Process for manufacture of detergent powder

Abstract: A particulate detergent composition is prepared by spray drying a slurry containing a surfactant system, which may contain anionic surfactants, nonionic surfactants and/or soap, a non-phosphate builder such as an aluminosilicate or an alkalimetal carbonate and a sugar such as sucrose or sorbitol. The sugar provides the powders with adequate structure without the necessity to utilise sodium silicate.

Description: TECHNICAL FIELD This invention relates to the use of sucrose or a related material in detergent powders and in particular to a process for the production of spray-dried powders containing these materials. BACKGROUND ART It is anticipated that in some countries at least it will be a requirement in the future that detergent powder should be free from phosphorus. One of the options for making a phosphorus-free detergent composition is to replace the normal phosphate detergency builder with a non-phosphate builder material such as an aluminosilicate, for example a zeolite, and that has been done at least partially in some countries. One of the problem which adoption of aluminosilicates introduces is that of ensuring that the powder has adequate structure. Not only is the inherent capacity of aluminosilicate detergency builders to structure powders lower than that of the sodium tripolyphosphate which it replaces, but it is extremely difficult to use sodium silicate, a powerful powder structurant. Sodium silicate leads to the formation of insoluble silicate/aluminosilicate aggregates which can give undesirable deposits on clothes. Consequently, we have been looking for alternative powder structurants. We are aware of FR-A-2 401 987 (Colgate-Palmolive Company) which discloses the use of water-soluble organic materials, including sugars, as binding agents for aluminosilicate detergency builder materials, such as finely divided zeolites to improve the handling properties thereof. Starches are the preferred binding agents. This prior art is concerned primarily with the granulation of zeolite powder with binding agents to form particulate detergent builder agglomerates suitable for adding to spray dried particles containing other ingredients including a surfactant system. While reference is made to the possible formation of these agglomerates by spray-drying, other methods are preferred and the possibility that any of the binding agents mentioned could perform as structurants of spray-dried powders which contain both the zeolite and a surfactant system is not foreseen. We have now surprisingly discovered that spray dried powders containing aluminosilicate detergency builder materials and having satisfactory dispersibility properties can be produced by the use of specific structurants. DISCLOSURE OF THE INVENTION According to the present invention there is provided a process for preparing a particulate detergent composition comprising the steps of (i) forming an aqueous crutcher slurry comprising: (a) a surfactant system; (b) an aluminosilicate detergency builder material or a mixture thereof with a phosphate detergency builder material; and (c) sugar selected from the group consisting of sucrose, glucose fructose, maltose, cellobiose, lactose and sorbitol; and (ii) spray-drying the slurry to form a detergent powder. THE SUGAR By the term "sugar" is meant a mono- or di-saccharide or a derivative thereof, which is water soluble. By "water-soluble" in the present context it is meant that the sugar is capable of forming a clear solution or a stable colloid dispersion in distilled water at room temperature at a concentration of 0.01 g/l. Amongst the sugars which are useful in this invention are sucrose, which is most preferred for reasons of availability and cheapness, glucose, fructose, maltose (malt sugar), cellobiose and lactose which are disaccharides. A useful saccharide derivative is sorbitol. We are aware of United States Patent Specification US-A-3615811 (Barrett assigned to Chemical Products Corporation) which discloses the use of sugars as binding agents for alkaline earth metal carbonates, such as barium carbonate, for use in the ceramic industry. Such water-insoluble carbonate materials are not considered to be non-phosphate detergency builders in the context of the present invention. The level of sugar is preferably at least 1% by weight of the spray-dried composition up to 20%, although a level of 5% to 15% by weight is most preferred. THE SURFACTANT SYSTEM The surfactant system will include an anionic surfactant and/or soap, a nonionic surfactant or a mixture of these. Typical amounts of such surfactants are from 2 to 30% by weight based on the weight of the spray-dried powder of the anionic surfactant or soap or mixtures thereof when these are used alone, from 2 to 20% by weight of nonionic surfactant when used alone and, when a binary mixture of anionic surfactant and nonionic surfactant is used, from 2 to 25% by weight of anionic surfactant and from 0.5 to 20% by weight of nonionic surfactant. Such binary mixtures can be either anionic rich or nonionic rich. When a so-called ternary mixture of anionic surfactant, nonionic surfactant and soap is used, preferred amounts of the individual components of the mixture are from 2 to 15% by weight of anionic surfactant, from 0.5 to 7.5% by weight of nonionic surfactant, and from 1 to 15% by weight of soap. Examples of anionic surfactants which can be used are alkyl benzene sulphonates, particularly sodium alkyl benzene sulphonates having an average alkyl chain length of C₁₂; primary and secondary alcohol sulphates, particularly sodium C₁₂-C₁₅ primary alcohol sulphates, olefine sulphonates, primary and secondary alkane sulphonates, alkyl ether sulphates, amine oxides and zwitterionic compounds such as betaines and sulphobetaines. The soaps which can be used are preferably sodium soaps derived from naturally-occurring fatty acids. In general these soaps will contain from 12 to 20 carbon atoms and may be saturated or partly unsaturated. Three groups of soaps are especially preferred: those derived from coconut oil and palm kernel oil, which are saturated and predominantly in the C₁₂ to C₁₄ range, those derived from tallow which are saturated and predominantly in the C₁₄ to C₁₈ range, and soaps containing sodium linoleate, sodium linoienate and sodium oleate. Oils which are rich in the unsaturated substances (as glycerides) include groundnut oil, soyabean oil, sunflower oil, rapeseed oil and cottonseed oil. Of course, all of these groups of soaps may be used in admixture with each other, with other soaps not included amongst the groups enumerated, and with non-soap detergent-active material. The nonionic surfactants which can be used are the primary and secondary alcohol ethoxylates, especially the C₁₂-C₁₅ primary and secondary alcohols ethoxylated with from 2 to 20 moles of ethylene oxide per mole of alcohol. THE NON-PHOSPHATE DETERGENCY BUILDER The non-phosphate detergency builder is an aluminosilicate material. The aluminosilicates used in the invention will normally be sodium aluminosilicates and may be crystalline or amorphous, or a mixture thereof. They will normally contain some bound water and will normally have a calcium ion-exchange capacity of at least about 50 mg CaO/g. The preferred aluminosilicates have the general formula: 0.8 -- 1.5 Na₂O.Al₂O₃.0.8 -- 6 SiO₂ Most preferably they contain 1.5-3.5 SiO₂ units in the formula above and have a particle size of not more than about 100 µm, preferably not more than about 10 µm. Suitable amorphous sodium aluminosilicates for detergency building use are described for example in GB-A-1 473 202 (HENKEL) and EP-A-150613 (UNILEVER). Alternatively, suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described in GB-A-1 473 201 (HENKEL) and GB-A-1 429 143 (PROCTER & GAMBLE). The preferred sodium aluminosilicates of this type are the well known commercially-available zeolites A and X, and mixtures thereof. The level of non-phosphate builder is preferably at least 5% by weight of the spray-dried composition, up to 75%, although a level of 20% to 50% by weight is most preferred. Of course, it is perfectly permissible for the process of the invention to be applied for the manufacture of detergent compositions containing small amounts of phosphate builders, ie amounts of phosphate builders which, by weight, are less than the amounts of the non-phosphate builders. The detergency builder material may be a mixture of an aluminosilicate material with other builders, which may be other non-phosphate builders, or phosphate builders, these other builders may be selected from sodium tripolyphosphate. sodium pyrophosphate and sodium orthophosphate, sodium nitrilotriacetate, sodium carboxymethyloxysuccinate and mixtures thereof. These materials may be present in amounts up to 25% by weight. OTHER INGREDIENTS The detergent compositions produced by the process can contain the normal components of these products in conventional amounts. In particular, the following optional ingredients may be mentioned. In addition to the sugar as herein defined, other structurants may be used in the process of this invention: sodium succinate or the commercial mixture of succinic, adipic and glutaric acids sold by BASF GmbH, West Germany as Sokalan DCS (Registered Trade Mark) the sodium salt of which acts as a structurant, film-forming polymers of either natural or synthetic origin such as starches, ethylene/maleic anhydride co-polymers, polyvinyl pyrrolidone, polyacrylates and cellulose ether derivatives such as Natrosol 250 MHR (trade mark) and inorganic polymers such as clays and borates of various types may be used. These materials may be present in an amount generally from 0.5 to 30% by weight, preferably from 1 to 10% by weight, of the spray-dried powder. Some sodium silicate is a desirable component of the powders of the invention intended for use in washing machines since without it, or its precipitated form which we believe to be substantially equivalent to silica, the wash liquor containing the powders produces corrosion of vitreous enamel and/or aluminium machine parts. Against that, its presence in conjunction with non-phosphate builders may result in formation of poorly dispersing aggregates, as has already been explained, so it will be necessary to balance these two factors. Generally sodium silicate will not be present in amounts of more than 20%, preferably not more than 15% by weight of the spray-dried powder. It may be desired to include a water-soluble silicate material such as sodium silicate in the powder for purposes other than providing structure to the powder. In this case, in order to avoid production of a powder having poor solubility/dispersibility properties, it will be necessary to carry out the additional step of adding an acid in an amount equivalent to 1.5-3 parts by weight of hydrogen chloride per 6 parts of sodium silicate having a sodium oxide to silica ratio of 1:1.6, to precipitate at least part of the sodium silicate. This process is fully described in European Patent Specification No EP-A-139523. Alternatively, silicates or silica may be added to the spray-dried powder in a dry-dosing step. Other components of detergent powders which may optionally be present include lather controllers, anti-redeposition agents such as sodium carboxymethyl cellulose, oxygen and chlorine bleaches, fabric softening agents, perfumes, germicides, colourants, enzymes and fluorescers. Where such optional ingredients are heat-sensitive, or in any case, they may be post-dosed to the spray-dried granules rather than be included in the crutcher slurry for spray-drying. The invention will be further described in the following examples. Example 1 Spray-dried powders having the following formulations were made by spray-drying of aqueous crutcher slurries containing 40% by weight of water: Parts by Weight Powder A B C Sodium C₁₂ alkyl benzene sulphonate 6.0 6.0 6.0 Nonionic surfactant 2.0 1.5 1.5 Sodium aluminosilicate (Zeolite 4A) 21.0 21.0 21.0 Sodium silicate (1.6 ratio) - 6.0 - Sucrose - - 6.0 Sodium sulphate 20.5 15.2 15.2 Sodium carboxymethylcellulose 1.0 0.6 0.6 Minor components and water 5.0 5.0 5.0 The physical properties - bulk density, dynamic flow rate and compressibility - and the dispersibility of the resultant spray-dried powders were measured by conventional methods with the following results: Powder: A B C Bulk density (g/l) 324 350 408 Dynamic flow rate (ml/s) 69 80 89 Compressibility (% v/v) 39 16 16 Insolubles (particles >120 µm (% w/w): Water temperature: 20°C Nil 20 0.2 40°C Nil 15 0.2 60°C Nil 10 0.4 It can be seen from those figures that formulation C, the formulation containing sucrose, has physical properties comparable with formulation B, containing 6 parts of sodium silicate, and its dispersibility is markedly superior. Example 2 A spray-dried powder having the following formulation was made by spray-drying an aqueous crutcher slurry as in Example 1. Parts by Weight Sodium C₁₂ alkyl benzene sulphonate 6.0 Nonionic surfactant 1.5 Sodium aluminosilicate (Zeolite 4A) 21.0 Sodium silicate (3.3:1 ratio) 4.8 Sulphuric acid 0.8 Sodium carboxymethyl cellulose 0.6 Sucrose 3.0 Minor components and water 5.4 This slurry, which contains sodium silicate, was acidified with sulphuric acid as shown. The physical properties of the powder were measured and are as follows: Bulk density (g/l) 401 Dynamic flow rate (ml/s) 104 Compressibility (% v/v) 19 Insolubles (particles >120 µm (% w/w): Water temperature: 20°C 1.4 40°C 1.3 60°C 1.1 Examples 3, 4 and 5 Spray dried powders were made having the following nominal formulations by spray drying an aqueous slurry. In case of Example 3 the slurry contained about 40% water, while the water content of the slurry in Example 4 and 5 was 41% and 56% respectively. Example No 3 4 5 Ingredients (parts by weight) Sodium C₁₂ alkyl benzene sulphonate 9.0 9.0 9.0 Nonionic surfactant 4.0 4.0 4.0 Zeolite 4A 35.0 35.0 35.0 Sodium carboxymethyl cellulose 0.6 0.6 0.6 Sucrose 6.0 ---- ---- Sorbitol ---- 6.0 ---- Maize starch (water insoluble) ---- ---- 0.6 Minor ingredients 0.36 0.36 0.36 Water 10.0 10.0 10.0 Total 64.96 64.96 64.96 The 10 part of water in these formulations is a nominal figure representing a target level for the sum of free and bound water. Only free water (or moisture) is normally measured in spray dried powders. This target level is equivalent to a free water content in the spray dried powders of 8.6% by weight. In practice the free moisture content of the spray-dried powders was approximately 9% in the case of Example 3 and 7% by weight in the other Examples. Free moisture is defined as the water lost from the product after 2 hours at 135°C. The physical properties of these powders were measured and were as follows. Example No 3 4 5 Property Bulk density (g/l) 378 462 574 Dyanamic flow rate (ml/s) 114 120 120 Compressibility (% v/v) 18 32 7 Insolubles (particles > 120 µm) (% w/w) - -20°C --- 0.4 28 -40°C --- 0.2 21 These results demonstrate that the use of the water -soluble saccharide material, sorbitol, as with sucrose used in Examples 1C, 2 and 3, leads to products with acceptable physical properties, in particularly relatively good dispersibility. The use of a water-insoluble saccharide material, maize starch, as with the sodium silicate used in Example 1 B leads in particular to relatively poor dispersibility and confirms the need to use a water-soluble saccharide in the process of the present invention.

Claims: A process for preparing a particulate detergent composition comprising the steps of (i) forming an aqueous crutcher slurry comprising: (a) a surfactant system; (b) an aluminosilicate detergency builder material or a mixture thereof with a phosphate detergency builder material; and (c) a mono- or di-saccharide selected from the group consisting of sucrose, glucose, fructose, maltose, cellobiose and lactose; and (ii) spray-drying the slurry to form a detergent powder. A process according to claim 1, wherein the level of mono- or di-saccharide in the spray-dried detergent powder is between 1% and 20% by weight. A process according to claim 1, wherein the surfactant system is selected form the group consisting of anionic surfactants, nonionic surfactants, soap and mixtures thereof. A process according to claim 3, wherein the level of the surfactant system in the spray dried detergent powder is between 2% and 30% by weight when the surfactant system is an anionic surfactant, soap or mixtures thereof, between 2 and 20% by weight when the surfactant system consists of a nonionic surfactant or a mixture of between 2% and 25% of an anionic surfactant together with between 0.5% and 20% of a nonionic surfactant. A process according to claim 1, wherein the level of non-phosphate detergency builder in the spray-dried powder is from 5% to 75% by weight. A process according to claim 1, wherein the aqueous crutcher slurry contains further ingredients selected form phosphate detergency builder materials, non-sugar powder structuring agents and anti-redeposition agents. A process according to claim 1, wherein the spray-dried detergent powder is subsequently mixed with heat-sensitive ingredients. A process according to claim 1, wherein the aqueous crutcher slurry contains a water-soluble silicate and an acid is added to the slurry to precipitate at least part of the water-soluble silicate.

Inventors: DAVIES JAMES FRANCIS, KNIGHT PETER CORY, TRAVILL ANDREW WILLIAM, WILLIAMS ROBERT JOSEPH PATON, DAVIES, JAMES FRANCIS, KNIGHT, PETER CORY, TRAVILL, ANDREW WILLIAM, WILLIAMS, ROBERT JOSEPH PATON
Applicants: UNILEVER NV, UNILEVER N.V.
Application year: 1986
Main classification: C11D11
IPC codes: C11D3, C11D17, C11D11