Free flowing, zeolite-containing spray dried beads, useful for
the manufacture of a particulate built syntyhetic nonionic organic
detergent composition of reduced zeolite deposition characteristics
due to the presence of bentonite and a low content of water soluble
silicate or the absence of such silicate, include about 5 to 60%
of water softening aluminosilicate (zeolite), about 2 to 40% of
bentonite, about 5 to 60% of polyphosphate and up to about 5% of
water soluble silicate. Preferably, for least zeolite deposition
on the fabrics of laundry washed with the detergent composition,
the spray dried beads contain no soluble silicate. Normally the
moisture content of the beads will be in the range of about 3 to
12%, not being so high as to interfere with the flowability thereof
(and of detergent compositions based on the beads) and not so low
as to diminish the moisture content of the bentonite to a point
at which it becomes less effective as an anti-deposition agent for
the zeolite or zeolite-silicate aggregate and does not disperse
readily in wash water. In addition to the polyphosphate, which serves
as a very effective builder in these products, other water soluble
builders may also be present. The invention also relates to nonionic
detergent compositions based on such beads, which may be made by
spraying such a nonionic detergent onto the beads so that it is
absorbed by them.
What is claimed is:
1. Free flowing, zeolite-containing spray dried beads, useful for
the manufacture of a particulate built synthetic nonionic organic
detergent composition, which composition is of reduced zeolite deposition
characteristics due to the presence of bentonite and the absence
of water soluble silicate, comprising by weight from 5% to 60% of
water softening zeolite, about 2% to 40% of bentonite, containing
sufficient moisture to facilitate dispersion of the bentonite about
5% to 60% of polyphosphate and 0% of water soluble silicate.
2. Beads according to claim 1, of a bulk density in the range of
0.2 to 0.8 g./cc. and particle sizes in the range of No. 10 to 100,
U.S. Sieve Series, wherein the water softening zeolite is a hydrated
water softening zeolite containing from about 15% to 25% by weight
thereof of water of hydration and having an exchange capacity for
calcium ions which is in the range of 200 to 400 milligram equivalents
of calcium carbonate hardness per gram of anhydrous zeolite, the
bentonite is a swelling clay having a swelling capacity, in water,
of 3 to 15 ml./g. and a viscosity of 3 to 30 centipoises at 6% concentration
in water, and includes at least 2% of moisture on an anhydrous bentonite
basis, the polyphosphate is a sodium salt, and the moisture content
of the beads is from 3% to 12% thereof.
3. Beads according to claim 2 wherein the proportion of bentonite
to zeolite is within the range of about 1:6 to 1:1, the proportion
of sodium polyphosphate to zeolite is within the range of about
1:3 to 3:1 and the proportion of bentonite to sodium polyphosphate
is within the range of about 1:10 to 1:1.
4. Beads according to claim 3 comprising from 10% to 40% of hydrated
sodium zeolite, 2% to 25% of bentonite, which bentonite is of a
type which has a swelling capacity in the range of 7 to 15 ml./g.
and is of a viscosity in the range of 8 to 30 cp. at 6% concentration
in water, 10 to 50% of a polyphosphate selected from the group consisting
of pentasodium tripolyphosphate, tetrasodium pyrophosphate and mixtures
thereof, and 5% to 10% of moisture.
5. Beads according to claim 4 comprising from 15% to 35% of zeolite
A, 5% to 20% of beneficiated Wyoming bentonite containing at least
4% of moisture therein, 15% to 40% of pentasodium tripolyphosphate,
0.05% to 1% of sodium polyacrylate of a molecular weight in the
range of about 1,000 to 5,000, and 0% of sodium silicate, and in
which the proportion of bentonite : zeolite is in the range of 1:6
to 1:2, that of tripolyphosphate : zeolite is within the range of
1:2 to 2:1 and that of bentonite : tripolyphosphate is within the
range of 1:6 to 1:2.
6. Beads according to claim 1 wherein the bentonite includes at
least 4% of moisture, on an anhydrous bentonite basis.
7. Beads according to claim 1 which comprise from 1% to 40% of
a water soluble builder selected from the group consisting of carbonates,
bicarbonates, orthophosphates, borates, gluconates and citrates,
and mixtures of two or more thereof.
8. Beads according to claim 7 wherein the content of water soluble
builder, excluding polyphosphate, is from 5% to 30% and such builder
is selected from the group consisting of sodium carbonate and sodium
bicarbonate, and mixtures thereof.
9. Beads according to claim 1 wherein the polyphosphate is pentasodium
10. Beads according to claim 1 wherein the polyphosphate is tetrasodium
11. A detergent composition which consists essentially of beads
in accordance with claim 1 having absorbed in them a nonionic detergent
so that the percentage of such nonionic detergent in the detergent
composition is within the range of 5% to 30%.
12. A detergent composition according to claim 11 wherein the nonionic
detergent is a condensation product of 6 to 12 mols of ethylene
oxide and a higher fatty alcohol of 12 to 16 carbon atoms and the
proportion of such nonionic detergent in the composition is within
the range of 10% to 25%.
13. A detergent composition comprising a mixture of one to ten
parts of beads according to claim 11 and ten to one part of beads
of a different detergent composition which includes 5% to 30% of
a synthetic anionic organic detergent, 30% to 90% of builder for
such detergent, 2% to 20% of adjuvant(s) and 3% to 15% of moisture,
with both the detergent beads and the different detergent composition
being of particle sizes in the range of No. 10 to 100, U.S. Sieve
Series, and of bulk densities before mixing within 0.1 g./cc. of
each other and of the final composition bulk density, which is within
the range of 0.5 to 0.8 g./cc.
14. Beads according to claim 14 wherein the polyphosphate is a
mixture of pentasodium tripolyphosphate and tetrasodium pyrophosphate,
and which beads contain 5% to 30% of sodium carbonate as a supplementary
water soluble builder salt.
15. A detergent composition consisting essentially of beads in
accordance with claim 5 having 5% to 30%, on a final composition
basis, of nonionic detergent absorbed in them.
The following examples illustrate but do not limit the invention.
Unless otherwise indicated, all temperatures are in .degree. C.
and all parts are by weight in the examples and throughout the specification.
When any weights and proportions of zeolite are given, these are
intended to be for the normal hydrate being used, because it is
considered that the zeolite water of hydration does not leave the
zeolite and does not become part of the aqueous solvent medium in
the present crutching operations. Also, part of the water present
in the base beads and the detergent compositions is present as water
of hydration of the zeolite. Similarly, the moisture associated
with the bentonite may also be considered not to be free moisture
but because of the lesser percentage present this distinction can
often be neglected, as a practical matter.
A crutcher mix for spray drying base beads according to this invention
for subsequent conversion to a detergent composition by addition
of synthetic nonionic organic detergent thereto is made at a solids
content of about 55% in an aqueous medium by adding to the aqueous
medium in the crutcher 22 parts of Linde hydrated zeolite 4A (20%
water of crystallization), 0.1 part of sodium polyacrylate (Alcosperse
107D), 1.7 parts of fluorescent brightener (Tinopal 5BM, extra concentrated),
0.2 part of ultramarine blue powder, 24 parts of pentasodium tripolyphosphate,
10 parts of tetrasodium pyrophosphate, 8.3 parts of sodium carbonate
and 10 parts of Mineral Colloid No. 101 (formerly THIXO-JEL No.
1, bentonite). During mixing of the various components the mixer
speed, which at the start is low, is increased to medium and ultimately
to high. After addition of all the constituents, which takes approximately
fifteen minutes, mixing is continued for about an hour (in some
cases as long as four hours of mixing may occur), during which time
some of the water present, e.g., about two to six parts, may be
lost by evaporation, and may be replenished, if desired. During
the mixing time the crutcher slurry is continuously mobile and does
not gel, set or cake. If desired, after all the components are in
the crutcher and the mix is homogeneous the speed of the mixer may
Starting about five minutes after all the components of the crutcher
mix are present, the mix is dropped from the crutcher to a pump,
which pumps it at a pressure of about 21 kg./sq. cm. into the top
of a countercurrent spray tower wherein the initial temperature
is about 430.degree. C. and the final temperature is about 105.degree.
C. The base beads resulting are of a bulk density of about 0.4 g./cc.
and a particle size range substantially between No. 10 and 60, U.S.
Sieve Series (they are screened to such range, or they may be screened
to another range, such as 10 to 100). The moisture content of the
beads is in the range of 3% to 15% and almost always is in the range
of 5% to 12%, normally being close to about 10%, e.g., 8% to 10%.
The base beads are found to be satisfactorily free flowing, non-tacky
and porous, yet sufficiently firm on the surfaces thereof to be
commercially marketable. They are capable of absorbing significant
proportions of liquid nonionic detergent without becoming objectionably
Detergent products are made from the spray dried beads by spraying
onto the surfaces of such tumbling base beads a normally waxy nonionic
detergent in liquid state. Neodol 23-6.5 is used but Neodol 23-7
or Neodol 25-7 (and sometimes Neodol 45-11) may be substituted.
The nonionic detergent is in heated liquid state (at a temperature
of about 45.degree. C. to 55.degree. C.). The quantity sprayed is
such as to result in a final product containing about 15% of nonionic
detergent. Proteolytic enzyme (Alcalase 1.7T or Maxazyme 375) is
applied in powdered form to result in about a 1.5% concentration
in the product, and perfume is sprayed onto the product to produce
a 0.25% concentration therein. The resulting detergent compositions
are of a bulk density of about 0.5 to 0.6 g./ml., with the increase
in density being due to the absorption of the nonionic detergent.
The detergent made, of the above formula, is an excellent heavy
duty laundry detergent and is especially useful for washing household
laundry in automatic washing machines. It is physically and aesthetically
advantageous and attractive because it is non-dusting and satisfactorily
free flowing, which allows it to be packaged in narrownecked glass
and plastic bottles, from which it flows readily for dispensing.
The detergent compositions of the invention, containing bentonite,
as described, are of improved calcium ion binding rates but more
importantly, they leave less zeolite residue on laundry washed with
them (in an automatic washing machine at usual concentrations for
such products and at normal wash temperatures), especially when
such laundry is line dried, than do similar compositions containing
less or no bentonite and with sodium silicate in the spray dried
base beads, as in the formulations of my "grandparent"
patent application, Ser. No. 238,619. This difference is accentuated
when the wash water is high in hardness, e.g., 200 p.p.m., as calcium
carbonate, when the wash water is cold, and when a gentle agitation
cycle is employed.
Following normal procedure, crutcher mixes will be made quickly
and may be emptied quickly from the crutcher, sometimes being made
within a period of as little as five minutes and being pumped out
of the crutcher in as little as ten minutes. Yet, it is often important
that the present mixes be able to withstand at least an hour in
the crutcher without gelling or solidifying because sometimes holdups
for such times are encountered in commercial production. The described
crutcher mix is capable of being held for as long as four hours,
and often appreciably longer, without gelling or solidifying, which
is attributed, at least in part, to the presence of bentonite and
the absence of silicate. This action of the bentonite is unexpected
because bentonite also has a thickening effect on the crutcher mix,
but although the mix may thicken appreciably it remains pumpable.
Minor components of the crutcher mix, such as the fluorescent brightener
and pigments, may be omitted therefrom and enzyme and perfume may
be omitted from the final product, although it is highly preferable
for all such materials to be present. The crutcher mix temperature
may be modified, as by elevation to 52 .degree. C., and the proportions
of the various components may be varied .+-.10%, .+-.20% and .+-.30%,
while still maintaining them within the ranges previously given,
and workable mixes that result in the desired beads and detergent
compositions will be obtainable. The crutcher mix solids content
may be varied over the range of 45% to 65%, preferably 50% to 65%,
and good mixing and spray drying can result.
Other orders of addition of components to the crutcher may be employed
but normally it will be desired to add silicate, if any is to be
employed, last or near the end, and it is preferred that the bentonite
also be added late in the process, preferably just before the silicate.
Instead of using zeolite 4A, zeolites X and Y may be substituted,
as may be other types of zeolite A. While it is preferred to employ
the approximately 70% hydrated zeolite 4A (about 20% moisture content)
of this example, various degrees of hydration of the zeolite are
acceptable and in some instances nearly anhydrous crystalline zeolites
or amorphous zeolites may be employed. Variations in the amount
of bentonite within the range given, to 5%, 7%, 13% and 19% in the
base bead, for example, still result in the making of useful products,
but products containing the larger proportions of bentonite will
,generally be more effective in helping to prevent zeolite deposition
on laundry. In some instances it may be desirable to utilize even
higher percentages of bentonite, within the ranges set forth in
this specification, taking care that the other components of the
base bead will be such that the beads will be free flowing and effective
detergents. The proportion of bentonite suitable to be employed
commercially depends on a number of factors and usually will represent
a balance struck between the desired diminution of zeolite residue
and the desired building and other functional effects of other detergent
composition components that could be incorporated in place of an
increased amount of bentonite.
When the polyphosphate content is varied over the described range
useful detergents result, with those of higher such contents being
more effective detergents due to the excellent building effect of
the polyphosphates. However, a balance of components is desirable
to obtain the best physical properties of the product and sometimes
therefore it may be better to utilize smaller proportions of polyphosphate,
e.g., 20% to 40%, which are still very effective in detergency building
action. When the proportion of nonionic detergent is modified, so
as to be increased to over 20%, sometimes some difficulty may be
obtained in having all the detergent absorbed into the interiors
of the base beads of the present formula. By modifying the structure
of the base beads, either by changing the proportion of polyacrylate
utilized (increasing it) or by adding a small proportion of water
soluble silicate in the crutcher, preferably following anti-gelling
agents (a combination of citric acid and magnesium sulfate is preferred),
the character of the base beads may be modified and their holding
power for nonionic detergent may be increased, thereby improving
flowability of the detergent composition beads. A similar improvement
in flowability may be obtained by employing more zeolite and bentonite,
both of which improve flowability of such types of particulate detergents.
The improvement noted in the detergent compositions of this invention
depositing less residue on washed laundry may be verified by testing
the described product against a control product of essentially the
same formula, with no bentonite present and containing about 8%
of sodium silicate in the final product. In such an evaluation a
Whirlpool Suds Saver Model washing machine may be employed, with
the washing periods being eight minutes at a gentle wash cycle.
The detergent composition concentration should be about 0.06% and
the wash water may be of mixed calcium and magnesium hardnesses,
with a total of 200 p.p.m. hardness, as calcium carbonate. A test
water temperature of 24.degree. C. is used and the items washed
are cotton, polyester, mixed acetate and nylon, and mixed polyester
and cotton. After washing, the washed materials are observed wet
and after line drying. Such testing will verify that moderate residue
will be observed on all the control specimens but those washed with
the invented detergent compositions will show appreciably less residue.
The experiment of Example 1 is repeated, without the polyacrylate
being present in the crutcher mix. The throughput rate through the
spray drying tower is diminished and the absorption capability of
the base beads for nonionic detergent is also less. However, the
crutcher mix does not freeze in the crutcher, the base beads can
be manufactured by spray drying and the resulting detergent composition,
although it is held lower in nonionic detergent content, e.g., about
15% nonionic detergent, is also a very useful product and is of
satisfactory flow characteristics. Still, a minimum polyacrylate
content (0.05% to 0.2%) is desirably present.
The procedure described in Example 1 is repeated, with 5% (final
product basis) of sodium silicate of Na.sub.2 O:SiO.sub.2 ratio
of 1:2.4 being added to the crutcher as a 47.5% solids aqueous solution.
The product made does not gel in the crutcher, following normal
manufacturing procedures, but it is desirable to utilize magnesium
sulfate and citric acid, as per my parent application Ser. No. 279,550
and the foregoing instructions, to prevent gelation or freezing
when the holdup time may be appreciably longer than is normal. Also,
the detergent composition made leaves more residue on washed laundry,
which is especially noticeable, when the colors of such laundry
are dark, the laundry is line dried, and the water soluble silicate
is crutcher added.
The experiment of Example 1 is repeated with 5% of hydrous sodium
silicate (Britesil) being post-added with the enzyme powder. Such
post-added silicate does not adversely affect zeolite deposition
on washed laundry as much as would be expected from a comparable
proportion that is added to the crutcher, and in the present case
the color lightening effect is not considered to be as objectionable.
The post-added hydrous silicate does aid in corrosion prevention
with respect to aluminum washing machine parts, and functions as
a water softener and detergent builder.
By a process essentially like that of Example 1 base beads are
made and from them is made a detergent product containing 30 parts
of zeolite 4A, 30 parts of pentasodium tripolyphosphate, 20 parts
of the nonionic detergent (Neodol 23-6.5 or 25-7), 5 parts of bentonite,
5 parts of water, 5 parts of sodium carbonate, 5 parts of sodium
silicate (Na.sub.2 O:SiO.sub.2 =1:2.4), 1.7 parts of fluorescent
brightener, 1.5 parts of magnesium sulfate, 1.3 parts of enzyme,
0.4 part of citric acid (as sodium citrate), 0.2 part of perfume,
0.2 part of ultramarine blue and 0.1 part of sodium polyacrylate.
Such product is a useful heavy duty laundry detergent of good washing
and flow characteristics but, while it deposits less zeolite-silicate
aggregate on washed clothing than conventional zeolite- and silicate-containing
detergents, its zeolite deposition characteristics are not as good
as those of a comparable formula from which the silicate, magnesium
sulfate and citric acid are omitted. Similar products result when
the pentasodium tripolyphosphate is half or completely replaced
with tetrasodium pyrophosphate.
Detergent compositions like those of Example 1 are made, utilizing
5 parts of tetrasodium pyrophosphate in place of 5 parts of the
tripolyphosphate. The product resulting is as capable of absorbing
nonionic detergent as the Example 1 product without any appreciable
change in flow properties, and it is a good heavy duty detergent
product, possibly somewhat superior to the Example 1 product in
some cleaning aspects. Zeolite deposition prevention characteristics
of this product are as good as those of the product of Example 1.
A conventionally spray dried detergent composition is made, containing
about 15% of sodium linear tridecyl benzene sulfonate, 25% of zeolite
4A, 25% of pentasodium tripolyphosphate, 10% of tetrasodium pyrophosphate,
10% of bentonite, 5% of normal adjuvants and 10% of moisture, and
such is blended with the composition of Example 1 in equal parts.
Of course, the compositions are of approximately the same moisture
contents (about 10%) and particle sizes, in the No. 10 to 100 (or
10 to 60) U.S. Sieve Series range and are of bulk densities before
mixing within about 0.1 g./cc. of each other (about 0.5 g./cc. for
this product and 0.5 to 0.6 g./cc. for that of Example 1). The combined
product is of approximately the same flowability as that of Example
1 and is an excellent detergent, possessing the properties of both
compositions, while being of reduced zeolite deposition characteristics,
compared to a control containing the normal binding and corrosion
preventing percentage of water soluble sodium silicate.
Following substantially the procedure described in Example 1 a
crutcher mix is made from 36.9 parts of water, 1.2 parts of fluorescent
brightener (Tinopal 5BM, extra concentrated) 0.1 part of ultramarine
blue, 2.1 parts of magnesium sulfate (heptahydrate), 0.3 part of
sodium citrate, 22.4 parts of zeolite 4A powder (partially hydrated,
to about 20% moisture content), 23.0 parts of pentasodium tripolyphosphate,
7.4 parts of a 47.5% solids water solution of sodium silicate (Na.sub.2
O:SiO.sub.2 =1:2.4), 3.7 parts of sodium bentonite (formerly marketed
as THIXO-JEL No. 2), and 2.8 parts of natural soda ash. The crutcher
mix was spray dried in a manner like that previously described,
with the moisture loss in drying being about 45.2%.
Onto 78.4 parts of the spray dried base beads, of particle sizes
in the No. 10 to 100 range (screened), are sprayed 20 parts of Neodol
23-6.5, after which the beads are mixed with 1.3 parts of high activity
proteolytic enzyme, and 0.3 part of detergent perfume is sprayed
onto them. The final product has a zeolite content of 25%, a polyphosphate
content (some TSPP is formed during crutching and spray drying)
of 33%, a sodium bentonite content of 5% and a water soluble sodium
silicate solids content of 5%. The moisture content is 5% and the
active detersive ingredient (polyethoxylated higher fatty alcohol)
content is 20%. The bulk density is about 0.7 g./cc. and the pH
of its 1% solution is about 10.
The detergent composition made by this method is a satisfactory
heavy duty nonionic detergent but does deposit somewhat more zeolite-silicate
aggregate on washed clothing that is line dried than does a corresponding
composition made without any water soluble silicate solids. It is
preferred that in such corresponding composition there is also present
about 0.1% to 0.5% of low molecular weight sodium polyacrylate,
of the type previously described herein. Both products wash laundry
well and are especially effective in cold water washing, due at
least in part to the bentonite contents thereof and the almost instantaneous
dispersion that is observed when the detergent is added to wash
water (which dispersion also diminishes time for any reaction between
soluble silicate and zeolite to form objectionable aggregates).
The invention has been described with respect to various examples
and illustrations thereof but is not to be limited to these because
it is clear that one of skill in the art, with the present description
before him, will be able to utilize substitutes and equivalents
without departing from it.