Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~2~$~34
LAUNDRY SOFTENING DETERGENT
This invention relates to detergent compositions.
More particularly, it relates to particulate heavy duty
laundering and textile softening detergent compositions
intended for use in the machine washing of laundry. It also
relates to methods for the manufacture of such compositions.
Bentonite is advantageous as a softening agent
in detergents. The softening properties of bentonite and its
desirable adherence to substrates are important advantages
but its "gelling" characteristics can cause an objectionable
gumminessin the deterg~nt, which sometimes will tend to hold
detergent beads and/or bentonite beads or agglomerates to
surfaces, thereby tending to inhibit free flow. Thus, under
conditions of high humidity or in the presence of free mois-
ture bentonite can "gel" and become sticky or of reduced
flowability, even becoming held to passageway or chamber
walls despite applications of forces to the particles to
remove them (such as the force of flowing water being charged
to an automatic washing machine). Such adherence could be
significantly disadvantageous for a desirably ~ree flowing
commericial particulate detergent product and could lead to
a lesser degree of acceptance of the product by the consumer.
Even when flowability through production lines during the
manufacturing and packaging processes, and flowability from
the dispensing carton when,the product is being employed by
the ultimate consumer are satisfactory, the presence of
bentonite can cause the detergent composition particles to
be held to ~ppliance part walls, especially charging com-
partment walls, of washing machines equipped with means for
automatically charging detergent composition to the wash
~,:
--2--
1~2~34
water in the machine tub or drum, when such particles and
the bentonite present are moistened. In such circumstances
the bentonite may tend to swell, with the production of
moist adherent surfaces, so ~ha~ the particl~s may resist
removal from surfaces against which they are resting. For
example, in washing machines and other appliances equipped
with automatic dispensers or charging compartments, the
detergent particles may not entirely fall from the dispen-
ser or be washed out of the dispenser, especially if the
dispenser walls had been wet before addition of the deter-
gent. Failure to dispense part of the desired charge to the
washing machine diminishes the effective detergent and
softener concentrations of the wash water and can lead to
inaccurate detergent and softener concentrations being
employed. Also, it may create an unsightly build-up, which
may be objectionable to the consumer. In either situation
the result is undesirable and should be avoided, if possible.
In accordance with the present invention a heaYy
duty laundering ~nd textile softening particulate detergent
composition, useful for automatic machine washing of laundry
in water and dispensable from a charging or dispensing com-
partment, of such a machine by action of water being fed
through such compartment, comprises a built synthetic organic
detergent which is an anionic or nonionic detergent or a
mixture thereof, a building proportion of a builder for the
synthetic organic detergent which is a water soluble or
water insoluble builder or a mixture thereof, and a softening
proportion of bentonite, with the bentonite being in part-
icles with which there is included a dispensing assisting
proportion, preferably at least 0.15%, of a siliconate and~or
~2t~ 3~
a dispensingassistingderivative thereof. In preferred
embodiments of the invention the synthetic organic deter-
gent includes both an anionic detergent, which is prefer-
abl~ a sodium linear higher alkylbenzene sulfonate, and a
nonionic detergent, which is preferably a condensation
product of a higher fatty alcohol and polyethylene oxide,
a higher fatty acid soap is present, the builder salt is
primarily pentasodiumtripolyphosphate or NTA or a mixture
thereof, with a small proportion of sodium silicate, the
bentonite is a swelling bentonite of a moisture content of
at least 3%, the siliconate is an alkali metal lower alkyl
siliconate, more preferably potassium methyl siliconate,
and 5 to 35~ of a bleaching agent which releases oxygen
in aqueous solution at elevated temperature, such as sodium
perborate, is present. Also within the invention are
methods for making the improved products that have been
described herein.
The synthetic organic detergent~s) employed will
normally be either nonionic or anionic and very preferably
will be a combination of both, but suitable amphoteric or
ampholytic detergents, such as those sold under the Miranol
trademark, may also be used in conjuction with nonionics
and anionics in the present compositions. Cationic deter-
gQ~ts, such as the ~uaternary ammonium halides, e.g., those
sold under the Arosurf trademark, can also serve as supple-
mentary fabric softeners in these products but normally will
not be used.
Various synthetic anionic organic detergents, such
as those characterized as sulfonates and sulfates, usually
as alkali metal or sodium salts, may be employed, but those
--4--
~Z~34
which are most preferred are linear higher alkyl benzene
sulfonates, higher alkyl or fatty alcohol sulfates and
higher fatty alcohol polyethoxy or polyethoxylate sulfates.
Preferably, in the higher alkyl benzene sulfonates the
higher alkyl is linear and of 10 to 14 carbon atoms, more
preferably 11 to 13, e.g., 12, and the sulfonate is a
sodium salt. The alkyl sulfate is preferably a higher
fatty alkyl or alcohol sulfate of 10 to 16 carbon atoms,
more preferably 12 to 14 carbon atoms, e.g., 12, and is
also employed as the sodium salt. The higher fatty alcohol
polyethoxy sulfates will preferably be of 10 to 18 carbon
atoms, more preferably 12 to 16, e.g., 12l in the higher
fatty alcohol, the ethoxy content will preferably be from
3 to 30 ethoxy groups per mol, more preferably 3 or 5 to
20, and the detergent will be a salt of sodium. Thus, it
will be seen that the alkyls of the sulfonates and sulfates
are preferably linear or fatty higher alkyls of 10 to 18
carbon atoms, the cation is preferably sodium, and when a
polyethoxy chain is present the sulfate is at the end thereof.
Other useful anionic detergents include the higher olefin
sulfonates and paraffin sulfonates, e.g., the sodium salts
wherein the olefin or paraffin groups are of 10 to 18 carbon
atoms. Specific examples of the preferred detergents are
sodium dodecyl benzene sulfonate, sodium tallow alcohol
polyethoxy (3 EtO) sulfate, and sodium hydrogenated tallow
alcohol sulfate. In addition to the preferred anionic deter-
gents mentioned, others of this well known group may also
be present, especially in only minor proportions with respect
to those previously described. Also, mixtures thereof may
be employed and in some cases such mixtures can be superior
--5--
~2~ 3~
to single detergents.
Although various nonionic detergents of satis-
factory physical characteristics may be utilized, including
condensation products of ethylene oxide and propylene oxide
with each other and with hydroxy-containing aromatic and
aliphatic bases, such as nonyl phenol and Oxo-type alcohols,
it is highly preferred that the nonionic detergent be a
higher fatty alkoxy poly-lower alkoxy lower alkanol, which
may also be described as a condensation product of ethylene
oxide (and/or propylene oxide) and higher fatty alcohol.
In such products the higher fatty alkoxy or alcohol is of
10 to 16 carbon atoms, preferably 12 to 15 carbon atoms,
and the nonionic detergent contains from about 3 to 20
lower alkoxy groups, preferably 5 to 15, and more preferably
to 13 ethylene oxide groups per mol, e.g., 11.
The builder for the synthetic organic detergent,
which helps to improve the washing action of the detergent,
is either a water soluble or a water insoluble builder or
a mixture thereof. Of course, mixtures of water soluble
builders may also be utilized, e.g., polyphosphate and NTA
(nitrilotriacetic acid salt, normally the sodium salt), but
of the water insoluble builders usually only the zeoliteswill
be present, although mixtures of such zeolites may also be
found to be advantageous. While zeolites are useful com-
ponents of the present compositions, generally it will be
preferable to employ water soluble builder(s), and often
such will be the only builder(s) present.
The water soluble builder or mixture thereof
employed may be one or more of the conventional materials
that have been used as builders or suggested for such purposeO
These include inorganic and organic builders, and mixtures
~2~3~
..
thereof. Among the inorganic builders those of pre~erence are
the various phosphates, preferably polyphosphates, e.g., tri-
polyphosphates and pyrophosphates, such as pentasodium tripoly-
phosphate and tetrasodium pyrophosphate. Trisodium nitrilotri-
acetate (NTA), prefera~ly em.ployed as the monohydrate, and othernitrilotriacetates, such as disodium nitrilotriacetate, are
preferred organic builders. The d~ignation NTA, which normally
; stands for nitrilotriacetic acid, in this specification is
employed to also refer to the various salts thereof, prefer~
ably the alkali metal salts and most preferably the trisodium
salt. Sodium tripolyphosphate, sodium pyrophosphate and
NTA may be utili~ed in hydrated forms, which are often
preferred, but anhydrous forms may also be used. Of course,
carbonates, such as sodium car~onate, are useful builders
and may desixably be employed, alone or in conjunction
with bicarbonates, sucll as sodium bicarbonate. ~hen the
polyphosphates are emplo~ed it may be preferr~d to have sodium
pyrophosphate presellt with scdium tr-polypl;osphate in propor-
tion from 1:10 to ln:l, preferably 1:5 to 5:1 with respect to
it, with the total proportion of both builders being about the
same as that mentioned hexein fr~r the sodium tripolyphosphate.
Other water soluhle builders that are considered to be effPc-
tive include the ~arious othex inorganic and organic phosphates,
boxates, e.g., boxax, citrates, glucorlates, E~TA ancl iminodi--
acetate5. Preerably the various builders will be in the formsof their alkali metal salts~ either the sodium or potassium
salts, or a mixture thereof, ~ut socium salts are normally
12~33~
more preferred. In same instances, as when ne~tral or
slightly acidic detergent compositions are being produced,
acid forms of the builders, especlally of the organic builders,
may be preferable but normally the salts will either be
S neutral or basic in nature. The silicates, preferably
sodi~-m silicate of Na20:SiO2 ratio ~7ithin the range of 1:1.6
to 1:3.0, preferably 1:2 to 1:2.8, e.g., 1:2.35 or 1:2.4,
also serve as builder salts but because of their strong
binding properties and because they could promote objection-
able adherence of detergent particles to dispenser wallsthey are considered to be special cases of builders, and
relatively small proportions thereof wilI be present (such
proportions will be described separately from the other
builders). When it is desired for greater proportions of
; 15 silicate to be in the detergent composition it may be prefer-
able for hydrated sodium silicate particles to be post-added
to spray dried particles containing other builder(s~.
The water insoluble builders, as that term is
employed in the present specification, are those which help
to improve the detergency of synthetic organic detergents,
especially that of synthetic anionic organic detergents, and
in such cases the mechanism for increasing deter~ency appears
to be related to water softening effects of the builder,
such as calcium and/or magnesium ion removal from the wash
water, usually by an ion exchange mechanism. While it is
lZ~ 3~ ~
. . :
within the invention to utilize water insoluble build~rs
other than the zeolites, as a practical matter, at the
present timeS the zeolites are the principal such insoluble
builders that are used.
The zeolites employed include crystalline,
amorphous and mixed crystalline-amorphous zeo;ites, of both
natural and synthetic origins. Pre~erably, such materials
are capable of reacting sufficientl~ rapidly with calcium
ions so that, alone or in conjunction with other water
softening compounds in the detergent, they soften the wash
water before adverse reactions of such ions with other
components of the ~ynthetic organic detergent composition
occur~ The zeolites employed may be characterized as having
a high exchange capacity for calcium iOIl, which is normally
from about 200 to 400 or more milligram equ~valenLs of
calcium carbonate hardness per gram of the aluminosilicate,
preferably 250 to 350 mg. eq./g.
Although otner ion exchanging zeolites m2y also be
utiliæed, normally the ~inely divi~ed synthetic zeolite
builder particles employed in the practice of this invention
will be of the formula
(Na2O)x'~Al~33y (Si2)z 2
wherein x is 1, y is fxom 0.8 to 1.2t preferably about 1, z
. ~Z~3~
is from 1.5 to 3~5, preferably 2 to 3 or about 2, and w is
from 0 to 9, preferably 2.5 to 6. The zeolite should be a
univalent cation-exchanging zeolite, i.e., it should be an
aluminosilicate of a uni~alent cation such as sodium or
potassium.
Crystalline types of zeoli~es utilizable as good
ion exchangers in the invention, at least in ~art, include
zeolites of the following crystal structure groups- A, X, Y,
L, mordenite and erionite, o~ which types A, X and Y are
preferred. Mixtures of such molecular sieve type zeolites
can also be useful, especially when type A zeolite i~
present. These crystalline types of zeolites are well known
in the art and have been described in many patents in
recent years for use as detergent composition builders.
Crystalline z~oli~es of ion exchanging and water
softening properties that are preferred are those which are
in hydrated or water loaded form, containing bound water in
an amount from ahout 41 up to about 36% of the z~lite total
weight, depending on the type of zeolit~ used, and are
.. .
~D
~2~ 3~
preferably hydrated to about 15 to 70% of their capacities.
Normally, water contents are in the range of about 5 to 30~,
preferably about 10 or 15 to 25%, such as 17 to 22%, e.g.,
20%.
Preferably the zeolite should be in a finely
divided state, with the ultimate particle diameters being
up to 20 microns, e.g., 0.005 or 0.01 to 20 microns, more
preferably being from 0.01 to 15 microns, e.g., 3 to 12
microns, and especially preferably being of 0.01 to 8
microns mean particle size, e.g., 3 to 7 microns, if cry-
stalline, and 0.01 to 0.1 mi~ron, e.g., 0.01 to 0.05 micron,
if amorphous. Although the ultimate particie sizes are much
lower, usually the zeolite particles will be of sizes within
the range of No's. lO0 to 400 sieves, preferably 140 to
325. However, they may sometimes be agglomerated, separ-
ately with spray dried detergent composition particles, to
sizes like those of the particles, for example, +10 or 25%.
Although sodium sulfate and sodium chlroide and
other filler salts possess no building properties they are
sometimes utilized in detergent compositions for filling
characteristics, and sodium sulfate is especially useful as
a processing aid. In addition to increasing the volume and
weight of the product to facilitate measuring, they also
sometimes improve bead stabilities and physical properties
of the detergent composition beads in which they are incor-
porated. Nevertheless, because the present compositions are
satisfactory without any fillers being present r such are often
preferably avoided entirely or any proportion thereof present
may be minimized.
The softening clay that is an important component
``~. '
34~
of the present detergent compositions is of the type char-
acterized as "bentonite". Bentonites are colloidal clays
(aluminum silicates) contain:ing montmorillonite. They are
of varying compositions and are obtainable from natural
deposits in many countries, including Italy, Spain, U.S.S.R.,
Canada and the United States (principally Wyoming, Mississi-
ppi and Texas). The bentonites which are useful in accord-
ance with the present invention are those which have "lub-
ricating" and dispersing properties, which are associated
with swelling capacity in water. Although some bentonites,
principally those which may be characterized as calcium
(or magnesium) bentonites, have low or negligible swelling
capacities, these may be converted or "activated" so as to
increase such swelling capacity. Such conversion may be
effected by appropriate treatment with alkaline material,
preferably aqueous sodium carbonate solution, in a manner
known in the art, to insert sodium (or potassium) into
the clay structure. In addition to improving the swelling
capacity of the bentonite, which benefits fabric softening
and dispensing capabilities thereof, the sodium carbonate
solution treatment of the non-swelling clay or poorly flowing
clay replaces, for example, 5 to 100%, 10 to 90% or 15 to
50~ of the divalent metal content thereof, with sodium,
~':
~z~
:
and thereby improves the exchange capacity of th~ clay for
water hardness ions, such as those of calcium and magnesium.
The resulting byproducts, calcium carbonate and magnesium
carbonate, are left with the bentonite, and appear to have
desirable adjuvant properties in the final products.
Although ion exchange capacities of bentonites
have been mentioned in the patent liierature as being
relevant to softening capacity, it is a feature of the
present invention that good textile softening is obtainable
with sodium bentonites of comparatively low ion exchange
capacities. Whether the swelling bentonite (also called
sodium bentonite herein) is a naturally occurring clay or
is obtained by alkali treatment of a non-swelling or poorly
swelling bentonîte, it may ~e used in the present textil~
softening detergent compositions. Treated Italian bentonites
have been found to be especially u~eful and are considered
most appropriate for products intended for European markets~
For American markets W~o~ning bentonite is often preferable
and such does not have to ~e treated because it already
contains sodium ion in the bentonite structure and has
swelling properties. Analysi~ of a typical Italian bentonite
(after alkali treatment) shows that it may contain 66.2% of
SiO2, 17.9% of ~12O3, 2.~0% of MgO, 2.43~ of Na2O, 1.26~ of
Fe2O3, 1.15~ of Ca~, 0.14% of TiO2 and 0.13% of X7OO A
typical Wyoming or western bentonite (untreated) may contain
~Z~ 93~
from 64.8 to 73.0% of sio2, 14 to 1~ of A12O3, 1.6 ~o
2.7% of MyO, 0.8 to 2.8% of Na2O, 2.3 to 3.4% of Fe2O3, 1.3
to 3.1% of CaO and 0.4 to 7.0% of K2O. Thus, it is seen
that the compositions of the bentonites are quite different
although both types have swelling properties. It is consider-
ed that if ~he Na2O content of the clay is at least about
0.5%, preferably at least 1% and more preferably at least 2
(the equivalent proportion of ~2 may also be taken into
account) the clay will be satisfactorily swelling for the
purposes of the present i~vention, with satisfactory soften-
ing and dispersing properties in aqueous suspension. While
it is e~pected that proportions of the various constituents
of the swelling bentonites (which may herein be referred to
as sodium bentonites, whether natural or "activated")
within the ranges between the typical analyses given will
result in useful components of the present compositions, it
is also considered that the percentages of the components of
the natural swelling bentonite may be raised or lowered
about 10% and that the typical analysi~ of the treated
bentonite may be expanded 10%, with the bentonites within
those ranges still being useful. Add.itionally, other swelling
bentonites may be substituted, at least in part. Generally
the useful bentonite.s will ha~e swelling capacities of at least
1 or 2 milliliters per gram, more pre~erably at least 5 or 10
ml./g. Of course, higher swellin~ capacity bentonites will
also he useful. I~ormally tlle range of swelling capacities
,~
12~33~
will be from 5 to 30 ml./g. and fre~uently wili be in the 5
to 20 ml./g. range.
The sodium bentonite or swelling bentonite will
normally be agglomerated before being blended with spray
dried built detergent beads and any other adjuvants to be
post-added. Such agglomeration will be carried out in known
manner, as by utili~ing moisture spray application to tumbling
bentonite powder, extrusion, compact~on, pan agglomeration
or other technique. However, it is highly desirable that
the bentonite be in finely divided powder form before agglom-
eration so that when the a~glomerate breaks up in the wash
water the particles of bentonite will be small enough to be
effective lubricants, as deposited on the laundry. Thus, it
will normally be desirable for essentially all of the
bentonite powder, before a~glomeration, to pass through a
No. 100 sieve (U.S. Sieve Series), with at least 99% passing
such a sieve and with over a major proportion thexeof passing
through a No. 2C0 sieve, prefexably with less than about 30%
by weight of the particles failing to pass through such a
sleve and more preferably with n~ more than 20~ restin~ on
such sieve.
~ lso important to promote ready break-llps of
bentonite aggIomerates and dispersion in the wash water, so
that the minute particl~s thereo~ ma~ be adhered to textile
fibers to soften them,i.s the moisture content of the bentonite.
~2~ 93~
Although it is desirable to limit the free moisture content
of the bentonite utilized to about 10% or so, with moisture
contents above 15% not normally being employed, it is even
more important to make certain that the bentonite includes
enough free moisture, most of which is considered to be
present between adjacent plates of the bentonite, to facil-
itate quick disintegration of the bentonite and any adjacent
materials in the particles when such particles or detergent
compositions containing them are brought into contact with
water, such as wash water. It has been found that at least
about 2%, preferably at least 3% and more preferably, about
4% or more of water should be present in the bentonite (so-
called "internal" moisture), and that the bentonite should
not be dried so that less than such percentages of water are
even temporarily present in it. In other words, overdrying
to the point where the bentonite loses its internal moisture
can significantly diminish the utility of the present compos-
itions. When the bentonite moisture content is too low
the bentonite does not aid in satisfactorily swelling and
disintegrating the agglomerated beads in the wash water.
Preferred swelling bentonites of the types described
above are sold under the trade marks Laviosa and Winkelmann,
e.g., Laviosa AGB andWinkelmannG 13, both of which are
treated Italian bentonites, and Mineral Colloid No. 101 (and
other similar designations) corresponding to Thixo-Gels No's.
1,
--16--
.
,~
~Z~ 34
.
.
2, 3 and 4 (market2d by-Benton Clay Company, an a~filiate of
Georgia ~Caolin Co.). As will be described later, the treated
bentonites .~ill al50 preferably be ree of grit and will
preferably have been further processed by grinding to a fine
powder before agglomeration. Usually the commercial bentonite
used will have a pH in water ~at 6% concentration) in the
rang~ of 8 to 9.~, a maximum free moisture content of about
~, a spe~ific gravity of about 2.6 and a viscosity, at 10%
concentration in water, within the range of 5 to 30 centipoises,
preferably 10 to 30 cp.
Tl~e siliconate, which is employed in con~unction
with the bentonite, preferably to coat it, and also can be
used to coat the detergent composition partlcles, and which
acts to inhibit sticking of the b~ntonite and the detergent
to charging compartment walls of an automatic washing machine
~and to walls of other "containers" ~or the product), is one
which may be easily applied to the bentonite and which can
at least partially coat the particles thereof and inhibit
their adhesion to walls of ~ compa~tent in which they may
be stored temporarily, even when such walls are damp or wet.
The siliconate is a salt of siliconic acid, preferably an
alkali metal salt thereof, and the siliconic acid is prefer-
ably a lower alkyl siliconic acid. While it is desirable
that the salt-~orming metal or other cation be one which
will produce a water soluble siliconate, so that it may be
l7
~2~ 3~
applied to the bentonite in aqueous solution, such may not
be necessary and it is contemplated that water dispersible
siliconates ~lill also be utilized. Furthermore, it is
within the invention to employ lipophilic siliconates, which
may be applied in organic solvent solution or in aqueous
or~anic solvent solution, or in corresponding emulsions or
dipersions. The alkali metal of the siliconate is prefèr-
ably either sodium or potassium, but other salt-formin~
cations may also be utilized providing that the siliconate
is suitable for the present purposes. It is contemplated
that other alkali metal salts of ~iliconic acids than the
lower alkyl siliconates may be utilized, including both
aliphatic and aromatic siliconates, but the ]ower alkyl
siliconates, wherein the lower alkyl is of 1 to 3 or 4
carbon atoms, e.g., potassium methyl siliconate and sodium
propyl siliconate, are considered to be preferred. Instead of
employing the siliconate an equivalent charge of the corres-
ponding siliconic acid and a corresponding base may be
utilized.
For most effective results it is much preferred to
employ the lowcr alkyl siliconates previously describcd but it
is reco~nized that such compounds may polymerize, at least
partially, to siliconiC or other film-formin~ and Eoam-
inllibitin~ compounds or polymers and accordin~ly it i.5
within the broader bounds of this invention to utilize such
~l2~3~
.
,
"derivative" materials dire~tly, at least in part, as a
component of the present detergent compositions. When such
a derivative of the siliconate is employed it will be one
which aids in improving the dispensing of the bentonite
beads or detergent composition particles from a charging
compartment of an automatic washing machine, such as a
compartment wherein the parkiculate contents are washed out
by the flow of water into the washing tub of the machine.
Although the operation of the present invention
o should not be considered to be limited by the mechanism to ,
be described, it may well be that the water soluble alkali
metal ~ower alkyl siliconates (w,hich may also be described
as alkali metal lower alkyl silanolates), may be conver~ed
to polymethyl siloxanes, as by the action of atmospheric
carbon dioxids or other acidic acting material, which could
also result in ~he production of alkali metal carbonate,
such as sodium carbonate, a useful builder salt. The
polymethyl siloxanes are known to be hydrophobic and it is
possible that their presence is the cause of the improved
properties of the coa1,ed hentonite (or other detergent
particles) with respect to being of improved dispen~,ing
properties from the charging compartment of an automatic
washing machine. The production of siloxanes by the described
reaction has been mentioned in the text Chemis~ry and Technology
of Silicones, by Walter Noll, published by Academic Press
in 1968. ~lowever, although silicones have been included in
detergent compositic,ns in the past, often for their anti-
~:r~$~3~
foaming properties, no disclosure of the use of watersoluble siliconates to coat bentonite and detergent
particles to promote free release from damp surfaces of
charging compartments, as in the present invention, is
known and such process and the resulting compositions are
considered to be unobvious from the prior art.
The water soluble soap, which is a desirable
component of the present detergent compositions and which
has a useful foam limiting action in the wash water, which
is especially advantageous for side loading or horizontal
tub washing machines, is normally a higher fatty acid
soap of alkali metal, such as sodium or potassium, with
sodium soaps being highly preferred. Such soaps may be
made from natural fats and oils, such as those from animal
fats and greases and from vegetable and seed oils, for
example, tallow, hydrogenated tallow, coconut oil, palm
kernel oil, and corresponding "natural'i and synthetic
fatty acids, and that they are normally of lO to 24 carbon
atorns, preferably 14 to 18 carbon atoms. Preferably such
soaps are of hydrogenated tallow or hydrogenated tallow
fatty acids, e.g., stearic acid. The water soluble soap
will preferably be chosen so as to have a desirable balance
of good detergent properties, effective foam reducing
effect and other good physical properties. Specifically,
among those other physical properties will be desirable
hardness, good binding effect and limited tendency to
produce adhesive gels under use conditions. It has been
found that the sodium hydrogenated tallow soaps satisfy
these conditions best but even compositions containing
them are desirably also treated with siliconate to further
-20-
.
~Z~ 3~
inhibit adhesion to damp compartment walls. Of course,
for compositions wherein foaming is desirable the soap
content is lowered, the soap is omitted or a lower fatty
acid soap, e.g., sodium laurate, may be used instead.
Bleaching agents do not have to be incorporated
in all of the detergent compositions of this invention
but for best cleaning and whitening of laundry it is often
preferable that a bleach be employed. When the wash water
temperature in the automatic washing machine is high
enough sodium perborate is the bleaching agent of choice
because the elevated temperature, especially when it is
above 80C. (and it may be almost up to the boiling point,
e.g., 90 or 95C.) can cause decomposition of the perborate
and release of bleaching oxygen from it. Thus, under such
conditions the sodium perborate, which is often referrred
to as sodium perborate tetrahydrate or sodium borate
perhydrate, and which will usually have an active oxygen
content of at least about 10%, releases such oxygen without
the need for employment of an activating agent or decompos-
ition catalyst. When lower temperature laundering isundertaken, either in cold water or hot water, for example,
at temperatures from 20C. to 60C, the sodium perborate
will not usually sufficiently decompose to satisfactorily
bleach textiles
-21-
;,
93~
.' ' ': .
.
being washed and in such circumstances an activator will be
employed or another suitable bleaching agent will be used, also
usually with an activator. Many such systems have been
described i~ the literature, most of which belong to the
class of peroxygen compounds, such as persulfuric acid,
peracetic acid, performic acid, perphthalic and perbenzoic
acid, and salts thereof, such as the al~ali metal and alkaline
earth metal salts, e.g., sod.ium and magnesium salts. Various
activators for such compositions are known which promote the
controlled release of oxygen from them in hot and cold water
systems, includ~d among which activators are heavy metal
salts, such as copper salts, and various inorganic and organic
compounds, which have ~een described in the art. Among
the l~wer temperature bleaches that which is preferred is
magnesium dimonoperoxyphthalate. Of course, various other
oxygen releasing bleaching materials, such as the hydro-
peroxides, may be employed and in the proper circumstances
chlorine releasing bleaclling materials can ~e incorporated
ln the present detergent compositions.
Various adiuvants may be present in the crutcher
mix from which bas~ beads or detergent compositions ma~ be
spray dried, or such adjuvants may be post-added, with the
decision as to the mode of addition often being determlned
by the physical properties of the adjuvant, its resistance
to heat,`its resistance ~o degradation in the aqueous crutch-
er medium, and its vola~ility. Among the adjuvants often
~2~$~33~
employed are enzyme powders, which normally are post-
added to the base beads because they are heat sensitive.
These may be any of a variety of commercially available
products, included among which are Alcalase*, manufactured
by Novo Industri, A/S, and Maxatase*, both of which are
alkaline proteases (subtilisin). Among specific enzyme
preparations that may be employed are Novo Alcalase 2M*
(2 Anson units per gram) and Maxatase P 440,000. Although
the alkaline proteases are most frequently employed, amyl-
olytic enzymes, suchas alpha-amylase~ may also be utilized.
The mentioned compositions usually contain active enzymes
; in combination with an inert powered vehicle, such as
sodium or calcium sulfate, and the proportion of active
enzyme may vary widely, usually being from 2 to 80% of
the commerical preparation. In this specification pro-
portions referred to are of the enzyme preparations, not
the active part thereof.
Among the fluorescent brighteners those most
commonly employed are the stilbene brighteners, e.g.,
Tinopal 5 BM*, especially in extra concentrated form.
Among the stilbene compounds are cotton brighteners, such
as those sometimes referred to as CC/DAS brighteners,
derived from the reaction product of cyanuric chloride
and the disodium salt of diaminostilbene disulfonic acid,
including variations thereof with respect to substituents
on the triazine and aromatic rings. This class of bright-
eners is known in the detergent art and will most often be
used when bleaching components are not
* trade mark
present in the final product. When it i5 desired for the
detergent composition to include a bleach, such as sodium
perborate or other oxidiæing bleach, bleach stable brighteners
may be incorporated in the cru~cher mix. Among these there
may be mentioned the benzidine sulfone disulfonic acids,
naphthotriazolyl stilbene sulfonic acids and benzimidazolyl
derivatives. Polyamide brighteners, which also may be
present, in~lude aminocoumarin or diphenyl pyrazoline deriva-
tives, and polyester brighteners, which can also be used,
include naphthotriazolyi stilbenes~ Such brighteners 2re
normally used as their soluble salts, e.g., sodium salts, but
they may be charged as the corresponding acids. The cotto~
brighteners will usually comprise major proportions of the
brightener system3 employed~
When it is desired that ~he product made he entirely
or partially colored,various suitable dyes and dispersible
pigments may be employed. When blue dyes, such as Acilan
blue, or pigments, such as ultramarine blue, axe utilized
they may have a dual eEfects of serving to color some or all
of the deteryent composition particles, or particles of
components of the deteryen~ composition, and helping to give
the washed laundry a desirable bluish 1int. Coloring of
agglomerated bentonite particl~s by s~itable dyes or pigments
m~y be especially d~sirable because natural bentonite sometimes
may ~e off-color, 50 that the agglomerates may be conver~ed
_ ~_
:~L2~?3~
from particles that look dirty to those which are of
attractive color and appearance.
Perfumes employed, which are usually heat
sensiiive andmay contain volatiles, including a solvent,
such as alcohol or a suitable glycol, polyol or hydro-
carbon, are normally of synthetic perfumery materials,
sometimes mixed with natural components, and generally
will include alcohols, aldehydes, terpenes, fi~atives
and/or other normal perfume components, known in the art.
In addition to the adjuvants mentioned there
may also be present flow promoting agents, anti-setting
materials employed to prevent premature gelation of the
crutcher mix, dispersion aids, anti-redeposition agents and,
in some cases, additional softening agents, e.g., cationic
softeners such as the quaternary ammonium halides, e.g.,
dimethyldioctadecyl ammonium chloride. However, as was
indicated previously, normally the cationic softening
agents will not be employed and if used, they will be
post-added.
Of course, water is present in the crutcher from
which the spray dried component of the present composition
is made, wherein it serves as a medium for dissolving or
dispering the various components of the spray dr~ed beads.
Therefore, some water, in both free and hydrate forms, is
in the product. Similarly, water may be employed to agglom-
erate the bentonite and perborate powers and dissolve the
siliconate.
~25
~l2~3~
.
. . . . . .
- .
While it may be preferred to employ deioniæed water, 50 that
the hardness ion contents thexeof may be very low and so
that metallic ions that can promote decomposition of any
organic materials which may be present will be minimized,
city or tap water may be utilized instead and sometimes, ~or
economic or supply reasons, will be used exclusively.
Normally the hardness content of such water will be no
greater tilan about 300 parts per milli~n~ a5 calcium
carbonate.
The proportions of the various components in the
final product of this invention will be such as to result in
their being effective as a fabric softening detergent, free
flowing and of improved di~pensability from a charging
compartment of an automatic washing machine by action of
wash water passing through such compartment. The proportion o~
anionic detergent will ncrmally be from 3 to 10% o the
final product, preferably 3 to 7~ and more preferably 4 to
6%, e.g., 5~ Usually the nonionic detergent content will
be from 1 to 5~, preferabiy 2 to 4%, eOg., 3 or 4%. In those
instances when nonionic detergent is not being employed the
proportion of anionic detersent may be increased by as much
as 5~ and in cases in which the anlonic detergent is omitted
the nonionic detergent cont~nt may be increased by up to
10%, providing that the detergent compo.sition remains satisfac-
torily dispensable. While it is possible for effectivedetergent compositions to be made without either the anionic
~6
_ ~ ~ .
~2~ 39~
or nonionic detergent, such products will not be as useful
as preferred compositions of this invention. The builder
content will generally be in the range of 20 to 75%, pre-
ferably 30 to 50% (and such is often preferably entirely
water soluble builder salt) and more preferably 30 to 40%,
e.g., about 35%. As was previously indicated, sodium
tripolyphosphate and NTA are preferred water soluble
builders, which may be the sole builders employed. When
they are utilized in mixture the mixture will pre~erably
contain from 10 to 90% of one of them, with the balance
being the other such builder, and within such ranges
preferred proportions may be 20 to 80% and 40 to 60%, and
complementing percentages. Similar ranges of percentages
are applicable when the builder is a mixture o~ water sol-
uble builder salt and water insoluble builder, such as a
zeolite.
The bentonite content of the textile softening
detergent, preferably in the form of a siliconate coated
agglomerate of more finely divided ~entonitepowderparticles,
will be a satisfactorily softening proportion thereof, which
usually will be within the range of 5 to 25%, preferably lO
to 20%, more pr~ferably 14 to 18%, e.g., about 16%.
The siliconate used will be employed in a pro-
portion sufficient to have the desired dispensing assisting
effect and such proportion will normally be from 0.05 to
1%, preferably 0.15 to 1%, although up to 3% can be employed.
A preferred range of proportions of the siliconate is from
0.1 or 0.15 to 0.3 or 0.4%, for examples, 0.15~ or 0.3%.
When the siliconate is used to cover agglomerated bentonite
only, on a coated bentonite agglomerate basis the siliconate
-27-
~l2~$~3~
content will usually be at least 0.15~, often 0.15 to 5%,
preferably 0.15 to 1% and more preferably 0.15 to 0.5%,
e.g., 0.4%.
When a fatty acid soap is present the proportion
thereof will usually be no greater than 10%. A preferred
range of soap contents is from 2 to 6%, more preferably
from 2 to 4%, e.g., 3%. When a bleaching agent is present
the proportion thereGf will usually be within the range of
5 to 35%, preferably 15 to 25%, e.g., 20%. However, it
will be kept in mind that such proportions are based on
employ~ent of sodium perborate and will be modified when
other oxidizing agents are utilized, so as to have approx-
imately the same bleaching effect (or active oxygen
content). The moisture content of the product~ which does
not include hydrate moisture which is not removable during
standard heating at 105C. for two hours, will usually
be within the range of 3 to 20~, with the higher percentages
thereof being permissible when a substantial proportion, at
least 1/4 and preferably at least 1/2 of the moisture is
in hydrate form. A preferred moisture content is from 5
to 17~ and the more preferred such content is from 10 to
15%. Any moisture not removable by the standard test
mentioned above is considered to be a part of the compound
in which it is present as a hydrate, eOg., a zeolite.
The total proportion of various adjuvants which
may also be present in the detergent composition will
usually be no more than 20~, preferably being limited to
15% and
~2~$~3~
more preferably to 10~. Although water soluble sodium
silic~e has building properties, especia1ly with respect to
its action against magnesium ions in hard wa';er, because it
also acts a~ a binder the proportion thereof present will
not be limited by the ~uilder content proportions previously
~3iven and will be considered herein with othe~ adjuvants for
the ~esent compositions. Usually it will constitute no
mol-e ~l~an 8~ of the product, with a normal range oL 1 to 5%,
prefera~ly 2 to 4P6, e.cJ., 3~. The content of filler salt,
such as sodium sulfate, when it ls present, will also normal-
ly be limited, to no more than 10%, and will normally constitute
from 0.5 to 5~, pre~erably 0.5 to 2~, e.g., 1 or 1.5~ of the
product. The perc-r~age of proteolytlc enzym~ u~d will
normally he from 0.1 to 2~" preferably 0.~ to 1~, e.g., 0.3~,
and the percenta~e of optical brightener dye will b~ from
0.1 to 2~, preferably 0.1 to 0.5%, e.g., about 0.2%. Perfumc
content will normally be from 0.05 to 2~, preferably 0.]
to 13, and more preferably 0.2 to 0.5~, e.g., about 0.3%.
Among other adjuvants it may sometimes be deslrable to have
pre5ent small proportion~ of particular sequestexing agents
and flow promoters. Among such materials a preferred sequestrant '
is diethylenetriamine pentaacetic acid, magnesium salt (magnesium
DTPA) but other diethylenetriamine acetates may be substituted for
it. Magnesium silicate is a preferred flow promoter, which also
may serve a5 a carrier fo- thc sequestrant. Commercially, a
~.q
_ ~ ~
~2~
mixture of such products is available comprising 15% of the
magnesium DTPA and 85% of MgSiO3 and when such is employed the
proportion thereof is preferably from 0.1 to 1%, more preferably
0.1 to 0.5%, e.g., 0.2%. Proportions of the sequestrant (or
stabilizer) may be from 0.01 to 0.2%, preferably 0.02 to 0.1%,
and for the MgSiO3 concentrations are in the range o~ 0.1 to
0.9%, preferably 0.2 to 0.5%. Amounts of other adjuvants
employed will be such as to accomplish the purpose for which the
adjuvant is included in the detergent composition but normally
such proportions will not be in excess of 1 or 2% and generally
will be within the range of 0.05 to 1%.
In addition to the detergent composition containing
synthetic organic detergent, builder, bentonite and siliconate,
with soap, bleach and adjuvants often also being present, also
within the present invention are siliconate-treated bentonite,
siliconate-treated perborate and siliconate-treated enzyme.
These aspects of the invention have been made the subject of a
divisional application. For the siliconate-treated bentonite
the siliconate content will be from 0.2 to 10%, preferably 0.5
to 5% and more preferably 1 to 3%. For the corresponding deter-
gent composition without bentonite and for the enzyme and perbor-
ate the proportions of siliconate will be the same as those for
the final detergent composition but such proportions may be in-
creased from 10 to 100%, depending on conditions and the propor-
tions of the various ad~uvants in the detergent composition.
_ ~ _
~2~3~
.
To make the products of this invention known spray
drying, agglomerating and mixing techniques (preferably all
three) may be employed. Because such are not considered to
be significant features of the invention they will be refer-
red to only briefly herein. In the spray drying operation acrutcher mix containing various components desired to be
present in the spray dried bead and sufficiently stable to
withstand the crutching and spray drying operations, such as
de~ergent, builder and suitable adjuvants, is spray dried
from an aqueous crutcher mix, which normally will contain
from about 40 to about 70 or 75% of solids, preferahly So to
- 65~ thereof, with the balance being ~Jater. The crutcher mix
may contain the anionic detergent and a portion o all of the
nonionic detergent, although usually no more than 5% of
nonionic detergent (on the basis of the final product) will
be in ~he crutcher (the rest, if any, being post-added).
All of the builder or mixture of builders will normally be
added in the crutcher, although this is not necessary. The
bentoni~e is preferably separately agglomerated and is
post-added to the spray dried product but sometimes it may
be incorporated in the crutcher mix. Aqueous silicate
solution, stable fluorescent brightenin~ dye, soap and
fil]er salt are usuai]y added in the crutcher, toyether with
any stable pigment and other colorants that may be employed.
Instead of charging a neutralized detergent ~he crutcher may
~31
J1 2~3~ -
be utili ed as a neutralizing vessel, in which anionic
organic deter~ent acid i~ neutralized with aqueous caustic.
Such acid, for e~:ample, may be dodecylbenzene sulfonic acid
containing about 45 to $0% of active ingredient, which may be
neutralized with an aqueous sodium hydroxide solution, SUCII
a~ one containing 33~ Na2O. If the alkylbenzene is sulfonated
with sulfur trioxide the active ingredient content of the acid
may be as higll as 99~. A higher fatty acid mixture may also be
neutralized in the crutcher with the detergent ~cid to produce
a desired higher fatty acid soap-detergent mixture.
The crutcher mix may be spray dried in a conventional
spray tower, utllizing either concurrent or countercurrent
flow. Normally the mi~ will be at a temperature in the 20
to 80C. range, p-eferably 40 to 70C. and will be s~ray
dried in a tower in which the drying air is at a temperature
of 200 to 400C., to produce ~pray dried beads of particle
sizes in the range of No's. 10 to 100 (U.S. Sieve Series)
sieves. Any particles that are outside the desired range may
be removed by screening and may be reprocessed. The beads
made have a bulk densi.ty in the range of 0.3 to 0.6 g./ml.,
e.g., 0.5 g./ml. They are of a moisture content in a range
which may be as broad as about 3 to 20% but normally will be
about 10 to 15~.
After pro~uction ~f the spray dried portion of
the compositions other components thereof may be mixed with
the beads or sprayed onto them (and onto other components of
~2~3~
the product, when desired). Generally it will be preferred
for the bentonite, enæyme, bleach, and any other particu-
late products, such as those in powder, agglomerate or
prill form(eXCePt ~he siliconate), which are intended to
be post-ad~ed to the spray dried beads, to be mixed with
them, after which any liquids (including siliconate in
solution) to be post~added may be sprayed onto the mixture.
However, orders of post-addition of components may be
varied and sometimes part of the particulate material may
be post-add~d after ane or more of the liquids. Two or
more of the particulate materials may be pre-mixed before
post-addition and similarly, mixtures of liquids may also
be made.
Solvents may be employed for various components
to be applied as liquids and in some cases emulsions may
be employed. Thus, while the siliconate is preferably
applied in solution form, in water, if a less soluble
siliconate is employed it may be applied as an aqueous
emulsion. In some instances it may be desirable to utilize
the siliconate in an aqueous emulsion with perfume and/or
nonionic detergent. However, it is much preferred first
to coat the unperfumed detergent composition with an
aqueous siliconate solution spray and subsequently to
spray perfume onto the "siliconated" product. In some
instances it may be desirable to extend the perfume with
a suitable solvent, such as a comparatively ordorless
alkylate (hydrocarbon). Instead of spraying the silicon-
ate onto the mixture
-33-
~ '.3~3~
of spray dried (or otherwise manufactured to similar product
characteristics) detergent beads, bentonite agglomerate,
enzyme prills or agglomerates, and perborate particles in
mixture, the siliconate may be applied to such individual
components separately or in various combinations. Such can
be accomplished with separate sprays of siliconate, in which
case the proportion thereof deposited on the different
components may be readily controllable, or a single siliconatç
spray may be directed onto different feed streams of such
components as they enter a suitable mixer. When nonionic
detergent is post-added ~and it will sometimes be preferred
that all of the nonionic detergent be added in the crutcher
so that the siliconate will be of greatest dispensing
assisting effect) it may be ~prayed onto or otherwise
5atisfactorily applied to the surfaces of the spray dried
beads before admixing with the other particulate components
of the final product and before application of siliconate
spray thereto. ~lso, as previou.sly indicated, the nonionic
detergent, in liquid form, may be mixed with the siliconate
and/or perfume to be sprayed onto the product, in which case
it may act like an emu 3ifier.
The apparatus for effecting the various mixings
and sprayings is known in the art and accordingly will not
be descr1bed in detail herein. Spraying may be through
conventional nozzles, usually of wide spray pattern design,
but other types of spraying equipment may also ~e employed.
The mixers may be of various designs but preferably include
3~
~L2~ 34
revol~ing inclined tubes or drums, inside which spraying may
be effected. ~owever,-V-shaped blenders, especially those
of continuous feed design, and other commercial powder
blenders can also be satisfactory.
The amount of siliconate that will he sprayed onto
the surfaces of tlle various particulate components of the
detergent composition ~ill be such that the final product
includes a dispensiny assisting proportion of the siliconate
(or a derivative thereof). Because it is thought that the
bentonite agglom2rates can to some extent interfere ~.ith
satisfactory dispensing of the particulate deter~ellt ColilpOsi-
tion from the ~eed chamber of an automatic washing machine
(of the "European type"), it may be pref~rable for a greater
proportion of siliconate to be applied to such bentonite
a~glomerate particlcs, e.g., up to 5~, when such is feasible.
In some cases only the bentonite particles will be treated
with the siliconate, in which instances the proportion o
siliconate in the final detergent composition may often be
decreased, e.g., hy as much as 50%. Applications of the
siliconate involve addition of moisture to the composition
being treated, ~lhen the siliconate is in aqueous solution or
emulsion (but not if in non-aqueous solution). Such can
either be desirable 01 not, depending on the ~.oisture content
and the properties of the detergent composition and process-
ing apparatus. ~ccordin~ly, the concentration of siliconate
~l2t~
in the spray liquid may be adjusted. Of course, thegreater the volume of the spray and the greater the
dilution of the siliconate the more uniformly a spray
may be distributed on the particulate material. On the
other hand, if the product is borderline or too high in
moisture concentration a dilute siliconate spray may
exacerhate this condition. Generally the concentration
of siliconate in the liquid will be at least 5%, and
preferably will be at least 10%. Because the siliconate
is completely miscible with water higher concentrations
may be employed, which are usually within the ranges of
5 or 10 to 25 or 50~.
The various mixing and spraying operations will
normally take place at about room temperature but operations
in the range of 10 to 40C., preferably 20 to 30C., are
preferred. The particle sizes of the materials being coated
with siliconate will usually be like those of the final
product, within the No's. 10 to 100 or 200 sieve range (the
perborate and enzyme ranges may extend to No. 200). The
agglomerated bentonite particles will be those resulting
from agglomeration or compaction of more fine~y divided
particles, such as those of which over 50% pass through a
No. 200 sieve. Such particles will be essentially grit-
free and will normally have from 0.05 or 0.15 to 3 or 5% t
preferably 0.1 or 0.15 to 0.5 or 1% of siliconate, such as
potassium methyl siliconate or sodium propyl siliconate,
sprayed onto the surfaces thereof to at least partially
coat such surfaces. They may be colored with a suitable
dye or pigment, such as Acilan Brilliant Blue FFR*, or such
or other suitable colorant ~ay be applied with the siliconate.
* trade mark
-36-
~2~3~
The siliconate does not obscure the color. Sometimes
the bentunite agglomerates may be larger than the other
particles in the product, eOg./ 10 to 50% greater in dia-
meter, to accentuate their difference. In many instances
the bentonite agglomerates will preferably be of sodium
carbonate treated bentonite (such treatment i~proves the
color of off-color clay) and will contain magnesium car-
bonate and/or calcium carbonate therein, resulting from
such treatment. When the particles are only partially
coated with siliconate it is desirable for at least 10%
of the surface area (of the equivalent spheres) to be
covered by the siliconate/ and more preferably a greater
percentage will be covered, e.g., 50%, to facilitate
dispensing. Similar considerations and conditions apply
when the enzyme, bleach and detergent particles are being
treated, with the exception that in such cases a lesser
proportion of siliconate may be employed than that used
for coating bentonite agglomerates.
In the various cases mentioned above the coating
of the solia siliconate will normally be on the outer 1%
of the thicknesses of the particles. For example, for a
particle that is one millimeter in thickness such a sili-
conate coatiny would be about 5 microns thick. Preferably
the coating will be on the outer 0.5% of the particle bead
diameter, more preferably the
-37-
-
f~ 34
outer 0.2% thereof. Of course, when only partial coatincjs
are applied and when great~r percentages of siliconate are ~`
utilized, as when only the bertonite agcJlomerates are coated,
the siliconate thicknesses will be greater, but ~ref~bly less
than 2%. Normally, such thicknesses will be at least 0.05%
of the particle thickness.
The products and processes of this in~ention
possess many advantaqes,several of w~ich have already been
mentio~ed. With respect to the products, the application of
siliconate to par-ticle surfaces, even when the entire particle
is not covercd with the siliconate, improves the dispensirs
characteristics o~ such particle without having any adverse
effects. Thus, detercJent compositions of the types described
herein, and the particulate components of such com~ositions
mentioned, are easier to dispense from a chargin~ compartment
of an automatic washin~ machine of the European type than
are control products untreated with siliconate. This
difference is most pronounced with respect to the ayglomerated
bentonite particles. The tests for comparing such results
are praGtical use tests, employing a variety of different
rna]ces of such European washing machines, with the evaluator
noting the number of particles remaining in the chargin~
compartment after a normal char~in~ and dispensiny operations
or after repeated such operations. To accentuate the dif-
fcrences and make the test more difficult, the walls of thecharc3in~ com~)artment are lirst w~t to promote adherence to
them of the bentonite (and other materials). To simulate
such a test one may sprinkle equal weights of test and
control product onto a wet horizontal surface, allow them to
_ ~ _
~2~ 3~
stand for one or two minutes, and then direct a gcntle spray
of ~ater onto the particles for a measured time, e.g., 30 seconds,
after which the numbers of particles may be colnpared.
By such tests the products of this invention show a mar~ed
5 improvement over the controls; normally one may expect to
obtain less than half the number of particles still adherin~
to the pre-moistened surfaces when the "exp~rimental" product
is used, compared to the control. Often no particles will be
adhering to the pre-moistened surface when at least 0.15~ of
siliconate is used, several particles will be sticking when at
least 0.05% but less than 0.15~ of siliconate is employed, and
an appreciable number of particles will be adhering when
no siliconate is present~
While most of the detercJent will be charged to t}le
washing tub in normal use of the automatic washing machine
so that the reterltioll of some particles in the char~ing
chamber may not initially be more than psychologically
objectionable, with repeated washings greater numbers may be
retained, thereby changing the composition of the fabric
softening detergent and possibly even significantly affecting
the charge wei~ht. Also, the appearance of the char~ing
compartment with particles retained therein is unsatisfactory
and can lead to consumcr re~ection of the product. Because
of the different washinq techniques employed in America,
coating bentonite detergent particles with siliconate may
not be as important there but it is considered that the presence
of the siliconate on the particle will assist in making the
detergent more stablc and more freely flowin~, especially in
,~
` ~LZ~34
.
damp conditions, and wil~ help t", counteract any ~elation of
the bentonite under such conditions.
In addition to promoting dispensing, the siliconate
also has the desirable effect of preventing eY.cessive foaming
of the deter~ent composition in aqueous solution., The
bentonite also helps to limit foaming and the ccmbination is
superior to the individual components. The siliconate also
appcars to have a stabilizing effect on enzymes and bleaches
coated with it and helps to prevent interaction between
perfume components and other detergent constituents, thereby
helping to stabi3i~e the pcrfume. It can also have such an
e~'fect on colorants. Yet, these various advanta~es arc
obtained witllout the disadvantages of the product b~ing
excessively hydrophobic, because it is initiallywater solu~le.
I~ does not interfere with the desired quiclc dissolving and
dispersing of the detergent components and does not appear
to cause an objectionable buildup of hydrophobic deposits on
washed and softened laundry. It does not interfere with the,
particular softening effect of the hydrophilic bentonite and
do~s not interfere with the good detergency of the composition.
The deter~ent compos'tions resulting are excel]ent laundry
; detergents and effectively soften washed laundry, as has
been estab'~ished by comparative tests against similar
compositions containin~ neither bentonite nor siliconate.
The products are 5ati3factorily free flowin~ and of desired
bulk density and appearance. They are also non-dusting, which
may at least in part be at-tributable to the siliconate.
~0
~2~ 34s
Processes in which siliconate solutions or emulsions
are sprayed onto detergent, bentonite and other detergent
component particles are easily carried out and do not require
special equipment. Due to the water solubility of the
5 siliconate it may be applied in aqueous solvent without
adding other components to the detergent formula. Yet, it
can also be emulsified or otherwise distributed with other
detergent components. The processes lend themselves to
modification to allow different concentrations o~ siliconate
10 on different detergent components. The coatin~ materials
do not gel or thicken objectionably, do not block spray
no~zles and do not form gummy deposits in the spraying and
mixing equipment. The siliconate may b~ applied at room
temperature because it does not require heating, as do some
lS other protective coating materials. The siliconate can be
retained principally on the surfaces of the particles,
allowing less to be employed while still producing the J
; desired dispensing assisting effect. Also, apparently due
to the nature of the siliconate or derivative thereof on the
20 detergent or component particle,it is effectlve even when
the particle is not completely covered by it.
The followin~ examples illustrate but do not limit
this invention. Unless otherwise indicated, all parts are
by weight and all temperatures are in C.
4~
~2~
- EXAMPT.E 1
A crutcher mix totalling 3,199.5 kilograms of
material is made by reacting 364 kg. of dodecylbenzene
sulfonic acid (Dobane JNQ [48.8~ active ingredient]) and 167
kg. of hydro~enated fatty acids (16 to 18 carbon atoms per
mol of fatty acid) with 47 kg. of caustic soda (38~ Na2O)
in an aqueous medium containing a suitable proportion 5to
maintain the reaction) of 952 kg. of city water (300 p.p.m.
hardness, as CaCO3). The balance of such water is employed
to cool the rcaction mix, as desirable, and to dilute other
components of the crutcher mix. Subsequently there are
added to the crutcller 2~2 k~. of.aqueous sodium silicate
solution (Na2O:SiO2 - 1:2.4) at a 44.1~ solids concentration,
7.5 k~. of fluorescent stilbene type brightener, 7 ~g. of
Sydex 808 (85~ M~SiO3 and 15% magnesium DTPA)~ 1,252 kg. of
hydrated sodium tripolyphosphate (TPP "Il"), 5~ kg. of anhydrous
sodium sulfate (99.5~8 pure) and 107 k~. of a nonionic detergent,
which may be considered as the condensation product of 11 mols
of ethylene oxide with one mol of hi~her ~atty alcohol
having 12 to 15 carbon ato~.s per mol.
The crutchcr mix is heated for about an hour, with
stirring, so that its temperature rises to about 55C.,
after which it is pl~mped to a spray dryin~ tower where it is
sprayed at elevated pressure throu~h multiple spray nozzles
into dryin~ air at a tempeîat.ure of a~out 300C. From thc
spray dryin~ particles of a moisture content of about 12%
Y~
~Z~ 34
result, most of which are within the No's. 10 to 100
sieve range. Particles outside this range are screened
out.
63.1 Parts of the spray dried powder (bulk
density of about 0.4 g./ml) are then blended with 0.3
part of prilled proteolytic enzyme (Alcalase, of 2 Anson
units per gram, although Maxatase P 440,000 may be sub-
stituted), 20 part of granular sodium perborate and 16
parts of agglomerated bentonite~ All such powders are of
particle sizes within the particle size range for the
spray dried detergent composition component but smaller
particles of the enzyme and perborate may also be employed,
down to about No. 200. The bentonite particles are com-
posed of 82~3 parts of anhydrous bentonite, 16.1 parts
of water, 1.5 parts of sodium silicate (previously des-
cribed) and 0.06 part of Acilan Brilliant Blue dye, with
the dye being appIied to the surface of the particles.
The bentonite particles are made by agglomeration of
more finely divided particles of bentonite (Laviosa AGB)*
with the dilute sodium silicate solution (in the water),
after which they are dyed. The bentonite employed is one
which has been treated with sodium carbonate tG replace
calcium and magnesium therein with sodium (see the pre-
ceding specification for description of this material) and
~rom which a natural content of gritty material (hard
enough to be difficu]t to smash with a hammer) had been
removed, after treatment, by centrifugal separation. The
moisture content of suitable agglomerated bentonite may be
varied and can be as low as 3%, when mixed with other
components of the present softening detergent.
* trade mark
43
~J
~L2~ 93~
Onto the mi~ture of spray dried beads, enzyme,
perborate and colored bentonite particles, in an inclined
drum mixer, there is sprayed a mix of 0.5 part of the non-
ionic detergent, 0.25 part of Rhodorsil Siliconate 51 T
(50% solution of potassium methyl siliconate) and 0.25
part of detergent perfume. The spraying is regulated so
that the liquid sprayed evenly coats the particles in the
mixer or tumbling drum to produce about 100 parts of uni-
form product.
The final product is of particle sizes within
the range of No's. 10 to 60 sieve, a bulk density of about
0.5 g./ml. and a moisture content of about 12% (although
on standing this may be reduced to about 9~). The
particulate fabric softening detergent resulting is free
flowing and attractive in appeaxance, with the somewhat
larger (averaging 20 to 200% greater in diameter) blue
agglomerated bentonite particles contrasting with the
other white particles, and is non-dusting.
The product made is subjected to practical laundry
testing and is found to be an excellent detergent with desir-
able fabric softening properties. When evaluated, it is
noted that it is more readily dispensable, leaving fewer
particles behindin the charging cGmpartment of a European
type automatic washing machine, than a control in which the
siliconate coating :is not present. This is especially
important when the bentonite ~articles are larger, since
they may tend more to adhere to wet chamber walls during
dispensing.
-44-
` : :
~Z~$6:43~ ~
When the above experiment is repeated but with 100
kg. of dodecylbenzene sulfonic acid, 1,324 kg. of TPP"H" and
0.6 part of Rhodorsil Siliconate 51 T being employed instead
of the amounts previously used the product resulting is of
as satisfactory physical properties and functions but addi-
tionally is even more readily automatically dispensable,
leaving no particles behind in the charging compartment of a
European type automatic washing machine.
In modifications of the above example the anionic
detergent is replaced by equal weights, respectively, of
sodium lauryl sulfate, sodium hydroqenated tallow alcohol
sulfate and sodium tallow alcohol polyethoxy (3EtO) sulfate.
Alternatively, mixtures of such materials, e.g., equal parts
of sodium dodecylbenzene sulfonate and sodium-hydrogenated
tallow alcohol sulfate, are employed together. In all such
cases the final detergent composition resulting is one which
is an excellent textile softening laundry detergent. All
such products are also of improved dispensing characteristics,
when tested by the methods previously described. Similar
results are also obtainable when, instead of the anionic
deteryent being varied, the nonionic detergent is changed,
being replaced by a block copolymer of propylene oxide and
ethylene oxi~e, sucll as Pluronic L-44 or L-62, nonyl phenol
polyoxyethylene (12 EtO) glycol or a condensation product of
Cl2_l5 fatty alcohol with 3 or 7 mols of ethylene oxide p~r
mol, or with a mixture of t~o or more of such detergents,
e.g~, in equal parts.
When half or all of the sodium tripolyphosphat~ is
replaced by NTA the final product is also a satisfactory
_ ~_
~2~ 3~
detergent, with softening properties, and is of improved
dispensing properties compared to a control of the same
formula without the siliconate.
When the soap is omitted from theformula dimin-
ished foam control results but otherwise the product is
acceptable and is like those previously described. When
the sodium perborate is replaced by other bleaching agents,
such as sodium persulfate and magnesium dimonoperoxyphthalate,
good bleaching and cleaning by the product is still obtain-
able. When known activators foroxidizing agents arepresent bleaching may be effected by use of the composition
at lower temperatures than those near the boil (which are
normally employed in the processes of this example to
obtain maxi~num bleaching activity). When it is desired
to include more silicate in the product the amount of
silicate is doubled by post-adding similarly sized hydrous
sodium silicate particles with the other post-added part~
iculate solids. When sodium propyl siliconate is substi-
tuted for potassium methyl siliconate comparable products
are obtainable and this is also the case when siliconates
of lesser degrees of water solubility are employed in
replacement of some, e.g., 25%, of the other siliconates.
EXAMPLE 2
The procedures of Example 1 are varied by
applying the siliconate, in aqueous solution (20% solids),
as a finely divided spray (preferably with the spray drop-
lets being "micron sized", e.g., 1 to 50 or 1 to 10 microns
in diameter), or otherwise as satisfactorily small sized
liquid droplets,
-46-
~2~3~
to each of the particulate components to be !lended together
separately before such blending. The various coated particles
are all of bulk densities in the prescribed range (0.3 to
G.6 g./ml., e.g., 0.5 ~./ml.3. Subsequently, the perfume is
similarly sprayed onto the mix. The nonionic detergent is
not post-sprayed but instead, is incorporated in the crutcher
mix. The resulting product is one which is also of improved
dispensing properties. The siliconate coated agylomerated
bentonite, spray dried detergent composition beads (without
bentonite), enzyme and perborate can all be separately
produced and stored, and subsequently are useful for formulat-
ing fabric softening detergents of differen. compositionsand
different desired L~roperties, e.g., coated bentonite plus u;.ccated
spray dricd beads.
XAMPLE 3
.~ softening detergent likc that of the first formula
of Exa~ple 1 is macle from a crutcher mix of 10.2~ parts of
the doAecylbenzene sul~onic acid, 2.81 parts of the hydro~enated
fatty acid, 0.81 part of the caustic soda, 26.5~ parts of water,
37.2 parts of pen~asodium tripolyphosphate (hydrated), 6.8
parts of sodium silic~te 501ution, 0.21 part of fluorescent
bri~ht ner, 1~46 parts of sodium sulfate and 3.0 parts ~f the
nonionic detergent, added sequentially. This is spray dried by
thc metho~ descri~ed in ~xamplc 1 to produce 62.5 parts of a
product of similar bul]c density and particle size. The spray
dried particles are then mlxed with 0.3 p~rt of proteolytic enzyme,
20.0 parts of the soAium perborate granules, 16.0 parts of the
agglomerated bentonite and 0.2 part of Sydex 808, and ont-o the
,~ _
~2~ ?3~
tumbling powder mix there is sprayed a blend of 0.3 part
of the detergent perfume and 0.4 part of C10_13 linear
alkylate, and 0.15 part of potassium methyl siliconate is
sprayed onto the product in suitable liquid state, pre-
ferably dissolved in water (50% concentration). The
product made is of better dispensing properties for dis-
pensing from the charging compartment of an automatic
washing machine in normal use. It exhibits a slightly
greater foaming tendency than the similar products of
Example 1. When 0.3 part of the siliconate is used the
dispensing properties of the detergent composition are
further improved.
When, instead of employing an agglormerated
sodium carbonate-treated Italian bentonite from which
grit has been removed, as in Example 1, a competitive
product (Winkelmann agglomerate) or a Wyoming type ben-
tonite, such as that sold under the trade mark Mineral
Colloid No. 101 (formerly Thi~ogel No. 1) is employed,
similar final products are obtained which are good soft-
ening detergents and are readily dispensed. Also, whenother lower alkyl siliconates, such as sodium propyl
siliconate, are utilized, comparable results are obtainable.
When the Acilan Blue dye, used to color the bentonite
agglomerates, is replaced by ultramarine blue, good color-
ing and bluing effects are also obtained~ Similarly, when
the siliconate is applied only to the agglomerated bentonite,
with the total proportion of siliconate in the product
being the same, or 50% less in some cases, the properties
of the detergent resulting are similar to those previously
described and dispensing is also improved, compared to control.
-48_
~Z~ 3~
EXAMPLE 4
When the proportions of the various components
in the preceding ~xamples are modified +10~, +20% and
+30~, maintaining them within the ranges previously given
and keeping the ratios of anionic detergent to nonionic
detergent within the range of about 1:1 to 3:1, the ratio
of total detergent content to builder content within the
range of about 1:3 to 1:8 and the ratio of sodium bento-
nite to total detergent within the range of about 1:1 to
2O1, products of properties similar to those described in
Example 1 are obtained. Such is also the case when the
water soluble builder salt(s) of Example 1 are replaced
with zeolite A (20% hydrated) and when any of a variety of
synthetic anionic and nonionic detergents is employed in
mixture, optionally with an amphoteric detergent, such as
one of the Miranol type. Also, the invention may be used
to improve the dispensing properties of various other
bentonites and particulate detergent compositions of widely
different formulas, densities (0.2 to 0.9 g./ml.) and
sizes (preferably No. 10-40 sieve).
The invention has been described with respect to
various illustrations of preferred embodiments thereof but
is not to be limited to these because one of ordinary skill
in the art, with the present specification bef~re him, will
be able to utilize substitutes and equivalents witllout
departing from the invention.
-49-
