WO1997005221A1

WO1997005221A1 - Detergent composition

Info

Publication number: WO1997005221A1
Application number: PCT/US1996/012503
Authority: WO
Inventors: Gerard Marcel Baillely
Original assignee: The Procter & Gamble Company
Priority date: 1995-08-02
Filing date: 1996-07-31
Publication date: 1997-02-13
Also published as: AR003172A1; GB9515851D0; GB2303858A

Abstract

A solid form detergent composition is disclosed containing (a) a zeolite builder comprising zeolite P having a silicon to aluminium ratio of not greater than 1.33 (zeolite MAP); and (b) a cationic ester surfactant, wherein the pH of a 1 % solution of said composition measured at 20 °C is greater than 9.25. Granular detergent compositions made by agglomeration processes are preferred and methods of making such compositions are disclosed.

Description

DETERGENT COMPOSITION The present invention relates to a granular alkaline detergent composition comprising a cationic ester surfactant and a zeolite component as a sequestering agent for water hardness.

Conventionally, water soluble inorganic phosphates, such as sodium tripolyphosphate, have been used as builders for laundry detergents.

More recently, alkali metal aluminosilicate ion-exchangers, particularly crystalline water insoluble sodium aluminosilicate zeolites, have been proposed as replacements for the inorganic phosphates.

For example, EP 21 491A (Procter & Gamble) discloses detergent compositions containing a builder system which includes zeolite A, X or P (B) or a mixture thereof. EP 384070A (Unilever) discloses specific zeolite P materials having an especially low silicon to aluminium ratio not greater than 1.33 (hereinafter referred to as zeolite MAP) and describes their use as detergency builders.

Surfactant components have traditionally been employed in detergent products to facilitate the removal of greasy soils/stains. In particular, surfactant systems comprising cationic esters have been found to be of utility in greasy soil/stain removal.

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

US-A-4,228,042 discloses biodegradable cationic surfactants, including cationic ester surfactants for use in detergent compositions to provide greasy/oily soil removal. The combination of these cationic surfactants with nonionic surfactants in compositions designed for particulate soil removal is also described. Anionic surfactants are disclosed as optional components of the compositions, but are present at low levels relative to the cationic surfactant component. US-A-4,239,660 discloses laundry detergent compositions containing cationic ester surfactant and nonionic surfactant at defined weight ratios and an alkalinity source. The alkalinity source enables a wash solution having a pH of from 8 to 10 to be formed within 3 minutes of dissolution of the composition in water at 100°F (37°C) at a solution concentration of 0.15%.

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

The Applicants have found that a problem with the use of cationic ester surfactants in solid alkaline detergent products is the propensity for the surfactant to degrade on storage. In more detail, the cationic ester surfactant has a tendency to be hydrolysed, particularly when stored under conditions of high moisture and/or elevated temperatures.

The Applicants have suφrisingly found that this storage degradation problem may be ameliorated by the co-incorporation of a zeolite MAP builder material into the composition together with the cationic ester surfactant. The use of crystalline layered silicate as a cobuilder has been found to further aid cationic ester storage stability. In a preferred aspect, the zeolite MAP builder and optionally any cobuilder are in close physical proximity, more preferably in intimate admixture within the composition.

Whilst the prior art, as represented for example by European Patent Aplications, EP 384070 A, EP 448297 A, EP 522726 A, EP 533392 A, EP 544492 A, EP 552053 A, and EP 552054 A has envisaged the use of surfactants in combination with zeolite MAP in laundry detergent compositions, none of these prior art documents specifically disclose the co-incorporation of cationic ester surfactant with a zeolite MAP component in a solid detergent composition. Furthermore, none of these prior art documents provides any teaching relating to the surfactant storage stability problem addressed by the current invention, nor of any solution thereto involving the co-incorporation of a zeolite MAP builder component.

According to the present invention there is provided a solid form detergent composition containing

(a) a zeolite builder comprising zeolite P having a silicon to aluminium ratio of not greater than 1.33 (zeolite MAP); and

(b) a cationic ester surfactant

wherein the pH of a 1% solution of said composition measured at 20°C is greater than 9.25.

In a preferred aspect, the cationic ester surfactant is selected from those having the formula:

*ι - (X)_u-( C H₂ )_m— (Y)_v— (CH₂ )_t-N-R₃ M

wherein R-j is a C5-C31 linear or branched alkyl, alkenyl or alkaryl chain or M". N⁺(R6R7Rβ)(CH2)_s; X and Y, independently, are selected from the group consisting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO group; R2, R3, R , RQ, R7, and Rβ are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxy- alkenyl and alkaryl groups having from 1 to 4 carbon atoms; and R5 is independently H or a C1-C3 alkyl group; wherein the values of m, n, s and t independently lie in the range of from 0 to 8, the value of b lies in the range from 0 to 20, and the values of a, u and v independently are either 0 or 1 with the proviso that at least one of u or v must be 1 ; and wherein M is a counter anion.

Detailed Description of the Invention Zeolite MAP builder

The first essential component of the present invention is a zeolite MAP builder, optionally in conjunction with one or more supplementary builders.

The zeolite MAP is typically present at a level of from 1% to 80%, more preferably from 15% to 40% by weight of the compositions.

Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.

Of particular interest is zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.

Zeolite P having a Si:AI ratio of 1.33 or less may be prepared by the following steps:

(i) mixing together a sodium aluminate having a mole ratio Na2θ:Al2θ3 within the range of from 1.4 to 2.0 and a sodium silicate having a mole ratio SiO2:Na2O within the range of from 0.8 to 3.4 with vigorous stirring at a temperature within the range of from 25°C to boiling point usually 95°C, to give a gel having the following composition; AI2O3: (1.75-3.5) Siθ2 : (2.3-7.5) Na2θ :P (80- 450)H₂O;

(ii) ageing the gel composition for 0.5 to 10 hours, preferably 2 to 5 hours, at a temperature within the range of from

70°C to boiling point, usually to 95°C, with sufficient stirring to maintain any solids present in suspension; (iii) separating the crystalline sodium aluminosilicate thus formed, washing to a pH within the range of from 10 to 12.5, and drying, preferably at a temperature not exceeding 150°C, to a moisture content of not less than 5 wt.%.

Preferred drying methods are spray-drying and flash drying. It appears that oven drying at too high a temperature may adversely affect the calcium binding capacity of the product under certain circumstances.

Commercial sodium metasilicate pentahydrate dissolved in water and commercial sodium silicate solution (waterglass) are both suitable silica sources for the production of zeolite P in accordance with the invention. The reactants may be added together in any order either rapidly or slowly. Rapid addition at ambient temperature, and slow addition at elevated temperature (90-95°C) both give the desired product.

Vigorous stirring of the gel during the addition of the reactants, and at least moderate stirring during the subsequent ageing step, however, appear to be essential for the formation of pure zeolite P. In the absence of stirring, various mixtures of crystalline and amoφhous materials may be obtained.

Zeolite MAP generally has a calcium binding capacity of at least 150 mg CaO per g of anhydrous aluminosilcate, as measured by the standard method described in GB 1473201 (Henkel). The calcium binding capacity is normally 160 mg CaO/g and may be as high 170 mg CaO/g.

Although zeolite MAP like other zeolites contains water of hydration, for the puφoses of the present invention amounts and percentages of zeolite are expressed in terms of the notional anhydrous material.

The amount of water present in hydrated zeolite MAP at ambient temperature and humidity is generally about 20 wt.%.

In a preferred aspect the zeolite MAP detergent builder has a particle size, expressed as a dso value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres. The d5Q value indicates that 50% by weight of the particles have a diameter smaller than that figure. The particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods of establishing dso values are disclosed in EP 384070A.

Cationic ester surfactant

The second essential element of the detergent compositions of the invention is a cationic ester surfactant. That is, a preferably water dispersible compound having surfactant properties comprising at least one hydrolysable ester (ie -COO-) linkage and at least one cationically charged group.

The cationic ester surfactant is present in amount from 0.1% to 90%, preferably from 0.5% to 40%, most preferably from 1% to 10% by weight of the detergent composition.

The weight ratio of zeolite MAP to cationic ester component is typically from 100:1 to 2:1, preferably from 50:1 to 3:1, most preferably from 30:1 to 4:1.

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

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

^Rl ^~ 0+(CH)_nO (X)_u-( C H₂ )_m— (Y)_v— (CH₂ )_t-N-R₃ M

R

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

Preferably R2.R3 and R4 are independently selected from CH3 and -CH₂CH₂OH.

Preferably M is selected from the group consisting of halide, methyl sulfate, sulfate, and nitrate, more preferably methyl sulfate, chloride, bromide or iodide.

Preferred water dispersible cationic ester surfactants are the choline esters having the formula:

wherein R-j is a C<| -j-C-jg linear or branched alkyl chain.

Particularly preferred choline esters of this type include the stearoyl choline

C17 alkyl), and any mixtures thereof. Most preferred choline ester compounds among the above disclosed are cocoyi choline ester quaternary methylammonium halides.

The particularly preferred choline esters, given above, may be prepared by the direct esterification of a fatty acid or fatty acid mixture of the desired chain length with dimethylaminoethanol, in the presence of an acid catalyst. The reaction product is then quaternized in a suitable solvent (e.g. water, ethanol, fatty acid) with a methyl halide, forming the desired cationic material.

They may also be prepared by the direct esterification of a long chain fatty acid of the desired chain length together with 2-haloethanol, in the presence of an acid catalyst material. The reaction product is then quaternized with trimethylamine, forming the desired cationic material.

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

pH of the compositions

The present compositions have a pH measured as a 1 % solution in distilled water of at least 9.25, preferably from 10.0 to 12.5, most preferably from 10.5 to 12.0. Additional detergent components

The detergent composition according to the invention may contain other detergent components such as surfactants, cobuilders, bleaches, fluorescers, antiredeposition agents, inorganic salts such as sodium sulphate, enzymes, lather control agents, fabric softening agents, pigments, coloured speckles and perfumes.

Surfactant

The detergent composition according to the invention preferably includes an additional surfactant selected from anionics, nonionics, zwitterionics, ampholytics and non-cationic ester cationics.

The additional surfactant is preferably present in the detergent compositions at a level of from 1 % to 50%, preferably from 3% to 30%, most preferably from 5% to 20% by weight of the compositions.

Many suitable detergent-active compounds are available and fully described in the literature (for example "Surface Active Agents and Detergents" Volumes I and II by Schwartz, Perry and Berch).

Examples of suitable additional anionic surfactants include anionic sulfates, olefin sulphonates, alkyl xylene sulphonates, dialkylsulphosuccinates, and fatty acid ester sulphonates. Sodium salts are generally preferred.

Anionic sulfate surfactant

Anionic sulfate surfactants suitable for use herein include the linear and branched primary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C-17 acyl-N-(C<|- C4 alkyl) and -N-(Cι-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).

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

Anionic sulfonate surfactant

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

Nonionic surfactant

Examples of suitable alkoxylated nonionic surfactants include alkoxylated adducts of fatty alcohols containing an average of from 1 to 7 alkylene oxide groups per molecule.

The alkylene oxide residues may, for example, be ethylene oxide residues or mixtures thereof with propylene oxide residues.

Preferred alkylene oxide adducts of fatty alcohols useful in the present invention can suitably be chosen from those of the general formula:

R-0-(C_nH_2nO)yH

wherein R is an alkyl or alkenyl group having at least 10 carbon atoms, most preferably from 10 to 22 carbon atoms, y is from 0.5 to 5 and n is 2 or 3.

Suitable nonionic surfactants include primary C11-C15 aliphatic alcohols condensed with an average of no more than five ethylene oxide groups per mole of alcohol, having an ethylene oxide content of less than 50% by weight, preferably from 25% to less than 50% by weight. A preferred aliphatic alcohol ethoxylated is a primary alcohol having an average of 12 to 15 carbon atoms in the alkyl chain condensed with an average of three ethoxy groups per mole of alcohol.

Specific examples of suitable alkoxylated adducts of fatty alcohols are Synperonic A3 (ex ICI), which is a C13-C15 alcohol with about three ethylene oxide groups per molecule and Empilan KB3 (ex Marchon), which is lauric alcohol 3EO.

Another class of nonionic sufactants comprises alkyl polyglucoside compounds of general formula

RO(C_nH_2nO)tZ_x

wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.1 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides. Compounds of this type and their use in detergent compositions are disclosed in EP-B 0070074, 0070077, 0075996 and 0094118.

Cobuilders

In addition to zeolite MAP, the builder system may contain an organic or inorganic cobuilder.

Suitable organic cobuilders can be monomeric or polymeric carboxylates such as citrates or polymers of acrylic, methacrylic and/or maleic acids in neutralised form. Suitable inorganic cobuilders include carbonates and amorphous and crystalline layered silicates. Crystalline layered silicates are most preferred.

Suitable crystalline layered silicates have the composition:

NaMSi_xθ2χ+i . _yH2θ where M is sodium or hydrogen, preferably sodium; x is a number from 1.9 to 4; and y is a number from 0 to 20. Such materials are described in US Patents No. 4664839; No. 4728443 and No. 4820439 (Hoechst AG). Especially preferred are compounds in which x = 2 and y = O. The synthetic material is commercially available from Hoechst AG as δ -Na2 Si2θ5 (SKS6) and is described in US Patent No. 4664830.

The cobuilder may include an aluminosilicate zeolite A material, but where present such zeolite A builder is at a level of no more than 2% by weight of the detergent composition. Preferably the detergent composition is free of zeolite A.

The total amount of detergency builder in the granular composition typically ranges from 1 to 80 wt.%, more preferably from 15 to 60 wt% and most preferably from 10 to 45 wt.%.

Bleach

Detergent compositions according to the invention may also suitably contain a bleach system. This preferably comprises one or more peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, which may be employed in conjunction with bleach precursors to improve bleaching action at low temperatures.

The bleach system preferably comprises a peroxy bleach compound, preferably an inorganic persalt, optionally in conjunction with a peroxyacid bleach precursor. Suitable persalts include sodium perborate monohydrate and tetrahydrate and sodium percarbonate, with sodium percarbonate being most preferred. In one preferred aspect the composition is substantially free of perborate tetrahydrate to ensure good storage stability of the composition at elevated temperatures.

Preferred bleach precursors are peracetic acid precursors, such as tetraacetylethylene diamine (TAED); peroxybenzoic acid precursors. Physical form

The detergent composition according to the invention is in solid form, for example powder, granular or tablet form. However, granular compositions are preferred.

in a preferred aspect at least part of, more preferably all of the cationic ester surfactant is in close physical proximity to the zeolite MAP component in the composition, preferably the two components are in close contact, most preferably they are in intimate admixture. Particles, particularly made by agglomeration methods, in which such close physical proximity and especially such intimate admixture may be achieved are especially preferred. Suitable coagglomerate materials include polycarboxylate builders, especially citrates, crystalline layered silicate, carbonate and bicarbonate salts.

Making process

The solid detergent compositions of the invention may be prepared by any suitable method. Particulate detergent compositions are suitably prepared by any tower (spray-drying) or non-tower process.

In processes based around a spray-drying tower, a base powder is first prepared by spray-drying a slurry and then other components unsuitable for processing via the slurry can be sprayed on or admixed (postdosed).

The zeolite MAP is suitable for inclusion in the slurry, although it may be advantageous for processing reasons for part of the zeolite MAP to be incoφorated post-tower.

In a preferred aspect, particulate detergent compositions in accordance with the invention may be prepared by wholly non-tower processes such as agglomeration using any commonly known detergent agglomeration methods.

Granular detergent compositions of the invention may be prepared to any suitable bulk density. The compositions preferably have a bulk density of at least 400 g/l preferably at least 550 g/l, most preferably at least 700 g/l and, with particular preference at least 800 g/l.

The benefits of the present invention are particularly evident in powders of high bulk density, for example, of 700 g/l or above. Such powders may be prepared either by post-tower densification of spray-dried powder, or by wholly non-tower methods such as dry mixing and agglomeration; in both cases a high-speed mixer/granulator may advantageously be used. Processes using high-speed mixer/granulators are disclosed, for example, in EP340013A, EP 367339A, EP 390251 A and EP 420317A (Unilever).

Illustrative compositions according to the present invention are presented in the following Examples.

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

Cationic ester RlCOOCH₂CH₂.N⁺(CH3)3CI- with R< = C11-C13

246AS: Sodium alkyl sulfate surfactant containing a alkyl chain length weight distribution of 15% C12 alkyl chains, 45% C-|4 alkyl chains, 35% C16 alkyl chains, 5% C-jβ alkyl chains

LAS: C12 linear alkylbenzene sulfonate

TAS: Sodium alkyl sulfate surfactant containing predominantly C15 - C-jβ alkyl chains derived from tallow oil.

24AE3S: C12-C14 alkyl ethoxysulfate containing an average of three ethoxy groups per mole.

XYEZ: A C<ιχ_ιγ primary alcohol condensed with an average of Z moles of ethylene oxide.

Carbonate: Anhydrous sodium carbonate. Perborate: Sodium perborate tetrahydrate.

Percarbonate: Sodium percarbonate.

TAED : Tetra acetyl ethylene diamine.

Silicate: Amoφhous Sodium Silicate (SiO2:Na2O ratio normally follows).

Zeolite MAP: Hydrated sodium aluminosilicate zeolite MAP having a silicon to aluminium ratio of 1.07.

MA/AA: Copolymer of 1:4 maleic/acrylic acid, average molecular weight about 80,000.

Amylase: Amylolytic enzyme sold under the tradename Termamyl 60T by Novo Industries A/S (approx. 0.9% enzyme activity).

BSA: Amylolytic enzyme sold under the tradename LE17 by Novo Industries A/S (approx 1 % enzyme activity).

Protease: Proteolytic enzyme sold by Novo Industries AS of activity 4.0 KNPU.

DTPMP: Diethylene triamine penta (methylene phosphonic acid).

Silicone suds: 12% silicone/siiica, 18% stearyl alcohol, 70% suppressor starch in granular form.

Example 1 The following granular laundry detergent compositions were prepared (parts by weight) in accordance with the invention. All amylase enzyme levels relate to levels of active enzyme, expressed on a 4 KNU/g activity basis. A B C D E

Cationic ester 2.0 1.5 1.0 0.5 3.0

246AS 7.6 6.5 4.8 6.8 _

TAS - - - - 8.6

24AE3S 2.4 - 1.2 1.7 _

25E3 3.26 - - _ 6.3

35E3 - 5.0 5.0 5.0 _

Zeolite MAP 20.0 25.0 20.0 25.0 31.0

Carbonate 15.0 15.0 20.0 10.0 12.0

MA/AA 4.25 4.25 4.25 4.25 2.0

Perborate - 16.0 - 16.0 20.0

Percarbonate 20.0 - 20.0 _ _

TAED 5.0 5.0 5.0 5.0 6.7

Amylase 0.2 0.5 - 0.1 0.1

BSA - - 0.2 _ -

Protease 0.04 0.08 - 0.05 0.05

Silicate (2.0 ratio) 4.0 - - 4.0 3.0

Water and miscellaneous (Including suds suppressor, sodium sulphate, perfume) to balance.

Example 2

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

F G H

Blown Powder

Zeolite MAP 13.0 10.0 25.0

MA/AA 4.0 3.6 5.0

DTPMP 0.4 0.4 0.5

Magnesium sulfate 0.4 0.4 0.4

Surfactant agglomerate

LAS 7.0 6.8 9.0

TAS 2.0 1.4 2.6 Zeolite MAP 7.0 6.6 9.0

Carbonate 7.0 6.8 9.0

Cationic ester agglomerate

LAS 1.8 1.8 3.6

Cationic ester 1.0 1.0 2.0

Bentonite clay - 12.0 -

Sodium sulfate 3.0 - 6.0

Silicate (2.8 ratio) - 1.0 -

Zeolite MAP 4.0 2.0 8.0

Spray On

Perfume 0.3 0.3 0.3

Silicone suds suppressor 0.5 0.5 0.5

45E7 4.0 2.0 4.0

68E11 1.0 1.0 1.0

Dry additives

Percarbonate 20.0 20.0 -

TAED 5.0 5.0 -

Balance (Moisture and 100.0 100.0 100.0 Miscellaneous)

Density (g/litre) 850 850 850

Claims

What is claimed is:

1. A solid form detergent composition containing

(b) a cationic ester surfactant

2. A detergent composition according to Claim 1 wherein said zeolite builder is present at a level of from 1% to 80% by weight of the composition

3. A detergent composition according to either Claims 1 or 2 wherein said zeolite MAP builder has a particle size, expressed as a dso value of from 1.0 to 10.0 micrometres.

4. A detergent composition according to any of Claims 1 to 3 wherein said cationic ester surfactant is selected from those having the formula:

^Rι - O (CH)_nO Wu^~ C H₂ )_m— M

wherein R-| is a C5-C31 linear or branched alkyl, alkenyl or alkaryl chain or M". N⁺(R6R7RδXCH2)_s; X and Y, independently, are selected from the group consisting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO group; R₂, R3, R4, Rβ, R7, and Rβ are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxy-alkenyl and alkaryl groups having from 1 to 4 carbon atoms; and R5 is independently H or a C-j- C3 alkyl group; wherein the values of m, n, s and t independently lie in the range of from 0 to 8, the value of b lies in the range from 0 to 20, and the values of a, u and v independently are either 0 or 1 with the proviso that at least one of u or v must be 1 ; and wherein M is a counter anion.

5. A detergent composition according to Claim 4 wherein R2.R3 and R4 are independently selected from the group consisting of CH3 and - CH₂CH₂OH.

6. A detergent composition according to Claim 4 wherein the cationic ester is selected from the choline esters having the formula:

wherein R-\ is a C-j 1-C19 linear or branched alkyl chain.

7. A detergent composition according to any of Claims 1 to 6 containing an additional surfactant at a level of from 1% to 50% by weight of the composition.

8. A detergent composition according to any of Claims 1 to 7 containing an organic or inorganic cobuilder.

9. A detergent composition according to Claim 8 wherein said cobuilder is a crystalline layered silicate builder.

10. A detergent composition according to any of Claims 1 to 9 wherein said composition is in particulate form.

11. A particulate detergent composition according to Claim 10 made by an agglomeration process.