.0 TAS 2.0 - -CEQ 1.5 3.0 3.5 Silicate 7.0 8.0 8.0 CMC 1.0 1.0 0.5 BrightPner 2 0.2 0.2 0.2 Soap 1.0 1.0 1.0 DTPMP 0.4 0.4 0.2 Spray On C45E7 2.5 2.5 2.0 C25E3 2.5 2.5 2.0 Silicone antifoarn 0.3 0.3 0.3 Perfume 0.3 0.3 0.3 Dry additives Carbonate 26.0 23.0 25.0 PB4 18.0 18.0 10 PB 1 4.0 4.0 0 TAED 3.0 3.0 1.0 Photoactivated bleach 0.02 0.02 0.02 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Arnylase 0.25 0.30 0.15 Dry mixed sodium sulfate 3.0 3.0 5.0 Malicacid 2.5 2.0 5.0 Balance (Moisture & 100.0 100.0 100.0 Mi~cell~nloous) Density (g/litre) 630 670 670 Example 4 The following nil bleach-cor-l~ining detergent formulations of particular use in the S washing of colored clothing, according to the present invention were prepared:

, . . . .

W O 98/04667 PCT~US97/12896 F G
Blown Powder Zeolite A 15.0 Sodium sulfate LAS 3.0 CEQ 2.0 1.3 DTPMP 0.4 CMC 0.4 MA/AA 4.0 Agglomerates C45AS - 11.0 LAS 6.0 TAS 3.0 Silicate 4.0 Zeolite A 10.0 13.0 CMC - 0.5 MA/AA - 2.0 Carbonate 9.0 7.0 Spray On Perfume 0.3 0.5 C45E7 4.0 4.0 C25E3 2.0 2.0 Dry additives MA/AA - 3.0 NaSKS-6 - 12.0 Maleic acid 4.0 3.0 Citrate 10.0 8.0 Bic&ll,onate 7.0 5.0 Carbonate 8.0 7.0 PVPVI/PVNO 0.5 0.5 Acalase 0.5 0.9 Lipase 0.4 0.4 Amylase 0.6 0.6 Cellu}ase 0.6 0.6 Silicone antifoam 5.0 5.0 .

W O 98/04667 PCT~US97tl2896 Dry additives Sodium sulfate 0.0 0.0 Balance (Moisture and Miscellaneous) 100.0 100.0 Density(g/litre) 700 700 Example S

The following detergent formulations, according to the present invention were plelJa~cd:

H I J K

LAS 12.0 12.0 12.0 10.0 QAS 0.7 1.0 - 0.7 TFAA - 1.0 - -C25E5/C45E7 - 2.0 - 0.5 C45E3S - 2.5 CEQ - - - 1.0 STPP 30.0 18.0 15.0 Silicate 9.0 7.0 10.0 Carbonate 15.0 10.5 15.0 25.0 Bicarbonate - 10.5 - -DTPMP 0.7 1.0 SRP 1 0.3 0.2 - 0.1 MA/AA 2.0 1.5 2.0 1.0 CMC 0.8 0.4 0.4 0.2 Protease 0.8 1.0 0.5 0.5 Amylase 0.8 0.4 - 0.25 Lipase 0.2 0.1 0.2 0.1 Cellulase 0.15 0.05 Photoactivated 70ppm 45ppm - 1 Oppm bleach (ppm) Bright~n~ r 1 0.2 0.2 0.08 0.2 PB 1 6.0 2.0 NOBS 2.0 1.0 .

W O 98/04667 PCT~US97/12896 Malonicacid 3.5 5 0 3.0 2.0 Balance (Moisture 100 100 100 100 and Miscellaneous) Exarnple 6 The following detergent formulations, according to the present invention were prepared:
s L M N

Blown Powder Zeolite A 10.0 15.0 6.0 Sodium sulfate 19.0 5.0 7.0 MA/AA 3.0 3.0 6.0 LAS 10.0 8.0 10.0 C45AS 4.0 5.0 7.0 CEQ - 2.0 Silicate - 1.0 7.0 Soap - - 2.0 Brightener 1 0.2 0.2 0.2 Carbonate 28.0 26.0 20.0 DTPMP - 0.4 0.4 Spray On C45E7 1.0 1.0 1.0 Dry additives PVPVI/PVNO 0.5 0.5 0.5 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Arnylase 0.1 0.1 0.1 Cellulase 0.1 0.1 0.1 NOBS - 6.1 4.5 PB 1 1.0 5.0 6.0 Sodium sulfate - 6.0 Tartaric acid 2.5 2.5 2.0 W O 98/04667 PCT~US97/12896 Balance (Moisture and 100 100 100 Miscellaneous) Example 7 The following high density and bleach-cont~ining d~h~ t formulations, according to 5 the present invention were prepared:

O P

Blown Powder Zeolite A 15.0 15.0 Sodim sulfate 0.0 0.0 LAS 3.0 3.0 QAS - 1.5 DTPMP 0.4 0.4 CMC 0.4 04 MA/AA 4.0 2.0 Agglomerates LAS 4.0 4.0 TAS 2.0 1.0 Silicate- 3.0 4.0 Zeolite A 8.0 8.0 Carbonate 8.0 6.0 Spray On Perfume 0.3 0.3 C45E7 2.0 2.0 C25E3 2.0 Dry additives Fumaric acid 2.0 3.0 Citrate 5.0 2.0 Bicarbonate Carbonate 8.0 l 0.0 TAED 6.0 5.0 PBl 14.0 10.0 W 098/04667 PCTrUS97/12896 Polyethylene oxide of MW 5,000,000 - 0.2 Bentonite clay - 10.0 Protease 1.0 1.0 Lipase 0.4 0.4 Amylase 0.6 0.6 Cellulase 0.6 0.6 Silicone antifoam S.0 5.0 Dry additives Sodiurn sulfate 0.0 0.0 Balance (Moisture and 100.0 100.0 Miscellaneous) Density (g/litre) 850 850 Exarnple 8 S The following high density detergent formulations, according to the present invention were prepaled:

Q R

Agglomerate C45AS 11.0 14.0 Zeolite A 15.0 6.0 Carbonate 4.0 8.0 MA/AA 4.0 2.0 CMC 0.5 0.5 DTPMP 0.4 0.4 Spray On C25E5 5.0 5.0 Perfume 0.5 0.5 Dry Adds Maleic acid 1.5 2.0 HEDP 0.5 0.3 W O 98/04667 PCT~US97/12896 SKS 6 13.0 10.0 Citrate 3.0 1.0 TAED 5.0 7.0 Percarbonate 20.0 20.0 SRP 1 0.3 0.3 Protease 1.4 1.4 Lipase 0.4 0-4 Cellulase 0.6 0.6 Arnylase 0.6 0.6 Silicone antifoarn 5.0 5.0 Bri~hten~?r 1 0.2 0.2 Brightener 2 0.2 Balance (Moisture and 100 100 Miscellaneous) Density (g/litre) 850 850 .

Claims (11)

WHAT IS CLAIMED IS:

1. A detergent composition comprising a detergent surfactant, a dicarboxylic acid source and an alkaline source wherein said dicarboxylic acid source and alkaline source are capable of reacting together to produce a gas; said dicarboxylic acid source has an effervescence optimum index (EOI) of ~ 4.00, where EOI = [MW x HI] x [10.2 - pKa1]-1 x [10.2 - pKa2]-1 MW = molecular weight of the dicarboxylic acid of the acid source;
HI - hydrophobicity index = ratio of the number of carbon atoms in the chemical formula of the dicarboxylic acid of the acid source: number of oxygen atoms in the chemical formula of the dicarboxylic acid of the acid source;
pKa1 is the logarithm of the reciprocal of the dissociation constant of one of the carboxylic acid groups;
pKa2 is the logarithm of the reciprocal of the dissociation constant of the second carboxylic acid group;
and pKa's ~ 10.20 are not taken into consideration;
and the mole ratio of the dicarboxylic acid source to the alkaline source is between 0.005 :1 and 2.00:1;
with the proviso that the detergent composition does not contain an alkali metalchloroisocyanurate.

2. A detergent composition according to claim 1 wherein the EOI is ~ 3.40, 3.10, 2.80 or 2.40.

3. A detergent composition according to claim 1 wherein the dicarboxylic acid source is fumaric acid, malic acid, maleic acid, tartaric acid, malonic acid, or a salt or ester thereof.

4. A detergent composition according to any preceding claim wherein the alkalinesource comprises an alkaline salt selected from an alkali metal or alkaline earth metal carbonate, bicarbonate, sesqui-carbonate or alkali metal percarbonate salt..

5. A detergent composition according to any preceding claim wherein the mole ratio between 0.008:1 and 1:1 or 0.01:1 and 0.07:1.

6. A detergent composition according to any preceding claim wherein the surfactant is present in an amount greater than 1.0% by weight of the composition.

7. A detergent composition according to any preceding claim in the form of a granular detergent composition.

8. A detergent composition according to claim 7 wherein the acid source or alkaline source is added as a separate granular component.

9. A detergent composition according to any preceding claim wherein the composition further comprises a detergent builder.

10. A method of manufacturing the detergent composition of any preceding claim comprising mixing the detergent surfactant, acid source and alkaline source.

11. A method of washing laundry in a domestic washing machine comprising, introducing into a dispensing device which is placed in the drum of the washing machine, or introducing into the dispensing drawer of a washing machine an effective amount of a detergent composition of any one of claims 1 to 9.