CA2226637A1 - Laundry washing method - Google Patents

Abstract

There is provided a method of washing soiled laundry in a domestic or industrial washing machine wherein a delivery means is provided for dispensing an effective amount of a detergent composition directly to the drum of a washing machine before the commencement of the wash and subsequently enabling release of said detergent composition to the wash liquor during the wash. Said detergent composition contains a cationic ester surfactant and an alkalinity system comprising alkaline salts. The delivery means enables the delivery of said cationic ester surfactant to said soiled laundry prior to the establishment of an alkaline wash liquor environment around the soiled laundry. A washing method including a pretreatment step is also provided.

Description

CA 02226637 l998-0l-l2 Laundry washin~ method Technical field This invention relates to a method of washing laundry in a domestic or industrial washing machine, and more especially to such a method wherein a detergent composition cont~ininp a cationic ester surfactant is delivered directly to the soiled fabrics in the early stages of the wash.

BackDloulld to the invention The satisfactory removal of greasy soils/stains, that is soils/stains having a high proportion of triglycerides or fatty acids, is a challenge faced by the form~ tor of detergent compositions for use in machine laundry hing methods. Surf~ct~nt components have traditionally been employed in deter~ent products to facilitate the removal of such greasy soils/stains. In particular, surf~ct~nt ~y~Lems comprising cationic esters have been described for use in greasy soil/stain removal.

For example, EP-B-21,491 discloses detergent compositions cont~inin~ a nonionic/cationic surfactant mix~-re and a builder mixture comprising minosilicate and polycarboxylate builder. The cationic surfactant may be a cationic ester. Improved particulate and greasy/oily soil removal is described.

US-A~,228,042 discloses biodegradable cationic surfactants, including cationic ester surfactants for use in detergent compositions to provide STIT~ITE SX~T ~R~ E 26) ~ =

W O 97/03161 PCTrUS96/11282 greasy/oily soil removal. The combination of these cationic surfactants with nonionic surfactants in compositions designed for particulate soil removal is also described. Anionic surfactants are disclosed as optional components of the compositions, but are present at low levels relative to the cationic surfactant component.

US-A-4,239,660 discloses laundry detergent compositions cont~ininf~
cationic ester surfactant and nonionic surfactant at defined weight ratios and an ~lk~linity source. The ~lk~linity source enables a wash solution having a pH of from 8 to 10 to be formed within 3 minlltee of dissolution of the composition in water at 100~F (37~C) at a solution concentration of 0.15% .

US-A-4,260,529 discloses laundry detergent compositions having a pH of no greater than 11 cont~ining cationic ester surfactant and nonionic suAactant at defined weight ratios. Anionic surfactants are disclosed as optional components of the compositions, but are present at low levels relative to the cationic ester surfactant component.

The Applicants have now found that the in solution stability of the cationic ester surfactant is reduced in the presence of a highly ~lk~lin~
wash environment. It is believed that the origin of this problem is the hydrolysis of the ester linkage of the cationic ester surfactant, which accurs more rapidly in highly ~lk~line conditions and which thereby leads to degradation of the surfactant.

The Applicants have now found that a solution to this problem may be achieved if tlie cationic surf~ct~nt is delivered directly to the soiled fabricsprior to the establiehment of a highly ~lk~line environment around the fabrics by an ap~ro~liately ~leei~ned delivery means. The delivery means may, in a prefer~ed execution, comprise a dispensing device enabling delivery of detergent directly to the soiled fabrics via a dispensing aperture.

Dispensing devices in the form of flexible containers, such as bags or pouches but having no ~ie~inct dispensing aperture are known in the art, SUBSTI~UTE S~ ULE 26) W O 97/03161 PCT~US96/11282 but are not suitable for use in the laundry method of the current invention.
The containers are typically made from water-insoluble, but water-permeable material. Dispensing of the detergent product occurs as wash water perme~t~ the container thereby dissolving the cont~in~-l detergellt product which can then pass as a solution into the wash through the container walls. Such containers are not suitable herein in that the surf~ct~nt components have a tendency to gel inside the container and thus to be dispensed more slowly, as opposed to simple ~Ik~line salt components which dissolve rapidly and thus dispense rapidly. An ~lk~lin~
wash environment is thus established prior to the release of the cationic ester surf~ct~nts.

Similarly, laundry detergent dispensing means in the form of detergent impre~n~te~l fabric sheets are known in the art, but are also not suitable for use in the laundry method of the current invention. Such sheets are typically made from water-insoluble, but water-permeable material.
Dispensing of the detergent product occurs as wash water contacts the sheet thereby dissolving the impre~n~t~-l detergent product which is then released as a solution into the wash. One problem with such dispensing means is that the impre n~te~ fabric sheets tend to get enfolded or trapped with the soiled laundry in the wash which hampers dispensing.
Furthermore, the surf~ct~nt components again have a tendency to gel and thus form a gel~tinous surface on the fabric sheet which delays dispensing, as opposed to any simple ~lk~line salt components which dissolve rapidly and thus dispense rapidly. This again leads to ~Ik~lin~
wash environment being established prior to the release of any cationic ester surf~ct~ntc.

The Applicants have also found an alternative but related solution to the problem of decrease in stain removal performance as a result of cationic ~ ester ~lk~linP hydrolysis in the wash. Direct delivery of cationic ester surfactant to the soiled fabrics prior to the establishment of a highly ;31k~1ine environment around the fabrics may also be achieved by a~ropliate pretreatment of the fabrics with a detergent cont~inin~ the cationic ester surf~ct~nt.

SUBSTITlJTE SHEET (~ULE 26 WO 97/03161 PCT~US96/11282 In a ~reft;lled aspect, the soiled fabrics are pretreated prior to their introduction into the washing m~chin~ with a liquid detergent composition formulated to a relatively low pH (i.e. pH < 9) and cont~inin~ ~lk~line components having effect only during the wash. In another preferled aspect, the soiled fabrics are pleli~ated with a dete~ t composition cont~ininF~ cationic ester surf~ct~nt but no ~lk~line components. A second dete~gcnt composition including ~lk~line components may then be employed in the wash cycle.

All docllments cited in the present description are, in relevant part, incorporated herein by reference.

S~mm~ry of the Invention According to the present invelltion there is provided a m~othori of washing soiled laundry in a domestic or infhlctrial washing m~c.hine wherein a delivery means is provided for dispencin~ an effective amount of a delel~cllt composition directly to the drum of a washing nl~chinP before the commencement of the wash and subsequently enabling release of said delergent composition to the wash liquor during the wash wherein said delel~ent composition contains (a) from 1 % to 90% by weight of the detergent composition of a cationic ester surf~t-t~nt and (b) from 1.5% to 95~o of the detergent composition of an ~lk~linity ~y~elll co~ lising ~lk~lin~ components selected from the group concicting of aL~cali metal or ~lk~lin~ earth carbonate, bicarbonate, hydroxide or eili~te, in~ in~ cryst~lline layered silic~te~ salts and any mi~t~res thereof characterized in that said delivery means enables the delivery of said cationic ester surfactant to said soiled laundry prior to the establichmpnt of a hydrolysing ~lk~linP wash liquor environment around the soiled laundry.
SUBSTITUTE SHEET (RULE 26) W O 97/03161 PCTnUS96/11282 In a preferred aspect, the cationic ester surfactant is selected from those having the formula:

R5 1+
R~ (C~nO b (~u (CH2)m-(~V-(CH~)t-N-R3 M
-a wherein R1 is a Cs-C31 linear or branched alkyl1 alkenyl or alkaryl chain or M-. N+(R6R7R8)(CH2)S; X and Y, independently, are selected from the group con~i.ctin~ of COO, OCO, O, CO, OCOO, CONH,NHCO, OCONH and NHCOO wherein at least one of X or Y is a COO, OCO, OCOO,OCONH or NHCOO group; R2, R3, ~, R6, R7, and R8 are independently selected from the group consisting of alkyl, alkenyl, hydroxyaLkyl, hydroxy-alkenyl and aL~caryl groups having from 1 to 4 carbon atoms; and Rs is indepen~çntly H or a C1-C3 alkyl group;
wherein the values of m, n, s and t independently lie in the range of from 0 to 8, the value of b lies in the range from 0 to 20, and the values of a, u and v independently are either 0 or 1 with the proviso that at least one of u or v must be 1; and wherein M is a counter anion.

According to another aspect of the invention, there is provided a method of w~chin~ soiled laundry having a pretreat step comprising application of an effective amount of a deLelgel,t composition directly to the soiled laundry before subjecting the soiled laundry to a washing step wherein said deter~ent composition contains (a) from 0.1 ~o to 90~o by weight of the detergent composition of a cationic ester surfactant; and (b) from 10% to 99.9% of the detergent composition of detergent components selected from additional surfactants, bleaches, builders, ~lk~linity sources, organic polymeric compounds, enzymes, suds SUBSTITUTE SHEET (hULE 2~) W O g7/03161 P ~ nUS96/11282 suppressors, lime soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors charac~eli~ed in that said pretreat step enables the delivery of said cationic ester surf~ct~nf to said soiled laundry prior to the establichm~-nt of an ~Ik~line wash liquor environment around the soiled laundry.

Detailed description of the invention Laundry washin~ method Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a defined laundry deter~el~t composition. By an effective amount of the detel~e.lt composition ;t is typically meant from 20g to 300g of product dissolved or dispersed in a wash solution of volume from 3 to 65 litres, as are common product dosages and wash solution volumes commonly employed in conventional machine laundry methods. In practice, dosage will alter in accordance with the size of the laundry load and degree of soiling.

A delivery means is employed in the washing method of the invention to directly deliver an effective amount of detergent product to the drum of the washing m~chin~ before comm~on~ ement of the wash cycle and to enable release of the detergent product into the wash liquor, particularly during the early stages of the wash, more particularly during the first two ...i..l.les of the wash. In an essential aspect, the delivery means enables the delivery of cationic ester surfactant to the soiled laundry prior to the establi~hm~nt of a hydrolysing ~lk~line wash liquor environment around the soiled laundry.

By hydrolysing ~lk~line wash liquor environment herein it is meant a wash liquor environment that is sufficiently and sustainedly ~lk~line as to cause si~nific~nt and rapid hydrolysis of the ester linka~e of the cationic ester surfactant, such that its surf~ct~nt capability is reduced. In particular, this means a pH environment of greater than 9, particularly SUBSTITVTE S11EET (~ULE ~~~3 CA 02226637 l998-0l-l2 W O 97/03161 P~l/U~r~/11282 greater than 10. Higher temperatures can also serve to promote the hydrolysis reaction.

In one plert;rred aspect said delivery means is a dispensing device having a defined dispensing aperture, particularly one of cross-sectional area greater than S cm2, preferably greater than 7 cm2. The dispensing device is charged with the deter~ent product, and is used to introduce the product directly into the drum of the w~chin~ m~t~hin~. Its volume capacity should be such as to be able to contain sufficient detel~ellt product as would normally be used in the w~chin~ method without having to compress the product in the device, which would reduce its release rate.

Once the washing machine has been loaded with laundry the dispensing device cont~inin~ the detergent product is placed inside the drum on top of the laundry load, and preferably ~ cent to the most soiled areas of the fabrics in the laundry load. At the comm~n~e-m~nt of the wash cycle of the w~chin~ m~rhine water is intro~llce-l into the drum and the drum periodically rotates. As the drum rotates the delergent product is dispensed from the dispensing aperture and thus is delivered directly to the soiled laundry. The device may possess more than one dispensing aperture through which the product may be dispensed in response to its agitation in the rotating drum. Preferably, the detergent product will be rapidly released at the start of the wash cycle thereby providing tr~ncient localised high concçntrations of product in the drum of the w~chin~
machine at this stage of the wash cycle.

r~efe,red dispensing devices are reusable and are ~esi~n~ in such a way that container integrity is m~int~ine~l in both the dry state and during the wash cycle. Especially ~lefei~ed dispensing devices for use in accord with the invention have been described in the following patents;
GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A~201376, EP-A-0288345 and EP-A-0288346. An article by J.Bland published in ~m-f~ctl-ring ~ Chemist, November 1989, pages 41-46 also describes especially ~refelred dispensing devices for use with granular laundry products which are of a type com~nonly know as the "granulette". Another preferred dispensing SUBSTITUTE Sl~ T (P~UL~ s~ ~7 W O 97/03161 PCT~US96/11282 device for use in accord with the invention is disclosed in PCT Patent Application No. WO 94/11562.

~specially preferred dispensing devices are disclosed in European Patent Application Publication Nos. 0343069 & 0343070. The latter Application discloses a device comprising a flexible sheath in the form of a bag e~tt-.n~lin~ from a support ring defining an orifice, the orifice being adapted to admit to the bag sufficient product for one washing cycle in a w~hin~ process and to allow for its dispçn.~ing during the early stages of the wash cycle. The support ring is provided with a m~kin~ arrangemnt to prevent egress of wetted, undissolved, product, this arrangement typically comprising radially exten-lin~ walls extending from a central ~boss in a spoked wheel configuration, or a ~imil~r structure in which the walls have a helical form.

In another aspect the delivery means is provided by comr~ctin~ a d~lcrgcl~t composition cont~ining both cationic ester and ~lk~lin~
components into a tablet formed such as to provide release of cationic ester surf~cPnt to the soiled laundry prior to the full release of any ~lkz~lin~s. components. The tablets are then introduced directly to the drum of the w~hin~ m~hine prior to commencement of the wash cycle.

In a l,refel~ed aspect, t_e tablet comprises layers of distinct productc~omposition with the cationic ester surf~ct~nt, being present in a layer outwardly located relative to the layer comprising the ~lk~linity ~y~lelll, and preferably fully separated from that layer.

Pretreat waSiiin~ method According to another aspect of the present invention, the direct delivery of cationic ester surfactant to the soiled fabrics prior to the establishrnent of a hydrolysing ~Ik~line enviro~ment around the fabrics may also be achieved by pretre~tment of the fabrics with a detergent composition cont~ininP the cationic ester surfactant.

SUBSTlTUTE SHEET (RULE 26) W O 97/03161 PCTnUS96tll282 For the avoidance of doubt, l~lcl~e~tmPnt herein means the direct application of a pielre~tment detel~ent composition to a soiled fabric prior to subjecting the soiled fabric to a washing step. The l,lelre~tmPnt composition is generally fluid in nature, that is a solution, liquid, gel, foam or mousse. Application may be achieved by any suitable means including pouring the fluid l,~ell~at composition on the fabric possibly using a suitable dosing means, spray application of a mousse or foam, or applying the fluid using an applicator means such as a sponge or a brush.
rrereldbly, the ~lelle~ nt composition is then m~ml~lly rubbed into the soiled fabric. The ~rel~eat composition is allowed to remain in contact with the soiled fabric for an effective time interval prior to subjecting the ,relleated fabric to the w~shing step. Said time interval will typically be from 10 seconds to 1800 seconds, more preferably from 60 seconds to 600 seconds. The subsequent w~hin~ step is preferably carried out using a washing m~chinp~.

In a l,r~fer~ed aspect, the soiled fabrics are pretreated with a liquiddetel~e~t composition forml-l~teA to a relatively low pH, that is pH less than 9.5, more ~lefeiably less than 9, most preferably less than 8, but C4.~ k~linP. components capable of providing ~lk~linity during the wash. The ~lk~line components may for example be coated with a substance which remains intact during the pretreatment step but is removed, e.g. by abrasion, during the washing step.

In another ~refe~red aspect, the soiled fabrics are pretreated with a detef~,e~t composition cont~inin~ cationic ester surfactant but no ~lk~line components. A second deteL~ent composition including ~Ik~inP
components may then be employed in the wash cycle.

Cationic ester surfactant The first e~esçnti~l element of the detergent compositions of the invention is a cationic ester surfactant. That is, a preferably water dispersible compound having surfactant properties comprising at least one ester (ie -COO-) linkage and at least one cationically charged group.

SUBSTITUTE S~iE,T ~iJ,~ 2~J

CA 02226637 l998-0l-l2 W O 97/03161 PCTrUS96/11282 The cationic ester surfactant is present in amount from 0.1 % to 90%, ~rerelably from 0.5% to 40%, most preferably from 15~o to 30% by weight of the detergent composition.

Suitable cationic ester surfactants, including choline ester surf~et~n~have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.

Preferred water dispersible cationic ester surfactants are those having the formula:

R~ I +
Rl-- (~(CH)nO b (X~u ( C H2 )m--(Y)v--(C H2 )t--N--R3 M
- a wherein Rl is a Cs-C31 linear or ~ranched alkyl, alkenyl or alkaryl chain or M-. N+(R6R7Rg)(CH2)S; X and Y, independently, are selected from the group con~i.citing of COO, OCO, O, CO, OCOO, CONH,NHCO, OCONH and NHCOO wherein at least one of X or Y is a COO, OCO, OCOO,OCONH or NHCOO group; R2, R3, R4, R6, R7, and R8 are indepen-lently selected from the group consisting of aLkyl, alkenyl, hydro~yalkyl, hydroxy-alkenyl and aLkaryl groups having from 1 to 4 carbon atoms; and Rs is independently H or a C1-C3 alkyl group;
wherein the values of m, n, s and t independently lie in the range of from 0 to 8, the value of b lies in the range from 0 to 20, and the values of a, u and v independently are either 0 or 1 with the proviso that at least one of u or v must be 1; and wherein M is a counter anion.

r~efeldbly R2,R3 and R4 are independently selected from CH3 and -CH2CH20H.

rre~rdbly M is selected from the group consisting of halide, methyl sulfate, suIfate, and nitrate, more pre~erably methyl sulfate, chloride, bromide or iodide.
SUBSTITUTE SHEET (RULE 2~) W O 97/03161 PCT~US96/11282 P~efe~icd water dispersible cationic ester surf~ct~ntc are the choline esters having the formula:

Rl--C--O--CH2CH2--I--CH3 Mr wherein R1 is a Cl 1-C1g linear or branched alkyl chain.

Particularly preferred choline esters of this type include the stearoylcholine ester quaternary methyl~mmonium h~IiAes (R1 =C17 alkyl), p~lmitoyl choline ester quaternary methyl~mmonium halides (R1 =C1s alkyl), myristoyl choline ester quaternary methyl~mmonium h~ les (R1 =C13 alkyl), lauroyl choline ester methyl~mmonium h~ es (Rl=Cll alkyl), cocoyl choline ester quaternary methyl~mmonium h~lirles (Rl=Cll C13 aLkyl), tallowyl choline ester quaternary methyl~mmonium h~ les (Rl =C1s C17 alkyl), and any mixtures thereof.

Most l~erel~cd choline ester compounds among the above disclosed are cocoyl choline ester quaternary methyl~mmonium h~ les.

The particularly preferred choline esters, given above, may be prepared~y the direct esterification of a fatty acid of the desired chain length with tlimethyI~minoeth~nol, in the presence of an acid catalyst. The reaction product is then quaternized with a methyl halide, forming the desired cationic material. They may also be prepared by the direct esterification of a long chain fatty acid of the desired chain length to~ether with 2-haloethanol, in the presence of an acid catalyst material. The reaction product is then quaternized with trimethyl~minP, forming the desired cationic material.

Other suitable cationic ester surfactants have the structural formulas below, wherein d may be from 0 to 20.

SUBSTITUTE SHEET (RULE 2~) CA 02226637 l998-0l-l2 W O g7/03161 PCT~US96/11282 Rl- O -C -(CH2)d C - O - CH2CH2- I+ CH3 M-M CH3--1--CH2--CH2--O--C--~CH2)-- C--O--CH2--CH2--I--CHM -In a ~rerelled aspect the cationic ester surfactant is hydrolysable under the conditions of a laundry wash metho~l.

SUBSTITUTE SHEET (RULE 26) W O 97/03161 PCTrUS96/11282 ~lk~ itv ~y~lel~l The second eS~enti~l component of the detergent compositions is from 1.55'o to 95%, preferably from 5% to 60%, most preferably from 10% to 40% by weight of the composition of an ~lk~linity ~y~lell- comprising components capable of providing ~lk~linity species in solution. By ~lk~linity species it is meant carbonate, bicarbonate, hydroxide and the various silicate anions. Such ~lk~linity species can be formed for e~cample, when ~lk~lin~ salts selecte~l from alkali metal or ~lk~line earth carbonate, bicarbonate, hydroxide or silicate, including cryst~lline layered silicate, salts and any mixtures thereof are dissolved in water. Alkali metal percarbonate and persilicate salts are also suitable sources of ~lk~linity species.

F~mples of carbonates are the ~lk~line earth and alkali metal carbonates, including sodium carbonate and sesqui-carbonate and any mixtures thereof with ultra-fine calcium carbonate such as are disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
Alkali metal percarbonate salts are also suitable sources of carbonate species and are described in more detail in the section 'inorganic perhydrate salts' herein.

Sodium hydroxide is a ~lerc;lled alkali metal hydroxide herein.

Suitable silicates include the water soluble sodium s~licates with an SiO2:
Na20 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 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. Alkali metal persilicates are also suitable sources of silicate herein.

Preferred crystalline layered silicates for use herein have the generalformula NaMSix02x+1 YH20 SUBSTITUTE SHEET (RULE 26 W O 97/03161 PCT~US96/11282 14 wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Cryst~lline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation 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 ~l~feiably 2. The most ~r~lled material is ~-Na2Si20s, available from Hoechst AG as NaSKS-6.

The cryct~lline layered silicate material is ~re~elably present in granular deleig~nt compositions as a particulate in intim~t~ 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.

Additional deter~ent components The de~er~;ent compositions of the invention also contain additional detergent components at a level of from 10% to 99% by weight. 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.

The compositions of the invention contain one or more additional detelge~t components selected from additional surfactants, bleaches, builders, organic polymeric compounds, enzymes, suds ~u~pressors, lime soap dispel~s~ls, soil suspension and anti-redeposition agents and corrosion inhibitors.

Additional surfactant The detel~ent compositions of the invention preferably contain an additional surf~ct~nt selected from anionic, nonionic, non-ester cationic, amphoteric and zwitterionic surfactants and mixtures thereof.

SUBSTITUTE SHEET (RULE 26) W O 97/03161 PCTnUS96/11282 The additional surfactant is preferably present at a level of from 0.1% to 50%, more ~referably from 1% to 40% by weight, most preferably from 5% to 30% by weight of the surfactant ~ys~e~

A typical listing of anionic, nonionic, ampholytic, and ;~wi~erionic classes, and species of these surfactants, is given in U.S.P. 3,929,678 issued to T ~ hlin and Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Detelgellts" (Vol. I and II by Schwartz, Perry and Berch). A list of suitable cationic surfactants is given in U.S.P. 4,2~9,217 issued to Murphy on March 31, 1981.

Where present, ampholytic, amphoteric and zwitteronic surfactants are generally used in combination with one or more anionic and/or nonionic surf~ct~nts .

Anionic surf~ct~nt A preferred component of the deter~ellt compositions is an anionic surf~ct~nt The weight ratio of anionic surfactant to cationic ester surf~ct~nt in the surf~ct~nt system is ~refeiably from 3:1 to 15:1, more pre~e~ablyfrom4:1 to 12:1, mostpreferablyfromS:l to 10:1.
Fcsen~i~lly any anionic surf~ct~ntc useful for detelsive purposes are suitable. These can include salts (including, for e~ample, sodium, pot~csillm, ammonium, and substituted ammonium salts such as mono-, di- and kieth~nc!~mine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfaçtants are preferred.

Suitable anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and llnc~hlrated C12-C18 monoesters) diesters of sulfosuccinate (especially saturated and ~lnc~lrated C6-C14 diesters), N-acyl sarcosinates. 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.
SUBSTITUTE SHEET (RULE ~6) W O 97/03161 PCTrUS96/11282 Anionic sulfate surfactant Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the Cs-C17 acyl-N-(Cl-C4 alkyl) and -N-(Cl-C2 hydroxyalkyl) gluc~minP-sulfates, and sulfates of alkylpolysaccharides such as the sulfates of aL~ylpolyglucoside (the nonionic nonsl~lf~t~-l compounds being described herein).

Alkyl sulfate surfactants are ~refeldbly selected from the linear and branched primary Clo-Clg alkyl slllf~te~ more preferably the Cll-Cls branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.

Alkyl ethoxysulfate surf~ct~ntc are preferably selected from the group con~i~tin~ of the Clo-Clg alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a Cll-Clg, most preferably Cll-Cls alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.

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

Anionic sulfonate surfactant Anionic sulfonate surf~ct~nts suitable for use herein include the salts of Cs-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.

Anionic carboxylate surf~ct~nt W O 97/03161 PCTrUS96/11282 Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.

Suit~ble alkyl ethoxy carboxylates include those with the formula RO(CH2CH20)X CH2COO-M+ wherein R is a C6 to C1g alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M
is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHR1-CHR2-O)-R3 wherein R is a C6 to Clg alkyl group, x is from 1 to 25, R1 and R2 are selected from the group concictin~ of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixt~lres thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstit.~lte-l hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.

Suitable soap surf~ct~nts include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are water-soluble members selected from the group con.cictinfr of the water-soluble salts of 2-methyl-1-1mrlec~noic acid, 2-ethyl-1-~lec~noic 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 suppressors.

Alkali metal sarcosinate surfactant Other suitable anionic surf~ct~ntc are the aLkali metal sarco.cin~tes of formula R-CON (R1) CH2 COOM, wherein R is a C~-C17 linear or br~nch~1 alkyl or aLkenyl group, Rl is a Cl-C4 alkyl group and M is an alkali metal ion. Preferred e~camples are the myristyl and oleoyl methyl sarcosin~tes in the form of their sodium salts.

Alko~ylated nonionic surfactant W O 97/03161 PCTrUS96/11282 F~se.nti~lly any alkoxylated nonionic surfactants are suitable herein. The ethoxylated and propoxylated nonionic surf~ct~n~ are pler~lled.

rrefelled alkoxylated surfactants can be selected from the classes of the nonionic con~ n~tes of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate conrlçn.c~tes with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene mint~ ctc.

SUBSTITlJTE SHEET (~UEE 26) W O 97/03161 PCTrUS96/11282 Nonionic alkoxylated alcohol surfactant The con~lene~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 aLkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group cont~inin~ from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.

Nonionic polyhydroxy fatty acid amide surfactant Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R2CONRlZ wherein: Rl is H, Cl-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, etho~cy, propoxy, or a mixture thereof, preferable Cl-C4 alkyl, more preferably Cl or C2 alkyl, most preferably Cl alkyl (i.e., methyl); and R2 is a Cs-C31 hydrocarbyl, 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 mixt~lre 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 ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive ~min~tion reaction; more preferably Z is a glycityl.

Nonionic fatty acid amide surfactant Suitable fatty acid amide surfactants include those having the formula:
R6CoN(R7)2 wherein R6 is an alkyl group cont~ining from 7 to 21, plefe,ably from 9 to 17 carbon atoms and each R7 is selected from the - group coneietin~ of hydrogen, C1-C4 alkyl, Cl-C4 hydroxyalkyl, and - (C2H4O)XH, where x is in the range of from 1 to 3.

Nonionic alkylpolysaccharide surfactant SUBSTITUTE SHEET (RULE 26) CA 02226637 l998-0l-l2 Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647, T I~n~lo, issued January 21, 1986, having a hydrophobic group cont~inin~ from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group cont~inin~ from 1.3 to 10 saccharide units.

Pr~r~ d alkylpolyglycosides have the formula R20(CnH2nO)t(glycosyl)x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mi~lres 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.

Amphoteric surfactant Suitable amphoteric surf~ct~nts for use herein include the amine oxide surf~t~t~ntc and the alkyl ~mrhocarboxylic acids.

Suitable amine oxides include those compounds having the formula R3(0R4)~NO(R5)2 wherein R3 is select~i from an aL~cyl, hydroxyal~yl, cyl~mi~lopropoyl and alkyl phenyl group, or mi~ct~lreS thereof, cont~ining from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group c~nt~inin~ from 2 to 3 carbon atoms, or m~ res thereof; x is from 0 to 5, yr~ bly from 0 to 3; and each R5 is an alkyl or hydroxyalkyl group co.~ from 1 to 3, or a polyethylene oxide group cont~inin~ from 1 to 3 ethylene oxide groups. Preferred are C1o-C1g alkyl dimethylamine oxide, and C10 18 acylamido aLkyl dimethyl~min~ oxide.

A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Conc. m~n~lf~rt~lred by Miranol, Inc., Dayton, NJ.

Zwitterionic surf~ct~nt SUBSTITUTE SHEET (P.ULE 6) W O 97/03161 ~CT~US96/11282 Zwillelionic surfactants can also be incorporated into the detel~ent compositions hereof. These surf~ct~ntc can be broadly described as derivatives of secondary and tertiary ~min~s, derivatives of heterocyclic secondary and tertiary ~min~, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sIlIt~ine surf~ct~n~c are exemplary zwitterionic surfactants for use herein.

Suitable bet~in~ are those compounds having the formula R(R')2N+R2COO- wherein R is a C6-C1g hydrocarbyl group, each Rl is typically C1-C3 alkyl, and R2 is a C1-Cs hydrocarbyl group. PrGfellGd bet~inp~ are C12 18 dimethyl-ammonio hexanoate and the C10-l8 acyl~mi-lopropane ~or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.

Cationic surfactants Additional cationic surf~ct~nt~ can also be used in the detergent compositions herein. Suitable cationic surfactants include the quaternary ammonium surfactants selected from mono C~-C16, preferably C6-Clo N-alkyl or aL~enyl ammonium surf~ct~ntc wherein the rem~inin~ N
positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.

~ater-soluble builder compound The deler~ent compositions of the present invention preferably contain a water-soluble builder compound, typically present at a level of from l ~o to 80% by weight, preferably from 10% to 70% by weight, most ~rGrGlably from 20% to 60% by weight of the composition.

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

SUBSTITUTE StlEcT (F(ULE 26) W O 97/03161 ~ 'll282 The carbo~cylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally ~lerelled for reasons of cost and pelrolmance.

Suitable carbo~cylates cont~inin~ one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
Polycarbo~cylates cont~ininS~ two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) ~ cetic 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 citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates 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-~roL,alle tricarboxylates described in British Patent No. 1,387,447.

Polycarbo~ylates cont~ining four carboxy groups include o~cydisuccinates disclosedinBritishPatentNo. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates cont~inin~ sulfo substitllent~ include t~e sulfosuccinate derivatives ~icclose~l 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. Prerelred polycarboxylates are hydroxycarboxylates cont~inin~ Up to three carboxy groups per molecule, more particularly citrates.

The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.

SUBSTITUTE SHEET (RULE 26) CA 02226637 l998-0l-l2 W O97/03161 PCTrUS96/11282 Borate builders, as well as builders cont~ininE borate-forming materials that can produce borate under detel~ ellt storage or wash conditions are useful water-soluble builders herein.

Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.

Partially soluble or insoluble builder compound The detergent compositions 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, most preferably from 20% to 60% weight of the composition.

Examples of largely water insoluble builders include the sodium ~ hlminosilicates .

Suitable aluminosilicate zeolites have the unit cell formula Naz[(AlO2)z(SiO2)y]. XH2O wherein z and y are at least 6; the molar r~tio 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 material are in hydrated form and are preferably crystalline, cont~ining from 10% to 28%, more preferably from 18% to 22% water i~ bound form.

The ~lllminosilicate zeolites can be naturally occurring materials, but are ~refelably synthetically derived. Synthetic cryst~llin~ aluminosilicate ion - exchange materials are available under the ~le~i~n~tions Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula Na 12 tA102) 12 (sio2)l2]. xH2O

SUBSTITUTE SHEET (RULE 26) WO 97/03161 PCTrUS96/11282 wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na86 [(Alo2)86(sio2)lo6]. 276 H2O.
Org~nic pçro~vacid bleachin~ ~y~lelll A ~lercr~ed feature of detelge~t compositions of the invention is an organic peroxyacid ble~rhin~ sy~lcll~. In one ~lererled e~ec~fion the ble~chin~ ~y~lem contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound. The pro-11lction of the organic peroxyacid occurs by an in situ reaction of the precursor with a source o~
hydrogen peroxide. ~refelled sources of hydrogen peroxide include inorganic perhydrate bleaches. In an alternative pleÇeiied execution a pleror~ed organic pero~cyacid is incorporated directly into the composition. Compositions cont~ining mi~ctures of a hydrogen peroxide source and organic pero~yacid precursor in combination with a preformed organic pero~yacid are also envisaged.

Inor~anic perhydrate bleaches Inorganic ~elllydrate salts are a ~lcfefrcd source of hydrogen pero~ide.
These salts are normally incorporated in the form of the alkali metal, erel~Lbly sodium salt at a level of from 1% to 40% by weight, more ~lercrably from 2% to 30% by weight and most preferably from 5% to 25 % by weight of the compositions.
Fs~mrles of inorganic perhydrate salts include perborate, percarbonate,perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are normally the aLkali metal salts. The inorganic perhydrate salt may be included as the crystalline soIid without additional protection. For certain perhydrate salts however, the pLere~led 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~finsJ.C comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic mateAals such as wa~es, oils, or fatty soaps.

SUBSTITUTE SHEET (RULE ~G) W O 97/03161 PCTrUS96/11282 Sodium perborate is a preferred perhydrate salt and can be in the form of the monohydrate of nominal formula NaBO2H2O2 or the tetrahydrate NaB02H202-3H20 Alkali metal percarbonates, particularly sodium percarbonate are ~r~fe~led perhydrates herein. Sodium percarbonate is an ~ ition compound having a formula colles~onding to 2Na2CO3.3H2O2, and is available commercially as a crystalline solid.
pot~cci~lm peroxymonopersulfate is another inorganic perhydrate salt of use in the deter~nt compositions herein.

Pero~cyacid bleach precursor Pero~yacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as o Il x-C--L

where L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is o Il x--c -OOH

Pero~cyacid bleach precursor compounds are preferably incorporated at alevel of from 0.5% to 20% by weight, more preferably from 1% to 15%
by weight, most preferably from 1.5% to 10~ by weight of the detergent compositions.

Suitable peroxyacid bleach precursor compounds typically contain one ormore N- or O-acyl groups, which precursors can be selected from a wide range of classes. Suitable classes include anhydri~s, esters, imirles, l~ct~m~ and acylated derivatives of imi~ oles an~ oximes. F~mrles of SUBSTITUTE SHEET (RULE 26) W O 97/03161 PCT~US96/11282 useful materials within these classes are disclosed in GB-A-1586789.
Suitable esters are disclosed in GB-A-8369~8, 864798, 1147871, 2143231 and EP-A-0170386.
vin~ proups The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a ble~chin~ composition.
rr~rerr~d L groups are selected from the group con~ict;n~ of:

O~ O~Y and --O~

~ --N N --N--C--CH--R4 A3 L~ R3 Y

--O--CH=C--C H=C H2 --O--C H=C--C H=C H2 i~l Y ~
-o--C--R1 _N~ NR4 ~C~NR4 O O

--O--C=CHR4 , and N S--CH--R4 R3 o SUBSTITUTE SHEET (RULE 26) CA 02226637 l998-0l-l2 W O 97/03161 PCTrUS96/11282 and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group cont~i~ing from 1 to 14 carbon atoms, R3 is an alkyl chain cont~inin~
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 substit~-tçtl by essenti~lly any functional group including, for example alkyl, hydroxy, aLkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ~mmmonium groups The pre~rled solubilizing groups are -SO3-M+, -CO2-M+, -SO4-M+, -N + (R3)$~ and O ~ --N(R3)3 and most preferably -SO3-M ~ and -C~2 M wherein R3 is an aLkyl chain cont~inin~ from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator.
Preferably, M is an alkali metal, ammonium or substit~-te-l ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.

Alkyl percarboxylic acid bleach precursors Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis. rrefelred precursors of this type provide peracetic acid on perhydrolysis.

Preferred alkyl percarboxylic precursor compounds of the imide type include the N-,N,NlNl tetra acetylated alkylene ~ min~s 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 (li~min~ (TAED) is particularly ~refel-ed.

Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl he~canoyloxyben7~nto sulfonate (iso-NOBS), sodium - nonanoylo~yben7Pnt- sulfonate (NOBS), sodium acetoxybçn~ene sulfonate (ABS) and pçnt~cetyl glucose.

Amide substituted alkyl peroxyacid precursors SUBSTITUTE SHEET (RULE 26) W O 97/03161 PCTrUS96/11282 Amide substituted allyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:

Il 1 5 O R O or R5 O O

wherein R1 is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene group cont~inin~ from 1 to 14 carbon atoms, and R5 is H or an aLkyl group cont~inin~ 1 to 10 carbon atoms and L can be ecsenti~lly any leaving group. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.

SUBSTITUTE SHEET (~IJLE 2~) W O 97/03161 PCTrUS96/11282 Perbenzoic acid precursor Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include the subst~tllte~l and unsubstitll~e~l benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl succinimirl~, tetrabenzoyl ethylene ~i~mine and the N-benzoyl substitllte~
ureas. Suitable imi~l~7ole type perbenzoic acid precursors include N-ben~oyl imitl~ole and N-benzoyl bçn7imi~1~70le. Other useful N-acyl group-cont~inin~ perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Cationic peroxyacid precursor~

Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.

Typically, c~tionic pero~cyacid precursors are formed by substitlltin~ the pero~yacid part of a suitable pero:~yacid precursor compound with a positively charged functional group, such as an ammonium or alkyl z~mmmonium group, preferably an ethyl or methyl ammonium group.
Cationic pero~cyacid precursors are typically present in the solid detergent ~ompositions as a salt with a suitable anion, such as a halide ion.

The pero~cyacid precursor compound to be so cationically substit~lte~ may be a perbenzoic acid, or substitllte-l derivative thereof, precursor compound as described hereinbefore. Alternatively, the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter Cationic pero~cyacid 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.

S~I~Sl ~T~ v3 W O 97/03161 PCTrUS96111282 Examples of preferred cationic peroxyacid precursors are described in UK Patent Application No. 9407944.9 and US Patent Application Nos.
08/298903, 08/2986~0, 08/298904 and 08/298906.
Suitable cationic peroxyacid precursors incIude any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides. Preferred cationic peroxyacid precursors of the N-acylated caprol~ct~m class include the triaLkyl ammonium methylene benzoyl caprol~ct~m~ and the trialkyl ammonium methylene alkyl caprolactams.

Benzoxazin organic peroxyacid precursors Also suitable are precursor compounds of the benzoxazin-type, as disclosed for example in EP-A-332,294 and EP-A~82,807, particularly those having the formula:

[~N~C R~

wherein Rl is H, alkyl, alkaryl, aryl, or arylalkyl.

~l~folmed or~anic peroxyacid The organic pero~cyacid bleaching system may contain, in addition to, or as an ~ltern~tive to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid, typically at a level of from 1 % to 15 ~ by weight, more preferably from 1 % to 10% by weight of the composition.

A ~l~rel,ed class of organic peroxyacid compounds are the amide suL,~ compounds of the following general formulae:

SUBSTiTUTE StiEET (RULE 26) -CA 02226637 l998-0l-l2 W O97/03161 PCT~US96/11282 0 or 1 5 11 ~

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 con~inin~ 1 to 10 carbon atoms. Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-phthaloyl~minoperoxicaproic 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 defined bleach catalytic activity, such as copper, iron or m~n~nese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or alllminllm cations, and a sequestrant having defined stability constants for the catalytic and au~iliary metal cations, particularly ethylen~ minetetraacetic acid, ethylen~ min~tetra(methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. Pat. 4,430,243.

Other types of bleach catalysts include the m~n~nese-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-triazacyclononane)2-(PF6)2, MnIII2(u-O)l(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(C104)2, MnIV4(u-0)6(1,4,7-triazacyclononane)4-(C104)2, MnIIIMnIV4(u-O)l(u-OAc)2 (1,4,7-trimethyl-1,4,7-triazacyclononane)2-(ClO4)3, and _ixtures thereof.
Others are described in European patent application publication no.
~49,272. Other li~n~lc suitable for use herein include 1,5,9-trimethyl-Sl lBSmUTE Sf~ RUi~ 2~) W O 97/03161 PCTrUS96/11282 1,5,9-triazacyclo~lo~lec~ne, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtllres 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 te~ch~s mononuclear m~ng~n~se (~V) 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 comple~c of m~n~n~se (II~, and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups.
Other e~camples include binuclear Mn complexed with tetra-N-~lent~te and bi-N~ent~te lig~nrlc, including N4MnIII(u-0)2MnIVN4)+and [Bipy2Mnm(u-O)2MnIVbipy2] -(C1O4)3.

Further suitable bleach catalysts are described, for example, in European patent application No. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455 (m~n~nese/mlllti~1ent3te ligand catalyst), U.S. 4,711,748 and Eu~o~can patent application, pUbli no. 224,952, (absorbed m~ng~nese on aluminosilicate catalyst), U.S.
4,601,845 (~hlminosilic~te support with m~n~nto~e and zinc or m~f~nesillm salt), U.S. 4,626,373 (m~n~nese/ligand catalyst), U.S.
4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019 (cobalt chelant catalyst) C~n~ n 866,191 (transition metal-cont~ining salts), U.S. 4,430,243 (chelants with m~np~nese cations and non-catalytic metal cations), and U.S. 4,728,455 (m~ng~n~se ~luconate catalysts).

Heavy metal ion sequestrant The delergc;Lt compositions of the invention preferably contain as an optional component a heavy metal ion sequestrant. By heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and m~gn~cium ch~l~tion c~r~city, but prefelelltially they show selectivity to binding heavy metal ions such as iron, m~ng~npse and copper.

SUBSTITUTE SHEET (RULE 26) W O 97/03161 PCTrUS96/11282 Heavy metal ion sequestrants are generally present at a level of from 0.005~ to 20%, ~refel~bly from 0.1% to 10%, more ~reÇe~bly from 0.25 % to 7.5 % and most preferably from 0.5 ~ to 5 % by weight of the compositions.

Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylene phosphonates.

Preferred among the above species are diethylene tri~mine penta (methylene phosphonate), ethylene rli~mine tri (methylene phosphonate) he~m~thylene ~ mine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate.

Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenP~ minotetracetic acid, ethylenetri~mine pentacetic acid, ethyleneAi~mine disuccinic acid, ethyleneAi~mi~e diglutaric acid, 2-hydro~y~ro~ylen~ min~ disuccinic acid or any salts thereof. Especially ~r~ ed is ethyle-neAi~mine-N,N'-disuccinic acid (EDDS) or the alkali metal, ~ line earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.

Other suitable heavy metal ion sequestrants for use herein are iminn~ cetic acid derivatives such as 2-hydroxyethyl Ai~cetic acid or glyceryl imino ~ retic acid, described in EP-A-317,542 and EP-A-399,133. The imino~i~cetic acid-N-2-hydro~ypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein. The ,B-~l~nir~-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.

SUBSTITUTE SHEET (RULE 25) CA 02226637 l998-0l-l2 O 97/03161 PCT~US96/11282 EP-A-476,257 describes suitable amino based sequestrants. EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A-~28,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane-1,2,~tricarboxylic acid are alos suitable. Glycin~mi-le-N,N'-disuccinic acid (GADS), ethylene li~mine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylen~ mine-N-N'-disuccinic acid (HPDDS) are also suitable.

Enzyme Another preferred ingredient useful in the detergent compositions is one or more additional enzymes.

Preferred additional enzymatic materials include the commercially available Iipases, cutinases, amylases, neutral and ~Ik~lint~ proteases, esterases, cellulases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.

Preferred commercially available protease enzymes include those sold under the tr~len~mes Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename M~t~ce, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor InterIlational, and those sold under the tr~len~me 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.

rrefelled amylases include, for example, a-amylases obtained from a special strain of B licheniformis, described in more detail in GB-1,269,839 (Novo). Preferred commercially available amylases include for example, those sold under the tr~tlen~m~ Rapidase by Gist-Brocades, and those sold under the tr~lçn~me Termamyl and BAN by Novo rn~ tries A/S. Amylase enzyme may be incorporated into the ~iU~STITUTE SHEEr (, .UL' ~û3 W O 97/03161 PCT~US96/11282 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 offrom 0.0001% to 2% by weight, ~referdbly 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 pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mllt~nt~ of these strains are also useful herein. A ~lefelled lipase is derived from Pseudomonas pseudoalcali~enes, which is described in Granted European Patent, EP-B-0218272.

Another ~lererLed lipase herein is obtained by cloning the gene from Humicola lanu~inosa and expressing the gene in Asper~illus orvza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo ~nrlllstri A/S, Bagsvaerd, Denmark, 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 polymeric compound Organic polymeric compounds are preferred additional components of the deterge~t 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 essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in de~e~ nt compositions, including any of the high molecular weight organic polymeric compounds described as clay flocc~ in~
agents herein.

Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1 % to 30%, preferably SUBSTITUTE SHEET (RULE 26) O 97/03161 PCTrUS96111282 fromO.5% to 15%, most~referdblyfrom 1% to 10% byweightofthe composltions.

Examples of organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarbo~ylic acid colllp.ises at least two carbo~cyl 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. F~mples 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 cont~ining monomer units selected from maleic acid, acrylicacid, polyaspartic acid and vinyl alcohol, particularly those having an average molec~ r weight of from 5,000 to 10,000, are also suitable herein.

Other organic polymeric compounds suitable for incorporation in the deter~ent compositions herein include cellulose derivatives such as methylcellulose, carbo~ymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.

Further useful organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most ~referably about 4000.

Suds ~u~r~ssin~ system The detergent compositions of the invention, when form~ t~ for use in machine washing 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 ~% by weight of the composition.

SUBSTITUTE SHEET (F~ULE 26) W O 97/03161 PCTrUS96/11282 Suitable suds suppressing systems for use herein may comprise essentially any known ~ntifo~m compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.

By allLi~am compound it is meant herein any compound or mistllres of compounds which act such as to depress the fo~mins~ or el~dsin~ pro~lce~l by a solution of a detergent composition, particularly in the presence of ~7~it~tion of that solution.

Particularly ~referred 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 component. The term "silicone" as used herein, and in general throughout the in~lllstry, encompasses a variety of relatively high moleclll~r weight polymers cont~inin~ silo~cane units and hy~rocarbyl group of various types. Preferred silicone antifoam compounds are the siloxanes, particularly the poly-limtothylsiloxanes having trimethylsilyl end blocking units.

Other suitable antifoam compounds include the monocarbo~cylic 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 monocarbo~ylic fatty acids, and salts thereof, for use as suds :ju~pressor 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, pof~sillm, and lithium salts, and ammonium and nol~mmonium salts.

Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic Clg-C40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to he~a-alkylmel~mines or di- to tetra alky~ mine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine cont~inin~ 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl SUBSTITUTE SHEET (RULE 26) WO 97/03161 P ~ rUS96/11282 di-alkali metal (e.g. sodium, pot~ci-~m, lithillm) phosphates and phosphate esters.

A ~refelred sllds suppressing system comprises (a) antifoam compound, preferably silicone antifoam compound, most ~l~fe,ably a silicone anlifoam 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%, ~refe~ably 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 dispersant compound, most ~r~felably 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, com~ercially available from DOW Corning under the tradename DCO544;

(c) an inert carrier fluid compound, most preferably comprising a C16-C1g ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, ~rerelably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;

A highly preferred particulate suds ~ pressing system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a meltin~ point in the range 50~C to 85~C, wherein the organic carrier material comprises a monoester of glycerol SUBSTITUTE SHEET (RULE 26) W O 97/03161 PCTrUS96111282 and a fatty acid having a carbon chain cont~inin~ from 12 to 20 carbon atoms. EP-A-0210721 discloses other ~refelled particulate suds ~u~pressing ~y~Lellls wherein the organic carrier material is a fatty acid or alcohol having a carbon chain cont~inin~ from 12 to 20 carbon atoms, or a mishlre thereof, with a melting point of from 45~C to 80~C.

Clay softeninp The delerg~llt compositions may contain a clay sorlk~ ys~e co~ rising a clay mineral compound and optionally a clay flocc~ tin~
agent.

The clay mineral compound is preferably a smectite clay compound.
Sm~ctite 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-299,575 and EP-A-313,146 in the name of the Procter and Gamble Co~ally describe suitable organic polymeric clay flocclll~tin~ agents.

Polymeric dye tr~n~fer inhibitin~ a~ents The deler~c~t compositions 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 selecte~l from polyamine N-o~ide polymers, copolymers of N-vinylpyrrolidone and N-~Lyli.~ 7ole, polyvinylpyrrolidonepolymers or combinations thereof.

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

SUBSTITUTE SHEET (RULE 26) -WO 97/03161 PCT~US96/11282 (I) I
R
wherein P is a polymerisable unit, and ~ Il 11 11 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 ~tt~h~orl or wherein the nitrogen of the N-O group is part of these groups.

The N-O group can be represented by the following general structures:
o (R1 ) X - I -(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 attached or wherein the nitrogen of the N-O group forms part of these groups. The N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.

Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. One class of said polyamine N-o~cides comprises the group of polyamine N-oxides SUBSTITUTE SHEET (RULE 26) CA 02226637 l998-0l-l2 W O 97/03161 PCTrUSg6/11282 wherein the nitrogen of the N-O group forms part of the R-group.
Frere~red polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imi~ ole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

Other suitable polyamine N-oxides are the polyamine o~cides whereto the N-O group is attached to the polymerisable unit. A plefelled class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an aromatic,heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R
group. F.x~mrles of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imid~7ole 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 ~aterial has the desired water-solubility and dye-susperltlin~ power.
Typically, the average molecular weight is within the range of 500 to 1000,000.
bl Copolymers of N-vinylpyrrolidone and N-vinylimidazole Suitable herein are coploymers of N-vinylimirl~701e and N-vinyl~y1lolidone having an average molecular weight range of from 5,000 to 50,000. The ~re~erred copolymers have a molar ratio of N-vinylimi~ ole to N-vinylpyrrolidone from l to 0.2.
c) Polyvinylpyrrolidone The dete~ lt compositions herein may also utilize polyvinylpyrrolidone ~ ("PVP") having an average molecular weight of from 2,500 to 400,000.
Suitable polyvinylpyrroIidones are commercially vailable from ISP
Corporation, New York, NY and Montreal, (~~n~ under the product names PVP K-15 (viscosity molecular weight of l0,000), 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 SUBSTITUTE SHEET t~ULE 26) O 97/03161 PCT~US96/11282 360,000). PVP K-15 is also available from ISP Corporation. Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 16~ and Sokalan HP 12.
d) Polyvinylo~azolidone The d~lergellt compositions herein may also utilize polyvinyloxazolidones as polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000.

e) Polyvinvlimidazole The det~lge~t compositions herein may also utilize po}yvinylimirl~7ole as polymeric dye transfer inhibiting agent. Said polyvinylimi~ oles ~rcrLrably have an average molecular weight of from 2,500 to 400,000.

O~tical briphtPner The detergellt compositions herein also optionally contain from about 0.005% to 5% by weight of Ce~ types of hydrophilic optical bri ~htpnprs .

Hydrophilic optical bright~Pners useful herein include those having the tructural formula:

Rl ~2 N (~ ~C--C ~ I ~ N( R2 SO3M SO3M Rl wherein R1 is selected from ~niiino, N-2-bis-hydroxyethyl and NH-2-hydro~cyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methyl~mino, morphilino, chloro and amino; and M is a salt-~,~lg cation such as sodium or pot~sinm SUBSTITUTE SHEET (RUEE 26) W O 97/03161 PCTrUS96/11282 When in the above formula, R1 is ~nilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the bri~h~ener is 4,4' ,-bis[(4-~nilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2 ,2 ' -stilbenedisulfonic acid and disodium salt. This particular bri~htener species is commercially marketed under the tr~len~mP Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the ~refeLled hydrophilic optical brightener useful in the detergent compositions herein.

When in the above formula, R1 is ~nilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4,4'-bist(4-anilino-6-(N-2-hydroxyethyl-N-methyl~mino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt. T_is particular brightener species is commercially marketed under the tr~len~me Tinopal SBM-GX by Ciba-Geigy Corporation.

When in the above formula, R1 is ~nilino, R2 is morphilino and M is a cation such as sodium, the bri~h~ener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbene-liclllfonic acid, sodium salt. This particular brightener species is commercially marketed under the tr~len~me Tinopal AMS-GX by Ciba Geigy Corporation.

SUBSTITllTE SHEET (RULE 26) O 97/03161 PCTrUS96/11282 Cationiç fabric softenin~ a~ents Cationic fabric soft~ninp agents can also be incorporated into compositions in accordance with the present invention. Suitable cationic fabric so*enin~ agents include the water insoluble tertiary ~mines or dilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0 011 340.
~tionic fabric softenin~ agents are typically incorporated at total levels of from 0.5 % to 15 % by weight, normally from 1 % to 5 % by weight.

Other optional ingredients Other optional ingre~lient~ suitable for inclusion in the compositions of the invention include perfumes, colours and filler salts, with sodium sulfate being a p~erelled filler salt.

pH of the compositions The present compositions p~erei~bly have a pH me~ red as a 1 ~o solution in ~ till~ water of at least 10.0, ~eferably from 10.0 to 12.5, most ~r~lably from 10.5 to 12Ø

Form of the compositions The solid compositions in accordance with the invention can take a variety of physical forms including granular and tablet forms. The compositions are particularly the so-called concçn~ated detef~ent compositions adapted to be added to a washing m~chin~ by means of a dispensing device placed in the m~hine drum with the soiled fabric load.

The mean particle size of the components of granular compositions in accordance with the invention should preferably be such that no more that ~% of particles are greater than 1 .7mm in ~ meter and not more than ~ %
of particles are less than 0.15mm in rii~m~ter.

SUBSTITUTE SHEET (RULE 26) The term mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of Tyler sieves. The weight fractions thereby obtained are plotted ~P~in~ct 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 delergellt compositions in accordance with the present invenLion typically have a bulk density of at least 500 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 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 funnel to be emptied into an axially n~ cylindrical cup disposed below the funnel. The funnel is 130 mm high and has internal ~ meters of 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base. The cup has an overall height of 90 mm, an internal height of 87 mm and an internal (li~m~ter of 84 mm. Its nominal volume 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 wei~h~l and the value obtained for the weight of powder doubled to provide a bulk density in g/litre.
Replicate m~Sllrements are made as required.

Tablet forms are generally made by compressing granular compositions into tablet shape using any of the tabletting process commonly known in the art. By ayyroyriate selection of the compositional form and of the pressure employed in the tablet pressing operation the hardness of the tablet may be varied. The size of the tablets is selected to enable ease of dosing to the wash solution. Typically, a tablet will comprise from 5 to lOOg, preferably from 10 to 50g of detergent product.

SUBSTITUTE SHEET (RULE ~J) W O 97/03161 PCTrUS961112X2 The tablet may be of essentially any shape including cubes and spheres.In a preferred aspect the tablet is formed such as to have at least two distinct and separate layers, wherein an outer layer contains cationic ester surf~ct~n~ and an inner layer the ~Ik~linity system.

Surfac~ant ~pPlomerate particles The surf~ct~n~ system herein is prefelably present in granular compositions in the form of surfactant agglomerate 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. ~ minosilicate~ carbonate) 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 agglomerator, a Z-blade mixer or more ~r~rt;lably an in-line mixer such as those m~nllf~ctllred by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH~ D~790 Paderborn 1, Flcenerstrasse 7-9, Postfach 2050, Germany. Most ~le~lably a high shear mixer is used, such as a Lodige CB (Trade Name).

A high active surfactant paste comprising from 50% by weight to 95~ by weight, ~rer~ldbly 70% by weight to 85% by weight of surfactant is typically used. The paste may be pumped into the agglomerator at a temperature high enoug~ to m~int~in a pumpable viscosity, but low enough to avoid degradation of the anionic surfactants used. An operating temperature of the paste of 50~C to 80~C is typical.

Pack~pinp for the compositions Con~mercially marketed executions of the bleaching compositions can be packaged in any suitable container including those constructed from paper, cardboard, plastic materials and any suitable l~min~te~s. A
~refel~ed p~cl~gin~ execution is described in European Application No.
94921505.7.

SUBSTITUTE SHEET (RULE 26) ,, W O 97/031~1 PCTAUS96/11282 Abbreviations used in Examples .

In the detergent compositions, the abbreviated component iclentifications have the following me~nin~Ec LAS : Sodium linear C12 alkyl benzene sulfonate TAS : Sodium tallow alkyl sulfate C45AS : Sodium C 14-C 15 linear alkyl sulfate CxyEzS : Sodium Clx-Cly branched aL~yl sulfate condensed with z moles of ethylene oxide C45E7 : A Cl~ls predomin~ntly linear primary alcohol condensed with an average of 7 moles of ethylene oxide C25E3 : A C12 15 branched primary alcohol condensed with an average of 3 moles of ethylene oxide C25E5 : A C12 15 branched primary alcohol condensed with an average of 5 moles of ethylene oxide CEQ : RlCOOCH2CH2.N+(CH3)3 with Rl = Cll-QAS : R2.N + (CH3)2(C2H4OH) with R2 = C 12 - C 14 Soap : Sodium linear aLt~yl carboxylate derived from an 80/20 mixture of tallow and coconut oils.
TFAA : C16-Clg alkyl N-methyl ghlc~mille TPK~A : C12-C14 topped whole cut fatty acids STPP : Anhydrous sodium tripo~yphosphate Zeolite A : Hydrated Sodium ~lllminosilicate of formula Nal2(A1~2Si~2)12. 27H20 having a primary particle size in the range from 0.1 to 10 micrometers NaS~S-6 : Crystalline layered silicate of formula ~ -Na2Si20s Citric acid : Anhydrous citric acid Carbonate : Anhydrous sodium carbonate with a particle size between 200~Lm and 900~m SUBSTITUTE S,'IEET (RULE 2~) W O 97/03161 PCT~US96/11282 Bicarbonate : Anhydrous sodium bicarbonate with a particle size distribution between 400~Lm and 1200~1m Silicate : Amorphous Sodium Silicate (SiO2:Na2O; 2.0 ratio) Sodium slllf~te: Anhydrous sodium sulfate Citrate : Tri-sodium citrate dihydrate of activity 86.4%
with a particle size distribution between 425~m and 850 ~m MA/AA : Copolymer of 1:4 maleic/acrylic acid, average molecular weight about 70,000.
CMC : Sodium carboxymethyl cellulose Protease : Proteolytic enzyme of activity 4KNPU/g sold by NOVO Industries A/S under the tradename Savinase Alcalase : Proteolytic en_yme of activity 3AU/g sold by NOVO ~nrlustries A/S
Cellulase : Cellulytic enzyme of activity 1000 CEVU/g sold by NOVO rnr1~lstries A/S under the tr~ n~m~o.
Carezyme Amylase : Amylolytic enzyme of activity 60KNU/g sold by NOVO Tn~stries A/S under the tr~-le~me Tel~a~yl 60T
Lipase : Lipolytic enzyme of activity 100kLU/g sold by NOVO rn~lllctries A/S under the tr~-len~me Lipolase Endolase : Endo,~lnn~e enzyme of activity 3000 CEVU/g sold by NOVO Tn-lllctries A/S
PB4 : Sodium perborate tetrahydrate of nominal formula NaB02.3H20-H202 PBl : Anhydrous sodium perborate monohydrate bleach of nominal formula NaBO2.H2O2 Percarbonate : Sodium Percarbonate of nominal formula 2Na~C03.3H202 NOBS : Nonanoyloxyben7~rle sulfonate in the form of the sodium salt.
TAED : Tetraacetylethyle,ne~ mint~, SUeSTlTUTE ~ IEET (~

DTPMP : Diethylene tri~mine penta (methylene phosphon~te), marketed by Monsanto under the Trade name De4uest 2060 Photoactivated: Sulfonated Zinc Phthlocyanine encaps~ te~l in ~ bleach de~ctrin soluble polymer BrightPn~r 1 : Disodium 4,4'-bis(2-sulphostyryl)biphenyl Bri~htP-ner 2 : Disodium 4,4'-bis(~anilino-6-morpholino-1.3.5-triazin-2-yl)amino) stilbene-2:2'-disulfonate.
HEDP : 1,1-hydro~cyethane diphosphonic acid PVNO : Polyvinylpyridine N-oxide PVPVI : Copolymer of polyvinylpyrolidone and vinylimi~7ole SRP 1 : Sulfobenzoyl end capped esters with oxyethylene oxy and terephtaloyl backbone SRP 2 : Diethoxylated poly (1, 2 propylene tereph~ te) short block polymer Silicone a- Liroau~: Poly~imetllylsilo~ane foam controller with silo~ane-o~yaLkylene copolymer as dispersing agent with a ratio of said foam controller to said di~ersillg agent of 10:1 to 100:1.

In the following Examples all levels are guoted as % by weight of the ,osi~ion:

F,Y~rnPIe 1 The following laundry deLer~;ellt compositions A to F were prepared in accord with the invention:

Setl A B C D E F
LAS 8.0 8.0 8.0 8.0 8.0 8.0 SUBSTITUTE SHEET (RULE 26) W O 97/03161 PCT~US96/11282 C25E3 3.4 3 4 3 4 3 4 3 4 3 4 C E Q 0.8 0.8 1.5 2.0 0.8 0.5 Zeolite A 18.1 18.1 18.1 18.1 18.1 18.1 Carbonate 13.0 13.0 13.0 27.0 27.0 27.0 Silicate 1.4 1.4 1.4 3.0 3.0 3.0 Sodium sulfate 26.1 26.1 26.1 26.1 26.1 26.1 PB4 9.0 9.0 9.0 9.0 9.0 9.0 T A E D 1.5 1.5. 1.5 1.5 l.S 1.5 D E T P M P 0.25 0.25 0.25 0.25 0.25 0.25 H E D P 0.3 0.3 0 3 0 3 0 3 0 3 Protease 0.26 0.26 0.26 0.26 0.26 0.26 Amylase 0.1 0.1 0.1 0.1 0.1 0.1 MA/AA 0.3 0.3 0.3 0.3 0.3 0.3 C M ~ 0.2 0.2 0.2 0.2 0.2 0.2 Photoactivated 15 15 15 15 15 15 bleach (ppm) ppm ppm ppm ppm ppm ppm Bri~h~e.ner 1 0.09 0.09 0.09 0.09 0.09 0.09 Perfume 0.3 0.3 0.3 0.3 0.3 0.3 SUBSTITUTE SHEET (RULE 26) CA 02226637 l998-0l-l2 W O 97/03161 PCT~US96/11282 Silicone antifoam 0.5 0.5 0.5 0.5 0.5 0 5 Misc/minors to 100%

Density in g/litre 630 670 670 500 670 670 ~lk~linity 6.8 6.8 6.8 18.5 18.5 18.5 SUBSTITUTE SHEET (RULE 26) WO 97/03161 PCT~US96111282 Set 2 G H
LAS 5.25 5.61 4.76 TAS 1.25 1.86 1.57 C45AS - 2.24 3.89 C25AE3S - 0.76 1.18 C45E7 3.25 - 5.0 C25E3 5,5 CEQ 0.8 2.0 2.0 STPP 10.7 Zeolite A - 19.5 19.5 NaSKS-6/citric acid - 10.6 10.6 (79:21) Carbonate 16.1 21.4 21.4 Bicarbon~te - 2.0 2.0 Silicate 6.8 Sodium sulfate 39.8 - 14.3 PB4 5.0 12.7 TAED 0.5 3.1 SUBSTITUT~ SHEET (RULE 26) , CA 02226637 l998-0l-l2 W O 97/03161 ~"11282 DETPMP 0.25 0.2 0.2 HEDP 0.3 o 3 Protease 0.26 0.85 0.85 T.i~e 0.15 0.15 0.15 Cellulase 0.28 0.28 0.28 Amylase 0.1 0.1 0.1 MA/AA 0.8 1.6 1.6 CMC 0.2 0.4 0.4 Photoactivated bleach 15 ppm 27 ppm 27 ppm (ppm) Bri~htPnPr 1 0.08 0.19 0.19 Bri~h~e~P.r 2 0.04 0.04 ullle 0.3 0.3 0.3 Silicone antifoam 0.5 2.4 2.4 Minors/misc to 100%

SUBSTITUTE SHEET (~ULE 26) W O 97/03161 PCT~US96/11282 Set 3 J K L
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 Bri~htener 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 antifoam 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 Amylase 0.25 0.30 0.15 Dry mi~ced sodium 3.0 3.0 5.0 sulfate R~l~nce (Moisture & 100.0 100.0 100.0 Miscellaneous) Density (g/litre) 630 670 670 SUBSTITUTE SHEET (RULE 26) CA 02226637 l998-0l-l2 W O 97/03161 PCT~US96/11282 Set 4 The following nil bleach-con~inin~ detergent formulations of particularuse in the washing of colored clothing were prepared:

M N O
Blown Powder Zeolite A 15.0 15.0 Sodium sulfate 0.0 5.0 LAS 3.0 3.0 CEQ 2.0 1.5 1.3 DTPMP 0.4 0.5 CMC 0.4 0.4' MA/AA 4.0 4.0 Agglomerates C45AS - - 11.0 LAS 6.0 5.0 TAS 3.0 2.0 Silicate 4.0 4.0 Zeolite A 10.0 15.0 13.0 MA/AA - - 2.0 Carbonate 9.0 7.0 7.0 Spray On Perfume 0.3 0.3 0.5 C45E7 4.0 4.0 4.0 C25E3 2.0 2.0 2.0 Dry additives MA/AA - - 3.0 NaSKS-6 - - 12.0 Citrate 10.0 - 8.0 Bicarbonate 7.0 3.0 5.0 Carbonate 8.0 5.0 7.0 PVPVI/PVNO 0.5 0.5 0.5 Alcalase 0.5 0.3 0-9 Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 SUBSTITUTE SHEET (P.ULE 26) CA 02226637 l998-0l-l2 W O 97/03161 PCTrUS96/11282 Cellulase 0.6 0.6 0.6 Silicone antifoam 5.0 5.0 5.0 Dry additives Sodium sulfate 0.0 9.0 0.0 R~l~nce (Moisture and 100.0 100.0 100.0 Miscellaneous) Density (g/litre) 700 700 700 ~UBSTITUTE SHEET (F~ULi- 2u) CA 02226637 l998-0l-l2 W O 97/03161 PCT~US96/11282 Set 5 The following deter~;ellt formulations were prepared:
D P Q R S
LAS12.012.012.0 10.0 QAS 0.7 1.0 - 0.7 TFAA - 1.0 C25E5/C45E7 - 2.0 - 0.5 C45E3S - 2.5 CEQ 2.0 1.5 1.0 0.5 STPP30.018.015.0 Silicate9.0 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 Protease0.8 1.0 0.5 0.5 Amylase0. 8 0.4 - 0.25 Lipase 0.2 0.1 0.2 0.1 Cellulase 0.15 0.05 Photoactivated70ppm 45ppm - 10ppm bleach (ppm) Bri~ht.o.ner 10.2 0.2 0.08 0.2 PB 16.0 2.0 NOBS2.0 1.0 B~l~nce 100 100 100 100 (Moisture and Miscellaneous) SUBSTITUTE SHEET (RULE 26) CA 02226637 l998-0l-l2 W O g7/03161 1~liU~/11282 Set ~i The following detergent formulations were prepared:
T U V
Blown Powder Zeolite A10.0 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 l0.0 C45AS 4.û 5.0 7.0 CEQ 2.0 2.0 2.0 Silicate - 1.0 7.0 Soap - - 2.0 Bri~ht~ner l 0.2 0.2 0.2 Carbonate 28.0 26.0 20.0 DTPMP - 0.4 0.4 Spray On C45E7 1.0 l.0 1.0 Dry additives PVPVI/PVNO 0.5 0.5 0.5 Protease 1.0 1.0 l.0 Lipase 0.4 0.4 0 4 Amylase 0.1 0.1 0.1 Cellulase 0.1 0.1 0.1 NOBS - - 6.1 4.5 PB l 1.0 5.0 6.0 Sodium sulfate - 6.0 R~l~n~e (Moisture 100 100 l00 and Miscellaneous) SUBSTITUTE SHEET (RULE 26) -P ~ ~US96111282 Set 7 The following high density and bleach-cont~inin~ detergent formulations, were prepared:

W X Y

Blown Powder Zeolite A 15.0 15.0 15.0 Sodim sulfate 0.0 5.0 0.0 LAS 3.0 2.0 3.0 QAS - 1.5 1.5 CEQ 2.0 1.5 2.0 DTPMP 0.4 0.4 0 4 CMC 0.4 0.4 0.4 MA/AA 4.0 2.0 2.0 A~lomerates LAS 4.0 4.0 4.0 TAS 2.0 2.0 1.0 Silicate 3.0 3.0 4.0 Zeolite A 8.0 8.0 8.0 Carbonate 8.0 8.0 6.0 Spray On Perfume 0.3 0.3 0 3 C45E7 2.0 2.0 2.0 C25E3 2.0 - -Dry additives Citrate 5.0 - 2.0 Bicarbonate - 3.0 Carbonate 8.0 15.0 10.0 TAED 6.0 2.0 5.0 PB1 14.0 7.0 10.0 Polyethylene oxide of MW - - 0.2 5,000,000 Bentonite clay - - 10.0 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 SUBSTITUTE SHEET (RULE 26~

W O 97/03161 PCTrUS96/11282 Amylase 0.6 0.6 0.6 Cellulase 0.6 0.6 0.6 Silicone antifoam 5.0 5.0 5.0 Dry additives Sodium sulfate 0.0 3.0 0.0 R~l~nce (Moisture and 100.0 100.0 100.0 Mi~cell~n~ous) Density (g/litre~ 850 850 850 SUBSTITUTE SHEET (RULE 26) W O 97/03161 P ~ ~US96/11282 Set 8 The following high density detergent formulationswere prepared:

Z AA
A~lomerate C45AS 11.0 14.0 CEQ 3.0 3.5 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 Pe~ ru~e 0.5 0.5 Dry Adds HEDP 0.5 0.3 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 Celhll~e 0.6 0.6 Amylase 0.6 0.6 Silicone a~ oaLu 5.0 5 0 Bri~ht~n~r 1 0.2 0.2 Bri~htPner 2 0.2 R~l~nr~e (Moisture and 100 100 Miscellaneous) Density (~/litre) 850 850 SUBSTITUTE SHEET (RULE 26) =

W O g7/03161 PCTnUS96/11282 Washina method Each of the compositions A to AA of Sets 1 to 8 was employed in a laundry washing method i.~ which a Miele 820 a~lLolllatic w~.~hin~
m~chine was employed, and the 40~C short cycle programme selected. At the start of the laundry wash method, 100g of deter~;ent was placed in a gr~n-llette dispensing device of the type known as an 'Arielette' and commonly supplied with Ariel (tradename) deLer~ ent products, as made by the Procter and Gamble Co~a~y, for sale across Europe. The charged granulette was then placed on top of the wash load in the drum of the washing machine. The wash load co~ ised 2.4Kg of 60/40 mixhlre of lightly soiled cotton, polycotton and polyester fabrics. Good washing performance was obtained.

Comparative performance tes~ins The greasy stain removal pelr~ ance of Composition I when used in a w~ching method involving gr~nlllette dispensing into a washing machine was compared to that obtained when the detergent was dispensed through a di~ s...g drawer using the following test method:

Three white cotton sheets were prewashed three times in a non-biological bleach-free heavy duty detergent at 60~. Margarine stains were then e,venly applied using a paint brush to one sheet, lard stains to the second sheet and beef dripping stains to the third one. Sets of test swatches of size 6cm ~ 6cm were cut from each sheet.

The sets of fabric swatches were subjected to one wash cycle in an automatic washing machine with the de~ergent dispensed either from a gr~nlllette or from the rli~pen~in~ drawer of the washing m~hin~. The swatches were then ~sesse~l for removal of the various fatty stains by a four person grading panel using the well-known four-point Scheffe scale.

ID more detail, a Miele 820 automatic washing m~t~hin~ was employed, and the 40~C short cycle programme selected. Water of 10~ Clark hardness ( = 1.5 mmol Ca2+/litre) was used. 100g of delergent was SUBSTITUTE SHEET (RULE 26) W O 97/03161 P ~ AUS96/11282 employed. One swatch of each fabric type was washed along with a ballast load comprising 2.4Kg of 60/40 mixtllre of lightly soiled synthetic and cotton fabrics. The ballast load was positioned prior to comm~ncement of the wash cycle to ensure an even distribution around the test swatches.

In the case of the gr~nlllette dispensing, the deter~ellt was placed in a gr~nlllette dispensing device of the type known as an 'Arielette' and commonly supplied with Ariel (tradename) detergent products, as made by the Procter and Gamble Company, for sale across Europe. The charged gr~mllette was then placed on top of the ballast wash load and adjacent to the st~in~A swatches in the drum of the washing machine and the wash cycle started.

In the case of the drawer dispensing, the 100g of deter~ ent was placed in the drawer of the washing machine and the wash cycle started.

The following results were obt~in Drawer dispensingGr~nnlPtte dispensin~
Margarine removal Ref 1.0*
(PSU) Lard removal (PSU) Ref 0.9*

Beefdripping removal Ref 1.2*
(PSU) , * = st~tictically significant at 95% confi-lence level SUBSTITUTE SHEET (RULE 26) W O 97/03161 PCTrUS96/11282 Example 2 The following liquid detergent formulations of pH < 9 were prepared:

AB AC AD AE AF AG AH AI
C45AS 10. 11.0 9.0 - 13.0 o C25AS 4.0 1.0 2.0 10. - 11.0 15.0 15.0 o C25E3S 1.0 - - 3.0 - - 2.0 4.0 C25E7 6.0 8.0 11. 2.510.0 2.0 4.0 4.0 o TFAA - - - 4.S - 6.0 8.0 8.0 C12-14 alky1 - - - - 3 dimt~-thylhydroxy ethyl ammonium chloride Cationic ester 0.5 1.5 1.0 0.7 2.0 1.5 1.8 2.0 s TPKFA 2.0 - 11. 2.0 - 13.0 7.0 7.0 o Rapeseed fatty acids - - - 5.0 - - 4.0 4.0 Citric acid 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1.0 Dodecenyl/tetradecenyl 12. 10.0 - - 15.0 succinic acid 0 Oleic acid 4.0 2.0 1.0 - 1.0 Fth~n~l 4.0 4.0 7.0 2.0 7.0 2.0 3.0 2.0 1,2 Propanediol 4.0 4.0 2.0 7.0 6.0 8.0 8.0 13.0 Mono Ethanol Amine - - - 5.0 - - 9.0 9.0 Tri Fth~nnl Amine - - 8.0 NaOHup to p H 8.0 8.0 7.6 7.7 8.0 7.5 8.0 8.2 Etho~ylated 0.5 - 0.5 0.2 - - 0.4 0.3 tetraethylene pent~mine DTPMP 1.0 1.0 0.5 1.0 2.0 1.2 1.0 SRUP 2 0.3 - 0.3 0.1 - - 0.2 0.1 P V N O - - - - - - - 0.10 SUBSTITUTE SHEET(RULE 26~

W O 97/03161 PC~rrUS96111282 6~

Protease O.S O.S 0.4 0.2 - O.S 0.3 0.6 s Alcalase - - - - 1.5 T ir~Qe - 0.10 - o~o - - 0.15 0.15 Amylase 0.2 0.25 0.6 O.S 0.25 0.9 0.6 0.6 S
f~ell~ Qe - 0 0 - 0.15 O.lS
S
EndoLase - - - 0.1 0 0.07 Boric acid 0.1 0.2 - 2.0 1.0 l.S 2.5 2.5 Na folll,ate - - 1.0 - - - - -Ca chloride - 0.015 - 0.0 - - - -Bentol~lle clay - - - - 4.0 4.0 Suspen~lin~ clay SD3 - - - - 0.6 0.3 R~l~n~e (water and 100 100 100 100 100 100 100 100 Miscellaneous) Each of the deteL~t;llt products AB to AI was used separately in a prehe~tmP-nt washing method involving the following steps:

A load of 2 Kg of soiled polycotton and cotton fabrics was taken. In the pletlc~ nt step, approximately Sml aliquots of detergent product were applied directly to fatty soiled areas, until the area was at least wetted with the detergent. The deteL~ llt was allowed to remain in contact with the soiled area for S minlltec. In the wash step, the load was then placed in a Miele 820 automatic washing and the 40~C short cycle programme selected. 100ml of the same deter~ellt product was employed in the wash cycle. The deter~cllt was dispensed from a solid plastic dosing ball. Good w~hin~
pelrul~ce was obtained for each of products AB to AI.

SUBSTITUTE SHEET (RULE 26)

Claims (10)

WHAT IS CLAIMED IS:

1. A method of washing soiled laundry in a domestic or industrial washing machine wherein a delivery means is provided for dispensing an effective amount of a detergent composition directly to the drum of a washing machine before the commencement of the wash and subsequently enabling release of said detergent composition to the wash liquor during the wash wherein said detergent composition contains (a) from 0.1 % to 90% by weight of the detergent composition of a cationic ester surfactant; and (b) from 1.5% to 95% of the detergent composition of an alkalinity system comprising alkaline salts selected from the group consisting of alkali metal or alkaline earth carbonate, bicarbonate, hydroxide or silicate, including crystalline layered silicate, salts and any mixtures thereof characterized in that said delivery means enables the delivery of said cationic ester surfactant to said soiled laundry prior to the establishment of an alkaline wash liquor environment around the soiled laundry.

2. A method according to Claim 1 wherein said delivery means is provided by a dispensing device having a dispensing aperture which is charged with the detergent composition and then placed into the drum of the washing machine prior to the commencement of the wash cycle.

3. A method according to Claim 1 in which said delivery means is provided by forming said detergent composition as a tablet formed such as to provide release of cationic ester surfactant to the soiled laundry prior to the full release of said alkalinity system wherein the tablets are introduced into the drum of the washing machine prior to commencement of the wash cycle.

4. A method according to Claim 3 wherein said tablet comprises layers of distinct product composition with the cationic ester surfactant being located in a layer outwardly located relative to the layer comprising the alkalinity system.

5. A method according to any of Claims 1 to 4 wherein said cationic ester surfactant is selected from those having the formula:

wherein R1 is a C5-C31 linear or branched alkyl, alkenyl or alkaryl chain or M-~ N+(R6R7R8)(CH2)S; X and Y, independently, are selected from the group consisting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO group; R2, R3, R4, R6, R7, and R8 are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxy-alkenyl and alkaryl groups having from 1 to 4 carbon atoms; and R5 is independently H or a C1-C3 alkyl group;
wherein the values of m, n, s and t independently lie in the range of from 0 to 8, the value of b lies in the range from 0 to 20, and the values of a, u and v independently are either 0 or 1 with the proviso that at least one of u or v must be 1; and wherein M is a counter anion.

6. A detergent composition according to Claim 5 wherein R2,R3 and R4 are independently selected from the group consisting of CH3 and -CH2CH2OH.

7. A detergent composition according to Claim 5 wherein the cationic ester is selected from the choline esters having the formula:

wherein R1 is a C11-C19 linear or branched alkyl chain.

8. A method of washing soiled laundry having a pretreat step comprising application of an effective amount of a detergent composition directly to the soiled laundry before subjecting the soiled laundry to a washing step wherein said detergent composition contains (a) from 1% to 90% by weight of the detergent composition of a cationicester surfactant; and (b) from 10% to 99.9% of the detergent composition of detergent components selected from additional surfactants, bleaches, builders, alkalinity sources, organic polymeric compounds, enzymes, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors characterized in that said pretreat step enables the delivery of said cationic ester surfactant to said soiled laundry prior to the establishment of an alkaline wash liquor environment around the soiled laundry.

9. A method according to Claim 8 wherein said detergent composition is a fluid composition formulated to a pH of less than 9.5.

10. A method according to either Claim 8 or 9 wherein the detergent composition contains no alkaline components.