WO1997013835A1

WO1997013835A1 - Detergents delivering a stronger organic peroxyacid bleach to a wash first followed by delivering a weaker peroxyacid

Info

Publication number: WO1997013835A1
Application number: PCT/US1996/016566
Authority: WO
Inventors: Gerard Marcel Baillely; Nour-Eddine Guedira; Robin Gibson Hall
Original assignee: The Procter & Gamble Company
Priority date: 1995-10-12
Filing date: 1996-10-15
Publication date: 1997-04-17
Also published as: ES2225891T3; EP0861315A1; EP0861315B1; GB9520921D0; ATE272703T1; DE69633060D1; BR9610927A; DE69633060T2; EP0861315A4

Abstract

There is provided a detergent composition containing an organic peroxyacid bleaching system capable of releasing a plurality of organic peroxyacids of different strength to a wash solution. A means is provided for delaying the release of a stronger organic peroxyacid relative to the release of a weaker organic peroxyacid. The detergent composition provides bleachable soil/stain removal capability when employed in laundry or dishwashing methods.

Description

DETERGENTS DELIVERING A STRONGER ORGANIC PEROXYACID BLEACH TO A WASH FIRST FOLLOWED BY DELIVERING A WEAKER

PEROXYACID.

Technical field

This invention relates to detergent compositions containing an organic peroxyacid bleaching system capable of releasing a plurality of organic peroxyacids of different strength to a wash solution.

Background to the invention

The satisfactory removal of bleachable soils/stains such as blood, spinach, chocolate, coffee, tea and tomato sauce from soiled/stained substrates is a particular challenge to the formulator ofa detergent composition for use in a washing method sucn as a laundry or machine dishwashing method.

Traditionally, the removal of such bleachable soils/stains has been enabled by the use of bleach components such as oxygen bleaches, including hydrogen peroxide and organic peroxyacids. The organic peroxyacids are often obtained by the in situ perhydrolysis reaction between hydrogen peroxide and an organic peroxyacid bleach precursor. Alternatively, a preformed organic peroxyacid can be used.

Usually, a single organic bleach precursor compound or preformed organic peroxyacid is employed. It has however, now been established that the use of certain bleaching systems capable of releasing a plurality of organic peroxyacids of different strength to a wash solution can provide bleachable soil/stain removal benefits.

In addition the Applicants have now found that when the release ofthe stronger of the organic peroxyacids to the wash solution is delayed relative to the release ofthe weaker organic peroxyacid further enhanced bleachable stain removal performance is obtained.

Altematively the Applicants have found that equivalent bleachable stain removal performance may be obtained from a mixed organic peroxyacid bleach system containing lower levels ofa stronger organic peroxyacid whose release to the wash solution is delayed, as may be obtained for an, otherwise comparable, organic peroxyacid bleach system having no delayed release of the stronger peroxyacid to the wash solution. In other words, by requiring delayed release of the stronger peroxyacid, equivalent bleaching performance can be obtained even though less of the stronger peroxyacid is used overall.

Without wishing to be bound by theory, it is believed that the mechanism behind the present development is as follows: In the first stage the weaker organic peroxyacid is released rapidly to the wash solution where it can act on readily bleachable stains, but also where it can fall prey to wasteful decomposition reactions in the early parts of the wash. Such decomposition most often arises as a result of reactions with components (such as heavy metal ions) present in the wash solution, which themselves are often derived from the soiled washload. In the second stage, the stronger peroxyacid is released and can act on the less readily bleachable (i.e. more stubborn) stains in an environment where it will be less susceptible to decomposition, in that any undesirable 'reactive components' ofthe washload will essentially have previously been 'exhausted' in attacking the weaker acid. Thus, the stronger peroxyacid is used to its greatest effect in dealing with only the more difficult to address stains, and any 'wastage' due to side reactions is minimized.

Binary organic peroxyacid precursor compound-containing compositions have been disclosed in the art. For example, US 5,405,412 A discloses a detergent composition containing both n-acyl caprolactam and alkanoyloxybenzene sulfonate bleach precursor compounds. The Applicant is however, unaware of any disclosure of mixed organic peroxyacid precursor systems in which the release ofa stronger organic peroxyacid is deliberately delayed relative to the release ofa weaker organic peroxyacid, nor of any teaching of performance benefits related thereto.

It is therefore an object ofthe present invention to provide compositions suitable for use in laundry and machine dishwashing methods having enhanced bleachable soil/stain removal.

Summary ofthe Invention

According to one aspect ofthe present invention there is provided a detergent composition containing an organic peroxyacid bleaching system capable of releasing two different organic peroxyacid bleaches to a wash solution wherein a means is provided for delaying the release to a wash solution ofthe stronger peroxyacid relative to the release of a weaker peroxyacid such that in the T50 test method herein described the time to achieve a concentration that is 50% ofthe ultimate concentration of said stronger peroxyacid is at least 120 seconds more than the time to achieve a concentration that is 50% ofthe ultimate concentration of said weaker peroxyacid, wherein the relative strength ofthe peroxyacids is measured according to the 'dye bleaching protocol' described herein.

According to a preferred aspect of the present invention there is provided a detergent composition containing an organic peroxyacid bleaching system capable of releasing two different organic peroxyacid bleaches to a wash solution wherein a means is provided for delaying the release to a wash solution of the stronger peroxyacid relative to the release ofthe weaker peroxyacid such that in the T50 test method herein described the time to achieve a concentration that is 50% ofthe ultimate concentration ofthe weaker peroxyacid is less than 60 seconds and the time to achieve a concentration that is 50% ofthe ultimate concentration ofthe stronger peroxyacid is more than 180 seconds, wherein the relative strength ofthe peroxyacids is measured according to the 'dye bleaching protocol' described herein.

According to a preferred aspect ofthe present invention the detergent composition contains only two organic peroxyacid bleach precursor compounds, i.e. it is a binary bleach precursor system.

Detailed description ofthe invention

Organic peroxyacid bleaching svstem

According to one aspect ofthe present invention the detergent compositions contain an organic peroxyacid bleaching system. In one preferred execution the bleaching system contains a hydrogen peroxide source and a plurality of organic peroxyacid bleach precursor compounds capable of releasing at least two different organic peroxyacids to a wash solution. The production ofthe organic peroxyacid occurs by an in situ reaction ofthe precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In an alternative preferred execution a preformed organic peroxyacid is used as a substitute for one, many or all ofthe organic peroxyacid bleach precursor compounds. Compositions containing mixtures ofa hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are thus envisaged.

Inorganic perhydrate bleaches

Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These salts are normally incorporated in the form ofthe alkali metal, preferably sodium salt at a level of from 1% to 40% by weight, more preferably from 2% to 30% by weight and most preferably from 5% to 25% by weight ofthe compositions.

Examples 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 solid without additional protection. For certain perhydrate salts however, the preferred executions of such granular compositions utilize a coated form ofthe material which provides better storage stability for the perhydrate salt in the granular product. Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as waxes, oils, or fatty soaps.

Sodium perborate is a preferred perhydrate salt and can be in the form ofthe monohydrate of nominal formula NaBθ2H2θ2 or, more preferably, the tetrahydrate NaBO₂H2θ2.3H₂O.

Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates herein. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2Cθ3-3H2θ2, and is available commercially as a crystalline solid.

Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in the detergent compositions herein.

Peroxyacid bleach precursor

Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as O X C - L

where L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure ofthe peroxyacid produced is

O X C OOH

Peroxyacid bleach precursor compounds are preferably incoφorated at a level 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 or more N- or O-acyl groups, which precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A- 1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

Leaving groups

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 bleaching composition.

Preferred L groups are selected from the group consisting of:

R³ Y

I I

-O-CH=C-CH=CH₂ -O— CH=C-CH=CH₂

and mixtures thereof, wherein R is an alkyl, aryl, or alkaryl group containing from

1 to 14 carbon atoms, R 3 is an alkyl chain containing from 1 to 8 carbon atoms, R 4 is H or R 3 , and Y is H or a solubilizing group. Any of R 1 , R3 and R 4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups

alkyl chain containing 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 substituted 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. Preferred precursors of this type provide peracetic acid on perhydrolysis.

Preferred alkyl percarboxylic precursor compounds of the imide type include the N- ,N,N'N' tetra acetylated alkylene diamines 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 diamine (TAED) is particularly preferred.

Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.

Amide substituted alkyl peroxyacid precursors

Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those ofthe following general formulae:

R¹ — C — N — R² — C — L R¹ — N — C — R² — C — L

O R⁵ O or R⁵ O O

wherein Rl is an alkyl group with from 1 to 14 carbon atoms, R^ is an alkylene group containing from 1 to 14 carbon atoms, and R^ is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. Most preferably Rl is an alkyl group with 9 carbon atoms, R^ is an alkylene group containing 4 carbon atoms, R^ is H, thus the organic peroxyacid released on perhydrolysis is a nonyl amide of peroxy adipic acid (NAPAA). Amide substituted bleach activator compounds of this type are described in EP-A-0170386. Perbenzoic acid precursor

Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol. glucose, and all saccharides with benzoylating agents, and those ofthe imide type including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas. Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole. Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrroiidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Suitable N-acylated lactam perbenzoic acid precursors have the formula:

wherein n is from 0 to 8, preferably from 0 to 2, and R is an aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbon atoms, or a substituted phenyl group containing from 6 to 18 carbon atoms, preferably a benzoyl group.

Cationic peroxyacid precursors

Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.

Typically, cationic peroxyacid precursors are formed by substituting the peroxyacid part ofa suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammmonium group, preferably an ethyl or methyl ammonium group. Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion. The peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described 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 peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127.852; 5,093.022; 5,106,528; U.K. 1 ,382,594; EP 475,512, 458,396 and 284.292; and in JP 87-318,332.

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

Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides. Preferred cationic peroxyacid precursors ofthe N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.

Benzoxazin organic peroxyacid precursors

Also suitable are precursor compounds ofthe benzoxazin-type, as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula:

wherein R, is H, alkyl, alkaryl, aryl, or arylalkyl. Preformed organic peroxyacid

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

A preferred class of organic peroxyacid compounds are the amide substituted compounds ofthe following general formulae:

R - - c — - N — R² — C — - OOH

O R⁵ O or

R - N — C — R² - — C — OOH

R⁵ O O

wherein Rl is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R^ is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group containing 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-phthaloylaminoperoxicaproic acid are also suitable herein.

Strength ofthe organic peroxyacid - 'dye-bleaching protocol'

In accord with the invention the release to a wash solution ofa stronger organic peroxyacid is delayed relative to the release ofa weaker organic peroxyacid.

For the purposes ofthe present invention the strength ofthe organic peroxyacid is assessed by reference to the 'peroxyacid dye-bleaching' protocol now described. In essence, this protocol compares the kinetics of bleaching action ofthe organic peroxyacid on a representative dyestuff under controlled conditions of pH and temperature. In accord with the protocol, a first solution is made up containing 0.5M of an organic peroxyacid precursor compound in distilled water (or a mixture of distilled water/spectrometric grade ethanol for poorly water-soluble precursor compounds).

A second solution is made in three stages. In the first stage 0.3 mg EDTA, and 0.277g uncoated sodium percarbonate are added to 100ml of distilled water. The resulting peroxide solution, which is equivalent to a 0.025M solution of active oxygen, is buffered to pH 10.5 using an appropriate buffering agent (e. g. sodium carbonate). In the second stage 18mg of Direct Blue No. 1 is added to 100ml of distilled water together with buffering agent to give a constant pH of 10.5. In the third stage, the peroxide solution is mixed with the dye solution.

The kinetics of bleaching action are measured spectrometrically as follows. Initially, 20 microlitres ofthe first solution are added to a 1 cm polystyrene cuvette placed within the spectrometer, then 4ml ofthe second solution is added by an autopipette. The time of addition ofthe second solution is taken to be time = 0, and the rate of bleaching ofthe dye is measured over a 1800 second run time. The wavelength measured is 596 nm, and the spectrometer is preferably a HP 8452 A (tradename) diode array spectrophotometer, although other suitable spectrometers within the knowledge ofthe skilled person could be used. Spectrophotometric measurements are typically taken at 0.5 second intervals and the readings processed using known single cell kinetics software.

With the given levels of organic peroxyacid and dye components the dye bleaching action will follow essentially first order kinetics. Thus, by fitting the data to an appropriate first order kinetics (i.e. exponential) curve a rate constant may be obtained for the organic peroxyacid.

Comparison ofthe rate constants gives a measure ofthe strength ofthe organic peroxyacid, a stronger acid having a higher first order rate constant.

A bleaching effectiveness ratio, which compares the bleaching strength of two organic peroxyacids, may be defined as the rate constant for the stronger organic peroxyacid divided by the rate constant for the weaker organic peroxyacid. According to a preferred aspect ofthe invention, the bleaching effectiveness ratio is preferably at least 1.1, more preferably at least 1.3, most preferably at least 1.5. Relative release kinetics

In an essential aspect ofthe invention a means is provided for delaying the release to a wash solution ofa stronger organic peroxyacid relative to the release of a weaker organic peroxyacid.

Said means may comprise a means for delaying the release ofthe stronger peroxyacid to the wash solution. Altematively said means may comprise a means for enhancing the rate of release ofthe weaker organic peroxyacid to the wash solution.

Delayed rate of release - means

The delayed release means can include coating the stronger organic peroxyacid bleach precursor compound with a coating or mixture of coatings designed to provide the delayed release. The coating may therefore, for example, comprise a poorly water soluble material, or be a coating of sufficient thickness that the kinetics of dissolution ofthe thick coating provide the controlled rate of release.

The coating material may be applied using various methods. Any coating material is typically present at a weight ratio of coating material to bleach of from 1 :99 to 1 :2, preferably from 1 :49 to 1 :9.

Suitable coating materials include triglycerides (e.g. partially) hydrogenated vegetable oil, soy bean oil, cotton seed oil) mono or diglycerides, microcrystalline waxes, gelatin, cellulose, fatty acids and any mixtures thereof.

Other suitable coating materials can comprise the alkali and alkaline earth metal sulphates, silicates and carbonates, including calcium carbonate.

Preferred as a coating material is sodium silicate of Siθ2 : Na2θ ratio from 1.6 : 1 to 3.4 : 1, preferably 2.8 : 1, applied as an aqueous solution to give a level of from 2% to 10%, (normally from 3% to 5%) of silicate solids by weight ofthe percarbonate. Magnesium silicate can also be included in the coating. Any inorganic salt coating materials may be combined with organic binder materials to provide composite inorganic salt/organic binder coatings. Suitable binders include the C \ 0-C20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole of alcohol and more preferably the C15-C20 primary alcohol ethoxylates containing from 20 - 100 moles of ethylene oxide per mole of alcohol.

Other preferred binders include certain polymeric materials. Polyvinylpyrrolidones with an average molecular weight of from 12,000 to 700,000 and polyethylene glycols (PEG) with an average molecular weight of from 600 to 10,000 are examples of such polymeric materials. Copolymers of maleic anhydride with ethylene. methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent ofthe polymer are further examples of polymeric materials useful as binder agents. These polymeric materials may be used as such or in combination with solvents such as water, propylene glycol and the above mentioned C10-C20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole. Further examples of binders include the C10-C20 mono- and diglycerol ethers and also the C 10-C20 f^attv acids.

Cellulose derivatives such as methylcellulose, carboxymethylcellulose, ethyl hydroxyethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their salts are other examples of binders suitable for use herein.

One method for applying the coating material involves agglomeration. Preferred agglomeration processes include the use of any ofthe organic binder materials described hereinabove. Any conventional agglomerator/mixer may be used including, but not limted to pan, rotary drum and vertical blender types. Molten coating compositions may also be applied either by being poured onto, or spray atomized onto a moving bed of bleaching agent.

Other means of providing the required delayed release include mechanical means for altering the physical characteristics ofthe bleach to control its solubility and rate of release. Suitable protocols could include compaction, mechanical injection, manual injection, and adjustment ofthe solubility ofthe bleach compound by selection of particle size of any particulate component. Whilst the choice of particle size will depend both on the composition of the particulate component, and the desire to meet the desired delayed release kinetics, it is desirable that the particle size should be more than 500 micrometers, preferably having an average particle diameter of from 800 to 1200 micrometers.

Additional protocols for providing the means of delayed release include the suitable choice of any other components of the detergent composition matrix such that when the composition is introduced to the wash solution the ionic strength environment therein provided enables the required delayed release kinetics to be achieved.

Enhanced rate of release - means

All suitable means for enhancing the rate of release of the weaker organic peroxyacid to the wash solution are envisaged.

The enhanced release means can include coating the weaker organic peroxyacid component with a coating designed to provide the enhanced release. The coating may therefore, for example, comprise a highly, or even effervescently, water soluble material.

Other means of providing the required enhanced release could include mechanical means for altering the physical characteristics of the weaker organic peroxyacid to enhance its solubility and rate of release.

A suitable protocol could include deliberate selection ofthe particle size ofthe weaker organic peroxyacid component. The choice of particle size will depend both on the composition ofthe particulate component, and the desire to meet the desired enhanced release kinetics.

Delayed release - kinetic parameters

The release ofthe stronger organic peroxyacid relative to that ofthe weaker organic peroxyacid component is such that, in the T50 test method herein described, the T50 value for the weaker organic peroxyacid component is at least 120 seconds less than the T50 value for the stronger organic peroxyacid component. According to a preferred aspect, the time (T50) to achieve a concentration that is 50% ofthe ultimate concentration of said weaker organic peroxyacid is less than 60 seconds, preferably less than 50 seconds, more preferably less than 40 seconds, and the time (T50) to achieve a concentration that is 50% ofthe ultimate concentration of said stronger organic peroxyacid is more than 120 seconds, preferably from 180 to 480 seconds, more preferably from 240 to 360 seconds.

Delayed release - test method

The delayed release kinetics herein are defined with respect to a 'TA test method' which measures the time to achieve A% ofthe ultimate concentration/level of that component when a composition containing the component is dissolved according to the standard conditions now set out.

The standard conditions involve a 1 litre glass beaker filled with 1000 ml of distilled water at 20°C, to which lOg of composition is added. The contents ofthe beaker are agitated using a magnetic stirrer set at 100 φm. The magnetic stirrer is pea/ovule- shaped having a maximum dimension of 1.5cm and a minimum dimension of 0.5cm. The ultimate concentration/level is taken to be the concentration/level attained 10 minutes after addition ofthe composition to the water-filled beaker.

Suitable analytical methods are chosen to enable a reliable determination ofthe incidental, and ultimate in solution concentrations ofthe component of concern, subsequent to the addition ofthe composition to the water in the beaker.

Such analytical methods can include those involving a continuous monitoring ofthe level of concentration ofthe component, including for example photometric and conductrimetric methods.

Alternatively, methods involving removing titres from the solution at set time intervals, stopping the disssolution process by an appropriate means such as by rapidly reducing the temperature ofthe titre, and then determining the concentration of the component in the titre by any means such as chemical titrimetric methods, can be employed. Suitable graphical methods, including curve fitting methods, can be employed, where appropriate, to enable calculation ofthe the TA value from raw analytical results.

The particular analytical method selected for determining the concentration ofthe component, will depend on the nature of that component, and ofthe nature of the composition containing that component.

Additional detergent components

The detergent compositions ofthe invention may also contain additional detergent components. The precise nature of these additional components, and levels of incoφoration thereof will depend on the physical form ofthe composition, and the nature ofthe cleaning operation for which it is to be used.

The compositions ofthe invention may for example, be formulated as hand and machine laundry detergent compositions, including laundry additive compositions and compositions suitable for use in the pretreatment of stained fabrics and machine dishwashing compositions.

When formulated as compositions suitable for use in a machine washing method, eg: machine laundry and machine dishwashing methods, the compositions ofthe invention preferably contain one or more additional detergent components selected from surfactants, builders, enzymes, heavy metal ion sequestrants, organic polymeric compounds, suds suppressors, lime soap dispersants, soil suspension and anti- redeposition agents and corrosion inhibitors. Laundry compositions can also contain, as additional detergent components, softening agents.

Surfactant

The detergent compositions ofthe invention may contain as an optional detergent component a surfactant selected from anionic, cationic, nonionic ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof. The surfactant is typically present at a level of from 0.1 % to 60% by weight. More preferred levels of incoφoration of surfactant are from 1% to 35% by weight, most preferably from 1 % to 20% by weight.

The surfactant is preferably formulated to be compatible with any enzyme components present in the composition. In liquid or gel compositions the surfactant is most preferably formulated such that it promotes, or at least does not degrade, the stability of any enzyme in these compositions.

A typical listing of anionic, nonionic, ampholytic, and zwitterionic classes, and species of these surfactants, is given in U.S.P. 3,929,678 issued to Laughlin and Hewing on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A list of suitable cationic surfactants is given in U.S.P. 4,259,217 issued to Muφhy on March 31 , 1981.

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

Anionic surfactant

Essentially any anionic surfactants useful for detersive puφoses can be included in the compositions. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) ofthe anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants.

Other 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 unsaturated C, 2^_C, o monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C₆-C , . 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.

Anionic sulfate surfactant Anionic sulfate surfactants suitable for use herein include the linear and branched primary alkyl sulfates, alkyl ethoxysulfates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N-(C _j -C4 alkyl) and -N-(Cι - C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).

Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C -C 1 g alkyl sulfates which have been ethoxylated with from about 0.5 to about 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C6-Cj8 alkyl sulfate which has been ethoxylated with from about 0.5 to about 20, preferably from about 0.5 to about 5, moles of ethylene oxide per molecule.

Anionic sulfonate surfactant

Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.

Anionic carboxylate surfactant

Anionic carboxylate surfactants suitable for use herein include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.

Preferred alkyl ethoxy carboxylates for use herein include those with the formula RO(CH2CH2θ)_x CH2C00-M^"1" wherein R is a C^ to C\ 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 about 20 %, and the amount of material where x is greater than 7, is less than about 25 %, the average x is from about 2 to 4 when the average R is C13 or less, and the average x is from about 3 to 10 when the average R is greater than Cπ_» and M is a cation, preferably chosen from alkali metal, alkaline earth metal, ammonium, mono-, di-, and tri-ethanol-ammonium, most preferably from sodium, potassium, ammonium and mixtures thereof with magnesium ions. The preferred alkyl ethoxy carboxylates are those where R is a C12 to Cj g alkyl group.

Alkyl polyethoxy polycarboxylate surfactants suitable for use herein include those having the formula RO-(CHRι-CHR2-O)-R3 wherein R is a Cg to C \g alkyl group, x is from 1 to 25, R\ and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, wherein at least one R\ or R2 is a succinic acid radical or hydroxysuccinic acid radical, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.

Anionic secondary soap surfactant

Preferred soap surfactants are secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon. The secondary carbon can be in a ring structure, e.g. as in p-octyl benzoic acid, or as in alkyl-substituted cyclohexyl carboxylates. The secondary soap surfactants should preferably contain no ether linkages, no ester linkages and no hydroxyl groups. There should preferably be no nitrogen atoms in the head-group (amphiphilic portion). The secondary soap surfactants usually contain 11-15 total carbon atoms, although slightly more (e.g., up to 16) can be tolerated, e.g. p-octyl benzoic acid.

The following general structures further illustrate some ofthe preferred secondary soap surfactants:

A. A highly preferred class of secondary soaps comprises the secondary carboxyl materials ofthe formula R^ CH(R^)COOM, wherein R is CH3(CH2)x and R^ is CH3(CH2)y, wherein y can be O or an integer from 1 to 4, x is an integer from 4 to 10 and the sum of (x + y) is 6-10, preferably 7- 9, most preferably 8.

B. Another preferred class of secondary soaps comprises those carboxyl compounds wherein the carboxyl substituent is on a ring hydrocarbyl unit, i.e., secondary soaps ofthe formula R^-R^-COOM, wherein R^ is C^-C^O, preferably C^-C^, alkyl or alkenyl and R > is a ring structure, such as benzene, cyclopentane and cyclohexane. (Note: R^ can be in the ortho, meta or para position relative to the carboxyl on the ring.)

C. Still another preferred class of secondary soaps comprises secondary carboxyl compounds ofthe formula CH3(CHR)j_c-(CH2)_m-(CHR)_n- CH(COOM)(CHR)₀-(CH2)p-(CHR)_q-CH3, wherein each R is C1 -C4 alkyl, wherein k, n, o, q are integers in the range of 0-8, provided that the total number of carbon atoms (including the carboxylate) is in the range of 10 to 18.

In each ofthe above formulas A, B and C, the species M can be any suitable, especially water-solubilizing, counterion.

Especially preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl- 1-undecanoic acid, 2-ethyl- 1-decanoic acid, 2-propyl-l -nonanoic acid, 2-butyl-l- octanoic acid and 2-pentyl-l-heptanoic acid.

Alkali metal sarcosinate surfactant

Other suitable anionic surfactants are the alkali metal sarcosinates of formula R- CON (R¹) CH2 COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, Rl is a C1-C4 alkyl group and M is an alkali metal ion. Preferred examples are the myristyl and oleyl methyl sarcosinates in the form of their sodium salts.

Nonionic surfactant

Essentially any anionic surfactants useful for detersive purposes can be included in the compositions. Exemplary, non-limiting classes of useful nonionic surfactants are listed below.

Nonionic polvhvdroxy fatty acid amide surfactant

Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R²CONR!Z wherein : Rl is H, Ci -C4 hydrocarbyl, 2-hydroxy ethyl, 2- hydroxy propyl, or a mixture thereof, preferable C1-C4 alkyl, more preferably C\ or C2 alkyl, most preferably C\ alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C5-C19 alkyl or alkenyl, more preferably straight-chain C9-C1 7 alkyl or alkenyl, most preferably straight-chain Cj 1 -C ] 7 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.

Nonionic condensates of alkyl phenols

The polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use herein. In general, the polyethylene oxide condensates are preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 18 carbon atoms in either a straight chain or branched chain configuration with the alkylene oxide.

Nonionic ethoxylated alcohol surfactant

The alkyl ethoxylate condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use herein. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of alcohol.

Nonionic ethoxylated/propoxylated fatty alcohol surfactant

The ethoxylated Cg-Cjg fatty alcohols and C -C\^ mixed ethoxylated/propoxylated fatty alcohols are suitable surfactants for use herein, particularly where water soluble. Preferably the ethoxylated fatty alcohols are the Cio-Cjg ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to 50, most preferably these are the Ci2-Cι ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40. Preferably the mixed ethoxylated/propoxylated fatty alcohols have an alkyl chain length of from 10 to 18 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to 10.

Nonionic EO PO condensates with propylene glvcol The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use herein. The hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility. Examples of compounds of this type include certain ofthe commercially-available Pluronic^M surfactants, marketed by BASF.

Nonionic EO condensation products with propylene oxide/ethylene diamine adducts The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are suitable for use herein. The hydrophobic moiety of these products consists ofthe reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000. Examples of this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.

Nonionic alkylpolysaccharide surfactant

Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties. (Optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.) The intersaccharide bonds can be, e.g., between the one position ofthe additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.

The preferred alkylpolyglycosides have the formula

R2θ(C_nH_2nO)t(glycosyl)_x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3; t is from 0 to 10, preferably 0, and X is from 1.3 to 8, preferably from 1.3 to 3, most preferably from 1.3 to 2.7. The glycosyl is preferably derived from glucose.

Nonionic fatty acid amide surfactant

Fatty acid amide surfactants suitable for use herein are those having the formula: R6C0N(R7)2 wherein R > is an alkyl group containing from 7 to 21 , preferably from 9 to 17 carbon atoms and each R? is selected from the group consisting of hydrogen, C1-C4 alkyl, C1 -C4 hydroxyalkyl, and -(C2H4θ)_xH, where x is in the range of from 1 to 3.

Amphoteric surfactant

Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.

A suitable example of an alkyl aphodicarboxylic acid for use herein is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.

Amine Oxide surfactant

Amine oxides useful herein include those compounds having the formula R3(OR )_XNO(R5)2 wherein R^ is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms, preferably 8 to 18 carbon atoms; R^ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, preferably 2 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R^ is an alkyl or hydyroxyalkyl group containing from 1 to 3, preferably from 1 to 2 carbon atoms, or a polyethylene oxide group containing from 1 to 3, preferable 1, ethylene oxide groups. The R^ groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.

These amine oxide surfactants in particular include Cio-Cj g alkyl dimethyl amine oxides and Cg-C_jg alkoxy ethyl dihydroxyethyl amine oxides. Examples of such materials include dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2- hydroxyethyl)dodecylamine oxide, dimethyldodecylamine oxide, dipropyltetradecylamine oxide, methylethylhexadecylamine oxide, dodecylamidopropyl dimethylamine oxide, cetyl dimethylamine oxide, stearyl dimethylamine oxide, tallow dimethylamine oxide and dimethyl-2- hydroxyoctadecylamine oxide. Preferred are C jo-Ci alkyl dimethylamine oxide, and C l o- 18 acylamido alkyl dimethylamine oxide.

Zwitterionic surfactant

Zwitterionic surfactants can also be incoφorated into the detergent compositions hereof. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.

Betaine surfactant

The betaines useful herein are those compounds having the formula R(R')2N⁺R2cθO" wherein R is a C -Cig hydrocarbyl group, preferably a C\_Q-C\ alkyl group or C J Q-16 acylamido alkyl group, each Rl is typically C1 -C3 alkyl, preferably methyl,m and R² is a C1-C5 hydrocarbyl group, preferably a C1-C3 alkylene group, more preferably a C \ -C2 alkylene group. Examples of suitable betaines include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; C12-14 acylamidopropylbetaine; Cg.14 acylamidohexyldiethyl betaine; 4 [C j 4.16 acylmethylamidodiethylammonio]- 1 -carboxybutane; C \ 5. j g acylamidodimethylbetaine; C12-I6 acylamidopentanediethyl-betaine; [C12-I6 acylmethylamidodimethylbetaine. Preferred betaines are Cj2-lg dimethyl-ammonio hexanoate and the Cjo-lg acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.

Sultaine surfactant

The sultaines useful herein are those compounds having the formula (R(Rl)2N⁺R2sθ3" wherein R is a Cό-Cjg hydrocarbyl group, preferably a C \ Q- Cι g alkyl group, more preferably a C12-C13 alkyl group, each R* is typically C\- C3 alkyl, preferably methyl, and R² is a Cj-Cg hydrocarbyl group, preferably a Cj- C3 alkylene or, preferably, hydroxyalkylene group. Ampholytic surfactant

Ampholytic surfactants can be incoφorated into the detergent compositions herein. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched.

Cationic surfactants

Cationic surfactants can also be used in the detergent compositions herein. Suitable cationic surfactants include the quaternary ammonium surfactants selected from mono Cg-Cjg, preferably Cg-Cjo N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.

Water-soluble builder compound

The detergent compositions ofthe present invention contain as a preferred optional component a water-soluble 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% by weight ofthe 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 carboxylic radicals separated from each other by not more that two carbon atoms, carbonates, bicarbonates, borates, phosphates, silicates and mixtures of any ofthe foregoing.

The carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.

Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, digiycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxy succinates described in British Patent No. 1,379,241, lactoxysuccinates described in British Patent No. 1.389,732, and aminosuccinates described in Netherlands Application 7205873. and the oxypolycarboxylate materials such as 2-oxa- 1,1, 3 -propane tricarboxylates described in British Patent No. 1,387,447.

Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261 ,829, 1,1,2,2-ethane tetracarboxylates, 1,1, 3, 3 -propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1 ,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis- tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran - cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran - cis - dicarboxylates, 2,2,5,5- tetrahydrofuran - tetracarboxylates, 1,2,3,4,5,6-hexane - hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343.

Ofthe above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.

The parent acids ofthe 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.

Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions can also be used but are not preferred at wash conditions less that about 50°C, especially less than about 40°C.

Examples of carbonate builders are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesqui-carbonate and mixtures thereof with ultra- fine calcium carbonate as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.

Specific 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.

Suitable silicates include the water soluble sodium silicates with an Siθ2: Na2θ ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.4 being preferred, and 2.0 ratio being most preferred. The silicates may be in the form of either the anhydrous salt or a hydrated salt. Sodium silicate with an Siθ2: Na2θ ratio of 2.0 is the most preferred silicate.

Silicates are preferably present in the detergent compositions in accord with the invention at a level of from 5% to 50% by weight ofthe composition, more preferably from 10% to 40% by weight.

Partially soluble or insoluble builder compound

The detergent compositions ofthe 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 partially water soluble builders include the crystalline layered silicates. Examples of largely water insoluble builders include the sodium aluminosilicates.

Crystalline layered sodium silicates have the general formula

NaMSi_x0₂χ₊ι .yH₂0

wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A- 0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE- A-3742043. For the puφose ofthe present invention, x in the general formula above has a value of 2, 3 or 4 and is preferably 2. The most preferred material is δ- Na2Si2θ5, available from Hoechst AG as NaSKS-6.

The crystalline layered sodium silicate material is preferably present in granular detergent compositions as a particulate in intimate admixture with a solid, water- soluble ionisable material. The solid, water-soluble ionisable material is selected from organic acids, organic and inorganic acid salts and mixtures diereof.

Suitable aluminosilicate zeolites have the unit cell formula Na_z[(AlO2)z(SiO2)y]. XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.

The aluminosilicate ion exchange materials can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeoilte MAP, Zeolite HS and mixtures thereof. Zeolite A has the formula

Na ₁₂ [AlO₂) i2 (Siθ2)i2] xH2θ

wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nagg [(Alθ2)86(Siθ2)l06-- 276 H₂O.

Heavy metal ion sequestrant

The detergent compositions ofthe invention may contain as a preferred 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 magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper. Heavy metal ion sequestrants are generally present at a level of from 0.005% to 20%. preferably from 0.1% to 10%, more preferably from 0.25% to 7.5% and most preferably from 0.5% to 5% by weight ofthe compositions.

Heavy metal ion sequestrants, which are acidic in nature, having for example phosphonic acid or carboxylic acid functionalities, may be present either in their acid form or as a complex salt with a suitable counter cation such as an alkali or alkaline metal ion, ammonium, or substituted ammonium ion, or any mixtures thereof. Preferably any salts/complexes are water soluble. The molar ratio of said counter cation to the heavy metal ion sequestrant is preferably at least 1 : 1.

Suitable heavy metal ion sequestrants for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2- hydroxypropylenediamine disuccinic acid or any salts thereof.

Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts diereof, or mixtures thereof. Preferred EDDS compounds are the free acid form and the sodium or magnesium salt or complex thereof. Examples of such preferred sodium salts of EDDS include Na2EDDS and Na3EDDS. Examples of such preferred magnesium complexes of EDDS include MgEDDS and Mg2EDDS.

Other suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133.

The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N- carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A- 516,102 are also suitable herein. The β-alanine-N,N'-diacetic acid, aspartic acid- N,N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also suitable.

EP-A-476,257 describes suitable amino based sequestrants. EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2- phosphonobutane-l,2,4-tricarboxylic acid are alos suitable. Glycinamide-N,N'- disuccinic acid (GADS) is also suitable.

Organic polymeric compound

Organic polymeric compounds are particularly preferred components ofthe detergent compositions in accord with the invention. By organic polymeric compound it is meant essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions.

Organic polymeric compound is typically incoφorated in the detergent compositions ofthe invention at a level of from 0.1% to 30%, preferably from 0.5% to 15%, most preferably from 1% to 10% by weight ofthe compositions.

Examples of organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers ofthe latter type are disclosed in GB-A- 1,596, 756. Examples of such salts are polyacrylates of MWt 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 100,000, especially 40,000 to 80,000.

Other suitable organic polymeric compounds include the polymers of acrylamide and acrylate having a molecular weight of from 3,000 to 100,000, and the acrylate/fumarate copolymers having a molecular weight of from 2,000 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 containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000 are also suitable herein.

Other organic polymeric compounds suitable for incoφoration in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose 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 preferably about 4000.

Bleach catalyst

The compositions optionally contain a transition metal containing 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 manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(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 manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include

O) j (u-OAc)2( 1 ,4,7-trimethyl- 1 ,4,7-triazacyclononane)2-(CIO4)2, Mn^4(u- O)6( 1 ,4,7-triazacyclononane)4-(Clθ4)2, Mn^Mn^{1 V}4(u-O) i (u-OAc)2-( 1 ,4,7- trimethyl-l,4,7-triazacyclononane)2-(Clθ4)3, and mixtures thereof. Others are described in European patent application publication no. 549,272. Other ligands suitable for use herein include l,5,9-trimethyl-l,5,9-triazacyclododecane, 2-methyl- 1 ,4,7-triazacyclononane, 2-methyl-l ,4,7-triazacyclononane, 1 ,2,4,7-tetramethyl- 1 ,4,7-triazacyclononane, and mixtures thereof.

For examples of suitable bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear manganese (IV) complexes such as Mn(l,4,7-trimethyl-l,4,7-triazacyclononane)(OCH3)3_(PF6). Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,1 14,606, is a water- soluble complex of manganese (III), and/or (IV) with a ligand which is a non- carboxylate polyhydroxy compound having at least three consecutive C-OH groups. Other examples include binuclear Mn complexed with tetra-N-dentate and bi-N- dentate ligands, including N4Mn^^(u-O)2Mn^N4)⁺and [Bipy2MnHI(u- O)₂Mn^Ivbipy2]-(ClO4)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-poφhyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,71 1 ,748 and European patent application, publication no. 224,952, (absorbed manganese on aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,1 19,557 (ferric complex catalyst), German Pat. specification 2,054,019 (cobalt chelant catalyst) Canadian 866,191 (transition metal-containing salts), U.S. 4,430,243 (chelants with manganese cations and non-catalytic metal cations), and U.S. 4,728,455 (manganese gluconate catalysts).

Enzyme

A preferred component of the detergent compositions is an enzyme.

Suitable enzymes include the commercially available lipases, amylases, neutral and alkaline proteases, cellulases, pectinases, lactases and peroxidases, that is enzymes having lipolytic, amylolytic, proteolytic, cellulolytic, pectolytic, lactolytic and peroxidolytic activity respectively, conventionally incoφorated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.

Protease enzymes are especially preferred as the enzyme component. Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incoφorated into the compositions in accordance with the invention at a level of from 0.0001% to 4% active enzyme by weight ofthe composition.

Preferred amylases include, for example, α-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 tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl and BAN by Novo Industries A/S. Amylase enzyme may be incoφorated into the composition in accordance with the invention at a level of from 0.0001% to 4% active enzyme by weight of the composition.

Lipolytic enzyme (lipase) which are also preferred may be present at levels of active lipolytic enzyme of from 0.0001% to 4% active enzyme by weight, preferably 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 mutants of these strains are also useful herein.

A preferred lipase is derived from Pseudomonas pseudoalcaligenes. which is described in Granted European Patent, EP-B-0218272.

Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza. as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge- Jensen et al, issued March 7, 1989.

Enzyme Stabilizing System

Preferred enzyme-containing compositions herein may comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%,most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such stabilizing systems can comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, and mixtures thereof. Such stabilizing systems can also comprise reversible enzyme inhibitors, such as reversible protease inhibitors.

The compositions herein may further comprise from 0 to about 10%, preferably from about 0.01% to about 6% by weight, of chlorine bleach scavengers, added to prevent chlorine species present in many water supplies from attacking and inactivating the enzymes, especially under alkaline conditions. While chlorine levels in water may be small, typically in the range from about 0.5 ppm to about 1.75 ppm, the available chlorine in the total volume of water that comes in contact with the enzyme during washing is usually large; accordingly, enzyme stability in-use can be problematic.

Suitable chlorine scavenger anions are widely available, and are illustrated by salts containing ammonium cations or sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc. Antioxidants such as carbamate, ascorbate, etc., organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof, monoethanolamine (MEA), and mixtures thereof can likewise be used. Other conventional scavengers such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate. malate, tartrate, salicylate. etc. and mixtures thereof can be used if desired.

Lime soap dispersant compound

The compositions ofthe invention may contain a lime soap dispersant compound, which has a lime soap dispersing power (LSDP), as defined hereinafter of no more than 8, preferably no more than 7, most preferably no more than 6. The lime soap dispersant compound is preferably present at a level of from 0.1 % to 40% by weight, more preferably 1% to 20% by weight, most preferably from 2% to 10% by weight ofthe compositions.

A lime soap dispersant is a material that prevents the precipitation of alkali metal, ammonium or amine salts of fatty acids by calcium or magnesium ions. A numerical measure ofthe effectiveness ofa lime soap dispersant is given by the lime soap dispersing power (LSDP) which is determined using the lime soap dispersion test as described in an article by H.C. Borghetty and CA. Bergman, J. Am. Oil. Chem. Soc, volume 27, pages 88-90, (1950). This lime soap dispersion test method is widely used by practitioners in this art field being referred to , for example, in the following review articles; W.N. Linfield, Surfactant Science Series, Volume 7, p3; W.N. Linfield, Tenside Surf. Det. , Volume 27, pages 159- 161, (1990); and M.K. Nagarajan, W.F. Masler, Cosmetics and Toiletries, Volume 104, pages 71-73, (1989). The LSDP is the % weight ratio of dispersing agent to sodium oleate required to disperse the lime soap deposits fonned by 0.025g of sodium oleate in 30ml of water of 333ppm CaCO3 (Ca:Mg=3:2) equivalent hardness. Surfactants having good lime soap dispersant capability will include certain amine oxides, betaines. sulfobetaines, alkyl ethoxysulfates and ethoxylated alcohols.

Exemplary surfactants having a LSDP of no more than 8 for use in accord with the invention include Cjg-Ci dimethyl amine oxide, C^-Cj alkyl ethoxysulfates with an average degree of ethoxylation of from 1-5, particularly C12-C15 alkyl ethoxysulfate surfactant with a degree of ethoxylation of about 3 (LSDP=4), and the C13-C15 ethoxylated alcohols with an average degree of ethoxylation of either 12 (LSDP=6) or 30, sold under the trade names Lutensol A012 and Lutensol A030 respectively, by BASF GmbH.

Polymeric lime soap dispersants suitable for use herein are described in the article by M.K. Nagarajan and W.F. Masler. to be found in Cosmetics and Toiletries, Volume 104, pages 71-73, (1989). Examples of such polymeric lime soap dispersants include certain water-soluble salts of copolymers of acrylic acid, methacrylic acid or mixtures thereof, and an acrylamide or substituted acrylamide, where such polymers typically have a molecular weight of from 5,000 to 20,000.

Suds suppressing svstem

The detergent compositions ofthe invention, when formulated 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 5% by weight ofthe composition.

Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.

By antifoam compound it is meant herein any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution ofa detergent composition, particularly in the presence of agitation of that solution.

Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component. The term "silicone" as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types. Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.

Other suitable antifoam compounds include the monocarboxylic 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 monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium 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 C\ g-C4ø ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.

A preferred suds suppressing system comprises

(a) antifoam compound, preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination

(i) polydimethyl siloxane, at a level of from 50% to 99%, preferably 75% to 95% by weight ofthe silicone antifoam compound; and

(ii) silica, at a level of from 1 % to 50%, preferably 5% to 25% by weight ofthe silicone/silica antifoam compound;

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

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

A highly preferred particulate suds suppressing system is described in EP-A- 0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50°C to 85°C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45°C to 80°C.

Polymeric dye transfer inhibiting agents

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

The polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.

a) Polyamine N-oxide polymers

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

(I) A*

R

wherein P is a polymerisable unit, and

O O O

A is NC, CO, C, -O-, -S-, -N-; x is O or 1 ;

R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be attached or wherein the nitrogen ofthe N-O group is part of these groups.

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

O

▲

O (R^ x -N-fR^y ^A

(R₃)_{z or} = N-(R.,)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 ofthe N-O group can be attached or wherein the nitrogen ofthe N-O group forms part of these groups. The N-O group can be part ofthe 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 ofthe polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. One class of said polyamine N- oxides comprises the group of polyamine N-oxides wherein the nitrogen ofthe N-O group forms part ofthe R-group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof. Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O group is attached to the polymerisable unit. A preferred 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 ofthe N-O functional group is part of said R group. Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.

The polyamine N-oxides can be obtained in almost any degree of polymerisation. The degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power. Typically, the average molecular weight is within the range of 500 to 1000,000.

b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole

Suitable herein are coploymers of N-vinylimidazole and N-vinylpyrrolidone having an average molecular weight range of from 5,000 to 50,000. The preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2.

c) Polyvinylpyrrolidone

The detergent compositions herein may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from 2,500 to 400,000. Suitable polyvinylpyrrolidones are commercially vailable from ISP Coφoration, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000). PVP K-15 is also available from ISP Coφoration. Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.

d) Polyvinyloxazolidone The detergent 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) Polyvinyiimidazole

The detergent compositions herein may also utilize polyvinyiimidazole as polymeric dye transfer inhibiting agent. Said polyvinylimidazoles preferably have an average molecular weight of from 2,500 to 400,000.

Optical brightener

The detergent compositions herein also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners.

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

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

When in the above formula, Rj is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis- hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Coφoration. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein. When in the above formula, R\ is anilino, R2 is N-2-hydroxyethyl-N-2- methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino- 6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Coφoration.

When in the above formula, R\ is anilino, R2 is moφhilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-moφhilino-s-triazine-2- yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Coφoration.

Softening agents

Fabric softening agents can also be incoφorated into laundry detergent compositions in accordance with the present invention. These agents may be inorganic or organic in type. Inorganic softening agents are exemplified by the smectite clays disclosed in GB-A-1 400 898. Organic fabric softening agents include the water insoluble tertiary amines as disclosed in GB-A-1 514 276 and EP-B-0 01 1 340.

Levels of smectite clay are normally in the range from 5% to 15%, more preferably from 8% to 12% by weight, with the material being added as a dry mixed component to the remainder ofthe formulation. Organic fabric softening agents such as the water-insoluble tertiary amines or dilong chain amide materials are incoφorated at levels of from 0.5% to 5% by weight, normally from 1% to 3% by weight, whilst the high molecular weight polyethylene oxide materials and the water soluble cationic materials are added at levels of from 0.1% to 2%, normally from 0.15% to 1.5% by weight.

Other optional ingredients

Other optional ingredients suitable for inclusion in the compositions ofthe invention include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.

Form ofthe compositions The detergent compositions of the invention can be formulated in any desirable form such as powders, granulates, pastes, liquids and gels. The compositions are preferably not in tablet-form. Most preferably, the compositions are in granular form.

Liquid compositions

The detergent compositions ofthe present invention may be formulated as liquid detergent compositions. Such liquid detergent compositions typically comprise from 94% to 35% by weight, preferably from 90% to 40% by weight, most preferably from 80% to 50% by weight ofa liquid carrier, e.g., water, preferably a mixture of water and organic solvent.

Gel compositions

The detergent compositions ofthe present invention may also be in the form of gels. Such compositions are typically formulated with polyakenyl polyether having a molecular weight of from about 750,000 to about 4,000,000.

Solid compositions

The detergent compositions ofthe invention are preferably in the form of solids, such as powders and granules. Granular form is preferred.

The particle size ofthe components of granular compositions in accordance with the invention should preferably be such that no more that 5% of particles are greater than 1.4mm in diameter and not more than 5% of particles are less than 0.15mm in diameter.

The bulk density of granular detergent compositions in accordance with the present invention typically have a bulk density of at least 450 g/litre, more usually at least 600 g/litre and more preferably from 650 g litre to 1200 g litre.

Bulk density is measured by means ofa simple funnel and cup device consisting ofa conical funnel moulded rigidly on a base and provided with a flap valve at its lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylindrial cup disposed below the funnel. The funnel is 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base. The cup has an overall height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.

To carry out a 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 e.g. a knife, across its upper edge. The filled cup is then weighed and the value obtained for the weight of powder doubled to provide the bulk density in g/litre. Replicate measurements are made as required.

Making processes - granular compositions

In general, granular detergent compositions in accordance with the present invention can be made via a variety of methods including dry mixing, spray drying, agglomeration and granulation.

Washing methods

The compositions ofthe invention may be used in essentially any washing or cleaning method, including machine laundry and dishwashing methods.

Machine dishwashing method

A preferred machine dishwashing method comprises treating soiled articles selected from crockery, glassware, hollowware and cutlery and mixtures thereof, with an aqueous liquid having dissolved or dispensed therein an effective amount ofa machine dishwashing composition in accord with the invention. By an effective amount ofthe machine dishwashing composition it is typically meant from 8g to 60g of product dissolved or dispersed in a wash solution of volume from 3 to 10 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine dishwashing methods.

Machine laundry methods Machine laundry methods herein comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount ofa machine laundry detergent composition in accord with the invention. The detergent can be added to the wash solution either via the dispenser drawer of the washing machine or by a dispensing device. By an effective amount ofthe detergent composition it is typically meant from 40g to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.

In a preferred washing method herein a dispensing device containing an effective amount of detergent product is introduced into the drum of a. preferably front- loading, washing machine before the commencement ofthe wash cycle.

The dispensing device is a container for the detergent product which is used to deliver the product directly into the drum ofthe washing machine. Its volume capacity should be such as to be able to contain sufficient detergent product as would normally be used in the washing method.

Once the washing machine has been loaded with laundry the dispensing device containing the detergent product is placed inside the drum. At the commencement ofthe wash cycle ofthe washing machine water is introduced into the drum and the drum periodically rotates. The design ofthe dispensing device should be such that it permits containment ofthe dry detergent product but then allows release of this product during the wash cycle in response to its agitation as the drum rotates and also as a result of its immersion in the wash water.

To allow for release ofthe detergent product during the wash the device may possess a number of opemngs through which the product may pass. Alternatively, the device may be made of a material which is permeable to liquid but impermeable to the solid product, which will allow release of dissolved product. Preferably, the detergent product will be rapidly released at the start ofthe wash cycle thereby providing transient localised high concentrations of components such as water- soluble builder and heavy metal ion sequestrant components in the drum of the washing machine at this stage ofthe wash cycle. Preferred dispensing devices are reusable and are designed in such a way that container integrity is maintained in both the dry state and during the wash cycle. Especially preferred dispensing devices for use in accord with the invention have been described in the following patents; GB-B-2, 157, 717, GB-B-2, 157, 718, EP- A-0201376, EP-A-0288345 and EP-A-0288346. An article by J.Bland published in Manufacturing Chemist, November 1989, pages 41-46 also describes especially preferred dispensing devices for use with granular laundry products which are of a type commonly know as the "granulette".

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

Examples

In the detergent compositions, the abbreviated component identifications have the following meanings:

Abbreviations used in Examples

LAS Sodium linear C 2 alkyl benzene sulfonate TAS Sodium tallow alkyl sulfate C45AS Sodium C14-C15 linear alkyl sulfate CxyEzS Sodium Cι_x-Ciy branched alkyl sulfate condensed with z moles of ethylene oxide C45E7 A C 14_ 15 predominantly linear primary alcohol condensed with an average of 7 moles of ethylene oxide

C25E3 A C 12-15 branched primary alcohol condensed with an average of 3 moles of ethylene oxide

C25E5 A C 12- 15 branched primary alcohol condensed with an average of 5 moles of ethylene oxide

CEQ Rl COOCH₂CH₂.N⁺(CH3)3 with Rj = Cj \-C QAS R2.N⁺(CH3)₂(C₂H₄OH) with R₂ = Cj₂ - C 14 Soap Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut oils.

TFAA C j 6-C j g alkyl N-methyl glucamide TPKFA C 12-C 14 topped whole cut fatty acids STPP Anhydrous sodium tripolyphosphate Zeolite A Hydrated Sodium Aluminosilicate of formula Naj2(Alθ2Siθ2)i2- 27H2O having a primary particle size in the range from 0.1 to 10 micrometers NaSKS-6 Crystalline layered silicate of formula δ -Na2Si2θ5

Citric acid Anhydrous citric acid Carbonate Anhydrous sodium carbonate with a particle size between 200μm and 900μm

Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400μm and 1200μm

Silicate Amoφhous Sodium Silicate (Siθ2:Na2θ; 2.0 ratio)

Sodium sulfate Anhydrous sodium sulfate

Citrate Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425 μm and 850 μm

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 enzyme of activity 3AU/g sold by NOVO Industries A/S

Cellulase : Cellulytic enzyme of activity 1000 CEVU/g sold by NOVO Industries A/S under the tradename

Carezyme Amylase Amylolytic enzyme of activity 60KNU/g sold by NOVO Industries A/S under the tradename Termamyl 60T

Lipase Lipolytic enzyme of activity lOOkLU/g sold by NOVO Industries A/S under the tradename Lipolase

Endolase : Endoglunase enzyme of activity 3000 CEVU/g sold by NOVO Industries A/S

PB4: Sodium perborate tetrahydrate of nominal formula NaBO2.3H2O.H2O2

PB1 : Anhydrous sodium perborate bleach of nominal formula NaBθ2-H2θ2

Percarbonate Sodium Percarbonate of nominal formula

2Na₂CO₃.3H2θ2 NOBS : Nonanoyloxybenzene sulfonate in the form ofthe sodium salt.

TAED Tetraacetylethylenediamine - in particulate form, designed to have a T50 value, as defined herein, of less than 60 seconds DTPMP Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Trade name Dequest 2060

Photoactivated Sulfonated Zinc Phthlocyanine encapsulated in bleach dextrin soluble polymer

Brightener 1 : Disodium 4,4'-bis(2-sulphostyryl)biphenyl Brightener 2 : Disodium 4,4'-bis(4-anilino-6-moφholino-l .3.5- triazin-2-yl)amino) stilbene-2:2'-disulfonate.

HEDP : 1,1 -hydroxyethane diphosphonic acid PVNO Polyvinylpyridine N-oxide PVPVI Copolymer of polyvinylpyrolidone and vinylimidazole

SRP 1 Sulfobenzoyl end capped esters with oxyethylene oxy and terephtaloyl backbone

SRP 2 Diethoxylated poly (1 , 2 propylene terephtalate) short block polymer

Silicone antifoam Polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10: 1 to 100: 1. Nonionic C\ 3-C 15 mixed ethoxylated/propoxylated fatty alcohol with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5 sold under the tradename Plurafac LF404 by BASF Gmbh (low foaming)

Metasilicate Sodium metasilicate (SiO2:Na2O ratio = 1.0)

Phosphate Sodium tripolyphosphate

480N Random copolymer of 3:7 acrylic/methacrylic acid, average molecular weight about 3,500

NAPAA precursor Coated particle containing an amide substituted particle precursor particle alkyl peroxyacid precursor compound capable of releasing on perhydrolysis a nonyl amide of peroxy adipic acid (NAPAA), wherein the coating comprises sodium silicate (2.0 ratio) present at a weight ratio relative to the precursor compound of

3 : 97. The particle is designed to have a T50 value, as defined herein, of at least 180 seconds. NOBS particle Particle formed by agglomerating sodium nonanoyloxybenzene sulfonate (NOBS) with citric acid and polyethylene glycol (PEG) of Mw=4,000 with a weight ratio of components of NOBS itric acid:PEG of 75:10:15, coated with an external coating of citric acid at a weight ratio of agglomerate: citric acid coating of 95:5, designed to have a T50, as defined herein of > 180 seconds.

Benzoyl Caprolactam Benzoyl caprolactam particle formed by particle agglomerating the precursor compound with citric acid and polyethylene glycol (PEG) of Mw=4,000, with a weight ratio of components of precursor compound: citric acid:PEG of 63:21 : 16, coated with an extemal coating of citric acid at a weight ratio of agglomerate itric acid coating of 95:5, designed to have a T50, as defined herein, of > 180 seconds.

Cationic Caprolactam Particle containing p-(N,N,N triethylammoniummethyl) benzoyl particle caprolactam chloride precursor compound formed by agglomerating the precursor compound with citric acid and polyethylene glycol (PEG) of Mw=4,000, with a weight ratio of components of precursor compound: citric acid.PEG of 63:21:16, coated with an external coating of citric acid at a weight ratio of agglomeratexitric acid coating of 95:5, designed to have a T50, as defined herein, of > 180 seconds.

DAP particle Coated particle containing diperoxydodecanedioc acid, wherein the coating comprises sodium silicate (2.4 ratio) at a coating level of 5%. The T50 ofthe particle is designed to be greater than 200 seconds.

Bismuth nitrate Bismuth nitrate salt

Paraffin Paraffin oil sold under the tradename Winog 70 by

Wintershall. BSA Amylolytic enzyme sold under the tradename LEI 7 by Novo Industries A/S (approx 1% enzyme activity) Sulphate Anhydrous sodium sulphate.

pH Measured as a 1% solution in distilled water at 20°C.

Examples

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

Example 1 The following laundry detergent compositions A to F were prepared in accord with the invention:

A B C D E F

LAS 8.0 8.0 8.0 8.0 8.0 8.0

C25E3 3.4 3.4 3.4 3.4 3.4 3.4

CEQ - 0.8 - - 0.8 -

QAS - - 0.8 - - 0.8

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 26.1 26.1 26.1 26.1 26.1 26.1 sulfate

PB4 9.0 9.0 9.0 9.0 9.0 9.0

NAPAA 0.8 0.6 0.4 1.0 0.5 1.0 precursor particle

TAED 0.7 0.9 0.6 1.0 1.5 1.5

DETPMP 0.25 0.25 0.25 0.25 0.25 0.25

HEDP 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

CMC 0.2 0.2 0.2 0.2 0.2 0.2

Photoactivated 15 ppm 15 ppm 15 ppm 15 ppm 15 ppm 15 ppm bleach (ppm)

Brightener 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

Silicone 0.5 0.5 0.5 0.5 0.5 0.5 antifoam

Misc/minors to 100%

Density in 850 850 850 850 850 850 g/litre

The following T50 values (in seconds) were obtained for each of products A to D:

Example 2

The following granular laundry detergent compositions G to I of bulk density 750 g/litre were prepared in accord with the invention: G H I

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 19.7 - -

Zeolite A - 19.5 19.5

NaSKS-6/citric acid 10.6 10.6 (79:21)

Carbonate 6.1 21.4 21.4

Bicarbonate - 2.0 2.0

Silicate 6.8 - -

Sodium sulfate 39.8 - 14.3

PB4 5.0 12.7 -

TAED 0.5 1.0 1.0 Benzoyl 0.5 1.0 0.5 caprolactam particle

DETPMP 0.25 0.2 0.2

HEDP - 0.3 0.3

Protease 0.26 0.85 0.85

Lipase 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 15 ppm 27 ppm 27 ppm bleach (ppm)

Brightener 1 0.08 0.19 0.19

Brightener 2 - 0.04 0.04

Perfume 0.3 0.3 0.3

Silicone antifoam 0.5 2.4 2.4

Minors/misc to 100%

Example 3 The following detergent formulations, according to the present invention were prepared, where J is a phosphorus-containing detergent composition, K is a zeolite- containing detergent composition and L is a compact detergent composition:

J K L

Blown Powder

STPP 24.0 - 24.0

Zeolite A - 24.0 -

C45AS 9.0 6.0 13.0

MA/AA 2.0 4.0 2.0

LAS 6.0 8.0 1 1.0

TAS 2.0 - -

Silicate 7.0 3.0 3.0

CMC 1.0 1.0 0.5

Brightener 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 6.0 13.0 15.0

PB4 18.0 18.0 10.0

PB1 4.0 4.0 0

TAED 2.0 1.5 1.0

Cationic caprolactam particle 1.0 0.5 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 mixed sodium sulfate 3.0 3.0 5.0

Balance (Moisture & 100.0 100.0 100.0 Miscellaneous)

Density (g/litre) 630 670 670

Example 4

The following machine dishwashing compositions were prepared in accord with the invention.

DETPMP 0.13 0.13 - - - 0.4 0.2

HEDP - 1.0 1.0 1.0 - - -

EDTA - - - 0.5 0.5 - -

Sulphate 23.0 22.8 22.4 22.7 22.2 21.5 0.3

misc inc moisture to balance pH (l% 10.7 10.7 10.7 10.7 10.7 10.7 1 1.0 solution)

Example 5

The following detergent formulations, according to the present invention were prepared:

T U V W

LAS 20.0 14.0 24.0 22.0

QAS 0.7 1.0 - 0.7

TFAA - 1.0 - -

C25E5/C45E7 - 2.0 - 0.5

C45E3S - 2.5 - -

STPP 30.0 18.0 30.0 22.0

Silicate 9.0 5.0 10.0 8.0

Carbonate 13.0 7.5 - 5.0

Bicarbonate - 7.5 - -

DTPMP 0.7 1.0 - -

SRP 1 0.3 0.2 - 0.1

MA/AA 2.0 1.5 2.0 1.0

CMC 0.8 0.4 0.4 0.2

Protease 0.8 1.0 0.5 0.5

Amylase 0.8 0.4 - 0.25

Lipase 0.2 0.1 0.2 0.1

Cellulase 0.15 0.05 - - Photoactivated 70ppm 45ppm - lOpp bleach (ppm)

Brightener 1 0.2 0.2 0.08 0.2

PB1 6.0 2.0 - -

NOBS particle 2.0 1.0 0.5 1.0

TAED 1.0 1.0 2.0 2.0

Balance 100 100 100 100 (Moisture and Miscellaneous)

Example 6

X Y Z

Blown Powder

Zeolite A 30.0 22.0 6.0

Sodium sulfate 19.0 5.0 7.0

MA/AA 3.0 3.0 6.0

LAS 14.0 12.0 22.0

C45AS 8.0 7.0 7.0

Silicate - 1.0 5.0

Soap - - 2.0

Brightener 1 0.2 0.2 0.2

Carbonate 8.0 16.0 20.0

DTPMP - 0.4 0.4

Spray On

C45E7 1.0 1.0 1.0

Dry additives

PVPVI PVNO 0.5 0.5 0.5

Protease 1.0 1.0 1.0

Lipase 0.4 0.4 0.4

Amylase 0.1 0.1 0.1

Cellulase 0.1 0.1 0.1

NOBS particle 2.0 - 2.5

DAP particle 1.0 3.0 -

TAED 2.0 3.0 3.0

PB1 1.0 5.0 6.0

Sodium sulfate - 6.0 -

Balance (Moisture and 100 100 100 Miscellaneous) Example 7

The following high density and bleach-containing detergent formulations, according to the present invention were prepared:

AA AB AC

Blown Powder

Zeolite A 15.0 15.0 15.0

Sodim sulfate 0.0 5.0 0.0

LAS 3.0 3.0 3.0

QAS - 1.5 1.5

DTPMP 0.4 0.4 0.4

CMC 0.4 0.4 0.4

MA/AA 4.0 2.0 2.0

Agglomerates

LAS 5.0 5.0 5.0

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 4.0

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 4.0 2.0 2.0

NAPAA precursor particle 2.0 1.0 3.0

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

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 Balance (Moisture and 100.0 100.0 100.0 Miscellaneous)

Density (g/litre) 850 850 850

Example 8

The following high density detergent formulations, according to the present invention were prepared:

AD AE

Agglomerate

C45AS 1 1.0 14.0

Zeolite A 15.0 6.0

Carbonate 4.0 8.0

MA/AA 4.0 2.0

CMC 0.5 0.5

DTPMP 0.4 0.4

Spray On

C25E5 5.0 5.0

Perfume 0.5 0.5

Dry Adds

HEDP 0.5 0.3

SKS 6 13.0 10.0

Citrate 3.0 1.0

TAED 2.0 3.0

NAPAA precursor particle 3.0 4.0

Percarbonate 20.0 20.0

SRP 1 0.3 0.3

Protease 1.4 1.4

Lipase 0.4 0.4

Cellulase 0.6 0.6

Amylase 0.6 0.6

Silicone antifoam 5.0 5.0

Brightener 1 0.2 0.2

Brightener 2 0.2 -

Balance (Moisture and Miscellaneous) 100 100

Density (g/litre) 850 850

Claims

What is claimed is:

1. A detergent composition containing an organic peroxyacid bleaching system capable of releasing two different organic peroxyacid bleaches to a wash solution wherein a means is provided for delaying the release to a wash solution ofthe stronger peroxyacid relative to the release of a weaker peroxyacid such that in the T50 test method herein described the time to achieve a concentration that is 50% ofthe ultimate concentration of said stronger peroxyacid is at least 120 seconds more than the time to achieve a concentration that is 50% ofthe ultimate concentration of said weaker peroxyacid, wherein the relative strength ofthe peroxyacids is measured according to the 'dye bleaching protocol' described herein.

2. A detergent composition according to Claim 1 wherein the time to achieve a concentration that is 50% ofthe ultimate concentration ofthe weaker peroxyacid is less than 60 seconds and the time to achieve a concentration that is 50% ofthe ultimate concentration ofthe stronger peroxyacid is more than

180 seconds.

3. A detergent composition according to Claim 2 wherein the time to achieve a concentration that is 50% ofthe ultimate concentration ofthe stronger organic peroxyacid is from 240 to 480 seconds.

4. A detergent composition according to any of Claims 1 to 3 wherein said organic peroxyacid bleaching system contains a hydrogen peroxide source and a plurality of organic peroxyacid bleach precursor compounds.

5. A detergent composition according to Claim 4 wherein said organic peroxyacid bleaching system contains two organic peroxyacid bleach precursor compounds.

A detergent composition according to Claims 4 or 5 wherein one organic peroxyacid precursor compound is an N-,N,N'N^ tetra acetylated alkylene diamine, preferably TAED.

7. A detergent composition according to Claim 6 wherein a second organic peroxyacid precursor compound is an amide substituted alkyl peroxyacid precursor compounds selected from those of the following general formulae:

R¹ - - C — N — R² — C — L R¹ — N — C — R² — C — L

O R⁵ O or R⁵ O O

wherein R Ms an alkyl group with from 1 to 14 carbon atoms, R^ is an alkylene group containing from 1 to 14 carbon atoms, and R^ is H or an alkyl group containing 1 to 10 carbon atoms and L is a leaving group.

8. A detergent composition according to any of Claims 4 to 7 wherein said hydrogen peroxide source is an inorganic perhydrate salt.

9. A detergent composition according to any of Claim 8 wherein said inorganic perhydrate salt is sodium perborate tetrahydrate.

10. A detergent composition according to any of Claims 1 to 9 which is in granular form.

1 1. The use of a detergent composition according to any of Claims 1 to 10 in a laundry washing method wherein the detergent composition is delivered to the wash solution by means of a dispensing device introduced into the drum of a washing machine before the commencement ofthe wash.