Note: Descriptions are shown in the official language in which they were submitted.
iL1 527~3
-- 1 --
TECHNICAL FIELD
The present invention relates most generally to
particulate solid fabric conditioning materials adapted
for convenient application to fabrics during a launder-
ing operation. More particularly, the invention relates
to improvements in particulate solid fabric softening
compositions which allow the latter agents to be more
easily dispersed in a laundry rinsing liquor.
BACKGROUND ART
U.S. Patent 4,259,373 issued March 31, 1981 to
Demessemaekers and Pracht, assigned to the owners of the
present invention, discloses a method of conditioning
fabrics in which a granular solid fabric conditioning
material i-s enclosed in an envelope with a porous wall
communicating between the granular composition and the
water of a washing machine. This is sometimes a preerred
delivery system for fabric softeners for reasons disclosed
in that application,
However, some fabric sof~ening compositions are not
efficiently delivered to a laundry rinsing liquor using
this and other delivery systems, for the reason that
certain softening materials, particularly those in a
solid, granular form, are not easily dispersed in the
rinsing liquor. This problem is especially prominent when
cold water is used in the washing machine rinse cycle
during which softening is to take place. (The rinse cycle
is the preferred stage at which the softener should be
transferred to the fabrics.) Since the cost of energy
has increased enormously in recent years, it is now very
important to provide fabric conditioning compositions
which will work well in a cold rinse. An improvement
in the dispersibility of granular fabric
~S2738
softeners in cold water is required if the need to reduce
the energy cost of laundering is to be met.
Several patents state or suggest that certain
quaternary ammonium compounds which are very useful in the
softening of fabrics are not easily dispersed in the rinse
water of a washing machine. U.S. Pat. No. 3,356,526, issued
to Waldman et al., on December 5, 1967, and U.S. Pat. No.
3,573,091, issued to Waldman et al. on March 30, 1971, each
disclose the use of powdered carriers to render quaternary
compounds water dispersible; the '526 reference teaches the
practice of that invention using the chloride analog of
ditallow dimethyl ammonium methyl sulfate. U.S. Pat.No.
3,892,669, issued to Rapisarda et al. on July 1, 1975, and
U.S. Pat. No. 3,325,404, issued to ~ohen et al. on June 13,
1967, each disclose solubilizing agents which may be com-
bined with ditallow dimethyl ammonium methyl sulfate or
other di-(short chain), di-(long chain) quaternary ammonium
compounds in order to solubilize these compounds in aqueous
liquid fabric softening compositions.
The following references disclose liquid fabric
softening compositions which contain mixtures of softening
ingredients relevant to the present invention: U.S. Pat. No.
3,349,033, issued to-Zuccarelli on October 24, 1967, dis-
closes a liquid fabric softening composition which may
contain 6% of a softening agent which may be, for example,
ditallow dimethyl ammonium methyl sulfate and 2% of a micro-
biological control agent which may be, for example, dodecyl
or hexadecyl trimethyl ammonium chloride. ~.S.Pat. No.
3,904,533, issued to Neiditch et al. on September 9, 1975,
discloses a liquid fabric softener which may contain, for
example, ditallow dimethyl ammonium methyl sulfate tor one
of many other homologs thereof) in combination with myristyl
trimethyl ammonium bromide (or one of many other homologs
thereof) as a low temperature stabilizing agent. U.S. Pat.
No. 3,329,609, issued to Blomfield on July 4, 1967, teaches
a composition of 20% to 80% of a generic material which
~15~27~8
-- 3 --
includes ditallow dimethyl ammonium methy~ sulfate in its
definition; 5% to 10~ of a material which may be myristyl
trimethyl ammonium bromide; and 80% to 20~ of a salt of
hydrofluorosilicic acid. In Col. 4 this reference indicates
that a large quantity of inert filler material may be added
to the composition, and further indicates that the composi-
tion may be blended together in the form of dry ingredients.
The overall suggestion of this reference is that the com-
position is a solid material.
SUMMARY OF THE INVENTION
The invention is a solid comelted granular fabric
softening composition which is freely dispersible in a
washing machine cold water rinse, comprising about 60%
to about 85~ of a first compound having the formula:
Rl +
R4 - N ~ R2 X
R3
and about 15% to 40% of a second compound having the
formula:
-
[~8 ~ N - R6 +
R7
(Note: All percentages herein are percentage by weight
unless otherwise indicated.)
In the above formulas~ Rl, R2, R5, R6 and R7 are lower
alkyl moieties, each preferably selected from a group com-
prising methyl, ethyl, and propyl moieties, each most
preferably a methyl moiety. R3 and R4 are each higher
alkyl or alkenyl moieties having from about 14 to about 22
carbon atoms, each preferably comprising tallow cuts, each
more preferably comprising one or more aliphatic hydrocarbon
moieties having from about 14 to about 18 carbon atoms, and
each most preferably having from about 16 to about 18 carbon
~1527~8
-- 4 --
atoms. R8 is an alkyl or alkenyl moiety having from about
10 to about 14 carbon atoms, preferably a coconut alkyl cut,
in which dodecyl and myristyl moieties predominate, and most
preferably a myristyl (C14) moiety. x and Y are anions
which are associated with the quaternary ammonium compounds
of the pxesent invention, ~s will be appreciated by those
skilled in the art, X and Y may be any of a wide variety of
anions which do not interfere with the utility of the compo-
sition. In a preferred mode of the present invention,
either of X and Y may be selected from the following anions:
chloride, bromide, iodide, fluoride, acetate, phosphate,
nitrite, methyl sulfate, ethyl sulfate or nitrate. In a
most preferred embodiment of the present invention, X is
methyl sulfate and Y is bromide. Optional ingredients (as
specified hereinafter) may also be present in the composi-
tions of the present inventionl but the resulting composi-
tion must be a granular solid. ~he advantage of this par
ticular softening composition over those of the prior art is
that it maximizes the use of the most effective softening
agents, while providing for those agents improved dispersi-
bility, particularly in cold water.
DESCRIPTION OF P~EFERRED EMBODIMENTS
What follows is a description of the preferred
embodiments of the present invention. It will be understood
that the description herein of preferred-embodiments or of
particular species is presented to exemplify the invention,
not to limit it. The scope of the invention is defined
solely by the claims which are found at the end of this
specification.
In order to explain certain terms used in this
specification the following definitions are provided:
By a "fabric softening" agent or composition is
meant an agent or composition which is substantive to tex-
tiles and which softens, lubricates, or reduces static
accumulations on abrics to which it is applied. Such a
,~j
`` ~lSZ~8
-- 5 --
material typically has a melting point within the range of
from about 20C to about 115C~ preferably within the range
of from about 30C to about 68C. The fabric softening
agents of the present invention are the cationic quaternary
ammonium compounds further described hereinafter.
As used herein, a solid, comelted granular substance is
said to be "water dispersible" if it is able to be dispersed
throughout the water of the rinse cycle of a washing machine
with no more mechanical agitation than is provided by the
washing machine. In the context of a composition contained
within a receptacle, water dispersibility is the degree to
which the composition can escape from the receptacle during
a normal washing machine rinse cycle, when the receptacle is
in contact with the rinse water. Water dispersibility may
either be measured directly by measuring the amount of mat-
erial which is dispersed during a test cycle, or indirectly
by measuring the degree to which fabrics subjected to the
agent in question are softened (indicating the presence of
a dispersed fabric softening agent in the laundry rinsing
2~ liquor). The solid comelted granular compositions of this
invention are comelted and then flaked or spray dried using
conventional techniques. It has been discovered that the
comelted material is superior to drymixed material. There-
fore, it is important that the compositions o~E this
invention be prepared by comelting.
The present invention is a fabric softening composition
comprising from about 60% to about 85%, preferably from
about 70~ to about 80%, most preferably about 75% of a
first compound having the formula:
. Rl +
R4 - N R2 X
R3
and Erom about 15% to about 40%, preferably from about 20
to about 30%, and most preferably about 25% of a second
compound having the formula:
R5 +
R8 ~ N R6
R7
~SZ7C!8
-- 6 --
wherein the substituents for the above formulas are defined
in the SUMMARY OF THE INVENTION section above. In the de-
scription which follows, each of the individual components
noted above, the mixture of these components to form a
fabric conditioning active mixture, optional ingredients
which round out a commercial composition, and finally the
preferred mode of delivery will be more fully described.
Di-(Long Chain) Quaternary Ammonium Substituent
The first component of fabric softening composi-
tions within the scope of the present invention is knownhereinafter simply as a di-(long chain) quaternary ammonium
component. The formula of this component is as follows:
Rl +
4 , 2 X
R3 l
In the above formula each of Rl and R2 is a lower alkyl
moiety. As used herein, "lower alkyl" is indicative of a
substituent having 1, 2 or 3 carbon atoms. This will be
understood to include substituents which include atoms other
than hydrogen or carbon. For example, the lower alkyl
substituent may be a hydroxy alkyl substituent. Other
substituents which may be used within the definition of
"lower alkyl" are methyl, ethyl and propyl moieties. Of
these, methyl moieties are most preferred as Rl and R2
substituents.
In the above formula R3 and R4 are each alkyl
moieties which may contain from about 14 to about 22 carbon
atoms in an aliphatic configuration. In a preferred mode of
practicing the present invention, the R3 and R~ moieties can
be tallow cuts, which is to say that they can be the alkyl
and alkenyl residues of tallow fatty acids. According to
The Merck Index, 9th Edition, Entry 8820, the principal
.
-- ~lS27~18
tallow ~atty acids are oleic acid, palmitic acid, stearic
acid, myristic acid and linoleic acid. Tallow also contains
such minor constituents as cholesterol and arachidonic,
elaidic and vaccenic acids. More preferred species for use
herein are alkyl moieties having from about 14 to about 18
carbon atoms. The most preferred R3 and R4 moieties are
alkyl moieties having from about 16 to a~out 18 carbon
atoms, which are the predominant species found in tallow
cuts.
X is an anion. As those skilled in the art are
well aware, it frequently makes very little difference which
anion from a wide selection is used in a given quaternary
ammonium compound selected for use as a softener. Suffice
it to say that this anion may be selected from any suitable
anion known to the art, such as the chloride, bromide,
fluoride, iodide, acetate, phosphate, nitrite, methyl sul-
fate, ethyl sulfate and nitrate anions (or their equiva-
lents). In the di-(long chain) substituent, the most pre-
ferred anion is the methyl sulfate anion.
A number of examples of di-(long chain) quaternary
ammonium compounds which may be used in the practice of the
present invention are the following: ditallow dimethyl
ammonium chloride; ditallow dimethyl ammonium methyl sul-
fate7 dihexadecyl dimethyl ammonium chloride; di(hydrogen-
ated tallow) dimethyl ammonium chloride; dioctadecyl di-
methyl ammonium chloride; dieicosyl dimethyl ammonium
chloride; didocosyl dimethyl ammonium chloride; di(hydrogen-
ated tallow) dimethyl ammonium methyl sulfate; dihexadecyl
diethyl ammonium chloride; dihexadecyl diethyl ammonium
methyl sul~ate; dihexadecyl dimethyl ammonium acetate;
ditallow dipropyl ammonium phosphate; and ditallow dimethyl
ammonium nitrate.
X
527~8
Mono-(Lohg Chaih) Quater~y Ammonium Compounds
The second major component of ~he present novel
fabric softening composition is a quaternary ammonium
compound having the following formula:
_ _ +
8 , 6 ye
R7
In this compound, R5,R6 and R7 are lower alkyl moieties, as
previously defined. R5, R6 and R7 are independently
selected, and preferably are selected from the group con-
sisting of methyl, ethyl, and propyl moieties. Each of R5,
R6 and R7 is preferably a methyl moiety.
R8 is the sole long chain substituent of the mono-
(long chain) quaternary ammonium compounds defined herein.
R8 can most broadly be selected from the alkyl and alkenyl
residues of one or more coconut fatty acids (or their chemi-
cal equivalents derived from other raw material sources),
known hereinafter as "coconut cuts." While coconut cuts
have chain lengths of from about 8 to about 18 carbon atoms,
the predominant species are those with a chain length of
from about 12 to about 14 carbon atoms. The latter species
are those which are believed to confer the benefit of the
presen~ invention. In a preferred mode of the invention, R8
i8 selected from moieties having 10 to 14 carbon atoms, such
as decyl, undecyl, dodecyl, tridecyl or tetradecyl moieties,
or the unsaturated analogs of these alkyl radicals. The
most preferred long chain substituent of this compound is a
tetradecyl or myristyl moiety.
The anion ~ found in the above formula may be any
anion which is suitable for use in conjunction with a quat-
ernary ammonium compound which is to be used as a fabric
softening material. Specific anions which are useful herein
3~ are described above in connection with the description of
the di-(long chain) quaternary ammonium compound.
~SZ~8
.
_ 9 _
Examples of complete mono-(long chain) quaternary
ammonium compounds useful herein are as follows: coconut
trimethyl ammonium bromide; myristyl trimethyl ammonium
bromide; myristyl triethyl ammonium bromide; decyltrimethyl
ammonium bromide; and dodecyl trimethylammonium bromide.
Complete Fabric Softening Formulations
It will be understood that a fabric softening com-
position in accordance with the present invention can be
formulated from the di-(long chain) and mono-(long chain)
components alone, in the proportions described above.
However, certain optional ingredients can be added to the
composition in order to accomplish a variety of objectives.
In a preferred embodiment of the invention, the
fabric softening composition is in the form of a free-
flowing powder. When necessary to facilitate the creationof such a powder, any of a wide variety of fillers can
be added to the present composition. Such fillers are
inorganic compounds such as sodium sulfate, calcium
carbonate, aluminum oxide, and smectite clays or organic
compounds such as high molecular weight polyethylene
glycols. Smectite clays and aluminum oxide are preferred
fillers for use herein. A description of smectite clays
may be found in U.S. PatO No. 3,862,058, issued on January
21, 1975, to Nirschl et al. The filler material, if
present, may be present at a level ranging from 5% to 25%
by weight of the fabric softening composition.
The fabric softening compositions described herein
can also optionally contain minor proportions ~i.e., 0.1%
to about 15~ by weight, in total~ of various other
ingredients which provide additional fabric conditioning
benefits. Such optional ingredients include perfumes,
bleaches, fumigants, bactericides, fungicides, optical
brighteners and the like. Specific examples of typical
solid, water soluble additives useful herein can be found
in any edition of the publication, Year Book of the
3L~5~71:P8
-- 10 --
American Association of Textile Chemists and Colorists
Such additional components can be selected from those
compounds which are known to be compatible with the fabric
softening agents employed herein, or they can be coated
with water soluble coatings such as solid soaps and the
like, and they can thereby be rendered compatible with the
fabric softening agents described herein. A preferred
optional ingredient is a fabric substantive perfume having
a melting point greater than 38C, such as musk ambrette,
musk ketone, musk xylol, ethyl vanillin, musk tibetine,
coumarin, aurantiol, or mixtures thereof. These perfumes
can be added directly to the fabric conditioning agent,
or they may be encapsulated with a polyvinyl acetate and
sodium alginate mixture. From about 0.1% to about 5% by
weight of a perfume is preferably added to the fabric
softening composition.
Other optional ingredients useful herein are
inorganic peroxide compounds such as alkali metal and
ammonium perborates, percarbonates, monopersulfates and
monoperphosphates. Solid, water soluble organic peroxides
having the formula:
M - O - O - C - R - Y
wherein R is a substituted or unsubstituted alkyl, alkylene
or arylene group containing from 1 to about 14 carbon
atoms, M is an alkali metal or hydrogen and Y is
O O O
I~ 11 1~
-C-O-O-H, -S-OH or O-C-O-OH
o
or any other group which yields an anionic group in aqueous
solution are also useful herein. Many of these bleaches
are more fully described in U.S. Pat. No. 3,749,673, issued
July 31, 1973 to Jones et al.
t ~
~lSZ~8
The water soluble silicate compounds recognized in the
art as corrosion inhibitors can be employed in the present
composition at levels of up to about 5% by weight.
Release aids in the form of electrolytes ~for example,
CaC12) or nonionic surfactants can also be advantageously
employed in the present invention.
Optional ingredients generally should be added by dry
mixing after the comelted material is dried.
It will be recognized that any of the foregoing optional
components can be provided in a solid, particulate form which
can be dispensed onto fabrics concurrently with the fabric
softening material to provide the desired additional fabric
treatment benefits.
Preferred Mode of Delivery
As has already been described hereinabove, the fabric
softening compositions of the present invention can be de-
livered to fabrics by placing a measured amount of the desired
composition within a porous envelope which is inserted in a
laundry washing machine during the rinse cycle of a laundering
operation along with a load of clothes to be treated. A more
particulate description of dispensers suitable for this
purpose ollows.
~ he receptacle which releasably holds the fabric softening
composition of the present invention is preferably a closed,
flexible article having at least one porous wall comprising
inner and outer layers. Inasmuch as the receptacle is to be
used in an automatic clothes washer, it should be comprised
of a water insoluble material. Therefore, the receptacle
herein can be made of any natural or manmade material meeting
the above requirements, The porous wall can be made from
woven, nonwoven, or foamed material.
In one preferred receptacle for use herein, the inner
layer of the porous receptacle wall or walls is an elastic
open cell foam. The open cell foams are distinguished from
closed cell foams in that the closed cell structure consists
essentially of isolate~ individual cells, while in the open
cell structure a large proportion of adjacent cells commun-
icate, forming an open matrix of material which allows the
passage of fluids under certain conditions.
J7~8
- 12 -
Open cell foams can be made from polystyrene,
polyurethane, polyethylene, polyvinyl chloride, cellulose
acetate, phenol-formaldehyde and other materials such as
cellular rubber. Many of these materials and their method
of manufacture are disclosed in standard references such
as Encyclopedia of Polymer Science and Technolo~y,
Interscience Publishers, John Wylie & Sons, Inc. (1965).
In another preferred embodiment, elastic nonwoven
material may be used as the material for the inner layer
of the porous receptacle wall. The preferred nonwoven
materials used in the inner layer are bonded fibrous
carded webs (if the fiber strength is suitable to allow
carding) or fibrous batts in which the fibers are randomly
distributed. The fibers or filaments can be natural
materials such as wool, silk, jute, hemp, cotton, linen,
sisal or ramie, or synthetic materials such as rayon,
cellulose ester, polyvinyl derivatives, polyolefins, poly-
amides, or polyesters. Preferred materials include poly-
esters, polyamides, polyolefins, and polyvinyl derivatives
and mixtures of these with rayon or cotton to achieve the
desired elasticity.
Methods of making nonwoven materials are not a
part of this invention and are not described in detail
herein. Generally, however, such materials are made by
air or water-laying processes or by spin-bonding pro-
cesses, any of which are well known to persons skilled
in the art of making nonwoven webs.
The inner layer of the receptacle serves to
preserve the shape of the receptacle, and to moderate the
release of the fabric softening composition somewhat,
although the rate of dispersion of the fabric conditioning
compositions is controlled primarily by the outer layer of
the article.
Especially preferred materials for use as the
inner layer of the dispensing article are open pore poly-
urethane foams or spin-bonded nonweven materials, especially
"` ~lS27~8
those made from polyester. The polyurethane foam preferably
has a density of from about 0.02 grams per cubic centimeter
to about 0.04 grams per cubic centimeter, while the poly-
ester nonwoven preferably has a density of from about 0.005
grams per cubic centimeter to about 0.02 grams per cubic
centimeter. The thickness of this layer can vary depending
on the release characteristics desired by the manufacturer,
but will preferably be from about 0.2 centimeters to about
2.0 centimeters for polyurethane, and from about 0.2 centi-
meters to about 2.0 centimeters for polyester.
The outer layer of the preferred receptacledescribed herein is a moderately porous fabric. The fabric
can be any of the above-described woven or nonwoven
materials which meet the requirements set forth herein, but
will generally be a nonwoven material made rom polyester,
polypropylene or mixtures of polyester with rayon or cotton.
The outer layer generally has a lower porosity than the
inner layer.
The receptacle described herein provides con-
trolled release of the fabric conditioning compositionduring the rinse cycle of an automatic washing machine. The
double layers of the receptacle provide more efficient
release than a single layer receptacle, while also providing
a more aesthetically pleasing consumer product, for the
outer layer remains more free of stains and discolorations
than does the inner layer.
In addition, the two-layered construction helps
to insure that fabric staining is minimized by preventing a
large amount of the fabric conditioning composition from
being released at a single time.
When preparing the articles described herein the
rate of release of the fabric softening composition from the
receptacle is preferably optimized by selecting an appropri-
ate receptacle for a particular fabric softening composition.
The rate of release of the fabric softening composition
depends on the porosity of the layered walls of the recep-
tacle and on the physical characteristics of the fabric
~527~8
- 14 -
softening composition.
The receptacle can be provided in a variety of
sizes and shapes, and the particular configuration of the
receptacle is not critical to the practice of this inven-
tion. For example, the receptacle herein can be providedwith a single wall or with a portion of one wall which
exhibits the double-layered porous structure through which
the fabric softening composition is dispensed. Preferably,
the entire envelope of the receptacle will comprise double-
layered porous material.
The fabric conditioning receptacle is preparedas follows. First, a pouch with one open end is prepared.
This may be done by positioning sheets of the inner and
outer layers of material one over the other (so that two
inner layers are disposed between two outer layers), and
then sealing a large portion of the perimeter of the pouch,
as by forming a border of heat-sealed point bonds. The
pouch is now ready to be filled with fabric softening
material.
Second, an effective amount of the fabric soften-
ing composition is placed in the open pouch produced accord-
ing to the first step above, between the ~wo inner layers
thereof. An "effective" amount of the fabric softening
composition described herein is an amount sufficient to
condition an average load of fabrics in an automatic washer.
Of couxse, the actual amount of the fabric softening compo-
sition employed will depend on the fabric load and on the
identity of the fabric softening composition selected for
use in the receptacle. For an average 2 to 4 kilogram load
of fabrics, roughly 4 to 12 grams of any of the foregoing
fabric softening compositions provide good fabric softening
results.
After the fabric softening composition is added to
the pouch through the open portion of the pouch, the balance
of the pouch perimeter is sealed, as with a pattern of heat
sealed point bonds, in order to complete the receptacle.
.
~1l5~8
- 15 -
Using the Fabrl'c'S'o'f'ten'i'n'g Articles
The articles of the present invention can be
utilized in a variety of ways dependiny on the desires of
the consumer. In one process, an article prepared as
described herein is placed in a washing machine with a load
of fabrics at the start of the rinse cycle and left with the
fabrics during the rinse and spin drying cycles of the
washing machine. The rinsing water can be supplied at any
temperature desired by the user, but generally is selected
to have a temperature of from about 4C to about 60C. The
spent fa~ric softening article can be removed and discarded
when the washing machine completes its cycle and stops.
Alternatively, the pouch can be left with the load through
the drying cycle, after which it is easier ~o find and to
separate from the laundered fabrics. The dryer is operated
in standard fashion ~o dry the fabrics, usually at a tem-
perature of from about 50C to about 80C for a period of
from about 10 to about 60 minutes, depending on the fabric
load and type. The performance delivered by the receptacles
descri~ed herein when used as described above i5 essentially
equivalent to that of rinse-added liquid softeners in terms
of softness.
The invention will further be illustrated by the
following examples:
EXAMPLE~ 1-6
These examples demonstrate that the addition of a
mono- (long chain) quaternary ammonium compound to a di-(long
chain) quaternary ammonium compound in a granular compo-
sition increases the water dispersibility of the latter
compound.
The mono-(long chain) quaternary ammonium com-
pound selected for use herein was myristyl trimethyl ammonium
bromide ~MTMAB). The di-(long chain) quaternary ammonium
fabric softener selected for use herein was ditallow dimethyl
ammonium methylsulfate (DTDMAMS). These materials were
~1
~5~ 8
- 16 -
mixed together, in the proportions noted in Table I below,
by comelting and stirring them. The DTDMAMS was heated
over a steam bath or water bath until molten, then the
MTMAB (trade mark "Mytab") was added while stirring. About
5% to 10~ ethanol (95%) was added to reduce the viscosity
of the comelt to facilitate pumping and spray drying. The
comelted mixed softeners were then each sprayed through a
fine nozzle to form droplets which solidified to form, in
aggregate, a granular composition.
Next, double-walled pouches were constructed. The
pouch outer walls were made of SONTARA~nonwoven polyester
fabric having a basis weight of 20 grams per square yard
(24 grams per square meter), available from E. ~ du Pont
de Nemours and C~mpany, Inc. The pouch inner walls were
made of BONDAIRE~ IBERFILL nonwoven polyester material,
available from J. P. Stevens Company. 7 centimeter by fi
centimeter pieces of the respective materials were stacked
so that the bottom and top pieces of the stack were the
material intended to form the pouch outer walls, and so
that the two central pieces in the stack were the material
intended to form the inside walls of the pouches. The
stacks were each secured to form an openmouthed pouch by
heat-sealing the stacks together around three sides of
their perimeter.
6.0 grams of each of the compositions to be tested were
placed in one of the open-mouthed pouches between the
facing inner layers thereof, and the pouches were stapled
across their open mouths to complete their construction.
Each pouch was placed in a washing machine containing
a load of laundry at the beginning of the washing machine
rinse cycle. The temperature of the entering rinse water
was about 50F (10C). After the washing machine had
ceased to operate the pouch was removed and extracted with
a 50:50 mixture of methanol and chloroform. The solvent
was removed from the extract and the weight of remaining
residue was measured. (The extraction and measurement
technique is described in the Appendix section below.)
~,
~S?J7~8
- 16a -
The difference between this final weight and the initial
6.0 gram charge was calculated in order to find the weight
of material dispersed to the water in the washing machine.
This weight of material dispersed was then compared to
the weight of material initially placed in the pouch to
determine what proportion of the initial pouch contents
remained in the
l~S~7~8
- 17 -
pouch as an insoluble residue. The results of this test
are stated in Table I below as a percentage of residue
for a composition containing stated proportions of the
respective starting materials.
TABLE I
Example % DTDMAMS % MTMAB % Residue
l 0 lO0 0-5
2 75 25 lO
3 80 20 34
4 85 15 50
6 lO0 0 95
EXAMPLES 7~12
These examples are intended to compare the soften-
ing performance of various compositions when delivered to a
load of laundry in the rinse cycle of a washing machine asdescribed in connection with Examples 1-6 above.
Pouches were made as described above and each
filled with six grams of one of the materials listed in
Table II below. The pouches were then sealed to form
completed articles.
Each pouch was placed in a washing machine with a
standard load of laundry which included 4 test terry towels
made of 86% cotton and 14% polyester. (The towels had pre-
viously been stripped with an organic solvent to removeany fabric finish or softener residue which might obscure
the test results.) The pouches were added at the beginning
of the washing machine rinse cycle. In separate groups of
tests the respective rinse water temperatures were 50F
(10C) and 90F (32C). The test terry towels were than
paired with equivalent towels which had been washed with
DOWN ~ (a water-dispersible liquid fabric softener produced
and marketed by The Procter ~ Gamble Company and its affil-
iated corporations) to form graded pairs of towels. Each
graded pair was compared blind by a panel of three expert
graders to determine the relative softness of the paired
,r~
.
1527~8
- 18 -
towels. The softness difference between the towels was
reported on a scale of O to 4; 0 represented a grade of "no
difference," 4 represented a grade of "a whole lot differ-
ent," and intermediate grades represented more moderate
degrees of difference. The softness grades were then sta-
tistically combined into a single result for each test. A
positive softness grade in Table II below indicates per-
formance which is better than that of DOWNY, while a nega-
tive softness grade indicates the opposite result.
TABLE II
Example Material 50F 90F
Rinse Rinse
7 Stearyl trimethyl -2.0 -1.1
ammonium chloride
15 8 Palmityl trimethyl -G.9 -2.4
ammonium chloride
9 Palmityl trimethyl -1.0 -1.0
ammonium bromide
Ditallow dimethyl -1.0 -0.6
ammonium chloride
11 Myristyl trimethyl -0.8 -0.75
ammonium bromide
12 75~ Ditallow dimethyl
ammonium methylsulfate;
25% Myristyl trimethyl
ammonium bromide +0.3 0
Appendix - Measurement of Cationic Surfactant Residue
What follows is a description of the procedure
used to measure the residual amount of cationic materials
found in the pouches of Examples 1-6 above.
The method described herein is an adaptation
of the titration of anionic surfactants described in Reid et
al., "Determination of Anionic Active Detergents by Two-Phase
Titration," Tenside 4, 1967, pp. 292-304.
~5~7~8
-- 19 --
To measure the residual quaternary ammonium
softeners in the pouches of Examples 1-6 after they were
used in a laundering operation, the following stepwise
procedure was used:
1. First, a 0.004 N solution of Hyamin ~ 1622
was prepared. ~yamine 1622 is available from Rohm and
Haas Company, Philadelphia, Pennsylvania.
2. A 0.004 N solution of reagent grade linear
alkyl benzene sulfonate having an alkyl chain length of
11.8 (LAS) was prepared. This LAS solution was used in
place of the sodium lauryl sulfate reagent described in
the Tenside article already cited, page 302.
3. The residual quaternary ammonium softeners
were extracted from the test pouches. This was done
by cutting up the pouch and residue into small pieces,
placing these pieces in a flask, and adding to the flask
250.0 milliliters of methanol and 250.0 milliliters of
chloroform. A magnetic stirring bar was placed within the
flask, the flask was stoppered, and the contents of the
flask were stirred at room temperature for 2-4 hours by
actuating the magnetic stirring bar with a magnetic
stirring base.
,4. A aliquot was prepared to be titrated. To do
this, 10 milliliters of solution were withdrawn from the
stirred flask of Step 3, the methanol and chloroform were
evaporated, and the dried contents were quantitatively
transferred to a 100 milliliter graduated cylinder with
20-30 milliliters of chloroform.
5. An indicator solution was prepared. A suit-
able indicator is described on pages 302-303 of the Reid
article cited above. (Solution 8.3.g)
6. 10 milliliters of the indicator solution
and 10 milliliters of distilled water were added to the
graduated cylinder containing the titration aliquot.
7. The aliquot was titrated with the LAS
solution until the bottom layer was pink. The number
of millimeters of LAS solution used were recorded.
~'~J'
'
~527~8
- 20 -
8. The aliquot was then titrated with the
Hyamine solution until the bottom layer was gray. The
amount of Hyamine solution used (ml) was recorded. A gray
bottom layer is the endpoint of the titration.
9. The weight of residual quaternary ammonium
softeners in the pouch was then .calculated from the follow-
ing formula: -
V = 500 milliliters
a = 10 milliliters
MW is the average molecular weight of the two
components of the original quaternary
ammonium softener mixture
Q = grams of the quaternary ammonium softener
B = ml of LAS solution used
T = ml of Hyamine solution used
Q [ x 1 2] lOOOa
Nl = Normality of LAS
N2 = Normality of Hyamine
