DETERGENT COMPOSITIONS

Abstract: A laundry detergent composition providing cleaning and softening of textiles comprises an anionic surfactant, a water-insoluble di C₁₀-C₂₆ tertiary amine, and a water-soluble cationic compound which may be a mono C₁₀-C₁₈ alkyl primary, secondary or tertiary amine, or a water-soluble salt thereof or a water-soluble mono C₈-C₁₀ alkyl quaternary ammonium compound. A smectite clay serving as an additional textile softening agent and a detergent builder salt are preferred components of the granular form of the composition which may contain other conventional detergent ingredients.

Description: Field of the invention This invention relates to particulate detergent compositions that clean well and also act as textile softeners. Background of the invention Numerous attempts have been made to formulate laundry detergent compositions that have both good cleaning properties and also textile softening properties so as to avoid the necessity of using a separate rinse-added textile softener product in addition to the usual laundry detergent. As cleaning by definition involves the removal of material from the textile surface and as textile softening normally involves deposition of material onto the same surface, these attempts have necessarily required a compromise in formulation to be reached between cleaning and softening performance. The most common commercially available organic textile softening compounds are cationic materials that are reactive towards the anionic surfactants used in conventional laundry detergents. If both types of material are formulated in a single product, they tend to interact on addition to a wash liquor and, although in some instances the resulting complex has useful textile softening properties. its formation normally depresses the cleaning performance of the formulation and is therefore generally considered undesirable. In order to overcome this problem, compositions have been proposed which have sought to minimise the mutual reactivity of the anionic and cationic materials by the addition of compatibilising compounds as described for example in US-A-3,886,075 and 3,954,632. An alternative approach has been to incorporate one of the reactant materials in a form that inhibits its contact with the other in the wash liquor and examples of this type of formulation are taught in U.S.-A-3,936,537 and 3,644,203. The performance of these compositions is however sensitive to the washing conditions that are employed. In an attempt to avoid the reactivity problem altogether, nonionic surfactants have been proposed in place of the conventional anionic surfactants and compositions of this type are described in e.g. GB-H-1,079,388, DE-B-1,220,956 and U.S.-A-3,607,763. However it has been found that levels of nonionic surfactant sufficient to provide good cleaning impair the softening of the cationic softener. Another proposal to provide acceptable cleaning and textile softening by avoiding the surfactant-softener interaction has been made in GB-A-1,514,276 which teaches the use of certain long chain tertiary amines that are nonionic in character at the wash liquor pH existing when a conventional laundry detergent is ued. The commonly-assigned published EP-A1-11340 published May 28, 1980 and No. 23367 published February 4th, 1981 respectively also disclose built particulate cleaning and softening compositions comprising a combination of a long chain tertiary amine and a smectite-type clay in an anionic surfactant-based detergent. Both Applications disclose the use of from 10% to 80% by weight of the composition of water soluble organic or inorganic salts, preferably builder salts, so as to provide a 0.5% by weight aqueous solution of the composition with a pH in the range from 8.5 to 11 preferably from 9.0 to 10.5. The use of smectite-type clays as softening agents in detergent compositions is taught in GB-A-1,400,898. This type of softening agent does not affect the cleaning performance of the detergent composition but, if used on its own, requires a high level of incorporation for effective softening performance possibly because the deposition of the clay on fabrics is not very efficient in the presence of anionic surfactants. Detergent compositions exhibiting enhanced grease and oily soil removal for fabrics by means of a combination of anionic, water soluble cationic and nonionic surfactants in specific ratios are taught in EP-A-0000225, but there is no teaching of, or reference to, any fabric softening capabilities of such compositions. In summary therefore the prior art attempts to provide detergent compositions having textile softening capability have been of two general types. The first type has employed cationic fabric softening additives in anionic-surfactant based compositions and has sought to achieve the best compromise between these antagonistic components. The second type has replaced one or other of these components by a substitute which is not antagonistic but which is .Lot capable of providing the same level of performance. The current practice in providing fabric softeners benefits to fabrics in domestic laundering operations is to add a cationic fabric softener either as a liquid to the final rinse of the washing process or as a separative additive to a hot air tumbler dryer. Although this avoids direct antagonism between the cationic softener and the anionic surfactants conventionally used in laundry detergents, some decrease in fabric whiteness occurs because of the yellowing effect of the deposited fabric softener. It has now been found that detergent compositions can be formulated which have cleaning performance equivalent to that of commercially available heavy duty laundry detergents together with textile softening performance that approaches that of rinse added fabric softeners without the yellowing effect normally associated with the use of such softeners. Summary of the invention According to the present invention there is provided a particulate textile softening detergent composition comprising by weight of the composition; (a) 5%-15% of an anionic surfactant selected from watter soluble salts of alkyl benzene sulfonates, alkyl sulfates, paraffin sulfonates, alpha olefin sulfonates, and soaps (b) 1%-6% of a water insoluble tertiary amine having the general formula: wherein R₁ represents a C₁₂-C₂₂ alkyl group, R₂ is the same as R₁ and R₃ has the formula -CH₂-Y wherein Y is H, C₁-C₆ alkyl, wherein R₄ is a C₁-C₄ alkyl group, each R₅ is independantly H or C₁-C₄ alkyl; and each R₆ is independently H or C₁-C₂₀ alkyl; (c) from 10% to 80% of a detergent builder salt such that the pH of a 0.5% by weight aqueous solution of the composition is in the range from 8.5 to 11, said composition optionally comprising other components that are usually found in laundry detergents, characterised in that the composition also comprises (d) from 0.5% to 3% of a water soluble quaternary ammonium compound of formula:- R₇R₈R₉R₁₀N⁺X⁻ wherein R₇ is a C₈-C₁₄ alkyl, each of R₈, R₉ and R₁₀ is independently C₁-C₄ alkyl or hydroxyethyl and X⁻ is an anion; and e) from 4 % to 12 % of an impalpable smectite-type clay mineral of particle size less than 50µm and having an ion exchange capacity of at least 50 meq per 100g, said clay mineral being selected from sodium and calcium montmorillonite, sodium saponite and sodium hectorite provided that the molar ratio of component (d) to component (a) does not exceed 1:1, the percentage weight of components (a), (b), (c), (d) and (e), together with that of any said optional components totalling 100 % by weight of the composition, wherein any optional components comprise nonionic and zwitterionic surfactants, bleaching agents and organic precursors therefor, suds suppression agents, soil suspending and anti-redeposition agents, enzymes, optical brighteners, colouring agents and perfumes. It is desirable that the molar ratio of (d) to (a) does not exceed 1:1.5 and normally the molar ratio will be less than 1:2 in heavy duty laundry detergent compositions. Preferably component (b) is a di C₁₆-C₂₂ alkyl C₁-C₄ alkyl amine in which the C₁₆-C₂₂ alkyl groups are derived from animal fats, and component (d) is a C₁₂-C₁₄ alkyl tri C₁-C₄ alkyl or hydroxy ethyl ammonium salt. In an especially preferred form of this embodiment the tertiary amine component (b) is added to preformed spray-dried detergent granules comprising the anionic surfactant component (a), the cationic component (d), the clay and the detergent builder salt component. Detailed description of the invention In its broadest aspect the invention comprises four components, namely the anionic surfactant component (a), the tertiary amine component (b), the detergent builder salt (c), the water soluble cationic component (d) and the clay component (e) (a) The anionic surfactant A wide range of anionic surfactants can be used in the compositions of the present invention. Suitable anionic non-soap surfactants are water soluble salts of alkyl benzene sulfonates, alkyl sulfates, paraffin sulfonates and alphaolefin sulfonates. Soaps are also suitable anionic surfactants. Especially preferred alkyl benzene sulfonates have 9 to 15 carbon atoms in a linear or branched alkyl chain, more especially 11 to 13 carbon atoms. Suitable alkyl sulfates have 10 to 22 carbon atoms in the alkyl chain, more especially from 12 to 18 carbon atoms. Suitable paraffin sulfonates are essentially linear and contain from about 8 to about 24 carbon atoms, more especially from 14 to 18 carbon atoms. Suitable alphaolefin sulfonates have 10 to 24 carbon atoms, more especially 14 to 16 carbon atoms; alphaolefin sulfonates can be made by reaction with sulfur trioxide followed by neutralization under conditions such that any sulfones present are hydrolyzed to the corresponding hydroxy alkane sulfonates. The alkyl chains of the foregoing non-soap anionic surfactants can be derived from natural sources such as coconut oil or tallow, or can be made synthetically as for example using the Ziegler or Oxo processes. Water solubility can be achieved by using alkali metal, ammonium, or alkanolammonium cations; sodium is preferred. Mixtures of anionic surfactants are contemplated by this invention; a satisfactory mixture contains alkyl benzene sulfonate having 11 to 13 carbon atoms in the alkyl group and alkyl sulfate having 12 to 18 carbon atoms in the alkyl group. Suitable soaps contain 8 to 18 carbon atoms, more especially 12 to 18 carbon atoms. Soaps can be made by direct saponification of natural fats and oils such as coconut oil, tallow and palm oil, or by the neutralization of free fatty acids obtained from either natural or synthetic sources. The soap cation can be alkali metal, ammonium or alkanol-ammonium; sodium is preferred. The compositions contain from 5% to 10% of anionic detergent. (b) The tertiary amine Tertiary amines suitable for the purposes of the invention are highly water insoluble compounds that have the general formula wherein R₁ and R₂ each independently represent a C₁₂-C₂₂ alkyl group or tallowyl and R₃ has the formula -CH₂-Y wherein Y is H, C₁-C₆ alkyl, wherein R₄ is a C₁-C₄ alkyl group, each R₅ is independently H or C₁-C₄ alkyl and each R₆ is independently H or C₁-C₂₀ alkyl. Preferably R₁ and R₂ are each straight chained, and R₃ is methyl, or ethyl. Suitable amines include di lauryl methylamine di myristyl methylamine di cetyl methylamine di stearyl methylamine di arachidyl methylamine di behenyl methylamine arachidyl behenyl methylamine or di (mixed arachidyl/behenyl) methylamine di (tallowyl) methylamine and the corresponding ethyl amines, propylamines and butyl amines. Especially preferred is ditallowyl methylamine. suitable amines include:- dilauryl benzylamine dimyristyl benzylamine dicetyl benzylamine distearyl benzylamine diarachidyl benzylamine dibehenyl benzylamine di(arachid/behenyl)benzylamine ditallowyl benzylamine and the corresponding allylamines, hydroxy ethylamines, hydroxy propylamines, and 2-cyanoethylamines. Especially preferred are ditallowyl benzylamine and ditallowyl allylamine. Mixtures of any of these amines may be used. The compositions contain from 1% to 6% by weight of the tertiary amine. (c) The detergent builder salt Detergent builder salts form component (c) of the compositions of the invention and can be inorganic or organic in character. Non-limiting examples of suitable water-soluble, inorganic alkaline detergent builder salt include the alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. Specific examples of such salts include the sodium and potassium tetraborates, bicarbonates carbonates, tripolyphosphates, pyrophosphates, penta-polyphosphates and hexametaphosphates. Sulphates are usually also present. Examples of suitable organic alkaline detergency builder salts are: (1) water-soluble amino polyacetates. e.g., sodium and potassium ethylenediaminetetraacetates, nitrilotriacetates. N-(2-hydroxyethyl) nitrilodiacetates and diethylene triamine pentaacetates (2) water-soluble salts of phytic acid. e.g. sodium and potassium phytates; (3) water-soluble polyphosphonates, including sodium, potassium and lithium salts of methylene diphosphonic acid and the like and aminopolymethylene phosphonates such as ethylenediamine tetramethylenephosphonate and diethylene triaminepentamethylene phosphonate, and polyphosphonates described in FR-A-2388045. (4) water-soluble polycarboxylates such as the salts of lactic acid, succinic acid, malonic acid, maleic acid, citric acid, carboxymethylsuccinic acid, 2-oxa-1,1,3-propane tricarboxylic acid, 1,1,2,2-ethane tetracarboxylic acid, mellitic acid and pyromellitic acid. Mixtures of organic and/or inorganic builders can be used herein. One such mixture of builders is disclosed in Canadian Patent No. 755,038, e.g. a ternary mixture of sodium tripolyphosphate, trisodium nitrilotriacetate, and trisodium ethane-1-hydroxy-1,1-diphosphonate. Another type of detergency builder material useful in the present compositions and processes comprises a water-soluble material capable of forming a water-insoluble reaction product with water hardness cations preferably in combination with a crystallization seed which is capable of providing growth sites for said reaction product. Such "seeded builder" compositions are fully disclosed in GB-A-1,424,406. Preferred water soluble builders are sodium tripolyphosphate and sodium silicate and usually both are present. In particular, it is preferred that a substantial proportion, for instance from 3 to 15% by weight of the composition of sodium silicate (solids) of ratio (weight ratio SiO₂:Na₂O) from 1:1 to 3.5:1 be employed. A further class of detergency builder materials useful in the present invention are insoluble sodium aluminosilicates, particularly those described in BE-A-814,874. This patent discloses and claims detergent compositions containing sodium aluminosolicate of the formula:- Na z (AlO₂) z (SiO₂) y xH₂O wherein z and y are integers equal to at least 6, the molar ratio of z to y is in the range of from 1.0:1 to about 0.5:1 and x is an integer from about 15 to about 264. A preferred material is Na₁₂ (SiO₂AlO₂)₁₂27H₂O. About 5% to 25% by weight of aluminosilicate may be used as a partial replacement for water-soluble builder salts, provided that sufficient water-soluble alkaline salts remain to provide the specified pH of the composition in aqueous solution. The detergent builder salts are normally included in amounts of from 10% to 80% by weight of the composition preferably from 20% to 70% and most usually from 30% to 60% by weight. (d) The water-soluble cationic compound The fourth essential component of the compositions of the present invention is a nitrogenous organic compound capable of existing in cationic form in 0.1% aqueous solution of pH 10. This compound may be of any of the : quaternary ammonium compounds of formula R₇R₈R₉R₁₀N⁻X⁻ wherein R₇ is C₈-C₁₄ alkyl, each of R₈, R₉, and R₁₀ is independently selected from C₁-C₄ alkyl and hydroxy ethyl and X is an anion. The preferred alkyl chain length for R₇ is C₁₂-C₁₄ particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived synthetically by olefin build up or OXO alcohol synthesis. Preferred groups for R₈, R₉ and R₁₀ are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosulphate, acetate and phosphate ions. Examples of suitable quaternary ammonium compounds are coconut trimethylammonium chloride coconut methyl dihydroxyethyl ammonium chloride decyl triethyl ammonium chloride decyl dimethyl hydroxyethyl ammonium bromide myristyl trimethyl ammonium methyl sulphate For the purposes of the present invention it is essential that the cationic compound should not be present in molar excess over the anionic detergent and it is highly preferable that the molar ration of cationic compound to anionic detergent be less than 1:1.5 and most preferably less than 1:2. For the laundry detergent compositions of the invention the water soluble cationic compound is present in an amount of from 0.5% to 3% by weight of the composition. (e) Clay compounds A further essential ingredient is a smectite-type clay serving as an auxiliary textile softening agent. The smectite clays useful in the practice of the present invention are sodium and calcium montmorillonites, sodium saponites, and sodium hectorites. The clays used herein are impalpable ie. they have a particle size which cannot be perceived tactilely of less than 50 µm and normally have a particle size range of from 5 µm to less than 50 µm. The clay minerals can be described as expandable, three-layer clays. i.e., aluminosilicates and magnesium silicates, having an ion exchange capacity of at least 50 meq/100 g. of clay and preferably at least 60 Meq/100 g. of clay. -The term "expandable" as used to describe clays relates to the ability of the layered clay structure to be swollen, or expanded, on contact with water. The three-layer expandable clays used herein are those materials classified geologically as smectites. These are two distinct classes of smectite clays that can be broadly differentiated on the basis of the numbers of octahedral metal-oxygen arrangements in the central layer for a given number of silicon-oxygen atoms in the outer layers. The dioctahedral minerals are primarily trivalent metal ion-based clays and are comprised of the prototype pyrophyllite and the members montmorillonite (OH)₄Si 4-y (Al 4-x Mg x )O₂₀, nontronite (OH)₄Si 8-y Al y (Al 4-x Fe x )O₂₀, and volchonskoite (OH)₄Si 8-y Al y (AL 4-x Cr x )O₂₀, where x has a value of from 0 to about 4.0 and y has a value of from 0 to about 2.0. Of these only montmorillonites having exchange capacities greater than 50 meq 100g provide appreciable fabric softening benefits and are useful for this purpose in compositions of the present invention. The trioctahedral minerals are primarily divalent metal ion based and comprise the prototype talc and the members hectorite (OH)₄Si 8-y Al y (Mg 6-x -Li x )O₂₀, saponite (OH)₄Si 8-y Al y (Zn 6-x Al x )O₂₀, vermiculite (OH)₄Si 8-y Al y (Mg 6-x Fe x )O₂₀, wherein y has a value of 0 to 2.0 and x has a value from 0 to about 6 0. Hectorite and saponite are the only minerals in this class that have appreciable fabric softening capability as the fabric softening performance is related to the type of exchangeable cation as well as to the exchange capacity it is to be recognized that the amount of water of hydration in the above formulas can vary with the processing to which the clay has been subjected. This is immaterial to the use of the smectite clays as fabric softening agents in that the expandable characteristics of the hydrated clays are dictated by the silicate lattice structure. As noted hereinabove, the clays suitable for use with the compositions of the present invention contain cationic counterions such as protons, sodium ions, potassium ions, calcium ions, and lithium ions. It is customary to distinguish between clays on the basis of one cation predominantly or exclusively absorbed. For example, a sodium clay is one in which the absorbed cation is predominantly sodium. Such absorbed cations can become involved in exchange reactions with cations present in aqueous solutions. A typical exchange reaction involving a smectite-type clay is expressed by the following equation. Smectite clay (Na)⁺ = smectite clay (NH₄)+NaOH. Since in the foregoing equilibrium reaction one equivalent weight of ammonium ion replaces an equivalent weight of sodium, it is customary to measure cation exchange capacity (sometimes termed "base exchange capacity") in terms of milliequivalent per 100 g. of clay (meq/100 g). The cation exchange capacity of clays can be measured in several ways, including by electrodialysis, by exchange with ammonium ion followed by titration or by a methylene blue procedure, all as fully set forth in Grimshaw, "The Chemistry and Physics of Clays", pp. 264-265, Interscience (1971). The cation exchange capacity of a clay mineral relates to such factors as the expendable properties of the clay, the charge of the clay, which, in turn, is determined at least in part by the lattice structure. The ion exchange capacity of clays varies widely in the range from about 2 meq/100 g. for kaolinites to about 150 meq/100 g., and greater, for certain smectite clays. Illite clays, although having a three layer structure, are of a non-expanding lattice type and have an ion exchange capacity somewhere in the lower portion of the range, i.e., around 26 meq/100 g. for an average illite clay. Attapulgites, another class of clay minerals, have a spicular (i.e. needle-like) crystalline form with a low cation exchange capacity (25-30 meq/100 g). Their structure is composed of chains of silica tetrahedrons linked together by octahedral groups of oxygens and hydroxyls containing Al and Mg atoms. It has been determined that illite, attapulgite, and kaolinite clays, with their relatively low ion exchange capacities, are not useful as fabric softening ingredients. However, the alkali metal montmorillonites. saponites, and hectorites. and certain alkaline earth metal varieties of these minerals such as calcium montmorillonites have been found to show useful fabric softening benefits when incorporated in compositions in accordance with the present invention. Specific non-limiting examples of such fabric softening smectite clay minerals are: Sodium Montmorillonite Brock Volclay BC Gelwhite GP Thixo-Jel Ben-A-Gel Sodium Hectorite Veegum F Laponite SP Sodium Saponite Barasym NAS 100 Calcium Montmorillonite Soft Clark Gelwhite L Imvite K Accordingly, smectite clays useful herein can be characterised as montmorillonite, hectorite and saponite clay minerals having an ion exchange capacity of at least 50 meq/100 g. and preferably at least 60 meq/100 g. Most of the smectite clays useful in the compositions herein are commercially available under various trade names, for example, Thixogel No. 1 and Gelwhite GP from Georgia Kaolin CO., Elizabeth, New Jersey; Imvite K from Industrial Mineral Ventures; Volclay BC and Volclay 325 from American Colloid Co., Skokie Illinois; and Veegum F from R. T. Vanderbilt. It is to be recognised that such smectite minerals obtained under the foregoing tradenames can comprise mixtures of the various discrete mineral entities. Such mixtures of the smectite minerals are suitable for use herein. Within the classes of montmorillonite, hectorite and saponite clay minerals having a cation exchange capacity of at least about 50 meq/100 g., certain clays are preferred for fabric softening purposes. For example. Gelwhite GP is an extremely white form of smectite clay and is therefore preferred when formulating white granular detergent compositions. Volclay BC, which is a smectite clay mineral containing at least 3% of iron (expressed as Fe₂O₃) in the crystal lattice, and which has a very high ion exchange capacity, is one of the most efficient and effective clays for use as a fabric softening component of detergent compositions. Imvite K is also very satisfactory. Appropriate clay minerals for use herein can be selected by viture of the fact that smectites exhibit a true 14 x 10⁻¹⁰ m x-ray diffraction pattern. This characteristic exchange pattern, taken in combination with exchange capacity measurements performed in the manner noted above, provides a basis for selecting particular smectite-type minerals for use in the compositions disclosed herein. The smectite clay materials useful in the present invention are hydrophilic in nature, i.e., they display swelling characteristics in aqueous media. Conversely they do not swell in nonaqueous or predominantly non aqueous systems. In compositions according to the invention, the smectite clay is present in an amount of from 4% to 11% by weight of the composition, preferably from 5% to 12%. Bleaching agents useful in the compositions of the invention include sodium perborate, sodium percarbonate and other perhydrates at levels of from 5% to 35% by weight of the composition. Organic peroxy bleach precursors such as tetra acetyl ethylene diamine and tetra acetyl glycoluril can also be included and these and other precursors are disclosed in BE-A-859461. In compositions incorporating oxygen bleaches, bleach stabilisers are also preferred components usually at levels of from 0.2% to 2% by weight of the composition. The stabilisers may be organic in nature such as the previously mentioned amino polyacetates and amino polyphosphonates or may be inorganic such as magnesium silicate. In the latter case the material may be added to the formulation or formed in situ by the addition of a water-soluble magnesium salt to a slurried detergent mix containing an alkali metal silicate. Suds controlling agents are often present. These include suds boosting or suds stabilising agents such as mono- or di-ethanolamides of fatty acids. More often in modern detergent compositions. suds suppressing agents are required. Soaps especially those having >18 carbon atoms, or the corresponding fatty acids, can act as effective suds suppressors if included in the anionic surfactant component of the present compositions. Usually 1% to 4% of such soap is effective as a suds suppressor. Very suitable soaps, when suds suppression is a primary reason for their use, are those derived from hardened marine oil fatty acids predominantly C₁₈ to C₂₂ acids. However, non-soap suds suppressors are preferred in synthetic detergent based compositions of the invention since soap or fatty acid tends to give rise to a characteristic odour in these compositions. Preferred suds suppressors comprise silicones. In particular there may be employed a particulate suds suppressor comprising silicone and silanated silica releasably enclosed in water soluble or dispersible substantially non-surface active detergent impermeable carrier. Suds suppressing agents of this sort are disclosed in GB-A-1,407,997. A very suitable granular (prilled) suds suppressing product comprises 7% silica/silicone (15% by weight silanated silica, 85 % silicone, obtained from Messrs. Dow Corning), 65% sodium tripolyphosphate, 25% Tallow alcohol condensed with 25 molar proportions of ethylene oxide, and 3% moisture. The amount of silica/silicone suds suppressor employed depends upon the degree of suds suppression desired but it is often in the range from 0.01% to 0.5% by weight of the detergent composition. Other suds suppressors which may be used are water insoluble, preferably microcrystalline, waxes having melting point in the range from 35 to 125°C and saponification value less than 100, as described in GB-A-1,492,938. Yet other suitable suds suppressing systems are mixtures of hydrocarbon oil, a hydrocarbon wax and hydrophobic silicas as described in EP-A1-0000216 and, especially, particulate suds suppressing compositions comprising such mixtures, combined with an ethoxylated nonionic surfactant having an HLB in the range from 14 to 19 and a compatibilising agent capable of forming inclusion compounds, such as urea. These particulate suds suppressing compositions are described in EP-A1-0008830. Soil suspending agents are usually present at 0.1 to 10%, such as water soluble salts of carboxymethyl cellulose, carboxyhydroxymethyl cellulose, polyethylene glycols of molecular weight of from 400 to 10000 and copolymers of methylvinylether and maleic anhydride or acid Proteolytic, amylolytic or lipolytic enzymes, especially proteolytic, and optical brighteners of anionic, cationic or nonionic types, especially the derivatives of sulphonated triazinyl diamino stilbene may be present. Photoactivated bleaches such as the tri and tetra sulphonated derivatives of zinc phthalocyanine are also useful components of the present composition. Colours, non-substantive, and perfumes, as required to improve the aesthetic acceptability of the product, are usually incorporated. Throughout the description herein where sodium salts have been referred to potassium, lithium or ammonium or amine salt may be used instead if their extra cost etc., are justified for special reasons. Preparation of the compositions The detergent compositions may be prepared in any way appropriate to their physical form such as by dry mixing the components, co-agglomerating them or dispersing them in a liquid carrier. However, a preferred physical form is a granule incorporating the detergent builder salt and this is most conveniently manufactured by spray drying at least part of the composition. For the purposes of the following discussion, components of the composition that are normally added to a detergent crutcher mix and spray dried are identified as (a), components which are applied in the liquid form by spray-on to other solid components are identified as (b) and components which are added as solids other than in the spray dried portion are identified as (c). Conventionally, the compositions are prepared by making up an aqueous slurry of the non-heat-sensitive components (a), comprising the anionic and cationic surfactants, builder and filler salts, clay, soil suspending agents and optical brighteners, and spray drying this slurry. The moisture content of the slurry is normally in the range 28% to 36% and its temperature is conveniently in the range 70°-95°C. The spray drying tower inlet temperatures are normally in the range 300°360°C and the resultant spray dried granules have a moisture content of 8-12% by weight. An optional, but preferred, additional processing step is to cool the dried granules rapidly by means of cool air from a temperature of 90°C to a temperature in the range 25°-35°C in order to facilitate the further processing of the product. Solid heat sensitive components (c), such as persalts and enzymes, are mixed with the spray-dried granules. Although the water-insoluble amine component may be included in the slurry for spray drying it may degrade under certain processing conditions and adversely affect product quality. It is therefore preferred that the water-insoluble tertiary amine be liquified by melting or solvent dissolution and that this liquid (b) be sprayed onto the spray dried granules before or after other heat sensitive solids have been dry mixed with them. If the amine is applied as a melt, a liquid temperature 10°-30°C in excess of the melting point can conveniently be used for the spray-on. Although the amine is generally a waxy solid of rather low melting point, the granules so made are surprisingly crisp and free-flowing. As noted above, the usual mode of incorporation of the water soluble cationic component is by addition to the slurried ingredients (a). as a convenient form of supply of the cationic component is as an aqueous solution. However, if the cationic component is supplied as a solid, it can be added with the heat sensitive solids (c), or dispersed in the liquified tertiary amine (b). The latter can be sprayed on to any particulate component or components of the composition which are able to act as carrier granules. Similarly the clay component can be dry mixed if so desired. The invention is illustrated by the following non-limiting examples. Example 1 The following compositions were made up The compositions were made by first forming designated ingredients (a) into spray dried base granules. A molten slurry of the designated ingredients (b) was then made up by melting the di-tallow methyl amine, and, in the case of compositions C+D, by dispersing the cationic material therein. This molten mixture was then sprayed onto the base powder and allowed to solidify to give crisp free flowing granules into which were dry mixed the remaining ingredients (c). The compositions were then used to wash 4 Kg (8lb) soiled fabric loads in a Miele Model 422 Drum Automatic machine set to a prewash-mainwash cycle in which the mainwash was a boil wash. The water hardness was 14° Clark (Ca:Mg molar ratio 2:1) and the product usage was 70 g in the prewash and 140 g in the mainwash. Artificially soiled cotton tracers and clean terry towelling tracers were added to each wash to permit evaluation of respectively, the cleaning and softening performance of the compositions. Following the wash each load was air dried at ambient temperatures before being assessed by an expert panel. In a paired comparison between tracers washed in compositions A and C using a Scheffe scale of assessment, composition C was rated better for softness than A by 1.5 panel score units with a least significant difference (LSD) of 1.12 psu at the 95% confidence level and also provided improved greasy soil removal relative to Composition A. In a similar comparison between tracers washed in compositions B and D, Composition D was rated better for softness by 2.0 panel score units than composition B with an LSD₉₅ of 0.64 and also showed improved greasy soil removal. It can be seen that composition D in accordance with the invention is superior in fabric softening performance to prior art softening composition B whilst being equivalent to or slightly better than that composition in cleaning performance. In this example the ditallow methylamine component (b) in either of compositions C and D may be replaced by distearyl benzyl amine, dicetyl hydroxy ethylamine, ditallowyl allylamine or ditallowyl benzyl amine and corresponding results are obtained. The C₁₄ alkyl trimethyl quaternary component (c) may be replaced by lauryl methyl dihydroxyethyl ammonium bromide and coconut alkyl trimethyl ammonium bromide. Examples 2 & 3 The following compositions are in accordance with the invention The compositions were made by forming 32-34 wt% aqueous slurry of components (a) at a temperature in the range 85-90°C and spray drying the slurry give a granular base powder. The order of addition of ingredients was anionic surfactant, silicate, minor ingredients, sulphate, nonionic clay, cationic and finally phosphate. The copolymer of Example 3 was added with the CMC. Inlet air temperatures in the range 320°C to 340°C were used and the spray dried granules were subsequently cooled to 25-35°C in an air lift using ambient air as the cooling medium. The heat sensitive solid ingredients (c) were then added to the base powder through feeding devices known to those skilled in the art and the granule mix was subjected to a spray-on of the tertiary amine component (b) into which perfume material had been biended. Examples 4-9 Further compositions in accordance with the invention are given below:

Claims: 1. A particulate textile softening detergent composition comprising by weight of the composition; a) 5% - 15% of an anionic surfactant selected from water soluble salts of alkyl benzene sulfonates, alkyl sulfates, paraffin sulfonates, alpha olefin sulfonates and soaps b) 1%-6% of a water insoluble tertiary amine having the general formula: wherein R₁ represents a C₁₂-C₂₂ alkyl group, R₂ is the same as R₁ and R₃ has the formula -CH₂-Y wherein Y is H, C₁-C₆ alkyl, wherein R₄ is a C₁-C₄ alkyl group, each R₅ is independently H or C₁-C₄ alkyl and each R₆ is independently H or C₁-C₂₀ alkyl; c) from 10% to 80% of a detergent builder salt such that the pH of a 0.5% by weight aqueous solution of the composition is in the range from 8.5- 11, said composition optionally comprising other components that are usually found in laundry detergents, characterised in that the composition also comprises d) from 0.5% to 3% of a water soluble quaternary ammonium compound of formula:- R₇R₈R₉R₁₀N⁺X⁻ wherein R₇ is a C₈-C₁₄ alkyl, each of R₈, R₉ and R₁₀ is independently C₁-C₄ alkyl or hydroxyethyl and X⁻ is an anion; and e) from 4% to 12% of an impalpable smectite-type clay mineral of particle size less than 50µm and having an ion exchange capacity of at least 50 meq per 100g, said clay mineral being selected from sodium and calcium montmorillonite, sodium saponite and sodium hectorite provided that the molar ratio of component (d) to component (a) does not exceed 1:1, the percentage weight of components (a), (b), (c), (d) and (e), together with that of any said optional components totalling 100% by weight of the composition, wherein any optional components comprise nonionic and zwitterionic surfactants, bleaching agents and organic precursors therefor, suds suppression agents, soil suspending and anti-redeposition agents, enzymes, optical brighteners, colouring agents and perfumes. 2. A detergent composition according to Claim 1 wherein the molar ratio of (d) to (a) does not exceed 1:2. 3. A detergent composition according to either one of Claims 1 and 2 wherein the water soluble quaternary ammonium compound is selected from salts in which R₇ is C₁₂-C₁₄ alkyl and R₈, R₉ and R₁₀ are selected from methyl and hydroxyethyl groups. 4. A detergent composition according to any one of Claims 1 to 3 comprising an ethoxylated nonionic surfactant of HLB 11.5-17.0 in an amount of less than 30%of the total anionic, cationic and nonionic surfactants.

Inventors: CRISP, PETER NORMAN, MCRITCHIE, ALLAN CAMPBELL, SPADINI, GIANFRANCO LUIGI
Applicants: PROCTER & GAMBLE LIMITED, THE PROCTER & GAMBLE COMPANY
Application year: 1980
Main classification: C11D1
IPC codes: D06M13, D06M23, C11D3, C11D1, D06M11