SK144695A3 - Partical detergent composition - Google Patents

Abstract

A particulate detergent composition which is not the direct product of a spray-drying process has a high bulk density ( >/= 650 g/l) and contains a surfactant system consisting essentially of ethoxylated nonionic surfactant and optional primary alcohol sulphate, zeolite builder, and a citrate salt. Delivery and dissolution in the wash are improved by the choice of ethoxylated nonionic surfactant having an average degree of ethoxylation of 5.2 to 8.0, preferably about 7.

Description

Technical field

The invention relates to particulate detergent compositions of high bulk density comprising anionic and nonionic surfactants and a zeolite component. ^FROM

BACKGROUND OF THE INVENTION

EP 544 492A (Unilever) discloses high bulk density detergent powders comprising an organic surfactant system (ethoxylated nonionic surfactant and primary alcohol sulfate), a zeolite detergent builder, and other optional ingredients. The ethoxylated nonionic surfactant, which is the predominant component (at least 60% by weight) in the surfactant system, has a degree of ethoxylation not exceeding 6.5, preferably from 3 to 6.5, and more preferably from 4 to 5.5. This highly efficient surfactant system provides excellent detergency and the use of relatively high levels of zeolite content allows the preparation of free-flowing powders containing high levels of these mobile surfactants.

These mixtures represent the latest trend towards high bulk density powders that are prepared by processes that eliminate or do not introduce the porosity typical of traditional spray-dried powders. These processes include post-tower densification of spray-dried powders and more preferably completely non-tower processes involving dry mixing, agglomeration, granulation and the like processes.

However, some problems with formulations of this type have been found in the delivery of the active ingredients of the washing machine in an automatic washing machine. Delivery is a two-step process: the first step is to dispense the powder into the wash fluid, either from the dispenser drawer of the washing machine or from a dispensing device (washing ball or the like) supplied by the powder manufacturer; and the second step is to release the powder when it enters the wash water.

Surprisingly, it has been found that the delivery of the high bulk density powder of the aforementioned type is greatly improved using a nonionic surfactant with a higher degree of ethoxylation, provided that a citric acid salt is also present. _from

Citrates are well known detergent ingredients used to supplement zeolites. Their use in powders based on zeolite is described, for example, in EP 313 143A, EP 313 144A, EP 448 297A, EP 448 298A (Unilever); GB 1,408,678, EP 1310A, EP 1853B, EP 326 208A, EP 456 315A and WO 91 15566A (Procter &Gamble); DE 2,336,128C (Lion); and GB 2,095,274B (Colgate).

However, the use of citrate in the presence of a specific nonionic surfactant to increase the solubility of a high bulk density detergent powder has not been described in the literature.

SUMMARY OF THE INVENTION

Accordingly, the invention provides a particulate detergent composition which is not a direct product of the spray-drying process and which has a bulk density of at least 650 g / l and comprises:

(a) from 15 to 50% by weight of a surfactant system consisting essentially of (i) an ethoxylated nonionic surfactant which is a primary C8 to C18 alcohol having a mean degree of ethoxylation ranging from 5.2 to 8; (Ii) optionally primary alcohol sulphate, (iii) optionally not more than 25% by weight (of the surfactant system) of alkylbenzene sulphonate, (b) from 20 to 70% by weight (anhydrous basis) of the alkali metal aluminosilicate detergent component, ( (c) from 5 to 40% by weight of a water-soluble citric acid salt; (d) optionally other detergent ingredients up to 100% by weight.

The invention further provides the use of a nonionic surfactant which is an ethoxylated primary C8 to C18 alcohol having a medium degree of ethoxylation in the range of 5.2 to 8.0 to improve the delivery and dissolution characteristics of the particulate detergent composition having a bulk density of 650 g / l or more which is not a direct product of the spray-drying process and which includes:

(a) from 15 to 50% by weight of a surfactant system consisting essentially of (i) an ethoxylated nonionic surfactant, (ii) optionally a primary alcohol sulfate, (iii) optionally not more than 25% by weight of an alkylbenzene sulfonate surfactant (b) from 20 to 70% by weight (anhydrous basis) of the alkali metal aluminosilicate detergent component; (c) from 5 to 40% by weight of the water-soluble citric acid salt; (d) optionally other detergent components to 100% by weight.

The high bulk density particulate detergent compositions of the present invention comprise as essential ingredients:

(a) a defined surfactant system; (b) a detergent aluminosilicate component; (c) a citric acid salt.

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Optionally, other detergent ingredients may be present if necessary or desired.

The mixtures are preferably produced by a mixing and granulating process that does not involve spray-drying.

However, the invention also encompasses compositions which have been prepared by spray-drying and subsequently subjected to granulation, densification or the like treatment which removes or reduces the porosity typical of spray-dried powders.

The compositions of the present invention typically have a low particle porosity. Preferably, the particles have an void volume not exceeding 10% by weight, more preferably not exceeding 5% by weight, and desirably the smallest possible. The void volume can be measured by mercury porosimetry.

Surface active system

The compositions of the invention comprise from 15 to 50% by weight, preferably from 15 to 30% by weight, of a defined surfactant system.

An essential component of the surfactant system is an ethoxylated alcohol nonionic surfactant having an average alkyl chain length of from Cg to Cg ^{and a} mean degree of ethoxylation ranging from 5.2 to 8.0.

The nonionic surfactant preferably has an alkyl chain length of from and more preferably of from C 1 to C 6.

The nonionic surfactant, whether of plant or petrochemical origin, is preferably predominant or completely linear. Particularly preferably, the nonionic surfactants are derived from coconut oil. However, synthetic materials containing some branched material are also within the scope of the invention.

The average degree of ethoxylation is preferably in the range of from 6 to 7.5, more preferably from 6.5 to 7.5, and most preferably is about 7.

The desired degree of ethoxylation can be achieved, for example, using a single commercial material having a nominal degree of ethoxylation of 7; for example coconut alcohol 7E0 (e.g. Imbentin * from Kolb or Lorodac * from DAC), intermediate degree of ethoxylation 6.9; or Synperonic * A7 from ICI, ethoxylation degree 6.9 (* denotes trademark).

Similarly, commercial materials with a nominal degree of ethoxylation of 6.5 are available and are suitable for use in the present invention.

Preferably, lower degrees of ethoxylation within the scope of the invention can be achieved as described in EP 544 492A (Unilever) discussed above by mixing commercial 7EC) (nominal) material with commercial 3E0 (nominal) material in appropriate proportions, provided that at least 55 % by weight of the composition consists of 7E0 (nominal) material.

Thus, the nonionic surfactant used in the compositions of the present invention may comprise a commercial nonionic surfactant having a nominal average degree of ethoxylation of 7 (55-100% by weight, preferably 60-100% by weight), optionally in combination with a commercial nonionic surfactant with a nominal an intermediate degree of ethoxylation of 3 (0 to 45% by weight, preferably 0 to 40% by weight).

The calculated mean degrees of ethoxylation of some 3EO / 7EO nonionic mixtures are shown in Table 1, together with the measured values for some commercial materials.

Of course, the desired overall degrees of ethoxylation between 5.2 and 7 can also be achieved using a single commercial material, or alternatively using three or more materials.

Table 1

7E0 (nominal) (% by weight)

3E0 (nominal) (% by weight)

Diameter EO of the mixture

calculated:

measured:

measured:

45 55 4.8 50 50 5.0 55 45 5.2 60 40 5.4 70 30 5.8 80 20 6.2 90 10 6.6 100 - 7.0 ethoxylated coconut alcohol 45 55 4.78 60 40 5.20 100 - 6.9 Synperonic (Trade brand, ICI) 45 55 4.76 60 40 5.34 100 - 4.76

The ethoxylated surfactant may be the only surfactant in the compositions of the invention.

Alternatively, according to a preferred embodiment of the invention, a primary alcohol sulfate (PAS) may also be present. In this embodiment, the ethoxylated nonionic surfactant preferably comprises from 30 to 90% by weight of the surfactant system, more preferably from 40 to 70% by weight; and the PAS preferably constitutes from 10 to 70% by weight, more preferably from 30 to 60% by weight of the surfactant system. Preferably, the entire composition comprises at least 5% PAS by weight.

Suitably, the PAS has a chain length in the range of Cg-Cg, preferably ¹²¹² ^ 16 ' ^, as desired, mixtures with chain lengths as described and claimed in EP 342 917A (Unilever) may be used.

Preference is given to wholly or predominantly linear PAS. PAS of plant origin, and in particular coconut oil PAS (cocoPAS), is particularly preferred. However, it is also within the scope of the invention to use branched PAS as described and claimed in EP 439 316A (Unilever).

The PAS is preferably present in the form of the sodium salt.

In principle, minor amounts of other anionic surfactants may be present, provided that the surfactant system contains no more than 25% by weight of alkylbenzenesulfonates. These materials appear to have an adverse effect on the delivery and dissolution of the wash liquid. Preferably, the compositions of the present invention contain no more than 5% by weight (of the total mixture) of alkylbenzene sulfonates and more preferably none.

Aluminosilicate detergent component

The detergent compositions of the present invention comprise a detergent aluminosilicate component of an alkali metal, preferably sodium. Sodium aluminosilicates may generally be incorporated in an amount of from 10 to 70% by weight (anhydrous basis) of the composition, preferably from 25 to 50% by weight.

The alkali metal aluminosilicates may be either crystalline or amorphous or mixtures thereof, having the general formula:

0.8-1.5 Na2O.Al2O3.0,8-6SiO2

These materials contain bound water and have a calcium exchange capacity of at least 50 mg CaO / g. Preferred sodium aluminosilicates contain 1.5 to 3.5 SiO 2 units (in the above formula). Both amorphous and crystalline material can be prepared readily by reaction between sodium silicate and sodium aluminate, as is amply described in the literature.

Suitable crystalline sodium aluminosilicates as ion exchange detergent ingredients are described, for example, in GB 1 429 143 (Procter & Gamble). Preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X and mixtures thereof.

The zeolite may be a commercially available zeolite 4A, at the same time widely used in laundry detergent powders. However, according to a preferred embodiment of the invention, the zeolite component incorporated in the compositions of the invention is maximum aluminum zeolite P (zeolite MAP) as described and claimed in EP 384 070A (Unilever). Zeolite MAP is defined as an alkali metal aluminate of zeolite P type having a silicon to aluminum ratio not exceeding 1.33, preferably in the range of 0.90 to 1.33, and more preferably in the range of 0.90 to 1.20.

Particularly preferred is a zeolite MAP having a silicon to aluminum ratio not exceeding 1.07, more preferably about 1.00. The calcium binding capacity of zeolite MAP is generally at least 150 mg CaO per gram of anhydrous material.

Citric acid salt

The compositions of the invention also contain a water-soluble citric acid salt, preferably sodium citrate, as an essential component.

The citrate salt is present in an amount of from 5 to 40% by weight, preferably from 10 to 35% by weight, more preferably from 15 to 30% by weight. Particularly good results have been obtained for mixtures containing from 20 to 25% by weight.

If the citrate salt is sodium citrate, the percentages correspond to the dihydrate.

Other detergent ingredients

Other detergent ingredients may also be present in the detergent compositions of the invention, if necessary or desired. For example, polycarboxylate polymers, more particularly polyacrylates and acrylate / maleate copolymers, may suitably be used in amounts of from 0.5 to 15% by weight, especially from 1 to 10% by weight.

Other ingredients

Compositions in accordance with the present invention may contain sodium carbonate to enhance detergency and facilitate processing.

Sodium carbonate may generally be present in amounts ranging from 1 to 60% by weight, preferably from 2 to 40% by weight, and most preferably from 2 to 13% by weight. However, the invention also includes mixtures without alkali metal carbonate.

The compositions also preferably contain a fatty acid soap as a powder structurant, suitably in an amount of from 1 to 5% by weight.

Other ingredients that may be present in the base powder include a fluorescent reagent; sodium silicate; and anti-redeposition agents such as cellulose polymers, for example sodium carboxymethylcellulose.

Optional ingredients that may be admixed (post-dosed) to provide the final product include bleaching ingredients such as sodium perborate or sodium percarbonate, bleach activators and bleach stabilizers; sodium carbonate; proteolytic and lipolytic enzymes; coloring agents; foam control granules; colored grains; perfumes; fabric softening agents. This list is not intended to be exhaustive.

Preparation of detergent compositions

As indicated above, the compositions of the present invention have a high bulk density and are preferably prepared by non-tower (not spray-drying) processes in which the solid and liquid components are mixed and granulated together. Such powders have relatively non-porous particles and may be susceptible to dosing, dispersion and dissolution problems in use.

According to a preferred method, the mixing and granulation is carried out in a high speed mixer / granulator which acts both by mixing and chopping. The high-speed mixer / granulator, also known as a high-speed mixer / densifier, can be a dispensing machine, such as a Fukae (trademark) FS, or a continuously operating machine, such as the Lodige (trademark) Recycler CB30.

Suitable methods are described, for example, in EP 544 492A, EP 420 317A and EP 506 184A (Unilever).

Generally, inorganic detergent ingredients and other inorganic materials (e.g., zeolite, sodium carbonate) are granulated with surfactants that act as binders and granulating and agglomerating reagents. Any optional ingredients, as previously mentioned, may be incorporated at any suitable stage of the process. The fatty acid soap may be prepared in situ by neutralization with sodium hydroxide solution during the mixing and granulation process.

In these processes, any PAS present may already be neutralized, i.e. in the form of a salt, when dosed into a high speed mixer / granulator, or alternatively it may be added in acid form and neutralized in situ. If desired, the PAS and the nonionic surfactant may be introduced in the form of a homogeneous liquid composition as described in EP 265 203A and EP 507 402A (Unilever). EP 420 317A and EP 506 184A (Unilever) disclose another process wherein the PAS acid, which is liquid, is mixed and reacted with a solid inorganic alkaline material such as sodium carbonate in a continuous high speed mixer. The resulting granules or addition is then metered into another high speed mixer with nonionic surfactants and solids. All of these processes are suitable for preparing the composition of the invention.

In accordance with normal practice in the manufacture of detergent powders, bleach components (bleach, bleach precursor, bleach stabilizer), proteolytic and lipolytic enzymes; colored grains; perfumes; The suds control granules are most preferably admixed (post-dosed) to the densified granular product - base powder - after leaving the high speed mixer / granulator.

The citrate salt may suitably be among the post-dosed ingredients.

Powder properties

The particulate detergent compositions of the present invention have a bulk density of at least 650 g / L, preferably at least 770 g / L, and more preferably at least 800 g / L.

As indicated above, the porosity of the powder is typically low: the void volume preferably does not exceed 10% by weight and more preferably does not exceed 5% by weight. Powders which are the direct products of the spray-drying processes do not exhibit such low values.

Preferably, the content of fine, i.e., particles smaller than 180 microns, does not exceed 10% by weight and more preferably does not exceed 5% by weight.

DETAILED DESCRIPTION OF THE INVENTION

The invention will be further illustrated by the following non-limiting examples in which parts and percentages are by weight unless otherwise indicated.

The test methods used in the Examples

Washing dosage, dispersion characteristics ει dissolution were evaluated using three different tests.

Test 1: cage test

Powder dosing characteristics were compared using a model system that simulated powder dosing in an automatic washing machine under more unfavorable conditions (low temperature, minimum agitation) than normal in a real washing situation.

For this test, a cylindrical vessel with a diameter of 4 cm and a height of 7 cm, made of a steel sieve with a pore size of 600 gm, with a top cap made of teflon and a bottom cap made of a sieve as described above, was used.

The top closure had a 30 cm metal wire attached as a hinge, and this hinge was attached to a stirrer arm placed above 1 liter of water at 20 ° C in an open container. Using this agitator, the cylindrical vessel, suspended at a 45 ° angle, could be rotated in a circle of 10 cm diameter over a period of 2 seconds and left to rest for 2 seconds before the start of the next rotation / idle cycle.

g a sample of powder was placed in a cylindrical container which was then closed. The vessel was attached to a stirrer arm that moved down to a position where the top of the cylinder vessel was just below the surface of the water. After a 10-second pause, the instrument performed 15 rotation / idle cycles.

The cylindrical vessel and hinge were removed from the water and the vessel was detached from the hinge. The surface water was carefully discarded and the powder residues transferred to a preweighed container and dried at 100 ° C for 24 hours. The percentage of the initial weight (50 g) was then calculated from the dry residue weight.

Test 2: dosing device test

Dosing characteristics for powders were also compared using a model system that emulated powder dosing in an automatic washing machine from a flexible dispensing device of the type supplied with Lever's Persil (trademark) Micro System Powder in the UK: a spherical container of resilient plastic material with a diameter of about 4 cm and an opening at the top of a diameter of about 3 cm.

In this test, the metering device was attached in the up position (the highest aperture) to an overhead stirrer arm. With this device, the device could move vertically up and down in the range of 30 cm, the lowest 5 cm of this track were underwater. Each up and down trip was 2 seconds, the device was allowed to stand 5 cm above the water for 4 seconds in the lowest position, and at the highest position 13 was rotated over 100 ° and left in the resulting tilted position for 2 seconds before dropping again. 5 liters of water at 20 ° C were used.

The weighed sample of powder was introduced into the machine in its uppermost position and the machine was allowed to run for six cycles and stopped when the machine was again in the uppermost position. The surface water was carefully poured off and the remainder of the powder was transferred to a pre-weighed container. The container was dried at 100 ° C for 24 hours and the percentage by weight of dry residue from the initial powder weight was calculated.

Test 3: Test the black sleeve

An automatic washing machine test was also used to determine the extent of the insoluble residue that was retained on the items being washed. The washing machine Siemens Siwamat Plus 3700 (trademark) with front loading was used.

A 100 g dose of powder was placed in a flexible dispensing device as described above

The metering device was placed inside a black cotton pillowcase with dimensions of 30 cm x 60 cm, taking care to hold it vertically, and the liner was then closed with a zipper. The liner containing the (vertical) dispensing device was placed on top of 3.5 kg of dry laundry in the drum of the washing machine.

The washing machine operated in a heavily soiled mode at a washing temperature of 40 ° C using 15 ° French water and an inlet temperature of 20 ° C. At the end of the wash cycle, the liner was removed, opened and inverted, and the level of powder residue on its inner surface was determined by visual evaluation using a score system of 1 to 5: score 5 corresponds to a residue of approximately 75% by weight of powder; A panel of five evaluators assessed each string and assigned a score. With each powder, the wash process was performed ten times and scores were averaged from ten replicates.

Example 1, Comparative Examples A to C

Four high density detergent powders were prepared according to the compositions shown in Table 2. Base powders were prepared using a continuous high speed mixer / granulator and the other ingredients were post-dosed as indicated. Sodium citrate, if present, was post-dosed as particulate sodium citrate dihydrate with an average particle size of about 800 prn.

All powders contained PAS, a nonionic surfactant and a zeolite detergent component. Comparative Example A and Example 1 contained sodium citrate; Comparative Example A contained 7E0 and 3E0 nonionic surfactant, while Example 1 had a similar composition containing only 7E0 nonionic surfactant with the same total level. Comparative Examples B and C were two similar mixtures containing no sodium citrate.

Table 3 shows powder properties and powder dispensing characteristics. Comparison of Examples A and 1 shows that by changing the nonionic surfactant to the total 7EO system in the citrate-containing formulation, the dosage characteristics were substantially improved. Comparison of Examples B and C showed that such an improvement was not observed in the absence of citrate.

Table 2: compositions

Example A 1 B C basis CocoPAS 6.37 6.36 5 & 81 5.81 Non-ionic PAL 7E0 6.37 14.42 5.81 13.17 Non-ionic PAL 3E0 8.05 - 7.35 - Zeolite MAP 39.49 39.20 36.04 35.77 Sodium carbonate 1.05 1.05 0.96 0.96 Fatty acid soap 2.37 2.37 2.04 2.16 SCMC 0.98 0.98 0.89 0.89 humidity 5.32 5.61 4.98 5.12 Pretty 70.00 70.00 63.88 63.88 Post / Portion Sodium citrate (dihydrate) 23.47 23.47 - - Sodium percarbonate - - 20.50 20.50 TAED granules - - 4.75 4.75 Catalyst granules - - 2.40 2.40 Sodium silicate - - 2.90 2.90 Antifoam / 3.15 3.15 3.00 3.00 fluorescent substance EDTMP Dequest 2047 1.43 1.43 0.37 0.37 enzymes 1.50 1.50 1.75 1.57 perfume 0.45 0.45 0.45 0.45 100.00 100.00 100.00 100.00

PAL surfactant

Table 3: properties

Example A 1 B C Non-ionic PAL % by weight 7E0 44 100 / · 44 100 % 3E0 56 - 56 - EO diameter 4.77 7.0 4.77 7.0 Powder properties Bulk density 914 899 890 898 % fine 5.2 3.0 5.4 1.5 Dosing properties Test 1 (wt% residue) 56 32 52 70 Test 2 (wt% residue) 31 0 15 12 Test 3 (scores 1-5) Insoluble substances 11.0 0.4 1.0 1.5 at 20 C 5.5 2.2 3.4 4.2

Example 2

Compositions having the composition as in Example 1 but containing the following surfactant system were prepared:

CocoPAS

Nonionic PAL 7E0 Nonionic PAL 3E0

6.37 8.65 5.77 (60%) (40%)

The mixtures gave zero residue when dosed into the dispenser drawer of three different types of washing machines (Phillips, Zanussi, Siemens).

Examples 3 to 6

Four other washing machine compositions of the present invention are listed below.

Example 3 4 5 / 6 CocoPAS 8.47 10.60 12.71 13.77 Nonionic PAL 6,5E0 12.71 10.58 8.47 7 41 Soap 1.95 1.63 1.30 1.14 Zeolite MAP 34.34 26.29 18.33 14.35 Sodium carbonate 1.44 1.80 2.16 2.34 SCMC 0.89 0.74 0.59 0.52 Moisture, salts 1.80 2.26 2.71 2.93 Sodium citrate 7.08 14.80 22.42 26.23 Antifoam / 3.00 3.00 3.00 3.00 fluorescent substance silicate 3.67 3.67 3.67 3.67 percarbonate 16.85 16.85 16.85 16.85 TAED 3.75 3.75 3.75 3.75 Mn catalyst 1.27 1.27 1.27 1.27 EDTMP 0.37 0.37 0.37 0.37 enzymes 1.75 1.75 1.75 1.57 perfume 0.65 0.65 0.65 0.65

100.00 100.00 100.00 100.00

Claims (10)

A particulate detergent composition which is not a direct product of a spray-drying process, a composition having a bulk density of at least 650 g / l, characterized in that it comprises: (a) from 15 to 50% by weight of a surfactant system consisting essentially of from (i) an ethoxylated nonionic surfactant which is a primary C8 to C18 alcohol having a medium degree of ethoxylation in the range of 5.2 to 8.0, (ii) optionally a primary alcohol sulfate, (iii) optionally not (b) from 20 to 70% by weight (anhydrous basis) of the alkali metal aluminosilicate detergent component; (c) from 5 to 40% by weight of the water-soluble citric acid salt; optionally other detergent ingredients up to 100% by weight. The detergent composition of claim 1, wherein the ethoxylated nonionic surfactant comprises a commercial nonionic surfactant having a nominal average degree of ethoxylation of 7 (55 to 100% by weight), optionally in combination with a commercial nonionic surfactant having a nominal average degree. ethoxylation 3 (0 to 45% by weight). 3. A detergent composition according to claim 1, wherein the nonionic surfactant has a mean degree of ethoxylation in the range of 6 to 7.5. 4. A detergent composition according to claim 1, wherein the surfactant system consists essentially of 30-60% by weight primary alcohol sulfate and 40-70% by weight of ethoxylated nonionic surfactant. 5. A detergent composition as claimed in claim 1 comprising at least 10% by weight (of the total composition) of an ethoxylated nonionic surfactant. 6. A detergent composition according to claim 1 comprising at least 5% by weight (of the total composition) of a primary alcohol sulfate. 7. A detergent composition according to claim 1 comprising from 10 to 35% by weight of the citric acid salt. 8. A detergent composition according to claim 1 wherein the citric acid salt is sodium citrate. 9. A detergent composition according to claim 1 wherein the alkali metal aluminosilicate is zeolite P having a silicon to aluminum ratio not exceeding 1.33 (zeolite MAP). Use of a nonionic surfactant which is an ethoxylated C 8 to C 8 alcohol having a mean degree of ethoxylation in the range of 5.2 to 8.0 to improve the delivery and dissolution characteristics of the particulate detergent grain 20 si having a bulk density. Not less than 650 g / l which is not a direct product of the spray-drying process and contains: (a) from 15 to 50% by weight of a surfactant system consisting essentially of: (i) an ethoxylated nonionic surfactant, (ii) optionally a primary alcohol sulfate, (iii) optionally not more than 25% by weight (a surfactant system) (b) from 20 to 70% by weight (anhydrous basis) of an alkali metal aluminosilicate detergent component; (c) from 5 to 40% by weight of a water-soluble citric acid salt; (d) optionally other detergent components to 100% by weight.