Note: Descriptions are shown in the official language in which they were submitted.
36`5~L
DETERGENT - C~P~TI3LE FABRIC SOFTENING
AND ANTI-STATIC COMP05ITIONS
John R. Berschied, Jr.
John A. Gregg
TECHNIC~L ~IELD
This in~entiQn relates to composltions
adapted to provide f~brlc softenin~ effects in fabric
laundering operations. More particularly it relates to
the pro~ision of ~oftening and antistatic effects to
fabrics while simultaneously cleansing fabrics by
means o~ conventional synthetic detergent compounds
and or~anic or inor~anic deter~ent builders.
BACKGROUND
Fabric "softness" is an expression well de-
fined in the art and is usually understood to be that
qual ty of the trea-ted fabric whereb~ the handle or
texture is smooth, pliable and flu~fy to the touch.
Moreover, optimally so~tened fabrics are characterized
by a desirable antistatic ef~ect~ which is exhibited by
a lack of statlc cling.
]5 It has long been known that various chemical
compounds possess the abil~ty to soften and impart anti-
static benefits to fabrics~ However, the effectiveness
~r~
)
--2--
of any given compound may depend on its mode of
use. For example, rinse-added ~abric so~teners,
especially the quaternary a~monium compounds used
in the detergent-free deep rinse cycle of a home
laundering operation, provide exceptional condi
tioning benefitsO Unfortunately, the cationic
nature of these softeners causes them to interact
undesirably with the com~on anionic surfactants
such as the alkyl benezene sulfonates and is
generally believed to preclude their use during
the dete~ging cycle of a laundering operation
involving commercial anionic detergents.
Nu~erous Attempts have been ~ade to
formulate laundry detergent compositions that have
both goQd cleanin~ p~operties and also textile
softening properites so as to avoid the necessity
o~ using ~ ,s,e~a~a,te ~nse - added textile softener
product in addition to the usual laundry detergent.
The most commonl~ commerci~lly available
organic textile softening compounds are cationic
~ateria,l~ that ~e xeacti~e toward the ~nionic
surfactants used in conventional laundry detergents.
If both types of material are formulated in a
sin~le prQduct, they tend to interact on addition
to a wash'liquor which results in undesirable
effects such aS increased soil redeposition on
fabrics and poorer soil removal. A further conse-
quence of this incompatibility is the inhibition
of the tendency of the cationic material to
deposit on the fabric surface and an associated
reduction in the softenin~ benefit delivered to
the laundered ~abric.
3f~
In oxder to ove~come this problem, compositions
have been proposed which have sought to minimize
the mutual reactivity o~ the anionic and cationic
materials by the addition of compatibilizing
compounds as described for example in U.S. Patent
No.'s 3,886,075 and 3,954,63Z.
~ n alternative approach has been to
inco.rporate one of the reactant materials in a
.form that inhibits its cont~ct with the other in
the wash liquor and exa~ples of thls type of
formula,tion are tau~ht in U.S. Patent No.'s 3,936,537,
3,644,203, and 4,076,072.
In an attempt to avoid the reactivity
problem altogether, nonionic suractants have been
proposed in place o~ the con~entional.anionic
surfactants and composi-tions of this type are
described in, ,for ex,ample ~,P~ 1,079,388 and U.S.
Patent 3~607,763.'
Another propos.al to px~vide acceptable
cleaning and textile 'so~tening by avoiding the
surfactant-so~tene~ inter,a,ction has been made in
B. P. Spec'. No. 1,514,276 ~hich teaches the use
of certain long chain tertiary amines that are
nonionic in cha~acter at the ~ash liquor pH
existing ~,hen a conventional laundry detergent is
used. The com~only-~ssi~ned Euxopean patent ApPli-
cation No.'s 11340, published ~ay 28, 1980, and
8023367 published February 4, 1981 respectively
. disclose cleanin~ and softening composi~ions
comprising a combination of a long chain tertiary
amine and a smectite-type clay in an anionic
surfactant based detergent. The use of smectite-
type clays as softening agents in detergent co~po-
sitions is taught in B. P. Specification No.
1,400,898. This type of softening agent does not
affect the cleaning performances of the detergent
3~
--4--
compo~ition but, if used on its own, requires a
high level of incorporation for effective softening
performance. Battrell in U.S.Patent 4,292,035
discloses the formation of complexes of clay and
organic textile softening agents for inclusion
into detergent compositions for fabric softening.
In summary~ there has been a continuing
search for fabric conditioning agents which are
compatible with anionic surfactants and which can
be used without regard to the presence or absence
o~ such materials. The current practice in providing
a softening benefit t~ fabrics in domestic laundering
operations continues to be to add a cationic
fabric softenerr elther as a liquid to the final
rinse Qf the washing procesS or as a separate
additive to hot air tumble dryer.
~ t has noW been found that detergent
compositions can be formulated wherein the cleaning
performance is not impaired together with effective
textile softening performance.
It i5 an obiect o~ this invention to
provide fabric conditioning particles for use in
detergent compositions, which particles do not
react with anionic surfactants and do deposit on
fabrics to pxovide a softening benefit without
the need of machine drying.
The present invention is based on the
di cQvery that fabric s~tening p~rticles prepared
from certain comelted mixtures of dilong chain
tertiary amines and quatexnary ammonium salts can
be included in a detergent co~position to provide
fabric softening benefits in a softening through-
the-wash operation. The inclusion of the tertiary
amine in the particles mitigates the interactive
~36~
e~fects of the quate~nary ~mmoniu~ softening
agents and further con-~ributes to fabric soEtening,
wherein the particles have a specified range of
particle size, solubility in ~ater and melting
point. These particulate materials can be employed,
either as additives to supplement conventional
laundering products when the latter are added to
the liquor or as part of a product designed to
provide te~tile materials ~ith simultaneous cleansing,
and fabric softening effects.
According to one aspect of the invention
there is provided a partlculate additive product
containing as essential ingredients a quaternary
ammonium fabric softening agent in intimate mixture
~-ith a tertiary amine which prQ~ides urther
fabric softening and also acts as a dispersion
inhibitor ~o~ the quaterna~y co~pound~
The present invention also encompasses,
as integral for~ulations, compositions containing
the materials defined herein in combination with
synthetic detergent co~pounds and organic and
inorganic builder salts. Such compositions,
merely added to water, pro~ide in a single step
the provision of a laundering bath adopted to the
provision of simultaneous cleansing and ~abric
softening e~fects. In this application, because
of the small size of the particles of fabric
softening agenks~ it i~ convenient to agglomerate
the particles with ~ater-soluble neutral or
alkaline salts and certain clays to prevent segregation
in the composition. The addition of clay is
useful for preventing caking of the ~gglomerate
during processing as well as providing further
softening properties.
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SU~R,Y OF T~IE INVENTION
The present invention in its broadest aspect
relates to fabric softening particles which are useful
as adjuvants for detergent compositions. The invention
also relates to detergent compositions containing said
particles~
The ~abric softening particles, ~hich are
especially adap~ed for use in combination with anionic,
nonionic, zwitterionic, and ampholytic surfactants, are
intimate ~ixtures con~isting essentially o~, by weight
of the particles:
A. fxom about 90~ to about 20% by wei~ht of a
~uaternary ammonium compound of the ~ormula
~RlR2~3R4N; Y ~he~ein at least one but not
more than two o~ RlR2R3 ~nd R4 is an organic
.15 ~adical c~nta~n~ng ~ ~roup selected f~om a
C16 to C22 aliphatic radical, or an alkyl
phenyl or alkyl ~enzyl xadical having 10 to
16 carbon atoms in the alkyl chain, the
~e~inin~ ~roup or g~oups being selected from
Cl to C4 alkyl, C2 to C4 hydroxyalkyl, and
cyclic structures in WhiCh the nitro~en atom
forms part of the rins, Y constituting an
anionic radical selected ~rom the group
consisting of hydrox~.de, halide, sulfate,
methylsulfate, ethylsulfate, and phosphate
iQnsi and
B from about 80~ to 10% of a tertiary amine
having the formula RlR2R3N ~herein Rl and R2
are lndependently selected from C10- C12
alkyl or alkenyl groups, and R3 represen-ts a
C1-C7 alkyl group,
~herein substanti.ally all the ir.dividual particles have
a size in the range of 10~ to 500 -~ , a solubility in
~2~6~
--7--
water of 5Q ppm maximum ~t 25C, ~nd a softening point
in the range of from 90F. to about 200F.
The in~ention also encompasses detergent
compositions adapted to imparting softening effects to
fabrics in an aqueous laundering medium, comprising:
A. from about 5% to about 85~ by weight cf a
water-soluble detergent component selected
from the group consisting of anionic, nonionic,
ampholytic, and z~ittexionic surf~ctant; and
B. from about 5.0% to about 50% ~y weight of a
fabrlc softening com~onent comprising parti-
cles of t~e intimate mixture of the type
disclosed above.
DET~ILED DESCRIPTION O~THE INVENTION
The fabric softener particles consist
essentially of an intimate mixture of two components;
a quaternary ammonium salt; and a di-long chain
tertiary amine in a ratio range of from 9:1 to 1:4
respectively. Pre~erred ratios are from 4:1 to
1:2 and especi~lly preferred ratios are from 3:20 to 2:3.
The fabric softening particles ernployed
herein are ln the form of substantially ~ater~
insoluble particle~ ha~lng an avera~e size(diameter)
range of from about 10 ~ to about 500 y, Preferably,
the size of the particles herein lies in the range
from about 25 ~ to about 200 ~, moxe pxefer~bl~
from 50 ~ to 100 ~, and particles within this
xange are efficiently entrained on fabrlc surfaces
which is especially important for cool water
washing and line dryin~. The water solubility of
the particles must be no greater than 50 ~pm at
25C in water. The fabric softening particles
3~S~
--8--
must also be in the solid form in the washing liquor so
that they deposit on the fabric as discrete particles.
The particles therefore should have a mel~ing point in
the range of from 90F. to 200F.
~HE_QUATERNARY AMMONIUM SALT
Suitable quaternary ammonium compounds are included in
U.S. Pat. No. 3,936,537, issued to Baskerville et al. The
following description is an abbreviated discussion.
The quaternary ammonium salts useful herein have the
formula [RlR2R3R4N] Y wherein Rl and preferably R~,
represent an organic radical containiny a group selected
rom a C16-C22 alkyl ra~ical or an alkyl phenyl or alkyl
benzyl radical having 10 to 16 carbon atoms in the alkyl
chain, the remaining group or groups being selected from
Cl-C4 alkyl, C2-C4 hydroxyalkyl, and cyclic structures in
which ~he nitrogen atom forms part of the rinq, and Y
constitutes an anionic radical selected rom the group
consisting of hydroxide, halide, sulfate, methylsul~ate,
or ethylsulfate~ The preferred anions for the quaternary
ammonium fabric softener salts are c'nloride and
methylsulfate.
The ~uaternary ammonium fabric sof~enins compounds
useful herein include both water-soluble and substantially
water-insoluble materialsO Imidazollnium compound~ enumer-
ated in the ~askerville patent possess appreciable wa~er
solubility and can be utilized in the present invention by
mixing with the appropriate type and level of tertiary
amine to give ultimate particle solubility in water of
_9_
less than 50 ppm (parts per million) at 25C~ Relatively
water-soluble quaternary fabric softeners can be used,
such as diisostearyl dimethyl ammonium chlorides disclosed
in U.S. Pat. No~ 3,3~5,100 to Fisher et al. Exemplary
quaternary ammonium imida~olinium compounds are specific-
ally ethyl, l-alkylamidoethyl, 2-alkyl imidazolinium
methyl sulfates, more specifically l-methyl-l[(tallowamido)
ethyl]-2-tallowimidazolinium methyl sulfateO ~owever, the
most useful quaternary ammonium fabric softening agents are
characterized by relatively limited solubility in water.
The quaternary ammonium fabric softening agents used
in this invention can be prepared in various ways well
known in the art. Many such materials are commercially
available. The quaternaries are often made from alkyl
halide mixtures corresponding to the mixed alkyl chain
lengths in fatty acids. For example, the 'iditallow"
~uaternaries are made from alkyl halides having mixed
C14-C18 chain lengths. ~uch mixed di-long chain quater-
naries are useful herein and are preEerred from a cost
standpoin~.
The following are representative examples of
substantially water-insoluble quaternary ammonium fabric
softening agents suitable for use in the composition~ and
processeC of the instant inven~ion. All of the quaternary
ammonium compounds listed can be formulated with the
detergent compositions herein, but the compilation of
suitable quaternary compounds llereinafter is only by way
of example and is not intended to be limiting of such
compounds~ Dioctadecyldimethylammonium chloride is an
especially preferred quaternary fabric softening agent
for use herein by virtue of its high fabric softening
~2~
--10--
ac-tiVity; ditallowdimeth~l ammonium chloride is
equally preferred because of its ready availability
and its good softening activity; other useful di-
long chain quaternary compounds are dicetyldimethyl
ammonium chloride; bis-docosyldimethyl ammonium
chloride; ditallowdimethyl ammonium bromide;
dioleoyldimethyl ammonium hydroxide; ditallowdimethyl
ammonium chloride, ditallowdipropyl ammonium
bromide; ditallo~dibutyl ammonium fluoride, cetyldecyl-
methylethyl ammonium chlorlde, bis-~ditallowdimethyl
ammonium]sulfate; tris-5ditallow-dimethyl ammonium]
phosphake; and the like.
THE TERTI~RY AMINE
.
The -tertiar~ amines sui-table for use in
makin~ the intimate particles have the general
~5 formula RlR2R3~ wherein Rl and R2 are independently
selected ~rom C10 to C22 alkyl or alkenyl groups,
and R3 represents a Cl to C7 alkyl. The ter-tiary
amines axe characterized by being ~ater insoluble.
Æxemplary tertiary amine compounds
include, but are not limited to, the followiny:
didecyl ~ethylamine, dicoconu-t methylamine, dim~ristyl
methylamine, dicetyl methylamine, distearyl methylamine,
diarachid~l meth~lamine, dibehenyl me~hylamine,
di(m~xed arachidy1/behenyl) methylamine, ditallowyl
me-thylamine, and the corresponding ethylamines,
propylamines, and butylamines, Especially preferred
is ditallowyl methylamine.
It ~as discovered -that the combination
of the quaternary ammonium salt and the -tertiary
amine in in-timate admixtures pravide compositions
tha-t are effective in softening fabrics through~
~ 3
the-wash. The term "effective" means th~t the
particles provide fabrics with a softer feel and
an antistatic effect as described hereinabove. The
tertiary amine, as shown by this invention, does
protect the quaternary ammonium compound from
interac-tive effects in the wash liquor and the
admixture, in the form of particles, does deposlt
on the fabrics to condition the fabrics as described
above.
The ~abric softening particles of the
present invention can be conveniently prepared by
co-melting the tertiary amine and the quaternary
ammonium sal-t compound and then converting ~he
molten mass into particles of the desired size by
an~ of the conventional ~eans for con~erting
melted materials to dry particlesl e.g., cooling
the ~olten mas5, followed by grinding to the
appropriate size, or simultaneously cooling the
mass and forming particles by spraying the mass
through a nozzle into a cool a,mosphere (prilling).
Particle size selection can be accomplished by
controlling -the process, or alternatively screening,
air stream segregation, etc.
~s disclosed herein, -the particles can
be added directly to a wash liquor containing a
conventional detergen-t composition for softening
fabrics through~the-wash. The particles can o~
course be dry-added to a ~ranular detergent
composition to provide a composition which can
simultaneously clean and so~ten fabrics. To
prevent segregation it is desirable to coat the
particles -to make agglomerates of the particles
which will ha~e approximately the sa~e partic]e
size as -the granular detergent composition. The
-12-
a~glomerhte can contain from 10% to 806~
preferably from 15~ to 50%~ more preferably from
20% to 40%~ by weight, o~ the particles of quaternary
ammonium salt and tertiary amine.
The fabric softener particles can be
agglomerated by mi~ins with a water-soluble,
neutral or alkaline salt and spraying the agitating
mixture with ~ater or an organic agglomerating
agent. Further, certain smectite clays can be
included which are useful as processing aids to
prevent caking of the a~glomerated during making.
The smectite clays can provide additional fabric
softenin~ benefit when used in laundering fabrics
wherein the water contains appreciable amounts of
soluble calcium and magnesium salts, ~.e., wa-ter
having at least 9 grains per gallon of such salts
calculated as CaC03.
~ he ~ater-solu~le neutral or alkaline
s~lt can be either organic or lnorganic and has a
pH in solution of seven or greater. The water-
soluble neutxal oX alkaline salt will be employed
in the agglomera~ed particulate in an amount from
about 10% to about 80% by weight, preferably ~rom
about 20% to about 60% by weight, more pre~erably
from about 25% to about 50% by weight, most preferably
from about 30% to a~out 40% by weight. SpecificallY,
some of the water-soluble, neutral or alkaline
salts, if not used in the hydrated form, will absorb
moisture during the processing of the agglomerated
particulate detergent additive, and ~n addi-tion
func-tion as detergency builders in wash water
solutions.
~ xamples o-f such wa-ter-soluble neu-tral
or alkaline salts include alkall metal chlorides
such as sodium chloride and po-tassium chloride,
alkali metal fluorides such as sodium fluoride
~v~
-13-
and potas~ium ~luoride, ~lkali metal carbona-tes
such as sodium carbonates, alkali metal silicates,
and mixtures thereof. ~ny conventional water-
soluble, neutral or ~lkaline inorganic salt such
as the alkali metal sulfates, notably sodium
sulfate, may be employed in the present invention.
~ ater-soluble, neutral or alkaline salts
also include the variety commonly known as detergency
builder salts, especially alkaline, poly~alent
anionic builder salts. Suitable detergency builder
salts include polyvalent inor~anic or organic
salts or mixtures thereo~. Suitable water-soluble,
preferred inoryanic alk~line detergency builder
salts include alkali metal carbonates borates,
phosphates, polyphosphates, bicarbonates, silicates,
and sulfates. Specific examples of such salts
include the sodium ~nd pot~sSium tetraborates,
perborates~ bicarbonates, carbonates, tripolyphos-
phates ! pyrophosphates, orthophosphates and hexa-
metaphosphateS
Examples o~ suitable organic alkalinedeteryency builder salts are: ~ater-soluble aminopoly-
acetates, e.g ~ sodium and potassium ethylenediaminetetra-
acetates, nitrilotriacetates and N~(2-hydrox~ethyl)ni-
trilodiacetates; ~ater-soluble salts of phytic
acid, e.y., sodium and potassium phytates; water-
soluble polyphosphonates, includin~ sodium,potassium,
and lithium salts o~ ethane~ hydroxy 1, l-di-
phosphonic acid; sodium, potassium and lithium
salts o~ methylene diphosphonic acid and comparable
examples.
~ dditional oryanic builder salts are
disclosed in U.S. Pat. No.'s 2,264,103 to N.B
Tucker, 3,308,067 to F, L. Diehl, 4,083,813 to
~93~
-14-
Rodney M. Wise et al. The Tucker patent particularly
discloses polycarboxylate and citrate salts, notably
sodium citrate which may be used in the present
invention as a water-soluble, alkaline salt. Further
detergency builder salts are disclosed in U.S. Pat.
No. 3,936,537 to Baskerville, Jr. et al.
As noted hereinabove the wa~er-soluble neutral
or alkaline saLt can be used as the agglomerating
material with water above or with an organic
agglomera~ing agent. The organic agglomerating agent
can be present at levels, on a dry basis, of up to
20% by weight, preferably from about 5% to about 15~
by weight, most preferably from about 7% to about 12%
by weight of the particle agglomerate detergent
additive.
The organic agglomerating agent ~often loosely
termed a "glue" or "glue mix") may include starches,
notably the dextrin starches. Dextrin starches, or
dextrins, are starches which are modified by heating
in their natural state~ Suitable dextrins include
those manufactured by the A. E. Staley Manufacturing
Company, Decatur, Illinois 62525 under the trade mark
STADEX and described in khe Staley Technical Bulletin
TDS No. 116.
The Stadex dextrins are produced by partially
hydrolyzing corn starch, by heating in a dry a~mos-
phere in the presence of acid. There are three main
types, white dextrins, canary or yellow dextrins, and
British Gums which are heated longer and catalyzed
3Q with little or no acid. The standard method of
dextrin manufacture was roasting the
~15-
starch in a horizontal cooker with agitation.
However, Stadex dextrins are made by 'Ifluidizing"
powdered starch during the heating cycle for grea~er
conversion uniformity o starch to dextrin by ensur-
ing a more even distribution of heat and acids.
Other exarnples of suitable dextrins andtheir preparation are contained in Starch and Its
Derivatives by J.A. Radley, Chapman and Hall Ltd;,
London (4th Ed. 19681, no~able in the essay by
Go V. Caesar on IlDextrins and Dextrinization" at
pages 282 289 and the essay on l'The Schardinger
dextrins" at pages 290-305. Suitable examples of
dextrins and their preparation are also contained in
Chemistry and Industry of Starch by Ralph W. Kerr,
Academic Press, Inc., New York (2nd Ed. 1950),
particularly in the essay "Dextrinization" by
G. V. Caesar at pages 345-355~ and the essay
"Manufacture of ~extrinsl' at pages 357~373.
Dextrin may be added to the agglomerate in a
water solution. This dextrin-in water solution may
comprise from about 10% to about 60~ by weight,
preferably from about 20% to about 50% by weight,
and most preferably from about 30~ to about 40% by
wei~ht of dextrin.
7.5 Other exemplary materials useful as agglomerat-
ing agents are described in U~S. Pat. No. 4,141/841
to McDanald. Briefly, these materials inc]ude
polyethylene glycols and polypropylene glycols having
a molecular weight of from about 950 to 30~000;
copolymers containing ethylene oxide and propylene
oxide units, condensation products of one mole of a
C10 to C18 saturated or
-16-
unsa-turated straigh-t or branched chain carboxylic
acid with ~rorn about 20 to about 50 mo]es of
ethylene oxide, C10- C2~ saturated or unsaturated,
straight or branched chain alcohols with from 9 to
about 50 moles of ethylene oxide, certain poly-
oxyethylene glyceride esters and polyoxyethylene
lanolin derivatives, amides which have a melting
point between about 30C and 100C, the condensation
of one mole of C~-C18 alk~l phenol With from about
25 to about 50 moles of ethylene, oxide, C12to C30
atty acids which rnelt bet~een 30C and lOO~C, and
C16 to C30 fatty alcohols which mel-t at between
30C and 100C~
The agglomerated particulate detergent
additive may op-tionally contain smectite clay as
an ingredient. Clay compounds, namely sodium and
calcium montmarillonites, sodium saponites, and
sodium hectorites, can be incoporated into the
agglomerated particulate detergent additive. These
smectite cla~s ~ay be admixed with the particulate
deter~ent additive o~ this invention at levels up
to 50% by ~reightl preferably ~rom ahout 5% to
about 25% by weight, most pre~erably from abou-t 7%
to about 15~ by weight, of the agglomera-ted particu~
late detergent additive. The clays used herein
are "impalpable" r i.e., have a particle size which
canno-t be perceived tactilely. ~mpalpable clays
have particle sizes below about 50 microns; the
clays used herein have a particle size range of
~rorn about 5 microns to about 50 rnicrons.
The clay minerals can be descri~ed as
expandable, three-layer clays, i.e,, aluminosilicates
and magnesium silicates, having an ion e~change
capacity of at least 50 meq/~lOOg. of clay and
-17-
pre~erably at least 60 me~lOOg. of clay.
The term "expandable" as used to describe clays
relates to the ability of the layered clay structure
to be s~llen, or expanded, on contact with water.
The three-layer expandable clays used herein are
those materials classified geologically as smectites.
There are two distinct classes of smectite
clays that can be broadly differentiated on the
basis of tne numbers of octahedral metal-oxygen
arrangements in the central layer ~or a given
number o~ silicon-oxygen atoms in the outer layers.
The clays employed ln the compositions
o~ the instant invention contaln cationic counterions
such as protons, sodium ions, potassium ions,
calcium ions, and lithium ions. It is customary
to distinguish bet~een clays on the basis of one
cation p~edo~in~ntly or exclusl~ely absorbed. For
example, a sodium clay is one in which the absorbed
cation is predominantly sodium. Such absorbed
cations can become in~olved in exchange reactions
~ith cations present in aqueous solutions. A
typical exchange reaction invol~lng a smectite-
type clay is expressed ~y the following equation;
smectite clay (Na)~ ~ NH40H ~ smectite cla~ -
(NH4)~ ~ NaOH. Since the foregoing equilibriumreaction, one equivalent weight of am~onium ion
replaces an equiv~lent ~eight of sodium, it is
customary to ~easure catlon exchange ca~acity
(sometimes termed "base exchange capacity") in
terms of ~illiequivalents per lOOg. of clay (meq/lOOg.).
The cation exchange capacity of cla~s can be
measured in several ways~ including by electro-
dialysis, by exchanye with ammonium ion followed
by titration or by a methylene blue procedure,
all as fully set forth in Grimsha~, "The Chemistry
and Physics of Clays", pp. 264-265, Interscienee
(1~71)~
The cation exchange capaeity of a elay
mineral relates to such faetors as the expandable
properties of the clay, the charge of the clay,
which, in turn, is determined at least in part by
the lattice strueture, and the like. The ion
exehange eapaeity of clays varies widely in the
ran~e from about 2 meq~lOOg. of kaolinites to
about 150 meq/lOOg., and ~reater, for eertain
~mectite clays. Illite clays although having a
three layer strueture, are of a nonexpanding
lattice type and have an ion exchan~e eapacity
~ome~here in the lo~er portion of the range, i.e.,
around 26 meq~100~. for an average lllite clay.
Attapulgites, another class o~ elay minerals, have
a spieulax (1.e. needle-like) crystalline form
with a lo~ eation exehange capaeity (25-30 q/lOOg.).
Their strueture is eomposed of ehains o-E siliea
tetrahedrons linked together ~y oetahedral groups
o~ oxygens and h~drox~l eontaining ~1 and Mg
~toms.
It has been determlned that illite,
attapulgite, and kaolinite elays, with their
relatively low ion exehange eapaeities, are not
use~ul in the instant eompositions. Indeed,
illite and kaolini-te cla~s constitute a major
eomponent of elay soils and, as noted above, are
removed from fabrie surfaces by means of the
instant eompositions. However, -the alkali metal
montmorillonites, saponites, and hectori-tes, and
eertain alkaline earth me-tal varieties of these
minerals sueh as e~leium montmorillonites have
been found to show useful fabric-softening benefits
--19--
when incorporal:ed in composition5 in accordance with
the present invention. Specific examples of such
fabric-softening smectite clay minerals are: sodium
montmorillonite, sodium hectorite, sodium saponite~
calcium montmorillonite, and lithium hectorite.
Accordingly, smec~ite clays useful herein can be
characterized as montmorillonite, hectorite, and
saponite clay minerals having an ion exchange
capacity of at least about 50 meq/lOOg., and
10 p.referably at least 60 meq/lOOg.
The above discussion of optional clay additives
is intended to only be a brief cursory review of the
subject matter contained in U.S. Pat~ No. 3,936,537.
It is intended that the particulate de~ergent
15 additive be incorporated in a detergent composition
to provide cleaning and softening to Eabrics. Because
of segregation problems due to the small particle size
of the particulate detergent additive J it is preferred
to agglomerate said detergen~ additive as disclosed
20 above. The detergent composition thus will contain an
agglomerate of the particulate detergent additive dry
admixed with the detergent composition which contains
a surfactant and optionally detergency builders. The
detergent composition can contain from about 5% to
25 about 50~, preferably from about 10~ to about 30%,
more preferably from about 12% to about 20%, by
weight, of the agglomerated particulate detergent
additive product.
SURFACTANT
The detergent composition which comprises
the agglomerated particulate detergent additive
: )
9 ':
3~
19a-
can contain frorn 5~ to 85%, preferably 5% to S0~,
most preferably from 10~ ~o 30~, of a surfactant
selected from the group conslsting of anion:lc,
nonionic, ampholytic and zwit~erionic sur~actants,
and mixtures thereof, inasmuch as the other components
are compatible with all such materials at the
concentrations and proportions disclosed herein.
A typical listing of the classes and
species of surfactants useful herein appears in
U.S. Pat. 3,579, 454,
column 11 line 45 to column 13 llne 64.
Examples of suitable surfactants of
these classes which can be employed in accordance
with the present invention are the followlngO
1. Anionic water-soluble soaps: Examples
of suitable soaps for use in ~his
invention are the sodium, potassium,
ammonium, and alkanolam~onium(mono-, di-
and triethanolammonium) sal~s of high~r
fatty acids tcl~-c223- P~rticularly
useful are the sodium and potassium
salts of the mixtures of ~atty acids
derived from coconut oil and tallow,
i.e., sodium and potassium tallow and
cooonut soaps.
2. Anionic synthetic non-soap surfactants:
A preferred class can be broadly described
as the water-soluble salts, paxticularly
the alkali me~al salts of organic sulfuric
acid reaction products
3~
~20~
having in their molecular structure an
alkyl ~roup containin~ from about 8 to
about 22 carbon atoms ~nd a sulfonic
acid or sulfuric acid ester group. (Included
in the term "alkyl" is the alkyl portion
of acyl groups.) Examples of this group
include C8-C18 alkyl sulfates, straight or
branched ch~in alkylbenzene or alkyltoluene
sulfonates containing from 9 to 15 carbon
atoms in the alkyl chain (especially valuable
are linear straight chain alkylbenzene
sul~onates in which the average of the
alkyl groups is about 11.8 carbon atoms and
cvmm,only a~breviated as Cl1 8LAS)IClo to
C20 alkyl ether sulfates having from 1 to
30 moles of ethylene oxide per molecule,
sodium alk~l gl~ceryl ether sulfonates,
ester of ~- sul-fon~ted ~atty acids, and C12
to C24 olefin sulfonates.
3. Nonionic surfactants obtained by the
condensation o~ 1 to 12 ethylene oxide
moieties ~ith a C10 to C18 aliphatlc alcohol~
4~ ZwitterioniC suxfactant~ such as
3 - (N~N - dimet~yl - N - hexadecyl ammonio)-
2 ~ hvdroxypropane - 1 sulfonate and
3 - (N~N ~ dimethyl - N - tallow~yl ammonio) -
2 - hydroxypropane - 1 - sulfonate~
DETERGENCY BUILDERS
The detergent compositions of the instant
invention may contain a detersency builder in an
amount from about 5% to about ~5% by weigh-t, preferably
from about 15% to about 60% by weight, ancl most
preferably from about 20% to about 40% by weight of
the entire detergent composition. The de-tergency
builders mentioned hereinabove are suitable for use
in this invention.
3~
-21-
OTHE~ ~TIQNAL IN~EDIENTS
-
Other optional ingredients which may be
lncluded in the detergent composition include deter-
gency builders enumerated in the Baskerville patent
from column 13, line 54 through column 16, line 17,
as well as ~ntltarnish and anticorrosion agents,
perfume and color additi~e, enzymes and other optional
ingredients enumerated in the Baskerville patent,
U.S. Pat. No. 3,936,537, from column l9, line 53
thxough c~lumn 21, line 21.
METHOD OF PREPARATION
-
The particulate detergent ~ddl-tive product
is made by mixing the ~uarternary ammonium compound
and tertiary amine by comelting the materials, cooling
to a solid mass and obtaining the desired particle
size by comminution and screening. ~n alternative
method is to spray the liquid mixture through a
pressure nozzle to ~orm droplets of the desired size
range which are -then solidified b~ cooling and
subject to screening (prilling process). It is a
requirement of this invention tha-t the ~ua-ternary
ammonium compound and the tertiary amine be intimately
mixed, i.e., comelted, in forming the particulate
softening composition. The suitable particle size
r~nge o~ the p~rticulate detergent additive is from 10
to about400~ ~ most preferably ~rom about 50~ to
about 10 0 1l .
The processes of comminutlng a solid ~ass
of comelt such as grinding, ball milling, hammering,
grating through a sieve etc. are well known in the
art. Similarly, prilling processes are also well
known.
It will be appreciated that in making the
comelt, the materials should be low in solvent and
ideally are subs-tan-tially free thereof. ~hile solvents,
3~
-22-
such as lso~ropanol, a~e conventionall~ present in
commercially available quarternary softening mater-
ials to aid dispersion in aqueous media, such sol-
vents are disadvantageous to the present invention in
that the particles mus-t have low solubility.
After initial combination of the quaternary
ammonium coumpound and tertiary amine to form a
comelt or prill of the desired particle size, said
particles are ac~glomerated with the water-soluble
neutral or alk~line salt ~or use as admix-tures in
detergent compositions and avoiding segregation.
Agglomeration serves the purpose of combining the
small particles to increase the apparent particle
size without affecting the particle size of the
individual particles. The salt also provides more
strength to the ag~lomerate and makes the resulting
mixture more ~ree-flowinq. In the wash liquor the
water-soluble saIt dissol~es to release the indi~id-
ual particles which then are distributed throughout
the wash liquor and are free to deposit on the fabrics
being washed.
The mixture of comelt or prill and salt,
preferabl~ sodium carbonate or sodium tripolyphosphate,
is fed into a highly eff~cient mixer where agglome-
rating agent (dextrin qlue solution) is sprayed ontothe mixture. Types of mixers which may be employed
include the Schugi mixer (Flexomix 160,250,335 or
400), the OIBrien mixer, the Littleforcd mixer, the
Patterson~Kelly mixer, rib~on mixers, and/or vir-
tually any of the conventionally-known pan agglome~
rators. This results in aqglomerates of water-
soluble, neutral or alkaline salt and prills or
comelt of quaternary ammonium compound ancl -tertiary
amine in the same size range as con~entional deter-
qent granules, thus ellminating the
-23-
prohlem of segrega-tiQn (abou-t 150-1190 y in size).
The final agglomerates are discharged from the (Schu-
gi) mixer and optionall~ admixed with particulate,
smectite clay. The resulting composition is aged for
approximately one hour, optionally mi~ed with silica
if increased flo~ability is desired, and admixed with
conventional detergent granules.
Certain of the water-soluble, neutral or
alkaline salts may absorb moisture during the pro-
cessing of the agglomerate. ~n addition, some of thewater-soluble neutral or alkaline salts Eunc-tion as
detergency builders in ~ash water. Further, the
mixture o~ prills and water-soluble neutral or al-
kaline salt, when aggl~merated, provides lncreased
fabric softening relative to prills alone in the
second wash load.
EX~MPLE ~
A particulate detergent additive was pre-
pared as follows:
Ingredient Weight Per Cent
Dimethyl di-hydrogenated
tallow ammonium chloride(:~5% ac-tive powder) 40
Di-hydrogenated -tallo~ methylamine 60
100
The quaternary (DTDM~C) and amine (DTMA)
were melted -together -to orm a clear solu-tion in a
steam bath. The molten mi.xture was cooled and became
solid at room temperature. The solid mass was broken
up and then ground in a mortar with a pestle -to a
particle size in the range not greater than 65~ to
~2~
-24-
80 ~ . A microscope with a ~rid was u$ed to check
the particle size during the grinding. (A con~enient
alternative process would be to make the particles by
a prilling process). The so~tening poin-t of the
particulate deter~ent additive was about 105 F. The
particles were essentially insoluble in water at
25C~ The particulate detergent additive in all the
subsequent examples had essentially the same solubi-
lity characteristics and ranged ln melting point from
about 90 F. to about 135 F~, depending on the ratio
o~ the components.
The particulate detergent additive can be
added to a was~ uor to provide softening to fabrics.
~s defined hereinabove softenin~ m,eans that the
fabrics treated there~ith have a so~ter feel to the
touch and e~hibit a lack o~ static cling.
Comparable results are obtained when the
quaternary ammonium compound utilized is ditallow-
dimethyl ammonium methylsulfate, ditallo~dlmethyl
ammonium ethylsul~ate, l-meth~ (tallowamido~ethyl]
-2-tallow imidazolinium methylsulfa-te~ or mixtures
thereo~ in place of the dl-tallowdimethyl ammonium
chloride on a par-t for part basis.
Substantially si~ilar results are obtained
when the ditallo~ methylamine is replaced with di-
decyl heptylamine, dicoconut butylamine, dimyristyl
ethylamine, dicetyl ~ethylamine, diarachidyl methyl-
amine, dibehenyl methylamine, and di(mixed arachi~
dyl/behenyl) methylamineO
EXAMPLE I~
The particulate detergent additive par-
ticles made in Example I were agglomerated with
sodium tripolyphosphate (STP) ! in a cement mixer~
The STP was a dry, anhydrous, powder with at least
~3~
-25-
90~ passin~ through a 100 mesh Tyler sieve.
To 33.75 parts of particles made in Example I
were added 28.95 parts of STP and sprayed with 8042
parts of dextrin glue (35 parts solid to 65 parts
water~ This resulted in agglomerates of the particu-
late detergent additive and STP having the same size
range as other deter~ent granules, about 150-1190
microns.
The product of this agglomerating step was
added to detergent granules to provide a composition
which simultaneously cleaned and softened fabrics.
The agglomerated fabric so~tening or conditioning
cornposition provided better second load fabric
softening than the addition of the particulate
detergent additive alone to wash water
As mentioned hereinbefore smectite clay can be
a component of the agglomerate The process is one
o~ simply admixing the agglomerate with the approp-
riate amount oE impalpable smectite clay For
example 71.1 parts of the agglomerate was admixed
with 29.9 parts of calcium montmorillonite clay of
good fabric softening performance and having an ion
exchange capacity of about 84 meq /lOOg. (available
from Industrial Minerals Ventures Inc. U.S.A.~ sold
under the trade mark Imvite K).
Substantially similar results are obtained when
sodium tripolyphosphate is replaced with sodium tetra-
borate, potassi~n tetraboratel sodium bicarbonate,
potassium bicarbonate, sodium carbonate, potassium
carbonate, potassium tripolyphosphate, sodium pyro-
phosphate, potassium pyrophosphate, sodium hexameta-
phosphate, potassium hexametaphosphate, sodi.um
sulfate, potassium sulfate, sodium citrate, potassi~m
citrate, and mixtures of these water-soluble, alkaline
salts~
,s
3 Ei~;~
-26-
Other types of smectite clay which when
substituted for calcium montmorillonite yield com-
parable ~abric~softening performance include sodium
hectorite, sodium saponite, calcium montmorillonite,
lithium hectorite, and mixtures thereof.
EXAMPLE III
P~rticulate detergent additives and agglo-
merates thereof made according to Examples I and II
were added to detergent granules to make detergent
compositions ~hich pro~ide cleaning and softening
through-the-wash and evaluated for cleaning and
so~tening performance relative to a detergent com-
position having no softening attribute and a second
composition h~ving a softening component outside this
invention.
-27-
Compositions Control 1 Control 2 No.l No.2
Detergent C~mporlent
C L~S 23.0% 15.0% 15.0% 15.0%
12
Na pyro.phosphate 17.1 14.06 15.18 15.18
5 Hardened tallcw fatty acid 1.25 ~ - -
Na silicate(2SlO2/Na2O)12.0 12.0 10.0 lO.O
Na2C3 15.0 15.0 5.71 15.0
Na alumlnosilicate 4.0 ~ - ~
Na2S4 18.83 16.39 32.58 42.39
10 Glass H* 0.85 0.85
~EG 6000** 0.85 0.85 0.85 0.85
C12Alkyl dimethylamine oxide
(sprayed on) - 0.25 5.25 0.25
Minors(brightener, perfume,
etc.) 0.82 0.6 0.62 0.62
~oisture 6.3 5.0 5.0 5.0
Ditallow methylamine(DIMA) - 5.33
DicQconut methylam~ne(PCMO ~ 2.67 - -
Clay-Ca montmorillonite ~ 12.0 - -
20 TOtal lOO.0% lOOeO% 85~19% 95~0%
~oftener component admix 14.81% 5~0%
3~
~28-
The composition of the softener components
were as follows:
Control 2 No.l No.2
2:3 DTDM~C:3TM~ - 33.74% 100%
2:1 DrMA:DcM~ 40
Na2CO3 ~ 28.95
Clay-Ca montmorillonite60 28.88
Dextrin glue(.35% solids) ~ 8~43
* Glas$ H is a com~lex phosphate having ~bout 21 atoms.of
phosphorus.
** PEG 60Q0 is polyethylene glycol of MW 6000.
Control 1 does not contaln any fabric softening
component Control 2 contains 8% of a mixture of
terti~X~ a~ine~ (.2;1 DT~: Dlcoconut ~ethylamine)
and 126 of cl~y. The' softener component of Compo-
sition No. l ~as added to the deter~ent componentas an a~glomera~e ha~ing the composition shown.
In Composition No. 2 the ~oftener co~ponent is an
admix of the product made 'in Example ~.
Several fabrics were washed with the
detergent compositions in a 10 minute wash at 70
F in soft ~ater (3 grains hardness/gal), line
dried, air -tu~bled in a dryer ~ithout heat ~or lO
minutes, and checked for total voltage using a
Fara,day ca~e, insta,nces ~ static cling of -the
~abrics, and for softness b~ a panel in paired
comparison tes-ting.
Static Test Results(68F~34% Rel~H.)
Total Volts Clings
Control 1 52.9 2
Control 2 44.6 0
Composition No.l 11.3 0
Composition No.2 9.0 0
~2ai~
-29-
SGftening Performance ~ Ranel ~core Units
lst load nd load
Control 1 STD STD
Control 2 0.5 0.8
Composition No. 1 1.4 1.4
5 Composition No. 2 1.5 0.7
LSD* at 95% confidence was. 0.5 ~nel $core units
*Least signi~icant dif~erence
As shown b~ the ~esults, CompoSitions No.'s 1 and
2, which are within the scope of this invention,
provide ~ sQ~tenins e~ect to fab~ics xelati~e to
Control 1 and the softening e~fect ls superior to
that provided by Control 2 which contains a mixture
o tertia,Xy ,a~ines.
In Co~position No. 1 when sodium tripoly-
phosph~te or sodium tetraborate replaced the
sodium carbonate as the soluble salt in the ~gglome-
rated par-ticul~te deter~ent additive substanti~lly
similar results were observed.
In Com~o$ition No. 1 when the 2;3 ratio
of DTDM~C: DTMA was replaced by a 3:2 ratio of
DTDMAC, DTM~ ~ubst~ntiall~ ~lmil~x ~esults were
observed.
In Composition N~. 1 when the 2.3 ratio
of DTDM~C: DT~ was replaced b~ a 1:4 ratio of
DTDMAC:DTM~ the softenin~ benefit observed was
less than Co~position N~ nd abou-t equal to
Control 2.
In Composition No. 1 when the 2:3 ratio
of DTDMAC: DTMA iS replaced by a 9:1 ra-tio of
DTDMAC:DTMA substantially similar results were
~3~
-30-
observed.
Comparable results are obtained when the
sodium carbonate in the agglomerated particulate
detergent additive of Composition No. 1 is replaced
by sodium tripolyphosphate, sodium tetraborate,
potassium tetraborate, sodium bicarbonate, potassium
bicarbonate, sodium carbonate, potassium carbonate,
potassium tripolyphosphate, sodium pyrophosphate,
potassium pyrophos~hate, sodium hexametaphosphate,
potassium hexametaphosphate, sodium sulfate,
potassium sul~ate, sodium citrate, potassium
citrate, and mixtures of the water-soluble, alkaline
salts.
Co~parable re~ults ~e obtained when the
~uaternar~ ammonium compound utilized is ditallow-
dimethyl ammonium methylsul~ate, ditallowdimeth~1
ammonium ethvlsulfate~ 1-meth~ (tallow amido~
ethyl] 2-tallow imidazolinium methyl sulfate, or
' mixtures thereof in place of the ditallowdimethyl
ammonium chIoride on a part for part basis.
Csmparable results. are obtained when the
DTM~ in the agglomerated par~iculate detergent
additive is replaced b~ didec~l ~eth~l~mine,
didecyl heptylamine, dicoconut methylamine, di-
coconut bu-tylamine, d.im~ri~tyl ~ethylamine, di-
myristyl ethylamine, dicetyl methylamine, diara-
chidyl methylamine, dibehenyl methylamine, and
di(mixed arachidyl~ behenyl) meth~lami,ne.
Since the intimate mixture of quaternary
ammonium salt and tertiary amine part:icles are
essentially water-insoluble ! e~en under alkaline
conditions, they are wholly compatible with all
manner of detersive surfactants and de-tergency
builders. Thus, the detergen-t component in C~mpo-
sition No. 1 can include any of the sur-factants
~nd builders disclosed he~einabove and ~till
deliver the softening to :Eabrics through-the-wash
provided by the agglomerated particulate detergent
additive.
Compositions 1 and 2 show that the
insoluble, small particles of the intimate mixture
of quaternary ammonium salt and textiary amine do
deposit on fabrics during washing -to provide a
softening benefit to the fabrics ~erel~ with line
drying. The softening benefit delivered to the
fabrics will be greater when the washed ~abrics
are machine dried with heat ~h~ch melts the parti-
cles on the fabric and provides a better coating
to the fibers.
15 WHAT I S CLAI~IED I S `
