CA1152262A - Fabric softening compositions - Google Patents

Abstract

FABRIC SOFTENING COMPOSITIONS

ABSTRACT

Fabric softening compositions are described containing a combination of an electrolyte and a complex of certain smectite clays with certain organic amines or their salts or certain quaternary compounds. The compositions provide fabric softening to laundered fabrics during the rinsing operation or can be incorpor-ated into detergent compositions to provide fabric soften-ing through the wash.

Description

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FAERIC SOFTENING COMPOSITIONS
Maxie Davis, Jr.

Technical Field This invention relates to solid com- -positions and methods for conditioning fabrics in home laundering operations. Compositions and methods are dis-closed which provide for conditioning fabrics in through-the-wash laundering operations as well as during the rinse cycle of home laundering operations. It is a common prac-n tice to impart to laundered fabrics a texture or handlethat is smooth, pliable and fluffy to the touch (i.e. soft) and also to impart to the fabrics a reduced tendency to pick up and/or retain an electrostatic charge (i.e. static control), especially when the fabrics are dried in an automatic dryer.
It has become commonplace today for homemakers to use fabric conditioning compositions. A common practice is to use fabric conditioning compositions for use in the rinse cycle which comprise major amounts of water, lesser amounts of fabric conditioning agents and minor amounts of optional ingredients such as perfumes, colorants, pre-servatives and stabilizers. Such compositions can be con-veniently added to the rinsing bath of home laundry oper-ations. An alternative method is to provide laundering compositions containing the fabric conditioning agent which deposits on the fabric and is carried through the wash and rinse cycles to provide the fabric conditioning property on the dried fabric.

Background Art 3C The use of organic cationic fabric softeners is known. Blomfield in U.S. Patent 3,095,373 discloses cationic chemical compounds having at least one hydrophobic -1~ 2 -chain having at least 16 carbon atoms for use as softening agents for laundered fabrics.
The use of clays as softening agents is also known. A number of kinds of clay have been suggested for 5 use in detergent compositions for many years, for example, British patents 401,413, Mariott, accepted Nov. 16, 1933 and 461,221, Marriott et al, accepted Feb. 12, 1937 disclose the use of colloidal bentonite in synthetic detergent com-positions, built or unbuilt, intended for the washing of hair, textiles, or hard surfaces. More recently British patent 1,400,898, Storm and Nirschl, sealed Nov. 19, 1975 disclosed the use of certain smectite clays in built deter-gent compositions to provide through-the-wash fabric sof'ten-ing, and British patent 1,401,726, Ohren, sealed Nov. 25, 1975 disclosed the use of those clays in soap compositions containing a minor amount of synthetic'detergents as curd dispersants. Other prior art references have disclosed the use of clay in washing compositions to provide other benefits, such as builder, water-softener, anticaking agent, suspending agent, soil release agent,'hair ulling agent, and filler.
The use of clay and organic cationic fabric softening ingredient combinations in detergent compositions for the simultaneous purpose of cleaning and softening fabrics, in addition to other auxiliary benefits, such as static control, is also known. Bernardino in U.S.
Patent 3,886,075 discloses compositions comprising par-ticular smectite clays, cationic anti-static agents and certain substituted amino compatibilizing agents which are detergent compatible and provide softening and anti-static benefits to fabrics washed therein. Speakman in U.S. Patent 3,948,790 discloses detergent compositions containing short chain quaternary ammonium clays which are effective in providing fabric softening with non-ionic detergents.

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C. F. Battrell, U.S. Patent 4,292,035, issued September 21, 1981 discloses that complexes of clay and the organic fabric softening agent are useful in softening clothes both in the rinse and through-the-wash. Battrell teaches that the composition must contain an anionic surfactant which is present in at least 30% molar equivalence to the organic fabric softening agent to provide wetting and dispersion of the complex.
Disclosure of the Invention The present invention relates to fa~ric condition-ing compositions in solid form for use in the home launder-ing process. These compositions comprise three essential components: (a) from about 10% to about 80% by weight of an impalpable smectite clay having an ion exchange capacity of at least 50 meq/100 grams; (b) from about 1% to about 50% by weight of said clay of a compound selected from the group consisting of organic primary, secondary, and tertiary amines,and their water soluble or water dispersible salts, and organic ~uaternary ammonium,phosphonium,and sulfonium compounds wherein said compounds have at least one hydro-carbon group having from 8 to 22 carbon atoms; and (c) from about 10% to about 90~ of an electrolyte having a solubility in water of at least about 7 parts per 100 parts of water at 20C.; wherein components (a~ and (b) are combined to form a complex. It has been unexpectedly discovered that the electrolyte provides sufficient wetting and dispersion of the clay/organic softening agent without requiring the inclusion of an anionic surfactant.

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.

These novel compositions provide fabric softening in the rinsing operation of typical laundering processes or can be admixed or incorporated into granular or solid detergent cleaning formulations to provide through-the-wash 5 fabric softening.

Detailed Description of the Invention .

The Clay The first of the three essential ingredients of this invention is smectite clay. The clay is com-plexed with the organic fabric softening agent to pro-vide the fabric conditioning utility. Smectite clay is present in the granular fabric conditioning compo-sition at levels from about 10~ to about 80%, preferably from about 20% to about 60%, by weight of the compo-sition.
The clay minerals used to provide part of thesoftening properties of the instant compositions can be described as impalpable, expandable, three-layer clays, in which a sheet of aluminum/oxygen atoms or magnesium/oxygen atoms lies between two layers of silicon/oxygen atoms, i.e., alumino-silicates and mag-nesium silicates, having an ion exchange capacity of at least 50 meq./100 g. of clay. The term "impalpable"
as used to describe the clays employed herein means that the individual clay particles are of such a size that they cannot be perceived tactilely. Such particles sizes are within the range below about 100 microns in effective diameter. In general, the clays herein have an ultimate particle size within the range from about l micron to about 50 microns. The term "expandable"

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as used to describe clays relates to the ability of the layered clay structure to be swollen, or e~panded, on contact with water. The three-layer expandable clays used herein are examples of the clay minerals classified ~geologically as smectites.
There are two distinct classes of smectite clays that can be broadly differentiated on the basis of the numbers of octahedral metal-oxygen arrangements in the central layer for a gi~en num~er of silicon-oxygen atoms in the outer layers. The dioctahedral minerals are primarily trivalent metal ion-based clays and are comprised of the prototype pyrophyllite and the members montmorillonite (OH)4Si8_yAly(A14_xMgx) 20 (OH34Si8_yAly(A14_xFex)O20, and volchonskoite lS (H)4si8_yAly(Al4-xcrx)o2ot where x has a value of from 0 to about 4.0 and y has a value of from 0 to about 2Ø Of these only montmorillonites having exchange capacities greater than 50 meq/100 g. are suitable for the present invention and provide fabric softening benefits.
The trioctahedral minerals are primarily divalent metal ion based and comprise the prototype talc and the members hectorite (OH)4Si8 yAly(Mg6 XLix)O20, saponite (oH)4(si8-yAly)(Mg6-xAlx)o2o~
(H)4Si8_yAIy(Zn6-xAlxlo2o~ vermiculite (OH)4Si8 Al (Mg6_xFex)O20, wherein y has a value of 0 to about 2.0 and x has a value of 0 to about 6Ø Hectorite and saponite are the only minerals in this class that are of value in the present invention, the static reduction or fabric softening performance being related to the type of exchangeable cation as well as to the exchange capacity.
The smectite clays useful in the present in-vention are hydrophilic in nature, i.e. they display swelling characteristics in aqueous media.
It is to be recognized that the range of the water of hydration in the above formulas can vary with the processing to which the clay has been subjected.
This is immaterial to the use of the smectite clays in I

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the present invention in that the expandable character-istics of the hydrated clays are dictated by the silicate lattice structure.
As noted hereinabove, the clay minerals employed in the compositions of the instant invention contain cationic counterions such as protons, sodium ions, potassium ions, calcium ions, magnesium ions, li'hium ions, and the like. It is customary to distinguish between clays on the basis of one cation predominantly or exclusively absorbed. For example, a sodium clay is one in which the absorbed cation is predominantly sodium. Such absorbed cations can become involved in exchange reactions with cations present in aqueous solutions. A typical exchange reaction involving a smectite clay is expressed by the following equation:

smectite clay (Na~ +NH40H ~ smectite clay (NH4) ~NaO~

Since in the foregoing equilibrium reaction, one equivalent weight of ammonium ion replaces an equivalent ~eight of sodium, it is customary to measure cation exchange ca-pacity (sometimes termed "base exchange capacity") interms of milliequivalents per 100 g. of clay(meq./100 g.).
The cation exchange capacity of clays can be measured in several ways, including by electrodialysis, by exchange with ammonium ion followed by titration or by a methylene blue procedure, all as fully set forth in Grimshaw, "The Chemistry and Physics of Clays", pp. 264-265, Interscience ~1971). The cation exchange capacity of a clay mineral relates to such factors as the 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 widely in the range from about 2 meq/
100 g. for kaolinites to about 150 meq/100 g., and greater, for certain smectite clays. Illite clays although having a three layer structure, are of a non-expanding lattice type and have an ion exchange capacity ` ` ilSZZ6Z

somewhere in the lower portion of the range, i.e., around 26 meq/100 g. for an average illite clay. Attapulgites, another class of clay minerals, have a spicular (i.e.
needle-like) crystalline form with a low cation exchange S capacity (25-30 meq/100 g.). Their structure is com-posed of chains of silica tetrahedrous linked together by octahedral groups of oxygens and hydroxyls containing Al and Mg atoms.
It has been determined that illite, attapulgite, and kaolinite clays, with their relatively low ion ex-change capacities, are not useful in the instant compo-sitions. However the alkali metal montmorillonites, saponites, and hectorites and certain alkaline earth metal varieties of these minerals such as calcium and sodium montmorillonites have been found to show useful fabric softening benefits when incorporated in compositions in accordance with the present invention.
Specific non limiting examples of such fabric softening smectite clay minerals are:

Sodium Montmorillonite Brock ~
Volclay ~C
Gelwhite GP
Thixo-Jel~ 1 Ben-A-Gel~
.
Sodium Hectorite Veegu ~
Laponite~SP

Sodium Saponite Barasy ~ AS 100 Calcium Montmorillonite Soft Clar Gelwhite~L

Lithium Hectorite ~a Barasym~IH 200 Most of the smectite clays useful in the com-positions herein are commercially available under various trademarks, for example, Thixo-Jel #1 and Gelwhite GP
from Georgia Kaolin Co., Elizabeth, New Jersey; Volclay BC and Volcaly #325, from ~merican Colloid Co., Skokie, Illinois; and Veegum F, from R. T. Vanderbilt. It is to be recognized that such smectite minerals obtained under the foregoing tradenames can comprise mixtures of the various discrete mineral entities. Such mixtures of the smectite minerals are suitable for use herein.
Within the classes of montmorillonite, hecto-rite, and saponite clay minerals having a cation e~-change capacity of at least about 50 meq/100 g., certainclays are preferred for fabric softening purposes. For example, Gelwhite GP is an extremely white form of smectite clay and is therefore preferred when formulating white or lightly colored agglomerates. Volclay BC which is a smectite clay mineral containing at least 3~ of iron (expressed as Fe2O3) in the crystal lattice, and which has a very high ion exchange capacity, is one of the most efficient and effective clays for use in agglomerated fabric conditioning compositions and is preferred from the standpoint of product performance. On the other hand, certain smectite clays marketed under the name "bentonite" are sufficiently contaminated by other silicate minerals, as evidenced by a low colloid content (~50~) that their ion exchange capacity falls helow the requisite range, and such clays are of no use in the instant compositions.
Bentonite, in fact, is a rock type originating from volcanic ash and contains montmorillonite (one of the smectite clays) as its principal clay component.
The Table shows that materials commercially available under the name bentonite can have a wide range of cation llSZ2f~Z

e.Ychange capacities and fabric softening performance.
Mixtures of two or more types of clay are con-templated within the scope of this invention.

EXCHANGE CAPACITY
5 BENTONITE meq/100 q. _FTENING ABILITY
Brock 1 63 Good Soft Clark 84 Good Bentolite L 1 68 Fair - Good Clarolite T-60 61 Fair 10 Granulare 2 Naturale Bianco 23 Fair - Poor Thixo-Jel #4 55 Poor*
Granular Naturale Normale 19 Poor 15 Clarsol FB 5 3 12 Poor PDL 1740 26 None Versuchs 4 Product FFI 26 None SUPPLIED BY AND TRADEMARK OF:
1 Georgia Kaolin Co. USA

2 Seven C. Milan Italy

3 Ceca Paris France

4 Sud-Chemie Munich Germany * Low colloid content ( ~50~) 2S It has also been found that certain smectite minerals can reduce or eliminate the buildup of static electricity on fabrics washed in the compositions. The visible evidence that static buildup has been prevented is the absence of "cling", i.e., the tendency of dif-ferent areas of fabric to adhere to one another. A

r :, `~ ~152262 measure of the approach to static charge elimination is the mean voltage of the fabric.
The smectite minerals that have proved to be beneficial in reducing static buildup when incorporated into agglomerated fabric conditioning compositions are the lithium and magnesium hectorites and saponites, i.e., minerals of the structure (OH~4Si8 yAl (Mg6 Li )20 and (H)4si8_yAlyMg6-xAlxo2o respectively in which the counter ions are predominantly magnesium or lithium, i.e., at least 50% of the counter ions are Li or Mg , the remainder being other alkaline earth or alkali metal counter ions.
Preferred minerals are those in which 75-90~
of the counter ions are lithium or magnesium and for which the cation exchange capacities are greater than 60 meq/
100 g. Specific examples of such preferred materials are magnesium hectorite, lithium hectorite, and magnesium saponite.
It is believed that the universal henefit given by the Mg+~ and Li~ hectorite and saponite clay minerals is related to the size to charge ratio of these cations and the unusually large nu~ber of moles of water that can be held by them.
Minerals that have fabric softening character-istics such as the sodium and calcium montmorillonitesand the sodium hectorites and saponites do not exhibit appreciable antistatic activity, nor does magnesium montmorillonite.
Accordingly, smectite clays useful in the fabric conditioning compositions of this invention can be characterized as montmorillonite, hectorite, and saponite clay minerals having an ion exchange capacity of at least about 50 meq/100 g. and preferably at least 60 meq/100 g.
Appropriate clay minerals for use herein can be selected by virtue of the fact that smectites e~hibit a true 14A x-ray diffraction pattern. This character-istic pattern, taken in combination with exchange capacity measurements performed in the manner noted above, pro-vides a basis for selecting particular smectite minerals for use in the granular fabric conditioning compositions disclosed herein.
The smectite clays described hereinabove function as fabric conditioning agents by depositing on fiber surfaces, particularly cotton surfaces that are negatively charged. They are effective, not only on the surfaces of 100% cotton fabric, but also upon fabric blends that contain significant amounts of cotton, for example a 50% cotton/50% polyester blend. The discrete, in-dividual smectite clay particles are in the form of flat platelets, having a predominantly positive charge around the edges where the crystal lattices are incomplete, and having a predominantly negative charge on the flat sides thereof.

The Organic Fabric Softening Aqent The second essential ingredient of this in-vention is the organic fabric softening agent which is reacted with the clay to form the water insoluble complex.
The organic fabric softening agent is present in compositions of this invention at levels of from 1~ to 53% by weight of the clay component. Preferred levels range from 3%
to 30%, most preferred 5% to 20%, of the clay component.
In general, useful softeners are organic com-pounds which contain primary, secondary, tertiary or quaternary nitrogen or which are phosphonium or sul-fonium compounds and have at least one relatively longhydrocarbon group substituent conferring hydrophobicity and lubricity. Mixtures of these compounds can also be used in this invention. Typical fabric softeners include A. Primary, secondary,and tertiary amines and their water soluble or water dispersible salts,and quaternary ammonium compounds~ The general formulas for this group are l~SZZ62 lR2R3 ; ~ 1 2 3 4 ~n wherein Rl represents an alkyl or alkenyl having from about 8 to about 22, prefera~ly 12 to 18, carbon atoms and R2, R3 and R4 each independently represent hydrogen or alkyl, alkenyl, arylalkyl or alkylaryl having from 1 to 22 carbon atoms, and X represents a water soluble or water dispersible anion and n is an integer from 1 to 3, preferably 1 to 2.
Examples of suitable anions include hydroxide, chloride, bromide, sulfate, methosulfate or similar anion.
Examples of the above include primary tallow amine, primary tallow amine hydrochloride, primary coconut amine, secondar~ tallow methyl amine, tallow dimethyl amine, coconut dibutyl amine, monostearyl dimethyl ammonium chloride, tri-oleyl ammonium chloride, dicoconut dimethyl ammonium chloride, tallow trimethyl ammonium chloride, ditallow dimethyl ammonium chloride, tetralauryl ammonium chloride, tetra-tallow ammonium chloride, ditallow methyl ammonium chloride and tallow dimethyl ammonium chloride. Preferred for use in this invention are secondary ditallow amine, trilauryl amine, tritallow amine, secondary dicoconut amine. A highly preferred compound is ditallow methyl amine.
` .
B. The diamine and diammonium salts having the general formulas RlR~NR5NR3R4 ; [RlR2NR5NR3R4 6]n 1 2 3 5 4 6]n X ; [RlR2R3NR5NR4R6R7]2+ X2-wherein Rl, R2, R3, R4, n and X are as defined above, R~
and R7 have the same definition as R2 to R4 and R5 is an alkylene chain having from 4 to 6 carbon atoms wherein the middle carbon atoms may be lin];ed to each other by an ether 30 oxygen or by a doul)le or triple hond. Common among the available diamines are N-al~yltrimetllylene diamines (R-I~EI-C3H6-NII2). ~ s~ecific example of a suitable diamine is 2~2~-biststearyl dimethyl ammonio) diethylether dichloride.

C. The ethoxylated amine and diamine salts with fatty alkyl groups of coconut, tallow, soya and stearyl having from 2 to 50 moles of ethylene oxide, typically with 2, 5, 15 or 50 moles ethylene oxide, are also suitable.

D. Alkyl imidazoline and imidazole salts wherein the alkyl group is lauryl, oleyl, stearyl, or tall oil, are also suitable for the invention provided the system is not too alkaline. Specific examples of these compounds are l-beta hydroxyethyl-2-stearyl imidazoline ammonium chlo-ride and 2-stearyl-1, l-methyl [(2-stearylamido) ethyl]
-imidazolinium methosulfate.

E. Yet another suitable softening agent includes alkyl pyridine and piperidine salts wherein the alkyl group has from abcut 8 to 22 carbon atoms. Examples include stear-amidomethyl pyridinium chloride, and stearyl pyridiniumchloride.

F. Yet other additional softening agents include alkyl sulfonium and alkyl phosphonium salts wherein the alkyl group has from 8 to 22 carbon atoms. Compounds in this group are quaternized and will combine with the clay.
An example of a salt of this type is ~6~3~ ~ ~ ~ C~ Cl-G. Further additional softening agents include esters of amino acids and amino alcohols wherein at least one of the two hydrocarbon chains has from 8 to 22 carbon atoms and the second hydrocarbon chain can be an alkyl having from 1 to 4 carbon atoms or an alkyl having from 8 to 22 carbon atoms.

` -- 1152262 H. Further additional softening agents include the fatty acid ester salts of mono-, di- ~nd tri-ethanolamine salts, and the alkyl guanidine salts in which the alkyl group contain 8 to 22 carbon atoms.

The suitable organic fabric softening agents will combine with the clay to form a complex including the compounds that are not in salt form.
The reaction of the organic cationic softener with the $mectite clay proceeds predominantly via an 10 ion exchange mechanism until the cation exchange capacity of the clay is approached and thereafter the mechanism is one of adsorption~ The once negativel~ charged clay particles become increasingly~ electropositive and with continued adsorption a reversal of charges occurs for 15 the organo-clay complex. The interactions between the clay and the organic cationic softener are strong and change the physical properties of the clay (i.e.
viscosity, colloid stability, and the clay becomes hydrophobic~.
; 20 ~ Conversely, the reaction of the neutral organic softeners ~ith the smectite clay proceeds predominantly via an adsorption mechanism. However, some ion exchange between the softener and labile inorganic cations of the clay has been observed. The interactions between the 25 neutral organic softener and the clay are strong and change the physical properties of the clay in the same way as was mentioned above for the organic cationic softener-clay complexes.

1~2262 The Electrolyte The third essential ingredient of this invention is the electrolyte which is the wetting and dispersing agent for the complex. The electrolytes suitable for this in-vention have a solubility of at least 7 parts, preferablyat least 10 parts, electrolyte per 100 parts of water at 20C. The electrolyte is present at levels of from about 10% to about 90%, preferably from about 20% to about 80~, and most preferably from about 30% to about 50%, by weight of the composition.
The electrolytes can be crystalline or amorphous in nature. Further, they can be in either an anhydrous or a hydrated form since either form is suitable for this in-vention. The electrolytes promote rapid admission of 15 water into the solid compositions of this invention, rapid dispersion of the composition into its ultimate particles, and rapid dispersion of the ultimate particles of clay throughout the rinsing bath.
When compositions of this invention are made by 20 agglomeration of the clay/organic fabric softening agent complex and the electrolyte, the discrete individual ; particles of electrolyte before agglomeration have an effective diameter below about 200 microns, and preferably from about 30 to about 100 microns.
Preferred electrolytes are aluminum sulfate and chloride and alkali metal and alkaline earth metal chlorides, sulfates, carbonates, bicarbonates, sesqui-carbonates, orthophosphates, pyrophosphates, tripoly-phosphates, borates, silicates, nitrates, acetates, 30 urea and mixtures thereof that meet the solubility test described hereinbeore. Sodium sesquicarbonate is a highly preferred electrolyte for use in this invention.
; Other highly preferred electrolytes are hardness-electrolyte salts, specifically salts of Ca and Mg Especially highl~ preferred are magnesium sulfate, magnesium chloride, and calcium chloride. These hardness-electrolyte salts still further and unexpectedly increase the fabric conditioning effectiveness of the instant compositions.
S While not wishing to be bound by theory, it is believed that there are two phenomena at work which effect the beneficial results of hardness-electrolytes on fabric conditioning. One factor appears to be that, the negative charges on fabric surfaces and the negative charges present 10 on the faces of the smectite clay platelets are bridged by the hardness-electrolyte thereby increasing the at-traction of the clay/organic fabric softening agent complex to the fabric surfaces, and hence increase their deposition.
The second factor is that the hardness-electrolyte will 15 destabilize the organic softening agent-clay complex disnersion by collapsing the double layer repulsion forces between the clay platelets allowing the complex to deposit more readily on the fabric surfaces.
It ~ill be appreciated that hardness-electrolyte 20 salts are especially beneficial when the ~ater used for the rinsing bath is soft, i.e., contains hardness below about 3 grains per U.S. gallon expressed as CaCO3. Increased effectiveness in fabric conditioning, relative to soft water, was noted for compositions of the instant invention 25 wherein the water hardness of the rinse bath was 15 grains per U.S. gallon.
Non-limiting examples of the solubility of electrolyte materials are (parts electrolyte per 1~
parts water at 20C.): aluminium sulate octadecahydrate 30 (36), calcium chloride hexahyclrate (74), magnesium chloride hexahydrate (54), magnesium sulfate heptahydrate (35), sodium carbonate decahydrate (21), sodium sulfate heptahydrate (19), sodium chloride (101), anhydrous sodium carbonate (15), anhydrous sodium bicarbonate (9), sodium sesquicarbonate (19).

` llsæ6z Optional Ingredients Anionic Surfactants The softener composition need only include the organo-clay complex and the eIectrolyte. The composition

5 can also include a minor amount of an anionic surfactant.
When included, the anionic surfactant is present at from about 1~ to about 29% molar equivalence to the organic softening agent. Preferably the anionic surfactant is present at a level of from about 5~ to about 25~, most 10 preferably from about 10% to about 20~, molar equivalence to the organic fabric softening agent.

Water-soluble salts of the higher fatty acids, i.e., "soaps" are useful as the anionic surfactant herein.
This class of surfactants includes ordinary alkali metal 15 soaps such as the sodium, potassium, ammonium, and alkanolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms and preferably from about 10 to about 20 carbon atoms. Soaps can be made by direct saponification of fats and oils or by neu-20 tralization of free fatty acids. Particularly usefulare the sodium and potassium salts of the mixtures of fatty acids, derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soaps.
The anionic synthetic surfactants suitable for 25 this invention include water-soluble salts, particularly the alkali metal salts, or organic sulfuric reaction products having in their molecular structur~ an alkyl group containing from about 8 to about 22 carbon atoms and a moiety selected from the group consisting of 30 sulfonic acid and sulfuric acid ester moieties. (Included ` 115Z262 in the term alkyl is the alkyl portion of higher acyl moieties.) Examples of this group of synthetic surfact-ants which form a part of the softener compositions of the present invention are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C8-C18 carbon atoms~ produced by reducing the glycerides of the tallow or coconut oil; sodium and po-tassium alkyl benzene or toluene sulfonates in which the alkyl group contains from about 9 to about 20, 9 to 15 preferred, carbon atoms in straight chains or branched-chain configuration, e~g. those of the type described in United States Patents Number 2,220,099 and 2,477,383 (especially Yaluable are linear straight chain alkyl benzene sulfonates in which the average of the alkyl groups is about 11.8 carbon atoms and com-monly abbreviated as Cll 8LAS); sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium and potassium salts of sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol (.e.g. tallow or coconut oil alcohols) and about 1 to 6 moles of ethylene oxide; sodium and potassium salts of alkyl phenol ethylene oxide ether sulfates with about L to about 10 units of ethylene o~ide per molecule and in which the alkyl groups contain from about 8 to about 12 carbon atoms.
Anionic phosphate surfactants are also useful in the present invention. These are surace active materials in which the anionic solubilizing group connecting hydrophoblc moieties is an o~y acid of phosphorus. The more common solubilizing groups, of ' course are -SO4H and -SO3H. Alkyl phosphate esters i such as (R-0)2PO2H and ROPO3H2 in which R represents an alkyl chain containing from about 8 to about 20 carbon atoms are useful herein.

ilS2Z62 These phosphate esters can be modified by in-cluding in the molecule from one to about 40 alkylene oxide units, e.g., ehtylene oxide units. Formulae for these modified phosphate anionic surfactants are o If [ ( 2 2 ) ]2 or [R-o-(cH2cH2o~n]-p-o-M
O-M

in which R represents an alkyl group containing from about 8 to 20 carbon atoms , or an alkylphenyl group in whieh the alkyl group contains from about 8 to about 20 earbon atoms, and M represents a soluble cation such as hydrogen, sodium, potassium, ammonium or substituted ammonium; and in which n is an integer from 1 to about 40.
Another class of suitable anionic organie sur-factants particularly useful in this invention includessalts of 2-ae~loxy-alkane-1-sulfonic acids. These salts have the formula Rl - CH - CH2S03M

where Rl i5 alkyl of about 9 to about 23 carbon atoms (forming with the two carbon atoms an alkane group);
R2 is alkyl of 1 to about 8 carbon atoms; and M is a water-soluble cation.
The water-soluble cation, M, in the herein-before described structural formula can be, for e~ample, 115~262 an alkali metal cation (e.g., sodium, potassium, lithium), ammonium or substituted-ammonium eation. Specific ex-amples of substituted ammonium cations include methyl-, dimethyl-, and trimethyl- ammonium cations and quaternary a~monium eations such as tetramethyl-ammonium and dimethyl piperidinium eations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
Speeifie examples of beta-aeyloxy-alkane-l-sulfonates, or alternatively 2-aeyloxy-alkanel-1-sul-fonates, useful herein include the sodium salt of 2-aeetoxy-tridecane-l-sulfonie aeid; the potassium salt of 2-propionyloxy-tetradeeane-1-sulfonie aeid; the lithium salt of 2-butanoyloxy-tetradecane-1-sulfonic acid; the sodium salt of 2-pentanoyloxy-pentadecane-1-sulfonie aeid;
the sodium salt of 2-aeetoxy-hexadecane-1-sulfonie acid;
the potassium salt of 2-oetanoyloxy-tetradecane-1-sulfonie aeid; the sod~um salt of 2-acetoxy-heptadeeane-1-sulfonie aeid; the lithium salt of 2-acetoxy-oetadeeane-1-sulfonie aeid; the potassium salt of 2-acetoxy-nonadecane-1-sulfonic aeid; the sodium salt of 2-acetoxy-uneosane-1-sulfonie aeid; the sodium salt of 2-propionyloxy-docosane-l-sulfonie acid; the isomers thereof.
Examples of beta-aeyloxy-alkane-l-sulfonate salts herein are the alkali salts of beta-acetoxy-alkane-l-sulfonie aeids corresponding to the above formula wherein Rl is an alkyl of about 12 to about 16 earbon atoms.
Typical examples of the above deseribed beta-aeetoxy alkanesulfonates are deseribed in the literature:
Belgium Patent 650,323 issued July 9, 1963, diseloses the preparation of eertain 2-aeylo~y alkanesulfonie aeids.
Similarly, U.S. Patents 2,094,451 lssuecl September 28, 1937, to Guenther et al. and 2,086,215 issued July 6, 1937,to DeGroote disclose certain salts of beta-acetoxy alkanesulfonie aeids.

~ li5ZZ62 Another preferred class of anionic surfactant compounds herein is the alkylated C~-sul~ocarboxylates, containing about 10 to about 23 carhon atoms, and having the formula o l~
R - CH - C - OR' so3 wherein R is C8 to C20 alkyl, M is a water-soluble cation as hereinbefore disclosed, preferably sodium ion, and R' is short-chain alkyl, e.g., methyl, ethyl, propyl, and butyl. These compounds are prepared by the esterification of ~ -sulfonated carboxylic acids, which are commercially available, using standard techni~ues. Specific examples of the alkylated ~-sulfocarboxylates preferred for use herein include:
ammonium methyl- ~-sulfopalmitate, triethanolammonium ethyl- d-sulfostearate, sodium methyl- d-sulfopalmitate, sodium ethyl- ~-sulfopalmitate, sodium butyl- ~-sulfostearate, potassium methyl- ~-sulfolaurate, lithium methyl- ~-sulfolaurate, i as well as mixtures thereof.
Another class of anionic organic surfactants is the ~ - alkyloxy alkane sulfonates. These compounds have the following formula:
l~2 ll Rl - C - f SO3M
H H
where Rl is a straight chain alkyl group having from

6 to 20 carbon atoms, R2 is a lower alkyl group having from 1 (preferred) to 3 carbon atoms, and M is a water-soluble cation as hereinbefore described.

llSZZ6Z

Specific examples of ~ -alkyloxyl alkane sul-fonates, or alternatively 2-alkyloxy-alkane-1-sulfonates, having low hardness (calcium ion) sensitivity useful herein to provide superior cleaning levels under househola washing conditions include:
potassium-~-methoxydecanesulfonate, sodium 2-methoxytridecanesulfonate, potassium 2-ethoxytetradecylsulfonate, sodium 2-isopropoxyhexadecylsulfonate, Iithium 2-t-butoxytetradecylsulfonate, sodium ~ -methoxyoctadecylsulfonate, and ammonium ~ -n-propoxydodecylsulfonate, Other synthetic anionic surfactants useful herein are alkyl ether sulfates. These materials have the formula RO(C2H4O)XSO3~ wherein R is alkyl or alkenyl of about 10 to about 20 carbon atoms, x is 1 to 30, and M is a water-soluble cation as defined hereinbefore. The alkyl ether sulfates useful in the present invention are condensation products of ethylene oxide and monohydric alcohols having about 10 to about 20 carbon atoms. Preferably, R has 14 to 18 carbon atoms. The alcohols can be derived from ~fats, e.g., coconut oil or tallow, or can be synthetic.
Lauryl alcohol and straight chain alcohols derived from tallow are preferred herein. Such alcohols are reacted with 1 to 30, and especially 6, molar proportions of ethylene oxide and the resulting mixture of molecular species, having, for example, an average of 6 moles of ethylene oxide per mole of alcohol, is sulfated and neutralized.
Specific examples of alkyl ether sulfates of the present invention are sodium coconut alkyl ethylene glycol ether sulfate, lithium tallow alkyl triethylene glycol ether sulfate; and sodium tallow alkyl he~aoxy-ethylene sulfate.
Preferred alkyl ether sulfates (commonly ab-breviated as AEXS) are the alkali metal coconut- and ~152Z6;2 tallo~-alkyl oxyethylene ether sulfates having an average of about 1 to about 10 oxyethylene moieties. The alkyl ether sulfates of the present invention are known compounds and are described in U.S. Pa~ent 3,332,876, to Walker (July 25, 1967) ~dditional examples of anionic non~SaP synthe-tic surfactants which come within the terms of the present invention are the reaction product of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amides of methyl tauride in which the fatty acids, for example, are derived from coconut oil.
Other anionic synthetic detergents of this variety are set forth in United States Patents 2,486,921; 2,486,922;
and 2,3~6,278.
Additional examples of anionic, non-soap, synthetic surfactants, which come withi.n the terms of the present invention, are the compounds which contain two anionic functional groups. These are referred to as di-anionic detergents. Suitable di-anionic surfactants are the disulfonates, disulfates, or mixtures thereof of which may be represented by the following formulae:

R(SO3)2M2, R(SO4)2M2, R(SO3)(SO4)M2, where R is an acyclic aliphatic hydrocarbyl group having 15 to 20 carbon atoms and M is a water-solubilizing cation, for e.xample, the C15 to C20 disc)dium 1,2 alkyldisulfates, C15 to C20 dipotassium-l, 2-alkyldisulfonates or disulfates, disodium 1,9-he~adecyl disulfates, C15 to C20 disodium-1,2-alkyldisulfonates, disodium l,9-stearyldisulfates and 6,10-octadecyldisulfates.
The aliphatic portion of the disulfates or disulfonates is generally substantially linear, thereby imparting desirable biodegradable properties to the surfactant compound.
The ~ater-solubilizing cations include the customary cations known in the detergent art, i.e., the alkali metals, and the ammonium cations, as well as other metals in group IIA, IIB, IIIA, IVA and IVB of the Periodic Table except for boron. The preferred water-solubilizing cations are sodium or potassium. These dianionic surfactants are more fully described in ~ritish 10 Letters Patent 1,151,392 which claims priority on an application made in the United States of America (No.
564,556) on July 12, 1966.
Still other anionic synthetic surfactants in-clude the class designated as succinamates and succinates.
This class includes such surface active agents as disodium N-octadecylsulfo-succinamate; tetrasodium N-(1,2-dicarboxyethyl)-N-octadecylsulfo-succinamate; diamyl ester of sodium sulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; dioctyl esters of sodium sul-fosuccinic acid.
Other suitable anionic surfactants utilizableherein are olefin sulfonates having about 12 to about 24 carbon atoms.
The c~-olefins from which the olefin sulfonates are derived are mono-olefins having 12 to 24 carbon atoms, preferably 14 to 16 carbon atoms. Preferably, they are straight chain olefins. Examples of suitable l-olefins include l-dodecene; l-tetradecene; l-hexadecene; 1-octadecene; l-eicosene and l-tetracosene.
In addition to the true alkene sulfonates and a proportion of hydro~y~alkanesulfonates, the olefin sul-fonates can contain minor amounts of other materials, such as alkene disulfonates depending upon the reaction conditions, proportion of reactants, the nature of the starting olefins and impurities in the olefin stoc~ and side reactions during the sulfonation process.

~52262 A specific anionic surfactant which has also been found excellent for use in the present invention is described more fully in the U.S. Patent 3,332,880 of Phillip F. Pflaumer and Adrian Kessler, issued July 25, 1967, titled "Detergent Composition".

Of all the above-described types of anionic surfactants, preferred compounds include sodium linear alkyl benzene sulfonate wherein the alkyl chain averages from about 10 to 18, more preferably about 12, carbon atoms in length, sodium tallow alkyl sulfate; 2-acetexy-tridecane-l-sulfonic acid; sodium methyl- ~-sulfopalmitate;
sodium ~ -methoxyoctadecylsulfonate; sodium coconut alkyl ethylene glycol ether sulfonate; the sodium salt of the sulfuric acid ester of the reaction product of one mole of tallo~ alcohol and three moles of ethylene oxide;
and mixtures thereof.

Additional Optional Ingredients Additional optional ingredients include from 0.01 to about 2%, preferred 0.02% to 1% of sodium toluene sul-fonate and/or sodium xylene sulfonate as processing aidsfor the anionic surfactant.
Additional optional ingredients include minor amounts, of from 0.01% to about 1% to colorant, perfume, fabric brighteners, photoacti.ve bleaching a~ent such as sulfonated zinc phthalocyanine, and the li~e.

Processing The softener composition is made by combining the three essential ingredients in two basic mcthods.
In one method, agglomeration, the first step in the process is to contact the smectite clay with the ', ~

il52Z62 organic softener to form the organo-clay complex. This step is conveniently carried out in an aqueous system.
The complçx will form at ambient temperatures especially if the organic softener is in the salt form. If the 5 organic softener is not in the salt form and is a solid then the softener should be melted before addition to the clay to conveniently form the complex. Temperatures up to about 80C. can conveniently be employed in making the organo-clay complex.
In the second step the organo-clay complex is aqqlomerated with the electrolyte by spraying onto the organo-clay complex and electrolyte mixture a binding/matrixing agent (e.g. water, electrolyte solution, anionic sur-factant, etc.).
When the second method, slurry-drying, is to be employed, the first step in making the composition is to make a slurry of the electrolyte in water, add the clay and then finally add the organic softener to complex the clay with the organic softener. This slurry 20 is then converted into a solid form by driving off the excess moisture.
Non-limiting examples of the equipment available for agglomeration include a cement mixer, Dravo pan ag-glomerator, KG/Schugi Blender-Granulator whirling knife 2S continuous vertical fluidized bed agglomerator, Niro Fluidized Bed and Obrian Mixed/Agglomerator.
Non-limiting examples of equipment available for the slurry-drying method include a spray drying tower, prilling tower, roll dryer and extr-lsion processes.
In the process of making the sof~ener compositions the optional ingredients can serve as processing aids.
The particle size of the granules, whether made by agglomeration or by slurry-drying will vary. The preferred size for use of the fabric softener compositions 35 of this invention in the granular form is from about 20 ; mesh to about 65 mesh (Tyler).

llSZ26Z

As disclosed herein the softener composition comprising the three essential ingredients is intended for use in providing softening for fabrics during the rinsing operation which follows washing. Alternatively the fabric softener compositions can simply be admixed with a detergent composition or added to a washing solution to provide fabric softening through the wash.

EXAMPLE I

Test towels consisting of 100% cotton were 10 washed in an upright machine using a regular granular detergent under thé following conditions:

Product concentration : 0.25% (127.5 g in 13.5 gal.
water) Product composition : 20% surfactant (70/30 C12 branched alkyl benzene sulfonate/C12 branched toluene sulfonate), 33%
STPP, 10% silicate solids (2SiO2/Na20), 25% Na2SO4, 2~ sodium toluene sulfonate, balance water and miscel-laneous.
Water hardness : 19 gr/gal, 3/1 Ca/Mg ratio Water temperature : 70~75F.
25 Water:Cloth ratio : 20 to 1 Towels of 86% cotton/14% polyester were included with the test towels to make up a full wash load Washing time : 20 minutes ...
After washing, the towels were hand wrung and agitated in the washer for 5 minutes in 13.5 gallons of 70~F, 9 grain hardness 3/1 Ca/~lg ratio water to rinse . `` ~lSZZ6Z

Following the first rinse the fabrics were again hand wrung and agitated as in the first rinse except that the second rinse Water included the fabric softening compositions as indicated below. The fabrics were then wrung and line dried following which the test fabrics were graded for softness in a round robin panel test. Three judges were employed in the grading using a 0 to 4 grading scale wherein the scale has the following meaning: 0 - no difference; 1 - guess that there is a difference; 2 - small difference; 3 - moderate difference; 4 - large difference.
The compositions tested and the results after two wash-rinse cycles are given below~

Softener Composit-ion No. No. 1No. 2 No. 3 Complex of Clay - Ca montmoEillonite 45.0%40.0% 30.0%
Primary tallow amine hydrochloride ----- ---- 5.0 Tertiary ditallow methyl ~ ¦
amine 5.0 5.0 ----Branched C12 alkyl-benzene sulfonate, Na salt ---- 9.09 9.09 Sodium toluenesulfonate ---- 0.91 0.91 Sodium carbonate -- - ----- 5.0 25 Sodium sulfate ---- 9.1 6.4 Sodium bicarbonate ~ --- 4.6 Sodium sesquicarbonate (anhyd. basis) ,' 39.4 25.2 28.2 Color/Perume 0.150.15 0.6 30 Water 10.0 10.0 10.0 Miscellaneous Bal. Bal. Bal.
Amount of product in 2nd rinse - g. 50 50 50 Concentration o~ product 0.1% 0.1~ 0.1%

~l~Z;262 Softness Results Blank No. 1 No. 2 No. 3 ~o softener in the 2nd rinse) 5 Softness panel score (averaged results)O(STD~ ~2.3 +2.3 +1.5 Least significant difference = 0.5 at 95% confidence All three softening compositions were made by spray drying.
As shown by the results all three compositions were effective in softening cotton towels. Composition 1, which is within the scope of this invention, was as effective in 15 fabric softening as Were compositions 2 and 3 which included a surfactant for dispersion of the complex.

EXAMPLE II
The compositions shown in Example I were tested for their dispersability in Water.
The procedure consisted of adding 500 ml. of tap water (7Q-75F., 9 grains/gallon hardness) to a glass quart jar. The water ~as stirred ~ith a 2 inch magnetic stirrer sufficient to produce about 1-1/2 inch vortex.
Then 1.25 grams of product was added to the vortex and the time re~uired for product to disperse was recorded.
The indication that the product dispersed was shown by the water becoming cloudy with inability to see the vortex in a side view of the glass jar.

Composi-tion Dispersion Time 30 No. 1 from Ex. I 10-12 seconds No. 2 from Ex. I 5-6 seconds No. 3 from Ex. I 5-6 seconds All three compositions dispersed well in this test including Composition No. 1 which is within the scope of this invention.

^` 1~52262 EX~MPLE III
Test towels consisting of 100% cotton were washed in a bench-scale laboratory washing machine using a regular granular detergent under the following conditions:

Product concentration ; 0.25~(9.45 g in l.0 gal.
water) Product composition : 20% surfactant (70/30 C12 branched alkyl benzene sulfonate/C12 ~ranched toluene sulfonate), 33~
STPP, 10% silicate solids (2SiO2/Na20), 25~ Na2SO4 2~ sodium toluene sulfonate, balance water and miscel-laneous.
Water hardness : 19 gr/gal, 3/1 Ca/Mg ratio Water temperature : 70-75F.
Water: Cloth ratio : 20 to 1 ~ashing time : 20 minutes After ~ash~ng, the towels were hand wrung and agitated in the washer for 5 minutes in 1.0 gallon of 70F., 9 grain hardness 3~1 Ca/Mg ratio water to rinse.
Following the first rinse the fabrics were again hand wrung and agitated as in the first rinse except that the second rinse water included the fabric softening compositions as indicated below. The fabrics were then wrung and line dried followlng which the test fabrics ~ere graded for softness in a round robin panel test as in Example I.
The compositions tested and the results obtained after one wash-rinse cycle are given below.

~ - 31 -Composition No. 4 5 6 Complex of Clay-Ca montorillonite 45.0 ~ 45.0 % 45.0 %
Primary tallow amine ---- 5.0 5.0 Ditallow methyl amine 5.0 ---- ----Branched C 2 alkylbenzene sulfonate, Na salt 0.91 ---- 1.48 Sodium toluenesulfonate 0.09 ---- 0.15 Sodium Carbonate 19.7 ---- 18.9 Sodium bicarbonate 17.9 ____ 17.2 Sodium sesquicarbonate (anhyd basis) ---- 39.4 -----Sodium sulfate 0.7 ---- 1.4 Colorant/perfume 0.65 0.15 0.65 Water 10.0 10.0 10.0 Miscellaneous Bal. Bal. Bal.

~Molar equivalence of surfactant to amine 29 % 0 % 25 %
Prod. conc. in 2nd rinse 0.1 % 0.1% 0.1%

Softness Results Blank No. 4 No. 5 No. 6 (No softener in the second rinse) Softness paneT1 sc~ore (a~Teraged results) O(STD) +2.8+1.1 +1.9 Least significient difference = 0.7 at 95S confidence.

~ ` 115Z262 The results show that all three compositions, which are all within the scope of this invention, softened the test towels. Composition No. 5 was not as effective in fa~ric softening as the other two compositions. Composition No. 6 which has the same clay-organic softener complex as No. 5 but additionally contains a minor amount of surfactant shows improved softening performance relative to No. 5.

~15;22~i2 EX~IPLE IV
The following fabric softening compositions are prepared in accordance with the invention.

ComPosition No. 7 8 9 10 11 12 13 5 Comp~ex of Clay Na hectorite 10 25 Na montmoril-lonite 70 15 50 Na saponite 40 40 Sec. Dicoconut amine 3 20 Dicoconut methyl amine 5 Sec dital~o~ 5 Dicoconut di-methyl am-monium chlo-ride 6.0 I Tallow tri-j~ methyl am-!: monium chlo-ride 5 Ditallo~ di-~ methyl am-I monium chlo-! ride 10 Na C12 0.54.0 0.3 1.0 1.0 Na C14-16 alkyl E S 0.5 0.3 Na toluene sul-fonate 0.05 0.3 0.03 0.1 0.1 Na sesquicar-bonate (anhyd.
basis~ 72.0 10.030.0 65~0 57.0 40.0 37.0 Na sulfate 0.05 0.3 0.03 0.1 0.
~ r^7ater + minors ', (perfume, ~ 40 colorant etc.) 15.012.9 S 4 14.34 lI. a ~_, k The above compositions can be used in the rinsing operation in the home laundering process to provide fabric softening.
Alternatively the above compositions can be 5 added to the washing solution to provide fabric softening through the wash provided the washing solution contains a predominant amount of anionic surfactant relative to other surfactants.

EXAMPLE V
The following fabric softener compositions are prepared in accordance with the in~ention.

Composition No. 14 15 16 .
Complex of Brock clay 50 50 50 Palmityl methyl ëthyl sulfonium chloride 5 Monostearyl tri-l~ methyl phosphonium ,~ 20 chloride 5 I l-beta hydoxyethyl-; 2-stearyl imidazo-line 5 12 1.0 1.0 1.0 25 Na toluene sulfonate 0.1 0.1 0.1 Na sesquicarbonate (anhyd. basis) 36.0 36.0 36.0 Water ~ minors (perfume colorant etc.) 7.9 7.9 7.9

Claims (16)

WHAT IS CLAIMED IS:

1. A fabric softening composition, free from an-ionic surfactant, in solid form comprising:
(a) from about 10% to about 80% by weight of an impalpable smectite clay having an ion exchange capacity of at least 50 meq/100 grams;
(b) from about 1% to about 50% by weight of said clay of a compound selected from the group consisting of organic primary, secondary, and tertiary amines,and their water soluble or water dispersible salts,and organic quaternary ammonium, phosphonium,and sulfonium compounds wherein said compounds have at least one hydro-carbon group having from 8 to 22 carbon atoms;
and (c) from about 10% to about 90% of an electrolyte having a solubility in water of at least about 7 parts per 100 parts of water at 20°C.;
wherein components (a) and (b) are present in the form of a complex.

2. A composition according to Claim 1 wherein the smectite clay is selected from the group consisting of alkali metal and alkaline earth metal montmorillonites, saponites,and hectorites.

3. A composition according to Claim 1 wherein component (b) is selected from the group consisting of primary, secondary,and tertiary amines,and their salts, and quaternary ammonium compounds having the formulas R1R2R3 ; [R1R2R3R4N]?Xn-wherein R1 represents an alkyl or alkenyl having from about 8 to about 22 carbon atoms, R2, R3 and R4 each independently represent hydrogen or alkyl, alkenyl, arylalkyl or alkylaryl having from 1 to about 22 carbon atoms, n is an integer of from 1 to 3, and X represents a water soluble or water dispersible anion.

4. A composition according to Claim 1 which additionally contains an anionic surfactant in the amount of from about 1% to about 29% molar equivalence to component (b).

5. A composition according to Claim 4 wherein the anionic surfactant is present in the amount of from about 5% to about 25% molar equivalence to component (b).

6. A composition according to Claim 5 wherein the anionic surfactant is selected from the group con-sisting of water soluble straight or branched chain alkyl benzene sulfonates or alkyl toluene sulfonates having from 9 to 15 carbon atoms in the alkyl portion, water soluble fatty acid soaps having from 10 to about 20 carbon atoms in the alkyl portion, water soluble alkyl sulfates having from 8 to 18 carbon atoms in the alkyl portion, and water soluble alkyl ether sulfates having from 8 to 18 carbon atoms in the alkyl portion and from about 1 to about 6 moles of ethylene oxide, and mixtures thereof.

7. A composition according to Claim 1 or 6 wherein component (b) is selected from the group consisting of primary tallow amine, primary tallow amine hydro-chloride, minutely dimethyl amine, monotallow dimethyl amine hydrochloride, tallow trim ethyl ammonium chloride, ditallow dimethyl ammonium chloride, dicoconut dimethyl ammonium chloride, ditallow methyl amine ditallow methyl ammonium chloride, secondary ditallow amine, trilauryl amine, tritallow amine, secondary dicoconut amine, and mixtures thereof.

8. A composition according to Claim 1 wherein component (b) is ditallow methyl amine.

9. A composition according to Claim 1 wherein the electrolyte is selected from the group consisting of sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, sodium sulfate, magnesium sulfate, sodium chloride,and mixtures thereof.

10. A fabric softening composition consisting essentially of:
(a) from about 20% to about 60% by weight of an alkali metal montmorillonite clay;
(b) from about 3% to about 30% by weight of component (a) of a compound selected from the group consisting of primary, secondary,and tertiary amines, and their salts,and quaternary ammonium compounds having the formulas R1R2R3N ; [R1R2R3R4N]n+Xn-wherein R1 represents an alkyl or alkenyl having from about 8 to about 22 carbon atoms R2, R3 and R4 each independently repre-sent hydrogen or alkyl, alkenyl, arylalkyl or alkylaryl having from 1 to 22 carbon atoms, n is an integer of from 1 to 3 and X- repre-sents a water soluble or water dispersible anion;
(c) from about 30% to about 50% of an electrolyte having a solubility in water of at least about 7 parts per 100 parts of water at 20°C., and (d) from about 5% to about 29% molar equivalence to component (b) of an anionic surfactant;
wherein components (a) and (b) are present in the composition in the form of a complex.

11. A method for imparting softness to fabrics which comprises contacting said fabrics with.
an aqueous dispersion of a fabric softening composition , free from anionic surfactant, wherein said fabric softening composition comprises:
(a) from about 10% to about 80% by weight of an impalpable smectite clay having an ion exchange capacity of at least 50 meq/100 grams;
(b) from about 1% to about 50% by weight of said clay of a compound selected from the group consisting of organic primary, secondary, and tertiary amines,and their water soluble or water dispersible salts,and organic quaternary ammonium,phosphonium,and sulfonium compounds wherein said compounds have at least one hydrocarbon group having from 8 to 22 carbon atoms; and (c) from about 10% to about 90% of an electrolyte having a solubility in water of at least about 7 parts per 100 parts of water at 20°C.;
wherein components (a) and (b) are present in the form of a complex.

12. A method according to Claim 11 wherein the smectite clay is selected from the group consisting of alkali metal and alkaline earth metal montmorillonites, saponites,and hectorites; component (b) is selected from the group consisting of primary, secondary, and tertiary amines,and their salts,and quaternary ammonium compounds having the formulas R1R2R3N ; [R1R2R3R4N]n+ Xn-wherein R1 represents an alkyl or alkenyl having from about 8 to about 22 carbon atoms, R2, R3 and R4 each independently represent hydrogen or alkyl, alkenyl aryl-alkyl or alkylaryl having from 1 to 22 carbon atoms, n is an integer of from 1 to 3, and X represents a water soluble or water dispersible anion; and component (c) is selected from the group consisting of sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, sodium sulfate, magnesium sulfate, sodium chloride,and mixtures thereof.

13. A method according to Claim 12 wherein component (b) is selected from the group consisting of primary tallow amine, primary tallow amine hydrochloride, monotallow dimethyl amine, monotallow dimethyl amine hydrochloride, tallow trimethyl ammonium chloride, di-tallow dimethyl ammonium chloride, dicoconut dimethyl ammonium chloride, ditallow methyl amine ditallow methyl ammonium chloride, secondary ditallow amine, trilauryl amine, tritallow amine, secondary dicoconut amine, and mixtures thereof.

14. A method for imparting softness to fabrics which comprises contacting said fabrics with an aqueous dispersion of a fabric softening composition wherein said fabric softening composition consists essentially of:
(a) from about 20% to about 60% by weight of an alkali metal montmorillonite clay;
(b) from about 3% to about 30% by weight of com-ponent (b) selected from the group consisting of primary, secondary,and tertiary amines,and their salts,and quaternary ammonium compounds having the formulas R1R2R3N ; [R1R2R3R4N]n + Xn-wherein R1 represents an alkyl or alkenyl having from about 8 to about 22 carbon atoms R2, R3 and R4 each independently repre-sent hydrogen or alkyl, alkenyl, arylalkyl or alkylaryl having from 1 to 22 carbon atoms, n is an integer of from 1 to 3 and X- repre-sents a water soluble or water dispersible anion;
(c) from about 30% to about 50% of an electrolyte having a solubility in water of at least about 7 parts per 100 parts of water at 20°C., and (d) from about 5% to about 29% molar equivalence to component (b) of an anionic surfactant;
Wherein components (a) and (b) are present in the composition in the form of a complex.

15. A method according to Claim 14 wherein component (b) is selected from the group consisting of primary tallow amine, secondary ditallow amine, mono-tallow dimethyl amine, secondary dicoconut amine, tri-lauryl amine, tritallow amine, tallow trimethyl ammonium chloride, ditallow dimethyl ammonium chloride, dicoconut dimethyl ammonium chloride, ditallow methyl amine and ditallow methyl ammonium chloride; component (c) is selected from the group consisting of sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, sodium sulfate, magnesium sulfate sodium chloride and mixtures thereof;
and component (d) is selected from the group consisting of water soluble straight or branched chain alkyl benzene sulfonates or alkyl toluene sulfonates having from 9 to 15 carbon atoms in the alkyl portion, water soluble fatty acid soaps having from 10 to about 20 carbon atoms in the alkyl portion, water soluble alkyl sulfates having from 8 to 18 carbon atoms in the alkyl portion, and water soluble alkyl ether sulfates having from 8 to 18 carbon atoms in the alkyl portion and from about 1 to about 6 moles of ethylene oxide and mixtures thereof.

16. A method according to Claim 15 wherein component (a) is sodium montmorillonite; component (b) is ditallow methyl amine; component (c) is sodium ses-quicarbonate; and component (d) is a straight or branched chain sodium alkyl benzene sulfonate or sodium alkyl toluene sulfonate or mixtures thereof wherein the alkyl portion has from 11 to 13 carbon atoms.