CA1203651A - Detergent - compatible fabric softening and anti- static compositions - Google Patents

Abstract

ABSTRACT

Detergent-compatible softening compositions containing a comelt of certain quaternary ammonium fabric softening compounds and di-long chain tertiary amine fabric softening compounds as discrete parti-cles are disclosed. Preferred compositions also contain certain types of smectite clay to enhance fabric softening properties.

Description

36`5~L

DETERGENT - C~P~TI3LE FABRIC SOFTENING

John R. Berschied, Jr.
John A. Gregg TECHNIC~L ~IELD

This in~entiQn relates to composltions adapted to provide f~brlc softenin~ effects in fabric laundering operations. More particularly it relates to the pro~ision of ~oftening and antistatic effects to fabrics while simultaneously cleansing fabrics by means o~ conventional synthetic detergent compounds and or~anic or inor~anic deter~ent builders.

BACKGROUND
Fabric "softness" is an expression well de-fined in the art and is usually understood to be that qual ty of the trea-ted fabric whereb~ the handle or texture is smooth, pliable and flu~fy to the touch.
Moreover, optimally so~tened fabrics are characterized by a desirable antistatic ef~ect~ which is exhibited by a lack of statlc cling.
]5 It has long been known that various chemical compounds possess the abil~ty to soften and impart anti-static benefits to fabrics~ However, the effectiveness ~r~
) of any given compound may depend on its mode of use. For example, rinse-added ~abric so~teners, especially the quaternary a~monium compounds used in the detergent-free deep rinse cycle of a home laundering operation, provide exceptional condi tioning benefitsO Unfortunately, the cationic nature of these softeners causes them to interact undesirably with the com~on anionic surfactants such as the alkyl benezene sulfonates and is generally believed to preclude their use during the dete~ging cycle of a laundering operation involving commercial anionic detergents.
Nu~erous Attempts have been ~ade to formulate laundry detergent compositions that have both goQd cleanin~ p~operties and also textile softening properites so as to avoid the necessity o~ using ~ ,s,e~a~a,te ~nse - added textile softener product in addition to the usual laundry detergent.
The most commonl~ commerci~lly available organic textile softening compounds are cationic ~ateria,l~ that ~e xeacti~e toward the ~nionic surfactants used in conventional laundry detergents.
If both types of material are formulated in a sin~le prQduct, they tend to interact on addition to a wash'liquor which results in undesirable effects such aS increased soil redeposition on fabrics and poorer soil removal. A further conse-quence of this incompatibility is the inhibition of the tendency of the cationic material to deposit on the fabric surface and an associated reduction in the softenin~ benefit delivered to the laundered ~abric.

3f~

In oxder to ove~come this problem, compositions have been proposed which have sought to minimize the mutual reactivity o~ the anionic and cationic materials by the addition of compatibilizing compounds as described for example in U.S. Patent No.'s 3,886,075 and 3,954,63Z.
~ n alternative approach has been to inco.rporate one of the reactant materials in a .form that inhibits its cont~ct with the other in the wash liquor and exa~ples of thls type of formula,tion are tau~ht in U.S. Patent No.'s 3,936,537, 3,644,203, and 4,076,072.
In an attempt to avoid the reactivity problem altogether, nonionic suractants have been proposed in place o~ the con~entional.anionic surfactants and composi-tions of this type are described in, ,for ex,ample ~,P~ 1,079,388 and U.S.
Patent 3~607,763.' Another propos.al to px~vide acceptable cleaning and textile 'so~tening by avoiding the surfactant-so~tene~ inter,a,ction has been made in B. P. Spec'. No. 1,514,276 ~hich teaches the use of certain long chain tertiary amines that are nonionic in cha~acter at the ~ash liquor pH
existing ~,hen a conventional laundry detergent is used. The com~only-~ssi~ned Euxopean patent ApPli-cation No.'s 11340, published ~ay 28, 1980, and 8023367 published February 4, 1981 respectively . disclose cleanin~ and softening composi~ions comprising a combination of a long chain tertiary amine and a smectite-type clay in an anionic surfactant based detergent. The use of smectite-type clays as softening agents in detergent co~po-sitions is taught in B. P. Specification No.
1,400,898. This type of softening agent does not affect the cleaning performances of the detergent 3~

compo~ition but, if used on its own, requires a high level of incorporation for effective softening performance. Battrell in U.S.Patent 4,292,035 discloses the formation of complexes of clay and organic textile softening agents for inclusion into detergent compositions for fabric softening.
In summary~ there has been a continuing search for fabric conditioning agents which are compatible with anionic surfactants and which can be used without regard to the presence or absence o~ such materials. The current practice in providing a softening benefit t~ fabrics in domestic laundering operations continues to be to add a cationic fabric softenerr elther as a liquid to the final rinse Qf the washing procesS or as a separate additive to hot air tumble dryer.
~ t has noW been found that detergent compositions can be formulated wherein the cleaning performance is not impaired together with effective textile softening performance.
It i5 an obiect o~ this invention to provide fabric conditioning particles for use in detergent compositions, which particles do not react with anionic surfactants and do deposit on fabrics to pxovide a softening benefit without the need of machine drying.
The present invention is based on the di cQvery that fabric s~tening p~rticles prepared from certain comelted mixtures of dilong chain tertiary amines and quatexnary ammonium salts can be included in a detergent co~position to provide fabric softening benefits in a softening through-the-wash operation. The inclusion of the tertiary amine in the particles mitigates the interactive ~36~

e~fects of the quate~nary ~mmoniu~ softening agents and further con-~ributes to fabric soEtening, wherein the particles have a specified range of particle size, solubility in ~ater and melting point. These particulate materials can be employed, either as additives to supplement conventional laundering products when the latter are added to the liquor or as part of a product designed to provide te~tile materials ~ith simultaneous cleansing, and fabric softening effects.
According to one aspect of the invention there is provided a partlculate additive product containing as essential ingredients a quaternary ammonium fabric softening agent in intimate mixture ~-ith a tertiary amine which prQ~ides urther fabric softening and also acts as a dispersion inhibitor ~o~ the quaterna~y co~pound~
The present invention also encompasses, as integral for~ulations, compositions containing the materials defined herein in combination with synthetic detergent co~pounds and organic and inorganic builder salts. Such compositions, merely added to water, pro~ide in a single step the provision of a laundering bath adopted to the provision of simultaneous cleansing and ~abric softening e~fects. In this application, because of the small size of the particles of fabric softening agenks~ it i~ convenient to agglomerate the particles with ~ater-soluble neutral or alkaline salts and certain clays to prevent segregation in the composition. The addition of clay is useful for preventing caking of the ~gglomerate during processing as well as providing further softening properties.

SU~R,Y OF T~IE INVENTION
The present invention in its broadest aspect relates to fabric softening particles which are useful as adjuvants for detergent compositions. The invention also relates to detergent compositions containing said particles~
The ~abric softening particles, ~hich are especially adap~ed for use in combination with anionic, nonionic, zwitterionic, and ampholytic surfactants, are intimate ~ixtures con~isting essentially o~, by weight of the particles:
A. fxom about 90~ to about 20% by wei~ht of a ~uaternary ammonium compound of the ~ormula ~RlR2~3R4N; Y ~he~ein at least one but not more than two o~ RlR2R3 ~nd R4 is an organic .15 ~adical c~nta~n~ng ~ ~roup selected f~om a C16 to C22 aliphatic radical, or an alkyl phenyl or alkyl ~enzyl xadical having 10 to 16 carbon atoms in the alkyl chain, the ~e~inin~ ~roup or g~oups being selected from Cl to C4 alkyl, C2 to C4 hydroxyalkyl, and cyclic structures in WhiCh the nitro~en atom forms part of the rins, Y constituting an anionic radical selected ~rom the group consisting of hydrox~.de, halide, sulfate, methylsulfate, ethylsulfate, and phosphate iQnsi and B from about 80~ to 10% of a tertiary amine having the formula RlR2R3N ~herein Rl and R2 are lndependently selected from C10- C12 alkyl or alkenyl groups, and R3 represen-ts a C1-C7 alkyl group, ~herein substanti.ally all the ir.dividual particles have a size in the range of 10~ to 500 -~ , a solubility in ~2~6~

water of 5Q ppm maximum ~t 25C, ~nd a softening point in the range of from 90F. to about 200F.
The in~ention also encompasses detergent compositions adapted to imparting softening effects to fabrics in an aqueous laundering medium, comprising:
A. from about 5% to about 85~ by weight cf a water-soluble detergent component selected from the group consisting of anionic, nonionic, ampholytic, and z~ittexionic surf~ctant; and B. from about 5.0% to about 50% ~y weight of a fabrlc softening com~onent comprising parti-cles of t~e intimate mixture of the type disclosed above.

DET~ILED DESCRIPTION O~THE INVENTION
The fabric softener particles consist essentially of an intimate mixture of two components;
a quaternary ammonium salt; and a di-long chain tertiary amine in a ratio range of from 9:1 to 1:4 respectively. Pre~erred ratios are from 4:1 to 1:2 and especi~lly preferred ratios are from 3:2 0 to 2:3.
The fabric softening particles ernployed herein are ln the form of substantially ~ater~
insoluble particle~ ha~lng an avera~e size(diameter) range of from about 10 ~ to about 500 y, Preferably, the size of the particles herein lies in the range from about 25 ~ to about 200 ~, moxe pxefer~bl~
from 50 ~ to 100 ~, and particles within this xange are efficiently entrained on fabrlc surfaces which is especially important for cool water washing and line dryin~. The water solubility of the particles must be no greater than 50 ~pm at 25C in water. The fabric softening particles 3~S~

must also be in the solid form in the washing liquor so that they deposit on the fabric as discrete particles.
The particles therefore should have a mel~ing point in the range of from 90F. to 200F.

~HE_QUATERNARY AMMONIUM SALT
Suitable quaternary ammonium compounds are included in U.S. Pat. No. 3,936,537, issued to Baskerville et al. The following description is an abbreviated discussion.
The quaternary ammonium salts useful herein have the formula [RlR2R3R4N] Y wherein Rl and preferably R~, represent an organic radical containiny a group selected rom a C16-C22 alkyl ra~ical or an alkyl phenyl or alkyl benzyl radical having 10 to 16 carbon atoms in the alkyl chain, the remaining group or groups being selected from Cl-C4 alkyl, C2-C4 hydroxyalkyl, and cyclic structures in which ~he nitrogen atom forms part of the rinq, and Y
constitutes an anionic radical selected rom the group consisting of hydroxide, halide, sulfate, methylsul~ate, or ethylsulfate~ The preferred anions for the quaternary ammonium fabric softener salts are c'nloride and methylsulfate.
The ~uaternary ammonium fabric sof~enins compounds useful herein include both water-soluble and substantially water-insoluble materialsO Imidazollnium compound~ enumer-ated in the ~askerville patent possess appreciable wa~er solubility and can be utilized in the present invention by mixing with the appropriate type and level of tertiary amine to give ultimate particle solubility in water of _9_ less than 50 ppm (parts per million) at 25C~ Relatively water-soluble quaternary fabric softeners can be used, such as diisostearyl dimethyl ammonium chlorides disclosed in U.S. Pat. No~ 3,3~5,100 to Fisher et al. Exemplary quaternary ammonium imida~olinium compounds are specific-ally ethyl, l-alkylamidoethyl, 2-alkyl imidazolinium methyl sulfates, more specifically l-methyl-l[(tallowamido) ethyl]-2-tallowimidazolinium methyl sulfateO ~owever, the most useful quaternary ammonium fabric softening agents are characterized by relatively limited solubility in water.
The quaternary ammonium fabric softening agents used in this invention can be prepared in various ways well known in the art. Many such materials are commercially available. The quaternaries are often made from alkyl halide mixtures corresponding to the mixed alkyl chain lengths in fatty acids. For example, the 'iditallow"
~uaternaries are made from alkyl halides having mixed C14-C18 chain lengths. ~uch mixed di-long chain quater-naries are useful herein and are preEerred from a cost standpoin~.
The following are representative examples of substantially water-insoluble quaternary ammonium fabric softening agents suitable for use in the composition~ and processeC of the instant inven~ion. All of the quaternary ammonium compounds listed can be formulated with the detergent compositions herein, but the compilation of suitable quaternary compounds llereinafter is only by way of example and is not intended to be limiting of such compounds~ Dioctadecyldimethylammonium chloride is an especially preferred quaternary fabric softening agent for use herein by virtue of its high fabric softening ~2~

ac-tiVity; ditallowdimeth~l ammonium chloride is equally preferred because of its ready availability and its good softening activity; other useful di-long chain quaternary compounds are dicetyldimethyl ammonium chloride; bis-docosyldimethyl ammonium chloride; ditallowdimethyl ammonium bromide;
dioleoyldimethyl ammonium hydroxide; ditallowdimethyl ammonium chloride, ditallowdipropyl ammonium bromide; ditallo~dibutyl ammonium fluoride, cetyldecyl-methylethyl ammonium chlorlde, bis-~ditallowdimethyl ammonium]sulfate; tris-5ditallow-dimethyl ammonium]
phosphake; and the like.

THE TERTI~RY AMINE
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The -tertiar~ amines sui-table for use in makin~ the intimate particles have the general ~5 formula RlR2R3~ wherein Rl and R2 are independently selected ~rom C10 to C22 alkyl or alkenyl groups, and R3 represents a Cl to C7 alkyl. The ter-tiary amines axe characterized by being ~ater insoluble.
Æxemplary tertiary amine compounds include, but are not limited to, the followiny:
didecyl ~ethylamine, dicoconu-t methylamine, dim~ristyl methylamine, dicetyl methylamine, distearyl methylamine, diarachid~l meth~lamine, dibehenyl me~hylamine, di(m~xed arachidy1/behenyl) methylamine, ditallowyl me-thylamine, and the corresponding ethylamines, propylamines, and butylamines, Especially preferred is ditallowyl methylamine.
It ~as discovered -that the combination of the quaternary ammonium salt and the -tertiary amine in in-timate admixtures pravide compositions tha-t are effective in softening fabrics through~

~ 3 the-wash. The term "effective" means th~t the particles provide fabrics with a softer feel and an antistatic effect as described hereinabove. The tertiary amine, as shown by this invention, does protect the quaternary ammonium compound from interac-tive effects in the wash liquor and the admixture, in the form of particles, does deposlt on the fabrics to condition the fabrics as described above.
The ~abric softening particles of the present invention can be conveniently prepared by co-melting the tertiary amine and the quaternary ammonium sal-t compound and then converting ~he molten mass into particles of the desired size by an~ of the conventional ~eans for con~erting melted materials to dry particlesl e.g., cooling the ~olten mas5, followed by grinding to the appropriate size, or simultaneously cooling the mass and forming particles by spraying the mass through a nozzle into a cool a,mosphere (prilling).
Particle size selection can be accomplished by controlling -the process, or alternatively screening, air stream segregation, etc.
~s disclosed herein, -the particles can be added directly to a wash liquor containing a conventional detergen-t composition for softening fabrics through~the-wash. The particles can o~
course be dry-added to a ~ranular detergent composition to provide a composition which can simultaneously clean and so~ten fabrics. To prevent segregation it is desirable to coat the particles -to make agglomerates of the particles which will ha~e approximately the sa~e partic]e size as -the granular detergent composition. The a~glomerhte can contain from 10% to 806~
preferably from 15~ to 50%~ more preferably from 20% to 40%~ by weight, o~ the particles of quaternary ammonium salt and tertiary amine.
The fabric softener particles can be agglomerated by mi~ins with a water-soluble, neutral or alkaline salt and spraying the agitating mixture with ~ater or an organic agglomerating agent. Further, certain smectite clays can be included which are useful as processing aids to prevent caking of the a~glomerated during making.
The smectite clays can provide additional fabric softenin~ benefit when used in laundering fabrics wherein the water contains appreciable amounts of soluble calcium and magnesium salts, ~.e., wa-ter having at least 9 grains per gallon of such salts calculated as CaC03.
~ he ~ater-solu~le neutral or alkaline s~lt can be either organic or lnorganic and has a pH in solution of seven or greater. The water-soluble neutxal oX alkaline salt will be employed in the agglomera~ed particulate in an amount from about 10% to about 80% by weight, preferably ~rom about 20% to about 60% by weight, more pre~erably from about 25% to about 50% by weight, most preferably from about 30% to a~out 40% by weight. SpecificallY, some of the water-soluble, neutral or alkaline salts, if not used in the hydrated form, will absorb moisture during the processing of the agglomerated particulate detergent additive, and ~n addi-tion func-tion as detergency builders in wash water solutions.
~ xamples o-f such wa-ter-soluble neu-tral or alkaline salts include alkall metal chlorides such as sodium chloride and po-tassium chloride, alkali metal fluorides such as sodium fluoride ~v~

and potas~ium ~luoride, ~lkali metal carbona-tes such as sodium carbonates, alkali metal silicates, and mixtures thereof. ~ny conventional water-soluble, neutral or ~lkaline inorganic salt such as the alkali metal sulfates, notably sodium sulfate, may be employed in the present invention.
~ ater-soluble, neutral or alkaline salts also include the variety commonly known as detergency builder salts, especially alkaline, poly~alent anionic builder salts. Suitable detergency builder salts include polyvalent inor~anic or organic salts or mixtures thereo~. Suitable water-soluble, preferred inoryanic alk~line detergency builder salts include alkali metal carbonates borates, phosphates, polyphosphates, bicarbonates, silicates, and sulfates. Specific examples of such salts include the sodium ~nd pot~sSium tetraborates, perborates~ bicarbonates, carbonates, tripolyphos-phates ! pyrophosphates, orthophosphates and hexa-metaphosphateS
Examples o~ suitable organic alkalinedeteryency builder salts are: ~ater-soluble aminopoly-acetates, e.g ~ sodium and potassium ethylenediaminetetra-acetates, nitrilotriacetates and N~(2-hydrox~ethyl)ni-trilodiacetates; ~ater-soluble salts of phytic acid, e.y., sodium and potassium phytates; water-soluble polyphosphonates, includin~ sodium,potassium, and lithium salts o~ ethane~ hydroxy 1, l-di-phosphonic acid; sodium, potassium and lithium salts o~ methylene diphosphonic acid and comparable examples.
~ dditional oryanic builder salts are disclosed in U.S. Pat. No.'s 2,264,103 to N.B
Tucker, 3,308,067 to F, L. Diehl, 4,083,813 to ~93~

Rodney M. Wise et al. The Tucker patent particularly discloses polycarboxylate and citrate salts, notably sodium citrate which may be used in the present invention as a water-soluble, alkaline salt. Further detergency builder salts are disclosed in U.S. Pat.
No. 3,936,537 to Baskerville, Jr. et al.
As noted hereinabove the wa~er-soluble neutral or alkaline saLt can be used as the agglomerating material with water above or with an organic agglomera~ing agent. The organic agglomerating agent can be present at levels, on a dry basis, of up to 20% by weight, preferably from about 5% to about 15~
by weight, most preferably from about 7% to about 12%
by weight of the particle agglomerate detergent additive.
The organic agglomerating agent ~often loosely termed a "glue" or "glue mix") may include starches, notably the dextrin starches. Dextrin starches, or dextrins, are starches which are modified by heating in their natural state~ Suitable dextrins include those manufactured by the A. E. Staley Manufacturing Company, Decatur, Illinois 62525 under the trade mark STADEX and described in khe Staley Technical Bulletin TDS No. 116.
The Stadex dextrins are produced by partially hydrolyzing corn starch, by heating in a dry a~mos-phere in the presence of acid. There are three main types, white dextrins, canary or yellow dextrins, and British Gums which are heated longer and catalyzed 3Q with little or no acid. The standard method of dextrin manufacture was roasting the ~15-starch in a horizontal cooker with agitation.
However, Stadex dextrins are made by 'Ifluidizing"
powdered starch during the heating cycle for grea~er conversion uniformity o starch to dextrin by ensur-ing a more even distribution of heat and acids.
Other exarnples of suitable dextrins andtheir preparation are contained in Starch and Its Derivatives by J.A. Radley, Chapman and Hall Ltd;, London (4th Ed. 19681, no~able in the essay by Go V. Caesar on IlDextrins and Dextrinization" at pages 282 289 and the essay on l'The Schardinger dextrins" at pages 290-305. Suitable examples of dextrins and their preparation are also contained in Chemistry and Industry of Starch by Ralph W. Kerr, Academic Press, Inc., New York (2nd Ed. 1950), particularly in the essay "Dextrinization" by G. V. Caesar at pages 345-355~ and the essay "Manufacture of ~extrinsl' at pages 357~373.
Dextrin may be added to the agglomerate in a water solution. This dextrin-in water solution may comprise from about 10% to about 60~ by weight, preferably from about 20% to about 50% by weight, and most preferably from about 30~ to about 40% by wei~ht of dextrin.
7.5 Other exemplary materials useful as agglomerat-ing agents are described in U~S. Pat. No. 4,141/841 to McDanald. Briefly, these materials inc]ude polyethylene glycols and polypropylene glycols having a molecular weight of from about 950 to 30~000;
copolymers containing ethylene oxide and propylene oxide units, condensation products of one mole of a C10 to C18 saturated or unsa-turated straigh-t or branched chain carboxylic acid with ~rorn about 20 to about 50 mo]es of ethylene oxide, C10- C2~ saturated or unsaturated, straight or branched chain alcohols with from 9 to about 50 moles of ethylene oxide, certain poly-oxyethylene glyceride esters and polyoxyethylene lanolin derivatives, amides which have a melting point between about 30C and 100C, the condensation of one mole of C~-C18 alk~l phenol With from about 25 to about 50 moles of ethylene, oxide, C12to C30 atty acids which rnelt bet~een 30C and lOO~C, and C16 to C30 fatty alcohols which mel-t at between 30C and 100C~
The agglomerated particulate detergent additive may op-tionally contain smectite clay as an ingredient. Clay compounds, namely sodium and calcium montmarillonites, sodium saponites, and sodium hectorites, can be incoporated into the agglomerated particulate detergent additive. These smectite cla~s ~ay be admixed with the particulate deter~ent additive o~ this invention at levels up to 50% by ~reightl preferably ~rom ahout 5% to about 25% by weight, most pre~erably from abou-t 7%
to about 15~ by weight, of the agglomera-ted particu~
late detergent additive. The clays used herein are "impalpable" r i.e., have a particle size which canno-t be perceived tactilely. ~mpalpable clays have particle sizes below about 50 microns; the clays used herein have a particle size range of ~rorn about 5 microns to about 50 rnicrons.
The clay minerals can be descri~ed as expandable, three-layer clays, i.e,, aluminosilicates and magnesium silicates, having an ion e~change capacity of at least 50 meq/~lOOg. of clay and pre~erably at least 60 me~lOOg. of clay.
The term "expandable" as used to describe clays relates to the ability of the layered clay structure to be s~llen, or expanded, on contact with water.
The three-layer expandable clays used herein are those materials classified geologically as smectites.
There are two distinct classes of smectite clays that can be broadly differentiated on the basis of tne numbers of octahedral metal-oxygen arrangements in the central layer ~or a given number o~ silicon-oxygen atoms in the outer layers.
The clays employed ln the compositions o~ the instant invention contaln cationic counterions such as protons, sodium ions, potassium ions, calcium ions, and lithium ions. It is customary to distinguish bet~een clays on the basis of one cation p~edo~in~ntly or exclusl~ely absorbed. For example, a sodium clay is one in which the absorbed cation is predominantly sodium. Such absorbed cations can become in~olved in exchange reactions ~ith cations present in aqueous solutions. A
typical exchange reaction invol~lng a smectite-type clay is expressed ~y the following equation;
smectite clay (Na)~ ~ NH40H ~ smectite cla~ -(NH4)~ ~ NaOH. Since the foregoing equilibriumreaction, one equivalent weight of am~onium ion replaces an equiv~lent ~eight of sodium, it is customary to ~easure catlon exchange ca~acity (sometimes termed "base exchange capacity") in terms of ~illiequivalents per lOOg. of clay (meq/lOOg.).
The cation exchange capacity of cla~s can be measured in several ways~ including by electro-dialysis, by exchanye with ammonium ion followed by titration or by a methylene blue procedure, all as fully set forth in Grimsha~, "The Chemistry and Physics of Clays", pp. 264-265, Interscienee (1~71)~
The cation exchange capaeity of a elay mineral relates to such faetors as the expandable properties of the clay, the charge of the clay, which, in turn, is determined at least in part by the lattice strueture, and the like. The ion exehange eapaeity of clays varies widely in the ran~e from about 2 meq~lOOg. of kaolinites to about 150 meq/lOOg., and ~reater, for eertain ~mectite clays. Illite clays although having a three layer strueture, are of a nonexpanding lattice type and have an ion exchan~e eapacity ~ome~here in the lo~er portion of the range, i.e., around 26 meq~100~. for an average lllite clay.
Attapulgites, another class o~ elay minerals, have a spieulax (1.e. needle-like) crystalline form with a lo~ eation exehange capaeity (25-30 q/lOOg.).
Their strueture is eomposed of ehains o-E siliea tetrahedrons linked together ~y oetahedral groups o~ oxygens and h~drox~l eontaining ~1 and Mg ~toms.
It has been determlned that illite, attapulgite, and kaolinite elays, with their relatively low ion exehange eapaeities, are not use~ul in the instant eompositions. Indeed, illite and kaolini-te cla~s constitute a major eomponent of elay soils and, as noted above, are removed from fabrie surfaces by means of the instant eompositions. However, -the alkali metal montmorillonites, saponites, and hectori-tes, and eertain alkaline earth me-tal varieties of these minerals sueh as e~leium montmorillonites have been found to show useful fabric-softening benefits when incorporal:ed in composition5 in accordance with the present invention. Specific examples of such fabric-softening smectite clay minerals are: sodium montmorillonite, sodium hectorite, sodium saponite~
calcium montmorillonite, and lithium hectorite.
Accordingly, smec~ite clays useful herein can be characterized as montmorillonite, hectorite, and saponite clay minerals having an ion exchange capacity of at least about 50 meq/lOOg., and 10 p.referably at least 60 meq/lOOg.
The above discussion of optional clay additives is intended to only be a brief cursory review of the subject matter contained in U.S. Pat~ No. 3,936,537.
It is intended that the particulate de~ergent 15 additive be incorporated in a detergent composition to provide cleaning and softening to Eabrics. Because of segregation problems due to the small particle size of the particulate detergent additive J it is preferred to agglomerate said detergen~ additive as disclosed 20 above. The detergent composition thus will contain an agglomerate of the particulate detergent additive dry admixed with the detergent composition which contains a surfactant and optionally detergency builders. The detergent composition can contain from about 5% to 25 about 50~, preferably from about 10~ to about 30%, more preferably from about 12% to about 20%, by weight, of the agglomerated particulate detergent additive product.

SURFACTANT
The detergent composition which comprises the agglomerated particulate detergent additive : ) 9 ':

3~

19a-can contain frorn 5~ to 85%, preferably 5% to S0~, most preferably from 10~ ~o 30~, of a surfactant selected from the group conslsting of anion:lc, nonionic, ampholytic and zwit~erionic sur~actants, and mixtures thereof, inasmuch as the other components are compatible with all such materials at the concentrations and proportions disclosed herein.
A typical listing of the classes and species of surfactants useful herein appears in U.S. Pat. 3,579, 454, column 11 line 45 to column 13 llne 64.
Examples of suitable surfactants of these classes which can be employed in accordance with the present invention are the followlngO
1. Anionic water-soluble soaps: Examples of suitable soaps for use in ~his invention are the sodium, potassium, ammonium, and alkanolam~onium(mono-, di-and triethanolammonium) sal~s of high~r fatty acids tcl~-c223- P~rticularly useful are the sodium and potassium salts of the mixtures of ~atty acids derived from coconut oil and tallow, i.e., sodium and potassium tallow and cooonut soaps.

2. Anionic synthetic non-soap surfactants:
A preferred class can be broadly described as the water-soluble salts, paxticularly the alkali me~al salts of organic sulfuric acid reaction products

3~

~20~
having in their molecular structure an alkyl ~roup containin~ from about 8 to about 22 carbon atoms ~nd a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl" is the alkyl portion of acyl groups.) Examples of this group include C8-C18 alkyl sulfates, straight or branched ch~in alkylbenzene or alkyltoluene sulfonates containing from 9 to 15 carbon atoms in the alkyl chain (especially valuable are linear straight chain alkylbenzene sul~onates in which the average of the alkyl groups is about 11.8 carbon atoms and cvmm,only a~breviated as Cl1 8LAS)IClo to C20 alkyl ether sulfates having from 1 to 30 moles of ethylene oxide per molecule, sodium alk~l gl~ceryl ether sulfonates, ester of ~- sul-fon~ted ~atty acids, and C12 to C24 olefin sulfonates.
3. Nonionic surfactants obtained by the condensation o~ 1 to 12 ethylene oxide moieties ~ith a C10 to C18 aliphatlc alcohol~

4~ ZwitterioniC suxfactant~ such as 3 - (N~N - dimet~yl - N - hexadecyl ammonio)-2 ~ hvdroxypropane - 1 sulfonate and 3 - (N~N ~ dimethyl - N - tallow~yl ammonio) -2 - hydroxypropane - 1 - sulfonate~

DETERGENCY BUILDERS
The detergent compositions of the instant invention may contain a detersency builder in an amount from about 5% to about ~5% by weigh-t, preferably from about 15% to about 60% by weight, ancl most preferably from about 20% to about 40% by weight of the entire detergent composition. The de-tergency builders mentioned hereinabove are suitable for use in this invention.

3~

OTHE~ ~TIQNAL IN~EDIENTS
-Other optional ingredients which may be lncluded in the detergent composition include deter-gency builders enumerated in the Baskerville patent from column 13, line 54 through column 16, line 17, as well as ~ntltarnish and anticorrosion agents, perfume and color additi~e, enzymes and other optional ingredients enumerated in the Baskerville patent, U.S. Pat. No. 3,936,537, from column l9, line 53 thxough c~lumn 21, line 21.

METHOD OF PREPARATION
-The particulate detergent ~ddl-tive product is made by mixing the ~uarternary ammonium compound and tertiary amine by comelting the materials, cooling to a solid mass and obtaining the desired particle size by comminution and screening. ~n alternative method is to spray the liquid mixture through a pressure nozzle to ~orm droplets of the desired size range which are -then solidified b~ cooling and subject to screening (prilling process). It is a requirement of this invention tha-t the ~ua-ternary ammonium compound and the tertiary amine be intimately mixed, i.e., comelted, in forming the particulate softening composition. The suitable particle size r~nge o~ the p~rticulate detergent additive is from 10 to about400~ ~ most preferably ~rom about 50~ to about 10 0 1l .
The processes of comminutlng a solid ~ass of comelt such as grinding, ball milling, hammering, grating through a sieve etc. are well known in the art. Similarly, prilling processes are also well known.
It will be appreciated that in making the comelt, the materials should be low in solvent and ideally are subs-tan-tially free thereof. ~hile solvents, 3~

such as lso~ropanol, a~e conventionall~ present in commercially available quarternary softening mater-ials to aid dispersion in aqueous media, such sol-vents are disadvantageous to the present invention in that the particles mus-t have low solubility.
After initial combination of the quaternary ammonium coumpound and tertiary amine to form a comelt or prill of the desired particle size, said particles are ac~glomerated with the water-soluble neutral or alk~line salt ~or use as admix-tures in detergent compositions and avoiding segregation.
Agglomeration serves the purpose of combining the small particles to increase the apparent particle size without affecting the particle size of the individual particles. The salt also provides more strength to the ag~lomerate and makes the resulting mixture more ~ree-flowinq. In the wash liquor the water-soluble saIt dissol~es to release the indi~id-ual particles which then are distributed throughout the wash liquor and are free to deposit on the fabrics being washed.
The mixture of comelt or prill and salt, preferabl~ sodium carbonate or sodium tripolyphosphate, is fed into a highly eff~cient mixer where agglome-rating agent (dextrin qlue solution) is sprayed ontothe mixture. Types of mixers which may be employed include the Schugi mixer (Flexomix 160,250,335 or 400), the OIBrien mixer, the Littleforcd mixer, the Patterson~Kelly mixer, rib~on mixers, and/or vir-tually any of the conventionally-known pan agglome~
rators. This results in aqglomerates of water-soluble, neutral or alkaline salt and prills or comelt of quaternary ammonium compound ancl -tertiary amine in the same size range as con~entional deter-qent granules, thus ellminating the prohlem of segrega-tiQn (abou-t 150-1190 y in size).
The final agglomerates are discharged from the (Schu-gi) mixer and optionall~ admixed with particulate, smectite clay. The resulting composition is aged for approximately one hour, optionally mi~ed with silica if increased flo~ability is desired, and admixed with conventional detergent granules.
Certain of the water-soluble, neutral or alkaline salts may absorb moisture during the pro-cessing of the agglomerate. ~n addition, some of thewater-soluble neutral or alkaline salts Eunc-tion as detergency builders in ~ash water. Further, the mixture o~ prills and water-soluble neutral or al-kaline salt, when aggl~merated, provides lncreased fabric softening relative to prills alone in the second wash load.

EX~MPLE ~
A particulate detergent additive was pre-pared as follows:
Ingredient Weight Per Cent Dimethyl di-hydrogenated tallow ammonium chloride(:~5% ac-tive powder) 40 Di-hydrogenated -tallo~ methylamine 60 The quaternary (DTDM~C) and amine (DTMA) were melted -together -to orm a clear solu-tion in a steam bath. The molten mi.xture was cooled and became solid at room temperature. The solid mass was broken up and then ground in a mortar with a pestle -to a particle size in the range not greater than 65~ to ~2~

80 ~ . A microscope with a ~rid was u$ed to check the particle size during the grinding. (A con~enient alternative process would be to make the particles by a prilling process). The so~tening poin-t of the particulate deter~ent additive was about 105 F. The particles were essentially insoluble in water at 25C~ The particulate detergent additive in all the subsequent examples had essentially the same solubi-lity characteristics and ranged ln melting point from about 90 F. to about 135 F~, depending on the ratio o~ the components.
The particulate detergent additive can be added to a was~ uor to provide softening to fabrics.
~s defined hereinabove softenin~ m,eans that the fabrics treated there~ith have a so~ter feel to the touch and e~hibit a lack o~ static cling.
Comparable results are obtained when the quaternary ammonium compound utilized is ditallow-dimethyl ammonium methylsulfate, ditallo~dlmethyl ammonium ethylsul~ate, l-meth~ (tallowamido~ethyl]
-2-tallow imidazolinium methylsulfa-te~ or mixtures thereo~ in place of the dl-tallowdimethyl ammonium chloride on a par-t for part basis.
Substantially si~ilar results are obtained when the ditallo~ methylamine is replaced with di-decyl heptylamine, dicoconut butylamine, dimyristyl ethylamine, dicetyl ~ethylamine, diarachidyl methyl-amine, dibehenyl methylamine, and di(mixed arachi~
dyl/behenyl) methylamineO

EXAMPLE I~
The particulate detergent additive par-ticles made in Example I were agglomerated with sodium tripolyphosphate (STP) ! in a cement mixer~
The STP was a dry, anhydrous, powder with at least ~3~

90~ passin~ through a 100 mesh Tyler sieve.
To 33.75 parts of particles made in Example I
were added 28.95 parts of STP and sprayed with 8042 parts of dextrin glue (35 parts solid to 65 parts water~ This resulted in agglomerates of the particu-late detergent additive and STP having the same size range as other deter~ent granules, about 150-1190 microns.
The product of this agglomerating step was added to detergent granules to provide a composition which simultaneously cleaned and softened fabrics.
The agglomerated fabric so~tening or conditioning cornposition provided better second load fabric softening than the addition of the particulate detergent additive alone to wash water As mentioned hereinbefore smectite clay can be a component of the agglomerate The process is one o~ simply admixing the agglomerate with the approp-riate amount oE impalpable smectite clay For example 71.1 parts of the agglomerate was admixed with 29.9 parts of calcium montmorillonite clay of good fabric softening performance and having an ion exchange capacity of about 84 meq /lOOg. (available from Industrial Minerals Ventures Inc. U.S.A.~ sold under the trade mark Imvite K).
Substantially similar results are obtained when sodium tripolyphosphate is replaced with sodium tetra-borate, potassi~n tetraboratel sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, potassium tripolyphosphate, sodium pyro-phosphate, potassium pyrophosphate, sodium hexameta-phosphate, potassium hexametaphosphate, sodi.um sulfate, potassium sulfate, sodium citrate, potassi~m citrate, and mixtures of these water-soluble, alkaline salts~

,s 3 Ei~;~

Other types of smectite clay which when substituted for calcium montmorillonite yield com-parable ~abric~softening performance include sodium hectorite, sodium saponite, calcium montmorillonite, lithium hectorite, and mixtures thereof.

EXAMPLE III
P~rticulate detergent additives and agglo-merates thereof made according to Examples I and II
were added to detergent granules to make detergent compositions ~hich pro~ide cleaning and softening through-the-wash and evaluated for cleaning and so~tening performance relative to a detergent com-position having no softening attribute and a second composition h~ving a softening component outside this invention.

Compositions Control 1 Control 2 No.l No.2 Detergent C~mporlent C L~S 23.0% 15.0% 15.0% 15.0%

Na pyro.phosphate 17.1 14.06 15.18 15.18

5 Hardened tallcw fatty acid 1.25 ~ - -Na silicate(2SlO2/Na2O)12.0 12.0 10.0 lO.O
Na2C3 15.0 15.0 5.71 15.0 Na alumlnosilicate 4.0 ~ - ~
Na2S4 18.83 16.39 32.58 42.39 10 Glass H* 0.85 0.85 ~EG 6000** 0.85 0.85 0.85 0.85 C12Alkyl dimethylamine oxide (sprayed on) - 0.25 5.25 0.25 Minors(brightener, perfume, etc.) 0.82 0.6 0.62 0.62 ~oisture 6.3 5.0 5.0 5.0 Ditallow methylamine(DIMA) - 5.33 DicQconut methylam~ne(PCMO ~ 2.67 - -Clay-Ca montmorillonite ~ 12.0 - -20 TOtal lOO.0% lOOeO% 85~19% 95~0%
~oftener component admix 14.81% 5~0%

3~

~28-The composition of the softener components were as follows:

Control 2 No.l No.2 2:3 DTDM~C:3TM~ - 33.74% 100%
2:1 DrMA:DcM~ 40 Na2CO3 ~ 28.95 Clay-Ca montmorillonite60 28.88 Dextrin glue(.35% solids) ~ 8~43 * Glas$ H is a com~lex phosphate having ~bout 21 atoms.of phosphorus.
** PEG 60Q0 is polyethylene glycol of MW 6000.

Control 1 does not contaln any fabric softening component Control 2 contains 8% of a mixture of terti~X~ a~ine~ (.2;1 DT~: Dlcoconut ~ethylamine) and 126 of cl~y. The' softener component of Compo-sition No. l ~as added to the deter~ent componentas an a~glomera~e ha~ing the composition shown.
In Composition No. 2 the ~oftener co~ponent is an admix of the product made 'in Example ~.
Several fabrics were washed with the detergent compositions in a 10 minute wash at 70 F in soft ~ater (3 grains hardness/gal), line dried, air -tu~bled in a dryer ~ithout heat ~or lO
minutes, and checked for total voltage using a Fara,day ca~e, insta,nces ~ static cling of -the ~abrics, and for softness b~ a panel in paired comparison tes-ting.
Static Test Results(68F~34% Rel~H.) Total Volts Clings Control 1 52.9 2 Control 2 44.6 0 Composition No.l 11.3 0 Composition No.2 9.0 0 ~2ai~

SGftening Performance ~ Ranel ~core Units lst load nd load Control 1 STD STD
Control 2 0.5 0.8 Composition No. 1 1.4 1.4 5 Composition No. 2 1.5 0.7 LSD* at 95% confidence was. 0.5 ~nel $core units *Least signi~icant dif~erence As shown b~ the ~esults, CompoSitions No.'s 1 and 2, which are within the scope of this invention, provide ~ sQ~tenins e~ect to fab~ics xelati~e to Control 1 and the softening e~fect ls superior to that provided by Control 2 which contains a mixture o tertia,Xy ,a~ines.

In Co~position No. 1 when sodium tripoly-phosph~te or sodium tetraborate replaced the sodium carbonate as the soluble salt in the ~gglome-rated par-ticul~te deter~ent additive substanti~lly similar results were observed.
In Com~o$ition No. 1 when the 2;3 ratio of DTDM~C: DTMA was replaced by a 3:2 ratio of DTDMAC, DTM~ ~ubst~ntiall~ ~lmil~x ~esults were observed.
In Composition N~. 1 when the 2.3 ratio of DTDM~C: DT~ was replaced b~ a 1:4 ratio of DTDMAC:DTM~ the softenin~ benefit observed was less than Co~position N~ nd abou-t equal to Control 2.
In Composition No. 1 when the 2:3 ratio of DTDMAC: DTMA iS replaced by a 9:1 ra-tio of DTDMAC:DTMA substantially similar results were ~3~

observed.
Comparable results are obtained when the sodium carbonate in the agglomerated particulate detergent additive of Composition No. 1 is replaced by sodium tripolyphosphate, sodium tetraborate, potassium tetraborate, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, potassium tripolyphosphate, sodium pyrophosphate, potassium pyrophos~hate, sodium hexametaphosphate, potassium hexametaphosphate, sodium sulfate, potassium sul~ate, sodium citrate, potassium citrate, and mixtures of the water-soluble, alkaline salts.
Co~parable re~ults ~e obtained when the ~uaternar~ ammonium compound utilized is ditallow-dimethyl ammonium methylsul~ate, ditallowdimeth~1 ammonium ethvlsulfate~ 1-meth~ (tallow amido~
ethyl] 2-tallow imidazolinium methyl sulfate, or ' mixtures thereof in place of the ditallowdimethyl ammonium chIoride on a part for part basis.
Csmparable results. are obtained when the DTM~ in the agglomerated par~iculate detergent additive is replaced b~ didec~l ~eth~l~mine, didecyl heptylamine, dicoconut methylamine, di-coconut bu-tylamine, d.im~ri~tyl ~ethylamine, di-myristyl ethylamine, dicetyl methylamine, diara-chidyl methylamine, dibehenyl methylamine, and di(mixed arachidyl~ behenyl) meth~lami,ne.
Since the intimate mixture of quaternary ammonium salt and tertiary amine part:icles are essentially water-insoluble ! e~en under alkaline conditions, they are wholly compatible with all manner of detersive surfactants and de-tergency builders. Thus, the detergen-t component in C~mpo-sition No. 1 can include any of the sur-factants ~nd builders disclosed he~einabove and ~till deliver the softening to :Eabrics through-the-wash provided by the agglomerated particulate detergent additive.
Compositions 1 and 2 show that the insoluble, small particles of the intimate mixture of quaternary ammonium salt and textiary amine do deposit on fabrics during washing -to provide a softening benefit to the fabrics ~erel~ with line drying. The softening benefit delivered to the fabrics will be greater when the washed ~abrics are machine dried with heat ~h~ch melts the parti-cles on the fabric and provides a better coating to the fibers.

15 WHAT I S CLAI~IED I S `

Claims (33)

1. A particulate detergent additive product adapted to soften textiles when applied thereto from a detergent wash liquor, said particulate product being an intimate mixture consisting essentially of:
A. from about 90% to 20% of a quaternary ammonium salt having the formula [RlR2R3R4N]+Y- wherein at least one but not more than two of R1R2R3 and R4 is an organic radical containing a group selected from a C16 to C22 aliphatic radical, or an alkyl phenyl or alkyl benzyl radical having 10 to 16 carbon atoms in the alkyl chain, the remaining group or groups being selected from C1 to C4 alkyl, C2 to C4 hydroxyalkyl, and cyclic-structures in which the nitrogen atom forms part of the ring, Y constitut-ing an anionic radical selected from the group consisting of hydroxide, halide, sulfate, methylsulfate, ethylsulfate, and phosphate ions; and B. from about 80% to 10% of a tertiary aamine having the formula R1R2R3N wherein R1 and R2 are independently selected from C10 - C22 alkyl or alkenyl groups, and R3 represents a C1 - C7 alkyl group, wherein substantially all the individual particles have a size in the range of 10µ to 500 µ , a solubility in water of 50 ppm maximum at 25°C. and a softening point in the range of from about 90°F.
to about 200°F.

2. An agglomerated particulate detergent addi-tive product adapted to soften textiles when applied thereto from a detergent wash liquor, said product being an agglomerate of A. from about 10% to about 80% by weight of the particles of Claim 1;
B, from about 10% to about 80% by weight of a water-soluble, neutral or alkaline salt; and C. from about 0% to about 20% by weight of an organic agglomerating agent.

3. The composition of Claim 2 where substantially all the particles (A) are from 25 µ to about 200 in size.

4. The composition of Claim 3 where substantially all the particles (A) are from about 50 µ to about 100 µ in size.

5. The composition of Claim 2 wherein the water-soluble, neutral or alkaline salt is selected from the group consisting of the alkali metal salts of carbonates, tetraborates, orthophosphates, poly-phosphates, bicarbonates, silicates t sulfates, citrates, and mixtures thereof.

6. The composition of Claim 5 where the water-soluble, neutral or alkaline salt is selected from the group consisting of sodium tetraborate, potassium tetraborate, sodium bicarbonate, potassium bicarbo-nate, sodium carbonate, potassium carbonate, sodium tripolyphosphate, potassium tripolyphosphate, sodium pyrophosphate, potassium pyrophosphate, sodium hexametaphosphate, potassium hexameta-phosphate, sodium sulfate, potassium sulfate, sodium citrate, potassium citrate, sodium silicate, and mixtures thereof.

7. The composition of Claim 5 which contains from about 20% to about 50% by weight of the water-soluble, neutral or alkaline salt.

8. The composition of Claim 7 which contains from about 25% to about 35% by weight of the water-soluble, neutral or inorganic salt.

9. The composition of Claim 7 where the quater-nary ammonium compound is selected from ditallow dimethylammonium chloride, ditallow dimethylammo-nium methylsulfate, 1-methyl-1-[(tallowamido)ethyl]-2-tallowimidazolinium methylsulfate, and mixtures thereof.

10. The composition of Claim 7 where the tertiary amine is selected from ditallow methylamine, dicoconut methylamine, dicetyl methylamine, distearyl methylamine, diarachidyl methylamine, dibehenyl methylamine, and mixtures thereof.

11. The composition of Claim 10 wherein the ratio of quaternary ammonium compound to tertiary amine is from 4:1 to 1:2.

12. The composition of Claim 11 where the ratio of quaternary ammonium compound to tertiary amine is from 3:2 to 2:3.

13. The composition of Claim 12 where the quaternary ammonium compound-tertiary amine particles are present at from about 15% to about 50% by weight.

14. The composition of Claim 13 where the quater-nary ammonium compound-tertiary amine particles are present at from 20% to about 40% by weight.

15. The composition of Claim 13 which contains from about 5% to about 15% by weight of an organic agglomerating agent selected from the group consist-ing of dextrin, a solution of dextrin in water, polyethylene glycol, polypropylene glycol, the condensation product of one mole of carboxylic acid having from about 10 to about 18 carbon atoms with from about 20 to about 50 moles of ethylene oxide, the condensation product of one mole of alcohol haying from about 10 to about 24 carbon atoms with from about 9 to about 50 moles of ethylene oxide, polyoxyethylene glyceride, polyoxyethylene lanolin derivative, amide, and the condensation product of one mole of alkyl phenol having an alkyl chain from about 8 to about 18 carbon atoms with from about 25 to about 50 moles of ethylene oxide, and mixtures thereof.

16. The composition of Claim 15 where the organic agglomerating agent comprises a dextrin-in-water solution containing from about 10% to about 60%
dextrin.

17. The composition of Claim 16 where the agglome-rated particulate detergent additive product is additionally admixed with about 5% to about 50% by weight of a smectite clay having an ion exchange capacity of at least 50 meg/100g.

18. The composition of Claim 17 where the smectite clay content is from about 10% to about 40% by weight.

19. The composition of Claim, 18 where the smectite clay content is from about 20% to about 35% by weight and the ion exchange capacity of the smectite clay is at least 60 meq/100g.

20. The composition of Claim 18 where the smectite clay is selected from the group consisting of sodium montmorillonite, sodium hectorite, sodium saponite, calcium montmorillonite, lithium hectorite, and mixtures thereof.

21. The composition of Claim 16 where the quaternary ammonium compound is ditallow dimethylammonium chloride.

22. The composition of Claim 21 where the tertiary amine is ditallow methylamine.

23. The composition of Claim 22 where the water-soluble salt is selected from sodium carbonate, sodium tripolyphosphate, and sodium tetraborate.

24. The composition of Claim 23 where the agglome-rated particulate detergent additive product is additionally admixed with from about 20% to about 35% by weight of sodium montmorillonite clay having an ion exchange capacity of at least 60 meq/100g.

25. A detergent composition for softening fabrics laundered therewith, comprising:
(1) from about 5% to about 85% by weight of surfactant selected from the group consisting of anionic, nonionic, ampholytic, and zwitterionic surfactants, and mixtures thereof;

(2) from about 5% to about 85% by weight of detergency builders;
(3) from about 5% to about 50% by weight of an agglomerated particulate detergent additive comprising:
(a) from about 10% to about 80% by weight of a water-soluble, neutral or alkaline salt; and (b) from about 10% to about 80% by weight of particles being an intimate mixture of from about 90% to about 20% by weight of the particles of a quaternary ammonium compound having the formula[R1R2R3R4N]+Y-wherin at least one but not more than two of R1R2R3 and R4 is an organic radical containing a group selected from C16 to C22 aliphatic radical, or an alkyl phenyl or alkyl benzyl radical having 10 to 16 carbon atoms in the alkyl chain, the remaining group or groups being selected from C1-to C4 alkyl, C2 to C4 hydroxyalkyl, and cyclic structures in which the nitrogen atom forms part of the ring, Y constituting an anionic radical selected from the group consisting of hydroxide, halide, sulfate, methylsulfate, ethylsulfate, and phosphate ions, and (ii) from about 80% to about 10% by weight of the particles of a tertiary amine having the formula R1R2R3N wherein R1 and R2 are independently selected from C10 to C22 alky or alkenyl groups, and R3 represents a C1 to C7 alkyl group; and (C) from about 5% to about 15% by weight of an organic agglomerating agent, wherein substantially all of the individual par-ticles (b) ahve a size of about 10µ to about 500 µ a solubility in water of about 50 ppm maximum at 25°C. and a softening point of from about 90°F. to about 200°F.

26. The composition of Claim 25 wherein the agglome-rated particulate detergent additive comprises from about 20% to about 50% by weight of a water-soluble neutral or alkaline salt selected from the group consisting of sodium carbonate, sodium tripolyphos-phate, sodium tetraborate, and mixtures thereof.

27. The composition of Claim 26 wherein the agglomerated particulate detergent additive comprises from about 15% to about 50% by weight of component(b).

28. The composition of Claim 26 wherein the agglomerated particulate detergent additive comprises from about 20% to about 40% by weight of component(b) which is a ditallow dimethylammonium to ditallow methylamine mixture in the ratio range of from 2:3 to 3:2, and wherein the size of the particles is in the range of from 50 µ to about 100 µ.

29. The composition of Claim 28 wherein the agglomerated particulate detergent additive comprises from about 5% to about 15% of dextrin glue as the agglomerating agent.

30. The composition of Claim 29 where the agglome-rated particulate detergent additive additionally contains from about 10% to about 40% by weight of admixed sodium montmorillonite clay having an ion exchange capacity of at least 60 meq./100g.

31. The composition of Claim 30 which contains from about 5% to about 50% by weight of surfactant.

32. The composition of Claim 31 which contains from about 10% to about 30% by weight of surfactant.

33. The composition of Claim 32 which contains from about 15% to about 60% by weight of detergency builder.