Note: Descriptions are shown in the official language in which they were submitted.
2~7~7 ~'3
Express Mail No. FB449229682US
Attorney's r ket No. IR 1150-F-B
FABRIC SOFTENING PRODUCTS BASED ON A COMBINATION OF
PENTAERYTHRITOL COMPOUND AND BENTONITE
This invention relates to fabric softening products,
which include fabric softening compositions and articles for
applications to laundry during washing, rinsing and/or drying
cycles, to apply to the fibers of the fabrics of such laundry
fabric softening amounts of fabric softening components of
such products. More particularly, it relates to such products
that include as fabric softening components higher fatty acid
esters of pentaerythritol, of pentaerythritol oligomers, or of
ethoxylated derivatives of such pentaerythritol or oligomer
esters, and any mixtures thereof, all of which may be designated
PEC (for pentaerythritol compound), together with a clay of the
montmorillonite typervery ~refer~bl~ bentonite, and which do not
contain quaternary ammonium salts.
Fabric softening compositions and articles have long
been employed to make washed laundry items softer to the touch
and more comfortable to the wearer. Such compositions include
solutions, emulsions and particulate and powder products, and
such articles include paper strips and sponges that have been
impregnated with fabric softener. The fabric softeners of
2 Q ~ 8
choice for most commercial products have usually been quaternary
ammonium salts, such as dimethyl ditallowyl ammonium chloride,
and emulsions of such softener have been added to the rinse water
in the washing machine to soften laundry. Rlternatively, such
emulsions or powder products including such fabric softener can
be added to the wash water, with a detergent composition, or the
detergent composition can include a fabric softenin~ component,
making it a so-called "softergent". Articles that contain a
fabric softening component, such as a quaternarY a~monium salt,
may be added to the automatic laundry dryer wherein, during
tumbling of the laundry in a heated enYironmen~ the fabric
softener is applied to the laundry by repeated contact, and
softens it.
Although various fabric softening (and antistatic)
compositions, including softergents, have been marketed over the
years, with varying degrees of commercial success, and although
different fabric sof~ening co~pou~ds h~e been included i~ them,
the most successful of such compounds have been quaternary
ammonium salts. Such compounds are often of the for~ula
R' - N - R"' X
R"
wherein R, R', R" and R"l are all alkyl g~oups, with at least one
of such alkyls being a higher alkyl ~of 8 to 22 or 24 or of 12
to 18 carbon atoms) and with the others being lower alkyl(s) of
~7 ~
1 or 2 carbon atoms, and with X being a salt-forming anion. Pre-
ferably, such quaternary ammonium salt is a di-lower alkyl, di-
higher alkyl ammonium halide but mono-lower alkyl tri-higher alkyl
ammonium halides have also found use in some instances.
While such quaternary ammonium salts have been effec-
tive fabric softeners in the described applications they are
characterized by disadvantageous properties too, which have led
to attempts to find replacements for them. For example, being
cationic, they tend to react with anionic materials, such as
anionic synthetic organic detergents and builders for synthetic
detergents, sometimes to the detriment of their intended fabric
softening function. They can deposit on laundry in such manner as
to appear as greasy spots, which axe highly objectionable. FiQal-
ly, and perhaps most important, they are not as readily biodeqrad-
able as is desirable and they have been found to be toxic toaquatic organisms, which could lead to harmful effects on aquatic
life in lakes, rivers and other waters into which waste waters
carrying such compounds could eventually be emptied.
In efforts to find a replacement fo~ quaternary ammonium
salts as fabric softeners, neoalkanamides, glyceryl esters, glycol
e~ters, silicones, cationic-anionic complexes, bentonite and various
lubricants have been suggested for use alone or in conjunction with
reduced amounts of the quaternary ammoniu~ salts but frequently the
softening effects thereof were insufficient or the replacement
softeners possessed other characteristics which made them even
less desirable than the quaternary ammonium salts. Now, however,
2~7~
applicants have discovered that the PEC's described hexein, includ-
ing the oligomers and lower alkoxylated derivatives, when employed
in conjunction with a montmorillonite clay, such as a swella~le
bentonite, can satisfactorily soften laundry essentially to the
same extent as the quaternary ammonium salts, and they don't
exhibit the adverse effects of the quaternary ammonium salts on
aquatic organisms. This is an especially important discover~ at
this time, when the seriousness of the problem is being recognized
and when several countries are passing laws and promulgating regula-
tions prohibiting the incorporation of quaternary ammonium compounds(hereafter "quats") in products that can be discharged into sewage
and drainage systems. The invented compositions are surprisingly
effective softergents, which clean as well as detergPnt composi-
tions based on the same detersive components, and they also act
synergi9tically with respect to fabric softening in non-detersive
products, such as wash cycle and rinse additives, and dryer products,
in all of which the combination of PEC and bentonite softens treated
laundry significantly better than would be expected from the addi-
tive effect of such components. Moreover, whereas fabric softenings
by each of the PEC and bentonite asymptotically approach limits
which are below the excellent softening that is desirable, a compo-
sition containing PEC and bentonite softens significantly better
and transcends such limits.
In accordance with the present invention a fabric
softening product, which is a composition or an article for
application to fibrous materials, so that a fabric softening
component thereof is deposited on the fibrous materials and
2 ~ ~ ~ 7 ~ 8
softens them, comprises a PEC, which is a fabric softening
component which is a higher aliphatic acid ester of penta-
erythritol, of an oligomer of pentaerythritol, of a lower
alkylene oxide derivative of pentaerythritol or of a lower
alkylene oxide derivative of an oligo~er of pentaerythritol,
or a mixture thereof, and a montmorillonite clay, very
preferably bentonite. Of the PEC's those which are preferred
are the pentaerythritol distearates and dipentaerythritol
dilaurates, and of the montmorillonites, sodium and calcium
bentonite are preferred. The invention also includes processes
for softening laundry with the invented products.
A search of prior art relevant to the invention
has resulted in the finding of the following:
U.S. Patents 3,928,212; 4,126,562; 4,142,978;
4,162,984; and 4,214,038;
European Patent Application 276999-A;
German Patent Application 3612479-A; and
Japanese Patent 90 47,370.
U.S. patent 3,928,212 describes various softening
agents which are polyhydric alcohol esters but none of them is a
pentaerythritol ester or an ester of an oligomer or ethoxylated
derivati~e of pentaerythritol or of an oligo~er thereof. V.S.
patent 4,126,562 mentions erythritol and pentaerythritol in a
list of alcohols which may be reacted with higher fatty acids
to produce fabric conditioning agents but no such co~pound is
2~7~`7i~
actually described and none is shown in a fabric softening
composition or article. Also, U.S. 4,126,562 is for a combina-
tion of a quaternary ammonium salt fabric softener and a nonionic
ester of an alcohol with a higher fatty acid, and there is no
teaching that the ester would be usefui alone as a fabric soft-
ener. U.S. patent 4,142,978 describes sorbitan esters with
phase modifying components, such as alkyl sulfates, on a dryer
sheet for softening laundry while it is being tumble dried in an
automatic laundry dryer. The patent does not mention any penta-
erythritol esters. U.S. patent 4,162,984 relates to a textile
treatment emulsion of a water insoluble cationic fabric softener,
which is preferab,ly a quaternary ammonium salt or an alkyl-
imidazolinium salt, with a water insoluble nonionic fabric soft-
ener, which is preferably a fatty acid ester of a mono- or poly-
hydric alcohol or an anhydride thereof, and an ~romatic mono-
or dicarboxylic acid. Among the polyhydric alcohols that may be
esterified, according to the patent, is pentaerythri~ol, but no
pentaerythritol ester is described specifically nox is an~ oligo~er
of pentaerythritol suggested, and none is shown to be a useful
fabric softening agent in the absence of ~uaternary a~monium
salt and aromatic carboxylic acid. It is clear that the patentees
did not know of the present invention beca,use they were aware of
the disadvantages of the quaternary ammo~ium salt component (re-
action with anionic detergent from the wash cycle) and found
that its content could be reduced if the pentaerythritol ester
207~7~8
and aromatic carboxylic acid were present, but they never re-
cognized and apparently never made a fabric softening composi-
tion which did not contain quaternary ammonium halide or equiva-
lent cationic fabric softener. U.S. patent 4,214,038 relates to
polyglycerol esters as softening agents suitable for deposition
on drying laundry from paper substrates char~ed to the laundry
dryer with the laundry being dried. Although polyglycerol is a
polyhydric alcohol, as is pentaerythritol, it is not the same as
pentaerythritol and the patent does not suggest the use of
applicants' pentaerythritol esters as fabric softeners. European
patent specification 276999-A mentions fabric conditioning compo-
tions that contain a non-cationic fabric softener and a nonionic
cellulose ether. ~lthough esters of polyhydric alcohols are
mentioned as suitable conditioning agents, ~entaerythritol esters
lS are not disclosed. German patent specification 3612479-A describes
textile softening compositions that contain ~uaternary ammoniu~
compounds with carboxylic acid esters, and among the esters are
those of various alcohGls and polyols, includin~ pentaerythxitol.
However, no such specific ester is described or even named, and
no softening composition which does not contain quaternary a~monium
compoun~ as the fabric softener is disclosed. Japanese-patent
90 47,370 discloses fabric softening compositions that ~re ~ased
on quaternary ammoniu~ salts but may contain a hi~her fatty acid
ester of pentaerythritol. No specific such ester is described
in the abstract.
~7 ~7 ~
In none of the disclosures mentioned above is it taught
that any pentaerythritol ester could be employed with a mont-
morillonite clay, such as bentonite , as a fabric softening combi-
nation, in place of a quaternary ammonium compound or quat soften-
er and would have essentially as good or better a softening action,and none of the disclosures mentions any specific pentaerythritol
ester nor does any mention any ester of an oligomer of penta-
erythritol, of lower alkoxylated pentaerythritol or of an oligomer
thereof as a fabric softening agent in a fabric softening composi-
tion. Thus, none of the references, either alone or in combi~a-
tion with any of the others, anticipates the present inyention
or makes it obvious.
A main component of the invented compositions and
articles of the present invention, which is usually the main
fabric softening compound in such products, other than the fabric
softening clay, such as bentonite, which will also be present in
them, is preferably a higher fatty acid ester of a pentaerythritol
compound, which term is used in this specifica~ion to descxibe
higher fatty acid esters of pentaerythritol, higher fatty acid
esters of pentaerythritol oligomers, higher fatty acid esters of
lower alkylene oxide derivatives of pentaerythritol a~d higher
fatty a~~id esters of lower alkylene oxide derivatiYes of penta-
erythritol oligomers. Pentaerythritol compound may be abbrevi~ted
as PEC herein, which description and abbreviation ~ay apply to
any or all of pentaerythritol, oligo~ers, thereo~ and alkoxy~ated
derivatives thereof, as such, or more preferably and more usually,
as the esters, as may be indicated by the context.
~7~7~8
The oligomers of pentaerythritol are preferably those
of two to five pentaerythritol moieties, more preferably 2 or 3,
with such moieties being joined together through etheric
bonds. The lower alkylene oxide derivatives thereof are prefer-
ably of ethylene oxide or propylene oxide monomers, di~ers orpolymers, which terminate in hydroxyls and are joined to the penta-
erythritol or oligomer of pentaerythritol through etheric linkages.
Preferably there will be one to ten alkylene oxide moieties in
each such alkylene oxide chain, more preferably 2 to 6, and there
will be one to ten such groups on a PEC, depending on the oligomer.
At least one of the PEC OH groups and preferably at least two, e.g ,
1 or 2 to 4,are esterified by a higher fatty acid or other higher
aliphatic acid, which can be of an odd number of carbon atoms.
The higher fatty acid esters of the pentaerythritol
compounds are preferably partial esters ~nd more preferably there
will be at least two free hydroxyls thereon after esterification
~on the pentaerythritol, oligomer or alkoxyalkane groups). Fre~ent-
ly the number of such free hydroxyls is two or about two b~t ~ome-
times it may be one, as in pentaerythritol tristearate, or as many
as eight, as in pentapentaerythritol tetrapalmitate.
The higher aliphati~ or fatty acids that may be employed
as esterifying a~ids are those of carbon atom contents in the
range of 8 to 24, preferably 12 to 22 and more preferably 12 to
18, e.g., lauric, myristic, palmitic, oleic, stearic and ~ehénic
acids. Such may be mixtures of such fatty acids, obtai~ed from
207~ i8
natural sources, usch as tallow or coconut oil, or from such natural
materials that have been hydrogenated. Synthetic acids of odd or
even numbers of carbon atoms may also be employed. Of the fatty
acids lauric and stearic acids are often preferred, and such prefer-
ence may depend on the pentaerythritol compound being esterified.
Examples of some esters (PEC's) within the present
invention follow:
2~7~7~ ~
o.
l~TO~ U~
~ "~ ~ ~rla~
" co~
o~
c~ e-c~l~ C~ I~OI.~lt
1 0 e~
~un~rT~m~n
ffllT~lm~ TOL 10 n~ ~ OXI
~-c~l~
~,.al ~,.0,,
c-lt o~c~S cn~
c--c~
c~ o~Cls-
n~ . ~o
2 5 ~-mwu~o~ Ion~o~oto~n;
~. ,
0~ C~ O~
cn~ ~S
~t--c--e~ o~ o--clto~ c_c~t.
e~ O~ oa~ C~ o~t c~c~ t 1~
_~I~L~n
- Ct~t~19CO
~"co ~ "~0 I~,-
2 0 7 ~ 7 ~ ~
Although in the formulas given herein some preferred
pentaerythritol compounds that are useful in the practice of this
invention are illustrated it will be understood that various
other such pentaerythritol compounds within the description
S thereof herein may be employed too, including such as pe~ta-
erythritol di-hydrogenated tallowate, pentaerythritol ditallowate,
pentaerythritol dipalmitate, and dipentaerythritol tetratallowate.
Also, in this specification when reference is to a co~pound of a
class, unless it is indicated otherwise therein it is to be
considered that the employment of mixtures of compounds of such
class are intended to be included (commercial co~pounds are often
mixtures).
The PEC's utilized in this inyention can have fabric
softening effects but such activities are rem~rkably increased
when a montmorillonite clay (bentonite) is also present. In
the absence of such bentonite the PEC may be s~bstantially un-
dispersed in wash and rinse waters, and m~y be less evenly and
less strongly applied to laundry fr~m softening articles. It
has been found that better dispersed PEC h~s greater softening
activity. When undispersed the PEC could be in solid agglomerate
form when cold or in molten foxm when hot, in ~either of which
states does it act as effectively to soften fabrics (and in both
of which cases it can deposit objectionably on tre~ted ~texials
to produce somewhat greasy spotting thereof). The bentonite acts
to disperse the PEC to ma~e it more effective as a softener, and at
the same time such "dispersing agent" also acts as a softener, which
avoids the undesirable dilution of softening action by an ordinary
dispersing agent, and it synergistically improves fabric softening.
The clays that are useful components of the invented
2~7~
products are those which cooperate synergistically with the PEC's
to soften laundry better than would be expected from such a combi-
nation. Such clays include the montmorillonite-containing clays
which have swelling properties (in water) and which are of smectite
structure, ~9 that they deposit on fibrous materials, especially
cotton and cotton/synthetic blends, such as cotton/polyester, to
give such fibers and fabrics made from them ~ surface lubricity
or softness. The best of the smectite clays for use in the pre-
sent invention is bentonite and the best of the bentonites are
those which have a substantial swelling cap~bility in water, such
as the sodium and potassium bentonites. Such swelling bentonites
are also known as western or Wyoming bentonites, which are essen-
tially sodium bentonite. Other bentonites, such as calcium
bentonite, are normally non-swelling and usually are, in the~selves,
unacceptable as fabric softening agents. However, the present
inventors have found that such non-swelling ~entonites exhi~it
even better fabric softening in combination with PEC's than do
the swelling bentonites, provided that there is pre5ent in the
composition being tested for softness, a source of alkali metal
or other solubilizing ion, such as sodium (which may come from
sodium hydroxide, added to the composition, or from sodium s~lts,
such as builders and fillers, which may be functional component~
of the composition~. This utility of the normally non-swe~ling
bentonite is surprising and the superiority of such in the
in~ented compositions (when a source of sodium is presentl ovex
2 0 7 6 7 1 8
normally swelling bentonite, such as sodium bentonite, is very
surprising. Among the preferred bentonites are those of sodium
and potassium, which are normally swelling, and calciu~ and
magnesium, which are normally non-swelling. Of these it is
S preferred to utilize calcium (with a source of sodium being
present) and sodium bentonites. The bentonites employed are
not limited to those produced in the United States of A~erica,
such as Wyoming bentonite, but also may be obtained from Europe,
including Italy and Spain, as calciu~ bentonite, which may be
converted to sodium bentonite by treat~ent with sodium carbonate,
or may be employed as calcium bentonite. Also, other mont-
morillor.ite-containing smectite clays of properties like those
of the bentonites described may be substituted in whole cr in part
for the bentonites described herein and simi~ar fabric softening
results will be obtained.
The swellable bentonites and sLmilarly operati~e c~ays
are of ultimate particle sizes in the micron range, e.g., 0.01
to 20 microns and of actual particle sizes in the range of ~o's.
100 to 400 sieves, preferably 140 to 325 sieves, U,S. Sieye
Series. Such size ranges also apply to the z~olite builders,
which will be described later herein. The bentonite and other
such suitable swellable clays may be ~gglomerated to larger
particle sizes too, such as 60 to 12Q sieves, but such
a~glomerates are not preferred unless they incl~de the PEC('s)
too (in any particulate products).
207L37 ~ 8
Liquid state preparations of this invention may be
emulsions (which term herein is also lntended to refer to disper-
sions and suspensions in liquid media, as well as to
emulsions), and any of such "emulsions" will normally be aqueous
emulsions in which the aqueous phase is the continuous phase.
However, solvents and cosoivents, such as ethanol, isopropanol,
propylene glycol and various mono- and di-lower alkyl esters of
diethylene glycol ~Carbitols~ may also be present in such
emulsions and microemulsions to promote formations of more stable
products, and may also be in the continuous media. Suitable
dispersing agents, such as emulsifiers, can be emp~oyed with the
mentioned clay to further help it to disperse the PEC in aqueous
media. Such are useful in liquid and solid (including particulate1
products.
Yarious emulsifiers can be e~ployed, and many such are
described in the various Detergents and Emulsifiers pub~ications
of John W. McCutcheon, issued annually, particularly those for
1969, 1973, 1980 and 1981, which are incorporated herein by
ref~rence. Preferred such emulsifiers are those which are alkyl
ethers or amines which contain one or ~ore hydroxyalkyl substi-
tuents too. Of these the more preferred are the alkyl dialk~nol-
amines or alkyl trialkanolpropylenediamines wherein the alkanol
moieties are of 2 to 4 carbon atoms, preferably being 2 or 3
and more preferably being 2, and the alkyl poly(ethylene oxide)
ethers are of 2 to 24 ethylene oxide units, preferably of 8 to
12 ethylene oxide units, in which e~ulsifiers the alkyl is of 8
to 24, preferably 12 to 18 carbon atoms. More preferred such
20~7 18
emulsifiers are: stearyl diethanolamine, available from Hoechst A.G.
as Genami ~ S-020; tallow triethanol propylenediamine, available
from CECA, S.A. as Dinoramo ~ S3; and R-O-(CH2CH2O)loH, wherein R
is a mixture of C12_15 alkyls, available from Hoechst A.G. as
Genapol~ OH-100.
When instead of emulsion form for the invented composi-
tions it is desired that they be in particulate, powder, solid
or gel form less water or moisture or even none is present but the ben-
tonite will still usually beofsmall (micron range) ultimate size.
Instead of or in addition to the bentonite there m~y be present
other swellable montmorillonite clays ~nd there may also be
present with the bentonite other non-functional substantially
water insoluble carriers or dispersing agents, such as calciu~
carbonate and silica. Even water soluble carriers, such as sodiu~
sulfate and other "filler salts" may be used, at least in part,
and such can sometimes act as dispersing ~gents, too. The
bentonite employed should desirably be of a type which is gel
forming in water and capable of softening fibrous materials,
and should be of micron range ultimate particle size, although
2~ it may be agglomerated to larger sizes, usually in the range
of 8 to 140 sieves, U.S. Sie~e Series.
When the pentaerythritol compound softening agent is to
be applied to laundry being dried in a laundry dryer, such as a~
automatic dryer, the PEC and bentonite may be applied to a
substrate material, from which it may be transferred to the dr~ing
~ Q ~
laundry under the influence of the heat in the drying air and the
rubbing action of the substrate against the moving laundry. The
substrate used may be paper or other fibrous material, sponge,
preferably cellulose or polyurethane, or other suit~ble base
material, with the pentaerythritol compound being such that it is
solid at room temperature and liquefiable and/or softenable at
dryer temperatures. The PEC may be blended with other suitable
waxy type material, plasticizex or hardener to control the
softening point thereof, when such is desirable. In use of such
articles the bentonite helps to distribute or spxead the PEC on
the substrate and the PEC helps to promote adherence of the
bentonite to the substrate. Additionally, the bentonite's
positive charge helps the PEC to adhere to usually negatively
charged laundry.
Normally, in the various applications mentioned, the
PEC will be employed without the presence of any other fabric
softening material ~e~cept the clay, such as bentonite, mont-
morillonite or other operative smectite) but it is ~ossible to
utilize such other materials with it if in the propoxtions and
quantities employed they are no~ ecologically unacceptable a~d
if they do not interfere with the fiber softening ac~ion of the
PEC. In fact, sometimes, when antistatic ~ction is desir~ble
in the product, such additions may be i~poxta~t because although
PEC's have some antistatic properties somet~es those axe
insufficient for the intended purposes. Thus, it is possible
2 ~
to formulate fabric softening compositions and articles with the
PEC supplemented by other antistatic agents and also by fabric
softeners. The foremost of such antistatic materials are the
quaternary ammonium salts but when they are present there can be
ecological problems, due to their toxicities to aquatic organisms.
For example, in standard toxicity tests against daphnia the
concentration for 50~ effect is less than 1 mg./l. for quaternary
ammonium compounds or quats, such as ditallowalkyl dimethyl
ammonium chloride, and that is often unacceptable, enYironmentally,
so in such circumstances quats are not employed. Other antistats
and fabric softeners include: higher alkyl neoalkanamides, e.g.,
N-stearyl neodecanamide; isostearamides; a~ines, such as ~
ditallowalkyl N-methyl amine; esterified ~uaternary salts or
esterquats; amidoamines; amidoquats; imidazolines; imidazolinium
salts; di-higher fatty acid esters of di-lower alkanolamies, such
as dicoco acid ester of diethanolamine; silicones; and alkox~ated
silicones;and representative examples of some of such classes
of such compounds are giYen below (those which may cause
significant ecological har~ will desirably be a~oided).
~1~ 7 ~ r~ ~ 8
I
~ _ o ~
2~7~
It should be kept in mind when employing supplementary antistats
and fabric softeners that they shouldn't make the compositions
in which they are incorporated of greater ecotoxicity than is
allowable by law and by re~ulatory authorities in the area of
intended use. Thus, quaternary a~monium compounds will usually
be avoided, as will be compounds that have similar adverse effects
on aquatic organisms, or the amounts thereof present will be
limited so as to avoid such undesirable effects.
Other materials that may be incorporated in the invent-
ed compositions include the usual adjuvants that nor~ally are
present in other fabric softening compositions (including soft-
ergents), such as perfumes, fixatives, solvents, cosolvents,
hydrotropes, antioxidants, stabilizers, pH adjusters, buffers,
biodegradable antimicrobials, builders, fillers, enzy~es, thick-
eners and fluorescent brighteners, all of which are known classes
of materials in the fabric softening compositions field, with
examples of several of these bein~ given in the art mentioned
in this specification, all of which is hereby incorporated here-
in by reference.
The last component of the present compositionS, which
is present in those which are aqueous emulsions (or dispersions~,
is water. Normally any clean water can be employed, such as any
of a hardness in the range of O to SOQ p.p.m., as CaC03, but it
will be preferred to use water of a haxdness of no more than lSQ
p.p.m., more preferably less than 50 p.p.m., and ~ost pxeferably
the water will be deionized water that has been irradiated.
~7~
The previous description of the components of the invent-
ed products is primarily directed to components of the fabric
softening compositions for addition to wash or rinse waters,
especially during automatic washing processes, which are simpler
embodiments of the invention but the invention also includes
detergent compositions (softergents) that contain the described
PEC and bentonite (or other suitable montmorillonite clay). Such
detergent compositions will contain at least one synthetic organic
detergent, preferably of the anionic or nonionic type (or a
mixture thereofJ, which may also function as a dispersing agent
for the PEC.
The anionic detergents are normally of the water soluble
sulfate and/or sulfonated lipophile type, which may be designated
"sulf(on)ated", and which include lipophile and sulf(on~ate
moieties, but analogous phosph(on)ates may also be utilized. Of
the synthetic anionic organic sulf(on)ated detergents those pre-
ferred are higher alkyl (preferably linear alkyl) benzene sulfo-
nates, higher fatty alcohol sulfates, higher fatty alcohol ethoxy-
late sulfates, olefin sulfonates and paraffin sulfonates. Usua
such compounds are water solu~le alkali metal salts, such as
sodium salts, and include higher fatty alkyl or other aliphatic
moieties, which serve as lipophilic moieties, and which increase
detergency, especially against greasy soils. Such higher alkyl
or higher aliphatic moieties will normally be of 8 to 22 carbon
atoms, preferably 10 or 12 to 16 or 18 carbo~ atoms and more
~ ~J7~
preferably, especially for the alkyl sulfates and alkylbenzene
sulfonates, the alkyl moieties will be of 12 to 14 carbon atoms.
The higher fatty alcohol ethoxylate sulfates that are useful
will normally be of 1 to 20 ethoxy groups per mol, preferably 3
s to 10 or 15, e.g., 3 or 7. As representatives of anionic detergents
there may be mentioned sodium linear dodecylbenzene sulfonate,
sodium linear tridecylbenzene sulfonate, sodium lauryl alcohol
sulfate, sodium coco alcohol triethoxylate sulfate, sodium C16
paraffin sulfonate and sodium olefin sulfonate derived from C14
olefin.
Among the nonionic detergents those which are ~ost pre-
ferred are ethylene oxide condensates with higher fatty alcohols
or with alkyl phenols, such as condensation products of 3 to 20,
5 to 15, 6 to 12 or 7 to 11 mols of ethylene oxide ~ith higher
fatty alcohols of 10 or 12 to 18 or 13 to 17 carbon atoms or with
alkyl phenols of 7 to 10 car~on atoms in the ~lkyl groups, e.g.,
Dobano ~ 25-7, Synperonic~ A7, Neodo ~ 25-3, Neodol 25-7, Neodol
45-11, and C13 17 alcohols condensed with 7 or 11 mols of ethylene
oxide per mol. Although the improved softeni~g obtained when
bentonite is employed with a PEC is noticeable in anionic, non-
ionic and anionic/nonionic detergent compositions, such increase
in softening action is even more surprising in the case of nonionic
detergent compositions because PEC alone (without bentonite) has
no fabric softening action at all in nonionic detergent composi-
tions (but does have some such action in anionic detergents).
2~7~7:~
In addition to the above examples of suita~le anionicand nonionic detergents, extensive listings of such detergents
that are useful may be found in standard textbooks relating to
synthetic organic detergents, such as the McCutcheon texts,
previously cited.
Of the water soluble builders for the anionic and
nonionic detergents it is preferred to e~ploy water soluble salts,
such as sodium or potassium salts, more preferably sodium salts,
and of these the carbonates, silicates, borates, bicarbonates and
1~ phosphates, especiall~ ~he polyphosphates, are preferred, such
as sodium carbonate, sodium bicarbonate, sodium silicate of
Na2O:SiO2 ratio in the range of 1:1.6 to 1:3, preferably 1:2 to
1:3, e.g., about 1:3, 1:2.35 or 1:2.4, sodium tripolyphosphate
and tetrasodium pyrophosphate, but sodium sesquicarbonate and
sodium sesquisilicate may also be used, as may be the correspond-
ing potassium and other soluble salts, when suitable. Of the
water insoluble builders, which builders also have water soften-
ing properties, the most preferred are the zeolites, especially
the hydrated zeolites. Such zeolites include crystalline,
amorphous and mixed crystalline and amorphous zeolites of both
synthetic and natural origins, which are of satisfactorily
quick and sufficiently effective activities in cou~teracting
calcium hardness ions in wash waters. Prefera~ly, the zeolites
employed are characterized as having high exchange capacities
for calcium ions, which exchange capacity is normally f~om abo~t
2 0 7 6 7 1 ~
200 to 4C0 milligram equivalents of calcium carbonate per gram
of the zeolite. Although other ion exchanging zeolites may also
be utilized, often the zeolite will be of the formula
(Na2)x (A123)y (SiO2) 2
wherein x is 1, y is from 0.8 to 1.2, z is fro~ 1.3 to 3.5 and w
is from 0 to 9, and prefera~ly is 2.5 to 6. ~f the crystalline
zeolites that are useful those preferred include Zeolites A, X
and Y, with A being more preferable, and the most preferred of
these is Zeolite 4A. These zeolites are preferably in finely
divided state when added to the crutcher with the synthetic deter-
gent prior to drying, and are of ultimate partlcle diameters
and actual sizes like those previously described for the bentonites,
Other builders that may be util zed include organic co~pounds,
which are often sequestrants for hardness ions. Such compounds
lS include organic acids, especially hydroxy and amino polycarboxylic
acids, such as citric and gluconic acids and ethylene diamine
tetraacetic acid (EDTA) and nitrilotriacetic acid (NTA), all
usually as their water soluble salts, e.g., sodium salts. ~ddi-
tional useful builders are the organo-phosphorus chelating agents,
such as the Dequests~, e.g., Dequest 2Q46, which are ~anufactured
by Monsanto Co.
The proportions of components of the inYented composi-
tions and articles will ~e those which r~sult in stable and
2~7~7 ~ g
effective products for fabric softening applications. For the
PEC's the concentrations in such liquid and gel softergent compo-
sitions will normally be in the range of about 1 to 25~, prefer-
ably 2 to 20~, more preferably 2 to 15% and most preferably 3 to
10%, e.g., about 5 or 6%. For the liquid rinse cycle and wash
cycle additive compositions, such ranges are 1 to 40 parts (with
60 to 99 parts of bentonite) in a liquid medium, which is prefer-
ably aqueous. Preferably such compositions include 1 to 10% of
PEC and more preferably, 3 to 7%, e.g., 6% or about 6~.
The particulate softergents will normally comprise 1 to
25% of PEC, preferably 2 to 20~, more preferably 2 to 15% and
most preferably 3 to 10%, e.g., 6%, and for the particulate non-
detersive rinse and wash water cycle additives such PEC co~tent range~
may be 1 to 25% or 40%, 1 to 10%, 3 to 10% and 3 to 7~, e.q.,
6~, respectively. For the dryer articles the operative, preferred,
more preferred and most preferred ran~es of PEC and bentonite)
~or equivalent clay) contents are S to 93~, 5 to 95%, 10 to 90%
and 20 to 80~, respectively, with the pxoportion of PEc:bentonite
being like corresponding proportions for the rinse and wash cycle
additives.
The bentonite or suitable clay contents of the liquid
or gel state softerqents will ~e in the operati~e xange of 1 to
50%, preferably 5 to 40%, more preferably 10 to 30~ and most
preferably 15 to 20%, e.g., 16% or 18%. For the particulate
softergents such ranges are 10 to 30%, 10 to 25~, 12 to 20%
and 15 to 20~, respectively. For the particulate and solid
2 Q ~ ~ 7 1 8
wash and rinse cycle additives the bentoni-te (or clay) percentages a
in the operative, preferred, more preferred and most preferred
rangesof 10 to 99%, 60 to 99%, 90 to 99% and 93 to 97%, e.g.,
94%, or about 94%.
In the liquid or gel state and particulate softergents
the operative percentage of synthetic organic detergent is 1 or 2 to
~5%, preferably 3 to 25~, more preferably 3 to 20% and most pre-
ferably 5 to 15%. Preferably, the synthetic orgqnic detergent
will be a mixture of anionic and nonionic detergents, with the
percentages thereof being in the ranges of 1 to 10% of each, pre-
ferably 1 to 5~ of each and more preferably 1 to 3% of anionic
detergent and 3 to 5% of nonionic detergent, e.g., about 2% and
about 4%, respectively. In the particulate or solid built
softergents the percentages of builder(s~ will nor~ally be in
the range of 5 to 80%, preferably being in the ra~ge of 10 to 60%,
more preferably 20 to 50% and ~ost preferably 30 to 40%, with
the percentages of sodium tripolyphosphate, sodiu~ carbonate and
sodium silicate, when such three b~ilders are present, oft~n
being in the ranges of 10 to 50%, 2 to 20% a~d 2 to 15%, respec-
tively, preferably 15 to 35%, 2 to 10~ ~nd 2 to 10%, and ~ost
preferably 20 to 30%, 3 to 8% and 2 to 6%, e.g., about 23%, 6%
and 4%, respectively. In liquid softergents such ranges of
contents for synthetic detergents and for builde~s will often be
multipl-ied by a factor that is proportional to the solids content
of the liquid composition diyided by the limiting solids con~ents
2~7~7 ~
of the range for the particulate or solid product. Normally,
rinse cycle compositions will not contain any builders but wash
cycle additives may utilize builders to improve cleaning of the
detergent compositions with which such wash cycle compositions
S may be employed and also to act as supplemental carriers (in addi-
tion to the bentonite) for the PE~. In such cases, where builder
is employed, the percentage ranges thereof will often be like
those for the softergents.
For invented compositions that contain emulsifier(s)
the content(s) of such emulsifier(s) will nor~ally be in the range
of 0.2 to 10%, preferably 0.4 or ~.5 to 5% and more preferably
0.7 or 1 to 3%, e.g., about 1.25 or 2%, When the e~ulsifier
contains both an alkyl alkanolamine and an alkyl poly(ethylene
oxide) ether, as may be preferred, the proportion of the alkanol-
amine will usually desirably be equal to or greater than that of
khe alkyl poly(ethylene oxide) ether alkanol, preferably being of
2 to 5 times as much, e.g., about 4 times as ~uch. Thus, such
percentages can be of 0.2 to 5~ of the alkanola~ine and O . 05 to 5%
of the ether alkanol, preferably 0.3 to 3% and 0.1 to 2~ and
more preferably 0.5 to 2% and 0.2 to 1%. When no detergents,
builders or adjuvants are present and the compositions are in
liquid state,aqueous medium or water contents may be the balances
thereof, which will usually be in the range of 20 to 93%,
preferably 50 to 94~, more preferahly S3 to 87~, ~nd ~ost
preferably 81 to 74~, e.g., about 78%- It is to be understo~d
7~
that the presences of any detergents, builders, adjuvants or
supplemental components of the emulsions will be compensated for
by corresponding decreases in the water contents of the composi-
tions. Usually the total adjuvants content will be no more than
25~, preferably will be no more than 15% and in many instances
will be held to a limit of 5%. None of the adjuvants, in the
amounts employed, will be such as to cause unacceptable levels
of toxicity which could adversely affect aquatiç organisms, in-
cluding fish, that inhibit lakes and streams into which there
are fed washing machine effluents that included the present
compositions. Thus, the invented compositions may be considered
to consist essentially of the named components, in additi~e or
softergent form, with only environmentally acceptable proportions
of adjuvants being allowed to be present therein. As was
previously mentioned, the present compositions and articles are
preferably essentially free of quaternary ammonium compounds.
Moqt preferably 0% of such are present but when the resulting
compositions and articles are not ecotoxic increasing limits
of 0.1%, 0.3% and 0.5% may be imposed, which ~re more preferred,
preferred and acceptable limits respectively, under such circu~-
stances, and are within the broader invention. Although the
described emulsifiers are more often employed in a~ueous compo-
sitions, they may also be present in solid or particulate pr~ducts
and the proportions thereof in such products will be proportionally
the same as for the liquids, on a solids basis.
A suitable adjuvant for the described products, especial-
ly for the rinse cycle additives, is an acidifying agent, such as
~7~
hydrochloric or other suitable acid, which is useful to adjust the
pH of tAe emulsion or other aqueous composition to within the
range of 2.5 to 5.5, preferably 2.5 to 4, e.g., 3.5. To do that
the percentage of HCl (concentrated basis) or equivalent other
acidifying agent present will usually be in the range of 0.01 to
0.4~, preferably 0.05 to 0.2%. A sodium-containing compound may
be present to provide sodium ions (alternati~ely, potassium
compounds can be present) to convert alkaline earth or magnesium
bentonite to swelling alkali metal bentonite, in which case the
proportion employed will usually be at least stoichiometric, and
may be up to 20% in excess of stoichiometric. Sodium hydroxide
may be a suitable source of sodium ions, especially for the softer-
gent compositions which are desirably alkaline.
To manufacture the invented solid, particulate and gel
compositions and to make the described articles is comparatively
simple, involving little more than mixings of components, (with
gelling, agglomeration and application steps sometimes) but to
produce applicants' dispersions a particular process is followed (and
that is the process of the working examples. In such cases it i5
preferable that the PEC be melted before addition to the aqueous
medium and the temperature to which the PEC i5 raised will desir-
ably be within 10C. of the melting point thereof. It is prefer-
red that the PEC be mixed with any meltable emulsifier especially
one of lipophilic character (or more lipophilic character than
another emulsifier present), such as the alkanolamine, when a
2 ~7 ~
mixed alkanolamine/ether alcohol (or alkanolamine/ethoxylated
alcohol)emulsifier is employed, and melted together with it, but
alternatively the two meltable materials, PEC and alkanolamine,
may be separately melted and added together or simultaneously
to the aqueous medium (usually water), which should also be at
about the same elevated temperature, about 60C., for example.
The smectite clay may be added before, with or after the emulsi-
fier/PEC mixture. The water employed is often desirably acidified,
as by addition to it of HC1 or other suitable acid, to generate
a final pH in the range of 2.5 to 5.5, preferably 2.5 to 4.0,
e.g., about 3.5. After emulsification the emulsion produced may
be cooled to room temperature, with the balance of emulsifier
being added before or after such cooling, preferably before. ~he
result is a stable emulsion, which resists separation under normal
elevated tamperature conditions for periods of six months or
more.
To manufacture the particulate or powdered product it
is only required for the PEC to be mixed with the smecti~e clay
and any other components of the formul~tion. Prefe~ably, the
melted PEC, at elevated temperature, will be sprayed onto a
tumbling mass of the particulate agglo~erated smectite or mont-
morillonite powder (such as bentonite) or agglo~er~te thereof
with any other particulate matexials of the produçt, and will
thereby be distributed throughout it evenly. 50metimes t~e mixer
employed will include size reduction means to make sure the PEC
2~7~''
is in small enough particles so as to be depositable evenly on the
laundry being treated. The bentonite or other smectite clay
particles may be at room temperature when the PEC is ~eing applied
to them and the PEC will be solidified on contact with the
particulate mass, usually with little agglomeration taking place,
but by controlling the PEC application, the temperature and mixer
speed, some agglomeration may be obtainable, when desired.
To make the softening article it is usually desirable
for the substrate material, in a continuous strip, to be passed
through a melt, emulsion or other bath of PEC, with or without
emulsifier,with any excess being removed by a doctor blade or
squeeze rolls, and the bentonite or other acceptable clay may
be applied to the PEC coated strip. After cooling or drying, the
strip, containing the PEC and other materials,may be cut into
individual pieces, which are then ready for use.
The softergents may be made in usual ~anners, with the
PEC and bentonite being post-added or being added at a suitable
stage of the manufacturing process, including crutching and spray
dxying, tak ng into account that they will not be subjected to
~o destabilizing or destructive tempexatures.
In use the various invented compositions and articles
are employed in the same ~anners are other softergents, emulsions,
powders and articles that apply fabric softener to laundry.
Softergents may be ch~rged to the washing machine as if they were
detergents, with the desired concentrations being in the range of
2~7 ~ r~ i~
0.1 to 1%, preferably 0.1 to 0.5%, e.g., about 0.15% in the U.S.A.
and about 0.5% in Europe, to compensate for different washing
conditions employed. The rinse cycle additive emulsion may be
added to the rinse water and so may the powder and particulate
compositions, with the concentrations of PEC being in the range
of about 0.01 to 0.05% of the rinse water, and that of bentonite
being proportionally greater, as previously described. Alterna-
tively, such compositions may be added to the wash water but in
such cases the concentrations may be increased, often about 1 to
3 times. Dryer treatment articles may be used in the same manner
as products currently being marketed for that purpose, with paper
strips (or towels) or equivalent sponges being added to the dryer,
usually with a sheet or strip of 300 to 800 sq. cm. being employed.
The following examples illustrate but do not limit the
invention Unless otherwise indicated all parts and percentages
in this specification and the appended cl~ims are by weight, and
all temperatures are in C.
2 ~ ~ ~g ~
EXAMPLE 1
Component ~ By Weight
Sodium linear dodecylbenzene sulfonate 2.00
Stearyl hydroxyethyl imidazoline 1.00
5 * Nonionic detergent 3.90
** Sodium silicate 4.00
Sodium tripolyphosphate 23.00
Sodium carbonate, anhydrous 6.00
Ethylenediamine tetra~methylene phosphonic acid) sodium 0.38
salt
*** Optical brightener 0.21
**** Methyl silicone 0.18
Sodium hydroxide 1.00
Sodium perborate tetrahydrate 12.00
15 Proteolytic enzyme 0,30
Calcium montmorillonite swellable clay 16.00
Potassium methyl siliconate 0.50
Hydroxylamine sulfate 0.30
Perfume 0.50
Tetraacetyl ethylenediamine 0.89
Sodium aluminosilicate 0.25
ooo Pentaerythritol distearate 6.00
Sodium sulfate, anhydrous lQ.59
Water 11.00
100. 00
* Condensation product of one mol of mixed C13_17 alcohols
and seven mols of ethylene oxide
** Na2O:SiO2 ratio of 1:2
*** Diaminostilbene disulfonic acid salt type
**** Dow-Corning X2-3302
Alcalase 2T
Calcium bentonite
2~7~7~8
A particulate built fabric softening detergent composition
(a softergent) of the above formula is made by spray drying a portion
of the formula to produce base beads, and then admixing such beads
with a mixture of the remaining components, except for the perfume,
which is sprayed onto the mixture of the beads and other materials.
The spray dried beads are made by spray drying a crutcher mix of
various heat stable components of the product, including sodium
sulfate, sodium linear dodecylbenzene sulfonate, stearyl hydroxyethyl
imidazoline, nonionic detergent, sodium silicate, sodium tripoly-
phosphate, sodium carbonate, ethylenediamine tetra(methylene phos-
phonic acid) sodium salt, optical brightener, silicone, sodium
hydroxide, PEC and water, with the solids conte~t of the crutcher mix
being about 55~, to base beads of particle sizes in the range of 10
to 100, U.S. Sieve Series. The bentonite is agglomerated to the same
particle size range and the agglomerated bentonite and the other
components (usually those which are heat sensitive), including the
sodium perborate tetrahydrate, the enzyme, the hydroxylamine sulfate
and the sodium aluminosilicate, are admixed with the base beads,
after which the siliconate and perfume are sprayed onto the mixture
resulting, to make the final softergent. I~ a variation of the manu-
facturing procedure the PEC may be post-added to the composition in
powdered form or as a co-agglomerate with bentonite.
The softergent produced and variations of the formula, in
which percentages of the bentonite and PEC are varied while all the
other percentages of components remain the same, except for the
sodium sulfate, which is changed to compensate for increases or
decreases in the total of bentonite and PEC, are made and are tested
for detergency and fabric softening effectivenesses. In tests against
various oily and clayey soils the softergent is found to be an
effective and commercially acceptable detergent, using visual
observations of the cleaning of soiled laundry and test swatches
as well as reflectometer reading comparisons with controls. When
2~7 ~ 4~
polysiloxanes and soap or quaternary ammonium compound, the
invented composition of the formula given above is as good as such
"ulti~ate" composition or better in fabric softening effect, using 60C
washing machine laundering of ordinary wash loads of dirty laundry
or test swatches, whether the washing machines and procedures are
of the American or European type, and whether the materials of the
items washed are natural, such as cotton, synthetic,such as
polyester, or blends thereof. In such tests a panel of experienced
evaluators, usually at least four, compares washed swatches (or
identical items), one of which was washed by a control detergent
composition and the other of which was washed using a softergent that
is being evaluated. The difference in softness between the swatches
washed with the control detergent and the softergent is judged and
a number is assiqned to indicate such difference, with 1 being for a
slight difference, 2 being for a moderate difference and 3 being for
a great difference. In all cases, of course, the swatches washed
with the softergent will be softer than the control, which was washed
in wash water that contained a detergent composition from which the
softening bentonite-PEC combination had been omitted.
When the invented softergent of the formula of this example
is tes'ed against a control detergent, from which the bentonite and
PEC were omitted and replaced by sodium sulfate, an inert filler,
the difference in softening effect i5 rated at 2.3. When the 6% of
PEC is in the formula but the bentonite is omitted and is replaced by
sodium sulfate the rating is 0.7 and when the PEC is replaced by
sodium sulfate and the bentonite (16~) is present,the rating is 0.8.
Thus, the additive effect of the PEC only and bentonite only
formulas would be 1.5 whereas actually it is found to be 2.3, which
represents a very significant improvement (synergism). Even greater
2 ~ ~ ~ 7 -~ ~
increasing the proportion of either bentonite or PEC does not
yield the same improvement; in fact, increasing the proportions of
bentonite to 30% and PEC to 20% (separately) results in decreasings
of the softening actions.
The synergistic result with respect to fabric softening
actions of the invented softergents will readily be apparent from
the appended drawing, in which:
FIG. 1 is a plot of fabric softening effect of a composition
of the basic formula of Example 1 of this specification, with the
bentonite content being varied, compared to such softening effect of
similar compositions in which the bentonite content is varied and the
PEC content is 0~; and
FIG. 2 is a plot of fabric softening effect of a composition
of the basic formula of Example 1, with the PEC content being varied,
compared to such effect in similar compositions in which the PEC con-
tent is varied and the bentonite content is 0%.
In FIG. 1 curve 11 shows the increase in fabric softening
action on the washed laundry as the bentonite content is increased
from 0 to 25% , with the dots on the curve representing specific
bentonite contents. The best softening obtained is rated at about
2.7, which is about the best ever obtained with a softergent. Curve
13 illustrates fabric softening action as the bentonite content is
increased, with the PEC being omitted from the formula. It is notable
that the curve heads downwardly, indicating less softening, when the
bentonite content is over 25%. Phantom curve 15 shows the expected
additive effect on fabric softening action of the 6~ of PEC plus the
indicated percentages of bentonite. Because curve 15 is substantially
lower than curve 11 for most of its length it proves that a synergistic
fabric softening effect attends the presence of both bentonite and
20~7~
constant while that of the PEC is being varied, from 0 to
20~. Curve 17 shows the increase in fabric softening action of
softergents of the invention which contain 16~ of clay and from
1 to 10~ of PEC, while curve 19 shows that when the clay content is 0
the increase in softening action as the PEC content is increased is at
a lower rate,and softening actually decreases at hiqher PEC contents.
Curve 21 plots the expected (additive) effect of 16% of clay plus
the indicated percentages of PEC. Because such curve is substantially
lower than the actual curve 17 it is established that the combination
of bentonite and PEC synerqistically improves fabric softeninq of
laundry washed with such softergents.
The described effect, synergistic improvement of fabric
softening action, is also obtained with various other combinations of
PEC'~ described herein and montmorillonite clays of the types
mentioned but the best results are obtained when the PEC's are
partial esters of pentaerythritol and pentaerythritol oligomers
which include at least one, and preferably two hydroxyls, and when the
clay is a calcium bentonite or a sodium or potassium bentonite that
i3 capable of swelling in the wash water. In the experiments
described above and plotted in the graphs of the figures the bentonite
employed is calcium bentonite and there is enough sodium ion in the
wash water (from the builder salts and the sodium hydroxide) to
convert it to swelling sodium bentonite. Surprisingly enough, the
calcium bentonite, when employed under such conditions, is even better
in fabric softening power than the sodium and potassium bentonites.
Another significant advantage of the invented softergents
of this invention is in the breaking through of a perceived
"softening barrier" by ~he invention. From FIG's. 1 and 2 it is
~7~ ~
evident that increasing the contents of either bentonite or PEC
alone will not result in a superior softergent because the softening
effects asymptotically approach limits less than or about 1 and even
the additive effects which could be predicted are less than 2, and
in all such cases the fabric softenings are diminished as greater
proportions of the mentioned softening agents are employed. Yet,
with the invented compositions this apparent limit on softening power
is transcended and lesser total quantities of the combination of PEC
and bentonite yield superior results, with the fabric softening
effects approaching those for rinse cycle additlve compositions,
which had previously been considered to be "an impossible dream". Suc
effects are obtainable with other types of softergents, including
those based on nonionic detergents only, anionic detergents only,
water insoluble builders, such as zeolites, non-phosphate formulas,
lS in which the builder composition can be a combination of zeolite,
carbonate and silicate, and softergents built with organic builders,
such as polyacetal carboxylates, NTA, E~TA, citric acid and gluconic
acid. Furthermore, such synergistic softening actions are also
obtainable for wash cycle and rinse cycle additive softening composi-
tions, which contain no detergent, and in such rinse cycle additivecompositions, whether in liquid state or in particulate or gel form,
~oftening action can be better than for such compositions which do
not utilize the described com~ination of clay and PEC.
- 38 -
2 ~ 7 ~ 'j
EXAMPLE 2
Com~onent % By Weight
Sodium linear dodecylbenzene sulfonate 3.00
Stearyl hydroxyethyl imidazoline 1.50
5 * Nonionic detergent 3.50
Sodium silicate (Na2O:SiO2 = 1:2) 5.50
Zeolite 4A 19.00
Sodium maleate methacrylate copolymer 1.10
Sodium carboxymethyl cellulose 0.50
Sodium carbonate, anhydrous 4.00
Ethylenediamine tetra(methylenephosphonic acid), sodium 0.44
salt
Stilbene optical brightener 0.25
Sodium hydroxide 0.10
Proteolytic enzyme (Alcalase~ 2T) 0.36
Sodium pexborate tetrahydrate 10.60
Calcium montmorillonite clay (calcium bentonite) 18.00
Hydroxylamine sulfate 0.50
Tetraacetylethylenediamine 1.00
Sodium aluminosilicate 0.40
Sodium ethylenediamine tetraacetate 0.13
Pentaerythritol distearate 3.00
Sodium sulfate, anhydrous 19.07
Water 7.50
Perfume 0.55
100. 00
* Condensation product of one mol of mixed C13 7
alcohols and seven mols of ethylene oxide
Mixture of 14% of the monostearate, 45% of the distearate
and 40% of the tristearate
2 ~ 7 ~ ~ . 8
The particulate product of this example is made by a
procedure described in Example 1, and,when tested for detergency
and fabric softening properties according to the procedures set forth
in that example,exhibits good detergency and synergistic fabric
softening, due to its contents of PEC and bentonite. The
synergistic improvement in fabric softening, compared to the expect-
able effects of the individual PEC and bentonite in such composition,
is not as striking as in Example 1 (wherein 6~ of PEC and 16% of
bentonite were present) but is significant. In variations of this
non-phosphate formula the PEC content is decreased to 1.5%, with
a corresponding increase in sodium sulfate content to 20.57%, and
synergistic fabric softening is ~till noted, but to a lesser
extent. When the PEC content is increased to 6% and the sodium
sulfate content is decreased to 16.07% to compensate, the synergistic
fabric softening effect is even more pronounced.
EXAMPLE 3
Component % By Weight
* Nonionic detergent 12.00
Sodium silicate (Na2O:SiO2 = 1:2) 5.50
Zeolite 4A 23.00
Sodium maleate methacrylate copolymer 1.50
Sodium carboxymethyl cellulose 0.55
Sodium carbonate, anhydrous 13.00
Ethylenediamine tetra(methylenephosphonic acid) 0.65
sodil~ salt
Stilbene optical brightener 0.30
Sodium hydroxide 0.15
Sodium perborate monohydrate 9.00
Proteolytic enzyme (Alcalase 2T) 0.70
207~7 ~8
Component (cont'd.) % By Weight (cont'd
Tetraacetylethylenediamine 3.86
Sodium aluminosilicate 0.50
Pentaerythritol distearate 3.50
Water 6.54
Perfume 0.75
100 . 00
* Condensation product of one mol of mixed
C13_17 alcohols and seven mols of ethylene oxide
14% of the monostearate, 45% of the distearate and
40~ of the tristearate
~he zeolite-built, non-phosphate, nonionic particulate
detergent composition of this example is made ~y the process or
processes of Examples 1 and 2 and is tested for detergency and
fabric softening properties in the same manner. It is a good
nonionic detergent and does not have the ecologically disadvantageous
properties of phosphates or non-biodegradable anionic detergents.
Also, due to its content of calcium bentonite and PEC it i8 of
excellent fabric softening properties, synergistically better than
would have been expected from the additive effects of the fabric
softening agents present in the formula ~and PEC is biodegradable).
To improve detergency of the composition even more one
may incorporate in it an anionic deterqent of the biodegradable
type, such as 5% of sodium lauryl sulfate or 10% of sodium C14_15
paraffin sulfonate, and in some instances such anionic detergents
may replace the nonionic detergent, with the total detergent content
being about the same as in the formula of this example. Such
products also exhibit the excellent fabric softening properties of
the formula of this example and such fabric softening is syner-
gistically improved over the additive effects of the fabric soften-
3~ ing components of the product.
2Q~7 ~8
EXAMPLE 4
Component ~ By Weight
Sodium linear tridecylbenzene sulfonate 6.00
+ Neodol~ 25-7 4.00
Pentaerythritol distearate 7.00
Swellable calcium bentonite 1~.00
Sodium carbonate 8.00
Sodium silicate (Na2O:SiO2 = 1:2.4) 4.00
++ Emulsifier 2.00
Water 51.00
100 . 00
+ Nonionic detergent which i~ a condensation product of
a fatty alcohol of 12-15 carbon atoms, with 7 mols of
ethylene oxide
++ Mixture of 4 parts of N-stearyl diethanolamine and 1
part of C12_1s alkyl decaethoxy ethanol
This basic liquid softerqent formula yields an excellent
cleaner and fabric softener, which exhibits the synergism of the
fabric so.ftening components,previously described in Examples 1-3.
EXAMPLE 5
Component ~ Bv Weight
Calcium bentonite 93.7
Pentaerythritol dipalmitate 5.8
Sodium hydroxide 0-5
100.0
This basic formula for a particulate or powder wash cycle
additive (for addition to ordinary wash waters containing non-
softening detergent compositions) is made by mixing the sodium
hydroxide, in powder or aqueous solution form, with the bentonite
and then melting the PEC and spraying or dripping it onto the
surfaces of a moving mass of the bentonite (+ NaOR), to produce
2~7~7~
such a proportion to result in 0.06% of PEC in the wash water and
proportionately more calcium bentonite, laundry washed with the
wash water resulting exhibits unexpectedly improved fabric softening
properties of the wash water. Instead of being in particulate or
powder form the wash cycle additive may be in liquid form, in which 2
of an emulsifier may be present, too, and the water content
may be about 70 to 90%, e.g., 80%.
Alternatively, a rinse cycle softener composition may be
made of essentially the same formula as that given for the particulat~
product, with the bentonite being sodium bentonite and the sodium
hydroxide being replaced by hydrochloric acid so as to make the
product acidic. Similarly, liquid rinse cycle compositions may be
manufactured, without detergent or builder being present, and with
emulsifier to help to maintain the liquid product homogeneous. In
such products the water content may be like that of the liquid
wash cycle additives, but with water also replacing the detergent(s)
and builder( R), and the pH would be in the range of 2.5 to 5.5, e.g.,
3~5. In a similar manner gel products can be mRde, with 0.5 to 5
of a gelling agent, such as 3~ of sodium alginate,being present,
and with the other components being the same as for the liquid
product (with the water content being diminished to compensate for
the gelling agent's presence). If desired, the concentrations of
bentonite and PEC may be decreased in the rinse cycle compositions
and will still ~e effective, e,~., when reduced to 1/3 the concentra-
tions in the softergents.
The described compositions, all of which contain bothbentonite and PEC, are all effective fabric softening agents and exhib-
it synergistic softenings like those described in the data given
previously and in the drawing,
28~ ~q ~18
EXAMPLE 6
Component % By Weight
Calcium bentonite 16.0
Sodium hydroxide 0.2
5 Pentaerythritol distearate 6.0
++ Emulsifier 3.0
Water 74.8
100 . O
14% Monostearate, 45~ distearate and 40% tristearate
++ Mixture of four parts of N-~tearyl diethanolamine and
one part of C12_15 alkyl decaethoxy ethanol
The components listed are mixed together to form a
wash cycle additive suspension that improves fabric conditioning by
the wash water containing the suspension. The concentrations of all
the components except water may be halved or reduced to thirds,
with the water content being increased to compensate, and the re~ult-
ing suspension may be used for rinse cycle softening. Alternatively,
the formula product may be used directly for rinse cycle softening
of the washed laundry, employing normal charges of such softener to
the rinse water, often about 1.3 fluid ounces of a 64 liter last rinse.
Synergistically improved fabric softening results, like that
mentioned previously in the other examples, for both types of uses.
EXAMPLE 7
comPonent ~ By Weight
Cellulosic Sponge 13.0
Sodium bentonite 54.0
Pentaerythritol distearate 18.0
++ Emulsifier 5.0
Water 10.0
100.0
2~ J~8
See Example 6.
++ See Example 6.
The PEC, bentonite and emulsifier are mixed together
with half the water and the sponge is moistened with the other half
of the water, after which the sponge is charged with the mixture of
the other components and the water is allowed to evaporate. The
resulting product is employed to soften laundry while it is being
dried in an automatic laundry dryer. The laundry is softened satis-
factorily and the previously described synergistic softening is
obtained. In a similar procedure paper towelling is charged with the
mix and is employed as a dryer softening agent, with essentially the
same results.
EXAMPLE 8
In this example cotton terrycloth swatches are washed in
an automatic washing machine in a 60C. wash water containing 0.5%
of a softergent composition of the formula of Example 1, rinsed and
dried. Other such swatches are washed in conventional detergent
compositions, which may be of the same formula except for the omis-
sion of the bentonite and PEC, which are replaced by inert filler
(sodium sulfate), and are then rinsed (in the last rinse), with
rinse water to which any quaternary a~moni~ or amine ~alt rinse
cycle fabric softening composition has been added, such as dimethyl
distearyl ammonium chloride, so that the rinse water contains about
0.05% (or more) of the fabric softening quat or amine, and such
swatches are dried.
Strips are cut of swatches subjected to these different
treatments and are tested for water absorption, by dipping lower
ends of such vertical strips into an aqueous solution of water
2Q7~7~8
soluble dye (red Iragon) and measuring the heights to which the water
rises, after 30 seconds, 1 minute, 3 minutes and 5 minutes. The
strips washed with the invented softergent absorb water to heights
that are about twice those for the strips from the swatches that are
washed, as described, and then treated with the rinse cycle softener.
Similar results are obtainable by utilizing rinse cycle
fabric softeners of this invention, in which PEC and bentonite are
present,when they are compared to rinse cycle fabric softening
compositions that are based on quat and/or amine fabric softeners.
Nevertheless, the invented softergents and rinse cycle compositions
soften the cotton (and other fabrics) about as well as the l-est of
comparable softening compositions, which is an exceptional result.
The results of these tests and similar absorption tests on
towelling and clothing are importa~t because they show that fabrics
treated with the invented compositions, instead of co~ercial quat-
based products, are more capable than such products of absor~ing
water (which is important for towels~ and body s~eat (which is
important for clothing items, such as underwear, T-shirts and sport
apparel).
In the illustrative examples of the invention ~iven above
various chan~es may be made within the invention and the described
synergistic results will still be obtained. For example, various
other swellable bentonites and montmorillonites may be substituted
for the calcium and sodium bentonites and other PEC's may be employed,
2~ including dipentaerythritol tetralaurate, monopentaerythritol
1~ ethylene oxide distearate and pentapentaerythritol tetrapalmitate.
207~ 3
Different detergents, PEC's and clays like those mentioned may be em-
ployed and various adjuvants and active components may be included in
the compositions and articles of the invention, and so long as the
combination of the acceptable clay and PEC is present the synergistic
fabric softening action is obtainable. Such is also the case when
proportions are varied within the ranges mentioned and when different
concentrations of the products are employed, within the ranges given.
In all variations, when the bentonite and the PEC of the
invention are present improved softening results, possibly due to the
mutual promotion of adherence to the laundry fibers of each of the
required softeners, and sometimes to the desirable dispersing effect
of the bentonite on the PEC. However, it seems that the synergism
obtained is due to more than the mentioned adherence promoting and
dispersing effects, and applicants are not bound by any theories
mentioned herein.
The invention has been described with respect to
illustrations and examples thereof but is not to be considered as
beinq limited to those because it is evident that one of skill in
the art,with the present specification before him or he~ will be able
to utilize substitutes and equivalents without departing from the
invention.
