DETERGENT COMPOSITIONS

DETERSIF

English Abstract

DETERGENT COMPOSITIONS
Terrell W. Gault
and
Edward J. Maguire, Jr.
ABSTRACT OF THE DISCLOSURE
Detergent compositions, including compositions for
use in automatic dishwashing machines, are prepared by
incorporating into the composition an intimate mixture of
a nonionic surfactant and a silicone-containing suds suppressing
agent. The compositions have reduced or controlled sudsing
characteristics even after extended storage periods. The
use of preferred self-emulsified silicone suds suppressors
permits the production of low-sudsing spray-dried detergent
granules without necessitating separate incorporation of the
suds suppressors.

Claims

The embodiments of the invention in which an exclusive
property or privilege is claimed are defined as follows:
1. A non-liquid detergent composition comprising an
ingredient capable of inactivating silicone suds suppressors
and, in intimate admixture therewith, from about 2.5 to about
100% by weight of the composition of an intimate mixture of a
nonionic surfactant and from about 0.01 to about 5% by weight
of silicone suds suppressor, said intimate mixture being
selected from the group consisting of
(a) a mixture of a normally solid nonionic surfactant
with a non-self-emulsified silicone suds suppress-
or, and
(b) a mixture of a nonionic surfactant with a self-
emulsified silicone suds suppressor,
wherein the nonionic surfactant is selected from the group
consisting of
(a) the condensation product of alkyl phenols with
from about 5 to 20 moles of ethylene oxide;
(b) the condensation product of C8-C22 aliphatic
alcohols with from about 3 to 18 moles of
ethylene oxide;
(c) the condensation product of ethylene oxide with
a hydrophobic base formed by the condensation
of propylene oxide with propylene glycol, wherein
the molecular weight of the hydrophobic portion
is from about 1,500 to about 1,800;
38

(d) the condensation product of ethylene oxide with
the product resulting from the reaction of
propylene oxide and ethylene diamine, wherein the
molecular weight of the hydrophobic portion is
from about 2,500 to about 3,000 and the conden-
sation product contains from about 40 to about
80% by weight of polyoxyethylene; and
(e) mixtures thereof.
2. A detergent composition according to Claim 1
wherein the suds suppressor comprises a self-emulsified sili-
cone suds suppressor.
3. A detergent composition according to Claim 2
wherein the self-emulsified silicone suds suppressor contains,
as an emulsifier, a modified polysiloxane having at least one
polyoxyalkylene moiety in the polymer.
4. A detergent composition according to Claim l
wherein said intimate mixture is incorporated into a
carrier granule comprising a detergent builder salt.
5. A detergent composition comprising
(A) from about 10 to about 60% of a detergent
builder salt, and
(B) an intimate mixture consisting essentially of
(i) from about 2.5 to about 12.5% by weight
of the composition of a normally solid
nonionic surfactant, and
(ii) from about 0.05 to about 0.5% by weight
of the composition of a non-self-emulsified
silicone suds suppressor;
39

wherein said nonionic surfactant is selected from the group
consisting of
(a) the condensation product of alkyl phenols with
from about 5 to 20 moles of ethylene oxide;
(b) the condensation product of C8-C22 aliphatic
alcohols with from about 3 to 18 moles of ethylene
oxide;
(c) the condensation product of ethylene oxide with
a hydrophobic base formed by the condensation
of propylene oxide with propylene glycol, wherein
the molecular weight of the hydrophobic portion
is from about 1,500 to about 1,800;
(d) the condensation product of ethylene oxide with
the product resulting from the reaction of pro-
pylene oxide and ethylene diamine, wherein the
molecular weight of the hydrophobic portion is
from about 2,500 to about 3,000 and the condensa-
tion product contains from about 40 to about 80%
by weight of polyoxyethylene; and
(e) mixtures thereof.
6. A detergent composition according to Claim 5
wherein the suds suppressor is a polydimethylsiloxane fluid.

7. A detergent composition according to Claim 5
wherein the nonionic surfactant is a C15-C20 aliphatic alcohol
condensed with from 6 to about 20 moles of ethylene oxide
per mole of alcohol.
8. A detergent composition according to Claim 5
wherein the suds suppressor is a mixture of a polydimethyl-
siloxane fluid and silica.
9. A detergent composition according to Claim 5
wherein the suds suppressor is a mixture which comprises:
(a) from about 10 parts to about 100 parts by
weight of a polydimethylsiloxane fluid having
a viscosity in the range from 20 cs. to 1500 cs.
at 25°C;
(b) from 5 to 50 parts by weight of a siloxane
resin composed of (CH3)3 SiO1/2 units and
SiO2 units in which the ratio of the (CH3)3SiO1/2
units to the SiO2 units is within the range of
from 0.6/1 to 1.2/1; and
(c) from 1 to 10 parts by weight of a silica aerogel.
10. A detergent composition comprising
(A) from about 10 to about 60% of a detergent
builder salt, and
(B) an intimate mixture consisting essentially of
(i) from about 2.5 to about 12.5% by weight
of the composition of a nonionic sur-
factant, and
(ii) from about 0.05 to about 0.5% by weight of
the composition of a self-emulsified
silicone suds suppressor;
41

wherein said nonionic surfactant is selected from -the
group consisting of
(a) the condensation product of alkyl phenols with
from about 5 to 20 moles of ethylene oxide;
(b) the condensation product of C8-C22 aliphatic
alcohols with from about 3 to 18 moles of
ethylene oxide;
(c) the condensation product of ethylene oxide with
a hydrophobic base formed by the condensation
of propylene oxide with propylene glycol, wherein
the molecular weight of the hydrophobic portion
is from about 1,500 to about 1,800;
(d) the condensation product of ethylene oxide with
the product resulting from the reaction of
propylene oxide and ethylene diamine, wherein
the molecular weight of the hydrophobic portion
is from about 2,500 to about 3,000 and the
condensation product contains from about 40 to
about 80% by weight of polyoxyethylene; and
(e) mixtures thereof.
11. A detergent composition according to Claim 10
wherein the nonionic surfactant is normally liquid.
12. A detergent composition according to Claim 11
wherein the self-emulsified silicone suds suppressor contains
as an emulsifier the condensation product of from about 300
to 2000 moles of ethylene oxide with a fatty acid.
13. A detergent composition according to Claim 10
wherein the self-emulsified silicone suds suppressor contains,
as an emulsifier, a modified polysiloxane having at least one
polyoxyalkylene moiety in the polymer.
42

14. A detergent composition according to Claim 13
wherein the self-emulsified silicone component contains an
emulsifier having the general formula RaSiY4-a' wherein a is 0
or an integer from 1 to 3; R is selected from the group con-
sisting of
(a) alkyl group containing from 1 to about 30
carbon atoms, and
(b) groups having the formula -R'-(OR')bOR''
wherein R' is an alkylene group containing from
1 to about 6, preferably from 2 to ~ carbon
atoms, b has a value of from 1 to about 100;
and R" is a capping group which can be selected
from the group consisting of hydrogen, alkyl,
aryl, alkaryl, aralkyl or alkenyl groups con-
taining up to 20 carbon atoms, sulfate, sulfonate,
phosphate, phosphonate, borate or isocyanate
groups, or mixtures thereof; and Y is a group
having the formula
<IMG>
wherein R has the formula given hereinbefore, and
c has a value from 1 to 200; and wherein at least
one R group in the compound has the formula
[-R'(OR')b-R''], in which b is sufficiently large
to create an emulsifier.
43

15. A detergent composition according to Claim 14
wherein the suds suppressor additionally comprises a polydi-
methylsiloxane fluid.
16. A detergent composition according to Claim 15
wherein the suds suppressor consists essentially of at least
50% by weight of a compound of the formula RaSiY4-a' from
about 5% to about 45% of a polydimethylsiloxane liquid and
from 0.05 to about 5% of silica.
17. A detergent composition according to Claim 16
wherein the nonionic surfactant is a C12-C15 aliphatic alcohol
condensed with from 3 to about 9 moles of ethylene oxide
per mole of alcohol.
18. A process for preparing the granular detergent
composition of claim 1 comprising the steps of:
(A) preparing an intimate mixture in a liquid phase
of a nonionic surfactant and a silicone suds
suppressor, said intimate mixture being selected
from the group consisting of
(i) a mixture of a normally solid nonionic
surfactant with a non-self-emulsified
silicone suds suppressor, and
(ii) a mixture of a nonionic surfactant with
a self-emulsified silicone suds suppressor;
wherein said nonionic surfactant is selected from the group
consisting of
44

(a) the condensation product of alkyl phenols with
from about 5 to 20 moles of ethylene oxide;
(b) the condensation product of C8-C22 aliphatic
alcohols with from about 3 to 18 moles of
ethylene oxide;
(c) the condensation product of ethylene oxide with
a hydrophobic base formed by the condensation
of propylene oxide with propylene glycol, wherein
the molecular weight of the hydrophobic portion
is from about 1,500 to about 1,800;
(d) the condensation product of ethylene oxide with
the product resulting from the reaction of pro-
pylene oxide and ethylene diamine, wherein the
molecular weight of the hydrophobic portion is
from about 2,500 to about 3,000 and the conden-
sation product contains from about 40 to about
80% by weight of polyoxyethylene; and
(e) mixtures thereof;
(B) spraying said intimate mixture in liquid phase onto
a carrier granule comprising a detergent builder salt.
19. A process according to Claim 18 wherein the suds
suppressor is a self-emulsified silicone suds suppressor con-
taining, as an emulsifier, a modified polysiloxane having
at least one polyoxyalkylene moiety in the polymer.

20. A process according to Claim 18 wherein the nonionic
surfactant is normally liquid and the process is carried
out at room temperature.
21. A process according to Claim 20 wherein the self-emulsified
silicone suds suppressor contains, as an emulsifier, the
condensation product of from about 300 to 2,000 moles of
ethylene oxide with a fatty acid.
22. A process according to Claim 18 wherein the nonionic
surfactant is normally solid and said intimate mixture is
formed by melting the nonionic surfactant, passing the
molten surfactant along a conduit to a spray nozzle and
introducing said silicone suds suppressor into the conduit
immediately upstream of said spray nozzle.
23. A process according to Claim 22 wherein at least one
mixing means is provided in the conduit downstream of the point
of introduction of the silicone suds suppressor.
46

24. A spray-dried granular detergent composition
comprising
(a) from about 2 to about 60% by weight of an
alkoxylated nonionic surfactant,
(b) from about 0.01% to about 5% by weight of the
composition of a self-emulsified silicone suds
suppressor containing a modified polysiloxane
having polyoxyalkylene moieties in the polymer,
and
(c) from about 10% to about 80% by weight of a
detergency builder;
said alkoxylated nonionic surfactant being selected from the
group consisting of
(i) the condensation product of alkyl phenols with
from about 5 to 20 moles of ethylene oxide;
(ii) the condensation product of C8-C22 aliphatic
alcohols with from about 3 to 18 moles of
ethylene oxide;
(iii) the condensation product of ethylene oxide
with a hydrophobic base formed by the condensation
of propylene oxide with propylene glycol, wherein
the molecular weight of the hydrophobic portion
is from about 1,500 to about 1,800;
(iv) the condensation product of ethylene oxide with
the product resulting from the reaction of propy-
lene oxide and ethylene diamine, wherein the
molecular weight of the hydrophobic portion is
from about 2,500 to about 3,000 and the condensa-
tion product contains from about 40 to about 80%
by weight of polyoxyethylene; and
(v) mixtures thereof.
47

25. A detergent composition according to Claim 24 wherein
the alkoxylated nonionic surfactant is present in an amount
of from about 5 to about 35% by weight of the composition.
26. A detergent composition according to Claim 25 wherein
the self-emulsified silicone component contains an emulsifier
having the general formula RaSiY4-a wherein a is 0 or an
integer from 1 to 3; R is selected from the group consisting of
(a) alkyl groups containing from 1 to about 30 carbon
atoms, and
(b) groups having the formula -R'-(OR')bOR" wherein
R' is an alkylene group containing from 1 to
about 6, preferably from 2 to 4 carbon atoms, b has
a value of from 1 to about 100; and R" is a capping
group which can be selected from the group consisting
of hydrogen, alkyl, aryl, alkaryl, aralkyl or
alkenyl groups containing up to 20 carbon atoms;
acyl groups containing up to 20 carbon atoms,
sulfate, sulfonate, phosphate, phosphonate,
48

borate or isocyanate groups, or mixtures thereof;
and Y is a group having the formula
<IMG>
wherein R has the formula given hereinbefore, and c has a value
from 1 to 200; and wherein at least one R group in the
compound has the formula [-R'(OR')b-R"] in which b is
sufficiently large to create an emulsifier.
27. A detergent composition according to Claim 26 wherein
the suds suppressor additionally comprises a polydimethyl-
siloxane fluid.
28. A detergent composition according to Claim 27 wherein
the suds suppressor consists essentially of at least 50%
by weight of a compound of the formula RaSiY4-a' from about
5 to about 45% of a polydimethylsiloxane liquid and from
0.05 to about 5% of silica.
29. A detergent composition according to Claim 28 wherein
the nonionic surfactant is selected from the group consisting
of C8-C18 aliphatic alcohols condensed with from 3 to about
15 moles of ethylene oxide per mole of alcohol and (C6-C9 alkyl)
phenols condensed with from about 6 to about 16 moles of
ethylene oxide per mole of phenol.
49

30. A detergent composition according to Claim 29 wherein the
nonionic surfactant is prepared by ethoxylating a C12-C13
alcohol containing approximately 20% of 2-alkyl, predominantly
methyl, branching, with 3 moles of ethylene oxide per mole of
alcohol and stripping the ethoxylated material to remove low-
molecular weight components to yield an ethoxylated alcohol
with an average of about 4.9 moles of ethylene oxide per
mole of alcohol and an HLB of about 10.55.
31. A detergent composition according to Claim 30 wherein
the detergency builder is selected from the group consisting
of water-soluble alkali metal phosphates, pyrophosphates,
orthophosphates, polyphosphates, phosphonates, carbonates,
polyhydroxysulfonates, silicates, polyacetates, carboxylates,
polycarboxylates and succinates.
32. A process for preparing the detergent composition of
Claim 24 comprising the steps of
(a) forming a homogeneous, aqueous slurry comprising
(i) from about 1 to about 40% by weight of
the slurry Of said alkoxylated nonionic
surfactant,
(ii) from about 0.005 to about 4% by weight of
the slurry of a self-emulsified silicone
suds suppressor containing a modified
polysiloxane having polyoxyalkylene moieties
in the polymer,
(iii) from about 10% to about 80% by weight of a
detergency builder, and

(iv) from about 15 to about 50% by weight of the
slurry of water; and
(b) drying the homogeneous slurry to form a granular
detergent composition.
33. A process according to claim 32 wherein the
drying step is performed by spray-drying the slurry.
51

Description

~ lQ85697
; BACKGROUND OF THE INVENTION
; This invention relates to detergent compositions and,
in particular, to detergent compositions which have controlled
' sudsing characteristics, especially those useful in auto-
` matic dishwashing.
Detergent compositions normally contain surfactants
which tend to produce foam when agitated in aqueous solution.
For many applications, especially in automatic washing and
dishwashing machines, excess foam production is a serious
problem with detergent compositions and with many effective
surfactants it is necessary to add foam inhibiting compounds,
hereinafter called suds suppressors, in order to achieve
acceptable sudsing characteristics.
Unfortunately, it has been found that the addition ~
of suds suppressors can in itself create new problems. For ~ ;
example, monostearyl acid phosphate, which is one conventional
suds suppressor, is very effective and useful at low levels
in the product, but as the level of suds suppressor is increased
~ to cope, for example, with increased surfactant, then the suds
- 20 suppressor becomes incompletely soluble in a wash solution and
precipitates out of solution onto utensil and machine surfaces
leaving them coated with unsightly streaks and deposits.
Another type of suds suppressor which has often been
suggested is that based on silicones, especially polydimethyl-
siloxane. These materials, referred to generically herein-
after as silicone suds suppressors, are known to be very useful
in industrial applications where the silicone suds suppressor
is added directly to an aqueous solution containing a sur-
factant. However, they have not lived up to their promise
when incorporated into detergent compositions; frequently, for
example, they beco~e inactivated in the presence of other de-
tergent incredients and require some type of special protection.
, ,,

~38S69~ :
It has now been found that stable suds suppressed
detergent compositions can be prepared by incorporating silicone
materials into the compositions in a particular manner.
Accordingly, it is an object of the invention to
provide detergent compositions which are storage-stable and
which include silicone suds suppressors.
It is a further object of the invention to provide
a process for the incorporation of silicone suds suppressors
into detergent compositions to provide storage-stable suds- ;
suppressed compositions.
Another problem exhibited by conventional silicone
suds suppressors, such as polydimethylsiloxane, is that they
are either completely inactivated in the spray-drying process
or they lose their activity very quickly after the spray-
dried granules have been made.
In the preparation of spray-dried detergent granules
an aqueous mixture of the various components of the granules
(the crutcher mix) is sprayed or otherwise introduced into
what is essentially a drying tower. As the droplets of the
crutcher mix proceed through the drying tower, the water
is flashed off and solid or semiporous detergent granules
are secured. The advantage of spray-dried detergent granules
over granules obtained by simple dry mixing of the individual
ingredients is their homogeneity. That is to say, each granule
contains the various ingredients ln the same ratio proportions
introduced into the original crutcher mix. This provides
obvious advantages over simple dry mix detergent formulations
inasmuch as dry mixing can result in a lack of homogeneity
in the final detergent formulations such that the user is
never certain of the composition of any given portion of the
product.
In order to provide a homogeneous spray-dried granule

~L~856~
it is necessary that the crutcher mix, itself, by substantially
homogeneous. In some instances, a crutcher mix may be a
homogeneous solution. However, in order to provide a crutcher
solution, excess amounts of water are needed to dissolve all
the components. Use of excess amounts of water requires
additional drying capacity in the spray-dry tower and is
not economically attractive. For the most part, the crutcher
mixes employed in the preparation of spray-dried detergent
compositions are semidissolved aqueous slurries of the various
components desired in the final spray-dried granules.
The crutching and spray-drying process, while possess-
ing the above advantages, does create a problem with regard to
the incorporation into the granules of relatively sensitive
ingredients, such as the conventional silicone suds suppressors,
at least partly as a result of the high alkalinity and temper-
; atures present during the crutching stage. Such ingredients
can of course be incorporated into the composition after
spray-drying, for example, by dry mixing or spraying on. But
the necessity of such an extra step in the process is unde-
sirable. In addition, certain ingredients, especially those
present in minor amounts, are not easy to distribute uniformly
throughout a spray-dried granular composition. Clearly then,
a very desirable way to include a silicone suds suppressor into
a detergent composition would be simply to add the material
directly to the crutcher mix before spray-drying.
Furthermore, it is known that the introduction of
alkoxylated nonionic surfactants into an aqueous detergent
crutcher mix tends to cause inhomogeneity in the mix. This
is because the nonionic materials tend to be oily and to
exist in a separate phase. This problem can be helped by
the use of agents such as certain alkyl phosphate esters

~al8~69t7
.`
or preferably, as is taught in Canadian Patent No. 1,039,141
of R. M. Wise, granted September 26, 1978, by using kaolinite or
bentonite clays. However, this problem of inhomogeneity in
the crutcher mix is exacerbated by the addition of conven-
tional silicone suds suppressors, such as polydimethysiloxane,
since these materials are themselves oily and do not disperse
well either in water or in nonionic surfactant.
It is therefore an additional object of this invention
to provide spray-dried detergent granules which include a
nonionic surfactant and also a silicone suds suppressor. ;
It is a further object herein to provid~ an improved
process for the incorporation of certain silicone suds suppress-
ors into spray-dried detergent granules containin~ substantial
quantities of nonionic surfactant.
DESCRIPTION OF THE PRIOR ART
Silicones are widely known as useful suds suppressing ;
agents in aqueous systems. For example, U.S. Patents 3,250,727;
3,383,327; and 3,455,839 relate to suds suppressors based on
polydimethyl-siloxane and their use in defoaming aqueous
solutions.
U.S. Patent 3,235,509 relates to silicone suds
suppressors which are absorbed into a solid silica material
in order to improve their stability towards alkaline materials.
However, even this silicone/silica material has been found
unsatisfactory for certain applications and U.S. Patent
3,933,672, Bartolotta et al, issued January 20, 1976, relates
to the further protection of silicone/silica materials by
their incorporation into a solid, substantially non-surface
active matrix.
Clearly, the additional step of encapsulating or
otherwise protecting the silicone material in an inert carrier
is both expensive and time-consuming, and it has therefore

- 16~1 3S69~7
been suggested in Canadian Patent No. 525,433 and in U.S.
Patent 3,829,386 that a silicone suds suppressor can be
incorporated into a base product (for example, a carrier granule
which may be alkaline) using a normally liquid surfactant as an
incorporation medium. Unfortunately, this approach has not
been found to be entirely satisfactory since most conventional
silicone materials, for example polydimethylsiloxane itself, do
not disperse wèll in liquid surfactants and tend to migrate out
of the surfactant into contact with other more harmful con-
stituents of the compositions. ~
It has further been suggested, in French Patent ! :
2,279,843, that certain silicone suds suppressor materials may
be formed into a powder and then mixed together with detergent
granules. As above, this procedure introduces additional steps
into the detergent-making process.
SUMMARY OF THE INVENTION
; According to the present invention there is provided
a detergent composition comprising an intimate mixture of from
about 2.5% to about 100% by weight of the composition of a
nonionic surfactant and a suds suppressing amount of a silicone
suds suppressor, said intimate mixture being selected from
the group consisting of (a) a mixture of a normally solid
nonionic surfactant with a non-self-emulsified silicone
suds suppressor and (b) a mixture of a normally liquid or
solid nonionic surfactant with a self-emulsified silicone suds
suppressor. Self-emulsified suds suppressors are characterized
~ by the presence of an emulsifying component, are highly dis-
; persible in solid nonionic surfactants and will self-emulsify
in liquid nonionic surfactants.
The silicone suds suppressor of the instant compo-
sitions is employed herein in a "suds suppressing amount".
- 5 -

569~7
By "suds suppressing amount" is meant that the formulator of
the compositions can select an amount of the suppressor which
will control the suds to the extent desired. For example, for
use in automatic dishwashers, a suds height of zero or near-
zero is desirable; accordingly relatively more of the suds
suppressor will be used. For hand dishwashing, relatively less
suds suppressors will be used. For laundry washing machines,
the amount of suds which can be tolerated may vary widely
depending on the particular application, and accordingly more
or less of the suds suppressors will be used. The amount of
suds controller will also vary with the detergent component
selected. For example, with high sudsing surfactants, relatively
more of the controller is used to achieve the desired suds
control than when low foaming detergents are selected for use
in the compositions herein.
The term "nonionic surfactant" is not intended to
include compounds which, although they have certain surface
active properties, provide substantially no detergent ability.
; Typical of such materials not encompassed by the invention are
the polyethyleneglycols and condensates of more than about 20_
moles of ethylene oxide with a long-chain alcohol. -
Preferred self-emulsified silicone suds suppressors
are those which contain a modified polysiloxane having poly-
oxyalkylene moieties in the polymer. When these materials
are utilized, the present invention provides a process for pre-
paring an aqueous crutcher mix containing a nonionic surfactant,
comprising the addition to the crutcher mix of this specific
type of silicone suds suppressor and blending the crutcher
mix at a temperature of at least 150F ~preferably 150F to
210F) until homogenous. The crutcher mix is then dried,
preferably spray-dried, to provide homogenous detergent granules.

;~ i
:l.O~S69r~'
In its compositional aspect, this embodiment provides
for homogeneous, granular, spray-dried detergent compositions
comprising
(a) from about 2% to about 60go tpreferably 5% to
35%) of an alkoxylated nonionic surfactant; and
(b) a suds suppressing amount of a self-emulsi~ied
silicone suds suppressor containing a modified
polysiloxane having at least one polyoxyalkylene
moiety in the polymer.
DETAILED DESCRIPTION OF THE INVENTION
The compositions of the pxesent invention comprise -
two essential components, a nonionic surfactant and a silicone
suds suppressor, which, it is believed, are in intimate ad- ~
mixture. By the term "intimate admixture" is meant that the `-
silicone suds suppressor is dispersed in and is in direct con-
tact with the nonionic surfactant and does not tend to migrate
- out of the surfactant during storage of the composition.
It will be understood that the compositions can
additionally comprise a wide range of other materials conven-
tionally found in detergent compositions of various types andit will also be appreciated that the compositions may contain
additional nonionic surfactant which are not mixed with the
silicone suds suppressors.
Silicone Suds Suppressor
The silicone materials employed as the suds suppres-
sors herein can be alkylated polysiloxane materials of several
types, either singly or in combination with various solid
materials such as silica aerogels and xerogels and hydrophobic
silicas of various types. In industrial practice, the term ~-
"silicone" has become a generic term which encompasses a
variety of relatively high molecular weight polymers containing

~ ~ ` ,' ` !
69~
siloxane units and hydrocarbyl groups of various types. In
general terms, the silicone suds controllers can be described
as containing siloxane moieties having the general structure
R
sio ) x
R'
wherein x is from about 20 to about 2,000, and R and R' are
each alkyl or aryl ~roups, especially methyl, ethyl, propyl,
butyl and phenyl. The polydimethylsiloxanes (R and Rl are
methyl) having a molecular weight within the range of from about
200 to about 200,000, and higher, are all useful as suds con-
trolling agents. Such silicone materials are commercially
available from the Dow Corning Corporation under the trade
mark "Silicone 200 Fluids".
Additionally, other silicone materials wherein the ` -
side chain groups R and R' are alkyl, aryl, or mixed alkyl
and aryl hydrocarbyl groups exhibit useful suds controlling ~
properties. These materials are readily prepared by the ;-
hydrolysis of the appropriate alkyl, aryl or mixed alkylaryl `~
silicone dichlorides with water in the manner well known in
the art. As specific examples of such silicone suds controll-
ing agents useful herein there can be mentioned, for example,
diethyl polysiloxanes; dipropyl polysiloxa~es; dibutyl poly-
siloxanes; methylethyl polysiloxanes; phenylmethyl polysiloxanes;
and the like. The dimethyl polysiloxanes are particularly
useful herein due to their low cost and ready availability.
A second type of silicone suds controlling agent use- -~
ful in the compositions herein comprises a mixture of an
alkylated siloxane of the type hereinabove disclosed and
solid silica. Such mixtures of silicone and silica can be
prepared by affixing the silicone to the surface of silica
-- 8 --

~85ti~7
(SiO2), for example by means of the eatalytie reaction disclosed
in U.S. Patent 3,235,509. Suds eontrolling agents comprising
mixtures of silicone and silica prepared in this manner
preferably comprise silieone and siliea in a silicone:silica
ratio of from l9:1 to 1:2, preferably 10:1 to l:l. The silica
can be chemically and/or physically bound to the silicone in
an amount which is preferably about 10% to 15~ by weight, based
on the silicone. The particle size of the silica employed
in sueh silica/silicone suds controlling agents should prefer-
ably be not more than lO0 millimicrons, preferably from 10millimicrons to 20 millimierons, and the specific surface area
of the silica should exeeed about 50 m /g.
Alternatively, suds controlling agents comprising
silicone and silica can be prepared by admixing a silicone
fluid of the type hereinabove disclosed with a hydrophobic ~ ;
silica having a particle size and surface area in the range
disclosed above. Any of several known methods may be used for
making a hydrophobic silica which can be employed herein
in eombination with a silicone as the suds eontrolling agent. ;~
For example, a fumed silica can be reacted with a trialkyl
chlorosilane (i.e., "silanated") to aPfix hydrophobic tri-
alkylsilane groups on the surfaee of the silica. In a preferred
and well known process, fumed silica is eontaeted with trimethyl-
chlorosilane and a preferred hydrophobic silanated silica use-
ful in the present eompositions is seeured.
In an alternate procedure, a hydrophobic silica
useful in the present compositions and processes is obtained
by eontacting silica with any of the following compounds: metal,
ammonium and substituted ammonium salts of long chain fatty
acids, such as sodium stearate, aluminum stearate, and the like;
silylhalides, sueh as ethyltrichlorosilane, butyltrichlorosilane,
tricyclohexylehlorosilane, and the like; and long chain alkyl

3S69~
:;
amines or ammonium salts, such as cetyl trimethyl amine, cetyl
trimethyl ammonium chloride, and the like. ;
A preferred suds controlling agent herein comprises
a hydrophobic silanated ~most preferably trimethylsilana-ted)
silica having a particle size in the range from about 10
millimicrons to 20 millimicrons and a specific surface area
above about 50 m2/g intimately admixed with a dimethyl sili-
cone fluid having a molecular weight in the range of from about
500 to about 200,000, at a weight ratio of silicone to silanated
silica of from about 19:1 to about 1:2. Such suds controlling
agents preferably comprise silicone and the silanated silica in
a weight ratio of silicone:silanated silica of from 10:1 to `
1:1. The mixed hydrophobic silanated (especially trimethylsilan-
ated) silica-silicone suds controlling agents provide suds con-
trol over a broad range of temperatures, presumably due to the ~
controlled release of the silicone from the surface of the ,~ -
silanated silica.
Yet another type of silicone suds controlling agent
herein comprises a silicone fluid, a silicone resin and silica.
The silicone fluids useful in such suds controlling mixtures are
any of the types hereinabove disclosed, but are preferably di-
methyl silicones. The silicone "resins" used in such composi~
tions can be any alkylated silicone resins, but are usually
those prepared from methylsilanes. ~ilicone resins are common- ~
ly described as l'three-dimensional" polymers arising from the -
hydrolysis of alkyl trichlorosilanes, whereas the silicone
fluids are "two-dimensional" polymers prepared from the
hydrolysis of dichlorosilanes. The silica components of such
compositions are the micro-porous materials such as the fumed
silica aerogels and xerogels having the particle sizes and
surface areas hereinabove disclosed.
-- 10 ~

~8S69q
The mixed silicone fluid/silicone resin/silica
materials useful in the present compositions can be prepared
in the manner disclosed in U.S. Patent 3,455,839. These mixed
materials are commercially available from the Dow Corning
Corporation. According to U.S. Patent 3,455,839, such materials
can be described as mixtures consisting essentially of:
(a) from about 10 parts of about 100 parts by
weight of a polydimethylsiloxane fluid having a viscosity in
the range from ~0 cs. to 1500 cs. at 25C.
10~b) 5 to 50 parts by weight of a siloxane resin
composed of (CH3)3SiOl/2 units and SiO2 units in which the
ratio of the (CH3)3SiOl/2 units to the SiO2 units is within
the range of from 0.6/1 to 1.2/1; and ~ ~
(c) 1 to 10 parts by weight of a silica aerogel. ~-
Such mixtures can also be sorbed onto and into a water-soluble
solid as disclosed above.
The above-discussed silicone suds suppressors are,
in general, not readily dispersible in nonionic surfactants~ :
and if they are aispersed by agitation, they tend to settle or
migrate out of the surfactant. For the purposes of the
present invention, therefore, these relatively non-dispersible
silicone suds suppressors are used in admixture with nonionic
surfactants which are normally-solid, i.e. solid at room
temperature. This will be discussed in greater detail here-
inafter.
There is a type of silicone suds suppressor which ~ -
is highly dispersible in solid surfactants and which self-
emulsifies in liquid surfactants. This type of suppressor ~;
has little or no tendency to migrate out of the surfactant
phase and, with this type of silicone material, the present
invention encompasses the use of liquid, as well as solid,

~L~85~7
nonionic surfactants.
The above-mentioned self-emulsifiable silicone suds
suppressors are characterized by the presence of an emulsify-
ing component in the suds suppressor compositions. The pre-
ferred self-emulsifiea suds suppressors are those which contain
emulsifiers which ha~e at least one polyoxyalkylene moiety
incorporated into a basic polysiloxane structure~ The polyoxy-
alkylene moieties are preferably incorporated as polymer groups
substituted on silicone atoms and pendant on the basic poly- --
siloxane chain. However, provided that the silicone compound is
rendered into an emulsifier, the polyoxyalkylene moieties can -~
be in other positions and may, for example, form a part o* the
basic polymer chain; i.e., as a block co-polymer. The use of
these preferred emulsifiers in the silicone suds suppressor
composition permits the inclusion of the suds suppressors in
an aqueous, alkaline crutcher mix, and the formation of a
spray-dried, granular detergent composition containing the suds
suppressors in active form.
Highly-preferred emulsifiers of the type described ``~
above are typically represented by the formula
a 4-a
wherein a is 0 or an integer from 1 to 3; R is selected from
the group consisting of (a) alkyl groups containing from 1
to about 30 carbon atoms, (b) groups having the formula
-R'--(OR')bOR
wherein R' is an alkylene group containing 1 to about 6,
preferably from 2 to 4, carbon atoms, b has a ~alue of from
1 to about 100; and R" is a capping group which can be selected
from the group consisting of hydrogen, alkyl, aryl, alkaryl,
aralkyl or alkenyl groups containing up to 20 carbon atoms;
acyl groups containing up to 20 carbon atoms, sulfate, sulfonate,
phosphate, phosphonate, borate or isocyanate groups, or mixtures
- 12 -

~(~856~7
thereof; and Y is a group having the formula
~ ,
(-O-Si-) -OSiR
R
wherein R has the formula given hereinbefore, and c has a
value from 1 to 200; and wherein at least one R group in the
compound has the aforesaid formula
[-R'(OR'~b-R"]
in which b is sufficiently large to create an emulsifier.
Preferred emulsifiers and self-emulsifiable silicone
suds controlling agents containing them are those described
in Morehouse, U.S. Patents 3,233,986 and 3,511,7~8. The agents
of U.S. Patent 3,511,788 are most preferred. Preferred
combinations of these emulsifiers together with silicone
suds controlling agents are disclosed in British Patent
1,373,903 and U.S. Patent 3,746,653. Preferably, the mixtures
will contain at least 50% of RaSiY4 a' from about 5% to about
45% of a polydimethylsiloxane li~uid and from 0.05% to about 5% ~; ;
of silica. The mixture can additionally comprise a minor `amount of a polydimethylsiloxane resin. `
Other effective self-emulsified silicone suds -
suppressors are those which contain a high ethoxylate of a
fatty acid as the emulsifying component. The condensation
products of from about 300 to about 2,000 moles of ethylene
oxide for each mole of fatty acid are particularly useful.
~atty acids are straight-chain saturated and unsaturated mono-
carboxylic acids, usually containing an even number of carbon
atoms (from about 10 to about 20), preferably around
eighteen in number. Examples of common fatty acids include
palmitic acid, stearic acid and oleic acid.
The emulsifying component may also be a ~witterionic

~8S69~
surface active agent. Zwitterionic surfactants useful herein
include derivatives of aliphatic quaternary ammonium, phos-
phonium and sulfonium compounds, in which the aliphatic
moieties can be straight or branched chain, and wherein one
of the aliphatic substituents contains from about 8 to 18
carbon atoms and one contains an anionic water-solubilizing :.'
group. Preferred 2witterionic materials are the ethoxylated
ammonium sulfonates and sulfates disclosed in U.S. Patent
3,925,262, Laughlin et al, issued December 9, 1975; and U.S.
10Patent 3,939,678, Laughlin et al, issued December 30, 1975. .
Particularly preferred ethoxylated zwitterionic sur-
factants are those having the formula:
CH3
C16H33 1 (C2H4OlgC2H4X wherein X is SO3 or SO4. ~ ~
CH .~ :
Additional preferred zwitterionic surfactants include
those having the formula: :
1 3
16 33 N (C2H4)yC2H4S4
t 2 4 )x
wherein the sum of x + y is equal to about 15. ;
The amount of silicone suds suppressing composition :.
~ used is from about 0.01% to about 5%, preferably from about
; 0.05% to about 0.5%, and most preferably from about 0.1%
to about 0.4% by weight of the detergent compositions of the
present invention.
Nonionic Surfactan-t
"
As indicated above, the nonionic surfactants use-
ful in the present invention may be solid or, when in admix-
ture with self-emulsifiable silicone materials, liquid.
Most commonly, nonionic surfactants are compounds
produced by the condensation of an alkylene oxide (hydrophilic
- 14 -

~8S6~7
in nature) with an organic hydrophobic compound which is
usually aliphatic or alkyl aromatic in nature. The length
of the hydrophilic polyoxyalkylene moiety which is condensed
with any particular hydrophobic compound can be readily
adjusted to yield a water-soluble compound having the desired
degree of balance between hydrophilic and hydrophobic elements.
The balance between the hydrophobic and hydrophilic
moieties of the nonionic surfactant and, more importantly,
the chain length of each of the moieties, determines whether
the surfactant is normally solid (i.e. melting point ~18C)
or normally liquid.
Examples of suitable types of nonionic surfactant
(without particular reference at this point to their phase)
include:
1. The polyethylene oxide condensates of alkyl
phenols. These compounds include the condensation products of -
alkyl phenols having an alkyl group containing from about 6
to 12 carbon atoms in either a straight chain or branched
chain configuration, with ethylene oxide, the said ethylene ``
oxide being present in amounts equal to 5 to 20 moles of ethylene
oxide per mole of alkyl phenol. The alkyl substituent in
such compounds may be derived, for example, from polymerized
propylene, diisobutylene, octene, or nonene. Examples of
compounds of this type include nonyl phenol condensed with
about 9.5 moles of ethylene oxide per mole of nonyl phenol,
dodecyl phenol condensed with about 12 moles of ethylene
oxide per mole of phenol, dinonyl phenol condensed with
about 15 moles of ethylene oxide per mole of phenol, di- ;
isoctylphenol condensed with about 15 moles of ethylene -
oxide per mole of phenol. Commercially available nonionic
surfactants of this type include "igepal CO-610*
*Trademark
- 15 -

:1~8S6~7
marketed by ~he GAF Corporation; and "Triton X-45"**, "Triton
X-114"***, "Triton X-100" and "Triton X-102" , all marketed
by the Rohm and Haas Company~ ~'
2. The condensation products of aliphatic alcohols
with ethylene oxide. The alkyl chain of the aliphatic alcohol
may either be straight or branched and generally contains from
about 8 to about 22 carbon atoms. Pre~erably, there are from
about 3 to about 18 moles of ethylene oxide per mole of
alcohol. Examples of such ethoxylated alcohols include
the condensation product of about 6 moles of ethylene oxide
with 1 mole of tridecanol, myristyl alcohol condensed with about
10 moles of ethylene oxide per mole of myristyl alcohol, the
condensation product of ethylene oxide with coconut fatty
alcohol wherein the coconut alcohol is a mixture of fatty
alcohols with alkyl chains varying from 10 to 14 carbon atoms
and wherein the condensate contains about 6 moles of ethylene
oxide per mole of alcohol, and the condensation product of about
9 moles of ethylene oxide with the above-described coconut
alcohol. Examples of commercially available nonionic sur-
factants of this type include "Tergitol 15-S-9"1 marketed by
the Union Carbide Corporation, "Neodol 23-6.5"2 marketed by `
the Shell Chemical Company and "Kyro EoB"3 marketed by the
Procter & Gamble Company.
3. The condensation products of ethylene oxide with
a hydrophobic base formed by the condensation of propylene
oxide with propylene glycol. The hydrophobic portion of these
compounds has a molecular weight of from about 1,500 to 1,800
and of course exhibits water insolubility. The addition of
polyoxyethylene moieties to this hydrophobic portion tends
** Trademark
*** Trademark
t Trademark
tt Trademark
Trademark
3 Trademark
Trademark
- 16 -

35~97
to increase the water-solubility of the molecule as a whole,
and the liquid character of the product is retained up to
the point where the polyoxyethylene content is about 50%
of the total weight of the condensation product. Examples
of compounds of this type include certain of the commerically
available "Pluronic"4 surfactants marketed by the Wyandotte
Chemicals Corporation.
4. The condensation products of ethylene oxide with
the product resulting from the reaction of propylene oxide
and ethylene diamine. The hydrophobic base of these products
consists of the reaction product of ethylene diamine and
excess propylene oxide, said base having a molecular weight
of from about 2,500 to about 3,000. This base is condensed `
with ethylene oxide to the extent that the condensation
product contains from about 40 to about 80 percent by weight ~-
of polyoxyethylene and has a molecular weight of from about
5,000 to about 11,000. Examples of this type of nonionic
surfactant include certain of the commercially available
"Tetronic" compounds marketed by the Wyandotte Chemicals
.,
Corporation.
Mixtures of the above surfactants are also useful in ~;
the present invention.
Of all of the above-described types of nonionic sur~
- factants, preferred surfactants which are normally solid include
the condensation product of nonyl phenol with about 9.5 moles
of ethylene oxide per mole of nonyl phenol, the condensation
product of tallow fatty alcohol with about 9 moles of ethylene
oxide per mole of fatty alcohol, the condensation product of
; a C15-C20 aliphatic alcohol with from about six to twenty
~ 30 moles of ethylene oxide, and the ethylene oxide/propylene
": 4Trademark
5Trademark
-
,

~s~q
oxide copolymer marketed under the designation of "Pluronic
2.5R5"6. Preferred surfactants which are normally liquid
include the condensation product of a C12-C13 alcohol with
3 moles of ethylene oxide per mole of alcohol, the conden-
sation product of a C14-C15 alcohol with 7 moles of ethylene
oxide per mole of alcohol, the condensation product of a
C12-C15 aliphatic alcohol with from about 3 to ~ moles of
ethylene oxide, and the ethylene/propylene oxide condensate
marketed by Wyandotte Chemicals Corporation under the
trademark of "Pluradot HA 430".
The preferred self-emulsified suds suppressors,
containing a modified polysiloxane having polyoxyalkylene
moieties in the polymer, may be combined with any of the
detersive alkoxylated surfactants well-known in the art and
be formed into granular spray-dried detergent compositions.
In general terms, these nonionics are water-soluble detersive
surfactants of the formula
R-O-(cyH2yo)a~(czH2zo)b CwH2w
wherein R is selected from the group consisting of primary,
secondary and branched chain alkyl hydrocarbyl moieties;
primary, secondary and branched chain alkenyl hydrocarbyl
moieties; and primary, secondary and branched chain alkyl-
and alkenyl-substituted phenolic hydrocarbyl moieties; said
hydrocarbyl moieties having a hydrocarbyl chain length of
from 8 to about 20, preferably 10 to 16, carbon atoms. In
the general formula for the alkoxylated nonionic surfactants
herein, y and z are each integers of from 2 to about 3, pre-
ferably 2, either z or y being 2 when the other integer is 3
(i.e., excluding the all-P0 surfactants); w is an integer of
from 2 to about 3, preferably 2, and a and b are each integers
of from 0 to about 8, the sume of a ~ b being in the range of
: ~ 6Trademark
- 18 -

1~85~9~7
~rom 6 to about 25, pre~erabl~ 6 to 10. The formula of the
surfactants therein encompasses ethylene oxide (EO) as well
as mixed etheylene oxide-propylene oxiae ~EO-PO~ alkoxylates,
all of which are useful herein. The all~PO surfactants do not
provide cleaning advantages in detergent compositions and are
not contemplated for use herein.
Preferred nonionic surfactants used herein are the
ethoxylated nonionics, both from the standpoint of avail
ability and cleaning performance.
Specific examples of alkoxylated nonlonic surfactants
include, but are not limited to, the di~ throu~h hexadeca-
alkoxylates of C8-C18 straight chain, primary alcohols, the
di- through hexadeca-alkoxylates of C~-C2Q straight chain,
secondary alcohols; the di- through hexadeca-alkoxylates of ~
alkyl phenols, the di- through hexadeca-alkoxylates of primary ~ -
and secondary alkenyl alcohols and alkenyl phenols; and the
di- through hexadeca-alkoxylates of branched chain primary
and secondary alcohols.
Particularly preferred alkoxylated nonionic surfactants
include C8-C18 aliphatic alcohols condensed with 3 to about 15
moles of ethylene oxide per mole of alcohol and (C6-C9 alkyl)
phenols condensed with from about 6 to about 16 moles of
ethylene oxide per mole of phenol.
One mixed alkoxylated nonionic system which is
useful herein comprises one or more of the foregoing detersive
alkoxylated nonionic surfactants having an HLB in the range
of from about 11 to 17 (preferably 12 to 15) and, as a
"co-surfactantl', one or more water-soluble alkoxylates having
an HLB in the range of 7 to 10.5 (preferably 9 to 10.5). The
two types of alkoxylated materials are combined in appropriate ~-
weight ratios to provide an overall HLB of the mixture of
- 19 -

~8S6~7
from about 10 to about 12.5 (preferably 10 to 12; most prefer-
ably 10.5 to 12.0). Such mixtures of nonionic surfactant and
nonionic co-surfactant provide superior fabric cleaning per-
formance and are particularly useful for removing greasy soil
from polyester and cotton/polyester fabric blends. These
preferred nonionic suxfactant-plus-nonionic "co-surfactant"
alkoxylate mixtures are more fully described in Belgian Patent
No. 821,093 issued April 15, 1975.
A further highly preferred alkoxylated nonionic sur-
factant system is that disclosed and claimed in the commonly
assigned Canadian Patent 2~o. 1,059,865 of Jerome H. Collins,
granted August 7, 1979. This surfactant system comprises a
base-catalysed primary alcohol eth~xylate having the formula
Rl-R2-O (CH2cH2O)n H wherein Rl i5 a linear alkyl residue
and R2 has the formula CH R3 CH2, R3 being selected from
hydrogen and mixtures thereof with Cl-C4 alkyl groups there
being not more than 70% by weight of said groups in the mixtures,
wherein Rl and R2 together form an alkyl residue containing `
a mean of 9 to 15 carbon atoms at least 65% by weight of said
residue having a chain length within ~ 1 carbon atom of the
mean, wherein 3 5 ~naV~ 6 5. Such a system is also character-
ised by an unethoxylated alcohol content of < 5 wt% and by at
; least 63 wt% of ethoxylates containing two to seven ethylene
oxide groups, the HLB of the system lying in the range
9 5-11.5. The system is otherwise free of alkoxylated non-
ionic surfactants.
Nonionic surfactant systems o~ the above described
type are produced by ethoxylating a suitable alcohol to less
than the desired degree with a base catalyst and then stripping
off the unethoxylated alcohol and lower ethoxylates to give a
product having the desired ethoxylate distribution.
- 20 - `

: L~18~
A preferred material of this type can be prepared from
"Neodol 23"*, a primary C12-C13 OXO alcohol sold by Shell
Chemical Company and containing approximately 20~ of 2-alkyl
(predominantly methyl) branching. To make the preferred
nonionic surfactant, "Neodol 23" is ethoxylated with an
average 3 moles of ethylene oxide per mole of alcohol and
the ethoxylated material is then stripped to remove unethoxyl-
ated alcohol and lower ethoxylates. Approximately 34% by weight ~;
of the ethoxylate is removed and the residue has an HLB of
about 10.55 and an ethoxylation level of about 4.9 moles per
mole of alcohol.
Other Ingredients
In the broadest aspect of the present invention, the
intimate mixture of the above-described two essential com-
ponents can be incorporated into any of a wide variety of
non-liquid detergent compositions. It will be understood
that the process of incorporation must be such that the
physical properties of the intimate mixture are not destroyed.
In general, a sufficient amount of the intimate mixture is
used to provide a concentration of from about 0.01% to about
5%, preferably 0.05% to 0.5~, by weight of the silicone suds
suppressors in the composition.
; The present invention encompasses detergent composi-
tions which contain surfactant materials other than the
essential nonionic surfactant. Such other surfactants are
selected from anionic, nonionic, zwitterionic and ampholytic
: .
surfactants.
Examples of the above type of surfactants are listed
in U.S. Patent No. 3,862,058 of Nirschl and Gloss.
Useful anionic surfactants include alkyl sulfates
*Trademark

iO~3S6~
and sulfonates containing from about 8 to about 18 carbon
atoms; alkyl benzene sulfonates having ~rom about 9 to -
about 20 carbon atoms in the alkyl chain, especially sodium
or alkanolamine salts of linear straight chain alkyl benzene
sulfonates in which the average chain length of the alkyl -
group is from about 10 to about 14, especially about 11.8
carbon atoms (normally abbreviated NaC11 8LAS); alkyl ether ;~
sulfates of the formula
R O (C H O) SO M
wherein R is alkyl or alkenyl of about 10 to about 20 carbon
atoms, n is 1 to 30 and M is an alkali metal cation; and
olefin sulfonates derived by the sulfonation of C12-C24
~-olefins with sulfur trioxide. Other useful anionic sur-
factants in combination with the silicone/surfactant mixture ~;
used in the present invention are alkaline earth metal, pre-
ferably magnesium or calcium, salts of linear alkyl benzene ~-
sulfonic acid. Useful nonionic surfactants, apart from those
already mentioned, include amine oxides, phosphine oxides and ~;~
sulfoxides. Specific examples of such surfactants include
dimethyldodecylamine oxide, dimethylstearylamine oxide, bis- ~-
(2-hydroxyethyl) dodecylamine oxide, dimethyldodecylphosphine ; ~;
oxide, dodecylmethyl sulfoxide and octadecyl methyl sulfoxide. ~
Preferred zwitterionic surfactants include higher ;-
alkyl or alkaryl ammonio propane sulfonates, such as
~; 3-(N,N-dimethyl N-hexadecylammonio~ propane -l-sulfonate,
3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxy propane-l-sul- ~ -
fonate and 3-(N,N-dimethyl-N-alkylammonio-2-hydroxy propane-
l-sulfonate, the alkyl group being derived from middle cut
coconut fatty alcohol and higher alkyl or alkaryl ammonio-
carboxylates such as (N-dodecylbenzyl-N,N-dimethyl ammonio)
acetate, (N,N-dimethyl-N-hexadecylammonio) acetate and
- 22 - ~-

t
1~1856~7
6-(N-dodecylbenzyl-N,N-dimethyl ammonio) hexanoate. Other ;
useful zwitterionic materials are the ethoxylated ammonio-
sulfonates and sulfates disclosed in U.S. Patent 3,929,678,
Laughlin et al, issued December 30, 1975.
Detergent compositions of the present invention nor-
mally include builder salts, especially alkaline, poly-
valent anionic builder salts. These alkaline salts serve
to maintain the pH of the cleaning solution in the range
from about 7 to about 12, preferably from about 8 to about 11.
When the compositions of the present invention are
formed by spray-drying, such builders may be employed in the
crutcher mix at concentrations of from about 1~% to about
80% by weight (preferably 15% to 50%) to yield dry detergent
compositions containing from about 15% to about 90% by weight,
preferably from about 20% to 60%, of said builders.
Suitable detergent builder salts useful herein can
be of the poly-valent inorganic or poly-valent organic types,
or mixtures thereof. Non-limiting examples of suitable
water soluble, alkaline detergent builder salts include
alkali metal phosphates, pyrophosphates, orthophosphates,
polyphosphates, phosphonates, carbonates, polyhydroxysulfonates,
silicates, polyacetates, carboxylates, polycarboxylates and
succinates. Specific examples of such salts include the
sodium and potassium tetraborates, perborates, bicarbonates,
carbonates, tripolyph~sphates, orthophosphates and hexa~
metaphosphates.
Examples of suitable organic alkaline detergency
builder salts are: (1) water-soluble amino polyacetates,
~: e.g., sodium and potassium ethylenediamine tetraacetates,
nitrilotriacetates and N-(2-hydroxyethyl) nitrilodiacetates;
(2) water-soluble salts of phytic acid, e.g., sodium and
potassium phytates; (3) water-soluble polyphosphonates,
- 23 - ~ -

~L~B5~9~7
including, sodiumr potassium and lithium salts of ethane-
l~hydroxy-l, 1-diphosphonic acid; sodium potassium and
lithium salts of methylenediphosphonic acid and the like.
Additional organic buildeL salts useful herein
include the polycarboxylate materials described in U.S.
Patent No. 2,264,103, including the water-soluble alkali
metal salts o~ mellitic acid. The water-soluble salts of
polycarboxylate polymers and copolymers such as are described
in U.S. patent No, 3,308,067, are also suitable herein. It is
to be understood that while the alkali metal salts of the
foregoing inorganic and organic poly-valent anionic builder
salts are preferred for use herein from an economic standpoint,
the ammonium, alkanolammonium, e.g., triethanolammonium, di-
ethanolammonium, and the like, water-soluble salts of any of
the foregoing builder anions are useful herein.
A further class of detergency builder materials useful
in the present invention are insoluble sodium aluminosilicates,
particularly those disclosed in Belgian Patent 814,874,
issued November 12, 1974. This patent discloses and claims ~
detergent compositions containing sodium aluminosilicates ~ -
of the formula
Na (AlO ) (SiO ) xH O
wherein z and y are in~egers equal to at least 6, the molar ;
-~ ratio of z to y is in the range of from 1.0:1 to about
0.5:1 and x is an integer from about 15 to about 264, said
aluminosilicates having a calcium ion exchange capacity of
- at least 200 mg. eq/gram and a calcium ion exchange rate of
at least about 2 grains/gallon/minute/gram. A preferred ; -
material is Nal2(SiO2 A1O2)12 2
Mixtures of organic and/or inorganic builders can
be used herein. One such mixture o~ builders is disclosed
in Canadian Patent No. 755,038, e.g., a ternary mixture of ~-~
- 24 -

~085697
sodium tripolyphosphate, trisodium nitrilotriacetate and
trisodium ethane-l-hydroxy-l, l-diphosphonate.
While any of the foregoing alkaline poly-valent
builder materials are useful herein, sodium tripolyphosphate,
sodium nitrilotriacetate, sodium mellitate, sodium citrate
and sodium carbonate are preferred herein for this builder
use. Sodium tripolyphosphate is especially preferred herein
as a builder both by virtue of its detergency builder activity
and its ability to suspend illite and kaolinite clay soils
and retard their redeposition on the ~abric surface.
In the non-spray-dried compositions of the present
invention the detergent builders are generally used at con-
centrations of from about 10~ to about 60~, preferably 20%
to 50%, by weight.
Bleaching agents may also be incorporated into the
compositions of the present invention and examples of typical
bleaching agents are chlorinated trisodium phosphate and -` the sodium and potassium salts of dichloroisocyanuric acid. ~,
The detergent compositions disclosed herein can of ~ :
course contain other materials commonly used in such com-
positions. For example, various soil-suspending agents
such as carboxymethylcellulose, corrosion inhibitors, dyes,
fillers such as sodium sulfate and silica, optical brighteners, ;~
germicides, anti-tarnishing agents pH adjusting agents such
as mono-, di- or tri-ethanolamine, enzymes, and the like, well-
known in the art for use in detergent compositions, can also
s be employed herein.
- Proce-ssing of the Co-mpositions
In a highly preferred processing aspect of the ~ ~
present invention, the intimate mixture of silicone suds ~ -
suppressors and nonionic surfactant is formed in a liquid ~ -
(if necessary molten) phase and the liquid mixture is sprayed,
- 25 -

~56~
coated onto, adsorbed onto or absorbed into a carrier granule
which contains the other ingredients of the detergent composition.
When a self-emulsified silicone material is used in
conjunction with a liquid or molten liquid surfactan-t, then
the silicone can readily be mixed into the surfactant and
form a stable emulsion or dispersion. Where the less dis-
persible silicones are concerned, then it is necessary that
the silicone/surfactant mixture (using molten surfactant)
is subjected to ag~tation o shear shortly before being
incorporated into the product. In this way, the silicone
material remains sufficiently dispersed in the molten sur-
factant that it does not migrate out before the surfactant
~` cools and sets after being sprayed on to product. Clearly,
after the surfactant has set, there is no likelihood that
the silicone material can escape.
When a normally solid surfactant is used, it is usual -~
to heat the surfactant to form a liquid phase, although the
use of a solvent to bring the surfactant into solution is
not excluded. ~In the heating process, it is important that
~-~ 20 the time during which silicone material isin contact with hot
surfactant is minimized. In certain cases, silicone materials -
can lose their efficacy if contacted by hot, i.e. in the
temperature range 120-200F., surfactant over relatively long
periods of time, for example, over 30 minutes~
In a preferred process, therefbre, liquid surfactant
is sprayed continuously on to carrier granules and the
silicone suds suppressor is injected into a conduit leading ~
to the spra~ nozzle, mixing means being provided down- -
stream of the point of injection. The mixing means may
comprise baffles in a conduit, or a foraminous plate in the
conduit which would cause the silicone material to disperse
effectively throughout the surfactant.
- 26 -

~856g7
For ease of mixing in the process, the self-emulsified
silicone compounds are preferred both in admixture with solid
and liquid surfactants.
Highly preferred detergent compositions of the present
invention are those intended for use in automatic dishwashing
machines. In these compositions, the intimate mixture of
nonionic surfactant and silicone suds suppressors can be ;
sprayed on to a base granule comprising, for example, sodium
tripolyphosphate, chlorinated trisodium phosphate and sodium
silicate. Such base granule can be prepared by agglomerating
the sodium tripolyphosphate and the chlorinated trisodium
~ phosphate with a solution of sodium silicate. Examples of
A~ useful processes for preparing such granules are found in
U.S. Patents 3,598,743 and 3,888,871. ` '-
, In the case of automatic dishwashing machine products
`, the compositions preferably comprise from about 20% to about
60% sodium tripolyphosphate, from about 10% to about 60%
sodium silicate and from about 15% to about 35% of chlorinated
trisodium phosphate in the base granule. Incorporated into ~`
- 20 this base granule is the intimate mixture of nonionic sur-
factant and silicone suds suppressor to give a level of sur~
factant in the composition of from about 2.5% to about 12.5%
and a level of suds suppressor from about 0.05% to about 0.5%.
The detergent compositions of the present invention
are preferably in granular form, but they can also be formulated
in other non-liquid forms, for example as powders, tablets,
pastes and gels.
When the particularly preferred self-emulsified
silicone suds suppressors containing a modified polysiloxane
having polyoxyalkylene in the polymer are used, the process
herein may be carried out by preparing a detergent crutcher mix
comprising the various components which are to be present in
- 27 -

`
:
the final detergent composition in an aqueous medium.
The crutcher mixes employed in this process can
conveniently comprise an aqueous slurry containing from
about 15% to about 50~ (preferably from about 25% to about 40
by weight of water, from about 1~ to about 40% (preferably
from about 5% to about 20%) by weight of a water-soluble
organic detergent component comprising predominantly a non-
ionic surfactant as hereinbefore described, and ~rom about
10% to about 80~ (preferably from about 15% to about 50%)
by weight of detergency builder and adjunct materials as
hereinbefore disclosed. . .
Use of the foregoing crutcher mixes in combination ~.
. with an amount of from about 0.005~ to about 5% by weight of :~
.. the crutcher mix of the preferred self-emulsified suds
suppressors results in the formation of substantially homo- ; :
geneous mixes suitable for preparing homogeneous powdered and
. granular detergent compositions. Of course, such detergent ..
: compositions contain the various ingredients originally pre-
~: sent in the crutcher mix. However, th-e final concentrations of ~
such ingredients in the dry detergent compositions may differ ::
somewhat from their concentrations in the crutcher, inasmuch
as a major portion of the water is removed on drying~
The preferred self-emulsified silicone suds suppressor,
although generally stable in the presence of nonionic sur-
factant, can become inactivated if subjected to extremes
of heat in the presence of surfactant. It is therefore
preferred that the crutcher mix is formed and blended as
quickly as possible and then spray-dried without undue delay.
Generally, residence time in the crutcher of the silicone-
containing mix should not exceed about 10-15 minutes.
It is preferred that the silicone suds suppressor is
intimately mixed with the nonionic surfactant be~ore being
- 28 -

s~
added to the crutcher, as it is believed to be important that
the silicone material remains in the same phase as the nonionic
surfactant.
The crutcher mix is generally prepared at a tempera-
ture of 140F to 150F and the hot mix is introduced into a
spray-drying tower and sprayed to provide a granular detergent
composition. The spray-drying part of the process is con-
ventional.
~.
The ~ollowing examples are representative of the
compositions and processes of the present invention.
EXAMPLE I
, A detergent composition for an automatic dishwashing -
machine was prepared having the following ingredients:
Component ~ by Wt. of
the Composition
~ Sodium tripolyphosphate (STP) 43.0 `
:~! Sodium silicate (SiO :Na O
ratio 2.8) 2 2 16.0
.
Chlorinated trisodium phosphate
(Cl TSP) 26.0
Tallow alcohol condensed with 9
moles of ethylene oxide per mole
of alcohol (TAEg~ 7.5
"Dow Corning DB 544"* suds
suppressor 0.4
Moisture and minors to 100 ;
To prepare the above composition, the STP and the
Cl TSP were mixed and agglomerated in a pan granulator using
a solution of the sodium silicate. After granulation was
complete, the TAEg was heated to above its melting point and
the "DB 544" suds suppressor was mixed into the TAEg to form a
stable emulsion. The molten emulsion was then sprayed onto
the granular material to form the detergent composition.
,
,
A silicone suds suppressor containing a siloxane/glycol
copolymer.
* Trademark
- 29 -

~L~8~
The above composition was tested in the following
manner:
Production of foam in an automatic dishwashing machine
causes a reduction in the speed of revolution of the rotor arm
which is activated by the force of water or detergent solution
passing throu~h the arm. Using the speed of the rotor arm
with pure water as a control (100% efficiency), the speed
of the rotor in a soiled surfactant solution is measured.
- In general, when a low-sudsing surfactant is used together -
; with a suds suppressor, the rotor arm revolves at around
90% of its speed in waterO The figure of 90% is termed the
"suds efficiency". The higher the figure, the more effective
is the suds suppressor.
The composition of Example I, freshly made, had a ;~
suds efficiency of 90%. After nine weeks storage at 90F,
the composition was tested again and was found still to have
a suds efficiency of 90%.
Substantially similar results are obtained where the
"DB544", in the above composition, is replaced by "DB31"*, a
silicone/silica suds suppressor containing a high ethoxylate
fatty acid emulsifying component, marketed by Dow Corning. ~;~
EXAMPLE II
A composition analogous to that of Example I but
containing 0.3% of polydimethylsiloxane in place of the "DB
544" suppressor was prepared. No substantial change in suds
efficiency of the composition was noted after three weeks.
EXAMPLE III
A composition analogous to that of Example I but
containing 0.4% of "Dow Corning DB 100"* suds suppressor (a
silicone/silica suppressor) in place of the "DB 544" suppressor
* Trademark

~3569~7 i
was prepared.
EXAMPLE IV
Using the procedure of Example I, the following
composition was prepared:
`` Component % by Wt.
Sodium tripolyphosphate 26.0
Sodium silicate (SiO2:Na2O ratio 2.4~ 5.0
Sodium silicate (SiO2:Na2O ratio 2~8) 12.0
Chlorinated trisodium phosphate 22.0
TAEg 5 0
;~ 'SAG loo~** 0.2
`, Moisture and minors to 100
~' Using the suds test detailed above, the above
-' composition was tested before ahd after three weeks storage
1 at 90F. No sig~iificant change in suds efficiency was
observed.
EXAMPLE V
A detergent composition suitable for use in an auto-
matic dishwashing machine and having a normally liquid
.. .
nonionic surfactant was prepared in a manner analogous to
that described in Example I and having the following com-
position:
Component % by Wt.
STP 46.0
Sodium silicate (SiO2:Na2O ratio 2.8)17.0
Cl TSP 26.0
Coconut fatty alcohol condensed with 6 ~ `
moles of ethylene oxide per mole of alcohol 7.5
"DB 544
Moisture and minors to 100 ~ ~ .
A polydimethylsiloxane marketed by Union Carbide. ~;
* Trademark
** Trademark
31 -
;''

~S6~7
This composition was relatively high-sudsing and, ~'~
freshly made, had a suds efficiency of 57%. After three ;:
weeks storage at 90F, the suds efficiency was measured .
and was found to be 54% which is not significantly reduced.
'. Substantially similar results were obtained where '~ ~, : - ~
: the "DB 544" in the above composition was replaced by "DB 31"*,
~ a silicone/silica suds suppressor containing a high ethoxylate
:' (containing from about 300 to 2000 ethoxy groups per moleculeq~
::
fatty acid emulsifying component, marketed by Dow Corning.
.~, 10 Comparable results are also obtained where the "DB 544" :.
'~ in the above composition is replaced by "DB 100 " suds suppressor ,~
together with a zwitterionic surfactant as an emulsifying
. component, such as I H3
16H33 1 (C2H40) 9C2H4S04 ~ '
CH3 ~-
EXAMPLE VI ;~
A composition similar to that of Example V was pre-
; pared, but using "Pluradot HA 430" (Wyandotte Chemical Cor- .' '~
poration) as the sole nonionic surfactant (a liquid surfactant). ':: ,
In this case, only 0.1% of "DB 544" was employed and the
composition was found to be storage-stable and to have good .
suds suppression.
All of the above examples provided compositions with
good storage stability as evidenced by the continued ''
activity of the suds suppressor after from three to nine weeks ~'~
of storage at 90F.
A composition comprising a carrier granule based on
sodium carbonate and sodium silicate and using the liquid
nonionic surfactant of Example V together with polydimethyl-
silox~n,e s,-uds suppressor was found to have a suds efficiency ~ ''
* Trademark
. ~
32 -
`:

~.~6lS69~7 ~
' of 89% when freshly made, but this dropped rapidly to 80
after two weeks and continued to fall thereafter.
EXAMPLE VII
A spray-dried detergent composition was prepared,
using the preferred self-emulsifying suds suppressors o~
the present invention and having the following composition:
Component ~ by Wt. of ~`
the Composit`ion `~
1 "Neodol 23" ethoxylated with 3 moles
of ethylene oxide and stripped to
HLB 10.55 11.0
~ ~ 10 i~,
Sodium tripolyphosphate 32.0 ;
Sodium silicate (1.6 ratio Na2O:SiO2~ 10.0
"DB 544" 0.2
Sodium sulfate 38.0
Moisture and minors to 100 ~
To prepare the above composition, all the ingredients ;
of the composition were slurried in water and blended at
150F to give a homogeneous crutcher mix. The mix was then
introduced into a spray-drying tower and spray-dried to form
homogeneous granules. .`
`
The resultant composition exhibited controlled sudsing ,
characteristics which were maintained after storage at 90F
and 80% relative humidity for three weeks.
The sa~e composition as above but with "Dow Corning DB
100"* suds suppressor replacing "DB 544" showed no suds
suppression after spray-drying, even when fresh. "DB 100" does
not contain a polyoxyalkylene-modified polysiloxane emulsifying
component. `~
:'
1 "Neodol 23" is obtainable from Shell Chemical Company ,~
From Dow Corning, a silicone suds suppressor containing a
copolymer of polydimethylsiloxane and a polyalkylene oxide.
* Trademark
- 33 - -

1(~15 5~;9~7 `
EXAMPLE VI I I
A granular heavy-duty detergent composition was pre-
pared by spray-drying in a conventional manner a detergent
slurry. The slurry has the following composition:
Ingredient Parts by Wt.
Condensate of C14-C15 1:1 blend alcohol
with 7 moles of ethylene oxide 17.0
4,4' thiobis t6-tertbutyl-m cresol~ 0.02
"~erol 525"* 0.7
Pentasodium tripolyphsophate anhydrous46.0
~,
Saturated C16-C22 fatty acid 0~7
Silicate solids, ratio SiO2:NaO 2.0 8.0
Sodium sulfate 14.0
Minor ingredients 3.0
Water 40.0
Suds regulating agent ("Dow Corning DB 544") 0.3
Substantially similar compositions were prepared
(a) without the addition of the "DB 544" suds regulator, and ~
(b) replacing the "DB 544" regulator by an identical amount ;
of the suds regulator described in Belgian Patent 803,101
of February 1, 1974 to Bartolotta et al.
Seventy-five parts by weight of the granular base
powder obtained after spray-drying the above slurry were
dry-mixed with 25 parts by weight granular perborate
tetrahydrate and 1% of additional minor ingredients inclusive
of a proteolytic enzyme, a perfume and a polyethylene glycol
having a molecular weight of about 400.
The suds regulating capacity of the granular bleach-
containing finished product so formulated was tested ~1)
freshly made, and (2) after an eccelerated storage test as ~ ;
more fully defined hereinafter. The suds regulating capacity
* Trademark
,
-- 34 --

~ 5697
.'. :
was measured with a front-loading Miele drum washing machine
under the following conditions.
Cloth load : 4, kg
Product concentration : 0.65% (weight/volume)
Temperature : mainwash up to the boil
The suds height, expressed in centimeters, was :~
measured at a temperature of 90C through the front window.
The results were as ~ollows~
. ~ .
"~

~` ~LO~!3S~i9~7
~ ` ~
,i~ ~ ~ :
~ C~
~ ~1 ., ! ~
~r~ '`
U~ ~9 ,
U~ ~ . ~'
~ .`,'
m ~
,. : ~ -:
~ .
~ ~ r m
~ ~j 8 .cl ~`
u~ ~tr ~: i~ ~ o N
. . . ~ m . . .~ .~ ~
. . I ~ `':
0 .. ,
z~ .~ , ~
. . ~
~ ~ ': `
a~ ~ ,
.~ 3 p; 3
~ ~ o\ ~ '~
o ~
~ a) o~ a) :
lQ ~ O
o oo oO
o
. 1~ `
- 3 6 - .. `

~ 35697 ; ~
In the above scale, 6 cm. represents a consumer
acceptable suds level at up to the boil conditions (90C).
Suds levels of 8 cm. and above are undesirable. Thus `
compositions according to this invention are at leas~ as
good as or better than identical compositions wherein the
suds regulator has been replaced with an equivalent amount ;`
of a suds suppressor which is known to be suitable for
commercial purposes. -
~
,. ~,
~ ~ '
~ ~
. ~:
;..- ' :;
- 37 -