Phosphate free detergent compositions

Technical field

The present invention relates to detergent compositions containing relatively low levels of a nil-phosphate builder, a hydrophobic peroxyacid bleaching system and a mixed heavy metal ion sequestrant system. The compositions are suitable for use in laundry washing methods.

Background to the invention

It is well established that peroxygen bleaches can aid stain and/or soil removal from fabrics, but that the performance of such bleaches is temperature dependent. At lower laundry wash temperatures, particularly below about 60°C, peroxygen bleaches are less effective than at higher wash temperatures. Accordingly, research efforts have been directed towards the development of bleaching systems, based on organic peroxyacids, which can provide effective stain and/or soil removal from fabrics at lower wash temperatures. The organic peroxyacids are often obtained by the in situ perhydrolysis of organic peroxyacid bleach precursor compounds (bleach activators).

A commonly employed precursor compound is tetraacetyl ethylene diamine (TAED) which provides peracetic acid on perhydrolysis. Peracetic acid provides effective hydrophilic cleaning especially on beverage stains, but has limited performance on dingy stains and body soils which are of a more hydrophobic nature. Hydrophobic organic peroxyacids have thus been developed to deal with such stains and soils. Such organic peroxyacids generally comprise long chain ( > 7 carbon atoms) alkyl moieties.

Heavy metal ion sequestrants are commonly included in detergent compositions which rely on organic peroxyacid bleaching systems. Such

heavy metal ion sequestrants have a primary stain/soil removal function, in that they aid the breakdown of stains/soils containing heavy metal ions such as tea (which contains Mn) and blood (which contains Fe). The sequestrants also act such as to sequester any heavy metal ions (e.g. Cu, Fe, Mn) in the laundry wash solution, or at the surface of the fabrics, which might otherwise give rise to wasteful catalytic decomposotion of the peroxyacid species.

Commonly used heavy metal ion sequestrants in detergent compositions include the organic amino phosphonates, such as the amino alkylene poly (alkylene phosphonates) and the organic amino carboxylates. These sequestrants each contain an amino linkage which is potentially oxidizable in a bleaching environment, although this has not previously been recognized as a general concern.

It has now been found that when a nil-phosphate built detergent composition containing a relatively low level of builder and a hydrophobic peroxyacid bleaching system is employed in the washing of fabrics which have previously been washed under hard water conditions the hydrophobic soil and stain removal performance of the peroxyacid is not as good as would normally be expected. It is believed that this problem of lack of performance is due to catalytic decomposition of the hydrophobic peroxyacid at the fabric surface, which is particularly severe as a result of the high level of metal ion encrustations on the surface of the fabrics which will have accumulated during previous washes under hard water conditions.

The problem is exarcerbated by the known tendency of hydrophobic bleaches to migrate rapidly to the surface of fabrics under wash conditions, most especially when used in a detergent containing high surfactant levels. Indeed, it is this 'surface preferential' character which would normally result in the effective dingy soil cleaning performance of the hydrophobic bleach.

It has now been found that the problem can be ameliorated by the inclusion of a specific heavy metal ion sequestrant system into the detergent composition. In an essential aspect, this system must contain

both a sequestrant which has a oxidizable amino linkage and a second sequestrant which does not. If only one of these sequestrant types is employed, the problem is not effectively addressed. It is believed that the sequestrant having the oxidizable amino linkage is susceptable to oxidation, and therefore denaturation, at the fabric surface where relatively high levels of hydrophobic bleach are to be found. However, this sequestrant can act effectively 'in solution' thereby contributing to the overall sequesterant system.

It has also been found that the problem is particularly addressed when the second sequestrant has crystal growth inhibition capacity. This is believed to be because, in this case, the sequestrant/crystal growth inhibitor binds relatively strongly to the metal ion (particularly Ca) encrustations on the fabric surface, thereby acting as a barrier which prevents close approach of the peroxyacid to the encrusted surface and hence acts to prevent metal ion catalysed decomposition of that peroxyacid at the surface.

Additionally, it has been found that particularly good soil/stain removal performance under the conditions described can be obtained when the heavy metal ion sequestrants employed in the composition have complementary affinities for different types of metal ion (measured by reference to binding constants). In particular, good performance is observed where the first sequestrant has a higher affinity for Ca2+ ions than for heavy metal ions, and the second sequestrant has a high affinity for heavy metal ions, but lower affinity for Ca2+ ions.

EP-A-0170,386 describes hydrophobic peroxyacids, including those of the amide peroxyacid (NAPAA) type, and precursors thereto. PCT Application No. US94/05371 describes a mixed hydrophobic precursor system comprising a hydrophilic n-acyl caprolactam and hydrophobic alkanoxy benzene sulfonate blech activator. PCT Application No. US94/05370 described detergent compositions containing hydrophobic precursors and enzymes. U.S. Patent 4,412,934, Chung et al, issued November 1, 1983, discloses hydrophobic alkanoyl-oxybenzenesulfonate bleach precursor compounds.

All documents cited in the present description are, in relevant part, incoφorated herein by reference.

Summary of the Invention

According to the present invention there is provided a phosphate-free detergent composition comprising

(a) from 1 % to 45 % by weight of the composition of a nil- phosphate builder system;

(b) a bleaching system capable of providing an organic peroxyacid compound having at least 7 carbon atoms;

(c) a first heavy metal ion sequestrant having a oxidizable amino linkage; and

(d) a second heavy metal ion sequestrant having no oxidizable amino linkage.

In one preferred aspect the detergent composition additionally comprises more than 15 % by weight of a surfactant system.

Detailed description of the invention

The detergent compositions of the invention are phosphate-free, that is to say contain no, or only trace amounts of phosphate builder compound.

Nil-phosphate builder system

The first essential element of the detergent compositions of the invention is a nil-phosphate builder system present in amount from 1 % to 45 % , preferably from 5% to 37%, most preferably from 15% to 35 % by weight of the detergent composition.

The nil-phosphate builder system may comprise water-soluble, partially water-soluble and water-insoluble builder compounds, or preferably any mixtures thereof. For clarity, the builder system is not to be held to

include any of the organic polymers described as 'organic polymeric compounds' hereinafter.

Water-soluble builder compound

Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxyhc acids or their salts in which the polycarboxyhc acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, carbonates, bicarbonates, borates, silicates and mixtures of any of the 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 carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in British Patent No. 1 ,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-l,l,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.

Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates. The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.

In a preferred aspect, the nil-phosphate builder system comprises from 5 % to 40% by weight, more preferably from 8% to 20% by weight of the nil-phosphate builder system of a polycarboxylate builder, especially when a sodium aluminosilicate builder is also present.

Examples of carbonate and bicarbonate builders include the alkali and alkaline earth metal carbonates, particularly sodium carbonate and sodium bicarbonate.

Partially soluble or insoluble builder compound

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 _x θ2 _x+ ι .yH 0

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 of the present invention, x in the general formula above has a value of 2, 3 or 4 and is preferably 2. The most preferred material is 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 thereof.

Suitable aluminosilicate zeolites have the unit cell formula Na _z [(Alθ2) _z (Siθ2)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 [AIO2) 12 (Siθ2)i2l. xH ₂ 0

wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na ₈₆ [<Alθ2)86(Siθ2)l06]- ^{276 H} 2°-

In a preferred aspect the nil-phosphate builder system comprises from 25% to 70%, preferably from 30% to 60% by weight of the builder system of a sodium aluminosilicate zeolite builder, and most preferably a polycarboxylate builder is also present.

Builders capable of providing alkalinity

The nil-phosphate builder system can include components which in addition to providing builder capacity also act as a primary source of alkalinity. Herein, these alkalinity sources are exhaustively deemed to be the carbonates, bicarbonates and silicates including crystalline layered silicates and any mixtures thereof, as described herein before which in combination may comprise an alkalinity system. In a preferred aspect these alkalinity sources comprise from 20% to 80% , more preferably from 30% to 70% by weight of the nil-phosphate builder system.

Organic peroxyacid bleaching system

An essential feature of detergent compositions of the invention is a hydrophobic organic peroxyacid bleaching system. By hydrophobic organic peroxyacid it is meant herein an organic peroxyacid containing at least 7 carbon atoms, more preferably at least 9 carbon atoms, most preferably at least 11 carbon atoms. In a preferred aspect the peroxyacid has an alkyl chain comprising at least 7 carbon atoms, more preferably at least 8 carbon atoms, most preferably at least 9 carbon atoms.

In one preferred execution the bleaching system contains a hydrogen peroxide source and a hydrophobic organic peroxyacid bleach precursor compound. The production of the hydrophobic organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In an alternative preferred execution a preformed hydrophobic organic peroxyacid is incorporated directly into the composition. Compositions containing mixtures of a hydrogen peroxide source and hydrophobic organic peroxyacid precursor in combination with a preformed hydrophobic organic peroxyacid are also envisaged.

Inorganic perhydrate bleaches

Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These salts are normally incoφorated in the form of the alkali metal, preferably sodium salt at a level of from 1 % to 40% by weight, more

preferably from 2% to 30% by weight and most preferably from 5% to 25% by weight of the compositions.

Examples of inorganic perhydrate salts include perborate, percarbonate, peφhosphate, 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 of the 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 of the monohydrate of nominal formula NaBθ2H2θ2 or the tetrahydrate NaBθ2H2θ ₂ .3H2θ.

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 perhydrolysis the structure of the peroxyacid produced is

O X C OOH

For the puφoses of the present invention X will thus contain at least 6 carbon atoms.

The hydrophobic peroxyacid bleach precursor compounds are preferably incoφorated at a level of from 0.05% to 20% by weight, more preferably from 0.1 % to 15 % by weight, most preferably from 0.2% to 10% by weight of the detergent compositions.

Suitable hydrophobic 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:

R ³ Y I I -O-CH=C-CH=CH ₂ -O-CH=C-CH=CH ₂

R ³ O Y

¹ II I ,

-O-C=CHR ⁴ , and — N— S— CH— R ⁴

I , II R ³ O

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

The preferred solubilizing groups are -SOg ^' M , -Cθ2 ^~ M , -S0 ₄ ^" M ⁺ , -N ⁺ (R ³ ) X~ and 0 < -N(R ³ ) ₃ and most preferably -S0 ₃ ^" M ⁺ and -Cθ2 ^~ M wherein R is an 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 alkyl percarboxylic precursor compounds of the imide type include the N-,N,NlNl tetra aeetylated alkylene diamines wherein the alkylene group contains at least 7 carbon atoms.

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

Amide substituted alkyl peroxyacid precursors

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

R ¹ — C — N — R ² — C — L R ¹ — N — C — R ² — C — L

O R ⁵ O or R ⁵ O O

wherein Rl is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene group containing from 1 to 14 carbon atoms, and R-5 is H or an alkyl group containing 1 to 10 carbon atoms such that Rl, R2 and R-5 in total contain at least 5 carbon atoms and L can be essentially any leaving group. Amide substituted peroxyacid precursor compounds of this type are described in EP-A-0170386.

Benzoxazin organic peroxyacid precursors

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

wherein Ri is an alkyl, alkaryl, aryl, or arylalkyl containing at least 5 carbon atoms.

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 hydrophobic organic peroxyacid , typically at a level of from 1 % to 15 % by weight, more preferably from 1 % to 10% by weight of the composition.

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

R ¹ — C — N — R 2 OOH 1 N C — R ² — C OOH O R ⁵ O or R ⁵ O O

wherein Rl is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene group containing from 1 to 14 carbon atoms, and R-5 is H or an alkyl group containing 1 to 10 carbon atoms such that Rl, R2 and R-5 in total contain at least 5 carbon atoms and L can be essentially any leaving group. Amide substituted preformed organic peroxyacid compounds of this type are described in EP-A-0170386.

Other suitable organic peroxyacids include diperoxyalkanedioc acids having more than 7 carbon atoms, such as diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.

Heavy metal ion sequestrant system

The detergent compositions of the invention contain as an essential component a heavy metal ion sequestrant system comprising at least two components. 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.

The heavy metal ion sequestrant system is generally present at a level of from 0.005 % to 20% , preferably from 0.1 % to 10% , more preferably from 0.2 % to 7.5 % and most preferably from 0.25 % to 5 % by weight of the compositions.

The heavy metal ion sequestrant system of the invention comprises a first sequestrant having a oxidizable amino (i. e. N-H or N-R) linkage, and a second sequestrant having no oxidizable linkage, preferably at a weight ratio of first to second sequestrant of rom 20: 1 to 1 :20, more preferably from 10: 1 to 1 : 10 most preferably from 3: 1 to 1 :3. By oxidizable amino linkage it is particularly meant that the amino linkage can be oxidised (to N-»0) under the oxidising/peroxidising conditions lo be found in a laundry wash solution.

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.

Heavy metal ion sequestrants having a oxidizable amino linkage

Suitable heavy metal ion sequestrants having a oxidizable amino linkage include organic amino phosphonates, such as the amino alkylene poly (alkylene phosphonates). Preferred sequestrants of this type include diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) and hexamethylene diamine tetra (methylene phosphonate). The binding constant for diethylene triamine penta (methylene phosphonate) at pH 10.4 is about 9.9 for Ca2+ ions, 9.3 for Mg2+ ions and 8.4 for copper ions.

Also suitable are amino carboxylates, including the poly aminocarboxylic 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).

Heavy metal ion sequestrants not having a oxidizable amino linkage

Suitable heavy metal ion sequestrants having a oxidizable amino linkage include organo diphosphonates which do not contain nitrogen as part of their chemical structure.

Suitable organo diphosphonates, which in addition provide crystal growth inhibition capacity, include the C1-C4 diphosphonates, more preferably the C2 diphosphonates, such as ethylene diphosphonate, or most preferably ethane 1 -hydroxy- 1 , 1 -diphosphonate (HEDP) . The binding constant for HEDP at pH 10.4 is about 3.9 for Ca ² + ions, 4.3 for Mg ² + ions and 8.2 for copper ions.

Additional detergent components

The detergent compositions of the 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 of the composition, and the precise nature of the washing operation for which it is to be used.

The compositions of the invention preferably contain one or more additional detergent components selected from surfactants, non- hydrophobic bleaches, organic polymeric compounds, enzymes, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition agents, brighteners, fluorescers and corrosion inhibitors.

Surfactant system

The detergent compositions of the invention preferably contain a surfactant system containing surfactant selected from anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.

High levels ( > 15 % by weight) of surfactant enhance the solublisation and dispersion of the hydrophobic organic peroxyacid bleaches, and any precursors thereto in the wash. Hence, high surfactant levels also enable enhanced rates of migration of the peroxyacid bleach to the surface of the fabrics in the wash.

The surfactant system is thus preferably present at a level of greater than 15 % , more preferably from 18% to 60% by weight, most preferably from 20% to 40% by weight of the detergent composition.

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 Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A list of suitable cationic surfactants is given in U.S. P. 4,259,217 issued to Muφhy on March 31, 1981.

Anionic surfactant

Essentially any anionic surfactants useful for detersive puφoses are suitable. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are preferred.

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^-C _j monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C^-C _j ^ 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 and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N-(Cι-C4 alkyl) and -N-(Cι-C2 hydroxyalkyl) glucamine sulfates, and sulfates of aUcylpolysaccharides such as the sulfates of aUcylpolyglucoside (the nonionic nonsulfated compounds being described herein).

Alkyl sulfate surfactants are preferably selected from the linear and branched primary C10-C18 alkyl sulfates, more preferably the C 11-C15 branched chain alkyl sulfates and the C12- 4 linear chain alkyl sulfates.

Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C10-C18 alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a Cn-Cis, most preferably C11-C15 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.

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

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, Cg-C24 olefin sulfonates, sulfonated polycarboxyhc acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.

Anionic carboxylate surfactant

Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the

soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.

Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH2θ) _x CH2COO-M + wherein R is a C6 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 20 % and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHRι-CHR2-0)-R3 wherein R is a C to Cis 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, hydroxysuccimc acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.

Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl- 1-undecanoic acid, 2-ethyl- 1-decanoic acid, 2-propyl-l-nonanoic acid, 2- butyl-1 -octanoic acid and 2-pentyl-l-heptanoic acid. Certain soaps may also be included as suds suppressors.

Alkali metal sarcosinate surfactant

Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON (Rl) CH 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 oleoyl methyl sarcosinates in the form of their sodium salts.

Alkoxylated nonionic surfactant

Essentially any alkoxylated nonionic surfactants are suitable herein. The ethoxylated and propoxylated nonionic surfactants are preferred.

Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxy late/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.

Nonionic alkoxylated alcohol surfactant

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

Nonionic polvhvdroxy fattv acid amide surfactant

Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R ² CONRlZ wherein : Rl is H, C1-C4 hydrocarbyl, 2- hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably Ci or C2 alkyl, most preferably Ci alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C5-C19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain C11-C17 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 fatty acid amide surfactant

Suitable fatty acid amide surfactants include those having the formula: R6cON(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) _x H, where x is in the range of from 1 to 3.

Nonionic alkylpolvsaccharide surfactant

Suitable alkylpoly saccharides for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic

group containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.

Preferred alkylpolyglycosides have the formula

R2θ(C _n H ₂ nO)t(glycosyl) _x

wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxy alkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived from glucose.

Cationic surfactants

Cationic ester surfactants, defined as preferably water dispersible compounds having surfactant properties, which comprise at least one ester (ie -COO-) linkage and at least one cationicaUy charged group, are suitable herein. Cationic ester surfactants, including choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.

Preferred cationic ester surfactants are those having the formula:

R, O- R ₃ M

wherein Ri is a C5-C31 linear or branched alkyl, alkenyl or alkaryl chain or M". N+(R6R7R8)(CH2) _S ; X and Y» independently, are selected from the group consisiting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO group; R2, R3> R4. 6. R7. and R8 are

independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxy-alkenyl and alkaryl groups having from 1 to 4 carbon atoms; and R5 is independently H or a C1-C3 alkyl group; wherein the values of m, n, s and t independently lie in the range of from 0 to 8, the value of b lies in the range from 0 to 20, and the values of a, u and v independently are either 0 or 1 with the proviso that at least one of u or v must be 1; and wherein M is a counter anion. Preferably R2,R3 and R4 are independently selected from CH3 and -CH2CH2OH.

Other suitable cationic surfactants include the quaternary ammonium surfactants selected from mono Cβ-Ciό, preferably C6-C10 N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.

Amphoteric surfactant

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

Suitable amine oxides include those compounds having the formula R ³ (OR4) _X NO(R5)2 wherein R ³ is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R-5 is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Preferred are Cio-Cjg alkyl dimethylamine oxide, and C10-I8 acylamido alkyl dimethylamine oxide.

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

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.

Suitable betaines are those compounds having the formula R(R')2N +R ² COO- wherein R is a C6-C18 hydrocarbyl group, each Rl is typically C -C3 alkyl, and R2 is a C1-C5 hydrocarbyl group. Preferred betaines are C 12- 18 dimethyl-ammonio hexanoate and the C10-I8 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.

Non-hvdrophobic organic peroxyacid bleaching system

The detergent compositions may additionally contain a non-hydrophobic organic peroxyacid bleaching system. This nature of this system is analogous to any of the hydrophobic peroxyacid bleaching systems described hereinbefore, other than that the organic peroxyacid is non- hydrophobic, that is it contains less than 7 carbon atoms, preferably less than 3 carbon atoms, amd most preferably is peracetic acid.

Thus, the bleaching system may contain a hydrogen peroxide source and a non-hydrophobic organic peroxyacid bleach precursor compound. Alternatively a preformed non-hydrophobic organic peroxyacid is incoφorated directly into the composition.

In a preferred aspect the detergent composition can provide both a hydrophobic organic peroxyacid and a non-hydrophobic organic peroxyacid, which are more preferably present at a weight ratio of from 1 :5 to 5: 1 , most preferably from 1 :3 to 3: 1.

Tetraacetylethylene diamine (TAED) is a preferred non-hydrophobic organic peroxyacid bleach precursor compound.

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 Mn ^IV 2( ^u -°)3(l-A7-trimethyl- 1,4,7- triazacyclononane)2-(PF6)2 , MnHl2(u-0) i (u-0 Ac)2( 1,4, 7-trimethy 1- 1 ,4,7-triazacyclononane)2-(Clθ4)2, Mnl ^V 4(u-0)6(l ,4,7- triazacyclononane)4-(C104)2 , Mn ^III Mn ^IV 4(u-0) 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 1,5,9-trimethyl- 1 ,5,9-triazacyclododecane, 2-methyl- 1 ,4,7-triazacyclononane, 2-methyl- 1 ,4,7-triazacyclononane, 1 ,2,4,7-tetramethyl-l ,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, 114,606, 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 N4MnUI(u-0)2MnrVN4)+and [Bipy2Mnπi( _u -0)2MnI bipy2]-(C104)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. 4,711 ,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, 119,557 (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).

Enzvme

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

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

Preferred commercially available protease enzymes include those sold under the 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 of the 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 2 % active enzyme by weight of the composition.

Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001 % to 2 % by weight, 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. , Thermomvces 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.

Organic polymeric compound

Organic polymeric compounds are preferred additional components of the detergent compositions in accord with the invention, and are preferably present as components of any particulate components where they may act such as to bind the particulate component together. By organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein.

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

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

The polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.

Teφolymers 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, hydroxypropylmethylcellulose and hydroxy ethylcellulose.

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.

Suds suppressing system

The detergent compositions of the 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 of the 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 of a 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 C18-C40 ketones (e.g. stearone) N- alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra alkyldiamine chiortriazines 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 of the silicone antifoam compound; and

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

wherein said silica/silicone antifoam compound is 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 DC0544, commercially available from DOW Corning under the tradename DC0544;

(c) an inert carrier fluid compound, most preferably comprising ϋ C\ - Ci8 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.

Clav softening system

The detergent compositions may contain a clay softening system comprising a clay mineral compound and optionally a clay flocculating agent.

The clay mineral compound is preferably a smectite clay compound. Smectite clays are disclosed in the US Patents No.s 3,862,058, 3,948,790, 3,954,632 and 4,062,647. European Patents No.s EP-A- 299,575 and EP-A-313, 146 in the name of the Procter and Gamble Company describe suitable organic polymeric clay flocculating agents.

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) Ax

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 of the 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-^y ^A

( ^R 3)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 of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups. The N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.

Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

Other suitable 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 of the 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 Polyvinylimidazole

The detergent compositions herein may also utilize polyvinylimidazole 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 Ri is selected from anilino, N-2-bis-hydroxyethyl and NH-2- hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2- hydroxyethyl-N-methy lamino, moφhiiino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.

When in the above formula, R\ 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'-stilbened isulfonic 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 moφhiiino 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.

Cationic fabric softening agents

Cationic fabric softening agents can also be incoφorated into compositions in accordance with the present invention. Suitable cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0 Oi l 340.

Cationic fabric softening agents are typically incoφorated at total levels of from 0.5% to 15% by weight, normally from 1 % to 5% by weight.

Other optional ingredients

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

pH of the compositions

The present compositions preferably have a pH measured as a 1 % solution in distilled water of at least 8.5, preferably from 9.0 to 12.5, most preferably from 10.0 to 12.0.

Form of the compositions

The compositions in accordance with the invention can take a variety of physical forms including granular, tablet, bar and liquid forms. The compositions are particularly the so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of a dispensing device placed in the machine drum with the soiled fabric load.

The mean particle size of the components of granular compositions in accordance with the invention should preferably be such that no more that 5% of particles are greater than 1.7mm in diameter and not more than 5% of particles are less than 0.15mm in diameter.

The term mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of Tyler sieves. The weight fractions thereby obtained are plotted against the aperture size of the sieves. The mean particle size is taken to be the aperture size through which 50% by weight of the sample would pass.

The bulk density of granular detergent compositions in accordance with the present invention typically have a bulk density of at least 600 g/litre, more preferably from 650 g/litre to 1200 g/litre. Bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel moulded rigidly on a base and provided with a flap valve at its lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylindrical cup disposed below the funnel. The funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base. The cup has an overall height of 90 mm, an internal height of 87 mm and an internal 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 eg; a knife, across its upper edge. The filled cup is then weighed and the value obtained for the weight of powder doubled to provide a bulk density in g/litre. Replicate measurements are made as required.

Laundry washing method

Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having

dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention. By an effective amount of the detergent composition it is meant from 40g to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.

In a preferred use aspect a dispensing device is employed in the washing method. The dispensing device is charged with the detergent product, and is used to introduce the product directly into the drum of the washing machine before the commencement of the wash cycle. 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 of the wash cycle of the washing machine water is introduced into the drum and the drum periodically rotates. The design of the dispensing device should be such that it permits containment of the dry detergent product but then allows release of this product during the wash cycle in response to its agitation as the drum rotates and also as a result of its contact with the wash water.

To allow for release of the detergent product during the wash the device may possess a number of openings through which the product may pass. Alternatively, the device may be made of a material which is permeable 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 of the wash cycle thereby providing transient localised high concentrations of product in the drum of the washing machine at this stage of the wash cycle.

Preferred dispensing devices are reusable and are designed in such a way that container integrity is maintained in both the dry state and during the wash cycle. Especially preferred dispensing devices for use with the composition of the invention have been described in the following patents; GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345

and EP-A-0288346. An article by J. Bland published in 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" . Another preferred dispensing device for use with the compositions of this invention is disclosed in PCT Patent Application No. W094/ 11562.

Especially preferred dispensing devices are disclosed in European Patent Application Publication Nos. 0343069 & 0343070. The latter Application discloses a device comprising a flexible sheath in the form of a bag extending from a support ring defining an orifice, the orifice being adapted to admit to the bag sufficient product for one washing cycle in a washing process. A portion of the washing medium flows through the orifice into the bag, dissolves the product, and the solution then passes outwardly through the orifice into the washing medium. The support ring is provided with a masking 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.

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

Packaging for the compositions

Commercially marketed executions of the bleaching compositions can be packaged in any suitable container including those constructed from

paper, cardboard, plastic materials and any suitable laminates. A preferred packaging execution is described in European Application No 94921505.7.

Abbreviations used in Examples

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

LAS Sodium linear C 2 alkyl benzene sulfonate

TAS Sodium tallow alkyl sulfate

C45AS Sodium C14- 5 linear alkyl sulfate

C245AS Mixture of sodium C12- 4-C15 alkyl sulfates

CxyEzS Sodium Cj _x -Ciy branched alkyl sulfate condensed with z moles of ethylene oxide

C45E7 A Ci4_i5 predominantly linear primary alcohol condensed with an average of 7 moles of ethylene oxide C24E3 A C 12- 14 branched primary alcohol condensed with an average of 3 moles of ethylene oxide

C24E5 A C 12- 14 branched primary alcohol condensed with an average of 5 moles of ethylene oxide

CEQ RlCOOCH2CH2.N+(CH3)3 with Ri = Cn-

Cl3

QAS R2.N+(CH3)2(C ₂ H ₄ OH) with R ₂ = C - C _i4 Soap Sodium linear alkyl carboxylate derived from an

80/20 mixture of tallow and coconut oils.

TFAA 6-C18 N-methyl glucamide TPKFA C12-C14 topped whole cut fatty acids STPP Anhydrous sodium tripolyphosphate Zeolite A Hydrated Sodium Aluminosilicate of formula

Nai2(Alθ2Siθ2)i2- 27H2θ having a primary particle size in the range from 0.1 to 10 micrometers

NaSKS-6 Crystalline layered silicate of formula δ -Na2Si2θs

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 3 AU/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

PBl Anhydrous sodium perborate monohydrate bleach of nominal formula NaBθ2-H2θ2

Percarbonate Sodium Percarbonate of nominal formula

2Na2Cθ3.3H2θ2 NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt.

TAED Tetraacetylethylenediamine NACA-OBS (6-ncαamido caproyl)oxybenzene sulfonate

NAPAA Nonyl amido peroxy adipic acid

EDDS Ethylenediamine-N,N' -disuccinic acid

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- 1.3.5- 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.

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

Example 1

The following laundry detergent compositions A to D were prepared, A to C are comparative compositions, D is in accord with the invention:

A B C D

C245AS 8.2 11.7 11.7 11.7

C25E3S 2.0 1.9 1.9 2.2

TFAA 2.3 4.0 4.0 4.0

C24E5 5.2 1.7 1.7 1.7

C24E3 - 6.2 6.2 6.2

Zeolite A 15.0 12.2 12.2 12.2

Carbonate 8.5 12.6 12.6 12.6

NaSKS-6 11.3 7.8 7.8 7.8

Citric acid 3.1 2.1 2.1 2.1

Percarbonate 21.2 17.0 17.0 17.0

TAED 4.9 3.9 3.9 3.9

NACA-OBS - 6.0 6.0 6.0

DETPMP 0.7 0.53 1.6 0.95

HEDP 0.5 - - 0.65

Protease 0.9 0.7 0.7 0.7

Lipase 0.2 - - -

Amylase 0.4 0.2 0.2 0.2

MA/AA 4.6 2.8 2.8 2.8

CMC 0.4 - - -

Photoactivated 27 ppm 27 ppm 27 ppm 27 ppm bleach (ppm)

Brightener 1 0.23 0.23 0.23 0.23

Perfume 0.5 0.5 0.5 0.5

Silicone antifoam 0.5 0.5 0.5 0.5

Misc/minors to 100%

Density in g/litre 850 800 800 800

Comparative Performance Testing

Test protocol 1 - stain removal

Three white cotton sheets were prewashed in a non-biological bleach-free heavy duty detergent. Sets of test swatches of size 6cm x 6cm were cut from each sheet. To each swatch were evenly added four classes of stain namely: non-food greasy (dirty motor oil, shoe polish, make-up, lipstick), food greasy (bacon grease, hamburger grease, burnt beef, burnt butter), enzymatic (grass, spinach) and particulate (clay, peat).

The sets of fabric swatches were subjected to one wash cycle in an automatic washing machine. The swatches were then assessed for removal of the various stains by a four person grading panel using the well-known four-point Scheffe scale.

In more detail, a Zanussi model FJ1093 with jet system 1000 automatic washing machine was employed, and the 40°C short cycle (75 minutes) programme selected. Water of 35° German hardness ( = 6.3 mmol Ca2+/litre) was used. 75g of detergent, dispensed from a granulette dispensing device was employed. One swatch of each fabric type was washed along with a ballast load comprising 2.5Kg of a mixture of lightly soiled synthetic and cotton garments, previously washed 15 times under hard water conditions. The ballast load was positioned prior to commencement of the wash cycle to ensure an even distribution around the test swatches.

Test protocol 2 - body soil removal

A mixed load comprising 2.5Kg of soiled laundry having previously been through 15 wash/wear cycles was employed. In detail, the load includes cotton/polycotton shirts, pillowcases, socks, tea towels and baby's bibs. The load was subjected to one wash cycle in a Zanussi FJ1093 washing machine using the wash conditions as defined for the stain protocol removal above. Each of the articles making up the load was then assessed for body soil removal/overall cleaning by a four person grading panel using the Scheffe Scale.

Comparative testing - results

The above stain removal and body soil removal test protocols was followed in comparing the efficiency of Compositions A to D in removing various representative stain types, and for overall body soil cleaning

The results were as follows:

Stain removal: C vs B D vs B D vs A

Non-food greasy +0.4 + 1.2s + 1.5s

Food - greasy +0.6 + 1.0s + l . ls

Enzymatic +0.7 +0.7 + 1.4s

Particulate +0.3 + l . ls +0.3

Body soil cleaning: +0.3 +0.7s +0.7s

s = significant at 95 % confidence level

The stain removal and body soil cleaning performance of Composition D is thus shown to be enhanced in comparison to that of Compositions A to C, in accord with the invention.

Example 2

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

G H I

LAS 7.0 7.0 7.0

TAS 2.5 2.0 3.0

C45AS - 4.0 6.0

C25AE3S - 1.0 1.5

C45E7 4.0 - 7.0

C24E3 - 6.5 -

CEQ - 2.0 2.0

Zeolite A 10.5 14.5 10.5

NaSKS-6/citric acid 10.5 8.5 7.5 (79:21)

Carbonate 8.0 9.0 9.0

Sodium sulfate 39.8 - 14.3

PB4 5.0 12.7 -

NACA-OBS 4.0 3.0 5.0

DETPMP 0.3 0.5 0.7

HEDP 0.4 0.5 0.6

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 H to J, according to the present invention were prepared:

H I J

Blown Powder

Zeolite A 15.0 20.0 20.0

C45AS 9.0 6.0 8.0

MA/AA 2.0 4.0 2.0

LAS 6.0 8.0 9.0

TAS 2.0 - -

CEQ 1.5 3.0 3.5

Silicate 7.0 8.0 8.0

CMC 1.0 1.0 0.5

Brightener 2 0.2 0.2 0.2

Soap 1.0 1.0 1.0

HEDP 0.6 0.4 0.5

DTPMP 0.4 0.4 0.7

Spray On

C45E7 2.5 2.5 2.0

C24E3 2.5 2.5 2.0

Silicone antifoam 0.3 0.3 0.3

Perfume 0.3 0.3 0.3

Dry additives

Carbonate 10.0 12.0 12.0

PB4 18.0 18.0 10

PBl 4.0 4.0 0

NACA-OBS 5.0 6.0 4.0

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 3.0 3.0 5.0 sulfate

Balance (Moisture & 100.0 100.0 100.0 Miscellaneous)

Density (g/litre) 630 670 670

Example 4

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

K L M

Blown Powder

Zeolite A 10.0 15.0 6.0

Sodium sulfate 19.0 5.0 7.0

MA/AA 3.0 3.0 6.0

LAS 10.0 8.0 10.0

C45AS 4.0 5.0 7.0

CEQ 2.0 2.0 2.0

Silicate - 1.0 7.0

Soap - - 2.0

Brightener 1 0.2 0.2 0.2

Carbonate 18.0 15.0 20.0

HEDP 0.5 0.8 0.6

DTPMP 1.0 0.4 0.4

Spray On

C45E7 3.0 3.0 4.0

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

NACA-OBS 5.0 6.1 4.5

PBl 1.0 5.0 6.0

Sodium sulfate - 6.0 -

Balance (Moisture 100 100 100 and Miscellaneous)

Example 5

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

N O P

Blown Powder

Zeolite A 15.0 15.0 15.0

Sodim sulfate 0.0 5.0 0.0

LAS 3.0 2.0 3.0

QAS - 1.5 1.5

CEQ 2.0 1.5 2.0

DTPMP 0.4 0.4 0.4

HEDP 0.4 0.6 0.8

CMC 0.4 0.4 0.4

MA/AA 4.0 2.0 2.0

Agglomerates

LAS 4.0 4.0 4.0

TAS 2.0 2.0 1.0

Silicate 3.0 3.0 4.0

Zeolite A 8.0 8.0 8.0

Carbonate 8.0 8.0 6.0

Spray On

Perfume 0.3 0.3 0.3

C45E7 2.0 2.0 2.0

C24E3 2.0 - -

Dry additives

Citrate 5.0 - 2.0

NAPAA 6.0 2.0 5.0

PBl 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 10.0 13.0 10.0

Balance (Moisture and 100.0 100.0 100.0 Miscellaneous)

Density (g/litre) 850 850 850