GB2179971A - Fabric softening and antistatic detergent composition - Google Patents

Abstract

A water-soluble diquaternary diammonium compound, such as N-methyl-N-(2-hydroxyethyl)-N-tallowalkyl- N'-methyl-N'-bis(2-hydroxyethyl)-propylene-diammonium methosulphate, is homogeneously and finely dispersed in a spray-dried detergent bead or granule. The spray-dried bead is blended with a clay mineral fabric softener. The final composition exhibits antistatic action even at low levels (e.g. less than 2%) of the antistat without adversely effecting softening cleaning or whitening. In a typical formulation, the spray-dried beads include linear alkyl benzene sulphonate or other anionic surfactant, an inorganic polyphosphate and/or other inorganic and/or organic detergent builder salt, the dimmonium compound antistatic agent, and other heat stable and pH insensitive detergent additives and fillers. In addition to a smectite clay fabric softener, other post-added ingredients typically include a nonionic surfactant, enzyme, perfume, bleach, and other detergent additives which may be pH sensitive, heat sensitive, water-insoluble, or reactive with one or more of the components of the spray-dried beads.

Description

SPECIFICATION Fabric softening and antistatic detergent composition The present invention relates to a laundry detergent composition based on clay softener and cationic antistatic agent. More particularly, this invention relates to a laundry detergent powder composition containing detergentsurfactant, clay softener, and a water-soluble diammonium salt antistatic agent, to the method of preparing the composition and tothe use thereof in laundering textile materials.

Powdery detergent compositions containing a detergentsurfactant(anionic, nonionic,etc.),witha clay softener and a cationic antistatic agent, such as quaternary ammonium compound, quaternary diammonium compound, etc., are known in the art.

Representative ofthe patent literature in this field are U.S. Patent 3,862,058 (Nirschl, et at); 3,886,075 (Bernardino); 3,915,882 (Nirschl, et al); 3,948,790 (Speakman); 4,203,851 (Ramachandran); U.K. Patent Application GB 2,141,152A (Ramachandran). Other patent art relating to clay fabric treating compositions include U.S. Patents 3,594,212 (Ditsch) and 4,062,647 (Storm, et al). The use of bentonitesfor softening textiles is known from British Patents 401,413 and 461,221.

While satisfactory cleaning and softening performance has been achieved with the known clay softenerdetergent compositions, it is generally difficultto achieve a reduction of static charge on laundered fabrics to a sufficiently high level so as to be perceivable by the ordinary consumer.

Generally, attempts to incorporate amounts of antistatic agent which would provide acceptable levels of antistatic performance have resulted in an overall reduction in cleaning, whitening and softening performance. This reduction in overall performance parameters has been observed whetherthe cationic antistatic agent is added to the formulation under conditions which would result in surface modification oftheclaysoftenerorunderconditions which would merely result in physical mixtures of the clay, cationic antistatic agent, detergent and other components oftheformulation.

Accordingly, the present invention aimsto provide a clay softener detergent composition containing a static charge reducing compound.

The present invention also aims to provide an antistatic laundry detergent composition in the form of spray-dried beads incorporating therein a watersoluble diammonium compound antistatic agent, wherein the spray-dried beads are compatible with clay mineral fabric softener, and a method for preparing the spray-dried beads.

The present invention also aims to provide a built clay softener detergent powder composition having consumer perceivable antistatic properties without diminishing cleaning, whitening or softening performance of the composition.

The present invention further aims to provide a clay-softener-detergent powder composition in which a water-soluble diammonium saltcationic antistatic agent can be added to the composition as a component ofthe crutcher mixture to be spray-dried whereby the antistatic agent can be uniformly and homogeneously incorporated into the composition, and the clay softener can be post-added to the spray-dried beads or granules.

According to the present invention there is used as the antistatic cationic compound in a clay-softener detergent laundry composition and particulately as a component of spray-dried beads or granules to be blended with the clay softener, a water-soluble diammonium salt ofthe formula (I):

where R1 represents an aliphatic hydrocarbon group having from about 12to about 30 carbon atoms; each of R2, R3, R4, R5 and R6 independently represent selected from the group consisting of aliphatic hydrocarbon groups having from 1 to 22 carbon atoms with the proviso that the total number of carbon atoms in all the aliphatic hydrocarbon groups, including R1, is no more than about 75 and withthefurtherprovisothatno morethantwoofthe R2-R6 groups have morethan 12 carbon atoms; or hydroxyl groups offormula (II)

wherein m and n are independently0 or positive numbers such thatthe sum ofm and n from all ofthe groups R2-R6 is at least 2 but no more than 30; with the still further proviso that at least one ofthe R2-R6 groups is offormula (all); R7 is a divalent linking radical, such as C2-C5 lower alkylene or substituted C2-C5 lower alkylene, k is a number of from 1 to 20, and Xis a water-soluble saltforming anion.

Because the useful diammonium compounds of formula (I) are water-soluble and are also stable under a broad range of pH values and at elevated temperatures they can be added directly to the crutcher mix as an aqueous solution with the other softener-detergentformulation ingredients to be spray-dried,therebyuniformlyand homogeneously incorporation the diammonium salt antistatic agents in the spray-dried granules or beads. As a result of this homogeneous distribution, the desired level of antistatic performance can be obtained using lower levels ofthe antistatic compound and without detrimentally effecting other detergent properties, including cleaning performance, whitening performance and softening performance.

As used herein and in the appended claims, the term "water-soluble" means that the antistatic di ammonium compoundsaresolubleoratleastform stable dispersions in water of at least 5% by weight at 20"C. The preferred compounds offormula (I) are soluble in water at ambient temperature to an extent of at least 10% by weight. Since the diammonium salt antistatic agents offormula (I) are available or can be prepared as organic solvent-free aqueous solutions or dispersions they can be easily and safely handled in powder processing plants and can be readily crutched and spray-dried as a component of heavy duty builtgranularor powdery laundry detergent compositions.

Atypical heavy duty builtformulation incorporat ing the spray-dried beads containing therein the water-soluble antistatic agent offormula (I) may includethefollowing ingredients: Amount (Weight%) Total Spray-Dried Ingredients Composition Beads Detergent surface-active 1-95 10-60 compound Organic and inorganic deter- 2-80 5-90 gent builders Clay softener 1-50 0 Antistatic agent of 0.2-5 0.4-15 formula (I) Fillers 0-25 0-10 Bleach and bleach additives 0-25 0-5 Optical brighteners, pigments, 0-10 0-8 dyes Anti-foaming agents; suds 0-10 0-8 suppressors, etc.

Enzymes 0-5 0 pH adjusting agents, buffers, etc 0-10 0-8 pH adjusting agents, buffers, 0-5 0-3 etc. antiredepostion agent, perfume, etc.

water balance In a preferred method for preparing the heavy duty built granular or powdery softener-detergent composition the antistatic agent offormula (I) and the remaining pH insensitive, heat stable ingredients will be mixed in a crutcher and spray-dried to form spray-dried beads and these beads will be uniformly mixed or over-sprayed with the ingredients ofthe formulation which are pH sensitive and/or heat sensitive or which may otherwise react with cationic antistatic agent, anionic surfactant or other compo nent of the spray-dried beads or granules. As examples of the post-added ingredients to be mixed with the spray-dried beads, mention may be made of, for example, bleach, clay softener, enzymes, per- fume, nonionic surfactant, etc.Formulation com pounding proceduresarewell known in the art and the practitionerwill be able to readily determine the optimum formulating conditions.

The laundry detergent compositions may contain one or more surface active agents selected from the group consisting of anionic, nonionic, ampholytic and zwitterionic detergents. The synthetic organic detergents employed in the practice of the invention may be any of a wide variety of such compounds which are well known and are described at length in the text "Surface Active Agents and Detergents", Vol.

II, by Schwartz, Perry and Berch, published in 1958 by Interscience Publishers, the relevant disclosures of which are hereby incorporated by reference. The total amount ofthe surface-active detergent compound or compounds can be as much as 95% by weight ofthe total detergent composition, although more preferred amounts are in the range offrom about 1 to 70% by weight, especially 5 to 50% by weight, and especially preferably from about 5 to 30% by weight of the total detergent composition.

The detergent compositions ofthe present invention preferably employ one or more anionic detergent compounds as the primary surfactants. The anionic detergent may be supplemented, ifdesired,with another type of surfactant, preferably non ionic detergent, especiallywhen used in combination with a detergent builder salt.

Among the anionic surface active agents useful in the present invention are those surface active compounds which contain an organic hydrophobic group containing from about 8 to 26 carbon atoms and preferably from about 10 to 18 carbon atoms in their molecular structure and at least one water-solubiliz ing group selected from the group ofsulphonate, sulphate, carboxylate, phosphonate and phosphate so astoform awater-solubledetergent.

Examples ofsuitable anionic detergents include soaps, such as,thewater-soluble salts (e.g. the sodium, potassium, ammonium and alkanolammo nium salts) of higherfatty acids or resin salts containing from about 8 to 20 carbon atoms and preferably 1 Oto 18 carbon atoms. Suitablefatty acids can be obtained from oils and waxes of animal or vegetable origin, for example, tallow, grease, coconut oil and mixtures thereof. Particularly useful are the sodium and potassium salts ofthe fatty acid mixtures derived from coconut oil and tallow, for example, sodium coconutsoap and potassiumtallow soap.

The anionic class of detergents also includethe water-soluble sulphated and sulphonated detergents having an aliphatic, preferably an alkyl, radical containing from about8to 26, and preferably from about 12to22 carbon atoms. (The term "alkyl" includes the alkyl portion ofthe higheracyl radicals.) Examples of the sulphonated anionic detergents are the higher alkyl mononucleararomaticsulphonates, such asthe higheralkyl benzenesulphonatescontaining from about 10 to 16 carbon atoms in the higheralkyl group in a straight or branched chain, such as, for example, the sodium, potassium and ammonium salts of higher alkyl benzene sulphonates, higher alkyl toluene sulphonates and higher alkyl phenol sulphonates.

Other suitable anionic detergents are the olefin sulphonates including long chain alkene sulphonates, long chain hydroxylalkane sulphonates or mixtures of alkene sulphonates and hydroxyalkane sulphonates. The olefin sulphonate detergents may be prepared in a conventional manner by the reaction ofsulphurtrioxide (SO3) with long chain olefins containing from about8to 25, and preferably from about 12 to 21 carbon atoms, such olefins having the formula RCH=CHR' wherein R represents a higher alkyl group of from about 6 to 23 carbons and R' represents an alkyl group contajning from about 1 to 17 carbon atoms, or hydrogen to form a mixture of sultonesandalkenesulphonicacidswhich isthen treated to convert the sultones to sulphonates.Other examples of sulphate or sulphonate detergents are paraffin sulphonates containing from about 1 0to 20 carbon atoms, and preferably from about 15 to 20 carbon atoms. The primary paraffin sulphonates are made by reacting long chain alpha olefins and bisulphites. Paraffin sulphonates having the sulphonate group distributed along the paraffin chain are shown in U.S. Nos. 2,503,280; 2,507,088; 3,260,741; 3,372,188 and German Patent No.735,096.

Othersuitableanionicdetergentsaresulphated ethoxylated higherfatty alcohols oftheformula RO(C2H4O)mSO3M, wherein R represents a fatty alkyl group offrom 10to 18 carbon atoms, mis from 2to 6 (preferably having a value from about 1/5to 1/2 the number of carbon atoms in the R group) and M is a solubilizing salt-forming cation, such as an alkali metal, ammonium, lower alkylamino or lower alkanolamino, ora higheralkyl benzenesulphonatewherein the higher alkyl group is of 10to 15 carbon atoms.The proportion of ethylene oxide in the polyethoxylated higheralkanol sulphate is preferably2to 5 moles of ethylene oxide groups per mole of anionic detergent, with three moles being most preferred, especially when the higheralkanol is of 1 to 15 carbon atoms.

To maintain the desired hydrophile-lipophile balance, when the carbon atom content ofthe alkyl chain is in the lower portion of the 10 to 18 carbon atoms range, the ethylene oxide content ofthe detergent may be reduced to about two moles per mole whereas when the higher alkanol is of 16to 18 carbon atoms inthe higher part of the range, the number of ethylene oxide groups may be increased to 4Or5 and in some casesto as high as 8 or9.

Similarly, the salt-forming cation may be altered to obtain the bestsolubility. It may be any suitably solubilizing metal or radical butwill mostfrequently be an alkali metal, e.g. sodium, or ammonium. If lower alkylamine to alkanolamine groups are utilized, the alkyl groups and alkanols will usually contain from 1 to 4 carbon atoms and the amines and alkanolamines may be mono-, di- and tri-substituted, as in monoethanolamine, di - isopropanolamine and trimethylamine. A preferred polyethoxylated alcohol sulphate detergent is available from Shell Chemical Company and is marketed as Neodol (Registered Trademark) 25-3S.

The most highly preferred water-soluble anionic detergent compounds are the ammonium andsubstituted ammonium (such as mono-, di and tri-ethanolamine), alkali metal (such as, sodium and potassium) and alkaline earth metal (such as, calcium and magnesium) salts ofthe higher alkyl benzene sulphonates, olefin sulphonates and higheralkyl sulphates. Among the above-listed anionics,the most preferred are the sodium linear alkyl benzenesul- phonates (LABS), and espcially those where the alkyl group is a straight chain alkyl radical of 12 or 13 carbon atoms.

The anionic surfactantwill generallyconstitutethe majordetergent component and maycomprisefrom about 30 to 100% of the total surface active ingredients. Preferably the anionic accounts for at least 50%, preferably at least 60%, especially preferably at least 70%, and up to about 99%, preferably up to about90%, especially preferably up to about 80% of the total surfactant detergent ingredients.

The anionicsurfactant compound will usually and preferably be included as a component ofthe antistatic-containing spray-dried beads and will be added to the crutcher mix as an aqueous solution or dispersion, and preferably as a highly concentrated aqueous slurry.

The next most preferred class of surfactant deter gent ingredient isthe nonionicsyntheticorganic detergent compounds.

The nonionic synthetic organic detergents are characterised by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically produced by the condensation of an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide (hydrophilic in nature). Practically any hydrophobic compound having a carboxy, hydroxy, amido or amino group with a free hydrogen attached to the nitrogen can be condensed with ethylene oxide or with the polyhydration productthereof, polyethylene glycol, to form a nonionic detergent. The length of the hydrophilic or polyoxyethylene chain can be readily adjusted to achieve the desired balance between the hydrophobic and hydrophilic groups.

The nonionic detergent employed is preferably a poly-loweralkoxylatedhigheralkanolwhereinthe alkanol has8to 22 carbon atoms, preferably lotto 18 carbon atoms, and wherein the number of moles of loweralkylene oxide (of or3 carbon atoms) is from 3 to 20. Of such materials it is preferred to employ those wherein the higheralkanol is a higher fatty alcohol of 11 to 1 carbon atoms and which contain from 5 to 13 lower alkoxy groups per mole. Preferably, the lower alkoxy group is ethoxy but in some instances it may be desirably mixed with propoxy, the latter, if present, usually being a minor (less than 50%) constituent.Exemplary of such compounds are those wherein the alkanol is of 12to 15 carbon atoms and which contain about7 ethylene oxide groups per mole, e.g. Neodol (Registered Trademark) 25-7 and Neodol 23-6.5, which products are made by Shell Chemical Company, Inc. The former is a condensation product of a mixture of higherfatty alcohols averaging about 12to 15 carbon atoms, with about7 moles of ethylene oxide and the latter is a corresponding mixture wherein the carbon atom content of the higherfatty alcohol is 12 to 13 and the number of ethylene oxide groups per mole averages about 6.5.

The higher alcohols are primary alkanols. Other examples of such detergents include Tergitol (Registered Trademark) 15-2-7 and Tergitol 15-S-9, both of which are linear secondary alcohol ethoxylates made by Union Carbide Corporation. Theformer is a mixed ethoxylation product of an 11 to 15 carbon atom linearsecondaryalkanol with seven moles of ethylene oxide and the latter is a similar product but with nine moles of ethylene oxide being reacted.

Highly preferred nonionics useful in the present compositions arethe higher molecularweight nonionic detergents, such as Neodol 45-11, which are similar ethylene oxide condensation products of higherfatty alcohols, the higherfatty alcohol being of 14to 15 carbon atoms and the number of ethylene oxide groups per mole being about 11. Such products are also made by Shell Chemical Company.

Ofthetotal surface-active detergent ingredients in the detergent composition, the nonionic surfactant may be present in amounts of up to about 70% by weight, preferably up to about 50%, more preferably uptoabout40% and especially preferably upto about 15%.Usually, the nonionic surfactantwhen used will be present in amounts of at least 1 %, preferably at least 10%, especially preferably at least 30% of the combined weights of all ofthe surface-active detergent ingredients. In terms ofthe total softenerdetergent composition, the nonionic surfactant compound will usually be present in amounts within the range offrom about 0.1 to 20%, preferably 0.3 to 15%, especially preferably 0.6 to 10%, byweight.

Since the nonionic surfactant compounds are often only sparingly soluble in water or form viscous solutions or gels when added to water they are usually made available in the form of organic solvent solutions, for example, in ethanol or isopropanol, alone ortogether with water. Accordingly, when the nonionic surfactant compound is obtained in the form of its organic solvent solution, it will not be included as part ofthe crutcher mix used to form the spray-dried granules or beads, but rather, will be post-added to the already-formed spray-dried beads.

Moreover, even where the nonionic surfactant compound is used in its pure liquid form (most ofthe nonionics being liquid at ambienttemperatures) or as an aqueous solution, it is still preferred to post-add the nonionic surfactant compound to the spray-dried beads.

Zwitterionic detergents such as the betaines and sulphobetaines having the following formula are also useful:

where R8 represents an alkyl group containing from about 8 to 18 carbon atoms, R9 and R10 each independently represent an alkyl or hydroxyalkyl group containing about 1 to 4carbon atoms, R represents an alkylene or hydroxyalkylene group containing 1 to 4carbon atoms, and Y represents a carbon atom oran S:O group. The alkyl group can contain one or more intermediate linkages such as amido, ether, or polyether linkages or nonfunctional substituents, such as hydroxyl or halogen which do not substantially affect the hydrophobic character of the group.When Y represents a carbon atom,the detergent is called a betaine; and when Y represents an S:O group, the detergent is called a sulphobetaine orsultaine.

Ampholytic detergents are also suitable forthe invention. Ampholytic detergents are well known in the art and many operable detergents of the class are disclosed by Schwartz, Perry and Berch in the aforementioned "SurfaceActiveAgents and Detergents". Examples of suitable amphoteric detergents include: alkyl betaiminodipropionates, RN(C2H4COOM)2; alkyl beta-amino propionates, RN(H)C2H4COOM; and long chain imidazole derivatives having the general formula

wherein in each of the above formulae R represents an acyclic hydrophobic group containing from about 8to 18 carbon atoms and M is a cation to neutralize the charge ofthe anion.Specific operable amphoteric detergents include the disodium saltofundecylcyc- loimidinium -ethoxyethionic acid - 2 - ethionic acid, dodecyl beta alanine, and the inner salt of 2 -trimethylamino lauric acid.

The amounts ofthe zwitterionic synthetic organic detergent and the ampholytic synthetic organic detergent when present in the compositions ofthe present invention are not particularly critical and can be selected depending on the desired results. Generally, either or both of these classes of detergent ingredients can be used to replace all or part ofthe anionic organic detergent surfactant and/or nonionic organic detergent su rfactantwithin the rangesdis- closed above.

As with the anionic and nonionic surfactant compounds, the practitioner will be readily able to determine whether two include the zwitterionic and ampholytic surfactant as a component ofthe crutcher mix used to form the spray-dried beads orgranules or to post-add these compounds to the spray-dried beads to form the final heavy duty built laundry detergent composition. Briefly, when available as aqueous solutions, they will preferably be added to the crutcher mix and when available in organic solvents, they will be post-added to the spray-dried beads.

The clay softener may be selected from any ofthe clay softeners known in the artto impart softness to fabrics laundered therewith. The preferred clays are smectite clay materials.

The smectite-type clays useful in the present invention arethree-layer clays characterised by the ability ofthe layered structureto increase its volume several-fold by swelling or expanding when in the presence ofwaterto form a thixotropic gelatinous substance. There are two distinct classes of smectitetype clays: in the first class, aluminium oxide is present in the silicate crystal lattice; in the second class, magnesium oxide is present in the silicate crystal lattice. Atom substitution by iron, magnesium, sodium, potassium, calcium and the like can occur within the crystal lattice of the smectite clays. It is customary to distinguish between clays on the basis of their predominant cation. For example, a sodium clay is one in which the cation is predominantly sodium.

The smectite clays used in the compositions herein are all commercially available. Such clays include, for example, montmorillonite, volchonskoite, nontonite, hectorite, saponite, sauconite, and vermiculite. These clays are available under various tradenames, for example,ThixogelNo.1 (also, "Thixo-Jei") and Gelwhite GPfrom Georgia Kaolin Co., Elizabeth, New Jersey; Volclay BC and Volclay No.325, from American Colloid Co., Skokie, Illinois. It is to be recognised that such smectite-type minerals obtained underthe foregoing tradenames can comprise mixtures ofthe various discrete mineral entities.

Such mixtures ofthe smectite minerals are suitable for use herein.

In the compositions ofthe present invention, the most preferred ofthe clay softeners are the aluminium silicates, wherein sodium is the predominate cation, such as, for example, bentonite clays. Among the bentonite clays, those from Wyoming (generally referred to as western or Wyoming bentonite) are especially preferred.

Preferred swelling bentonites are sold under the trademark Mineral Colloid, as industrial bentonites, by Benton Clay Company, an affiliate of Georgia Kaolin Co.

These materials which are the same as those formerly sold underthe trademarkTHIXO-JEL, are selectively mined and beneficiated bentonites, and those considered to be most useful are available as Mineral Colloid Nos. IOl,etc., corresponding to THIXO-JEL's Nos. 1,2,3, and 4. Such materials have pH's (6% concentration in water) in the range of 8 to 9.4, maximum free moisture contents of about 8% and specific gravities of about2.6, and forthe pulverized grade at least about85%) (and preferably 100%) passes through a 200 mesh U.S. Sieve Series sieve (which has openings 74 microns across).More preferably, the bentonite is one wherein essentially all ofthe particles (i.e. at least 90% ) thereof, preferably over 95% ) pass through a No.325 sieve (U.S. Sieve Series) (which has openings 44 microns across) and most preferably all the particles pass through such a sieve. The swelling capacity of the bentonites in water is usually in the range of 3to 15 ml/gram, and its viscosity, at a 6%) concentration in water, is usually from about8to 30 centipoises.

Instead of utilizing the THIXO-JEL or Mineral Colloid bentonities one may employ products, such as that sold by American Colloid Company, Industrial Division, as General Purpose Bentonite Powder, 325 mesh, which hasa minimum of 95% thereoffiner than 325 mesh or44 microns in diameter (wet particle size) and a minimum of 96% finerthan 200 mesh or74 microns diameter (dry particle size). Such a hydrous aluminium silicate is comprised principally of montmorillonite (90% minimum),with smaller proportions offeldspar, biotite and selenite.Atypical analysis, on an "anhydrous" basis, is 63.05% silica, 21.5% alumina, 3.3% offerric ion (as Fe2O3), 0.4%) of ferrous iron (as FeO), 2.7% of magnesium (as MgO), 2.6% ofsodium and potassium (as Na2O), 0.7% of calcium (as CaO), 5.6% of crystal water (as H2O) and 0.7% oftrace elements.

Although the western bentonites are preferred, it is also possible to utilize other bentonites, such as those which may be made by treating Italian or similar bentonites containing relatively small proportions of exchangeable monovalent metals (sodium and potassium) with alkaline materials, such as sodium carbonate, to increase the cation exchange capacities of such products. It is consideredthatthe Na2O content ofthe bentonite should be at least about 0.5%, preferably at least 1 % and more preferably at least 2% so thatthe clay will be satisfactorily swelling, with good softening and dispersing properties in aqueous suspension.Preferred swelling bentonites of the types described above are sold underthetradenames Laviosa and Winkelmann, e.g.

LaviosaAGBandWinkelmann G-13.

Naturally, anyotherclay minerals which are substantiveto and are capable of imparting "softness" to textile materials can be used in the present invention.

The preferred clays used herein are "impalpable", i.e. have a particle size which cannot be perceived tactiley. Impalpable clays have particle sizes below about 50 microns; the clays used herein have a particle size range of from about 5 microns to about 50 microns.

The clay softener compounds are present in the detergent compositions at levels of from about 1 to about 50 percent, preferably from about 2 to 30%, especially preferably from about 4to 20%, by weight, based onthetotalcomposition.

In the present invention, it is highly preferred that the clay softener be post-added to the antistat containing spray-dried beads or granules so asto avoid any interaction, e.g. ion-exchange, between the clay mineral particles and the cationicdiammonium compound antistatic agent. Thus, sincethe diammonium compound is homogeneously and very finely distributed throughoutthe spray-dried beads as a result ofthe crutching and spray-drying operations and since the post-added ingredients contact the spray-dried beads under substantially an hydrous conditions there will be substantially non ion-exchange between the clay softener and cationic diammonium salt antistatic agent.

The clay softener is present in the detergent compositions ofthe present invention in an amount sufficient to provide the desired softening effect when the composition is used in conventional amounts for laundry detergent compositions, e.g.

from about 1/8 to 11/2 cups of detergent per load of wash.

The detergent compositions of the present invention optionally, but preferably, contain at least one detergent builder of the type commonly used in detergent formulations. Useful builders include any of the conventional inorganicwater-soluble builder salts, such as, for example, water-soluble salts of phosphates, pyrophosphates, orthophosphates, polyphosphates, tripolyphosphates, silicates, car bonates, bicarbonates, borates, sulphates, and the like. Organic builders include water-soluble phos phonates, polyphosphonates, polyhydroxysulphon- ates, polyacetates, aminopolyacetates, carboxylates, polycarboxylates, succinates, phytates, and the like.

Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, pyrophosphates and hexametaphosphates. The organic polyphosphonates specifically include, for example, the sodium and potassium salts of ethane 1 - hydroxy - 1,1 -diphosphonicacidandthesodium and potassium salts of ethane - 1,1,2 -triphosphonic acid. Examples ofthese and other phosphorous builder compounds are disclosed in U.S. Patent Nos.

3,213,030; 2,422,021; 3,422,137 and 3,400,176. Pentasodium tripolyphosphate and tetrasodium pyrophosphate are especially preferred water-soluble inorganic builders.

Specific examples of non-phosphorous inorganic builders include water-soluble inorganic carbonate, bicarbonate and silicate salts. The alkali metal, for example, sodium and potassium, carbonates, bicarbonates and silicates are particularly useful herein.

Water-soluble organic builders are also useful. For example,thealkali metal,ammoniumandsubsti- tuted ammonium acetates, carboxylates, poiycarboxylates and polyhydroxysulphonates are useful builders forthe compositions and processes ofthe present invention. Specific examples of acetate and polycarboxylate builders include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diaminetetracetic acid, nitrilotriacetic acid, benzene polycarboxylic (i.e. penta- and tetrat-) acids, carboxymethoxysuccinic acid and citric acid.

Additional organic builder salts useful herein include the polycarboxylate materials described in U.S. Patent No.2,264,103, including the watersoluble alkali metal salts of mellitic acid. The watersoluble salts of polycarboxylate polymers and copolymers such as are described in U.S. Patent No.

3,308,067, are also suitable herein.

Water-insoluble builders may also be used, particu larly,the complex silicates and more particularly, the complex sodium alumino silicates such as, zeolites, e.g. zeolite 4A, a type of zeolite molecule wherein the univalent cation issodium and the pore size is about 4 A. The preparation of such type of zeolite is described in U.S. Patent 3,1 14,603.Thezeolites may be amor- phous or crystalline and have water of hydration as known in the art.

Mixtures of organicand/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. It is to be understood thatwhilethe alkali metal salts oftheforegoing inorganic and organic polyvalent anionic builder salts are preferred for use herein from an economic standpoint, the ammonium, alkanol ammonium, e.g.

triethanol ammonium, diethanol ammonium, and the like, water-soluble salts of any of the foregoing builder anions are useful herein.

The buildersalts, including both the inorganicand organic detergent builder salts are conveniently added to the crutcher mix to be included with the antistatic diammonium compound antistatic agent, anionic surfactant, etc., in the spray-dried beads or granules ofthe present invention to provide from about5to about 90%, preferablyfrom about 15to 65%, especially preferably from about 20 to 55%, by weight, of builder salts based on the weight ofthe spray-dried beads so as to provide in the finished composition, after mixing with the post-added ingre dients,from about 2 to 80%, preferably 10 to 70%, and especially preferably 20 to 50% of detergent builder salt(s), based on the total composition.

The antistatic agent compounds used in the present invention are diammonium compounds which are characterised by theirwater-solubility, i.e. ability to form stable, clear solutions, or dispersions in water at 25"C containing at least 5%, preferably at least 10%,byweightofthediammonium compound.

The diammonium compounds useful herein for reducing static chage buildup arethe water-soluble compoundsofthefollowing general formula (I)

wherein R1 represents an aliphatic hydrocarbon having from about 12 to about 30 carbon atoms; each of R2, R3, R4, R5 and R6 independently represent aliphatic hydrocarbon groups having from 1 to 22 carbon atoms with the proviso thatthe total number of carbon atoms in all the aliphatic hydrocarbon groups, including R1, is no more than about 75 and with thefurther proviso that no more than three of the R2-R6 groups have more than 12 carbon atoms; or alkanol groups offormula (II)

wherein m and n are independently 0 or positive numbers, with the sum of m and nfrom all the groups R2-R6 being at least 2 but no more than 30; with the still further proviso that at least one of R2-R6 is the said alkanol group; R7 is a divalent linking radical, such as CrC5 lower alkyleneorsubstituted C2-C5 lower alkylene, kisanumberoffrom 1 to 20, and Xis a water-soluble saltforming anion.

The preferred compounds offormula (I) are those containing only 1 or2, preferably only a single long carbon chain group, i.e. 12 or more carbon atoms.

Accordingly, in formula (I)the preferred definitions for R1-R6 are: R1 represents an aliphatic hydrocarbon group, which may be straight chain or branched chain, and saturated or unsaturated (i.e. linear or branched alkyl, alkenyl or alkynyl), having from 16 to 22 carbon atoms; R2-R6, independently, represent an alkyl or alkenyl group having from 1 to 16, preferably 1 to 12, especially preferably 1 to 6 carbon atoms, with the proviso thatthe total number of carbon atoms in all the aliphatic hydrocarbon groups R1-R6 is no more than about50, preferably no morethan about35,and with the further proviso that no more than 2, preferably no more than 1, and most preferably none of R2-R6 have more than 12 carbon atoms; and alkanol groups of the formula (C2CH2O)m(C(CH3 )CH2C2O)n wherein m and n may be 0 or a positive number such thatthesumofm plusn in all ofthealkanol groups R2-R6 is at least 3 but no more than 25, preferably no more than 15, with the still further proviso that at least one, preferably atieasttwo of R2-R6 is the said alkanol group;; R7 is an alkyleneof2to 4carbon atoms, such as ethylene (-CH2CH2-), propylene (-CH2CH2CH2-), isopropylene (-CH2CH(CH3)CH2-), butylene (-CH2CH2CH2CH2-), etc., or such alkylene having one or more, such as one or two, substitutents, such as hydroxyl, C1-C4 lower alkyl, hydroxylower (C1-C4) alkyl, etc., preferably -CH2CH2- or -CH2CH2CH2-, most preferably -CH2CH2CH2- k is from 1 to 10, preferably 1 to 5, especially preferably 1 to 3; and X is a water-soluble salt-forming anion, such as, for example, halide, e.g. bromide, chloride or iodide, sulphate, methosulphate, ethosulphate, hydroxide, acetate, propionate, or other similar inorganic or organic solubilizing monovalent anion.

Examples of preferred R1 groups include stearyl, tallow, hydrogenated tallow, eicosyl, soya, and the like.

Examples of preferred alkyl and alkenyl groups for R2to R6 include, methyl, ethyl, propyl, isopropyl, n-butyl,tertbutyl, n-butenyl, octyl, 1-octenyl, etc.

Methyl, ethyl, propyl and isopropyl are especially preferred. Methyl and ethyl are most preferred Examplesofpreferredalkanol groups for R2to R6 include ethanol (n=O, m=1); propanol (m=0, n=l) and ethoxy-, propoxy-, and mixed (ethoxy)(propoxy) ethanol and/or propanol, such as (CH2CH2O)m1 H, where m' is from 2 to 4;

where nl is 2 to 4, and (CH2CH2O)mI(CH(CH3)C520)nl where my and no are each numbers offrom 1 to 4 and ml + n' = 2 to 6.In the mixed ethoxy-propoxy alkanol groups, the order of addition ofthe ethoxy and propoxy groups is not critical and it is understood that either blocks ofthe ethoxy groups or blocks ofthe propoxy groups can be bonded to the N-atom ofthe diammonium compound orthatthe methoxy and propoxy groups may be randomly distributed. Thus, as is well known in the art, the distribution ofthe ethoxyand propoxygroupswill be determined bythe order in which the ethylene diamine or propylene diamine compound is condensed with ethylene oxide (or its precursor) and propylene oxide (or its precursor).

Specific examples of compounds offormula (I) which are either commercially available or readily manufactured by customary techniques include

etc. and the corresponding ethosulphate, halide, acetate, etc., water-soluble salts.

The above compound (2) (N - methyl - N - (2 - hydroxy-ethyl) - N -tallowalkyl - N'- methyl - N'bis(2 - hydroxyethyl) - propylene - diammonium methylsulphate is especially preferred. This compound is commercially available as Rewoquat DQ35 from Rewo Chemicals Co. of Germany and is a clear liquid solution with 35% solids dissolved therein.

Rewoquat DQ35 has a free amine content of less than 2% byweightand has a pH (1% solution in water) in the range offrom 3.5 to 5. This compound can be prepared in customary manner, for example, by reacting 1 mole of N -methyl - N -tallow-alkyl - N' methyl propylene diamine with 3 moles ethylene oxide and then quaternizing the resulting compound with methylsulphate. By ethoxylating with more than 3 moles ethylene oxide, the corresponding higher ethoxylated compounds can be prepared.

It is a critical feature ofthe present invention that the diammonium salt antistatic agent has the specified degree of water solubility but not be so water soluble as to be only difficultly exhaustible from the washing liquor during use ofthe detergent-softener composition. Generally, a degree of solubility upto about 50% byweight at 255C is sufficient to provide the required static charge reducing capability on laundered fabrics.

The aqueous (organic solvent-free) solution (or dispersion) ofthe diammonium salt antistatic agent is added to the crutcher mix together with the remaining pH insensitive and heat stable ingredients, such as builder(s), fillers, anionic surfactant, pH adjusting agent, water, etc., and the mixture is then spray-dried according to customary techniques. The amount of the antistatic agent in the crutcher mix is such thatthe spray-dried beads or granules will contain from about 0.4to 15%, preferably from 1 to 12%, especially preferably from about 2 to 12%, by weig ht of the beads, ofthe antistatic agent compound offormula (1). The antistatic agent is finely distributed completely homogeneously in the spray-dried beads and can most effectively exhibit its antistatic function without interfering with the other functional ingredients.

The antistat-containing spray-dried beads are then intimately mixed with the clay softener and remaining ingredients, e.g. nonionic surfactant, bleach, enzymes, perfumes and other pH or heat sensitive and/or water-insoluble ingredients to prepare the final softener-detergent-antistatic agent composition.The amount ofthe spray-dried beads and post-added ingredients is such that the final composition has the following amounts ofthe essential ingredients: Amount (wt%) Ingredient Broad Intermediate Preferred Detergent 1-95 5-50 5-30 Builders 2-80 10-70 20-50 Clay Softener 1-50 2-30 4-20 Diammonium Salt 0.2-5 0.4-3 0.5-2.5 (Compound of formula (I)) Detergent Additives, 0-60 2-50 5-30 Fillers, Moisture The balance ofthe composition, if any, will be filled by the conventional detergent additives, fillers, and moisture.

The use of an inert, water-soluble fillersalt is desirable in the laundering compositions ofthe invention. A preferred filler salt is an alkali metal sulphate, such as, potassium or sodium sulphate, h latter being especially preferred. The amount offille; will generally be upto about 5%, such as 0.1 to 2%, preferably 0.3 to 1%, by weight of the composition.

Various adjuvants may be included in the laundry detergent compositions ofthe present invention. In general,these include perfumes, colourants, e.g.

pigments and dyes; bleaches, such as sodium perborate, bleach activators, bleach stabilizers, antiredeposition or soil suspending agents, such as, alkali metal salts ofcarboxymethylcellulose; optical brighteners, such as, anionic, cationic or nonionic brighteners; foam stabilizers, such as, alkanolamides,foam boosters, germicides, antftarnishing agents, pH adjusting agents, enzymes and the like, all of which are well-known in the fabric washing art for use in detergent compositions. Flow promoting agents, commonly referred to as flow aids, may also be employed to maintain the particulate compositions as free-flowing beads or powder.Starch derivatives and special clays are commercially available as additives which enhance theflowability of otherwise tacky or pasty particulate compositions, two of such clay additives being presently marketed underthe tradenames "Satintone" and "Microsil". Bound wa terandfreewaterin minoramountswhich do not adversely effecttheflowability ofthe granular or powdery compositions may also be present in the detergent compositions. Amounts of moisture will normally befrom 1 to 15%, preferably 5 to 12%, most preferably 8 to 12% ofthe entire composition.Within these proportions, a satisfactorily flowing particulate, pulverulentorgranularproduct results; which, by control of particulate size and moisture content, can be prevented from being excessively dusty.

Suitable ranges ofthe detergent additives are: enzymes -- to 2%, especially 0.2 to 1%; corrosion inhibitors-about0to 15%, and preferably 2 to 8%; anti-foam agents and suds-su ppresso rs -- O to 15%, preferably Oto 8%,for example O.1 to 5%; soil suspending or antiredeposition agents and anti yellowing agents-Oto 10%, preferably 0.3 to 3%; colourants, perfumes, brighteners and bluing agents total weight0% to about 2% and preferably0% to about 1%, such as 0.2 to 0.8%; pH modifiers and pH buffers-0to 5%, preferably 0 to 2%, bleaching agent -0% to about 40% and preferably 0% to about 25%, for example,2 to 20%; bleach stabilizers and bleach activators 0 to about 15%, preferably O to 10%, for example, 0.1 to 8%. In the selections ofthe adjuvants, they will be chosen to be compatible with the main constituents ofthe detergent composition.

Whatever the form ofthe laundry detergent, its use in the washing process is essentially the same. The particulate composition is usually added to wash water in an automatic washing machine so that the concentration thereof in the wash water may range from about 0.05to 1.5%, usually 0.1 to 1.2%. The water to which it is added will preferably be of medium or low hardness, e.g. from 30 to 120 parts per million of hardness, as calcium carbonate, but both softer and harder waters may be usefully employed.

The watertemperature can be from 205Cto 1 005C and is preferablyfrom 600 to 1 005C in those caseswhere thetextile or laundry is capable of withstanding high temperatures without deterioration or fading of dyes.

When low temperature laundering is desired, the tempernture may be held at 20 to 40 C.

Withe concentrations of detergent composition mentioned, the pH ofthe wash water will usually be on the alkaline side,for examplefrom 7 to 12, preferablyfrom 8 to 11, especially from 9 to 10. The laundry:wash waterweight ratio will usually be from about 1 :4to 1 :30, preferabiy 1: 10 to 1:30.

The invention may be put into practice in various ways and a number of specific embodiments will be described to illustrate the invention with reference to the accompanying examples. Unless otherwise indicated, all parts and percentages are by weight.

EXAMPLE 1 Thefollowing composition is prepared by first forming the spray-dried beads (A) as set out in Table 1 and then post-adding the components (B) as set out in Table 2.

TABLE 1 "A"(Spray-driedBeads) Parts Tap Water 6.8 Hydrogenatedfish oil ortallowoil fatty acids NaOH (35.7%) 1.3 Tap Water 11.5 Sodium Silicate (40%)Na20:SiO2) 9.9 Anionic Surfactant1 16.0 Optical Brightener2 0.2 Sodium Carboxymethyl cellulose 0.7 Pentasodium Tripolyphosphate 36.4 Rewoquat DQ35 (30% diammonium compound) 4.7 Sodium sulphate (anhydrous) 0.7 Total: 91.03 Notes on Table 1: Linear dodecyl benzenesulphonate-as aqueous slurry.

2 Stilbene brightener No.4, high conc. granule.

3 64.2 parts afterdrying.

TABLE 2 Post added Ingredients (BJ Parts Sodium Perborate 15.0 Blue bentonite clay agglomerate 16.0 Enzyme 0.5 Magnesium silicate/DTPA mix No. 2 0.2 Potassium Methyl Siliconate (50%) 0.6 Nonionic surfactant4 3.0 Duet 787 (perfume) 0.5 Spray dried beads (A) 64.2 Total: 100.0 Note on Table 2: 4 C14-Clsfattyalcohol ethoxylatedwith 11 moles ethylene oxide per mole.

The concentration ofthe Rewoquat DO35 antistatic agent in the final composition was 1.63%.

For compa rison, the same com position was prepared except that the Rewoquat DQ35 was not used.

Each ofthe compositions was tested for their static charge reducing capability on four different types of fabric: acrylic; polyester; polyester/cotton blend; and nylon.

In Tables 3A and 3B below the results are reported for electrostatic charge values obtained by Bauman's instrumental method. l n Ta bles 4A and 4B below arse reported the results of an independent expert of degree of static charge (O=no charge to 3=highly charged). All data are obtained afterwashing at60 C and drying atfull dryer power in a Miele dryerfor40 minutes. The instrumental readingsweretaken after conditioning at 20"C and 40% relative humidity. Also shown in Table 3 and 4 arethe results for a second series of tests in which the composition of the present invention was compared with a commercially available softener-detergent-antistat powder composition (tallowtrimethyl ammonium chloride-2%, ditallow methylamine salt-4%).

TABLE 3A BAUMAN MEASUREMENTS (VOLTS)** I, Fabric Product Acrylic Polyester Run 1* Run 2* Run 1* Run 2* A+B 275 88 (invention) A+Bwithout 1038 219 Rewoquat DQ35 (comparison) A+B 538 438 350 131 (invention) Commercial 613 588 138 131 Product TABLE 3B BAUMAN MEASUREMENTS (VOLTS)** Cotton Product Polyester Nylon Run 1* Run 2* Run 1* Run 2* A+B 35 550 (invention) A+Bwithout 81 775 Rewoquat DQ35 (comparison) A+B 225 131 475 600 (invention) Commercial 131 188 650 588 Product * Each run is based on the average val ue for a total of 9 washings.

** The higherthevoltage reading the higherthe static charge buildup.

TABLE 4A JUDGE EVALUATION OF STATIC CHARGE Polyester Product Acrylic Polyester Cotton Run 1* Run 2* Run 1* Run 2* Run 1 Run 2* A+B O 0 0 (invention) A+B 2 1 0 (without Rewoquat) A+B 2 1 1 0 1 0 (invention) Commercial 2 2 1 2 0 0 Product * Each run is based on the average evaluation for a series of 9 washing.

TABLE 4B JUDGE EVALUATION OF STATIC CHARGE Product Nylon Full Load Run 1* Run 2* Run 1* Run 2* A + B 0/1 0 (invention) A+B 2 2 (without Rewoquat) A + B 2 1 0/1 0 (invention) Commercial 2 2 0/1 0 * Each run is based on the average evaluation for a series of 9 washing.

The softening, cleaning and whitening evaluation ofthe composition (A + B) ofthe invention showed that there was no negative effect on these performance parameters as compared to the formulation A + B without the Rewoquat DO35 antistatic agent.

EXAMPLE 2 When in Example 1, the same amount of Rewoquat DQ35 as used in componentAwas used instead with the post-added component B, the static charge reducing capabilitywas diminished.

EXAMPLE 3 Following the same general procedure as in Example 1, the following composition given in Tables 4and5isprepared: TABLE 4 Spray Dried Beads "A" Wt% Sodium tridecyl benzene sulphonate 15.0 Pentasodium tripolyphosphate 33.0 Sodium silicate (1Na20:2.4SiO2) 7.0 Sodium sulphate 4.0 Optical Brightener (Tinopal 5BM) 0.2 Na Carboxymethyl cellulose 0.25 RewoquatDQ35 1.8 NaOH (40%) 1.75 Subtotal 63.0 TABLE 5 Post-Added "B" Thixogel No. 1 clay 18.0 Sodium perborate 14.0 Enzyme 0.5 Potassium methyl siliconate 0.6 Nonionic surfactant1 3.0 Magnesium Silicate/DTPA Mix No. 2 0.3 Duet 787 0.6 Subtotal 37.0 Total 100.0 Note on Table 5 1 C12-C14fattyalcohol condensed with 9 moles ethylene oxide per mole.

EXAMPLE 4 The following composition given in Tables 6 and 7 is prepared by following the same general procedure in Example 1: TABLE 6 Spray-dried base beads "A" Wt% Anionic surfactant 16.6 Sodium tripolyphosphate 43.3 Sodium silicate 5.8 Sodium sulphate 10.0 Rewoquat DO35 2.0 Na Carboxymethyl cellulose 0.3 Subtotal 80.0 TABLE 7 Post-added "B" Nonionic2 60 Optical Brightener 0.2 Enzyme 0.6 Perfume 0.2 Gelwhite GP 13.0 Subtotal 20.0 Total 100.0 Aloes on Tables 6and 7: 1.22:1 ratio of sodium tallow alkylsulphate: sodium dodecylbenzene sulphonate.

coconut alcohol ethoxylate (EO=14:1).

Claims (16)

1. An antistatic laundry detergent composition in solid form and which is compatible with clay mineral fabric softener, the said composition comprising spray-dried beads composed of a homogenous mixture of at least on pH and heat insensitive detergent compound selected from the group consisting of anionic synthetic detergents, nonionic synthetic de tergents,zwitterionicsyntheticdetergents, ampholytic synthetic detergents, and mixtures thereof; at least one pH and heat insensitive inorganic or organic detergent builder salt; Water-soluble diammonium compound antistatic agent selected from the compounds having the following formula (I)

wherein R1 represents an aliphatic hydrocarbon group having from about 12 to about 30 carbon atoms;; each of R2, R3, 4, 5 and R6 independently represent aliphatic hydrocarbon groups having from 1 to22 carbon atoms with the provisothatthetotat number of carbon atoms in all the aliphatic hydrocarbon groups, including R1, is no more than about 75 and with the further proviso that no more than three ofthe R2-R6 groups have more than 12 carbon atoms; or alkanol groups of the formula

wherein m and n are independently 0 or positive numbers with the sum of m and n from all ofthe groups R2-R6 being at least 2 but no more than 30; with the still further proviso that at least one of R2-R6 groups isthesaidalkanol group; R7 is a divalent linking radical, such as CrC5 lower alkylene or substituted C2-C5 lower alkylene, k is a number from 1 to 20, and X is a water-solublesaltforming anion; and, optionally one or more of pH and heat insensitive detergent additives, fillers and moisture.

2. An antistaticdetergent composition as claimed in Claim 1 in which at least one detergent compound comprises an anionic synthetic detergent and at least one detergent builder salt comprises an inorganic polyphosphate builder salt.

3. An antistatic detergent composition as claimed in Claim 1 or Claim 2 inwhich in theformula(l) R' represents a linear or branched alkyl, alkenyl or akynyl group having from 16 to 22 carbon atoms, R2-R6, independently, representalkyl or alkenyl groups having from 1 to 16 carbon atoms, with the proviso that the total number of carbon atoms in all the aliphatic hydrocarbon groups R'-R6 is no more than about 50, and with the further proviso that no more than 2 of R2-R6 have more than 12 carbon atoms, oralkanol groups offormula (II)

wherein m and n are, independently, 0 or a positive number such thatthesum of man from all ofthe alkanol groups R2-R6is at least3 but no more than 25, with the proviso that at least one ofthe groups R2 to R6 is the said alkanol group, R7 represents an alkylene group of 2 to 4 carbon atoms, oran alkylene group of 2to 4carbon atoms having a substituent selected from the group consisting of hydroxyl, C1-C4 loweralkyl and hydroxy-lower (C1-C4) alkyl; and kisa numberoffrom 1 to 10.

4. An antistatic detergent composition as claimed in Claim 1 or Claim 2 in which R2-R6, independently, represent alkyl oralkenyl groups offrom 1 to 6 carbon atoms orthe said alkanol groups with the provisos thatthetotal numberofcarbon atoms in all ofthe aliphatic hydrocarbon groups R'-R6is no morethan about 35 and the sum of m+n from all ofthe alkanol groups R2to R6 is no more than 15, R7 is -CH2CH2- or -CH2CH2CH2- and kis 1.

5. An antistatic detergent composition as claimed in any one of Claims 1 to4which comprises from about 1 Oto about 60% by weight ofthe said at least one detergent compound, from about5to about 90% byweightofthesaid at least one detergent builder salt, from about 0.4 to about 15% by weight ofthe said antistaticagent; and from about 0 to about 50% by weight of detergent additives, fillers, and moisture.

6. An antistatic detergent composition as claimed in any one of Claims 1 to 5which comprises on a weight basis from about 15to about40% of a linear higher alkylbenzene sulphonate anionic synthetic detergent; from about 5 to 55% of a zeolite builder; from about 1 to 12% ofthesaiddiammonium compound antistatic agent; and from about 5 to 40% of at least one member selected from the group consisting of pH insensitive and heat stable detergent additives, fillers, moisture and mixtures thereof.

7. An antistatic detergent composition as claimed in anyone of Claims 1 to 6which comprises on a weight basis from about 15to about40% of a linear higher alkylbeneze sulphonate anionic synthetic detergent; from about 15to 65% of an inorganic polyphosphate detergent builder; from about 1 to 12% ofthe said diammonium compound antistatic agent; and from about 5 to 40% of at least one member selected from the group consisting of pH insensitive and heat stable detergent additives, filler, moisture and mixtures thereof.

8. An antistatic detergent composition as claimed in any one ofthe preceding claims in which the said linear higher alkylbenzene sulphonate is dodecylben- zene sulphonate, the polyphosphate detergent builder is pentasodium tripolyphosphate, and the diammonium compound is

9. Acomposition as claimed in Claim 1 substantially as specifically described herein with reference totheaccompanying examples.

10. An antistatic-softening-detergentcomposi- tion comprising a clay softener in admixture with a spray-dried antistatic laundry detergent composition as claimed in any one of Claims 1 to 9.

11. Afree-flowing powdery or granular laundery detergent and softener and antistatic composition which comprises (A) from about 1 to about 95% by weight of at least one detergent compound selected from the group consisting ofanionic synthetic detergent, nonionic synthetic detergent, amphoteric synthetic detergent, zwitterionic synthetic detergent and mixturesthereof; (B) from about 1 to about 50% by weight ofa clay mineral fabric softener; (C) fromabout2toabout80%byweightofat least one detergent builder; and (D) from about 0.2 to 5% by weight of a diammo- nium compound antistatic agent having the formula (I)

where R1 represents an aliphatic hydrocarbon having from about 12 to about 30 carbon atoms; each of R2, R3, R4, R5 and R6 independently represent aliphatic hydrocarbon groups having from 1 to 22 carbon atoms with the proviso thatthe total number of carbon atoms in all the aliphatic hydrocar- bon groups, including R', is no morethan about 75 and with the further proviso that no more than three ofthe R2-R6 groups have more than 12 carbon atoms; oralkanol groupsoftheformula (11)

wherein m and n are independently 0 or positive numbers with thesum ofm and nfrom all ofthe groups R2-R6 being at least 2 but no more than 30; with the still further proviso that at least one of R2-R6 isthesaidalkanoigroup; R7 is a divalent linking radical, such as C2-C5 lower alkylene or substituted C2-C5 loweralkylene, k is a number of from 1 to 20, and Xis a water-soluble salt forming anion; and (E) fromOtoabout50% ofat least one of detergent additives, fillers and moisture.

12. Acomposition as claimed in Claim 11 in which the diammonium compound offormula (i) is present in the composition as a componentofa spray-dried bead comprised of the said diammonium compound; and anionic surfactant; detergent builder salt and optionally, pH insensitive and heat stable detergent additives, fillers and mixtures thereof, and the said clay fabric softener is uniformly blended with the said spray-dried beads.

13. A composition as claimed in Claim t 1 or Claim 12 in which theformula (I) R' represents a linear or branched alkyl, alkenyl or alkynyl group having from 16 to 22 carbon atoms; R2-R6, independently, represent alkyl orakenyl groups having from 1 to 16 carbon atoms, with the proviso thatthetotal number of carbon atoms in all the aliphatic hydrocarbon groups R1-R6 is no more than about 50, and with thefurther proviso that no morethan 2ofR2-R6havemorethan 12 carbon atoms, oralkanol groups oftheformula (II)

wherein m and n are, independently, 0 or a positive numbersuch thatthe sum of m+nfrom all of the alkanol groups R2-R6 is at least 3 but no more than 25, with the proviso that at least one ofthe groups R2 to R6 is the said alkanol group, R7 is an alkylene of2to4carbon atoms, oran alkylene of 2 to 4 carbon atoms having a substituent selected from thegroup consisting of hydroxyl, C,-C4 lower alkyl and hydroxylower(C1-C4) alkyl; and kisa numberoffrom 1 to 10.

14. A composition as claimed in Claim 13 in which R2-R6, independently, representalkyl oralkenyl groupsoffrom 1 to carbon atoms orthe said alkanol groups with the provisosthatthetotal number of carbon atoms in all ofthe aliphatic hydrocarbon g roups R'-R6 is no more than about 35 and the su m of m+nfrom all ofthe alkanol groups R2to R6 is no more than 15, R7 is -CH2CH2- or -CH2CH2CH2- and kis 1.

15. A composition as claimed in any one of Claims 11 to 14 in which the diammoniun compound antistatic agent is

16. Acomposition as claimed in Claim 11 substantially as specifically described herein with reference to the accompanying examples.