Fabric conditioning compositions: natural hectorite clay and binding and dispersing agent

Fabric conditioning compositions are disclosed which comprise, as a fabric softening ingredient, a fabric softening clay. The fabric softening clay is a hectorite of natural origin, and has a layer change distribution such that at least 50% is in the range 0.23-0.31. The clays exhibit high relative deposition values.

TECHNICAL FIELD 
The present invention relates to granular fabric conditioning compositions. 
More specifically it relates to compositions containing a fabric-softening 
amount of a hectorite clay, the clay having a narrowly-defined layer 
charge distribution and preferably having a high level of deposition upon 
fabrics. 
BACKGROUND 
In fabric softening executions disclosed in the art, smectite clays have 
often been used in combination with other ingredients, such as 
conventional rinse-added fabric softening actives. Illustrative of this 
art are: 
GB-A-1 519 605, disclosing fabric softening compositions containing 
mixtures of smectite clays and water-insoluble quaternary ammonium 
compounds; 
U.S. Pat. No. 4,292,835 describing solid fabric softening compositions 
containing smectite clay complexed with an anionic surfactant, and fabric 
softening amines or salts thereof; 
EP-A-0 004 111 describing fabric-care compositions consisting of aqueous 
dispersion of a smectite-clay and a gelatinized vegetable starch. 
It is well recognized in the detergent industry that clays of the type 
disclosed above can provide significant fabric softening benefits. Yet, it 
is equally well recognized that deposition of these clays onto the fabrics 
during the laundering process is far from complete. Moreover, the 
softening effect obtained as a result of the clay deposition is affected 
by factors that are not well understood. 
It has now been found that a narrowly defined class of hectorite clays, not 
disclosed per se in the above-referred state of the art, surprisingly 
provides excellent fabric-softening benefits. 
It is an object of the present invention to provide granular and liquid 
fabric conditioning compositions that can be added to the laundry during a 
rinse and/or wash stage of the laundry process comprising a fabric 
softening clay from which the clay is more efficiently deposited onto 
fabrics during the laundry process. It is further object of this invention 
to select clay materials for use in conditioning compositions that provide 
a significantly better fabric-softening performance, based upon a constant 
amount of clay utilized, than the clay materials used to date in 
commercial fabric conditioning compositions. 
SUMMARY OF THE INVENTION 
The present invention relates to fabric conditioning compositions 
containing a specific hectorite clay for addition to laundry loads in the 
wash and/or rinse stage, and to a method of softening fabrics. In one 
aspect of the invention, the compositions are in granular form and 
comprise agglomerates of the clay and a binding/dispersing agent. In 
another aspect of the invention, the compositions are aqueous dispersions 
of the clay or are granular formulations (containing particulate or 
agglomerated clay) which also comprise at least one other fabric 
conditioning ingredient, such as an organic humectant, a clay-flocculating 
agent, a static control agent, or an organic softener. The clay has a 
narrowly defined layer charge distribution, such that at least about 50% 
of the clay has a layer charge of from about 0.23 to about 0.31.

DETAILED DESCRIPTION OF THE INVENTION 
The clay, utilized in the present invention which is of the smectite-type, 
is selected on basis of its layer charge properties. The hectorite clays 
of natural origin, suitable for the detergent compositions of the present 
invention, have the 35 general formula: 
##EQU1## 
wherein y=o; or, if y.noteq.o, Me.sup.III is Al, Fe, or B; M.sup.n+ is a 
monovalent (n=1) or divalent (n=2) metal cation, for example selected from 
Na, K, Mg, Ca, Sr. The value of (x+y) is the layer charge of the hectorite 
clay. The hectorite clays suitable for the detergent compositions of the 
present invention have a layer charge distribution such that at least 50% 
is in the range of from 0.23 to 0.31. 
Preferred are hectorite clays of natural origin having a layer charge 
distribution such that at least 65% is in the range of from 0.23 to 0.31. 
The layer charge distribution of the clay material can be determined using 
its swelling in the presence of cationic surfactants having specific chain 
lengths. This method is described in detail by Lagaly and Weiss, 
Zeitschrift fuer Pflanzenernaehrung und Bodenkunde, 130(1), 1971, pages 
9-24, the disclosures of which are incorporated herein by reference. 
As noted hereinabove, the clays employed in the compositions of the instant 
invention contain counterions, such as protons, sodium ions, potassium 
ions, calcium ions, magnesium 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. 
A calcium clay is one in which the absorbed cation is predominantly 
calcium. 
The hectorite clays of the present invention should preferably be sodium 
clays, for better softening activity. 
Sodium clays are either naturally occurring, or are naturally-occurring 
calcium-clays which have been treated so as to convert them to 
sodium-clays. If calcium-clays are used in the present compositions, a 
salt of sodium can be added to the compositions in order to convert the 
calcium clay to a sodium clay. Preferably, such a salt is sodium 
carbonate, typically added at levels of up to 5% of the total amount of 
clay. 
The preferred hectorite clays used in the fabric conditioning compositions 
can be further characterized by their high level of deposition onto 
fabrics. Deposition of hectorite clays of the present invention from 
fabric conditioning compositions onto fabrics is surprisingly greater than 
the deposition of other naturally occurring clays. Deposition can be 
measured according to the Relative Deposition Measurement procedure 
described in the Experimental section below. The Relative Deposition of 
the clays of the present invention for 77 ppm treatment levels, for 
addition of the clay to either the wash or rinse stage of the laundry 
cleaning process, is preferably at least about 2.5 more preferably at 
least about 2.7, and most preferably at least about 2.9 as defined herein. 
As used herein, "Relative Deposition" shall refer to the above-referenced 
procedure using a 77 ppm treatment level, unless otherwise specifically 
indicated. The deposition of these clays appears to be proportional to the 
softness of the treated fabric. Examples of suitable hectorite clays 
include Bentone EW and Macaloid, both mined in or near Amargosa Valley, 
Nev., (U.S.A.) and available from NL Chemicals, N.J. Naturally occurring 
hectorite clays within the scope of the present invention also include IMV 
Hectorite, available from Industrial Mineral Ventures, Amargosa Valley, 
Nev. Also encompassed herein are hectorites mined in Turkey such as, but 
not limited to, Turkish calcium hectorite clay. 
Granular Clay Agglomerate Compositions 
The granular clay agglomerate fabric conditioning compositions of the 
present invention contain from about 0% to 100% of the fabric softening 
clay described below. With regard to clay agglomerate compositions 
intended for rinse-added application, the composition preferably contains 
from about 10% to about 99% of the fabric softening clay described below, 
and from about 0.5% to about 40% of a binding/dispersing agent. As set 
forth above, the clay is in the form of an agglomerate. The composition 
may optionally contain other fabric conditioners, perfumes, dyes or other 
ingredients useful for fabric conditioning or cleaning compositions. 
Preferably, in the case of agglomerates to be added to the rinse stage of 
a laundry operation, these agglomerated particles will not contain 
detersive ingredients, such as surfactants, builders, clay soil removers, 
enzymes, and the like, in sufficiently large quantities to significantly 
interfere with the rinsing process. Generally, the compositions for 
rinse-added applications will contain less than about 30%, by weight of 
the agglomerate, of such detersive ingredient will be present, preferably 
less than about 15%, more preferably less than about 10%. 
The hectorite clay, thus, is provided as free-flowing agglomerates of clay. 
The agglomerates can comprise smaller particles of clay such as are 
commercially available in the industry. Typically, the particles will be 
from about 1 micron to about 50 microns. The clay agglomerates can also be 
made in the desired size range (discussed below) directly from an aqueous 
clay slurry by spray drying or other techniques known in the art. The 
agglomerates should have a median diameter of from about 75 microns to 
about 2000 microns, preferably a median diameter of from about 100 microns 
and about 1250 microns, most preferably from about 300 microns to about 
1000 microns. The clay agglomerates are preferably screened so as to 
separate agglomerates less than about 75 microns, preferably less than 
about 100 microns, and greater then about 2000 microns, preferably greater 
than about 1250 microns. 
It is an important aspect for rinse-added applications that the clay 
agglomerates contain, in addition to the clay, a binding/dispersing agent. 
It has been found that the clay, when agglomerated and added to the rinse 
stage of an automatic washing machine without presence of such 
binding/dispersing agent, does not provide well-distributed deposition of 
the clay upon the fabrics. Rather, the clay tends to further agglomerate 
at the surface of the rinse water and deposit upon the fabrics with poor 
distribution. It is important for obtaining even deposition that the clay 
agglomerates sink or otherwise remain below the surface of the rinse water 
during the rinse stage and, further, become well-dispersed prior to the 
end of the rinse stage. Typically, the rinse stage of an automatic washing 
machine will be between about 2 and about 5 minutes. 
Agglomeration methods and equipment suitable for use include those methods 
known in the art. Non-limiting examples of the equipment suitable for 
agglomeration of clay from smaller particles include a Dravo pan 
agglomerator, KG/Schugi Blender-Granulator, whirling knife continuous 
vertical fluidized bed agglomerator, Niro Fluidized Bed agglomerator, 
Obrian Mixer/Agglomerator, Loedige agglomeration and a Littleford mixer 
(Littleford Brothers, Inc., Florence, Ky., USA, eg. Model FM130D). 
Other methods and equipment which use larger amounts of water, including 
the manufacture of agglomerates (as defined herein) directly from a clay 
slurry, include a spray drying tower, and a prilling tower. 
On a laboratory scale, food processors which are widely available to the 
general public can be used to agglomerate smaller clay particles into 
agglomerates in the disclosed size ranges. 
In making the clay agglomerates, an aqueous mixture of water and the 
binding/dispersing agent can be first prepared and slowly added to the 
clay while the clay is subjected to the mechanical agitation of the 
agglomeration equipment. Once agglomerated, the clay can be dried, but 
should not be over-dried. Overdrying can, as will be understood by those 
skilled in the clay art, lead to reduced ability of the clay to disperse. 
Drying at ambient temperatures unaided or aided by forced air provides 
acceptable drying levels. 
Preferred binding/dispersing agents are water-soluble inorganic salts. 
These can include sodium carbonate, sodium sulfate, potassium carbonate, 
potassium sulfate, magnesium sulfate, lithium sulfate, lithium carbonate, 
sodium citrate, and sodium sesquicarbonate. Most preferred are sodium 
sulfate and sodium carbonate. Without limiting the invention, it is 
theorized that salts such as sodium carbonate which are basic in character 
are particularly advantageous for the present compositions. These water 
soluble inorganic salts are believed to act as binding agents which impart 
a temporary binding force that facilitates agglomerate integrity for a 
sufficiently long period after being added to the rinse stage of an 
automatic washing machine such that the agglomerates can sink or remain 
below the surface of the water. However, importantly, since the salts are 
water soluble, the binding force dissipates during the rinse stage so that 
the clay agglomerates can hydrate and disperse, to thereby facilitate even 
distribution of the clay upon the fabrics in the washing machine. 
Additionally, the salts are of relatively high density and inclusion of 
the salts into the agglomerates can aid with increasing the agglomerate 
density. Excessive compression of the clay to achieve the desired density 
can inhibit dispersion. The agglomerates preferably have a density of 
greater than about 1.0 g/cc. The agglomerates typically will contain from 
about 1% to about 40%, preferably from about 5% to about 35%, more 
preferably from about 10% to about 35% of water insoluble inorganic salt, 
based upon the total weight of the agglomerate. 
Another type of binding/dispersing agent that can be used, alone or in 
combination with a water insoluble inorganic salt, is specifically 
referred to as a "dispersing aid." Dispersing aids that can be used can 
generally include surfactants. These include surfactants commonly use as 
detersives in laundry detergents (though they will be present in 
substantially lower concentrations when added to the rinse stage as part 
of the present compositions). The surfactants suitable for use can 
comprise an anionic, nonionic, ampholytic or zwitterionic surfactant or a 
mixture thereof. Nonionic surfactants, or other surfactants, that can 
interfere with clay deposition should be used in low amounts only, 
preferably less than about 10% of the weight of the agglomerate, as 
previously discussed. Anionic surfactants are preferred. Typical anionic 
surfactants are the alkyl benzene sulfonates, alkyl- and alkylether 
sulfates, paraffin sulfonates, olefin sulfonates, alkoxylated (especially 
ethoxylated) alcohols and phenols, amine oxides, alpha-sulfonates of fatty 
acids and of fatty acid esters, and the like, which are well-known from 
the detergency art. In general, such surfactants contain an alkyl group in 
the C.sub.8 -C.sub.26 range, more generally in the C.sub.8 -C.sub.18 
range. The anionic surfactants can be used in the form of their sodium, 
potassium or triethanolammonium salts: Anionic phosphate surfactants are 
also useful in the present invention. These are surface active materials 
in which the anionic solubilizing group connecting hydrophobic moieties is 
an oxy acid of phosphorus. The more common solubilizing groups, of course 
are --SO.sub.4 H and --SO.sub.3 H. Alkyl phosphate esters such as 
(R--O).sub.2 PO.sub.2 H and ROPO.sub.3 H.sub.2 in which R represents an 
alkyl chain containing from about 8 to about 20 carbon atoms are useful 
herein. Suitable nonionic surfactants useful in the present invention 
include those obtained by the condensation of one to twelve ethylene oxide 
moieties with a C.sub.10 -C.sub.18 aliphatic alcohol. The alcohol may be 
completely linear as occurs in materials derived from the natural 
feedstocks such as vegetable oils and animal fats, or may be slightly 
branched as occurs in petroleum derived alcohols made by oxo-type 
synthesis. Other nonionic materials are C.sub.14 -C.sub.15 alcohol 
condensed with an average of seven ethylene oxide groups. 
C.sub.12-C.sub.13 alcohol condensed with an average of about four ethylene 
oxide groups and then subjected to stripping to remove unethoxylated and 
low ethoxylated materials, to leave an ethoxylated having a mean of 4.5 
ethylene oxide groups. Suitable zwitterionic materials include derivatives 
of quaternary ammonium compounds containing an aliphatic straight chain 
group of 14-18 carbon atoms and a sulfate or sulfonate anionic 
solubilizing group. Specific examples include 3-N, 
N-dimethyl-N-hexadecylammonio-2-hydroxpropane-1-sulfonates; 
3-(N,N-dimethyl-N-tallowylammonio)-2-hydroxypropane-1-sulfonate; 
3-(N,N-dimethyl-N-tetradecyl ammonio)-propane-1sulfonate; and 
6-(N,N-dimethyl-N-hexadecylammonion)-hexanoate. 
When the clay agglomerates are made from clay slurry, the 
binding/dispersing agent can be added and mixed with the slurry prior to 
formation of the clay into relatively small particles by, for example, 
prilling or spray drying. These particles can then be agglomerated into 
the agglomerate range defined above. Alternately, agglomerates encompassed 
by said size range can be formed directly from the slurry by the same 
general processing methods. In the former case, the particles are 
preferably agglomerated with the use of an aqueous solution which contains 
more of a binding/dispersing agent. 
The hectorite clays of the present invention can additionally be utilized 
in a non-agglomerated, or "particulate," form, as a powder or simple 
mixture of clay particles typically from about 1 to about 50 microns in 
diameter. 
Such particulate compositions according to the present invention typically 
contain from about 15% to 100%, preferably from about 50% to about 95%, by 
weight, of the hectorite clay. 
Aqueous dispersions for use according to the present invention comprise 
from about 0.5% to about 30%, preferably from about 2% to about 15%, by 
weight, of the hectorite clay, and water. 
In the preparation of the granular and liquid fabric conditioning 
compositions hereof, it may be desirable and appropriate to use certain 
additive ingredients, which are described in detail hereinbelow, 
especially a clay flocculating agent, a humectant, a static control agent, 
or an organic softener. 
Additive Ingredients 
Clay flocculating agent 
Clay-flocculating agents are very well known in industries like oil well 
drilling, and for ore flotation in metallurgy. Most of these materials are 
fairly long chain polymers and copolymers derived from such monomers as 
ethylene oxide, acrylamide, acrylic acid, dimethylamino ethyl metacrylate, 
vinyl alcohol, vinyl pyrrolidone, ethylene imine. Gums, like guar gum, are 
suitable as well. 
Preferred are poly(ethylene oxide), poly(acrylamide), and poly(acrylic 
acid). It has been found that these polymers enhance the deposition of a 
fabric softening clay if their weights (weight average) are in the range 
of from 100,000 to 10 million. Preferred are such polymers having (weight 
average) molecular weight of from 150,000 to 5 million. 
The most preferred polymer is poly (ethylene oxide). Molecular weight 
distributions can be readily determined using gel permeation 
chromatography, against standards of poly (ethylene oxide) of narrow 
molecular weight distributions. 
The compositions herein may comprise, from 0.05% to 20%, by weight of the 
clay, of clay flocculating agent, if its molecular weight is 
150,00-180,000 and from 0.005% to 2%, by weight of the clay, if its 
molecular weight is from 800,000 to 5 million. 
Clay-flocculating agents can be used in both aqueous dispersion and 
granular (agglomerate or particulate) forms of the present compositions. 
Aqueous Dispersion Aid 
Agents suitable as aqueous dispersion aids, in both aqueous dispersions 
herein, include surfactants described above in connection with agglomerate 
binding dispersing agents. More particularly, the aqueous dispersion aid 
can be advantageously selected from polycarboxylates of relatively low 
molecular weight (as compared to above clay-flocculating polymers). Such 
polycarboxylates can be copolymers of an unsaturated polycarboxylic acid 
such as maleic acid, as first monomer, and an unsaturated monocarboxylic 
acid such as acrylic acid as second monomer. Preferably, still, the 
polycarboxylates herein are homopolymers, having a molecular weight in the 
range of from 1000 to 10,000, most preferably polyacrylates. Such 
polycarboxylate dispersing aids may be used at levels of from 10% to 100%, 
preferably 20% to 50% by weight of the clay, in an aqueous dispersion 
execution, or from 5% to 50% by weight of the total composition in a 
particulate composition execution. 
Other agents which can be used as dispersing aids include electrolytes such 
as water-soluble phosphates, polyphosphates, acid and neutral 
pyrophosphates, carbonates, sulphates, chlorides, borates, silicates, and 
mixtures thereof. 
Stabilizing Agent 
If clay-flocculating agents are used in the present compositions, the 
presence of a stabilizing agent will be desirable. Such a stabilizing 
agent can be selected from conventional metal sequestering and chelating 
agents, well known used in the detergency art. Preferred for use herein 
are chelating agents, such as amino phosphonic acids and salts thereof. 
Preferred are ethylene diamine tetramethylenephosphonic acid, hexamethylene 
diaminetetramethylene phosphonic acid, diethylene triaminepentamethylene 
phosphonic acid, amino-trimethylene phosphonic acid, and salts thereof. 
Above stabilizing agent can be used at levels of from 0.1% to 5% by weight 
of the clay. Stabilizing agents are generally to be used in the aqueous 
dispersion form of the present invention. 
Organic Humectant 
An organic humectant may also be used in the compositions of the present 
invention. 
Organic humectants may be any of the various water soluble materials 
utilized for such a purpose. The organic humectants are preferably 
selected from the group consisting of a) aliphatic hydrocarbon polyols 
having from 2 to 9 carbon atoms; b) ether alcohols derived from the 
polyols of a); c) ester alcohols derived from the polyols of a); d) mono- 
and oligosaccharides; and mixtures thereof. 
Highly preferred humectants include glycerol, ethylene glycol, propylene 
glycol and the dimers and trimers of glycerol, of ethylene glycol and of 
propylene glycol. 
The compositions herein may comprise humectant levels from 0.5% to 30%, 
preferably from 2% to 15%, by weight of the clay. Humectants are useful in 
the aqueous dispersion form of the present invention. 
The compositions herein can contain, in addition to ingredients already 
mentioned, various other optional ingredients typically used in commercial 
products to provide aesthetic or additional product performance benefits. 
Typical ingredients include pH regulants, perfumes, dyes, bleach, optical 
brighteners, soil suspending agents, hydrotropes and gel-control agents, 
freeze-thaw stabilizers, bactericides, preservatives, carriers for such 
optional ingredients, and the like. 
Optional Softening Ingredients 
The fabric conditioning compositions of the present invention may further 
contain, in addition to the clay material, other fabric softening 
ingredients. Organic and inorganic materials can be included either as 
part of the hectorite-containing agglomerates, as separate particles or 
agglomerates admixed optional with the hectorite-containing agglomerates 
or smaller clay particles, or as part of aqueous dispersions of the 
hectorite clay. The compositions of the present invention preferably do 
not, however, contain substantial amounts of other clay softener 
materials, since such other clays known in the art generally do not 
provide as effective softening benefits as the claimed hectorites. Clays, 
in general, particularly naturally-occurring clays, generally contain 
impurities. This is true even with respect to most grades of processed 
clay. Included among the impurities that may be present in hectorite clays 
of this invention are species of hectorite clays not with the scope of the 
present invention and non-hectorite clays. Preferably, the clay ingredient 
used in the present invention consists essentially of the contemplated 
hectorite clays. "Consists essentially of" as used herein, requires that 
the clay material used contains no more than about 10%, more preferably no 
more than about 5%, of other clays, most preferably no more than about 1% 
of other clays. 
Suitable examples, optional of softening ingredients, include amines of the 
formula R.sub.1 R.sub.2 R.sub.3 N, wherein R.sub.1 is C.sub.6 to C.sub.20 
hydrocarbyl, R.sub.2 is C.sub.1 to C.sub.20 hydrocarbyl, and R.sub.3 is 
C.sub.1 to C.sub.10 hydrocarbyl or hydrogen. A preferred amine of this 
type is ditallowmethylamine. 
Preferably, the amine is present as a complex with a fatty acid of the 
formula RCOOH, wherein R is a C.sub.9 to C.sub.20 alkyl or alkenyl. It is 
desirable that the amine/fatty acid complex be present in the form of 
microfine particles, having a particle size in the range of from e.g., 0.1 
to 20 micrometers. These amine/fatty acid complexes are disclosed more 
fully in European Patent Application No. 0 133 804, the disclosures of 
which are incorporated herein by reference. Preferred are compositions 
that contain from 1% to 10% of the amine. 
Suitable are also complexes of the above described amine and phosphate 
esters of the formula 
##STR1## 
wherein R.sub.8 and R.sub.9 are C.sub.1 -C.sub.20 alkyl, or ethoxylated 
alkyl groups of the general formula alkyl-(OCH.sub.2 CH.sub.2).sub.y, 
wherein the alkyl substituent is C.sub.1 -C.sub.20, preferably C.sub.8 
-C.sub.16, and y is an integer of 1 to 15, preferably 2-10, most 
preferably 2-5. Amine/phosphate ester complexes of this type are more 
fully disclosed in European Patent Application No. 0 168 889, the 
disclosures of which are incorporated herein by reference. 
Further examples of optional softening ingredients include the amides of 
the formula R.sub.10 R.sub.11 NCOR.sub.12, wherein R.sub.10 and R.sub.11 
are independently selected from C.sub.1 -C.sub.22 alkyl, alkenyl, hydroxyl 
alkyl, aryl, and alkyl-aryl groups; R.sub.12 is hydrogen, or a C.sub.1 
-C.sub.22 alkyl or alkenyl, an aryl or alkyl-aryl group. Preferred 
examples of these amides are ditallow acetamide and ditallow benzamide. 
Good results are obtained when the amides are present in the composition 
in the form of a composite with a fatty acid or with a phosphate ester, as 
described hereinbefore for the softening amines. 
The amides are typically present in the compositions at 1%-10% by weight. 
Suitable conditioning ingredients are also the amines disclosed in U.K. 
Patent Application GB 2 173 827, the disclosures of which are incorporated 
herein by reference, in particular the substituted cyclic amines disclosed 
therein. Suitable are imidazolines of the general formula 1-(higher alkyl) 
amido (lower alkyl)-2-(higher alkyl) imidazoline wherein higher alkyl is 
alkyl having from 12 to 22 carbon atoms, and lower alkyl is alkyl having 
from 1 to 4 carbon atoms. Softener materials of this type are preferably 
added to the composition as particles or agglomerates as disclosed in U.S. 
patent application Ser. No. 922 912, filed Oct. 24, 1986 by Baker et al, 
the disclosures of which are incorporated herein by reference. 
Other suitable conditioning ingredients include quaternary ammonium 
compounds, such as ditallowdimethylammonium chloride, and similar 
compounds where at least one of the tallow chain is interrupted by an 
ester linkage such as described in EP-A-293 952. Also useful as 
co-softening agents are also the amines disclosed in EPA-A-199 383, in 
particular the substituted cyclic amines disclosed therein. Suitable are 
imidazolines of the general formula 1-(higher alkyl) amido (lower 
alkyl)-2-(higher alkyl)imidazoline wherein higher alkyl is alkyl having 
from 12 to 22 carbon atoms. A preferred cyclic amine is 
1-tallowamidoethyl-2-tallowimidazoline. 
A preferred cyclic amine is 1-tallowamidoethyl-2-tallow imidazoline. 
Preferred compositions contain from about 1% to about 10% of the 
substituted cyclic amine. 
Static Control Agents 
It may also be desirable to include a conditioning agent which controls 
static in the dryer. Suitable static control agents include ion-pair 
complexes of the formula (R.sub.1 R.sub.2 R.sub.3 N.sup.+ H) (A.sup.-) 
wherein R.sub.1 and R.sub.2 are C.sub.12 -C.sub.20 alkyl or alkenyl, 
R.sub.3 is H or CH.sub.3 and A.sup.- is an anion, such as benzene 
sulfonate a C.sub.1 -C.sub.18, preferably C.sub.1 -C.sub.5, more 
preferably C.sub.1 -C.sub.3, linear alkyl benzene sulfonate. These 
anti-static agents can also provide a softening benefit. These and other 
suitable anti-static agents are disclosed in U.S. Ser. No. 153,173, D. S. 
Caswell, filed Feb. 8, 1988, and U.S. Pat. No. 3,959,155, R. E. 
Montgomery, et al., issued May 25, 1976, both incorporated herein by 
reference. 
To avoid negative interactions with the clay materials, above organic 
conditioning agents, when appropriate, can be (releasably) encapsulated by 
suitable materials which, while ensuring the proper release of the organic 
material in the rinse water, remain stable and avoid negative 
interactions, upon storage of the products. 
The fabric conditioning compositions are typically used at a concentration 
to provide at least about 50 ppm of the clay in the aqueous laundry 
solution (exclusive of any fabrics). Addition to the wash and rinse stages 
are contemplated. Preferably, when the compositions are added in the rinse 
cycle of a washing machine, at least about 100 ppm and less than about 200 
ppm, more preferably between about 100 ppm and about 150 ppm, of clay is 
used based upon the weight of the laundry solution. When used at 
concentration of 150 ppm, the compositions encompassed by the present 
invention will typically have a Relative Deposition (wash added or rinse 
added applications), as measured by the test described in the 
Experimental, of at least about 13.0 in an aqueous laundry bath at pH 
7-11. The fabric conditioning can be carried out over the range from about 
5.degree. C. to the boil. 
When added during the wash stage of a washing machine, preferably between 
about 50 ppm and about 250 ppm, more preferably between about 75 ppm and 
about 150 ppm are added, based upon the weight of the laundry solution. 
Typically, no more than about 0.1 kg fabric (dry base) per liter of water 
are treated. Generally, from about 0.05 to about 0.08 kg fabric/liter 
water are treated. 
Recently, a method has developed for objective assessment of fabric 
softeners. The method consists of a battery of tests, known in the 
detergent industry as the KES-F system of Kawabata. The method is 
described in S. Kawabata, "The Standardization and Analysis of Hand 
Evaluation", 2nd Ed., Textile Mach. Soc. of Japan, Osaka, 1980, the 
disclosures of which are incorporated herein by reference. The shear 
hysteresis parameter 2HG5 of the KES-F system is believed to be 
particularly useful in the characterization of fabric softening clays. 
Preferred herein are hectorite clays which, when incorporated in fabric 
conditioning compositions at 10% by weight, reduce the shear hysteresis of 
fabrics laundered therein by at least 32%, more preferable by at least 
35%. The shear hysteresis parameter 2HG5 is discussed in more detail in 
Finnimore and Koenig, Melliand Textilberichte 67 (1986) pages 514-516, the 
disclosures of which are incorporated herein by reference. 
Softness measurements can also be obtained from expert panelists' 
subjective assessment of softness relative to a control. 
EXPERIMENTAL 
Relative Deposition Measurement 
A. Washing procedure 
Prewash: Cotton/Polyester (86%/14%) terry cloths (Style 4025, Dundee Mills, 
Griffin, Ga.) that are 11.times.11 square inches (27.9.times.7.9 square 
cm) and weigh about 50 g each are used for the Relative Deposition test. 
The cloths are washed two times with a conventional non-clay containing 
detergent formulation (shown below) in 0 grain/gallon water at 125.degree. 
F. (52.degree. C.) for 12 minutes each, then washed two times in 0 
grain/gallon water at 125.degree. F. (52.degree. C.) without detergent and 
dried in a Whirlpool 3 Cycle Portable Dryer (Model #LE4905XM, Whirlpool 
Corp., Benton Harbor, Mich.). 
Prewash Detergent Composition: 
______________________________________ 
Ingredient % (Wt.) 
______________________________________ 
C.sub.12 Linear Alkyl Benzene Sulfonate (Na Salt) 
4.1 
Tallow Alcohol Sulfate (Na Salt) 
5.0 
Neodol .RTM. 23-6.5 (Alkyl Ethoxylate) 
2.0 
Tallow Soap 1.9 
Sodium Tripolyphosphate 32.0 
Silicate 6.5 
Water and Miscellaneous balance to 100 
______________________________________ 
Test Wash: A miniwasher with five pots (such as those manufactured by 
Yorktown Tool & Die Corp., Yorktown, Ind.) is used. For wash-added clay 
softener tests, 9.12 g of detergent product (Testwash Detergent 
Composition, as shown below) and 0.58 g of a clay of the present invention 
(77ppm in the wash) are added to two gallons of 6 grain/gallon water at 
95.degree. F. (35.degree. C.) in each mini-washer pot and agitated for two 
minutes. For rinse-added tests, the clay is added at the beginning of the 
rinse stage (after the rinse water has filled the miniwasher). 
Alternately, where specifically set forth herein, higher clay 
concentrations, eg. 150 ppm, can be utilized. This, of course, will affect 
results and direct comparisons between clay concentrations are not 
reliable. A load of fabrics weighing about 341 g and including test 
fabrics of four of the prewashed terry cloths, six polyester/cotton 
(65%/35%) 11.times.11 square inch (27.9.times.27.9 square cm) swatches 
(product #7435, Test Fabrics, Middlesex, N.J.) weighing a total of about 
37 g, three 11.times.11 inch nylon swatches (product #322, Test Fabrics) 
weighing a total of about 18 g, three 11.times.11 inch polyester swatches 
(product #720-H, Test Fabrics) weighing a total of about 44 g, and one 
polyacrylic sock (Burlington Socks, Balfour Inc., Asheboro, N.C.) weighing 
about 42 g are added to the wash water. The fabrics are washed for 12 min. 
and spin dried for two minutes. The fabrics are then rinsed with two 
gallons of 6 grain/gallon water at 70.degree. F. (21.degree. C.) for two 
minutes, spin dried for two minutes, and dried in a Whirlpool 3 Cycle 
Portable (Model No. LE4905XM, Whirlpool Corp., Benton Harbor, Mich.). This 
test wash procedure is repeated for a second cycle, and the Relative 
Deposition is measured as described below. 
Test Wash Detergent Composition 
______________________________________ 
Ingredient % (Wt.) 
______________________________________ 
C.sub.13 Linear Alkyl Benzene Sulfonate 
9.0 
C.sub.14-15 Alkyl Sulfate 
9.0 
Neodol .RTM. 23-6.5T (Alkyl ethoxylate) 
1.5 
(Mfg. by Shell Chem. Co.) 
Sodium Tripolyphosphate 
38.4 
Silicate 14.6 
Sodium Carbonate 21.3 
Water and Miscellaneous 
balance to 100 
______________________________________ 
B. Relative Deposition Measurement 
The deposition of the clay containing compositions is calculated based on 
the deposition of silicon (Si) of terry cloth swatches washed with the 
test wash detergent composition relative to terry cloth swatches that were 
prewashed but not subjected to the test wash procedure (blank swatches). 
Silicon deposition is determined by measurement of the X-ray fluorescence 
of the silicon. Each Silicon fluorescence is measured in the following 
manner: An EDAX 9500 X-ray fluorescence unit with a rhodium anode X-ray 
source (Philips Electronics, Inc., Cincinnati, Ohio) is used. Each terry 
cloth swatch is analyzed for 100 live seconds. Count rate of Si (on a per 
second basis) for each sample is measured and recorded. 
##EQU2## 
wherein, STF is the Si count rate of clay-treated terry cloth fabric, SFB 
is the Si count rate of blank terry cloth fabric and SW is the Si count 
rate of a clay sample wafer (pressed clay particles of same area of terry 
cloth fabric). Count rates of Si for the clay sample wafer and clay 
deposition on fabric are measured as follows: 
(a) Si count rate for clay sample wafer: The X-ray generator is set at 20 
kV/500 microamps. About 2 g of clay powder is pressed at about 20,000 psi 
into a pellet with a 30 ton hydraulic press (Angstrom, Inc., Chicago, 
Ill.). The sample is rotated during the count rate analysis in a vacuum 
atmosphere (less than 300 millitorr). 
(b) Si count rate for the terry cloth treated with clay: The X-ray 
generator parameter is set at 15kV/500 microamps. A disk with a 3 cm 
diameter is cut from a terry cloth swatch. The disk is compressed at about 
20,000 psi to form a flat smooth disk using a ton hydraulic press, then 
rotated during the count rate analysis in a vacuum atmosphere. 
EXAMPLES 
The following product formulations exemplify the present invention. 
______________________________________ 
Ingredient Example # 
(all wt. percentages) 
I II III IV V 
______________________________________ 
Bentone EW (NL Industries) 
90% 67% 90% 76.5% 76.5% 
Sodium Carbonate 
10% 33% -- -- 15.0% 
Sodium Sulfate -- -- 10% 15.0% -- 
Silica/dye composite 
-- -- 8.5% 8.5% 
______________________________________ 
In the formulations above the Bentone EW can be replaced, in whole or part, 
with Macaloid (NL Industries), IMV Hectorite (Industrial Mineral 
Ventures), or Turkish Calcium Hectorite Clay, while still providing 
excellent results. 
The compositions can be prepared by agglomerating the clay in a commercial 
food processor, or other agglomeration equipment known in the art, with a 
solution of the salt dissolved in deionized water (eg. 15.0 g salt per 
30.0 ml water). The salt solution should be slowly added during the 
agglomeration procedure. The resulting product can be air-dried at ambient 
temperature. 
Optionally, a water-soluble dye can be incorporated into the composition. 
This can be done, as in Example IV and V, by stirring a carrier, such as 
formed silica gel particles (e.g. Syloid R 234), with the agglomeration 
equipment and slowly adding a dye solution (eg. 1.0 gram of F.D. & C Blue 
#1 per 30 ml of deionized water), at a final dye to silica weight ratio of 
about 1.0%, until the desired dye level (relative to the total weight of 
the composition) is obtained. The silica/dye particles can then be 
agglomerated, preferably with an aqueous salt solution (15.0 g Na.sub.2 
SO.sub.4 in 30.0 ml deionized water), air dried, and admixed with the clay 
particles. 
The agglomerated clay and silica/dye particles are screened with testing 
sieves known in the art to, separate agglomerates less than 100 microns 
and greater than 1250 microns. 
EXAMPLE VI 
This example shows an aqueous dispersion composition of the present 
invention. 
2 g of a natural hectorite clay (*) is added--under vigorous mixing--to 
97.5 g of deionized water. High speed mixing is maintained till complete 
dispersion of the clay. Dyestuff and perfume are added, to make up 100%. 
When applied in the rinse step of a laundry program, such a fabric 
softening composition delivers very significant softness benefits. 
EXAMPLE VII 
To 93.13 g of deionized water, 2.27 g of a low molecular weight 
polyacrylate (*) is added under moderate mixing conditions. High speed 
mixing is then used to optimally disperse 4 g of a natural hectorite clay 
(**). After dispersing, dyestuff and perfume are added (0.6 g) to finish 
the composition. 
FNT (*) Na - polyacrylate: 44% pure/MW=4500. 
FNT (**) Bentone EW as in Example I. 
EXAMPLE VIII 
30kg of a Bentone EW natural hectorite clay are added to a Loedige 
agglomerating equipment. Deionized water (+/-5 kg) is sprayed onto the 
clay powder till agglomeration is reached. The wet agglomerates are dried 
and sieved to a desired particle size (pref. 100% through 10 mesh and 0% 
through 100 mesh-Standard Tyler Sieves). 
The agglomerates are subsequently dyed and perfumed. 
EXAMPLE IX 
An intimate mixture of 24 kg of a natural hectorite clay powder (*) and 0.6 
kg of PEO clay-flocculating polymer (**) is added to a Loedige 
agglomerator. A mixture of deionized water (+/-4 kg), glycerol (0.65 kg) 
and the sodium salt of Ethylenediamine tetramethylene phosphonate (0.6 kg 
of a 25% solution) is sprayed onto the clay/PEO mixture. Extra deionized 
water is eventually added to obtain suitable agglomeration. The wet 
agglomerates are dried, sieved, dyed and perfumed. 
FNT (*) Macaloid clay ex Hector CA (NL Chemicals) Sodium form 
FNT (**) polymer of ethylene oxide/MW=300,000 
In Examples VI to VIII, the hectorite is used in its sodium form. The clay 
can also be used in its calcium form and converted to its sodium form 
during agglomeration, as shown in Example X. 
EXAMPLE X 
20 kg of a natural calcium hectorite clay powder and 0.4 kg of sodium 
carbonate are well mixed prior to their addition to a Loedige 
agglomerating equipment. +/-4 kg of deionized water is used for the 
agglomeration. The wet agglomerates are dried, sieved, dyed and perfumed.