NZ245202A - Particulate detergent containing ethoxylated c(8-18)primary alcohol, c(8-18)alkyl sulphate and zeolite; preparation - Google Patents

Abstract

A particulate high-density detergent composition having excellent flow properties comprises 15 to 50 wt% of a high-performance surfactant system - selected ethoxylated alcohol nonionic surfactant plus optionally a minor amount of primary alkyl sulphate - and from 20 to 60 wt% of zeolite. The ethoxylated nonionic surfactant preferably has a peaked ethoxylation distribution, and the zeolite may advantageously be maximum aluminium zeolite P. The composition is preferably prepared by an agglomeration process utilising a high-speed mixer/granulator.

Description

New Zealand Paient Spedficaiion for Paient Number £45202 245202 Priority Date(s): .. H- V * 1 ' ' ' » • i i i , , , , ( I Uo"^lfele Spe-tf'sst-on Filed: C((P..-?/^.^/p^pv , (t C"&?2>. ^ufclico-.on Date: ^94 n m?i, Mo: NO DilMiIHGS NEW ZEALAND PATENTS ACT, 1953 No.: Date: COMPLETE SPECIFICATION DETERGENT COMPOSITIONS We, UNILEVER PLC, a British company, of Unilever House, Blackfriars, London EC4P 4BQ, England, hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- - 1 -(followed by page la) 245202 - 10- C3431 TECHNICAL FIELD The present invention is concerned with particulate detergent compositions that combine exceptionally good cleaning performance with high bulk density and excellent powder properties. The compositions contain a high level of high-performance organic surfactant - selected ethoxylated alcohol plus a lessor amount of alkyl sulphate - and zeolite detergency builder, and are preferably prepared by an agglomeration process using a high-speed mixer/granulator.

BACKGROUND Recently the trend in detergent powders has been towards increased bulk density, for example, above 600 g/1. These high-density or "concentrated" powders have been prepared by various processes, some involving post-densification of a spray-dried powder, and others based on dry mixing, agglomeration or other wholly non-tower processes. 9 /■ ' * " H 9 WWM 4 - 'A - 2 - C3431 The move to higher densities, and thus inherently less porous particles, has made the incorporation of high levels of mobile organic ingredients without loss of powder flow properties more difficult. However, it has 5 become highly desirable to improve detergency performance by incorporating higher levels of surfactant, and by using surfactants having the greatest possible effectiveness against oily and fatty soils. One class of such surfactants consists of ethoxylated alcohols 10 having a relatively low degree of ethoxylation, and those are generally mobile liquids at ambient temperature.

In view of increasing environmental awareness, it has also become desirable to use alkyl sulphates in 15 preference to the linear alkylbenzene sulphonates traditionally used in laundry detergents. Alkyl sulphates are readily biodegradable and can be obtained from renewable sources such as coconut and palm oil. However, they are generally more difficult to process 20 into high quality detergent powders than are alkylbenzene sulphonates.

Nonionic surfactants, alkyl sulphates and mixtures of the two have been found to provide highly efficient 25 detergency, but because of their mobility are difficult to incorporate, even at moderate levels, into free-flowing powders that will disperse in the wash liquor. When higher proportions of these surfactants are required in order to push detergency performance to 30 ever higher levels, these difficulties would be expected to increase, and to be exacerbated even further in the highly concentrated, dense powders currently favoured by the consumer and the detergents industry. rt ? f* : '< • - " " / r "-i- - - 3 - C3431 The present inventors, however, have succeeded in formulating high bulk density free-flowing detergent powders combining excellent performance with good powder properties and dispersibility, despite their containing 5 relatively high levels of high-performance mobile surfactants. The powders of the invention contain relatively high levels of zeolite builder, and may be prepared by a granulation process in a high-speed mixer/granulator. Especially good powder properties may 10 be obtained by use of a novel zeolite P as the builder; and especially good detergency may be obtained by use of selected nonionic surfactants.

PRIOR ART EP 265 203A (Unilever) discloses a surfactant blend mobile at a temperature within the range of from 20 to 80°C, comprising from 20 to 80 wt% of alkylbenzene 20 sulphonate or alkyl sulphate, from 80 to 20 wt% of ethoxylated nonionic surfactant and from 0-10 wt% water. The surfactant blend may be sprayed on to an absorbent particulate solid material, for example, spray-dried polymer-modified Burkeite, to give free-flowing detergent 25 powder containing up to about 25 wt% of surfactant.

EP 436 24OA (Unilever) discloses a similar mobile surfactant blend additionally containing a fatty acid soap. When sprayed onto an absorbent solid material, 30 this blend gives powders having improved flow and dispensing properties.

GB 1 462 134 (Procter & Gamble/Collins) discloses linear or predominantly linear ethoxylated primary 35 alcohols of closely defined chain length, chain length distribution, ethylene oxide content, ethoxylation 245202 - 4 - C3431NZ1 distribution and free alcohol content. These materials give improved oily soil detergency as compared with conventional commercially available materials.

EP 133 715A (Union Carbide) discloses an alkoxylation product mixture having an especially highly peaked distribution of alkoxylation species, in which a single prevalent alkoxylation species constitutes 20 to 40 wt% and the amounts of species differing substantially from the prevalent species are strictly limited.

EP 384 070A (Unilever) discloses the use as a detergency builder of zeolite P having a silicon to aluminium ratio not greater than 1.33 (zeolite MAP).

This zeolite has been found to be a more effective and rapid binder of calcium ions than is conventional zeolite 4A.

EP 521 635A (Unilever), published on 7 January 1993, discloses free-flowing particulate detergent compositions based on zeolite MAP and containing high levels of liquid, viscous-liquid, oily or waxy components (for example, nonionic surfactants) while displaying excellent flow properties. Example K of that application discloses a high bulk density powder consisting of 50 wt% zeolite 4A, 23.4 wt% sodium carbonate, and 26.6 wt% of the nonionic surfactant Synperonic A3 (synthetic C12_15 alcohol having an average degree of ethoxylation of 3); and Example 7 discloses a high bulk density powder consisting of 56.6 wt% zeolite MAP, 13.3 wt% sodium carbonate, and 30.1 wt% Synperonic A3. These compositions are specifically disclaimed in the present application. 24 D 2^ - 5 - C3431NZ1 EP 544 365A (Unilever), with which the present application shares a common priority, claims a process for preparing a granular detergent composition having a bulk density of at least 650 g/1, which comprises treating a particulate starting material in a high speed mixer/densifier in the presence of a liquid surfactant composition comprising an alkyl sulphate (20-80 wt%), an ethoxylated nonionic surfactant (80-20 wt%) and water (0-20 wt%).

DEFINITION OF THE INVENTION The present invention provides a particulate detergent composition having a bulk density of at least 650 g/1, preferably at least 700 g/1 and advantageously at least 800 g/1, comprising: (a) from 15 to 50 wt% of a surfactant system consisting essentially of: (i) ethoxylated nonionic surfactant which is a primary C8-C18 alcohol having an average degree of ethoxylation not exceeding 6.5 (from 60 to 95 wt% of the surfactant system), and (ii) primary Ce-C18 alkyl sulphate (from 5 to 40 wt% of the surfactant system); (b) from 20 to 65.31 wt% of zeolite, (c) optionally other detergent ingredients to 100 wt%. 245202 - 6 - C3431NZ1 DETAILED DESCRIPTION OF THE INVENTION The particulate detergent composition of the invention is characterised by an especially high level of a high-performance organic surfactant system. At least 15 wt% of the composition is constituted by the surfactant, and as much as 50 wt"% may be present. Compositions may advantageously contain at least 20 wt%, more advantageously at least 25 wt%, of the surfactant system.

The surfactant system consists essentially of ethoxylated alcohol having a relatively low degree of ethoxylation, with a lesser proportion (not exceeding 40 wt% of the surfactant system) of primary alkyl sulphate.

The proportion of primary alkyl sulphate preferably does not exceed 35 wt% (of the surfactant system), and more preferably does not exceed 30 wt% of the surfactant system. Preferred proportions of alkyl sulphate in the surfactant system are from 5 to 35 wt%, and advantageously from 10 to 30 wt%.

Also preferred are surfactant systems in which the proportion of alkyl sulphate does not exceed 15 wt%.

The ethoxylated alcohol nonionic surfactant The ethoxylated alcohol nonionic surfactant employed in the detergent compositions of the present invention has a relatively low degree of ethoxylation, not exceeding 6.5. 2 h 5 2 0 2 - 7 - C3431NZ1 The ethoxylated alcohol preferably has an average degree of ethoxylation within the range of from 3 to 6.5. The preferred range for the average degree of ethoxylation of the nonionic surfactant is within the range of from 4 to 6.5, more preferably from 4 to 6 and most preferably from 4 to 5.5.

A mixture of differently ethoxylated materials may be used, provided that the overall degree of ethoxylation 10 meets the stated requirements.

The HLB value of the nonionic surfactant preferably does not exceed 11.0, and more preferably does not exceed .5. Desirably the HLB value is within the range of 15 from 9.5 to 10.5.

The chain length of the ethoxylated alcohol may generally range from C8 to C18, preferably from C12 to C16; an average chain length of C12-C15 is preferred. 20 Especially preferred is ethoxylated alcohol consisting wholly or predominantly of C:2-C14 material.

The ethoxylated alcohol is preferably primary, but secondary alcohol ethoxylates could in principle be used. 25 The alcohol is preferably wholly or predominantly straight-chain. Suitable alcohols are vegetable-derived, for example, coconut, which is the most preferred material. Among the synthetic alcohols, Ziegler alcohols are preferred to oxo-based alcohols.

C3431 According to a preferred embodiment of the invention, giving exceptionally good oily soil detergency, the ethoxylated alcohol (which of course is always a mixture of species having different numbers of 5 ethylene oxide units) is a "narrow range" material having a distribution of ethoxylated species that is more highly peaked about a single prevalent value than is the case in conventional commercial nonionic surfactants. The content of unethoxylated material is also generally 10 lower, and may be reduced further by so-called "stripping".

"Narrow range" alkoxylates are described and claimed, for example, in EP 133 715A (Union Carbide) 15 mentioned previously.

These are especially highly peaked mixtures having an average alkoxylation number of at least 4, in which at least one alkoxylation species (the "prevalent species") 20 constitutes about 20 to 40 wt% of the mixture; the proportion of species having 3 or more alkoxylation units above the mean is less than 12 wt%; and the species having 1 more and 1 less alkoxylation unit that the mean are each present in a weight ratio to the prevalent 25 species of 0.6:1 to 1:1. Preferred product mixtures contain from 80 to 95 wt% of alkoxylation species having alkoxylation numbers within plus or minus 2 of the mean.

However, the term "narrow range" as used in the 30 present specification also covers materials that are not so highly peaked as to meet the requirements of the Union Carbide patent claims, but yet are substantially more peaked than, for example, the commercially available ICI "Synperonic" (Trade Mark) ethoxylated alcohols.

I - 9 - C3431 The term therefore is defined herein as covering any ethoxylated alcohol product in which a single ethoxylation species constitutes 13 wt% or more, preerably 15 wt% or more, of the product. Conventional 5 ethoxylates contain no more than about 10 wt% of any one ethoxylation species. The prevalent species preferably contains 4 or 5 ethoxylation units.

Preferred "narrow range" ethoxylated alcohol used in 10 the compositions of the invention may have any one or more of the following characteristics: at least 20 wt% of the ethoxylated alcohol may be constituted by a single ethoxylation species? at least one ethoxylation species (hereinafter the prevalent species) may constitute from 20 to 40 wt% of the ethoxylated alcohol, the proportion of species having 3 or more ethoxylation units above 20 the mean being less than 12 wt%, and the species having 1 more and 1 less ethoxylation unit than the mean each being present in a weight ratio to the prevalent species of 0.6:1 to 1:1; from 80 to 95 wt% of the ethoxylated alcohol may be constituted by ethoxylation species having ethoxylation numbers within plus or minus 2 of the mean.

Differently defined "narrow range" ethoxylates are also described in GB 1 462 132 (Procter & Gamble/ Collins): these are materials having an average degree of ethoxylation between 3.5 and 6.5, the amount of material having a degree of ethoxylation within the 2-7EO 35 range being at least 63 wt%, and the amount of free alcohol not exceeding 5 wt%. These materials are also C3431 suitable for use in the compositions of the present invention.

The following table shows the ethoxylation distribution of some commercially available coconut-based ethoxylates, both narrow-range (NKE7, NRE5 etc), and broad-range (E7, E3), the figures indicating the nominal average degree of ethoxylation in each case.

It is within the scope of the invention to achieve the preferred value of 4 to 6.5 for the average degree of ethoxylation by using a mixture of commercial materials, eg a (nominal) 3E0 ethoxylate and a (nominal) 7E0 ethoxylate, in appropriate proportions.

However, it is especially preferred to use a single commercial material, and the materials designated NRE5, NRE4.6 and NRE4.2 are especially preferred, NRE4.2 being particularly favoured.

It is especially preferred, in accordance with the invention, to use wholly or predominantly straight-chain ethoxylated alcohol that is also "narrow range".

It may also be desirable to use a "narrow range" ethoxylate having a narrower distribution of chain length than do conventional commercial nonionic surfactants. For example, the nonionic surfactants described in the aforementioned 6B 1 462 134 (Procter & Gamble/Collins) are such that at least 65 wt% of the material has a chain length within ± 1 carbon atom of the mean value.

"Narrow range" ethoxylates are now commercially available in Europe and North America, for example, from Vista, Union Carbide and Hoechst.

C3431 EO distribution for coco-based nonionic surfactants EO NRE7 NRE5 NRE4.6 NRE4.2 NRE3 E7 E3 0 1.70 1.95 2.55 3.80 8.40 4.15 .05 1 1.20 1.10 1.40 2.25 .50 2.70 .95 2 2.45 2.35 3 .25 .15 12.30 3.80 12.50* 3 4.65 .85 8.00 11.85 22.25 4.80 12.20 4 7.10 13.60 16.05 19.80 24.25* .55 .40 12.30 .20 .55* .85* 14.45 .45 6.95 6 16.10 21.10* .25 18.35 9.25 6.20 6.75 7 17.80* 17.60 .85 12.05 2.85 6.75 6.15 8 16.30 .70 8.60 4.70 0.30 7.15 .30 9 11.70 3.95 2.60 0.95 - 7.25* 4.30 6.00 1.00 0.65 0.30 - 7.20 3.30 11 2.05 0.40 0.35 - - 7.00 2.40 12 0.55 - - - - 6.60 1.65 13-15 - - - - - .00 2.10 16-23 - - — — — .25 — Mean EO (peak*) 7 6 3 9 2 Mean EO (mol) .96 .20 4.86 4.27 3.01 6.87 2.9S The primary alkvl sulphate The primary alcohol sulphate (PAS) that may constitute from 5 to 40 wt% of the surfactant system, may have a chain length in the range of C8-C18, preferably C12-C16, with a mean value preferably in the C12-C15 range. Especially preferred is PAS consisting wholly or predominantly of C12-C14 material. " " If desired, mixtures of different chain lengths may be used as described and claimed in EP 342 917A (Unilever).

As for the ethoxylated alcohol, predominantly or wholly straight-chain material, is preferred. PAS of vegetable origin, and more especially PAS from coconut oil (cocoPAS) is especially 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 present in the form of the sodium or potassium salt, the sodium salt generally being preferred.

The zeolite detercrencv builder The amount of zeolite builder in the compositions of the invention may range from 20 to 60 wt%, usually from 25 to 55 wt% and suitably, in a heavy duty detergent composition, from 25 to 48 wt%.

Depending on the amount and composition of the surfactant system, the zeolite may be the commercially <r.

L. - 13 - C3431 powders. For example, the use of zeolite 4A can give powders having satisfactory flow properties when 17 wt% of surfactant consisting of 30 wt% PAS and 70 wt% nonionic surfactant is present.

However, as the total surfactant loading and/or the proportion of nonionic surfactant is or are increased, the more difficult it is to obtain acceptable powder flow properties. According to a preferred embodiment of the 10 invention, the zeolite builder incorporated in the compositions of the invention is zeolite MAP as described and claimed in EP 384 070A (Unilever Case T3047).

Zeolite MAP is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio 15 not exceeding 1.33, preferably within the range of from 0.90 to 1.33, and more preferably within the range of from 0.90 to 1.20.

Especially preferred is zeolite MAP having a silicon 20 to aluminium ratio not exceeding 1.07. The calcium binding capacity of zeolite MAP is generally at least 150 mg CaO per g of anhydrous material.

In the present invention, the use of zeolite MAP has 25 another advantage quite independent of its greater building efficacy: it enables more higher total surfactant levels, and more nonionic-rich surfactant systems, to be used without loss of powder flow properties.

Preferred zeolite MAP for use in the present invention is especially finely divided and has a d5Q (as defined below) within the range of from 0.1 to 5.0 microns, more preferably from 0.4 to 2.0 microns and most 35 preferably from 0.4 to 1.0 microns. The quantity "d50" i 'V, - 14 - C3431 indicates that 50 wt% of the particles have a diameter smaller than that figure, and there are corresponding quantities "dg0"/ "d9o" etc* Especially preferred materials have a dgQ below 3 microns as well as a dg0 5 below 1 micron.

Sodium carbonate The compositions in accordance with the invention may contain sodium carbonate, to increase detergency and to ease processing. Sodium carbonate may generally be present in amounts ranging from 1 to 60 wt%, preferably from 2 to 40 wt%, and most suitably from 2 to 13 wt%.

The optional powder structurant Powder flow may be improved by the incorporation of 20 a small amount of a powder structurant, for example, a fatty acid (or fatty acid soap), a sugar, an acrylate or acrylate/maleate polymer, or sodium silicate.

The preferred powder structurant is fatty acid soap, 25 suitably present in an amount of from 1 to 5 wt%. As will be discussed below in the context of processing, this is preferably incorporated as the free acid and neutralised in situ.

Powder flow properties The compositions of the invention are characterised by excellent flow properties, despite the high content of mobile high-performance organic surfactant. - 15 - C3431 For the purposes of the present invention, powder flow is defined in terms of the dynamic flow rate, in ml/s, measured by means of the following procedure. The apparatus used consists of a cylindrical glass tube having an internal diameter of 35 mm and a length of 600 mm. The tube is securely clamped in a position such that its longitudinal axis is vertical. Its lower end is terminated by means of a smooth cone of polyvinyl chloride having an internal angle of 15° and a lower outlet orifice of diameter 225 mm. A first beam sensor is positioned 150 mm above the outlet, and a second beam sensor is positioned 250 mm above the first sensor.

To determine the dynamic flow rate of a powder sample, the outlet orifice is temporarily closed, for example, by covering with a piece of card, and powder is poured through a funnel into the top of the cylinder until the powder level is about 10 cm higher than the upper sensor; a spacer between the funnel and the tube ensures that filling is uniform. The outlet is then opened and the time t (seconds) taken for the powder level to fall from the upper sensor to the lower sensor is measured electronically. The measurement is normally repeated two or three times and an average value taken. If V is the volume (ml) of the tube between the upper and lower sensors, the dynamic flow rate DFR (ml/s) is given by the following equation: DFR = V ml/s t The averaging and calculation are carried out electronically and a direct read-out of the DFR value obtained.

(L. - 16 - C3431 Compositions and components of the present invention generally have dynamic flow rates of at least 90 ml/s, preferably at least 100 ml/s. other optional ingredients Fully formulated laundry detergent compositions in accordance with the present invention may additionally contain any suitable ingredients normally encountered, for example, inorganic salts such as sodium silicate or sodium sulphate; organic salts such as sodium citrate; antiredeposition aids such as cellulose derivatives and acrylate or acrylate/maleate polymers; fluorescers; bleaches, bleach precursors and bleach stabilisers; proteolytic and lipolytic enzymes; dyes; coloured speckles; perfumes; foam controllers; fabric softening compounds.

Preparation of the detergent compositions The compositions of the invention may advantageously be prepared by granulating the zeolite and surfactants in a high-speed mixer/granulator. If the surfactant system includes PAS, that may be incorporated either in salt form (generally as an aqueous paste), or as the free acid (for neutralisation in situ).

An especially preferred process includes the steps of: (i) preparing the surfactant system in the form of a homogeneous mobile liquid blend, and 245202 - 17 - C3431NZ1 (ii) agglomerating the mobile liquid surfactant blend with the zeolite and other solids present in a high-speed mixer/granulator.

The homogeneous mobile liquid blend may be prepared by mixing PAS paste with the nonionic surfactant. Alternatively, the nonionic may be admixed during the neutralisation of PAS acid by alkali*/ for example in a loop reactor, as described and claimed in EP 507 402A (Unilever) filed on 31 March 1992 and published on 7 October 1992.

The high-speed mixer/granulator, also known as a high-speed mixer/densifier, may be a batch machine such as the Fukae (Trade Mark) FS, or a continuous machine such as the Lddige (Trade Mark) Recycler CB30.

The process is described in more detail, and claimed, in EP 544 365A (Unilever) filed on 26 November 1991.

The process allows the incorporation of high levels of surfactant without loss of powder flow properties, especially when the zeolite component of the composition is zeolite MAP and/or when soap is present as a structurant. it 0/ V " - ^ \ ^ : ■? r c /.

Z4 - 18 - C3431 If soap is to be included as a structurant, this is preferably incorporated in the mobile surfactant blend, either as such, or as the corresponding fatty acid (together with a suitable amount of alkali) for 5 neutralisation in situ.

The other optional ingredients mentioned above may be incorporated at any suitable stage in the process. In accordance with normal detergent powder manufacturing 10 practice, bleach ingredients (bleaches, bleach precursors and bleach stabilisers), proteolytic and lipolytic enzymes, coloured speckles, perfumes and foam control granules are most suitably admixed (postdosed) to the dense granular product after it has left the high-speed 15 mixer/granulator.

Of course the compositions of the invention may also be prepared by other processes, involving spray-drying or non-tower technology or combinations of the two.

The invention is further illustrated by the following non-limiting Examples, in which parts and percentages are by weight unless otherwise stated. ,y u.« ^ ^ /t. w"4) ' / j -y a - 19 - C3431 EXAMPLES The abbreviations used in the Examples indicate the following materials: CocoPAS Linear C12_14 primary alcohol sulphate (sodium salt) derived from coconut oil, ex Philippine Refining Co.

E7(s) C13-15 0x0 alcoho1 7E°/ not "narrow range": Synperonic (Trade Mark) A7 ex ICI E3(s) C13-15 0x0 alcoho1 3E0» not "narrow range": Synperonic (Trade Mark) A3 ex ICI E7 Coconut alcohol 7E0, not "narrow range" E3 Coconut alcohol 3E0, not "narrow range" NRE7(s) C12-14 z*e9ler linear "narrow range" alcohol 7EO: Alfonic (Trade Mark) 7 ex Vista NRE3(s) C12-14 z*e9ler linear "narrow range" alcohol 3EO: Alfonic (Trade Mark) 3 ex Vista NRE7 Coconut alcohol 7E0, "narrow range" NRE5 NRE4.6 5 NRE4.2 NRE3 Zeolite 4A Zeolite MAP Polymer LAS Perborate mono 25 TAED EDTMP Antifoam 2 /: ^ " H ? jj v*' •*.-!* V1»* - 20 - C3431 Coconut alcohol 5EO, "narrow range" Coconut alcohol 4.6EO, "narrow range" Coconut alcohol 4.2EO, "narrow range" Coconut alcohol 3E0, "narrow range" Wessalith (Trade Mark) P powder ex Degussa Zeolite MAP prepared by a method similar to that described in Examples 1 to 3 of EP 384 07OA (Unilever); Si:Al ratio 1.07.

Acrylic/maleic copolymer: Sokalan (Trade Mark) CP5 ex BASF Linear alkylbenzene sulphonate, sodium salt Sodium perborate monohydrate Tetraacetylethylenediamine, as 83 wt% granules Ethylenediaminetetramethylene-phosphonic acid, calcium salt: Dequest (Trade Mark) 2041 or 2047 ex Monsanto (34 wt% active) Antifoam granules in accordance with EP 266 863B (Unilever) - 21 - C3431 EXAMPLES 1 TO 10 - DETERGENCY Examples 1 to 4 Detergent compositions were prepared to the following general formulation: parts 1 Surfactant system (see below) 17 .11 Zeolite 4A 32 37.86 Polymer 4 4.73 Carbonate 14.5 17.16 Silicate 0.5 0.59 Metaborate 16.5 19.53 84.50 100.00 The surfactant systems were made up as follows i (wt%): Example CocoPAS E7(s) E3(s) NRE7(s) NRE3 (S) 1 40 - 2 40 3 40 50 - 4 40 50 Both mixtures of 30 parts of 7EO nonionic surfactant and 40 parts of 3EO nonionic surfactant had an average EO number of 4.7 and an HLB value of 10.1. o • L \ - - 22 - C3431 The percentage of the predominant ethoxylation species (4E0) in the NRE mix was estimated to be 14 wt%.

Detergencies (removal of radio-labelled triolein 5 soil from polyester) were compared in the tergotometer using a 5 g/1 product concentration, 24° (French) hard water and a wash temperature of 23°C. The results were as follows: Example % triolein removal 1 42.2 2 47.4 3 59.8 4 61.6 Comparison of the results for Comparative Example A, Example 1 and Example 3 shows how increasing the proportion of nonionic surfactant at the expense of PAS increases detergency: while comparison of the results 25 for Examples 1 and 2, and for Examples 3 and 4, shows the detergency benefit obtained by changing to "narrow range" ethoxylated alcohol. The outstandingly good result for Example 4 shows the benefit of combining these two measures.

■J""- * iL ' > - v? - 23 - C3431 Examples 5 to 7 A further detergency comparison was carried out, using test cloths carrying a number of different soils.

This experiment was carried out using a Miele (Trade Mark) computer-controlled washing machine, using a product concentration of 5 g/1, and a 30-minute wash at 20°C in 26° (French) hard water.

The compositions had the following general formulation: parts % Surfactant system (see below) 17.0 19.50 Zeolite 4A 30.5 35.00 Sodium carbonate 12.77 14.65 Sodium silicate 0.5 0.57 Sodium perborate monohydrate 16.25 18.65 TAED (83% granules) 7.25 8.32 EDTMP 0.37 0.42 Antifoam granules 2.50 2.87 87.14 100.00 The surfactant systems were made up as follows (wt%): Example CocoPAS E7(S) E3(s) NRE7(s) NRE3(s) 5 30 30 40 - - 6 30 30 40 7 10 40 50 1 ^ / l". ' • ,/ ■ j L -t - 24 - C3431 The results (expressed as reflectance changes at 460 nut) were as follows: Test cloth 1: kaolin and wool fat on polyester/cotton (WFK 10C) Reflectance change (delta R460) Example 5 10.9 Example 6 11.8 Example 7 12.4 Test cloth 2: kaolin and wool fat on polyester (WFK 30C) Reflectance change (delta R460) 20 Example 5 21.4 Example 6 24.5 Example 7 27.5 Test cloth 3: kaolin and sebum on cotton (WFK 10D) Reflectance change (delta R460) Example 5 16.5 Example 6 17.4 Example 7 18.8 iLt. ', - 25 - C3431 J Test cloth 4: kaolin and sebum on polyester (WFK 30D) Reflectance change (delta R460) Example 5 18.7 Example 6 21.5 Example 7 25.1 Example 8 Using the same tergotometer procedure as in Examples 1 to 4, the detergencies of various surfactant mixtures containing different ethoxylated coconut alcohols were compared.

In each case the compositions were as given in Example 1, and the surfactant systems consisted of 30 wt% cocoPAS, and 70 wt% ethoxylated alcohol. The ethoxylated alcohol component was made up (i) by mixing E7 and E3 (broad range) in varying proportions, or (ii) by mixing NRE7 and NRE3 (narrow range) in varying proportions, or (iii) by use of a single narrow range ethoxylate.

The true degrees of ethoxylation will be recognised from the Table given earlier in this specification. - 26 - " C3431 Detergencies (% removal of radio-labelled triolein from polyester) as a function of degree of ethoxylation and starting ethoxylated alcohol are shown in the following Table. (i) (ii) (iii) EO E7 + E3 NRE7 + NRE3 Single NRE (average) 6.88 9.9 (E7) .96 14.1 (NRE7) .90 15.7 5.22 18.4 .20 25.1 (NRE5) .17 21.0 4.94 21.2 4.86 30.7 (NRE4.6) 4.70 23.3 4.66 26.4 4.49 31.1 4.27 35.7 (NRE4.2) 3.96 27.3 3.75 35.5 3.01 36.4 (NRE3) 3.00 28.5 (E3) These results illustrate the advantage of average degrees of ethoxylation of 6 or below; the improvements obtained by moving to narrow range ethoxylates? and the especial benefits of using a single, narrow range material, in particular NRE4.2. r - 27 - C3431 '1 Example 9 The procedure of Example 8 was repeated using a series of compositions having a more nonionic-rich surfactant system: 10 wt% cocoPAS and 90 wt% ethoxylated alcohol. The results are shown in the following Table. (i) (ii) (iii) EO (average) E7 + E3 NRE7 + NRE3 Single NRE 6.88 5.96 5.20 5.17 4.94 4.70 4.66 4.49 4.31 4.27 3.75 3.01 3.00 22.6 (E7) .3 35.5 36.1 34.3 (NRE7) 44.1 45.5 (NRE5) 51.5 (NRE4.6) 44.5 43.0 43.1 53.5 (NRE4.2) 44.1 .4 (NRE3) 37.2 (E3) Again the benefits of using narrow range ethoxylates, especially single materials, are apparent. 245^02 EXAMPLES 10 TO 31 - POWDER PROPERTIES Examples 10. and 11.. Comparative Example A Detergent base powders of high bulk density, consisting of the surfactant system, zeolite and (in some cases) sodium carbonate, were prepared by agglomeration in a Fukae FSlOO batch high-speed mixer/granulator.

These powders are not intended as fully formulated detergent compositions, but are readily converted to such compositions by admixture (postdosing) of other components such as bleach ingredients, enzymes, lather control granules and perfume.

The surfactant system was as follows: wt% cocoPAS 30 wt% E7(s) 40 Wt% E3(s) The compositions, in parts by weight and percentages, are shown below. 11 Surfactant 17 (38.64) 17 (31.48) 17 (40.48) Zeolite 4A 27 (61.36) Zeolite MAP 27 (50.00) (59.52) Carbonate (18.52) M (100.00) M (100.00) 42 (100.00^^^ \A " ki VVv1' r- .. »c r v jy 2h5202 - 2? - C3431 A homogeneous liquid blend of the surfactants was prepared by neutralising PAS acid with sodium hydroxide solution in a loop reactor in the presence of the nonionic surfactants. Zeolite and (where present) sodium carbonate were dosed into the Fukae mixer, the liquid surfactant blend added and the mixture granulated. The granular product was then dried using a fluidised bed. in the case of Comparative Example A it proved impossible to obtain a granular product; the mixture formed a solid mass. The addition of 10 parts of sodium carbonate (Example io) enabled a granular product to be prepared. With zeolite MAP (Example 11), at a slightly 15 lower level, the same amount (in parts - actually a slightly higher percentage loading) of the surfactant system could be incorporated without the need for sodium carbonate, and a free-flowing granular product was obtained. 24 2 0 2 - 30 - C3431 Comparative Examples B to E Further attempts to prepare base powders containing zeolite 4A with differing amounts of surfactant (the same system as in Examples A, 10, and 11) and carbonate were unsuccessful: Compositions in parts bv weight B Surfactant 13 15.3 17.2 18.5 Zeolite 4A 27 27 27 27 Carbonate - 5 10 15 40 47.3 54.2 60.5 Compositions in percentages BCD E Surfactant 32.50 32.35 31.73 30.58 Zeolite 4A 67.50 57.08 49.82 44.63 Carbonate - 10.57 18.45 24.79 Composition B produced a solid mass, while Compositions C, D and E initially produced free-f<v^Vv powders which, however, lost their flow on dryimf.V o -o 1 24 5 2 0 2 C3431 Examples 11 to 14 An experiment similar to that of Comparative Examples B to E, but using zeolite MAP, gave powders having good flow properties, even at substantially higher surfactant contents. The compositions and powder properties are shown below. 11 12 Compositions in parts bv weight 13 14 Surfactant Zeolite MAP Carbonate 17 42 18.4 25 4.4 47.8 19.6 8.9 53.5 .8 25 13.9 59.7 Compositions in percentages Surfactant 40.48 38.49 36.64 34.84 Zeolite MAP 59.52 Carbonate Powder properties Bulk density (g/1) 794 DPR (ml/s) 52.30 9.21 100 817 93 46.73 16.64 829 56 41.88 23.2 867 72 245202 C3431 Examples l5 and lfi Compositions similar to those of Comparative Examples B to E were prepared, but this time fatty acid soap was present.

The method of preparation of these powders was slightly different from that used in previous Examples. A homogeneous mobile blend was prepared by mixing PAS in sodium salt form (70 wt%), fatty acid, sufficient sodium hydroxide solution to neutralise the fatty acid, and the nonionic surfactants. Ingredients were dosed into the Fukae mixer in the order zeolite, carbonate, surfactant blend, granulation/densification was carried out as in previous Examples, and the products were finally dried using a fluidised bed.

Powders having excellent flow properties were obtained.

Compositions JL£_ Surfactant Zeolite 4A Carbonate Soap parts 17 32 % .95 48.85 14.5 22.14 2 3.05 100-00 parts 17 32 7.25 2 58.25 1 29.18 54.94 12.45 3.43 199,90 « * 24 s c u 2 - 3J - C3431 Powder properties 16 - Bulk density (g/1) 918 872 DFR (rnl/s) 122 143 These Examples, when compared to Comparative Examples c to F, show that the inclusion of fatty acid soap made it possible to produce good high density powders from formulations unprocessable in its absence.

Examples 17 and 18 Compositions similar to those of Examples 15 and 16 20 were prepared, by the same method, but using zeolite MAP instead of zeolite 4A.

Compositions 17 18 parts & parts 4 Surfactant 17 25.95 17 29.18 Zeolite MAP 32 48.85 32 54.94 Carbonate 14.5 22.14 7.25 12.45 Soap 2 3.05 2 3.43 - 31V - 2*5202 C3431 Powder properties 17 18 Bulk density (g/1) 980 959 DFR (ml/s) 131 143 Comparison of these Examples with Examples 11 to shows that the inclusion of soap improved flow, but when zeolite MAP was used it was not essential in order to obtain acceptable powders. 245202 - 35" - C3431 Examples 19 and 20.. comparative Examples F and G Detergent base powders generally as described in Examples io, 11 and A were prepared using a different surfactant system: wt% cocoPAS 40 wt% E7(s) 50 wt% E3(s) The surfactant system was prepared as a homogeneous mobile blend by the method described in Examples 10, 11 and A, and the other process steps were also carried out as in those Examples.

Compositions in parts bv weight Surfactant 17 19 17 17 17 Zeolite 4A 27 27 Zeolite MAP Carbonate 44 69 42 15 57 2-.5202 C3431 Compositions in percentages F 19 6 Surfactant 38.64 24.64 40.48 29.82 Zeolite 4A 61.36 39.13 Zeolite MAP 59.52 43.86 Carbonate 36.23 26.32 In the case of Comparative Examples F and G it proved impossible to obtain a granular product; both mixture formed a solid mass. The addition of 25 parts of sodium carbonate to the zeolite 4A-based composition (Example 19) was required to enable a granular product to be prepared. With zeolite MAP (Example 2Q), only 15 parts of sodium carbonate were required. 245202 C3431 Examples 21 and *22. Comparative Example H_ Compositions similar to those of Examples 17 and 18 were prepared, but containing higher levels of zeolite.

Compositions in parts bv weight .

H 21 22 Surfactant 17 17 17 Zeolite 4A 32 32 Zeolite MAP Carbonate 32 49 59 49 Compositions in percentages H 21 22 Surfactant Zeolite 4A 34.69 65.31 28.81 54.24 34.69 Zeolite MAP 65.31 Carbonate 16.95 Composition H would not give a granular product: 10 parts of sodium carbonate were required to produce a processable formulation. With zeolite MAP at this level, however, no carbonate was required despite the high percentage level of surfactant in this composition° (Example 22).

'.A o • - o 2-.5202 C3431 Example 23. Comparative Examples J and K .

Formulations based on zeolite 4A, with and without soap, were prepared using the surfactant system of Examples 19 to 21. The fatty acid soap was incorporated by mixing fatty acid and an equivalent amount of sodium hydroxide solution into the surfactant blend (prepared as described in Example io) before addition of the blend to the Fukae mixer.

Compositions in parts bv weight 23 Surfactant 17 17 17 Zeolite 4A 32 32 32 Carbonate 14.5 14.5 14.5 Soap 2 4 63.5 65.5 67.5 Compositions in percentages Surfactant 26.77 25.95 25.19 Zeolite 4A 50.39 48.85 47.41 245202 - 39 - C3431 Composition J gave a non-flowing product both before and after drying, while Composition K initially gave a good product but lost its flow on drying. A larger amount of soap (Example 23) gave an excellent powder having a bulk density of 920 g/1 and a dynamic flow rate of 109 ml/s.

Examples 2 4 and 25 Compositions similar to those of Examples 23 and J but containing zeolite MAP and a higher level of surfactant were prepared.

Compositions 24 25 parts % parts % Surfactant 20.5 30.60 20.5 29.71 Zeolite MAP 32 47.76 32 46.37 Carbonate 14.5 21.64 14.5 21.01 Soap - - 2 2.90 67.0 69.0 UZloz - 40 - C3431NZ1 Powder properties 21 21 Bulk density (g/1) 928 898 DFR (ml/s) 115 114 245202 41 C3431NZ1 Example 26 A composition similar to that of Example 23 but containing a different nonionic surfactant, NRE.5, was prepared. All solid components had a particle size lower than 200 microns.

The method of preparation was "substantially as described in Example 10. The mean residence time of the granular detergent composition in the batch high-speed mixer/granulator was approximately 3 minutes.

Composition % Surfactant: PAS 8.3 NRE 5 19.5 Zeolite 4A 43.7 Carbonate 16.2 Water 12.3 100.0 The granular detergent composition obtained had a bulk density of about 770 g/1 and a dynamic flow rate of 101 ml/s. 245202 - 42 - C3431 Examples 27 and 28 Granular detergent compositions similar to that of Example 26 were prepared using a continuous high-speed 5 mixer/granulator, the LiSdige (Trade Mark) Recycler CB30.

The liquid surfactant mix included fatty acid in combination with a stoichiometric amount of sodium hydroxide, which during the course of the mixing and 10 densifying process formed soap.

The rotational speed was 1600 rpm and the mean residence time of the granular mixture in the Recycler was approximately 10 seconds.

The compositions of the granular materials leaving the Recycler were as follows. 27 28 Surfactant: PAS 8.5 8.3 NRE5 19.4 18.8 Zeolite 4A 52.6 47.1 Carbonate - 8.0 Soap 2.9 2.9 Water 16.4 14.9 100.0 100.0 Bulk densities were about 700 g/1, particle sizes 500-600 microns, and powder properties were good. 245202 C3431 Examples 29 to 30, Comparative Example L _ Fully formulated detergent powders were prepared to the formulations given below. .29- 31 Base powders LAS 7.85 - - — Coco PAS - .20 .20 1.70 E7(s) 3.92 .20 - - E3 (s) .23 6.60 - - NRE7(s) - - .20 6.80 NRE3(s) - - 6.60 8.50 Soap 2.00 2.00 2.00 2.00 Zeolite 4A 32.00 32.00 32.00 - Zeolite MAP - - - 32.00 Carbonate 11.52 11.52 11.52 - Fluorescers 0.81 0.81 0.81 0.81 SCMC 0.60 0.60 0.60 0.60 Moisture 9.00 9.00 9.00 9.00 Postdosed Carbonate - - - 11.52 Silicate 0.45 0.45 0.45 0.45 Perborate mono .00 .00 .00 .00 TAED 7.75 7.75 7.75 7.75 EDTMP 0.37 0.37 0.37 0.37 Enzymes 1.00 1.00 1.00 1.00 Antifoam 2.50 2.50 2.50 2.50 Perfume 0.60 0.60 0.60 0.60 JtQQiQQ IPOfPP 100.00 100.00 24 <3 2 0 - n - C3431 Comparative Composition l is a high-performance concentrated powder based on a different surfactant system (LAS with nonionic surfactants) similar to that used in premium powders presently on sale in Europe.

Surfactant systems (wt%) M 29 31 LAS Coco PAS E7(S) E3(s) NRE7(s) NRE3(s) 46 23 31 30 40 40 40 50 100 100 100 100 The total amount of (non-soap) surfactant in each formulation was 17 wt%.

All base powders were prepared in the Fukae FSlOO batch high-speed mixer/granulator mentioned previously.

Composition l was prepared as follows. Zeolite and carbonate (including an additional amount for neutralisation of LAS acid) were dosed into the Fukae mixer, followed by LAS acid, then a homogeneous surfactant blend (nonionic surfactant), fatty acid and an equivalent amount of sodium hydroxide solution). After granulation, the powder was dried using a fluidised bed, and the remaining ingredients postdosed. 2-.5202 C3431 Compositions 2 9 and 30 were prepared as follows. Homogeneous surfactant blends were prepared by mixing PAS paste (70%), nonionic surfactant, fatty acid and an equivalent amount of sodium hydroxide solution. Zeolite 5 and carbonate were dosed into the Fukae, followed by the surfactant blend. After granulation, the powders were dried using a fluidised bed, and the remaining ingredients postdosed.

Composition 31 was prepared similarly except that no carbonate was present during granulation.

Powder properties L 29 30 31 Bulk density 861 826 841 841 DFR 89 111 120 128 Detergency results Detergency was assessed in a Miele washing machine, in the presence of a soiled load, using a product concentration of 5 g/1, 26° (French) hard water, and a wash temperature of 30°C. The measure of detergency was the change in reflectance (460 nm) of a polyester test 30 cloth soiled with kaolin and sebum (WFK 30D).

Delta R„,a 16.2 15.0 15.7 17.2 460

Claims (6)

1. C~r u c [ - 4k - C3431NZ1 Examples 32 and 33 Further detergent powder formulations, containing zeolite MAP and coconut nonionic surfactants, are shown below. 22 11 Page powders Coco PAS 5.20 1.70 E7 5.20 6.80 E3 6.60 8.50 Soap 2.00 2.00 Zeolite MAP 32.00 32.00 Fluorescers 0.81 0.81 SCMC 0.60 0.60 Moisture 9.00 9.00 Postdosefl Carbonate 11.52 11.52 Silicate 0.45 0.45 Perborate mono 15.00 15.00 TAED 7.75 7.75 EDTMP 0.37 0.37 Enzymes 1.00 1.00 Antifoam 2.50 2.50 Perfume 0.60 0.60 1QQ.0Q 1QQ.QQ Similar compositions may be formulated containing the narrow-range coconut nonionic surfactants NRE7 and NRE3, instead of the broad range materials E7 and E3, in the same proportions; or instead using one of the single materials NRE5, NRE4.6 or NRE4.2. - 47 - C3431NZ1 ►. * ** ? ? * ** ■' yV, • *' • •"* "" » * /wr»."». XT v . ... niH'i '• ' 1 A particulate detergent composition having a bulk density of at least 650 g/1, comprising: (a) from 15 to 50 wt% of a surfactant system consisting essentially of: (i) ethoxylated nonionic surfactant which is a C8-C18 primary alcohol having an average degree of ethoxylation not exceeding 6.5 (from 60 to 95 wt% of the surfactant system), and (ii) primary C8-C18 alkyl sulphate (from 5 to 40 wt% of the surfactant system); (b) from 20 to 65.31 wt% of zeolite, (c) optionally other detergent ingredients to 100 wt%.

2. A particulate detergent composition as claimed in claim 1, wherein the surfactant system (a) comprises from 5 to 35 wt% of alkyl sulphate (ii) .

3. A particulate detergent composition as claimed in claim 2, wherein the surfactant system (a) comprises from 10 to 30 wt% of alkyl sulphate (ii).

4. A particulate detergent composition as claimed in any preceding claim, wherein the ethoxylated alcohol (t)'T if1 v r- has an average degree of ethoxylation of from 3 to 6.>5/ ' ■ 1 * r - us - *t3202 C3431NZ1 5 A particulate detergent composition as claimed in claim 4, wherein the ethoxylated alcohol has an average degree of ethoxylation of from 4 to 6.

5. 6 A particulate detergent composition as claimed in claim 5, wherein the ethoxylated alcohol has an average degree of ethoxylation of from 4 to

6. 7 A particulate detergent composition as claimed in claim 6, wherein the ethoxylated alcohol has an average degree of ethoxylation of from 4 to 5.5. 8 A particulate detergent composition as claimed in any preceding claim, wherein the ethoxylated alcohol has an alkyl chain length of CI0 to C16. 9 A particulate detergent composition as claimed in claim 8, wherein the ethoxylated alcohol consists wholly or predominantly of C12-C14 material. 10 A particulate detergent composition as claimed in any preceding claim, wherein the ethoxylated alcohol consists wholly or predominantly of straight-chain material. 11 A particulate detergent composition as claimed in any preceding claim, wherein the ethoxylated nonionic surfactant is an ethoxylated coconut alcohol. 2to202 C3431NZ1 12 A particulate detergent composition as claimed in any preceding claim, wherein at least 13 wt% of the ethoxylated alcohol is constituted by a single ethoxylation species. 13 A particulate detergent composition as claimed in claim 12, wherein at least 15 wt% of the ethoxylated alcohol is constituted by a single ethoxylation species. 14 A particulate detergent composition as claimed in claim 13, wherein at least 20 wt% of the ethoxylated alcohol is constituted by a single ethoxylation species. 15 A particulate detergent composition as claimed in any one of claims 12 to 14, wherein the single ethoxylation species contains 4 or 5 ethoxylation units per mole of alcohol. 16 A particulate detergent composition as claimed in any one of claims 12 to 15, wherein the ethoxylated nonionic surfactant consists of a single material having an average degree of ethoxylation within the range of from 4 to 5. 17 A particulate detergent composition as claimed in any preceding claim, wherein the ethoxylated nonionic surfactant has an HLB value within the range of from 9.5 to 10.5. 245202 - 50- C3431NZ1 18 A particulate detergent composition as claimed in any preceding claim, wherein the primary alkyl sulphate (ii) has an alkyl chain length of C10 to C16. 19 A particulate detergent composition as claimed in claim 18, wherein the primary alkyl .sulphate consists wholly or predominantly of C12-C14 material. 20 A particulate detergent composition as claimed in any preceding claim, wherein the primary alkyl sulphate (ii) consists wholly or predominantly of straight-chain material. 21 A particulate detergent composition as claimed in claim 20, wherein the primary alkyl sulphate (ii) is coconut alcohol sulphate (cocoPAS). 22 A particulate detergent composition as claimed in any preceding claim, which contains at least 17 wt% of the surfactant system. 23 A particulate detergent composition as claimed in claim 22, which contains at least 20 wt% of the surfactant system. 24 A particulate detergent composition as claimed in any preceding claim, wherein the zeolite is zeolite P having a silicon to aluminium ratio not exceeding 1.33. 4 5 2 0 2 - 51 ~ C3431NZ1 25 A particulate detergent composition as claimed in claim 24, wherein the zeolite P has a silicon to aluminium ratio not exceeding 1.20. 26 A particulate detergent composition as claimed in any preceding claim, which contains from 25 to 55 wt% of zeolite. 27 A particulate detergent composition as claimed in any preceding claim, which contains from 25 to 48 wt% of zeolite. 28 A particulate detergent composition as claimed in any preceding claim, which contains from 2 to 60 wt% of sodium carbonate. 29 A particulate detergent composition as claimed in claim 28, which contains from 2 to 13 wt% of sodium carbonate. 30 A particulate detergent composition as claimed in any preceding claim, which comprises a powder structurant selected from fatty acid soap, acrylic polymer, sugars, and sodium silicate. 31 A particulate detergent composition as claimed in claim 30, which comprises from 1 to 5 wt% of fatty acid soap. - 51 ~ 24 o - C3431NZ1 32 A particulate detergent composition as claimed in any preceding claim, having a bulk density of at least 700 g/1. 33 A particulate detergent composition as claimed in claim 32, having a bulk density of at least 800 g/1. 34 A particulate detergent composition substantially as hereinbefore described in any one of Examples 1 to 33. 35 A process for the preparation of a particulate detergent composition as claimed in claim 1, which comprises mixing and granulating the zeolite, ethoxylated alcohol, the primary alkyl sulphate in acid or salt form, and optionally other compatible ingredients, in a highspeed mixer/granulator. 36 A process as claimed in claim 35, which includes the steps of: (i) preparing the surfactant system in the form of a homogeneous liquid blend, and (ii) agglomerating the homogeneous liquid surfactant blend with the zeolite and other solids present in the high-speed mixer/granulator. ^ L ;j 2 - 53. - C3431NZ1 37 A process as claimed in claim 36, wherein the homogeneous liquid blend is prepared by mixing the ethoxylated alcohol with primary alkyl sulphate in salt form as an aqueous paste. 38 A process as claimed in claim 37, wherein the homogeneous liquid blend is prepared by neutralising primary alcohol sulphuric acid with alkali and 10 simultaneously admixing the ethoxylated alcohol. 39 A process as claimed in any one of claims 36 to 38, • wherein the homogeneous liquid surfactant blend also 15 comprises a fatty acid and an alkali, or a fatty acid soap. 40 A process for the preparation of a particulate detergent composition, carried out substantially as hereinbefore described in any one of Examples 10 to 31 Ac By the authorised agents A J PARK & SON 7/fkMhty