EP1115825A1

EP1115825A1 - Solid detergent compositions

Info

Publication number: EP1115825A1
Application number: EP98948562A
Authority: EP
Inventors: Richard Timothy Hartshorn; Zayeed Alam; Sylvestre Canceil; Alan Thomas Brooker; Kevin Norwood; David Scott Bohlen
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1998-09-25
Filing date: 1998-09-25
Publication date: 2001-07-18
Also published as: MXPA01003100A; WO2000018859A1; AU9510998A

Abstract

The invention relates to solid detergent compositions comprising improved builder systems and surfactant systems which have an improved delivery to the wash and an improved cleaning performance. The builder system comprises at least two builders selected from water-soluble or partially water-soluble builders or mixtures thereof, present at a level from 60 % to 100 % by weight of the builder system; and from 0 % to 40 % by weight of the builder system of water-insoluble builders, provided that less than 9 % by weight of the composition of aluminosilicate builder is present, and less than 5 % by weight of the composition of amorphous sodium silicate is present. The composition also comprises at least one particulate component, comprises at least one of the surfactants of the surfactant system, is intimately mixed with at least one of the water-soluble or partially water-soluble builders.

Description

SOLID DETERGENT COMPOSITIONS

Technical Field of the Invention

The invention relates to solid detergent compositions comprising improved builder systems and surfactant systems which have an improved delivery to the wash and an improved cleaning performance.

Background to the Invention

Detergent manufacturers spend much time and effort on further improving their products to meet consumer needs, for example by improving the performance of the products, the easy of handling of the products, or the delivery of the product to the wash.

Important ingredients in detergents which contributes to the performance are surfactants and builders. Builders are essential to provide building of the washing liquor, by binding, complexing or dispersing the hard water ions which interfere with various ingredients but in particular with the surfactants present in the detergents, which reduces their performance, for example their surfactancy, which is of course undesirable. Furthermore, certain builders can bind or complex certain heavy metal ions present in the washing process or in the detergent or introduced in the detergent during the making process, which can interfere with detergent ingredients such as oxygen bleach, both during the wash and during storage.

The most commonly used builders, present in about all commercially available detergents which do not contain phosphate builders, are aluminosilicates. They are inexpensive builders which have as an additional benefit that they are easy to process. In fact they are useful process aids because they are very good binders or carrier material for other detergent ingredients. Furthermore, they are useful as dusting agent, to reduce the stickiness or caking of the product.

Often the aluminosilicate builders are combined with other builder materials. For example EP-A-554287 describes builder systems comprising high levels of zeolite A, layered silicates and polymeric compounds. WO 97/17045 described builders systems with reduced levels of zeolite A, replaced with higher levels of amorphous silicates and carbonates.

The inventors have found that most detergent compositions leave residues in the washing machine and on the fabrics, which are difficult to remove. They have also found that these residues can become entrapped in the fibres of the fabric, which makes it even more difficult to remove the residues. The inventors have found that the one of the main reasons for this problem is the presence of in particular powdered, insoluble builders, including aluminosilicates and amorphous silicates.

The inventors have now found that an improved phosphate-free detergent composition is obtained when a specific builder system, preferably combined with specific surfactant system are used, preferably incorporated in the composition in the form of a specific particular component. Hereby, a reduction or even omission of the water-insoluble builders is possible.

The compositions herein have a surprisingly improved delivery to the wash. They have a reduced gelling upon contact with water, improved dispensing and a reduced residue formation. A fast and efficient building of the washing liquor is achieved, whereby a very effective cleaning performance is obtained.

The inventors have also found that when small amounts of water-insoluble builder are present, the delivery to the wash of the product may be further improved when a water soluble polymeric polycarboxylic acid or salt is present, and optionally further polymeric flocculating polymer is present, in particular combined with an monomeric (poly) carboxylate or more preferably the acid form thereof.

These detergent compositions may comprise particles which are free of sprayed-on nonionic alkoxylated alcohol surfactants. This may help to reduce the gelling and caking of the products. A further advantage can be that the omission of sprayed-on nonionic alkoxylated alcohols allows the reduction or omission of powdered materials such as fine aluminosilicate material and amorphous silicate material, which are normally used to dust the detergent particles containing these sprayed-on nonionic surfactants, to reduce caking. This also allows a reduction of the process complexity.

Summary of the Invention

The invention provides a phosphate-free detergent composition comprising at least one particulate components, from 5% to 90% by weight of the composition of a builder system and at least 10% by weight of the composition of a surfactant system, comprising one or more surfactants, characterised in that

a) the builder system comprises at least two builders selected from water-soluble or partially water-soluble builders or mixtures thereof, present at a level from 60% to 100% by weight of the builder system; and from 0% to 40% by weight of the builder system of water-insoluble builders, provided that less than 9% by weight of the composition of aluminosilicate builder is present, and less than 5% by weight of the composition of amorphous sodium silicate is present; and

b) the particulate component comprises at least one of the surfactants of the surfactant system is intimately mixed with at least one of the water-soluble or partially water- soluble builders. It has been found that theses detergent compositions have a reduced gelling upon contact with water, an improved dispensing and a reduced residue formation, whereby a very good building of the wash water and a very good cleaning performance is achieved.

Detailed Description of the Invention

The detergent composition preferably a builder system which comprises less than 30% or even less than 20% or even less than 10% by weight of water insoluble builder, whereby in the preferred embodiments the balance of the builder system are the water-soluble builders and/ or partially water soluble builders.

Hereby, preferably less than 6% or even less than 4% or even less than 2% by weight of the composition is aluminosilicate. When present, the aluminosilicate may be contained in a component containing other detergent ingredients, such as in a detergent agglomerate, extrudate or a blown powder. It may even be preferred that substantially no aluminosilicate is present as separate particulate ingredient.

Also, preferably less than 3% or even less than 1.5% or even less than 0.8% by weight of amorphous silicate is present. When present, the amorphous silicate is preferably contained in a component containing other detergent ingredients, such as in a detergent agglomerate, extrudate or a blown powder. It may be preferred that substantially no amorphous silicate is present as separate particulate ingredient.

The water-soluble builder and partially water-soluble builder are typically present at a level up to 50% by weight, preferably up to 35% by weight, most preferably from 3% to 30% by weight of the composition, or even from 6% to 30% or even from 8% to 25%.

The detergent composition of the invention comprises at least one particulate component containing an intimate mixture of one or more of the water soluble or partially water soluble builders and one or more surfactants. It may be preferred that the component comprises more than one of these builders.

Preferably, at least two particulate components are present in the detergent composition, which comprise intimate mixtures of a surfactants and a water-soluble builder.

Such intimate mixtures can be obtained by any process involving the mixing of the components, which can be part of a granulation processes including a spray-drying process, an extrusion process and an agglomeration processes and also a tableting process. Hereby, preferably a first step comprises forming of a mixture of the surfactant and the water soluble or partially water soluble builder, and granulation of the mixture to form a particular component, preferably a granule. The intimately mixing preferably results in an agglomerate or a spray-dried or blown powder, an extrudate .

The particulate components herein preferably has a particle size of at least 50 microns, preferably they have an weight average particle size of more than 150 or more than 250 microns or even more than 350 microns, as measured by sieving the composition on sieves of different mesh size, and calculating the fraction which remain on the sieve and the fraction which passes through the sieve.

Preferably, the density of the component is from 250 g/litre to 1500 g/litre, more preferably at least one of the components, preferably all of the components, has a density from 400 g/litre to 1200gr/litre, more preferably from 500 g/litre to 900g/litre.

Preferred components comprise an intimate mixture of at least one anionic surfactant and one or more of the water-soluble or partially water soluble builders.

When a partially water-soluble builder is present, it may be preferred that at least 50% thereof or even substantially all of the partially water-insoluble builder is present in a component herein, preferably in an intimate mixture with one or more anionic surfactants. A highly preferred additional ingredient of the detergent compositions herein may be oxygen based bleach, preferably containing an hydrogen peroxide source, preferably a perhydrogen compound and a bleach activator, described herein after. It has been found that the improved product delivery to the wash results in an improved delivery of the bleach system therein, which reduces the risk of deposition of bleach on the fabric and the risk of patchy fabric damage.

Depending on the precise formulation of the composition and the use thereof, it may be preferred that the compositions herein comprise a component which contains high levels of an alkyl sulfate or sulphonate surfactant or mixtures thereof, preferably an alkyl benzene sulphonate, intimately mixed with an sulphate salt and moisture. For example, such a component comprising from 85% to 95% of one an anionic sulfate or sulphonate surfactant and from 15% to 5% sulfate salt and moisture. Such a component may be in the form f a flake, which can be admixed or dry-added to the other components of the detergent composition herein.

It may be preferred that the components of the compositors herein are free of sprayed-on nonionic alkoxylated alcohol surfactants. It has been found that hereby the delivery of the composition to the washing water can be improved and the caking of the product can be reduced. It may be preferred that the composition comprises a nonionic surfactant which is solid at temperatures below 30°C or even 40°C, preferably present in an intimate mixture with other ingredients.

Other preferred ingredients comprises a perfume, brightener or dye or mixtures thereof, which may be sprayed onto the particular component herein.

Furthermore, the compositions may contain an effervescence system to further improve the delivery of the detergent composition to the washing water. Water-Soluble or Partially Water-Soluble Builders

The composition comprises two or more water-soluble or partially water soluble builders or mixtures thereof. These include crystalline layered silicates an organic carboxylates or carboxylic acids.

The preferred crystalline layered silicate herein have the general formula

NaMSi_x0_2x+l .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 purpose of the present invention, x in the general formula above has a value of 2, 3 or 4 and is preferably 2. M is preferably H, K or Na or mixtures thereof, preferably Na. The most preferred material is α-Na2Si2θ5₅ R. Na2SΪ2θ5 _or δ-Na2Si2θ5, or mixtures thereof, preferably being at least 75% -Na2Si2θ5 for example available from Clariant as

NaSKS-6.

The crystalline layered silicate material, in particular of the formula Na2Si2θ5 may optionally comprise other elements such as B, P, S, for example obtained by processes as described in EP 578986-B.

The partially water-soluble builder is preferably present at a level up to 40%, more preferably up to 35%. When present it may be preferred that the composition of the invention comprises from 10% to 40%, more preferably from 12% to 35% or even from 15% to 25%o by weight of the composition of the partially water-soluble builder. In a preferred embodiment of the invention, when crystalline layered silicate is present, part of or all of this is in an intimate mixture with a surfactant, preferably an anionic surfactant. Thus, a preferred particulate component herein may comprise an intimate mixture of preferably from 25% to 75% by weight, more preferably from 35%) to 68%, even more preferably from 45% to 62%> by weight of the component of a of a crystalline layered silicate and from 25% to 75% by weight, more preferably from 32% to 62% by weight more preferably from 38% to 48% by weight of the component of an anionic surfactant.

Such a particulate component preferably comprises less than 10% by weight of free moisture, preferably less than 5%, or even less than 3% or even less than 2% by weight. The free moisture content as used herein, can be determined by placing 5 grams of the particulate component in a petri dish and placing this petri dish in a convection oven at 50°C for 2 hours, and subsequently measuring the weight loss, due to water evaporation

Highly preferred may be that the anionic surfactant comprises from 50% to 100% by weight, preferably from 60% or even 75% to 100% of the anionic surfactant of a sulphonate surfactant preferably an alkyl benzene sulphonate surfactant, as described herein.

Preferably, the weight ratio of the crystalline layered silicate to the anionic surfactant in the intimate mixture is from 4:5 to 7:3, more preferably from 1 : 1 to 2:1, most preferably from 5:4 to 3:2.

Such a component may be prepared by any method, preferably by roller compaction or more preferably by agglomeration, as known in the art.

Such component may also comprise additional ingredients, for example in amounts of from 0% to 25%, generally no greater than 20% or even 15%) by weight of the agglomerate. The precise nature of these additional ingredients, and levels of incorporation thereof will depend on the application of the component or compositions and the physical form of the components and the compositions.

The crystalline layered silicate may also be in an intimate mixture with other materials, including one or more of the water-soluble builders or polymeric compounds such as acrylic and/ or maleic acid polymers, inorganic acids or salts, including carbonates and sulphates, or small levels of other silicate material, including amorphous silicate, meta silicates, and aluminosilicates, as described herein.

The water soluble builders include organic carboxylic acids and salts thereof. 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 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. In addition to these water-soluble builders, polymeric polycarboxylates may be present, including homo and copolymers of maleic acid and acrylic acid and their salts.

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, diglycolic 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- 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. 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.

Most preferred may be acetic acid, citric acid, malic acid, and fumaric acid, or their salts or mixtures thereof. It may be preferred that mixtures of the salt and acid form are present.

It has been found that when these highly water-soluble carboxylate- or carboxylic acid- containing compounds are present in an intimate mixture with one or more of the surfactants and optionally other ingredients, the rate of dissolution of the intimate mixture and also of the surfactants and other ingredients is increased. Thus, overall a faster delivery of the surfactants and other ingredients can be achieved.

The water soluble builder is preferably present at a level up to 40%, more preferably up to 35%). When present it may be preferred that the composition of the invention comprises from 10%) to 40%, more preferably from 12% to 35% or even from 15% to 25% by weight of the composition of the water-soluble builder. It may be preferred that part or even all of the monomeric or oligomeric (poly)carboxylic acid or salt thereof is in the form of a separate particle, whereby it may be preferred that the average particle size of this builder material is then preferably less than 150 microns, or even less than 100 microns. It may be preferred that part of the water-soluble or partially water-soluble builder is used as dusting agent, to reduce the caking of the product when necessary.

Other suitable water-soluble builder materials are polymeric polycarboxylic acids or polycarboxylates, including the water soluble 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 of the latter type are disclosed in GB-A-1, 596,756. Examples of such salts are polyacrylates of MWt 1000-50000, preferably 10000 or even 7000 and copolymers of (poly)acrylate and maleic acid or anhydride, such copolymers having preferably a molecular weight of from 2000 to 100,000, especially 40,000 to 80,000.

It may be preferred that, in particular when small amounts of insoluble builder are present in the compositions herein, a polycarboxylate polymer, such as polymer and copolymer of maleic anhydride or acid and (poly)acrylic acid and their salts, is incorporated at a level of from 0.5% to 15%, preferably from 1% to 12% or even from 2% to 8% by weight of the composition. Hereby, it may be preferred that the water-insoluble builder and the polymer are not in an intimate mixture with one another.

The inventors have also found that when a polymeric polycarboxylate is present, it may be preferred that the polymer is comprised in an intimate mixture, preferably a spray- dried particle, which is prepared by first mixing a carbonate salt and the polymer and then addition and intimately mixing of other ingredients.

It may also be useful that in certain embodiments of the invention , the degree of mixing between amorphous silicate and an anionic surfactant is reduced, when an amorphous silicate is present, in particular in mixtures containing anionic surfactant which are to be spray-dried, it may be beneficial to reduce the amount of silicate present, for example to levels of less than 3% by weight of the mixture, or even less than 2%, or even less thanl% or even 0% by weight of the mixture.

Surfactant System

The surfactant system preferably comprises at least one type of anionic surfactant and two or more anionic surfactants are preferably present. Fatty acid soaps may be present, also to control the sudsing in the wash.

When only anionic surfactant is present, it may be preferred that this is comprised in more than one particulate, intimately mixed component of the composition herein.

It may be preferred that the surfactant system also comprise cationic and it may be preferred that these or part thereof are intimately mixed with an anionic surfactant.

The surfactant system may also comprise nonionic surfactants and it may also be preferred that part or all of the nonionic surfactant is in an intimate mixture with the anionic surfactants.

In one embodiment, the surfactant system is substantially free of linear alkyl sulfate surfactant. Then, it may be preferred that at least an anionic sulphonate surfactant is present, preferably comprised in at least two particulate components, preferably at least at a level of 10% by weight of the composition, more preferably at least 12% or even 15% by weight.

Also preferred may be a mid-chain branched alkyl sulfate surfactant, whereby it may be preferred that only limited levels of sulphonate surfactant are present, for example less than 10% or even less than 8% or even form 0% to 5% by weight of the composition. Where present, ampholytic, amphoteric and zwitteronic surfactants are generally used in combination with anionic and/or nonionic surfactants.

Anionic Surfactant

The anionic surfactant herein preferably comprises at least a sulphate surfactant and/ or a sulphonate surfactant or mixtures thereof.

Depending on the precise formulation of the composition and the use thereof, it may be preferred that the compositions herein comprise a particulate component, preferably in the form of a flake of an alkyl sulfate or sulphonate surfactant, preferably an alkyl benzene sulphonate, present at a concentration of from 85% to 95% of the particle or flake, the balance being an sulfate salt and moisture, the particle or flake being admixed to the other detergent component(s) or ingredients.

Other possible 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, ^ monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C.--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 Sulphonate Surfactant

The anionic sulphonate surfactants include the salts of C5-C20 linear or branched alkylbenzene sulphonates, alkyl ester sulphonates, C6-C22 primary or secondary alkane sulphonates, Cg-C24 olefin sulphonates, sulphonated polycarboxylic acids, and any mixtures thereof.

Highly preferred is a C12-C16 linear alkylbenzene sulphonate. Preferred salts are sodium and potassium salts.

The alkyl ester sulphonated surfactant are also suitable for the invention, preferably those of formula

R¹ - CH(SO₃M) - (A)_x - C(O) - OR²

wherein R* is a Cg-C22 hydrocarbyl, R² is a Cj-C6 alkyl, A is a C6-C22 alkylene, alkenylene, x is 0 or 1, and M is a cation. The counterion M is preferably sodium, potassium or ammonium.

The alkyl ester sulphonated surfactant is preferably a α-sulpho alkyl ester of the formula above, whereby thus x is 0. Preferably, R^! is an alkyl or alkenyl group of from 10 to 22, preferably 16 C atoms and x is preferably 0. R² is preferably ethyl or more preferably methyl.

It can be preferred that the Rl of the ester is derived from unsaturated fatty acids, with preferably 1, 2 or 3 double bonds. It can also be preferred that R¹ of the ester is derived from a natural occurring fatty acid, preferably palmic acid or stearic acid or mixtures thereof.

Anionic Alkyl Sulphate Surfactant

The anionic sulphate surfactant herein include the linear and branched primary and secondary alkyl sulphates and disulphates, alkyl ethoxysulphates having an average ethoxylation number of 3 or below, fatty oleoyl glycerol sulphates, alkyl phenol ethylene oxide ether sulphates, the C5-C17 acyl-N-(Cι-C4 alkyl) and -N-(C]-C2 hydroxyalkyl) glucamine sulphates, and sulphates of alkylpolysaccharides.

Primary alkyl sulphate surfactants are preferably selected from the linear and branched primary C ] Q-C \ g alkyl sulphates, more preferably the C \ \ -C 5 linear or branched chain alkyl sulphates, or more preferably the C12-C14 linear chain alkyl sulphates.

Preferred secondary alkyl sulphate surfactant are of the formula

R³-CH(SO₄M)-R⁴

wherein R³ is a C₈-C₂₀hydrocycarbyl, R⁴ is a hydrocycarbyl and M is a cation.

Alkyl ethoxy sulphate surfactants are preferably selected from the group consisting of the Cio-Cj g alkyl sulphates which have been ethoxylated with from 0.5 to 3 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulphate surfactant is a C\ \ -C\ , most preferably Cj 1-C15 alkyl sulphate which has been ethoxylated with from

0.5 to 3, preferably from 1 to 3, moles of ethylene oxide per molecule.

A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulphate and alkyl ethoxysulphate surfactants. Preferred salts are sodium and potassium salts.

Mid-Chain Branched Anionic Surfactants

Preferred mid-chain branched primary alkyl_sulfate surfactants for use herein are of the formula

These surfactants have a linear primary alkyl sulfate chain backbone (i.e., the longest linear carbon chain which includes the sulfated carbon atom) which preferably comprises from 12 to 19 carbon atoms and their branched primary alkyl moieties comprise preferably a total of at least 14 and preferably no more than 20, carbon atoms. In the surfactant system comprising more than one of these sulfate surfactants, the average total number of carbon atoms for the branched primary alkyl moieties is preferably within the range of from greater than 14.5 to about 17.5. Thus, the surfactant system preferably comprises at least one branched primary alkyl sulfate surfactant compound having a longest linear carbon chain of not less than 12 carbon atoms or not more than 19 carbon atoms, and the total number of carbon atoms including branching must be at least 14, and further the average total number of carbon atoms for the branched primary alkyl moiety is within the range of greater than 14.5 to about 17.5.

R, Rl, and R² are each independently selected from hydrogen and Cj-C alkyl group (preferably hydrogen or Ci -C2 alkyl, more preferably hydrogen or methyl, and most preferably methyl), provided R, R*, and R² are not all hydrogen. Further, when z is 1, at least R or Rl is not hydrogen.

M is hydrogen or a salt forming cation depending upon the method of synthesis. w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z is an integer of at least 1 ; and w + x + y + z is an integer from 8 to 14.

A preferred mid-chain branched primary alkyl sulfate surfactant is, a C16 total carbon primary alkyl sulfate surfactant having 13 carbon atoms in the backbone and having 1, 2, or 3 branching units (i.e., R, Rl and/or R²) of in total 3 carbon atoms, (whereby thus the total number of carbon atoms is at least 16). Preferred branching units can be one propyl branching unit or three methyl branching units. Another preferred surfactant are branched primary alkyl sulfates having the formula

Rl R2

I I

CH₃CH₂(CH₂)χCH(CH₂)_yCH(CH₂)_zOSO₃M wherein the total number of carbon atoms, including branching, is from 15 to 18, and when more than one of these sulfates is present, the average total number of carbon atoms in the branched primary alkyl moieties having the above formula is within the range of greater than 14.5 to about 17.5; Rl and R² are each independently hydrogen or C1-C3 alkyl; M is a water soluble cation; x is from 0 to 11 ; y is from 0 to 11 ; z is at least 2; and x + y + z is from 9 to 13; provided Rl and R² are not both hydrogen.

Dianionic Surfactants

The dianionic surfactants are also useful anionic surfactants for the present invention, in particular those of formula

where R is an, optionally substituted, alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group of chain length C\ to C28, preferably C3 to C24, most preferably Cg to C20, or hydrogen; A and B are independently selected from alkylene, alkenylene, (poly) alkoxylene, hydroxyalkylene, arylalkylene or amido alkylene groups of chain length C\ to C28 preferably C\ to C5, most preferably C\ or C2, or a covalent bond, and preferably

A and B in total contain at least 2 atoms; A, B, and R in total contain from 4 to about 31 carbon atoms; X and Y are anionic groups selected from the group comprising carboxylate, and preferably sulfate and sulfonate, z is 0 or preferably 1 ; and M is a cationic moiety, preferably a substituted or unsubstituted ammonium ion, or an alkali or alkaline earth metal ion.

The most preferred dianionic surfactant has the formula as above where R is an alkyl group of chain length from C \ Q to C^g, A and B are independently C\ or C2, both X and

Y are sulfate groups, and M is a potassium, ammonium, or a sodium ion.

Preferred dianionic surfactants herein include:

(a) 3 disulphate compounds, preferably 1,3 C7-C23 (i.e., the total number of carbons in the molecule) straight or branched chain alkyl or alkenyl disulphates, more preferably having the formula:

wherein R is a straight or branched chain alkyl or alkenyl group of chain length from about C4 to about C 20

(b) 1 ,4 disulphate compounds, preferably 1 ,4 C8-C22 straight or branched chain alkyl or alkenyl disulphates, more preferably having the formula:

wherein R is a straight or branched chain alkyl or alkenyl group of chain length from about C4 to about Cjg; preferred R are selected from octanyl, nonanyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and mixtures thereof; and (c) 1,5 disulphate compounds, preferably 1,5 C9-C23 straight or branched chain alkyl or alkenyl disulphates, more preferably having the formula:

wherein R is a straight or branched chain alkyl or alkenyl group of chain length from about C4 to about C1 g.

It can be preferred that the dianionic surfactants of the invention are alkoxylated dianionic surfactants.

The alkoxylated dianionic surfactants of the invention comprise a structural skeleton of at least five carbon atoms, to which two anionic substituent groups spaced at least three atoms apart are attached. At least one of said anionic substituent groups is an alkoxy- linked sulphate or sulphonate group. Said structural skeleton can for example comprise any of the groups consisting of alkyl, substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine and amide groups. Preferred alkoxy moieties are ethoxy, propoxy, and combinations thereof.

The structural skeleton preferably comprises from 5 to 32, preferably 7 to 28, most preferably 12 to 24 atoms. Preferably the structural skeleton comprises only carbon- containing groups and more preferably comprises only hydrocarbyl groups. Most preferably the structural skeleton comprises only straight or branched chain alkyl groups.

The structural skeleton is preferably branched. Preferably at least 10 % by weight of the structural skeleton is branched and the branches are preferably from 1 to 5, more preferably from 1 to 3, most preferably from 1 to 2 atoms in length (not including the sulphate or sulphonate group attached to the branching). A preferred alkoxylated dianionic surfactant has the formula

where R is an, optionally substituted, alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group of chain length Cj to C28_> preferably C3 to C24, most preferably Cg to C20_> or hydrogen; A and B are independently selected from, optionally substituted, alkyl and alkenyl group of chain length C\ to C28, preferably C\ to C5, most preferably Cj or C2, or a covalent bond; EO/PO are alkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein n and m are independently within the range of from about 0 to about 10, with at least m or n being at least 1 ; A and B in total contain at least 2 atoms; A, B, and R in total contain from 4 to about 31 carbon atoms; X and Y are anionic groups selected from the group consisting of sulphate and sulphonate, provided that at least one of X or Y is a sulfate group; and M is a cationic moiety, preferably a substituted or unsubstituted ammonium ion, or an alkali or alkaline earth metal ion.

The most preferred alkoxylated dianionic surfactant has the formula as above where R is an alkyl group of chain length from C ^ Q to C^g, A and B are independently C\ or C2, n and m are both 1 , both X and Y are sulfate groups, and M is a potassium, ammonium, or a sodium ion.

Preferred alkoxylated dianionic surfactants herein include: ethoxylated and/or propoxylated disulphate compounds, preferably C10-C24 straight or branched chain alkyl or alkenyl ethoxylated and/or propoxylated disulphates, more preferably having the formulae: wherein R is a straight or branched chain alkyl or alkenyl group of chain length from about C6 to about C\g; EO/PO are alkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups; and n and m are independently within the range of from about 0 to about 10 (preferably from about 0 to about 5), with at least m or n being 1.

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

CH2C00"M⁺ wherein R is a Cg to Cjg 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-O)-R3 wherein R is a Cg to Ci 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, 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-l-undecanoic acid, 2-ethyl-l-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) 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 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 ethoxylate/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 Polyhydroxy Fatty Acid Amide Surfactant

Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R^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 Cj or C2 alkyl, most preferably C\ alkyl (i.e., methyl); and R 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 Cj 1-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: R^CON(R^)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, C\- C4 hydroxyalkyl, and -(C2H4θ)_xH, where x is in the range of from 1 to 3.

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 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_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 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived from glucose.

Amphoteric Surfactant

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

Suitable amine oxides include those compounds having the formula R3(OR4)_XNO(R->)2 wherein Ry 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^ 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 Ci Q-Cj alkyl dimethylamine oxide, and Cιo-18 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 incorporated into the detergent compositions in accord with the invention. 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⁺R2COO~ wherein R is a Cg-Cj g hydrocarbyl group, each Rl is typically C1-C3 alkyl, and R² is a C1-C5 hydrocarbyl group. Preferred betaines are Cj2-18 dimethyl-ammonio hexanoate and the ClO-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.

Cationic Surfactants

Suitable cationic surfactants to be used in the detergent herein include the quaternary ammonium surfactants. Preferably the quaternary ammonium surfactant is a mono Cg-

C\(, preferably Cg-Cjo N-alkyl or alkenyl ammonium surfactants wherein the remaining

N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. Preferred are also the mono-alkoxylated and bis-alkoxylated amine surfactants.

Another suitable group of cationic surfactants which can be used in the detergent compositions or components thereof herein are cationic ester surfactants. The cationic ester surfactant is a, preferably water dispersible, compound having surfactant properties comprising at least one ester (i.e. -COO-) linkage and at least one cationically charged group.

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

In one preferred aspect the ester linkage and cationically charged group are separated from each other in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms (i.e. of three atoms chain length), preferably from three to eight atoms, more preferably from three to five atoms, most preferably three atoms. The atoms forming the spacer group chain are selected from the group consisting of carbon, nitrogen and oxygen atoms and any mixtures thereof, with the proviso that any nitrogen or oxygen atom in said chain connects only with carbon atoms in the chain. Thus spacer groups having, for example, -O-O- (i.e. peroxide), -N-N-, and -N-O- linkages are excluded, whilst spacer groups having, for example -CH2-O- CH2- and -CH2-NH-CH2- linkages are included. In a preferred aspect the spacer group chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.

Cationic Mono- Alkoxylated Amine Surfactants

Highly preferred herein are cationic mono-alkoxylated amine surfactant preferably of the general formula I:

wherein R is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to about 14 carbon atoms; R² and R^ are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl, most preferably both R² and R^ are methyl groups; R^ is selected from hydrogen (preferred), methyl and ethyl; X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality; A is a alkoxy group, especially a ethoxy, propoxy or butoxy group; and p is from 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8.

Preferably the ApR^ group in formula I has p=l and is a hydroxyalkyl group, having no greater than 6 carbon atoms whereby the — OH group is separated from the quaternary ammonium nitrogen atom by no more than 3 carbon atoms. Particularly preferred ApR^ groups are — CH₂CH₂OH, — CH₂CH₂CH₂OH, — CH₂CH(CH₃)OH and —

CH(CH₃)CH2OH, with — CH2CH2OH being particularly preferred. Preferred R¹ groups are linear alkyl groups. Linear Rl groups having from 8 to 14 carbon atoms are preferred. Another highly preferred cationic mono-alkoxylated amine surfactants for use herein are of the formula

wherein Rl is Cjo-Cig hydrocarbyl and mixtures thereof, especially C1Q-C14 alkyl, preferably C ^ Q ^and Cj2 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide.

As noted, compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy, isopropoxy [CH(CH3)CH2O] and [CH2CH(CH3θ] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.

The levels of the cationic mono-alkoxylated amine surfactants used in detergent compositions of the invention is preferably from 0.1 %> to 20%, more preferably from 0.2% to 7%, most preferably from 0.3% to 3.0% by weight of the composition.

Cationic Bis-Alkoxylated Amine Surfactant

The cationic bis-alkoxylated amine surfactant preferably has the general formula II:

wherein Rl is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms; R² is an alkyl group containing from one to three carbon atoms, preferably methyl; R^ and R^ can vary independently and are selected from hydrogen (preferred), methyl and ethyl, X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, sufficient to provide electrical neutrality. A and A' can vary independently and are each selected from C1-C4 alkoxy, especially ethoxy, (i.e., -CH2CH2O-), propoxy, butoxy and mixtures thereof; p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30, preferably 1 to about 4, and most preferably both p and q are 1.

Highly preferred cationic bis-alkoxylated amine surfactants for use herein are of the formula

wherein Rl is C10-C18 hydrocarbyl and mixtures thereof, preferably CJO_* Cj2_> C14 alkyl and mixtures thereof. X is any convenient anion to provide charge balance, preferably chloride. With reference to the general cationic bis-alkoxylated amine structure noted above, since in a preferred compound Rl is derived from (coconut) C12- C 4 alkyl fraction fatty acids, R² is methyl and ApR^ and A'qR^ are each monoethoxy.

Other cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula:

wherein Rl is CjQ-Cig hydrocarbyl, preferably C10-C14 alkyl, independently p is 1 to about 3 and q is 1 to about 3, R² is C1-C3 alkyl, preferably methyl, and X is an anion, especially chloride or bromide. Other compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy (Bu) isopropoxy [CH(CH3)CH2θ] and

[CH2CH(CH3θ] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.

Water-Insoluble Builder

The water insoluble builder comprises in particular aluminosilicates.

The_aluminosilicates herein include zeolites which 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 aluminosilicates are in preferably in hydrated form and are preferably crystalline, containing from 10% to 28%>, more preferably from 18% to 22% water in bound form. However, it may be useful to incorporate overdried aluminosilictaes.

The aluminosilicates 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, Zeolite HS and mixtures thereof. Zeolite A has the formula

Na ₁₂ [AlO₂) 12 (SiO₂)i2J- H₂O

wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nagg [(Alθ2)86(Siθ2)i06J- 276 H₂O.

Effervescence System Any effervescence system known in the art can be used in the composition of the invention. A preferred effervescence system comprises an acid source, capable of reacting with an alkali source in the presence of water to produce a gas.

The acid source is preferably present at a level of from 0.5% o 35%, more preferably from 1.0% or even 2% to 20% or even form 4% to 20% by weight of the composition.

It may be preferred that the acid source or part thereof and the alkali source or part thereof are comprised in an intimate mixture, for example in the form of a compacted particle. Then, the molecular ratio of the acid source to the alkali source present in such a mixture, is preferably from 50:1 to 1 :50, more preferably from 20:1 to 1 :20 more preferably from 10:1 to 1 :10, more preferably from 5:1 to 1 :3, more preferably from 3:1 to 1 :2, more preferably from 2:1 to 1 :2.

It may also be preferred that such a particle is present and in addition thereto one or more separate acid sources and one or more separate alkali sources

The acid source component may be any organic, mineral or inorganic acid, or a derivative thereof, or a mixture thereof. Preferably the acid source component comprises an organic acid.

The acid compound is preferably substantially anhydrous or non-hygroscopic and the acid is preferably water-soluble. It may be preferred that the acid source is overdried. Some of these acids may be water-soluble builders, as described above and should be considered part of the builder system of the compositions herein, whilst also providing effervescing.

Suitable acids source components include citric, malic, maleic, fumaric, aspartic, glutaric, tartaric succinic or adipic acid, monosodium phosphate, boric acid, or derivative thereof. Citric acid, maleic or malic acid are especially preferred. Most preferably, the acid source provides acidic compounds which have an average particle size in the range of from about 75 microns to 1 180 microns, more preferably from 150 microns to about 710 microns, calculated by sieving a sample of the source of acidity on a series of Tyler sieves.

As discussed above, the effervescence system preferably comprises an alkali source.

Any alkali source which has the capacity to react with the acid source to produce a gas may be present in the particle, which may be any gas known in the art, including nitrogen oxygen and carbondioxide gas. Preferred can be perhydrate bleaches, including perborate, and silicate material. The alkali source is preferably substantially anhydrous or non- hydroscopic. It may be preferred that the alkali source is overdried.

Preferably this gas is carbon dioxide, and therefore the alkali source is a preferably a source of carbonate, which can be any source of carbonate known in the art. In a preferred embodiment, the carbonate source is a carbonate salt. Examples of preferred carbonates are the alkaline earth and alkali metal carbonates, including sodium or potassium carbonate, bicarbonate and sesqui-carbonate and any mixtures thereof with ultra-fine calcium carbonate such as are disclosed in German Patent Application No. 2,321,001 published on November 15, 1973. Alkali metal percarbonate salts are also suitable sources of carbonate species, which may be present combined with one or more other carbonate sources.

The carbonate and bicarbonate preferably have an amorphous structure. The carbonate and or bicarbonates may be coated with coating materials. It can be preferred that the particles of carbonate and bicarbonate can have a mean particle size of 75 microns or preferably 150μm or greater, more preferably of 250μm or greater, preferably 500μm or greater. It may be preferred that the carbonate salt is such that fewer than 20% (by weight) of the particles have a particle size below 500μm, calculated by sieving a sample of the carbonate or bicarbonate on a series of Tyler sieves. Alternatively or in addition to the previous carbonate salt, it may be preferred that the fewer than 60% or even 25% of the particles have a particle size below 150μm, whilst fewer than 5% has a particle size of more than 1.18 mm, more preferably fewer than 20% have a particle size of more than 212 μm, calculated by sieving a sample of the carbonate or bicarbonate on a series of Tyler sieves.

It should be understood that the compositions herein may also comprise an alkali source when no effervescence is required or when no acid source is present, but for example to provide the required pH of the composition or the wash water. In particular carbonate salts may be present in the detergent composition of the invention.

Additional Ingredients

The compositions herein may contain additional detergent components. The precise nature of these additional components, and levels of incoφoration thereof will depend on the physical form of the compositions comprising the builder component and the precise nature of the washing operation for which it is to be used.

Additional ingredients include bleach, enzymes, suds suppressors, lime soap, dispersants, soil suspension and anti-redeposition agents soil releasing agents, perfumes, brighteners, photobleaching agents and additional corrosion inhibitors.

Perhydrate Bleaches

A highly preferred additional components of the compositions herein is an oxygen bleach, preferably comprising a hydrogen peroxide source and a bleach precursor or activator.

A preferred source of hydrogen peroxide is a perhydrate bleach, such as metal perborates, more preferably metal percarbonates, particularly the sodium salts. Potassium peroxymonopersulfate, sodium per is another optional inorganic perhydrate salt of use in the detergent compositions herein.

Perborate can be mono or tetra hydrated. Sodium percarbonate has the formula corresponding to 2Na2Cθ3-3H2θ2, and is available commercially as a crystalline solid.

In particular the percarbonate salts are used herein and in particular percarbonate salts which are coated. Suitable coating agent are known in the art, and include silicates, magnesium salts and carbonates salts and mixtures thereof.

Organic Peroxyacid Bleaching System

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

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 of the 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 stabilise for use in a bleaching composition. Preferred L groups are selected from the group consisting of:

R³ Y

I I

-0-CH=C-CH=CH₂ -O-CH=C-CH=CH₂

II Y II

O CH₂-C > — C^ .

.o_i__Rι -N C * ,' -^N c/^NR4 o o

R³ O Y i » i

-O— C=CHR⁴ , and — N— S— CH— R⁴

R³ O

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. - + - + - + + 3 -

The preferred solubilizing groups are -SO., M , -CO- M , -SO^ M , -N (R )^X and

3 - + - + 3

O<~N(R )-, and most preferably -SO., M and -CO₂ 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 precursors of this type provide peracetic acid on perhydrolysis.

Preferred alkyl percarboxylic precursor compounds of the imide type include the N- ,N,N1N1 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. The TAED is preferably not present in the agglomerated particle of the present invention, but preferably present in the detergent composition, comprising the particle.

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 Plkyl Peroxyacid Precursors

Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae: R N — R' R _ _N _ -c - - R² C

O R^ O or R⁵ O 0

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^ is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. 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 of the 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 pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Preformed Organic Peroxyacid

The detergent composition 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 of the composition.

A preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae: R¹ — C — N — R² — C — OOH R¹ N R' C - OOH

O R^ O or 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 R^ 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.

Heavy Metal Ion Sequestrant

Heavy metal ion sequestrant are also useful additional ingredients herein. By heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have a limited calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper. The are thus not considered builders for the puφose of the invention.

Heavy metal ion sequestrants are generally present at a level of from 0.005%) to 10%, preferably from 0.1% to 5%, more preferably from 0.25% to 7.5% and most preferably from 0.3%> to 2% by weight of the compositions.

Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1 -hydroxy disphosphonates and nitrilo trimethylene phosphonates. Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate, 1,1 hydroxyethane diphosphonic acid and 1,1 hydroxyethane dimethylene phosphonic acid.

Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof.

Other suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3 -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 also suitable. Glycinamide- N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2- hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.

Especially preferred are diethylenetriamine pentacetic acid, ethylenediamine-N,N'- disuccinic acid (EDDS) and 1,1 hydroxyethane diphosphonic acid or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof. Enzyme

Another preferred ingredient useful herein is one or more additional enzymes.

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

Organic Polymeric Compound

Organic polymeric compounds are preferred additional components of the compositions herein.

By organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as binder, 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, including quatemised ethoxylated (poly) amine clay-soil removal/ anti-redeposition agent, not being polymeric polycarboxylte polymers.

Organic polymeric compound is typically incoφorated in the detergent compositions of the invention at a level of from 0.01% to 30%, preferably from 0.1% to 15%, most preferably from 0.5% to 10%o by weight of the compositions.

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 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.

Highly preferred polymeric components herein are cotton and non-cotton soil release polymer according to U.S. Patent 4,968,451, Scheibel et al., and U.S. Patent 5,415,807, Gosselink et al., and in particular according to US application no.60/051517.

Another organic compound, which is a preferred clay dispersant anti-redeposition agent, for use herein, can be the ethoxylated cationic monoamines and diamines of the formula:

(CH₂CH₂0 )- X (CH₂CH₂0 ^ X

wherein X is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof, a is from 0 to 20, preferably from 0 to 4 (e.g. ethylene, propylene, hexamethylene) b is 1 or 0; for cationic monoamines (b=0), n is at least 16, with a typical range of from 20 to 35; for cationic diamines (b=l), n is at least about 12 with a typical range of from about 12 to about 42. Other dispersants/ anti-redeposition agents for use herein are described in EP-B-011965 and US 4,659,802 and US 4,664,848.

Suds Suppressing System

The detergent compositions of the invention, when formulated for use in machine washing compositions, may comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.02% to 10%, most preferably from 0.05% to 3% 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- 40 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 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 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.

Other highly preferred suds suppressing systems comprise polydimethylsiloxane or mixtures of silicone, such as polydimethylsiloxane, aluminosilicate and polycarboxylic polymers, such as copolymers of laic and acrylic acid.

Polymeric Dye Transfer Inhibiting Agents

The 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, whereby these polymers can be cross-linked polymers. Optical Brightener

The compositions herein also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners, as known in the art.

Polymeric Soil Release Agent

Polymeric soil release agents, hereinafter "SRA", can optionally be employed in the present compositions. If utilised, SRA's will generally comprise from 0.01% to 10.0%>, typically from 0.1% to 5%>, preferably from 0.2% to 3.0% by weight, of the compositions.

Preferred SRA's typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles, thereby serving as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the SRA to be more easily cleaned in later washing procedures.

Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium(IV) alkoxide. Such esters may be made using additional monomers capable of being incoφorated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosslinked overall structure.

Suitable SRA's include a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Such ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG") in a two-stage transesterification/oligomerization procedure; and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRA's include the nonionic end- capped 1 ,2-propylene/polyoxyethylene terephthalate polyesters of U.S. 4,71 1,730, December 8, 1987 to Gosselink et al., for example those produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"). Other examples of SRA's include: the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8- hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S. 4,702,857, October 27, 1987 to Gosselink, for example produced from DMT, methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S. 4,877,896, October 31, 1989 to Maldonado, Gosselink et al., the latter being typical of SRA's useful in both laundry and fabric conditioning products, an example being an ester composition made from m- sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably further comprising added PEG, e.g., PEG 3400.

SRA's also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the C1-C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S. 4,000,093,

December 28, 1976 to Nicol, et al.; and the methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20°C as a 2% aqueous solution. Such materials are available as METOLOSE SMI 00 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.

Additional classes of SRA's include: (I) nonionic terephthalates using diisocyanate coupling agents to link polymeric ester structures, see U.S. 4,201,824. Violland et al. and U.S. 4,240,918 Lagasse et al.; and (II) SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. With the proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals of the polymer through an ester of the isolated carboxylic acid of trimellitic anhydride rather than by opening of the anhydride linkage. Either nonionic or anionic SRA's may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U.S. 4,525,524 Tung et al.. Other classes include: (III) anionic terephthalate-based SRA's of the urethane-linked variety, see U.S. 4,201,824, Violland et al.;

Other Optional Ingredients

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

Also, minor amounts (e.g., less than about 20% by weight) of neutralizing agents, buffering agents, phase regulants, hydrotropes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti-oxidants, bactericides and dyes, such as those described in US Patent 4,285,841 to Barrat et al., issued August 25, 1981 (herein incoφorated by reference), can be present.

Highly preferred are encapsulated perfumes, preferably comprising a starch encapsulte.

The dye which may be used herein can be any dye for example in the form of a dye stuff or an aqueous solution of a dye stuff. It may be preferred that the dye is an aqueous solution comprising a dyestuff, at any level to obtain suitable dyeing of the particles, preferably such that levels of dye solution are obtained up to 2% by weight of the speckle particle, or more preferably up to 0.5% by weight. Optionally, the dye also comprising other ingredients such as organic binder materials.

The dyestuff can be any suitable dyestuff. Specific examples of suitable dyestuffs include El 04 - food yellow 13 (quinoline yellow), El 10 - food yellow 3 (sunset yellow FCF), El 31 - food blue 5 (patent blue V), Ultra Marine blue (trade name), El 33 - food blue 2 (brilliant blue FCF), El 40 - natural green 3 (chlorophyll and chloφhyllins), El 41 and Pigment green 7 (chlorinated Cu phthalocyanine). Preferred dyestuffs may be Monastral Blue BV paste (trade name) and/ or Pigmasol Green (trade name).

In the compositions of the invention, it may be preferred that when dyes and/ or perfumes are sprayed onto the another component, the component does not comprise spray-on nonionic alkoxylated alcohol surfactant.

Form of the Compositions

The composition of the invention thereof can be made via a variety of methods involving the mixing of ingredients, including dry-mixing, compaction such as agglomerating, extrusion, tabletting, or spray-drying of the various compounds comprised in the detergent component, or mixtures of these techniques, whereby the components herein also can be made by for example compaction, including extrusion and agglomerating, or spray-drying.

The compositions herein can take a variety of physical solid forms including forms such as tablet, flake, pastille and bar, and preferably the composition is in the form of granules or a tablet.

The compositions in accord with the present invention can also be used in or in combination with bleach additive compositions, for example comprising chlorine bleach. The compositions preferably have a density of more than 350 gr/litre, more preferably more than 450 gr/litre or even more than 570 gr/litre.

Abbreviations used in Examples

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

LAS Sodium linear Cj ι_χ3 alkyl benzene sulfonate LAS (I) Flake containing sodium linear Cj ι_ 3 alkyl benzene sulfonate (90%>) and sodium sulphate and moisture

LAS(II) Potassium linear C] ι_i3 alkyl benzene sulfonate

MES α-sulpho methylester of C₁₈ fatty acid TAS Sodium tallow alkyl sulfate CxyAS Sodium Cj_x - Cjy alkyl sulfate

C46SAS Sodium Cj4 - Cjg secondary (2,3) alkyl sulfate

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

CxyEz Cl_χ-Cjy predominantly linear primary alcohol condensed with an average of z moles of ethylene oxide

QAS R2.N⁺(CH3)2(C₂H₄OH) with R2 = Cι₂ - C14

QAS 1 R2.N⁺(CH3)2(C₂H OH) with R₂ = Cg - Cu SADS Sodium C₁₄-C₂₂ alkyl disulfate of formula 2-(R).C₄ H₇.-l,4-

(SO₄-)₂ where R = C₁₀_C₁₈

SADE2S Sodium C₁₄-C₂₂ alkyl disulfate of formula 2-(R).C₄ H₇.-l,4-

(SO₄-)₂ where R = C₁₀-C_lg, condensed with z moles of ethylene oxide

APA Cg - C10 amido propyl dimethyl amine

Soap Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut fatty acids

STS Sodium toluene sulphonate CFAA l2" l4 (coco) alkyl N-methyl glucamide

TFAA l6" l 8 alkyl N-methyl glucamide

TPKFA Cl6-Cl8 topped whole cut fatty acids

STPP Anhydrous sodium tripolyphosphate TSPP Tetrasodium pyrophosphate Zeolite A Hydrated sodium aluminosilicate of formula

Naj2(Alθ2Siθ2)i2-27H2θ having a primary particle size in the range from 0.1 to 10 micrometers (weight expressed on an anhydrous basis) NaSKS-6 (I) Crystalline layered silicate of formula δ- Na2Si2θ5 ₀f weight average particle size of 18 microns and at least 90% by weight being of particle size of below 65.6 microns.

NaSKS-6 (II) Crystalline layered silicate of formula δ- Na2Si2θ5 ₀f weight average particle size of 18 microns and at least 90% by weight being of particle size of below 42.1 microns.

Citric acid Anhydrous citric acid

Borate Sodium borate

Carbonate Anydrous 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 (SiO2:Na2O = 2.0:1)

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

MA AA Copolymer of 1 :4 maleic/acrylic acid, average molecular weight about 70,000 MA/AA (1) Copolymer of 4:6 maleic/acrylic acid, average molecular weight about 10,000

AA Sodium polyacrylate polymer of average molecular weight

4,500 CMC Sodium carboxymethyl cellulose

Cellulose ether Methyl cellulose ether with a degree of polymerization of

650 available from Shin Etsu Chemicals

Protease Proteolytic enzyme, having 3.3% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Savinase

Protease I Proteolytic enzyme, having 4% by weight of active enzyme, as described in WO 95/10591, sold by Genencor

Int. Inc.

Alcalase Proteolytic enzyme, having 5.3% by weight of active enzyme, sold by NOVO Industries A/S

Cellulase Cellulytic enzyme, having 0.23% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Carezyme

Amylase Amylolytic enzyme, having 1.6% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Termamyl 120T

Amylase II Amylolytic enzyme, as disclosed in PCT/ US9703635 Lipase Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase

Lipase (1) Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase Ultra

Endolase Endoglucanase enzyme, having 1.5% by weight of active enzyme, sold by NOVO Industries A/S PB4 : Sodium perborate tetrahydrate of nominal formula

NaBθ2.3H₂O.H₂θ2

PB1 : Anhydrous sodium perborate bleach of nominal formula

NaBθ2.H2θ₂

Percarbonate : Sodium percarbonate of nominal formula

2Na₂Cθ3.3H₂θ2

DOBS : Decanoyl oxybenzene sulfonate in the form of the sodium salt

DPDA : Diperoxydodecanedioc acid

NOBS : Nonanoyloxybenzene sulfonate in the form of the sodium salt

NACA-OBS : (6-nonamidocaproyl) oxybenzene sulfonate

LOBS : Dodecanoyloxybenzene sulfonate in the form of the sodium salt

DOBS : Decanoyloxybenzene sulfonate in the form of the sodium salt

DOBA Decanoyl oxybenzoic acid

TAED Tetraacetylethylenediamine

DTPA Diethylene triamine pentaacetic acid

DTPMP Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Tradename Dequest 2060

EDDS Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer in the form of its sodium salt.

Photoactivated bleach: Sulfonated zinc phthlocyanine encapsulated in or carried by soluble polymer or sulfonated alumino phthlocyanine encapsulated in or carried by 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 -hydroxy ethane diphosphonic acid PEGx Polyethylene glycol, with a molecular weight of x

(typically 4,000)

PEO Polyethylene oxide, with an average molecular weight of

50,000 TEPAE Tetraethylenepentaamine ethoxylate PVI Polyvinyl imidosole, with an average molecular weight of

20,000

PVP Polyvinylpyrolidone polymer, with an average molecular weight of 60,000 PVNO Polyvinylpyridine N-oxide polymer, with an average molecular weight of 50,000

PVPVI Copolymer of polyvinylpyrolidone and vinylimidazole, with an average molecular weight of 20,000

QEA bis((C2H5θ)(C2H4θ)_n)(CH3) -N+-C₆H₁₂-N+-(CH3) bis((C2H5θ)-(C₂H O))_n, wherein n = from 20 to 30

SRP 1 Anionically end capped poly esters SRP 2 Diethoxylated poly (1, 2 propylene terephtalate) short block polymer

PEI Polyethyleneimine with an average molecular weight of

1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen

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

Opacifier Water based monostyrene latex mixture, sold by BASF

Aktiengesellschaft under the tradename Lytron 621

Wax Paraffin wax Example I

Example 2

The following compositions are in accord with the invention.

Example 3

The following are detergent formulations according to the present invention:

Example 4

The following formulations are examples of compositions in accordance with the invention, which may be in the form of granules or in the form of a tablet.

Example 5

The following are detergent formulations according to the present invention:

Example 6

A detergent composition was formed comprising blown powder, an agglomerate comprising crystalline layered silicate and anionic surfactant, an effervescent particle and dry-mixed bleach activator particle, sodium percarbonate, sodium citrate and suds supressor.

The individual particulates were prepared and dry-mixed together with gentle mixing e.g. in a Nautamixer for a period of at least 4 minutes.

Preparation of the Blown Powder

The composition of the final blown powder was as follows:-

Ingredient % in Blown Powder

Sodium Linear Alkyl Sulphonate (LAS) 20

Copolymer of Acrylic/Maleic Acid 5

Sodium Sulphate 16

Sodium Carbonate 31

Sodium Citrate 20

Water 8

The blown powder was prepared by a standard spray drying process. The above ingredients were mixed into a slurry with water. The aqueous slurry may be prepared by a batch or continuous process. In this case, a batch mixer, or "crutcher" was used in which the various detergent components were dissolved in, or slurried with, water to provide a slurry containing 35%> water. The water content my be varied from about 20%> to about 60%) by weight of water, preferably it is about from about 30% to about 40% by weight water. In this example the order of addition of the ingredients to water to form the aqueous slurry was as listed above in the final composition of the blown powder. The aqueous slurry was then pumped at high pressure through atomising nozzles into a spray- drying tower where excess water was driven off, producing a flowable powder product (blown powder). Fines were screened out through a mesh.

Preparation of Crystalline layered silicate/ Anionic Surfactant Particle

An agglomerate comprising 70% SKS6 and 30% LAS was prepared by a conventional agglomeration process.

Preparation of the Effervescent Particle Particles were prepared having the following composition:

Ingredient Composition %

Malic Acid 44

Sodium Bicarbonate 40

Sodium Carbonate 16

The particle was made via a roller compaction process. The raw materials in the proportions indicated above, were fed at a press force of 80kN into a Pharmapaktor L200/50 P roller, set up with concave smooth rolls with a 0.3mm axial corrugation installed. The flakes produced were then compacted using a Flake Crusher FC 200 with a mesh size selected to produce the required particle size. The product was screened to remove the fines.

These three components were mixed with the additional dry-added ingredients listed below, in the proportions given below, to form a detergent composition according to the invention.

Ingredient %> in Detergent Composition Spray Dried 42 Bleach Activator 3

Sodium Percarbonate 15

Sodium Citrate 10

SKS6/L AS granulate 10

Suds suppressor particle 4 (95% PEG, 5% silicone)

Effervescent Particle 16

Claims

1. A phosphate-free detergent composition comprising at least one particulate components, from 5% to 90% by weight of the composition of a builder system and at least 10% by weight of the composition of a surfactant system, comprising one or more surfactants, characterised in that

a) the builder system comprises at least two builders selected from water-soluble or partially water-soluble builders or mixtures thereof, present at a level from 60% to

100% by weight of the builder system; and from 0% to 40% by weight of the builder system of water-insoluble builders, provided that less than 9% by weight of the composition of aluminosilicate builder is present, and less than 5% by weight of the composition of amoφhous sodium silicate is present; and

b) the particulate component comprises at least one of the surfactants of the surfactant system is intimately mixed with at least one of the water-soluble or partially water- soluble builders.

2. A detergent composition according to claim 1 wherein substantially no water- insoluble builder is present as a separate powder component.

3. A detergent composition according to claim 1 or 2 comprising less than 3% by weight of aluminosilicate builder and less than 2% of amoφhous sodium silicate, preferably the composition is substantially free of aluminosilicate builder.

4. A composition according to any preceding claim wherein the builder system comprises a crystalline layered silicates of the formula

NaMSi_xO_2x+1.yH₂O wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20; whereby preferably the crystalline layered silicate or part thereof is comprised in a particulate component, preferably in an intimate mixture with an anionic surfactant of the surfactant system.

5. A composition according to any preceding claim wherein the builder system comprises an organic carboxylic acid or salt thereof, whereby preferably part or all of the organic carboxylic acid or salt thereof, is comprised in a particulate component.

6. A composition according to claim 5 wherein the organic carboxylic acid or salt thereof comprises a polymeric polycarboxylic acid or salt thereof and a monomeric polycarboxylic acid or salt or mixtures thereof.

7. A composition according to any preceding claim comprising an effervesce system.

8. A composition according to any preceding claim wherein the surfactant system comprises an anionic alkyl sulphate surfactant, an anionic sulphonate surfactant or mixtures thereof.

9. A detergent composition according to any preceding claim wherein the particular component is substantially free of spray-on nonionic alkoxylated alcohol surfactants.

10. A composition according to any preceding claim wherein the particular components comprises a perfume, brightener or dye or mixtures thereof, preferably as a spray-on a component.

11. A composition according to any preceding claim which is substantially free of anionic linear alkyl sulfate surfactants.

12. A detergent composition according to any preceding claim comprising an oxygen- based bleach, comprising a hydrogen peroxide source, preferably a percarbonate salt, and a bleach precursor.

13. Use of a particulate component comprising an intimate mixture of a water soluble or partially water-soluble builder, or mixture thereof and a surfactant to improve the delivery to the wash of a detergent composition, comprising from 5% to 90% by weight of a builder system and at least 10% by weight of a surfactant system which contains one or more surfactants, whereby the builder system comprises at least two builders selected from water-soluble or partially water-soluble builders or mixtures thereof, present at a level from 60%> to 100% by weight of the builder system; and from 0% to 40% by weight of the builder system of water- insoluble builders, provided that less than 9%> by weight of the composition of aluminosilicate builder is present, and less than 5%> by weight of the composition of amoφhous sodium silicate is present.