AU619733B2 - No phosphate fabric softening and detergent composition - Google Patents

Description

i 1 4 619733 COMMONWEALTH OF AUSTRALIA Patents Act 1952 COMPLETE S PECIF I CATI ON

(ORIGINAL)

Application Number Lodged Complete Specification Lodged Accepted Published Priority 20 February 1987 Related Art t* 1 i 1 0 Name of Applicant Address of Applicant Actual Inventor/s Address for Service COLGATE-PALMOLIVE COMPANY :300 Park Avenue, New York New York 10022, U.S.A.

Viviane DAFFE; Marcel GILLIS F.B. RICE CO.

Patent Attorneys 28A Montague Street, Balmatn N.S.W. 2041 Complete Specification for the invention entitled: NO PHOSPHATE FABRIC SOFTENING AND DETERGENT COMPOSITION The following statement is a full description of this invention including the best method of performing it known to us/m:- W1 2 This invention relates to a no phosphate laundry softergent, i.e. softening and detergent composition based on clay softener and cationic diammonium softener agent.

More particularly, this invention relates to a no phosphate laundry detergent composition containing detergent surfactant, clay softener, and a diammonium salt softener agent, to the method of preparing the composition and to the use thereof in laundering textile materials.

Powdery detergent compositions containing a detergent surfactant (anionic, nonionic, etc.), 7ith a clay softener and a cationic softener and/or antistatic agent, such as quaternary ammonium compound, quaternary, diammonium compound, etc., are known in the art. Representative of the patent literature in this field are U.S. Patents t- 15 3,862,058 (Nirschl, et. 3,886,075 (Bernardino); 3,915,882 (Nirschl, et. 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. The use of bentonites for softening textiles is known from British Patents 401,413 and 461,221.

While satifsfactory cleaning and softening performance has been achieved with the known clay softener 25 detergent compositions, it is desirable to reduce the amount of clay softener needed without adversely effecting the softening and cleaning performance of the compositions.

In addition the polyphosphate content of laundry detergents has been blamed for the undesirably high 30 phosphate content of surface water. An increased phosphate content in surface water has been found to contribute towards greater algae growth with the result that the biological equilibrium of the water can be adversely altered.

Recently enacted government legislation has been i 1 r 3 directed to reducing the amount of polyphosphate present in laundry detergents and in some jurisdictions in which polyphosphates have been a problem to require that the laundry detergents not contain any polyphosphate builders.

Accordingly, it is an object of this invention to provide a no phospiiate clay softener detergent composition containing a diammonium softener agent compound.

Another object of the invention is to provide a no phosphate laundry detergent composition in the form of spray-dried beads, wherein the spray-dried beads are mixed with a diammonium softener compound and a clay mineral fabric softener, and a method for preparing the cor-osition.

i, It is another object of this invention to provide a polyphosphate free built clay softener detergent powder :composition having a reduced clay softener content without negatively impacting cleaning, whitening or softening performance of the composition.

Still another object of this invention is to provide composition in which the diammonium salt cationic softener Ctr* agent and the clay softener can be post-added to the spray-dried beads or granules.

ScThese and other objects of the invention which will be more readily apparent from the following detailed aescription and preferred embodiments are achieved by using as the softener cationic compound a diammonium salt of the formula SV4 R- R *2 14

R

1 N R 5 .2X (I) R3

R

3a wherein R 1 is selected from the group consisting of an aliphatic hydrocarbon having from about 12 to about carbon atoms;stearyl, tallow, hydrogenated tallow, eicosyl and soya; each of the R 2

R

3

R

4

R

5 and R6 are independently I t i i t 4 selcted 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

R

1 is no more than about 75 and with the further proviso that no more than two of the R 2

-R

6 groups have more than 12 carbon atoms; and

R

7 is -CH2CH 2 or -CH2CH 2

CHC

2 and X is a water-soluble salt forming anion.

The diammonium compounds of formula can be dispersed in an aqueous or organic carrier and sprayed compounds can also be heated to a temperature above their melting temperatures and sprayed on to the detergent granules or beads. Alternately the diammnoium compounds can as an aqueous dispersion, organic solution or a melt be added to the clay softener and then mixed with the I detergent granules or beads. In accordance with the present invention, the desired level of softening 20 performance can be obtained using lower levels of the clay softener and without adversely effecting other detergent properties, including cleaning performance and whitening performance. Another advantage of the composition is that it is low foaming.

S 25 The diammonium softener compounds are soluble in conventional organic solvents and/or form stable dispersions in water. The dia uonium softener compounds ai i are generally insoluble in water. Since the diammonium salt softener agents of formula are available or can be prepared in organic solutions or aqueous dispersions they can be easily and safely handled in powder processing f, plants and can be readily sprayed onto or otherwise mixed with the heavy duty built granular or powdery laundry detergent compositions.

In a preferred embodiment of the invention the

I

5 diammonium softener agent and the clay softener agent are premixed and then incorporated as a post-addition ingredient to the spray-dried granules or powdery laundry detergent composition.

A typical heavy duty built spray-dried beads formulation incorporating the softener agent of formula and clay softener may include the following ingredients: Amount (Weight%) S I

I

It tiI S I I I

I

I t Ingredient Total Spray-Dried Composition Beads detergent surface-active compound 1-95 10-60 organic and inorganic detergent builders 2-80 15-90 clay softener 1-50 0 softener agent of formula 0.2-5 0 fillers 0-25 0-.10 20 bleach and bleach additives 0-25 optical brighteners, pigments, dyes 0-10 0.8 anti-foaming agents; suds suppressors, etc. 0-10 0-8 25 enzymes 0-5 0 pH adjusting agents, buffers, etc. 0-10 0-8 pH adjusting agents, buffers etc., 30 antiredeposition agent, perfume, etc. 0-5 0-3 water balance In a preferred method for preparing the heavy duty built granular or powdery softener-detergent composition II II Ir S I r it i

I

i; 6 the pH insensitive, heat stable detergent 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 formula 1 diammonium compound softener and clay mineral softener and with the ingredients of the formulation which are pH sensitive and/or heat sensitive or which may otherwise react with the anionic surfactant or other component 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, enzymes, perfume, nonionic surfactant, etc. The formula 1 diammonium compoud softener can be, as mentioned above, premixed with the clay softener and then rmixed with the spray-dried beads or granules. Formulation compounding procedures are well known in the art and the practitioner will be able to readily determine the optimum formulating conditions.

Synthetic Organic Detergent Compounds I The laundry detergent composition 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 S disclosures of which are hereby incorporated by reference. The total amount of the surface-active C 30 detergent compound or compounds can be as much as 95% by weight of the total detergent composition, although more preferred amounts are in the range of from about 1 to by weight, especially 5 to 50% by weight, and especially preferably from about 5 to 30% by weight of the total detergent composition.

L

1 l 7 The detergent compositions of the present invention preferably employ one or more anionic detergent compounds as the primary surfactants. The anionic detergent may be supplemented, if desired, with another type of surfactant, preferably nonionic detergent, especially when used in combination with a detergent builder salt.

Anionic Surfactants 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-solubilizing group selected from the group of sulphonate, sulphate, carboxylate, phosphonate and phosphate so as to form a water-soluble detergent.

Examples of suitable anionic detergents include Ssoaps, such as, the water-soluble salts the sodium, potassium, ammonium and alkanolammonium salts) of higher fatty acids or resin salts containing from about 8 to 20 carbon atoms and preferably 10 to 18 carbon atoms.

t t t Suitable faLty 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 of the fatty acid mixtures derived from coconut oil and tallow, for example, sodium coconut soap and potassium tallow soap.

The anionic class of detergents also include the water-soluble sulphated and sulphonated detergents having an aliphatic, preferbaly an alkyl, radical containing from about 8 to 26, and preferably from about 12 to 22 carbon atoms. (The term "alkyl" includes the alkyl portion of the higher acyl radicals.) Examples of the sulphonated anionic detergents are the higher alkyl mononuclear aromatic sulphonates, such as the higher alkyl benezene sulphonates containing from about 10 to 16 carbon atoms in r 8 the higher alkyl 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 hydroxyalkane sulphonates or mixtures of alkene sulphonates and hydroxyalkane sulphonates. The olefin sulphonate detergent may be prepared in a conventional manner by the reaction of sulphur trioxide (S03) with long chain olefins containing from about 8 to 25, and preferably from about 12 to 21 carbon atoms, such olefins having the formula RCH=CHR 1 wherein R respresents a higher alkyl group of from about 6 to 23 carbons and R 1 represents an alkyl group containing from about 1 to 17 carbon atoms, or hydrogen to form a mixture of sultones and alkene sulphonic acids which is then treated to convert the sultones to sulphonates. Other examples of Ssulphate or sulphonate detergents are paraffin sulphonates containing from about 10 to 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.P. Nos. 2,503,280; 2,507,088; 3,260,741; 3,372,188 and German Patent No. 735,096.

~Other suitable anionic detergents are sulphonated ethoxylated higher fatty alcohols of the formula RO(C2H 4 0)mSO 3 M, wherein R represents a fatty alkyl group of from 10 to 18 carbon atoms, m is from 2 to 6 (preferably having a value from about 1/5 to 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, or a higher alkyl benzene sulphonate wherein the higher alkyl 9 group is of 10 to 15 carbon atoms. The proportion of ethylene oxide in the polyethoxylated higher alkanol sulphate is preferably 2 to 5 moles of ethylene oxide groups per mole of anionic detergent, with three moles being most preferred, especially when the higher alkanol is of 11 to 15 carbon atoms. To maintain the desired hydrophile-lipophile balance, when the carbon atom content of the alkyl chain is in the lower portion of the 10 to 18 carbon atoms range, the ethylene oxide content of the detergent may be reduced to about two moles per mole whereas when the higher alkanol is of 16 to 18 carbon atoms in the higher part of the range, the number of ethylene oxide groups may be increased to 4 or 5 and in some cases to as high as 8 or 9. Similarly, the salt-forming cation may be altered to obtain the best solubility. It may be any suitably solubilizing metal or radical but will most frequently be an alkali metal, e.g., sodium, or ammonium. If lower alkylamine or alkanolamine tto groups are utilized, the alkyl groups and alkanol 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 t sulphate detergent is available from Shell Chemical Company and is marketed as Neodol (Registered Trademark) 25-3S.

The highly preferred water-soluble anionic detergent compounds are the ammonium and substituted ammonium (such as mono-, di- and triethanolamine), alkali metal (such as, sodium and potassium) and alkaline earth metal (such, calcium and magnesium) salts of the higher alkyl benzene sulphonates, olefin sulphonates and higher alkyl sulphates. Among the above-listed anionics, the most preferred are the sodium linear alkyl benzene sulphonates (LABS), and especially those wherein the alkyl group is a 10 straight chain alkyl radical of 12 or 13 carbon atoms.

The anionic surfactant will generally constitute the major detergent component and may comprise from about to 100% of the total surface active ingredients.

Preferably the anionic accounts for at least preferably at least 60%, especially preferably at least and up to about 99%, preferably up to about especially preferably up to about 80% of the total surfactant detergent ingredients.

The anionic surfactant compound will usually and preferably be included as a component of the spray-dried beads and will be added to the crutcher mix as an aqueous solution or dispersion, and preferably as a highly concentrated aqueas slurry.

Nonionic Surfactants The next most preferred class of surfactant detergent ingredient is the nonionic synthetic organic detergent 0r compounds.

EO The nonionic synthetic organic detergents are characterized 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 i t (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 Sproduct thereof, polyethylene glycol, to form a nonionic detergent. The length of the hydrophi polyoxyethylene chain can be readily a4, 'te. tco achieve v the desired balance between the hydrophob., and hydrophilic groups.

The nonionic detergent employed is preferably a poly-lower alkoxylated higher alkanol wherein the alkanol has 8 to 22 carbon atoms, preferably 10 to 18 carbon i 11 -11atoms, and wherein the number of moles of lower alkylene oxide (of 2 or 3 carbon atoms) is from 3 to 20. Of such materials it is preferred to employ those wherein the higher alkanol is a higher a fatty alcohol of 11 to carbon atoms and which contain from 5 to 13 lower alkoxy groups per mole. Preferably, the lower alkoxy group is ethoxy but in some instance it may be desirably mixed with propoxy, the latter, if present, usually being a minor (less that 50%) constituent. Exemplary of such compounds are those wherein the alkanol is of 12 to 15 carbon atoms and which contain about 7 ethylene oxide groups per mole, Neodol (Registered Trademark) 25-7 and Neodol 23-6.5, which products are mady by Shell Chemical Company, Inc. The former is a condensation product of a mixture of higher fatty alcohols averaging about 12 to 15 carobn atoms, with about 7 moles of ethylene oxide and the latter is a corresponding mixture wherein the carbon atoms 4 t content of the higher fatty alcohol is 12 to 13 and the number of ethylene oxide groups per mole averages about 6.5. The higher alcohols are primary alkanol. 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. The former is a mixed ethoxylation product of an 11 to 15 carbon atom linear secondary alkanol with seven moles of ethylene oxide and the latter is a similar t product but with nine moles of ethylene oxide being reacted.

Highly preferred nonionics useful in the present compositions are the higher molecular weight nonionic detergents, such as Neodol 45-11, which are similar S* ethylene oxide condensation products of higher fatty alcohols, the higher fatty alcohol being of 14 to carbon atoms and the number of ethylene oxide groups per mole being about 11. Such products are also made by Shell r 12 Chemical Company.

Of the total 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 up to about and especially preferaly up to about 15%. Usually, the nonionic surfactant when used will be present in amounts of at least preferably at least especially preferably at least 30% of the combined weights of all of the surface-active detergent ingredients. In terms of the total softener-detergent composition, the nonionic surfactant compound will usually be present in amounts within the range of from about 0.1 to preferably 0.3 to 15%, especially preferably 0.6 to by weight, Since the nonionic surfactant compounds are often t only sparingly soluble in water or form viscous solutions ti 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 or together 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 of the 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 f, Icompound is used in its pure liquid form (most of the nonionic being liquid at ambient temperatures) or as an aqueous solution, it is still preferred to post-add the 30 nonionic surfactant compound to the spray-dried beads.

SZwitterionic detergents such as the betaines and sulphobetaines having the following formula are also useful: 13

R

9

R

8

.N-R

1 X- 0 R 0 0 wherein R 8 represents an alkyl group containing from about 8 to 18 carbon atoms, R 9 and R 1 each independently represent an alkyl or hydroxyalkyl group containing about 1 to 4 carbon atoms, R 1 1 represents an alkylene or hydroxyalkylene group containing 1 to 4 carbon atoms, and X represents a carbon atom or an 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 haolgen which do not substantially affect the hydrophobic character of the group. When X represents a carbon atom, the detergent is called a betaine; and when X represents an S:O group, the detergent is called a sulphobetaine or 20 sultaine.

Ampholytic detergents are also suitable for the loss&: ,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 "Surface Active Agents and Detergents".

Examples of suitable amphoteric detergents include: alkyl *01 betairinodipropionates, RN(C 2

H

4

COOM)

2 alkyl 1. beta-amino propionates, RN(H)C 2

H

4 COOM; and long chain 4* imidazole derivatives having the general formula 30 C 2 N CH 2 SR-- C N---CH2 CH OCH 2

COOM

OH CH 2

COOM

wherein in each of the above formulae R represents an T 14 acyclic hydrophobic group containing from about 8 to 18 carbon atoms and M is a cation to neutralize the charge of the anion. Specific operable amphoteric detergents include the disodium salt of undecylcycloimidinum-ethoxyethionic acid-2-ethionic acid, dodecyl beta alanine, and the inner salt of 2-trimethylamino lauric acid.

The amounts of the zwitterionic synthetic organic detergent and the ampholytic synthetic organic detergent when present in the invention compositions 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 of the anionic organic detergent surfactant and/or nonionic organic detergent surfactant within the ranges disclosed above.

As with the anionic and nonionic surfactant compounds, the practitioner will be readily able to Sdetermine whether to include the zwitterionic and 20 ampholytic surfactant as a component of the crutcher mix f used to form the spray-dried beads or granules 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 water 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.

Clay Softener Compounds The clay softener may bs selected from any of the S* 30 clay softeners known in the art to impart softness to fabrics laundered therewith. The preferred clays are smectite clay materials, and those having an ion exchange capacity of at least about 50 meq/100 g clay millequivalents per 100 grams of clay) are preferred.

The smectite-type clay useful in the present I 15 invention are three-layer clays characterized by the ability of the layered structure to increase its volume several-fold by swelling or expanding when in the presence of water to form a thixotropic gelatinous substance.

There are two distinct classes of smectite-type clays: in the first class, aluminum 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 cation exchange capacity of a clay mineral relates to such factors as the expandable properties of the clay, the charge of the clay, which, in turn, is determined at least in part by the lattice structure and the like. The ion exchange capacity of clays varies S 20 widely in the range from about 2 meq/100 g for kaolinites to about 150 meq/100 g, and greater, for certain clays of .the montmorillonite variety. Illite clays have an ion exchange capacity somewhere in the lower portion of the range, around 26 meq./100 g for an average illite clay.

It has been determined that illite and kaolinite S'a clays, with their relatively low ion exchange capacities, are not or are only marginally useful as clay softener.

Indeed, such illite and kaolinite clays constitute a major 30 component of clay soils and, as noted above, are removed from fabric surfaces by means of the instant compositions. However, smectites, such as nontronite, having an ion exchange capacity of approximately meq/100 g, saponte, which has as ion exchange capacity of around 70 meq/l00g, and montmorillonite, which has an ion 16 exchange capacity greater than 70 meq/100 g, have been found to be highly useful softeners in that they are deposited on the fabrics to provide the desired softening benefits. Accordingly, preferred clay minerals useful herein can be characterized as expandable, three-layer smectite-type clays having an ion exchange capacity of at least about 50 meq/100 g. A smectite-type clay known as "fooler clay", found in a relatively thin vein above the Black Hills, also has the requisite ion exchange properties characteristic of the clays useful herein and such fooler clay is also encompassed by the term "smectite-type clay", as used herein.

The smectite clays used in the compositions herein are all commercially available. Such clays include, for example, montmorillonite, volchonskoite, nontronite, hectorite, saponite, sauconite, and vermiculite. These clays are available under various tradenames, for example, Thoxogel No. 1 (also, "Thixo-Jel") and Gelwhite GP from Georgia Kaolin Company, Elizabeth, New Jersey; Volclay BC S 20 and Volclay No. 325, from American Colloid Company, S- Skokie, Illinois; Black Hills Bantonite BH450, from t International Minerals and Chemicals; and Veegum Pro and t* Veegum F, from R.T. Vanderbilt. It is to be recognized that such smectite-type minerals obtained under the foregoing tradenames can comprise mixtures of the various discrete mineral entities. Such mixtures of the semctite minerals are suitable for use herein.

While any of the smectite-type clays having a cation exchange capacity of at least about 50 meq/100 g are especially useful herein, certain clays are preferred.

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-type clay mineral containing at least 3 percent of iron (expressed as Fe 2 03) in the crystal r r :Ij 17 lattice, and which has a very high ion exchange capacity, is one of the most efficient and effective clays for use in laundry compositions and is preferred form the standpoint of product performance.

Appropriate clay minerals for use herein can be selected by virtue of the fact that the smectites exhibit a true 14A X-ray diffraction pattern. This characteristic 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 granular detergent compositions disclosed herein.

In the compositions of the present invention, the most preferred of the clay softeners are the aluminum silicates, wherein sodium is the predominant 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.

o t Preferred swelling bentonites are sold under the trademark Mineral Colloid, as industrial bentonites, by S, Benton Clay Company, an affiliate of Georgia Kaolin Company. These materials which are the same as those formely sold under the trademark THIXO-JEL, are selectively mined and beineficiated bentonites, and those considered to be most useful are available as Mineral Colloid Nos. 101, 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 us free moisture contents of about 8% and specific gravities 30 of about 2.6, and for the pulverized grade at least about (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 where essentially all of the particles at least thereof, preferably over 95%) pass through a No. 325 sieve I' I 18 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 in usually :Ln the range of 3 to 15 ml/gram, and its viscosity, at a 6% concentration in water, is usually from about 8 to 30 centipoises.

Instead of utilizing the THIXO-JEL or Mineral Colloid bentonites one may employ products, such as that sold by American Colloid Company, Industrial Division, as General Purpose Bentonite Powder, 325 mesh, which has a minimum of thereof finer than 325 mesh or 44 microns in diameter (wet particle size) and a minimum of 96% finer than 200 mesh or 74 microns diameter (dry particle size). Such a hydrous aluminum silicate is comprised principally of montmorillonite (90% minimum), with smaller proportions of feldspar, biotite and selenite. A typical analysis, on an "anhydrous" basis, is 63.05% silica, 21.5% alumina, 3.3% ferric ion (as Fe 2 0 3 0.4% of ferrous iron (as FeQ), S2.7% of magnesium (as MgO), 2.6% of sodium and potassium (as NazO), and 0.7% of calcium (as CaO), 5.6% of crystal *water (as H 2 0) and 0.7% of trace elements.

Although the western bentonites are preferred, it is ttiO also possible to utilize other bentonites, such as those which may be made by treating Italian or similar bentonites containing relatively small proportions of exchangable monovalent metals (sodium and potassium) with alkaline materials, such as sodium carbonate, to increase the cation exchange capacities of such products, It is considered that the Na 2 0 content of the bentonite should 30 be at least about preferably at least 1% and more preferably at least 2% so that the clay will be satisfactorily swelling, with good softening and dispersing proporties in aqueous suspension. Preferred wret swelling bentonites of the types described above are sold under the tradenames Laviosa and Winkelmann, etg:, Laviosa 19 AGB and Winkelmann G-13.

Naturally, any other clay minerals which are substantive to and are capable of imparting "softness" to textile materials can be used in the present invention.

The preferred clays used herein are "impalpable", have a particle size which cannot be perceived tactilely. 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 levels of from about 1 to about percent, preferably from about 2 to 30%, especially preferably from about 4 to 20%, by weight, based on the total composition.

In the present invention, it is preferred that the clay softener and diammonium compound softener are post-added to the spray-dried beads or granules. The diammonium compound softener is preferably dissolved in an organic solvent or dispersed in an aqueous liquid and 20 mixed with the clay mineral particles. The diammonium compound softener and clay mineral softener are then thoroughly and evenly mixed with the spray-dried beads or t f f, granules.

The diammonium compound softener and clay softener are present in the invention detergent compositions in an amount sufficient to provide the desired softening effect ,when the composition is used in conventional amounts for laundry detergent composition, from about 1/8 to 1 1/2 cups of detergent per load of wash.

30 Detergent Builders The detergent compositions of the 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 inorganic water-soluble builder salts, such 20 as, for example, water-soluble salts of silicates, carbonates, bicarbonates, borates, sulfates, and the like. Organic builders include water-soluble polyhydroxy-sulphonates, polyacetates, aminopolyacetates, carboxylates, polycarboxylates, succinates, phytates and the like.

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.

The crystalline and amorphous aluminosilicate zeolites are particularly useful detergent builder salts.

The zeolites generally have the formula (M20)x (A120 3 )y (SiO 2 )z wherein x is 1, y is from 0.8 to 1.2 and preferably 1, z is from 1.5 to 3.5 or higher and preferably 2 to 3 and w is from 0 to 9, preferably 2.5 to 6 and M is preferably sodium. A typical zeolite is type A or similar structure, with type 4A particularly preferred. The preferred aluminosilicates have calcium ion exchange capacities of c about 200 milliequivalents per gram or greater, e.g.

*P0 400meg 1g.

Various crystalline zeolites alumino-silicates) that can be used are described in British Patent 1,504,168, U.S.P. 4,409,136 and Canadian Patents 1,072,835 X n and 1,087,477, all of which are hereby incorporated by reference for such descriptions. An example of amorphous zeolites useful herein can be found in Belgium Patent 30 835,351 and this patent too is incorporated herein by reference.

Water-soluble organic builders are particularly useful. For example, the alkli metal, ammonium and substituted ammonium acetates, carboxylates, polycarboxylates and polyhydroxy-sulphonates are useful t i 21 builders for the compositions and processes of the 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 penta- and tetra-) acids, carboxymethoxysuccinic acid and citric acid.

Additional organic builder salts useful herein include the polycarboxylate materials described in U.S.

Patent 2,264,103, including the water-soluble alkali metal salts of mellitic acid. The water-soluble salts of polycarboxylate polymers and copolymers such as are described in U.S. Patent No. 3,308,067, are also suitable herein.

Specific organic builder salts that can be used include alkali metal salts of hydroxy acrylic acid polymer, preferably the sodium and potassium salts. A Sparticularly preferred builder is the alpha-hydroxy acrylic acid and sodium salt polymers. The hydroxy acrylic acid and salt polymer detergent builder that can It" be used contains monomeric units of the formula

QH

-c c I I R 2 COOM wherein R i and R 2 can be the same or different and ,represent hydrogen or an alkyl group containing from 1 to 3 carbon atoms such as methyl, ethyl and propyl. The preferred substituents for Ri and R 2 are both 30 hydrogen. M represents hydrogen, or an alkali metal such as sodium or potassium, or an alkaline earth metal such as calcium, magnesium or barium. The preferred substituent for M is sodium. The terminal or end groups of the polymer are not critical and can be H, OH, CH 3 or a hydrocarbon chain. The degree of polymerization, i.e. the 22 value of n, is generally determined by the limit compatible with the solubility of the polymer in water.

The hydroxy acrylic acid or salt polymer can, for example, have a molecular weight of 2000 to 20,000. See for example U.S.P. Nos. 3,920,570 and 4,107,411 which describe methods of making the polymers.

Another useful organic builder salt comprises alkali metal or ammonium salts of carboxymethyloxy succinic acid, preferably the trisodium salt. The carboxymethyloxy succinic acid salts that can be used in the detergent compositions of the present invention have the following general formula

MOOC-CH-COOM

5

CH

3 0-CH-COOM 3 wherein M is a member selected from the group consisting of hydrogen, alkali metal and ammonium cation, and at least one M is an alkali metal or ammonium. The preferred alkali metals are sodium and potassium, with sodium being ther more preferred. The mono, di and trisodium salts can S be used, with the trisodium salt being the most preferred.

Another organic builder salt that can be used is the organic alkali metal lower polycarboxylic acid builder salt. The organic builder salt comprises alkali metal salts of lower polycarboxylic acids, e.g. two to four carboxyl groups. The preferred sodium and potassium lower polycarboxylic acids salts are the citric and tartaric acid salts. The sodium citric acid salts are the most preferred, especially the trisodium citrate.

S 30 Still other organic builders that can be used include polymers and copolymers of polyacrylic acid and polymaleic anhydride and the alkali metal salts thereof. More specifically such builders salts can be consist of a tt copolymer which is the reaction product of about equal moles of methacrylic acid and maleic anhydride which has 23 been completely neutralized to form the sodium salt thereof. The builder is commerically available under the tradename of Sokalan CP5. This builder serves when used even in small amounts to inhibit incrustation.

Examples of organic alkaline sequestrant builder salts which can be used with the alkali metal lower polycarboxylic acid builder salts or in admixture with other organic and inorganic builders are alkali metal, ammonium or substituted ammonium, aminopolycarboxylates, e.g. sodium and potassium ethylene diaminetetaacetate (EDTA), sodium and potassium nitrilotriacetates (NTA), and triethanolammonium N-(2-hydroxyethyl)nitrilodiacetates.

Mixed salts of these aminopolycarboxylates are also suitable.

Other suitable builders of the organic type include the polyacetal carboxylates. The polyacetal carboxylates and their use in detergent compositions are described, for example, in U.S.P. Nos. 4,144,226, 4,315,092 and 4,146,495.

Mixtures of organic and/or inorganic builders can be r 20 used herein, It is to be understood that while the alkali metal salts of the foregoing inorganic and organic polyvalent anionic builder salts are preferred for use herein from an economic standpoint, the ammonium, alkanolammonium, triethanol ammonium, diethanol ammonium, and the like, water-soluble salts of any of the foregoing builder anions are useful herein.

The builder salts, including both the inorganic and organic detergent builder salts are conveniently added to the crutcher mix to be included with the anionic S 30 surfactant, etc., in the spray-drid beads or granules to provide from about 15 to about 75%, preferably from about to 60%, especially preferably from about 22 to 55%, by weight, of builder salts based on the weight of the i spray-dried beads will generally be chosen so as to provide in the finished composition, after mixing with the

-I

post-added ingredients, Zf-VM abtot 12 to 80%, preferably to 70%, and especially .Wiably 20 o 50% of detergent builder salt(s), bas.#' -4n 1-taml composition.

The softener tmiw Alnds used in the present invention are diawaqWq w which are characterized by their general wato~-iz V ity The diammonium o sefu. herein for improving the softening performp, Vfnc ,ip composition are compounds of the following general im~~(1) R R NRs- N N 2X()

R

3 R 6 wherein R, Is an a.llpflat~ic hydrocarbon having trom abou 12 to about 30 carbon atoms; each of R 2 I R 3 I R 4 ,f R 5 and 16 are independently selected from the group consisting of aliphatic hydrocarbon groups having from 1 to 22 carbo atoms with the proviso that the total number of carb atoms in all, the aliphatic hydrocarb on groups, d ing R 1 is no a at a more than about 75 and with the fury :er proviso that no more than three of the R 2

-R

6 gro s have more than 12 carbon atoms; and

£R

7 is -CH 2

CH

2 or CH 2

CH

2 -1 and 4 t X is a water-solubl salt forming anion.

The preferred co ounds of formula are those acontaining only 1 2, preferably only a single long carbon chain gr p, 12 or more carbon atoms.

Accordingly, n formula the preferred definitions for 'o hi R44144 4IR are u /saturated linear or branched alkyl, alkenyl or i f 24a wherein R 1 is selected from the group consisting of an aliphatic hydrocarbon having from about 12 to about carbon atoms)stearyl, tallow, hydrogenated tallow, eicosyl and soya; each of R 2

R

3 R, R 5 and R 6 are independently 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 R 1 is no more than about 75 and with the further proviso that no more than three of the R 2

-R

6 groups have more than 12 carbon atoms; and R7is -CH2CH 2 or CH2 CH 2 CH-, and «X is a water-soluble salt forming anion.

t 15 The preferred compounds of formula are those containing only 1 or 2, preferably only a single long carbon chain group, 12 or more carbon atoms.

Accordingly, in formula the preferred definitions for

R

1

-R

6 are: 20 RI is an aliphatic hydrocarbon group, which may be straight chain or branched chain, and saturated or unsaturated linear or branched alkyl, alkenyl or K t t r_ SIr 25 alkynyl), having from 16 to 22 carbon atoms, such as 18 to carbon atoms;

R

2

-R

6 independently, are selected from the group consisting or alkyl or alkenyl having from 1 to 16, preferably 1 to 12, especially preferably 1 to 6 carbon atoms, with the proviso that the total number of carbon atoms in all the aliphatic hydrocarbon groups R 1

-R

6 is no more than about 50, preferably no more than about and with the further proviso that no more than 2, preferably no more than 1, and most preferably none of

R

2

-R

6 have more than 12 carbon atoms; and R7 is -CH 2

CH

2 or CH 2 C

CH

2

C

2 preferably.

-CHz CH CH 2 and X is a water-soluble salt-forming anion, such as, for example, halide, bromide, chloride or iodide, sulfate, methosulfate, ethosulfate, hydroxide, acetate, propionate, or other similar inorganic or organic solubilizing monovalent anion.

0. Examples of preferred Ri groups include stearyl, 20 tallow, hydrogenerated tallow, eicosyl, soya and the like.

t Examples of preferred alkyl and alkenyl groups for

R

2

-R

6 include, methyl, ethyl, propyl, isopropyl, n-butyl, tertbutyl, n-butenyl, octyl, l-octenyl, etc.

Methyl, ethyl, propyl and isopropyl are especially preferred. Methyl and ethyl are most preferred.

Specific examples of compounds of formula which S are either commercially available or readily manufactured by customary techniques include r

CH

3 CH 3 tallow-- N CH CH 2 C

N

CH .2C1 I

I

I CH 3

CH

3 (Adogen 477) I7 26 C H CA 3 tallow N N- CH 2 CH 2 CH 2 CH 3 OH 2C H 3 N 3 CH 3 stearyl C 16 H37

CH

3 I N CH 2 CH 2 CH 2 CH 3 OH 3 N CH 2 CH 2 UH 3

CH

3 N -C H 3 C H

H

U 16 m37 2C1

C

C t C16 H37 OH 3 1 N -CH 2 CH 2 CH 2

I

3

H

O H 1 3 CH 3 ,2CH 3 so 4 S~ C t set 6 is lit I C 27 etc. and the corresponding ethosulfate, halide, acetate, etc., water-soluble salts.

The above compound (1) dimethyl-N-tallowalkyl-N'-trimethyl-propylene-diammonium dichloride is especially preferred. This compound is commercially available as Adogen 477 from Rewo Company.

This compound can be prepared in customary manner, for example by reacting 1 mole N-methyl-N-tallow-N'-methyl propylene diamine with 3 moles of methyl chloride and the and then quaternizing the resulting compound with methyl sulfate.

The diammonium compound softener can be impregnated into the beads or granules without the use of a solvent or carrier liquid. It is generally preferred however to dissolve the diammonium compound softener in an organic solvent or to disperse the diammonium compound softener in San aqueous carrier liquid. The diammonium compound t 1 softener is preferably premixed with the clay mineral softener and the mixture added to the spray-dried beads or granules.

As aqueous solution and/or dispersion of the pH insensitive and heat stable ingredients, such as builders(s), fillers, anionic surfactant, pH adjusting agent, water, etc., are mixed together to form the crutcher mix and the mixture is then spray-dried according to to customary techniques.

The spray-dried beads are then intimately mixed with the diammonium compound softener and clay softener, and S* remaining ingredients, nonionic surfactant, bleach, 30 enzymes, perfumes and other pH or heat sensitive and/or water-insoluble ingredients to prepare the final

S

t softener-detergent agent composition. The amount of the t spray-dried beads and post-added ingredients is such that the final composition has the following amounts of the essential ingredients: _1 28 I Amount (Weiqht%) It I CT t t I I O II S SC aJ 4 5

I

Ingredient Broad Intermediate Preferred Detergent 1-95 5-50 5-30 Builders 2-80 10-70 20-50 Clay Softener 1-30 2-20 4-10 Diammonium Salt 0.25-10 0.5-5 1.0-2.5 (Compound of Formula Detergent Addivites, Fillers, Moisture 0-60 2.50 5-30 Ratio Clay Softener/ Diammonium Salt 10:1 to 1:1 6:1 to 3:1 The balance of the composition, if any, will be filled by the conventional detergent additives, fillers and moisture.

Optional Components The use of an inert, water-soluble filler salt is desirable in the laundering compositions of the invention.

A preferred filler salt is an alkali metal sulphate, such as, potassium or sodium sulphate, the latter being especially preferred. The amount of filler will generally be up to about such as 0.1 to preferably 0.3 to 1%, by weight of the composition.

Various adjuvants may be included in the laundry detergent compositions of the present invention. In general, these include perfumes, colorants, pigments and dyes; bleaches, such as sodium perborate, bleach activators, bleach stabilizers, antiredeposition or soil suspending agents, such as, alkali metal salts of carboxymethylcellulose; optical brighteners, such as, anionic, cationic or nonionic brighteners; foam stabilizers, such as, alkanolamides, foam boosters, germicides, antitarnishing 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 r 29 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 the flowability of otherwise tacky or pasty particulate compositions, two of such clay additives being presently marketed under the tradenames "Satintone" and "Microsil". Bound water and free water in minor amounts which do not adversely effect the flowability of the granular or powdery compositions may also be present in the detergent compositions. Amounts of moisture will normally be from 1 to 15%, preferably 5 to 12%, most preferably 8 to 12% of the entire composition. Within these proportions, a satisfactorily flowing particulate, pulverulent or granular product results; which, by control of particulate size and moisture content, can be prevented from being excessively dusty.

Suitable ranges of the detergent additives are: enzymes 0 to especially 0.2 to corrosion inhibitors about 0 to 15%, and preferably 2 to 8%, anti-foam agents and suds-suppressors 0 to preferably 0 to for example 0.1 to soil suspending or antiredeposition agents and anti-yellowing agents 0 to 10%, preferably 0.3 to colorants, perfumes, brighteners and bluing agents total weight 0% to about 2% and preferably 0% to about such as 0.2 to pH modifiers and pH buffers 0 to 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 0 to 10%, for example, 0.1 to in the selections of the adjuvants, they will be chosen to be compatible with the main constituents of the detergent composition.

Whatever the form of the laundry detergent, its use in the washing process is essentially the same. The particulate composition is usually added to wash water in t ac *r t a a. at at a; a *i 9 *i a ai a .rat 11~_1~ 1 _I~ 30 an automatic washing machine so that the concentration thereof in the wash water may range from about 0.05 to usually 0.1 to The water to which it is added will preferably be of medium or low hardness, e.g. from to 120 parts per million of hardness, as calcium carbonate, but both softer and harder waters may be usefully employed. The water temperature can be from 20 0 C to 100 0 C and is preferably from 60 0 C to 100 0 C in those cases where the textile or laundry is capable of withstanding high temperatures without deterioration or fading of dyes. When low temperature laundering is desired, the temperature may be held at 20 0 C to 40 0

C.

At the concentrations of detergent composition mentioned, the pH of the wash water will usually be on the alkaline side, for example, from 7 to 12, preferably from 8 to 11, especially from 9 to 10. The laundry;wash water weight ratio will usually be from about 1:4 to 1:30, preferably 1:10 to 1:30.

The following examples illustrate, but do not limit the invention. Unless othewise indicated, all parts and percents are by weight.

Example 1 The following composition is prepared by first forming the spray-dried beads and then post-adding the components S' (Spray-dried Beads) Parts T, ap water 6.8 Hydrogenated fish oil or tallow oil fatty acids 2.8 NaOH 1.3 Tap water 11.5 Sodium silicate (Na 2 0:SiO 2 9.9 Anionic surfactant i 16.0 Optical brightener2 0.2 Sodium carboxymethyl cellulose 0.7

N

Y i i ii 31 (Spray-dried Beads) Parts Zeolite inorganic detergent builder salt 33.9 Sodium sulfate (anhydrous) 0.7 SubTotal: 83.84 Post Added Ingredients Parts Sodium perborate 15.0 Blue bentonite clay agglomerate 16.0 Adogen 4773 Enzyme Magnesium silicate/DTPA mix No. 2 0.2 Potassium methyl siliconate 0.6 Nonionic surfactant 5 Duet 787 (perfume) SubTotal: 38.3 Itr t a llft4 a f r 44 ii C 4 it 4r 4 4 4 CIt it Spray dried beads 61.7 Total: 100.0 1. Linear dodecyl benzene sulfonatp as aqueous slurry.

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

3. Adogen 477 is N-tallowalkyl-N-(CH 3 )2 -CH2 CH 2

CH-N'-(CH

3 )3 *2CL.

25 4. 61.7 parts after drying.

5. C14-C 1 5 fatty alcohl ethoxylated with 11 moles ethylene oxide per mole.

The spray-dried beads are mixed with the post added ingredients to make product 1 (invention). The 30 concentration of the clay mineral softener in the final composition is 16% and the concentration of the Adogen 477 softener agent in the final composition is 2.5% in the product 1 (invention).

For comparison, the same composition is prepared except that the Adogen 477 is not used. The second j 32 composition, product 2 (comparison), has a clay mineral softener concentration of 16% and no Adogen 477.

The formulations product 1 and product 2 were used to wash test fabrics at 60 0 C using three cycles.

The softening, cleaning and whitening evaluation of the invention composition product 1 (invention) A B showed that there was no negative effect on the performance parameters as a result of the addition of Adogen 477 to the formulation, as compared to product 2 A B (without the Adogen 477 softener agent).

The soil removal effectiveness of product 1 (invention) was compared with product 2 (comparison) and the products 1 and 2 were found to be nearly equivalent.

The softness properties imparted to the test fabrics of the products 1 and 2 were compared and product 1 (invention was superior to product 2 (comparsion).

The whiteness and soil redeposition effectiveness of products 1 and 2 were compared on polyester/cotton, cotton t and nylon test fabrics washed with them, and product 1 (invention) was superior to product 2 (comparison) in all three comparisons.

The wash lipuor containing product 1 (invention) was found to produce no foam as compared to product 2 (comparison) which produced foam.

The Example 1 shows that the addition of Adogen 477 to the formulations results in obtaining about equivalent soil S*t' removal, while obtaining superior softness and whiteness/redeposition properties and low foam.

SExample 2 Following the same general procedure as in Example 1, the following composition is prepared.

(Spray-dried Beads) Weight Percent SSodium tridecyl benzene sulphonate 15.0 Zeolite inorganic detergent builder salt 39.3 Sodium silicate (lNa 2 O:2.4SiO 2

K

I 33 (Spray-dried Beads) weight Percent Sodium sulfate Optical brightener (Tinopal 5BM) 0.2 Na carboxymethyl cellulose 0.25 NaOH 1.75 SubTotal: 67.5 Post Added Ingredients Weight Percent Thixogel No. 1 clay 10.0 Adogen 477 Sodium Perborate 15.0 ,Enzyme Potassium methyl siliconate 0.6 Nonionic surfactant 1 Magnesium silicate/DTPA Mix No. 2 0.3 Duet 787 (perfume) 0.6 SubTotal: Total: 100.0 t ct 4r 4 1. C12-C14 fatty alcohol condensed with 9 moles ethylene oxide per mole.

In the Example 2 composition product 3 (invention) the clay softener concentration in the final composition was weight percent and the concentration of the Adogen 477 softener agent in the final composition was For purposes of comparison a second forumlation (product 4) was prepared in which the clay softener concentration was 16 weight percent and the Adogen 477 was omitted.

The soil removal effectiveness of product 3 (invention) was compared with product 4 (comparison) and the product 3 and 4 were found to be nearly equivalent.

The softeness properties imparted to fabric by the products 3 and 4 were compared and product 3 (invention) was superior to product 4 (comparison).

34 The whiteness and soil redeposition effectiveness of products 3 and 4 were compared on polyester/cotton, cotton and nylon test fabrics washed with them, and product 3 (invention) was superior to product 4 (comparison) on cotton and nylon and products 3 and 4 were about equally effective on polyester/cotton.

The product 3 (invention produced no foam as compared to product 4 (comparison) which produced foam.

Example 2 shows that the addition of Adogen 477 to the formulation allows a significant reduction in the amount of clay softener that is required to obtain the desired softening performance while still obtaining equivalent or superior effectiveness with regard to soil removal, softness, whiteness/redeposition and foaming.

It is understood that the foregoing detailed description is given merely by way of illustration and that i variations may be made therein without departing from the S spirit of the invention.

t It C 4 t 1 1

IPF(

Claims (10)

1. A no phosphate laundry softener detergent composition in solid form comprising spray-dried beads composed of a homogeneous mixture of at least one pH and heat insensitive detergent compound selected from the group consisting of anionic synthetic detergents, nonionic synthetic detergents, zwitterionic synthetic detergents, ampholytic synthetic detergents, and mixtures thereof; at least one pH and heat insensitive inorganic or organic detergent builder salt; clay mineral softener agent; diammonium compound softener agent selected from the compounds having the following formula 2 '4 R N RN+ R .2X (I) wherein R is selected from the group consisting of San aliphatic hydrocarbon having from about 12 to about carbon atomsstearyl, tallow, hydrogenated tallow, eicosyl and soya; and each of the R 2 R 3 R 4 R 5 and R 6 are independently selected from the group consisting of aliphatic hydrocarbon groups having from 1 to 22 carbon I 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 with the further proviso that no more than two of the R 2 -R 6 groups have more than 12 carbon atoms; and R7 is -CH 2 CH 2 or -CH 2 CH 2CH-; and X is a water-soluble salt forming anion; and optionally one or more of pH and heat insensitive detergent additives, fillers and moisture. 36

2. The no phosphate softener detergent composition of claim 1 wherein at least one detergent compound comprises an anionic synthetic detergent and at least one detergent builder salt comprises an inorganic builder salt or an organic builder salt.

3. The softener detergent composition of olaim. 1 wherein the formula (1) Ris a linear or branched alkyl, alkenyl or alkynyl group having from 16 to 22 carbon atoms, R6,R independently, are selected from the grov~q consisting of alkyl or alkenyl having from 1 to 16 carbon atoms, with the proviso that the total number of carbon atoms in all the aliphatic hydrocarbon groups R 1 -R 6 is no more than about 50 and with the further proviso that no more than 2 -of have more than 12 carbon atoms, 4, The no phosphate softener detergent composition of claim 2 wherein R 2 -R 6 independently, are alkyl or alkenyl of from 1 to 6 carbon atoms with the proviso that the total number of carbon atoms in all of the aliphatic hydrocarbon groups R 1 -R 6 is no more than about The no phosphate softener detergent composition of claim 1 which comprises from about 10 to about 60$ by weight of said at least one detergent compound; from about 15 to about 90% by weight of said at least one detergent builder salt; from about 0.25 to about 10% by weight of said diammonium, compound softener agent; from about 1 to 30% clay Mineral softener; and from about 0 to about 50% by weight of detergent additives, fillers and moisture,

6. The no phosphate softener detergent composition of claim 4 which comprises on a weight basis from about 15 to about 40% of a linear higher alkyl-bonzene sulfonate anionic synthetic: detergent; I 37 from about 25 to 65% of an inorganic zeolite detergent builder; from about 0.5 to 5% of said diammonium compound softener agent; from about 2 to 20% clay mineral softener 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. The no phosphate softener detergent composition of claim 6 wherein linear higher alkylbenzene sulfonate is dodecylbenzene sulfonate, the inorganic detergent builder is dodecylbenzene sulfonate, the inorganic detergent builder is zeolite, and the diammonium compound is C 3 CU tallow-- N+ 2 CH 2 CHQH- N+ -CH 3 .2C1 CH 3 CH 3 8, A no phosphate softening detergent composition comprising a clay softener and diammonium compound 2, softener agent in admixture with the spray-dried laundry detergent composition of claim 1.

9. A no phosphate free-flowing powdery or granular laundry detergent and softener composition which comprises from about 1 to about 95% by weight of at least one detergent compound selected from the group consisting of anionic synthetic detergent, nonionic synthetic detergent, amphoteric synthetic detergent, zwitterionic I 30 synthetic detergent and mixtures thereof; from about 2 to about 20% by weight of a clay mineral fabric softener; from about 2 abo u t bout 80% by weight of at least one detergent builder; and from about 0.5 to 5% by weight of a diammonium 38 compound softener agent having the formula R R 2 4 R N R N R5 .2X (I) R 3 6 wherein R 1 is selected from the group consisting of an aliphatic hydrocarbon having from about 12 to about carbon atoms, stearyl, tallow, hydrogenated tallow, eicosyl and soya; each of the R 2 R3, R 4 R and R 6 are independently 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 with the further proviso that no more than three of the R 2 -R 6 groups have more than 12 carbon atoms; and R 7 is -CH 2 CH 2 or -CH2CH 2 CH 2 and X is a water-soluble salt forming anion; and from 0 to about 50% of at least one of detergent t additives, fillers and moisture. The no phosphate composition of claim 9 in the form of spray-dried beads wherein the spray-dried beads 25 comprise an anionic surfactant; detergent builder salt and one or more of pH insensitive and heat stable detergent additives, fillers and mixtures thereof, and said S|diammonium compound is premixed with the clay fabric softener and the mixture is uniformly blended with said spray-dried beads.

11. The no phosphate composition of claim 9 wherein the formula (I) R 1 is a linear or branched alkyl, alkenyl or alkynyl group having from 16 to 22 carbon atoms; 39 R 2 -R 6 indenpendently, are selected from the group consisting of alkyl or alkenyl having from 1 to 16 carbon atoms, with the proviso that the total number of carbon atoms in all the aliphatic hydrocarbon groups R 1 -R 6 is no more than about 50 and with the further proviso that no more than 2 of R2-R 6 have more than 12 carbon atoms.

12. The no phosphate composition of claim 11 wherein R2-R independently, are alkyl or alkenyl of from 1 to 6 carbon atoms with the provisos that the total number of carbon atoms in all of the aliphatic hydrocarbon groups R 1 -R 6 is no more than about

13. The no phosphate composition of claim 9 wherein the diammonium compound softener agent is SCCH CH3 tallow- N CH 2 CH 2 CH 2 N CH 3 .2Cl CH 3 CH

14. The no phosphate composition of claim 13 wherein the clay mineal softener comprises about 10% and the *o diammonium compound softener comprises about 2.5% of the compositon. Dated this 6 day of November 1991 COLGATE-PALMOLIVE COMPANY Patent Attorneys for the Applicant: F.B. RICE CO.