Note: Descriptions are shown in the official language in which they were submitted.
17
PARTICLES FOR LAUNDRY SOFTENING DETERGENT
This invention relates to particles useful for in-
corporation into a particulate heavy duty detergent composition
for use in automatic washing machines and is a divisional app-
lication from Canadian Patent Application No. 425,408, filed
April 7th, 1983 which 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 de-
sirable adherence to substrates are important advantages but
its "gelling" characteristics can cause an objectionable gummi-
ness in the detergent, which sometimes will tend to hold deter-
gent 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 moisture bentonite
can "gell" and become sticky or of reduced flowability, even
becoming held to passageway or chamber walls despite applicat-
ions 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 disadvantag-
eous for a desirably free flowing commercial particulate de-
tergent 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 pro-
cesses, and flowability from the dispensing carton when the
i2~ 7
62301-1221D
product ls being employed by the ultimate consumer are
satisfactory, the presence of bentonite can cause the detergent
composition particles to be held to appliance part walls,
especially charging compartment walls, of washing machines
equipped with means for automatically charging detergent
composition to the wash 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 that the particles
may resist removal from surfaces against which they are
resting. For example, in washing machines and other appliances
equlpped with automatic dispensers or charging compartments,
the detergent particles may not entirely fall from the
dlspenser or be washed out of the dispenser, especially if the
dispenser walls had been wet before addition of the detergent.
Failure to dispense part of the desired charge to the washing
machine diminishes the effective detergent and softener
concentratlons of the wash water and can lead to inaccurate
detergent and softener concentrations being employed. Also, it
may create an unsightly bulld-up, which may be objectionable to
the consumer. In either situation the result is undesirable
and should be avoided, if possible.
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12fi~ ~17
62301-1221D
The invention provides particles useful for
incorporation into a particulate heavy du~-y detergent
compo3itlon for use in automatic washing machines made of
compositions selected from ~he group consisting of,
(a) bentonite with which there is included a dispensing
assisting proportlon of a siliconate or a dispensing assisting
derivative thereof;
~ b) sodium perborate at least partially coated wlth a
siliconate or a derivative thereof; and,
(c) enzyme at least partially coated with a siliconate or
a derlvatlve thereof.
The invention of the parent applicatlon provides a
heavy duty laundering and textlle softenlng particulate
detergent compositlon, useful for automatic machine washing of
laundry in water and dl~pensable from a charging or dispensing
compartment, of such a machine by action of water being fed
through such compartment, comprilses a bullt synthetic organic
deterqent whlch iB an anionic or nonionic detergent or a
mixture thereof, a building proportion of a builder for the
synthetic organlc detergent whlch ls a water soluble or water
lnsoluble bullder or a mixture thereof, and a softening
proportion of bentonite, with the bentonite being in particles
wlth whlch there ls included a dispensing assisting proportion,
preferably at least 0.15%, of a siliconate or
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126V417
a dispensing assisting derivative thereof. In preferred
embodiments of the invention the synthetic organic deter-
gent includes both an anionic detergent, which is prefer-
ably 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 pentasodium tripolyphosphate or NTA or a mixture
thereof, with a small proportion of sodium silicate, the
bentonite is a swellinq 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-
gents, such as the quaternary 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
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~26~7
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., 12, 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 EtOI sulfate, and sodium hydrogenated tallow
alcohol sulfate. In a~dition 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
lZ6~417
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 i~ of
10 to 16 carbon atoms, preferably 12 to lS carbon atoms,
and the nonionic detergent contains from about 3 to 20
lower alkoxy groups, preferably 5 to lS, and more preferably
9 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 purpose.
These include inorganic and organic builders, and mixtures
,
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6~7 62301-1221D
thereof. Among the inorganic builders those of preference are
the various phosphates, preferably polyphosphates, e.g., tri-
polyphosphates and pyrophosphates, such as pentasodium tripoly-
p~osphate and tetrasodium pyrophosphate. Trisodium nitrilotri-
acetate (NTA), preferably employed as the monohydrate, and
other nitrilotriacetates, such as disodium nitrilotriacetate,
are preferred organic builders. The designation NTA, which
normally stands for nitrilotriacetic acid, in this specifica-
tion is employed to also refer to the various salts thereof,
preferably the alkali metal salts and most preferably the tri-
sodium salt. Sodium tripolyphosphate, sodium pyrophosphate and
NTA may be utilized in hydrated forms, which are often pre-
ferred, but anhydrous forms may also be used. Of course,
carbonates, such as sodium carbonate, are useful builders and
may desirably be employed, alone or in conjunction with bicar-
bonates, such as sodium bicarbonate. When the polyphosphates
are employed it may be preferred to have sodium pyrophosphate
present with sodium tripolyphosphate in proportion from l:lO to
10:1, preferably 1:5 to 5:1 with respect to it, with the total
20 proportion of both builders being about the same as that
mentioned herein for the sodium tripolyphosphate. Other water
soluble builder~ that are considered to be effective include
the various other inorganic and organic phosphates, borates,
e.g., borax, citrates, gluconates, EDTA and iminodiacetates.
Preferably the various builders will be in the forms of their
alkali metal salts, either the sodium or potassium salts, or a
mixture thereof, but sodium salts are normally more preferred.
¦ In eome instances, as when neutral or slightly acidic detergent
compositions are being produced, acid forms of the builders,
especially of the organic builders, may be preferable but
.
, ~ - 7 --
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1~60~17 62301-122lD
normally the salts will either be neutral or basic in nature.
The silicates, preferably sodium silicate of Na2O:SiO2 ratio
within 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 objectionable adherence of detergent particles to
dispenser walls they are considered to be special cases of
builders, and relatively small proportions thereof will be
pregent (such proportions will be described separately from the
other builders). When it is desired for greater proportions of
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 em-
ployed 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 detergency 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 within the
invention to utilize water insoluble builders other than the
zeolites, as a practical matter, at the present time, the
zeolites are the principal such insoluble builders that are
; used.
The zeolites employed include crystalline, amorphous
~ and mixed crystalline-amorphous zeolites, of both natural and
; synthetic origins. Preferably, such materials are capable of
reacting sufficiently rapidly with calcium ions so that, alone
or in conjunction with other water softening compounds in the
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1~6~ ~17 62301-1221D
detergent, they soften the wash water before adverse reactions
of such ions with othe~ components of the synthetic organic
detergent composition occur. The zeolites employed may be
characterized as having a high exchange capacity for calcium
ionl which is normally from about 200 to 400 or more milligram
equivalents of calcium carbonate hardness per gram of the
aluminosilicate, preferably 250 to 350 mg. eq./g.
Although other ion exchanging zeolites may also be
utilized, normally the finely div,ided synthetic zeolite build-
er particles employed in the practice of this invention will beof the formula
(Na2)x(A123)y(sio2)zW H20
wherein x is 1, y is from 0.8 to 1.2, preferably about 1, z 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 alumino-
silicate of a univalent cation such as sodium or potassium.
Crystalline types of zeolites utilizable as good ion
exchangers in the invention, at least in part, include zeolites
of the following crystal structure groups: A, X, Y, L, morden-
ite and erionite, of which types A, X and Y are preferred.
Mixtures of such molecular sieve type zeolites can also be
useful, especially when type A zeolite is 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.
i2~ 17
62301-1221D
Crystalline zeolites 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 about 4~ up to about 36% of the zeolite total
weight, depending on the type of zeolite used, and are
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1~6(~417
preferably hydrated to about 15 to 70% of their capacitiesD
Normally, water contents are in the range of about S 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 mlcron, e.g., 0.01 to 0.05 micron,
if amorphous. Although the ultimate particle sizes are much
lower, usually the zeolite particles will ~e of sizes within
the range of No's. 100 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 com~ositions for filling
characteristics, and sodium sulfate is especially u~eful 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, such are often
preferably avoided entirely or any proportion thereof present
may be minimized.
The softening clay that is an important component
lZ6~ 62301-1221D
of the present detergent compositions is of the type character-
ized as "bentonite". Bentonites are colloidal clays (aluminum
silicates) containing 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, Mississippi and Texas).
The bentonites which are useful in accordance with the present
invention are those which have "lubricating" 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 solu-
tion, 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,
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lZ60 ~17 62301-1221D
and thereby improves the exchange capacity of the 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 literature as being relevant to
softening capacity, it is a feature of the present invention
that good textile softening is obtainable with sodium benton-
ites of comparatively low ion exchange capacities. Whether theswelling bentonite (also called sodium bentonite herein) is a
naturally occurring clay or is obtained by alkali treatment of
a non-swelling or poorly swelling bentonite, it may be used in
the present textile softening detergent compositions. Treated
Italian bentonites have been found to be especially useful and
are considered most appropriate for products intended for
European markets. For American markets Wyoming bentonite is
often preferable and such does not have to be treated because
it already contains sodium ion in the bentonite structure and
has swelling properties. Analysis of a typical Italian benton-
ite (after alkali treatment) shows that it may contain 66.2% of
SiO2, 17.9% of A12O3, 2.80% of MgO, 2.43% of Na2O, 1.26% of
Fe2O3, 1.15% of CaO, 0.14% of Tio2 and 0.13% of K2O. A typical
Wyoming or western bentonite (untreated) may contain from 64.8
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126~ ~17 62301-1221D
to 73.0~ of sio2, 14 to 18% of A12O3, 1.6 to 2.7% of MgO, 0.8
to 2.8~ of Na20, 2~3 to 3.4% of Fe203, 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 considered that if the ~a2O content
of the clay is at least about 0.5%, preferably at least 1% and
more preferably at least 2% (the equivalent proportion of K20
may also be taken into account) the clay will be satisfactorily
swelling for the purposes of the present invention, with
satisfactory softening and dispersing properties in aqueous
suspencion. While it is expected 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 analysis
given will result in useful components of the present composi-
tions, 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 analysis of the treated
bentonite may be expanded +10%, with the bentonites within
those ranges still being useful. Additionally, other swelling
bentonites may be substituted, at least in part. Generally the
useful bentonites will have swelling capacities of at least 1
or 2 milliliters per gram, more preferably at least 5 or
10 ml./g. Of course, higher swelling capacity bentonites will
also be useful. Normally the range of swelling capacities
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lZ60~i7 62301-1221D
will be from 5 to 30 ml./~. and frequently will 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
utilizing moisture spray application to tumbling bentonite
powder, extrusion, compaction, pan agglomeration or other tech-
nique. However, it is highly desirable that the bentonite be
in finely divided powder form before agglomeration so that when
the agglomerate 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 asglomera-
tion, to pass through a No. 100 sieve (U.S. Sieve Series), with
at least 99% passing such a sieve and with over a major propor-
tion thereof passing through a No. 200 sieve, preferably with
less than about 30% by weight of the particles failing to pass
through such a sieve and more preferably with no more than 20%
resting on such sieve.
Also important to promote ready break-ups of benton-
ite agglomerates and dispersion in the wash water, so that the
minute particles thereof may be adhered to textile fibers to
soften them, is the moisture content of the bentonite.
i ~ :
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:
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lZ6~417 62301-1221D
Although it is desirable to limit the free moisture content of
the bentonite utilized to about 10~ or so, with moisture con-
tents 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 facilitate 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%, prefer-
ably 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 compositions. When the
bentonite moisture content is too low the bentonite does not
aid in satisfactorily swelling and disintegrating the agglomer-
ated beads in the wash water.
Preferred swelling bentonites of the types describedabove are sold under the trade marks Laviosa and Winkelmann,
e.g., Laviosa AGB and Winkelmann G 13, both of which are treat-
ed Italian b~ntonites, and Mineral Colloid ~o. 101 (and other
si~ilar designations) corresponding to Thixo-Gels No's. 1,
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12604i7 62301--1221D
2, 3 and 4 (marketed by Benton Clay Company, an affiliate of
Georgia Kaolin Co.). As will be described later, the treated
bentonites will also preferably be free 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 range
of 8 to 9.4, a maximum free moisture content of about 8~, a
specific gravity of about 2.6 and a viscosity, at 10~ concen-
tration in water, within the range of 5 to 30 centipoises,
preferably 10 to 30 cp.
The siliconate, which is employed in conjunction with
the bentonite, preferably to coat it, and also can be used to
coat the detergent composition particles, and which acts to
inhibit sticking of the bentonite and the detergent to charging
compartment walls of an automatic washing machine (and to walls
of other "containers" for the product), is one which may be
easily applied to the bentonite and which can at least partial-
ly coat the particles thereof and inhibit their adhesion to
walls of a compartment in which they may be stored temporarily,
even when such walls are damp or wetO The siliconate is a salt
of siliconic acid, preferably an alkali metal salt thereof, and
the siliconic acid is preferably a lower alXyl siliconic acid.
While it is desirable that the salt-forming metal or other
cation be one which will produce a water soluble siliconate, so
, ~_
~26(~ ~17 62301-1221D
that it may be applied to the bentonite in aqueous solution,
such may not be necessary and it is contemplated that water
dispersible siliconates will also be utilized. Furthermore, it
is within the invention to employ lipophilic siliconates, which
may be applied in organic solvent solution o~ in aqueous
organic solvent solution, or in corresponding emulsions or
dispersions. The alkali metal of the siliconate is preferably
either sodium or potassium, but other salt-forming cations may
also be utilized providing that the siliconate is suitable for
the present purposes. It is contemplated that other alkali
metal salts of siliconic acids than the lower alkyl siliconates
may be utilized, including both aliphatic and aromatic silicon-
ates, but the lower alkyl siliconates, wherein the lower alkyl
i8 of 1 to 3 or 4 carbon atoms, e.g., potassium methyl silicon-
ate and sodium propyl siliconate, are considered to be pre-
ferred. Instead of employing the siliconate an equivalent
charge of the corresponding siliconic acid and a corresponding
base may be utilized.
For most effective results it is much preferred to
employ the lower alkyl siliconates previously described but it
is recognized that such compounds may polymerize, at least
partially, to siliconic or other film-forming and foam-
inhibiting compounds or polymers and accordingly it is within
the broader bounds of this invention to utilize such "deriva-
tive" materials directly, at least in part, as a component of
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126~417 62301-1221D
the present detergent compositions. When such a derivative of
the siliconate is employed it will be one which aids in improv-
ing the dispensing of the bentonite beads or detergent composi-
tion particles from a charging compartment of an automatic
washing machine, such as a compartment wherein the particulate
contents are washed out by the flow of water into the washing
tub of the machine.
Although the operation of the present invention
should not be considered to be limited by the mechanism to be
described, it may well be that the water soluble alkali metal
lower alkyl siliconates (which may also be described as alkali
metal lower alkyl silanolates), may be converted to polymethyl
siloxanes, as by the action of atmospheric carbon dioxide or
other acidic acting material, which could also result in the
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 coated bentonite (or
other detergent particles) with respect to being of improved
dispensing properties from the charging compartment of an auto-
matic washing machine. The production of siloxanes by the
described reaction has been mentioned in the text Chemistry and
Tcchnology of Silicones, by Walter Noll, published by Academic
Press in 19~8. However, although silicones have been included
in detergent compositions in the past, often for their anti-
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i~.60~17
62301-1221D
foaming properties, no disclosure of the use of water soluble
siliconates to coat bentonite and detergent particles to pro-
mote 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 com-
ponent 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" and synthetic fatty acids, and that they are normally
of 10 to 24 carbon atoms, preferably 14 to 18 carbon atoms.
Preferably such soaps are of hydrogenated tallow or hydrogen-
ated tallow fatty acids, e.g., stearic acid. The water solublesoap 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
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lZ~17 62301-122]D
with siliconate to furt}ler inhibit adhesion to damp compartment
walls. of course, for compositions wherein foaming is desir-
able 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 tempera-
ture, especially when it is above 80C. (and it may be almost
up to the boiling point, e.g., 90 or 95C.) can cause decom-
position of the perborate and release of bleaching oxygen from
it. Thus, under such conditions the sodium perborate, which is
often referred 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 decomposition
catalyst. When lower temperature laundering is undertaken,
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 -
~7'
~'~
126~417 62301-1221D
being washed and in such circums~ances an activator will be
employed or another suitable bleaching agent will be used, also
usually with an activator. Many such systems have been
described in 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 alkali metal and alkaline earth
metal salts, e.g., sodium and magnesium salts. Various
aetivators for such compositions are known whieh promote the
controlled release of oxygen from them in hot and cold water
systems, ineluded among which aetivators are heavy metal salts,
such as copper salts, and various inorganic and organic eom-
pounds, whieh have been deseribed in the art. Among the lower
temperature bleaches that which is preferred is magnesium
dimonoperoxyphthalate. Of eourse, various other oxygen releas-
ing bleaehing materials sueh as the hydroperoxides, may be
employed and in the proper circumstanees ehlorine releasing
bleaching materials can be ineorporated in the present
detergent eompositions.
Various adjuvants may be present in the crutcher mix
from whieh base beads or detergent eompositions may be spray
dried, or sueh adjuvants may be post-added, with the deeision
as to the mode of addition often being determined by the
physieal properties of the adjuvant, its resistance to heat,
its resistanee to degradation in the aqueous eruteher medium,
- 22 -
~ ' ,
lZ6~17 62301-1221D
and its volatility. Among the adjuvants often employed are
enzyme powders, which normally are post-added to the base beads
because they are heat sensitive. These rnay 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,
amylolytic enzymes, such as alpha-amylase, may also be util-
ized. 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 commercial
preparation. In this specification proportions 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 diamino-
stilbene disulfonic acid, including variations thereof with
respect to substituents on the triazine and aromatic rings.
This class of brighteners is known in the detergent art and
will mo~t often be used when bleaching components are not
* trade mark
- 23 -
126~3~17
62301-1221D
present in the final product. When it is desired for the
detergent composition to include a bleach, such as sodium
perborate or other oxidizing bleach, bleach stable brighteners
may be incorporated in the crutcher mix. Among these there may
be mentioned the benzidine sulfone disulfonic acids, naphtho-
triazolyl stilbene sulfonic acids and benzimidazolyl deriva-
tives. Polyamide brighteners, which also may be present,
include aminocoumarin or diphenyl pyrazoline derivatives, and
polyester brighteners, which can also be used, include naphtho-
triazolyl stilbenes. Such brighteners are normally used astheir soluble salts, e.g., sodium salts, but they may be
charged as the corresponding acids. The cotton brighteners
will usually comprise major proportions of the brightener
systems employed.
When it is desired that the product made be 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, are utilized they may
have a dual effects of serving to color some or all of the
detergent composition particles, or particles of components of
the detergent composition, and helping to give the washed
laundry a desirable bluish tint. Coloring of agglomerated
bentonite particles by suitable dyes or pigments may be
especially desirable because natural bentonite sometimes may be
off-color, so that the agglomerates may be converted from
- 24 -
'~.
1260417
62301-1221D
particles that look dirty to those which are of attractive
color and appearance.
Perfumes employed, which are usually heat sensitive
and may contain volatiles, including a solvent, such as alcohol
or a suitable glycol, polyol or hydrocarbon, are normally of
synthetic perfumery materials, sometimes mixed with natural
components, and generally will include alcohols, aldehydes,
terpenes, fixatives 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 dispers-
ing the various components of the spray dried beads. There-
fore, some water, in both free and hydrate forms, is in the
product. Similarly, water may be employed to agglomerate the
bentonite and perborate powers and dissolve the siliconate.
~- - 25 -
-: .. .... . ..
126~17 62301-1221D
While it may be preferred to employ deionized water, so that
the hardness ion contents thereof 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, for economic or
supply reasons, will be used exclusively. Normally the hard-
ness content of such water will be no greater than about 300
parts per million, as calcium carbonite.
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, from
flowing and of improved dispensability from a charging compart-
ment of an automatic washing machine by action of wash water
passing through such compartment. The proportion of anionic
detergent will normally be from 3 to 10% of 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%,
preferably 2 to 4%, e.g., 3 or 4%. In those instances when
nonionic detergent is not being employed the proportion of
anionic detergent may be increased by as much as 5% and in
cases in which the anionic detergent is omitted the nonionic
detergent content may be increased by up to 10%, providing that
the detergent composition remains satisfactorily dispensable.
While it is possible for effective detergent compositions to be
made without either the anionic or nonionic detergent, such
products will not be as useful as preferred compositions of
- 26 -
.~`,..
126~)41~
62301-1221D
thi~ invention. The builder content will generally be in the
range of 20 to 75%, preferably 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 preferably
contain from lO to 90% of one of them, with the balance being
the other such builder, and within such ranges preferred pro-
portions may be 20 to 80% and 40 to 60%, and complementing
percentages. Similar ranges of percentages are appliaable when
the builder i8 a mixture of water soluble builder salt and
water insoluble builder, æuch as a zeolite.
The bentonite content of the textile softening deter-
gent,~preferably in the form of a siliconate coated agglomerate
of more finely divided bentonite powder particles, will be a
satlsfactorily softening proportion thereof, which usually will
be within the range of 5 to 25%, preferably lO to 20%, more
preferably 14 to 18%, e.g., about 16%.
The ~iliconate used will be employed in a proportion
- sufficient to have the desired dispensing assisting e~ffect 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
ranqe 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
u~ed to cover agglomerated bentonite only, on a coated
bentonite agglomerate basis the siliconate
;~:,s~
~ 27 -
lZ6(~;117
content will usually be at least 0.15%, often 0.15 to 5%,
preferably O .15 to 1% and more preferably 0.15 to 0.5~,
e.g., 0.4%.
When a fatty acid soap is present the pro~ortion
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 thereof 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
employment 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 bei.ng 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, e.g., 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
-28-
i26~417 62301-1221D
more preferably to 10%. Although water soluble sodium silicate
has building properties, especially with respect to its action
against magnesium ions in hard water, because it also acts as a
binder the proportion thereof present will not be limited by
the builder content proportions previously given and will be
considered herein with other adjuvants for the present composi-
tions. Usually it will constitute no more than 8% of the
product, with a normal range of 1 to 5%, preferably 2 to 4%,
e.g., 3%. The content of filler salt, such as sodium sulfate,
when it is present, will also normally be limited, to no more
than 10%, and will normally constitute from 0.5 to 5~, prefer-
ably 0.5 to 2%, e.g., 1 or 1.5% of the product. The percentage
of proteolytic enzyme used will normally be from 0.1 to 2%,
preerably 0.2 to 1%, e.g., 0.3%, and the percentage of optical
brightener dye will be from 0.1 to 2%, preferably 0.1 to 0.5~,
e.g., about 0.2%. Perfume content will normally be from 0.05
to 2%, preferably 0.1 to 1%, and more preferably 0.2 to 0.5%,
e.g., about 0.3%. Among other ad~uvants it may sometimes be
desirable to have present small proportions of particular
sequestering 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 as a carrier for
.
1:`
~ - 29 -
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~260~17
62301-1221D
the sequestrant. Commercially, a miXtULe of such products i~
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 of 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.
For the siliconate-treated bentonite the siliconate content
will be from 0.2 to 10%, preferably 0.5 to 5% and more prefer-
ably l to 3%. For the corresponding detergent compositionwithout bentonite and for the enzyme and perborate the propor-
tions of siliconate will be the same as those for the final
; detergent composition but such proportions may be increased
from 10 to 100%, depending on conditions and the proportions of
the various adjuvants in the detergent composition.
!.
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- 30 -
i260417 62301-1221D
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 referred to
only briefly herein. In the spray drying operation a crutcher
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 detergent,
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, preferably 50 to 65% thereof, with
the balance being water. The crutcher mix may contain the
anionic detergent and a portion or all of the nonionic deter-
gent, although usually no more than 5~ of nonionic detergent
(on the basis of the final product) will be in the 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 neces~ary. The bentonite is preferably
~eparately agglomerated and i8 post-added to the spray dried
product but sometimes it may be incorporated in the crutcher
mix. Aqueous silicate solution, stable fluorescent brightening
dye, soap and filler aalt are usually added in the crutcher,
together with any stable pigment and other colorants that may
be employed. Instead of charging a neutralized detergent the
- 31 -
126(~9~17
62301-1221D
crutcher may be utilized as a neutralizing vessel, in which
anionic organic detergent acid is neutralized with aqueous
caustic. Such acid, for example, may be dodecylbenzene sul-
fonic acid containing about 45 to 50~ of active ingredient,
which may be neutralized with an aqueous sodium hydroxide solu-
tion, such as one containing 38% Na2O. If the alkylbenzene is
sulfonated with sulfur trioxide the active ingredient content
of the acid may be as high as 99%. A higher fatty acid mixture
may also be neutralized in the crutcher with the detergent acid
to produce a desired higher fatty acid soap-detergent mixture.
The crutcher mix may be spray dried in a conventional
spray tower, utilizing either concurrent or countercurrent
flow. Normally the mix will be at a temperature in the 20 to
80C. range, preferably 40 to 70C. and will be spray dried in
a tower in which the drying air is at a temperature of 200 to
400C., to produce spray dried beads of particle sizes in the
range of ~0'8. 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
20 density 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
a~ about 3 to 20% but normally will be about 10 to 15%.
After production of 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 the
"
, .
,
,
- 32 -
''' '~ `
126~417 62301-1221D
product, when desired). Generally it will be preferred for the
bentonite, enzyme, bleach, and any other particulate products,
such as those in powder, agglomerate or prill form (except the
siliconate), which are intended to be post-added 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-added after one 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 pre-
erred first to coat the unperfumed detergent composition withan 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,
~; su~h as a comparatively odorless alkylate (hydrocarbon).
; Instead o spraying the siliconate onto the mixture of spray
f~
Ji~
.~
~ 33 -
'~ ~
,
i~6~)~17 62301--1221D
dried (or otherwise manufactured to similar product character-
istics) detergent beads, bentonite agglomerate, enzyme prill~
or agglomerates, and perborate particles in mixture, the sili-
conate may be applied to such individual components separately
or in various co~binations. 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 siliconate spray may be directed onto
different feed streams of such components as they enter a suit-
able 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 great-
est dispensing assisting effect) it may be sprayed onto or
otherwiee satisfactorily applied to the surfaces of the spray
dried beads before admixing with the other particulate com-
ponents of the final product and before application of silicon-
ate spray thereto. Also, as previously 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 emulsifier.
The apparatus for effecting the various mixings and
SprayingB i8 known in the art and accordingly will not be
described in detail herein. Spraying may be through conven-
tional nozzles, usually of wide spray pattern design, but other
types of spraying equipment may also be employed. The mixers
: - 34 -
.. .
. .
: :
12f~ 17 62301--1221D
may be of various designs but preferably in~lude revolving
inclined tubes or drums, inside which spraying may be effected.
However, V-shaped blenders, especially those of continuous feed
design, and other commercial powder blenders can also be
satisfactory.
The amount of siliconate that will be sprayed onto
the surfaces of the various particulate components of the
detergent composition will be such that the final product in-
cludes a dispensing assisting proportion of the siliconate (or
a derivative thereof). Because it is thought that the benton-
ite agglomerates can to some extent interfere with satisfactory
dispensing of the particulate detergent composition from the
feed chamber of an automatic washing machine (of the "European
type"), it may be preferable for a greater proportion of sili-
conate to be applied to such bentonite agglomerate particles,
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 of siliconate in the final
detergent composition may often be decreased, e.g., by as much
as 50~. Applications of the siliconate involve addition of
moisture to the composition being treated, when the siliconate
i8 in aqueous solution or emulsion (but not if in non-aqueous
solution). Such can either be desirable or not, depending on
the moisture content and the properties of the detergent
composition and processing apparatus. Accordingly, the
concentration of siliconate
' ~
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- 35 -
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~ ,~,.... .. .
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12f~ 7
in the spray liquid may be adjusted. of course, the
greater the volume of the spray and the greater the
dilution of the siliconate the more uniformly a spray
may be distribùted on the particulate material. On the
other hand, if the product is borderline or too high in
moisture concentration a dilute siliconate s~ray may
exacerbate 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 finely 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~,
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 may be applied with the siliconate.
* trade mark
-36-
126~417 62301-1221D
The siliconate does not obscure the
color. Sometimes the bentonite agglomerates may be larger than
the other particles in the product, e.g., 10 to 50% greater in
diameter, to accentuate their difference. In many instances
the bentonite agglomerates will preferably be of sodium
carbonate treated bentonite (such treatment improves the color
of off-color clay) and will contain magnesium carbonate 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 en~yme, 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 solid siliconate will normally be on the outer 1% of the
~ 20 thicknesses of the particles. For example, for a particle that
-~ i8 one millimeter in thickness such a siliconate coating would
~I be about 5 microns thick. Preferably the coating will be on
the out~er 0.5~ of the particle bead diameter, more preferably
the outer 0.2~ thereof. Of course, when only partial coatings
are~applied and when greater percentages of siliconate are
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1~6~417 62301-1221D
utilized, as when only the bentonite agglomerates are coated,
the siliconate thicknesses will be greater, but preferably less
than 2%. Normally, such thicknesses will be at least 0.05~ of
the particle thickness.
The products and processes of this invention posses
many advantages, several of which have already been mentioned.
With respect to the products, the application of siliconate to
particle surfaces, even when the entire particle is not covered
with the siliconate, improves the dispensing characteristics of
such particle without having any adverse effects. Thus, deter-
gent compositions of the types described herein, and the
particulate components of such compositions mentioned, are
easier to dispense from a charging compartment of an automatic
washing machine of the European type than are control products
untreated with siliconate. This difference is most pronounced
with respect to the agglomerated bentonite particles. The
tests for comparing such results are practical use tests,
employing a variety of different makes of such European washing
machines, with the evaluator noting the number of particles
remaining in the charging compartment after a normal charging
and dispensing Operation# or after repeated such operations.
To accentuate the differences and make the test more difficult,
the walls of the charging compartment are first wet 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
,
,~
. .
~ 3~
~': ' '' ' ' '
lZ60~17
62301-1221D
stand for one or two minutes, and then direct a gentle spray of
water onto the particles for a measured time, e.g., 30 seconds,
after which the numbers of particles may be compared. By such
tests the products of this invention show a marked improvement
over the controls; normally one may expect to obtain less than
half the number of particles still adhering to the pre-
moistened surfaces when the "experimental" 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 appre-
ciable number of particles will be adhering when no siliconate
i8 present.
While most of the detergent will be charged to the
waehing tub in normal use of the automatic washing machine so
that the retention of some particles in the charging 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 qignificantly affecting the charge weight. Also,
the appearance of the charging compartment with particles
retained therein i~ unsatisfactory and can lead to consumer
rejection of the product. Because of the different washing
techniques employed in America, coating bentonite detergent
part~icles with siliconate may not be as important there but it
. : ~
~ is considered that the presence of the siliconate on the
s~ particle will assist in making the detergent more stable and
,:~
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~ 39 -
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126()~17
62301-1221D
more freely flowing, especially in damp conditions, and will
help to counteract any gelation of the bentonite under such
conditions.
In addition to promoting dispensing, the siliconate
also has the desirable effect of preventing excessive foaming
of the detergent composition in aqueous solution. The benton-
ite also helps to limit foaming and the combination is superior
to the individual components. The siliconate also appears 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 stabilize
the perfume. It can also have such an effect on colorants.
Yet, these various advantages are obtained without the dis-
advantages of the product being excessively hydrophobic,
because it is initially water soluble. It does not interfere
with the desired quick dissolving and dispensing of the deter-
gent components and does not appear to cause an objectionable
buil~up of hydrophobic deposits on washed and softened laundry.
It does not interfere with the particular softening effect of
the hydrophilic bentonite and does not interfere with the good
detergency of the composition. The detergent compositions
resulting are excellent laundry detergents and effectively
soften washed laundry, as has been established by comparative
tests against similar compositions containing neither bentonite
nor siliconate. The products are satisfactorily free flowing
and of desired bulk density and appearance. They are also
non-dusting, which may at least in part be attributable to the
siliconate.
~ 40 ~
lZ~ 7 62301-1221D
Processes in which siliconate solutions or emulsions
are sprayed onto detergent, bentonite and other detergent com-
ponent particles are easily carried out and do not require
special equipment. Due to the water solubility of the silicon-
ate 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 com-
ponents. The processes lend themselves to modification to
allow different concentrations of siliconate on different
detergent components. The coating materials do not gel or
thicken objectionably, do not block spray nozzles and do not
form gummy deposits in the spraying and mixing equipment. The
siliconate may be applied at room temperature because it does
not require heating, as do some 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 desired dispensing assisting effect. Also,
apparently due to the nature of the siliconate or derivative
thereof on the detergent or component particle, it is effective
even when the particle is not completely covered by it.
The following examples illustrate but do not limit
this invention. Unless otherwise indicated, all parts are by
weight and all temperatures are in C.
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:126~
62301-1221D
EXAMPLE 1
A crutcher mix totalling 3,199.5 kilograms of mater-
ial is ~ade by reacting 364 kg. of dodecylbenzene sulfonic acid
(Dobane JNQ [48.8% active ingredient]) and 167 kg. of hydrogen-
ated fatty acids (16 to 18 carbon atoms per mol of fatty acid)
with 47 kg. of caustic soda (38% ~a20) in an aqueous medium
containing a suitable proportion (to maintain the reaction) of
952 kg. of city water (300 p.p.m. hardness, as CaC03). The
balance of such water is employed to cool the reaction mix, as
desirable, and to dilute other components of the crutcher mix.
Subsequently there are added to the crutcher 242 kg. of aqueous
sodium silicate solution (Na20:SiO2 = 1:2.4) at a 44.1% solids
concentration, 7.5 kg. of fluorescent stilbene type brightener,
7 kg. of Sydex 808 (85% MgSiO3 and 15% magnesium DTPA),
1,252 kg. of hydrated sodium tripolyphosphate (TPP "H"), 54 kg.
of anhydrous sodium sulfate (99.5~ pure) and 107 kg. of a non-
ionic detergent, which may be considered as the condensation
product of 11 mols of ethylene oxide with one mol of higher
fatty alcohol having 12 to 15 carbon atoms per mol.
The crutcher mix is heated for about an hour, with
stirring, so that its temperature rises to about 55C., after
which it is pumped to a spray drying tower where it is sprayed
at elevated pressure through multiple spray nozzles into drying
air at a temperature of about 300C. From the spray drying
particles of a moisture content of about 12%
- 42 -
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126()417
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-
stitu~ed), 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 applied 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 to replace
calcium and magnesium therein with sodium (see the pre-
ceding specification for description of this material) and
from which a natural content of gritty material (hard
enough to be difficult 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-
12~ 7
Onto the mixture 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 sprayin~ 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 appearance, with the somewhat
larger (averaging 20 to 200% greater in diameter) blue
agglomerat~d bentonite particles contrasting with the
other white particles, and is non-dusting.
The product made is subjected to practical laundry
- 20 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 compartment 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 particles are larger, since
~f' ~;
they may tend more to adhere to wet chamber walls during
dispensing.
~: :
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~ ~ -44-
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"' . .. .
- , . ,-. ": .
lZ6V417
62301-1221D
When the above experiment is repeated but wlth 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 previou~ly used the product resulting is of as
satisfactory physical properties and functions but additionally
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 hydrogenated tallow alcohol sulfate and
sodium tallow alcohol polyethoxy (3EtO) sulfate. Alternative-
ly, 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 obtain-
able when, instead of the anionic detergent being varied, thenonionic detergent is changed, being replaced by a block co-
polymer of Propylene oxide and ethylene oxide, such as Pluronic
L-44 or L-62, nonyl phenol polyoxyethylene (12 EtO) glycol or a
condensation product of C12_1s fatty alcohol with 3 or 7 mols
of ethylene oxide per mol, or with a mixture of two or more of
suc~ detergents, e.g., in equal parts.
~ When half or all of the sodium tripolyphosphate is
; replaced by NTA the final product is also a satisfactory
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:
' , . .
;, , ~ .
126V~17
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 li~e 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 foroxidizin~ 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 maximum 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,
1260417 62301-1221D
to each of the particulate components to be blended together
separately before such blending. The various coated particles
are all of bulk densities in the prescribed range (0.3 to 0.6
g./ml., e.g., 0.5 g./ml.). 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 dispens-
ing properties. The siliconate coated agglomerated bentonite,
spray dried detergent composition beads (without bentonite),
10 enzyme and perborate can all be separately produced and stored,
and subsequently are useful for formulating fabric softening
detergents of different compositions and different desired
properties, e.g., coated bentonite plus uncoated spray dried
beads.
EXAMPLE 3
A softening detergent like that of the first formula
of Example 1 is made from a crutcher mix of 10.24 parts of the
dodecylbenzene sulfonic acid, 2.81 parts of the hydrogenated
fatty acid, 0.81 part of the caustic soda, 26.54 parts of
20 water, 37.2 parts of pentasodium tripolyphosphate (hydrated),
6.8 parts of sodium silicate solution, 0.21 part of fluorescent
brightener, 1.46 parts of sodium sulfate and 3.0 parts of the
^ nonionic detergent, added sequentially. This is spray dried by
~, ~
S the method described in Example 1 to produce 62.5 parts of a
,~
product of similar bulk density and particle size. The spray
dried particles are then mixed with 0.3 part of proteolytic
enzyme 20.0 parts of the sodium perborate granules, 16.0 parts
of the agglomerated bentonite and 0.2 part of Sydex 808, and
onto the
.
. ~ ~
~ 47 -
.'. X
'~'
i, ~- . .. . ~ . . .
lZ6~ 17
tumbli~g Dowder 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 e~hibits 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 underlthe trade mark Mineral
Colloid No. 101 (formerly Thixogel No. 1) is employed,
similar final products are obtained which are good soft-
ening detergents and are readily dispensed. Also, ~henother 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-
4~7
EX~1PLE 4
When the proportions of the various components
in the preceding Examples 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
2:1, 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 before him, will
be able to utilize substitutes and equivalents without
departing from the invention.
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