Note: Descriptions are shown in the official language in which they were submitted.
CA 02305324 2000-03-31
WO 99/19454 PCT/US98/21421
FIELD OF THE INVENTION
The present invention generally relates to processes for producing a granular
detergent composition. More particularly, the invention is directed to
processes during
which detergent granules or agglomerates are produced from starting detergent
materials,
one of which is a mid-chain branched surfactant. The mid-chain branched
surfactants are
mid-chain branched primary alkyl sulfate surfactants and mid-chain branched
primary alkyl
alkoxyiated sulfate surfactants having an average of greater than 14.5 carbon
atoms. The
process produces a free flowing, granular detergent composition which can be
commercially sold as a modern compact detergent product.
BACKGROUND OF THE fNVENTION
Recently, there has been considerable interest within the detergent industry
for
laundry detergents which are "compact" and therefore, have low dosage volumes.
To
facilitate production of these so-called low dosage detergents, many attempts
have been
made to produce high bulk density detergents, for example with a density of
600 g/1 or
higher. The low dosage detergents are currently in high demand as they
conserve resources
and can be sold in small packages which are more convenient for consumers.
Generally, there are two primary types of processes by which detergent
granules or
powders can be prepared. The first type of process involves spray-drying an
aqueous
detergent slurry in a spray-drying tower to produce highly porous detergent
granules. In
the second type of process, the various detergent components are dry mixed
after which
they are agglomerated with a binder such as a nonionic or anionic surfactant.
In both
processes, the most important factors which govern the density of the
resulting detergent
granules are the density, porosity and surface area of the various starting
materials and their
respective chemical composition.
There has been interest in the art for providing processes which increase the
density
of detergent granules or powders. Particular attention has been given to
densification of
spray-dried granules by post tower treatment. For example, one attempt
involves a hatch
process in which spray-dried or granulated detergent powders containing sodium
tripolyphosphate and sodium sulfate are densified and spheronized in a
Marumerizer~.
This apparatus comprises a substantially horizontal, roughened, rotatable
table positioned
within and at the base of a substantially vertical, smooth walled cylinder.
This process,
CA 02305324 2000-03-31
WO 99/19454 PCT/US98/21421
2
however, is essentially a batch process and is therefore less suitable for the
large scale
production of detergent powders. More recently, other processes have developed
for
increasing the density of "post-tower" or spray dried detergent granules.
Typically, such
processes require a first apparatus which pulverizes or grinds the granules
and a second
apparatus which increases the density of the pulverized granules by
agglomeration. These
processes achieve the desired increase in density by treating or densifying
"post tower" or
spray dried granules. The art is also replete with disclosures of processes
which entail
agglomerating detergent compositions. For example, attempts have been made to
agglomerate detergent builders by mixing zeolite and/or layered silicates in a
mixer to form
free flowing agglomerates.
Furthermore, it has been long-established practice for detergent formulators
to use
surfactants and combinations thereof in detergent compositions. By way of
example,
various anionic surfactants, especially the alkyl benzene sulfonates, alkyl
sulfates, alkyl
alkoxy sulfates and various nonionic surfactants, such as alkyl ethoxylates
and alkylphenol
ethoxylates are commonly used in detergent formulations. Surfactants have
found use as
detergent components capable of the removal of a wide variety of soils and
stains. A
consistent effort, however, is made by detergent manufacturers to improve
detersive
properties of detergent compositions by providing new and improved
surfactants. A
problem commonly associated with anionic surfactants is their sensitivity to
cold water
and/or hard water. Improved cleaning performance above and beyond current
standards,
especially for granular detergent compositions to be used under colder wash
water
conditions and/or in hard water, has been difficult to attain. Therefore, it
would be
desirable to have a process for making a detergent composition which exhibits
improved
cleaning performance over a wide variety of soils and stains.
Accordingly, there remains a need in the art for a process which produces a
granular and/or agglomerated detergent composition from starting detergent
ingredients
including a surfactant which exhibits improved cleaning performance over a
wide variety of
soils and stains. Also, there remains a need for such a process which is more
efficient and
economical to facilitate large-scale production of low dosage or compact
detergents.
$ACKGROUND ART
The following references are directed to densifying spray-dried granules:
Appel et
al, U.S. Patent No. 5,133,924 (Lever); Bortolotti et al, U.S. Patent No.
5,160,657 (Lever);
Johnson et al, British patent No. 1,517,713 (Unilever); and Curtis, European
Patent
Application 451,894. The following references are directed to producing
detergents by
agglomeration: Beerse et al, U.S. Patent No. 5,108,646 (Procter & Gamble);
Hollingsworth
et al, European Patent Application 351,937 (Unilever); Swatting et al, U.S.
Patent No.
5,205,958; and Capeci et al, U.S. Patent No. 5,366,652 (Procter & Gamble).
CA 02305324 2002-12-13
U.S. 3,480,556 to deWitt, et al., November 25, 1969, EP 439,316, published by
Lever July
31, 1991, and EP 684,300, published by Lever November 29, 1995, describe beta-
branched
alkyl sulfates. EP 439,316 describes certain laundry detergents containing a
specific
TM
commercial C14/C15 branched primary alkyl sulfate, namely LIAL 145 sulfate.
This is
believed to have 61% branching in the 2-position; 30% ofthis involves
branching with a
hydrocarbon chain having four or more carbon atoms. U.S. 3,480,5:16 describca
mixtures
of from 10 to 90 parts of a straight chain primary alkyl sulfate and from 90
to a 0 parts of a
beta branched (2-position branched) primary alcohol sulfate of formula:
R2
Rt CH CH2 0S03X
wherein the total number of carbon atoms ranges from 12 to 20 and R1 is a
straight chain
alkyl radical containing 9 to 17 carbon atoms and R2 is a straight chain alkyl
radical
containing 1 to 9 carbon atoms (67% 2-methyl and 33% 2-ethyl branching is
exemplified).
As noted hereinbefore, R.G. Laughlin in "The Aqueous Phase Behavior of
Surfactants", Academic Press, N.Y. (1994) p. 347 describes the observation
that as
branching moves away from the 2-alkyl position towards the center of the alkyl
hydrophobe
there is a lowering of Krafft temperatures. See also Finger et al., "Detergent
alcohols - the
effect of alcohol structure and molecular weight on surfactant properties", J.
A,mer. Oil
Chemists' Society, Vol. 44, p. 525 (1967) and Technical Bulletin, Shell
Chemical Co., SC:
364-80.
EP 342,917 A, Unilever, published Nov. 23, 1989 describes laundry detergents
containing a surfactant system in which the major anionic surfactant is an
alkyl sulfate
having an assertedly "wide range" of alkyl chain lengths (the experimental
appears to
involve mixing coconut and tallow chain length surfactants).
U.S. Patent 4,102,823 and GB 1,399,966 describe other laundry compositions
containing conventional alkyl sulfates.
G.B. Patent 1,299,966, Matheson et ai., published July 2, 1975, discloses a
detergent composition in which the surfactant system is comprised of a mixture
of sodium
tallow alkyl sulfate and nonionic surfactants.
Methyl- substituted sulfates include the known "isostearyl" sulfates; these
are
typically mixtures of isomeric sulfates having a total of I 8 carbon atoms.
For example, EP
401,462 A, assigned to Henkel, published December 12, 1990, describes certain
isostearyi
aicohois and ethoxyiated isostearyl aicohols and their sulfation to produce
the
corresponding alkyl sulfates such as sodium isostearyl sulfate. See also K.R.
'Wormuth and
S. Zushma, Langmuir, Vol. 7, {1991), pp 2048-2053 {technical studies on a
number of
branched alkyl sulfates, especially the "branched Guerbet" type); R..
Varadaraej et ai., J.
Phys. Chem., Vol. 95, (1991 ), pp 1671-1676 (which describes the surface
tensions of a
CA 02305324 2002-12-13
4
variety of"linear Guerbet" and "branched Guerbet"- class surfactants including
alkyl
sulfates); Varadaraj et al., J. Colloid and Interface Sci., Vol. 140, (1990),
pp 31-34 {relating
to foaming data for surfactants which include C 12 and C 13 alkyl sulfates
containing 3 and
4 methyl branches, respectively); and Varadaraj et al., Langmuir, Vol. 6
(1990), pp 1376-
1378 (which describes the micropolarity of aqueous micellar solutions of
surfactants
including branched alkyl sulfates).
"Linear Guerbet" alcohols are available from Henkel, e.g., EUTANO:L G-l6 TM
Primary alkyl sulfates derived from alcohols made by Oxo reaction on propylene
or
n-butylene oligomers are described in U.S. Patent 5,245,072 assigned to Mobil
Corp. See
also: U.S. Patent 5,284,989, assigned to Mobil Oil Corp. (a method for
producing
substantially linear hydrocarbons by oligomerizing a lower olefin a.t elevated
temperatures
with constrained inter~rnediate pore siliceous acidic zeolite), and U.S.
Patents ;5,026,933 and
4,870,038, both to Mobil Oil Corp. (a process for producing substantially
linear
hydrocarbons by oligomerizing a lower olefin at elevated temperatfares with
siliceous acidic
ZSM-23 zeolite).
See also: Surfactant Science Series, Marcel Dekker, N.Y. (various volumes
include
those entitled "Anionic Surfactants" and "Surfactant Biodegradation", the
latter by R.D.
Swisher, Second Edition, publ. 1987 as Vol. 18; see especially p.2(1-24
"Hydrophobic
groups and their sources"; pp 28-29 "Alcohols" , pp 34-35 "Primary Alkyl
Sulfates" and pp
35-36 "Secondary Alkyl Sulfates"); and literature on "higher" or "cletergent"
;ilcohols from
which alkyl sulfates are typically made, including: CEH Marketing Research
Report
"Detergent Alcohols" by R.F. Modler et al., Chemical Economics Handbook, 1993,
609.5000 - 609.5002; Kirk Othmer's Encyclopedia of Chemical Technology, 4th
Edition;
Wiley, N.Y., 1991, "Alcohols, Higher Aliphatic" in Vol. 1, pp 865-913 and
references
therein.
SUMMARY OF THE INV,~,~~
The present invention meets the aforementioned needs in the art by providing a
process which produces a granular and/or agglomerated detergent composition
directly
from mid-chain branched surfactants and other starting detergent ingredients..
The processes
include a variety of embodiments including spray drying, agglomerating,
mixing, blending,
and combinations thereof. The mid-chain branched surfactants are; mid-chain
branched
primary alkyl sulfate surfactants and mid-chain branched primary alkyl
alko~,:oxylated
sulfate surfactants having an average of greater than 14.5 carbon atoms: The
detergent
compositions resulting from the processes of the invention exhibit improved
cleaning
performance over a wide variety of stains and/or soils, even under relatively
'high water
hardness and low temperature wash water conditions.
CA 02305324 2002-12-13
As used herein, the term "agglomerates" refers to particles formed by build-up
agglomeration of starting detergent ingredients (particles) which typically
have a smaller
median particle size than the formed agglomerates. All percentages and ratios
used herein
are expressed as percentages by weight (anhydrous basis) unless otherwise
indicated.
All viscosities referenced herein are measured at 70°C (~5°C)
and at shear rates of
about 10 to 100 sec t.
In accordance with one aspect of the invention, a process for preparing a
crisp, free
flowing, high density detergent composition is provided. The process comprises
the steps
of: A process for continuously preparing a high density detergent composition
comprising
the steps of (A) continuously mixing a detergent surfactant paste and dry
starting
detergent material into a high speed mixerldensifier to obtain detergent
agglomerates,
wherein the ratio of the surfactant paste to the dry detergent material is
from about 1:10 to
about 10:1, the surfactant paste containing rnid-chain branched surfactant
compounds ofthe
formula:
Ab-X-B
wherein:
(a) Ab is a hydrophobic C9 to C22, total carbons in the moiety, preferably
from about C 12
to about C18, mid-chain branched alkyl moiety having: ( I ) a longest linear
carbon chain
attached to the - X - B moiety in the range of from 8 to 21 carbon atoms; (2)
one or more
C1 - C3 alkyl moieties branching from this longest linear carbon chain; (3) at
least one of
the branching alkyl moieties is attached directly to a carbon of the longest
linear carbon
chain at a position within the range of position 2 carbon, counting from
carbon # I which is
attached to the - X - B moiety, to position cep - 2 carbon, the terminal
carbon minus 2
carbons; arid (4) the surfactant composition has an average total number of
carbon atoms in
the Ab-X moiety in the above formula within the range of greater than 14.5 to
about 18,
preferably from about 15 to about 17; (b) B is a hydrophilic moiety selected
from sulfates,
sulfonates, amine oxides, polyoxyalkylene, alkoxylated sulfates, polyhydroxy
moieties,
phosphate esters, glycerol sulfonates, polygluconates, polyphosphate esters,
phosphonates,
sulfosueeinates, sulfosuccaminates, polyalkoxylated carboxylates, glucamides,
taurinates,
sarcosinates, glycinates, isethionates, dialkanolamides, monoalkanolamides,
monoalkanolamide sulfates, diglycolamides, diglycoiamide sulfates, glycerol
esters,
glycerol ester sulfates, glycerol ethers, glycerol ether sulfates,
polyglycerol ethers,
polyglycerol ether sulfates, sorbitan esters, polyalkoxylated sorbitan
esters.,
ammonioalkanesulfonates, amidopropyl betaines, alkylated quats,
alkylated/polyhydroxyalkylated quats, alkylated/polyhydrox.ylated
oxypropyl quats, imidazolines, 2-yl-succinates, sulfonated alkyl esters, and
sulfonated fatty
acids; and (c) X is -CH2-; (B) mixing the detergent agglomerates in a moderate
speed
CA 02305324 2000-03-31
WO 99/19454 PCT/US98/21421
6
mixer/densifier to densify further and agglomerate the detergent agglomerates;
and (C)
drying the detergent agglomerates so as to form the high density detergent
composition.
Another aspect of the invention involves similar steps, wherein step (A)
entails
continuously mixing an acid precursor of an anionic surfactant and dry
starting detergent
material containing an alkaline inorganic material capable of neutralizing the
acid precursor
into a high speed mixer/densifier to obtain detergent agglomerates.
In another aspect of the invention, a process involving spray drying and
agglomeration of detergent ingredients to provide a high density detergent
composition is
provided. More particularly, the process comprises the steps of-. (A) spray
drying an
aqueous slunry containing a mid-chain branched surfactant and adjunct
detergent
ingredients to form spray dried granules, wherein the mid-chain branched
surfactant has the
formula, as described above; (B) continuously mixing a detergent surfactant
paste and dry
starting detergent material into a high speed mixer/densifier to obtain
detergent
agglomerates, wherein the ratio of the surfactant paste to the dry detergent
material is from
about 1:10 to about 10:1; (C) mixing the detergent agglomerates in a moderate
speed
mixer/densifier to densify further and agglomerate the detergent agglomerates;
and (D)
blending the granules and the detergent agglomerates together so as to form
the high
density detergent composition.
Accordingly, it is an object of the present invention to provide a process for
producing a granular and/or agglomerated detergent composition directly from
starting
detergent ingredients which includes a surfactant having improved cleaning
performance.
It is also an object of the invention to provide such a process which is not
limited by
unnecessary process parameters so that large-scale production of low dosage or
compact
detergents is more economical and efficient. These and other objects, features
and
attendant advantages of the present invention will become apparent to those
skilled in the
art from a reading of the following drawing, detailed description of the
preferred
embodiment and the appended claims.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a flow chart illustrating a preferred process in which two
agglomerating
mixer/densifiers, fluid bed dryer, fluid bed cooler and screening apparatus
are serially
positioned in accordance with one process of the invention.
OFTAILED DESCR1_PTL(~N OF THE PRFFER_RFD EMBODIMENT
The present process is used in the production of detergent compositions by way
of
agglomeration of starting detergent ingredients including a mid-chain branched
surfactant
or by way of spray drying techniques which can include further processing of
the "post-
tower" detergent granules. By "post-tower" detergent granules, it is meant
those detergent
granules which have been processed through a conventional spray-
CA 02305324 2000-03-31
WO 99/19454 PCT/US98/21421
drying tower or similar apparatus.
~,g~lomeration Process
Reference is now made to Fig. 1 which presents a flow chart illustrating the
agglomeration process and various embodiments thereof. In the first step of
the process,
the invention entails continuously mixing into a high speed mixer/densifier 10
several
streams of starting detergent ingredients including a surfactant paste stream
12 which
includes the mid-chain branched surfactant and a dry starting detergent
material stream 14.
Based on the finished agglomerate weight basis, the surfactant paste 12
preferably
comprises water and from about 25% to about 75%, preferably from about 35% to
about
65% and, most preferably from about 38% to about 55%, of the mid-chain
branched
surfactant or combinations of such a surfactant and adjunct surfactants, all
of which is
described in detail hereinafter. Preferably, the dry starting detergent
material 14 comprises
from about 10% to about 50%, preferably from about 15% to about 45% and, most
preferably from about 20% to about 40% of an aluminosilicate or zeolite
builder and from
about 10% to about 40%, preferably from about 15% to about 30% and, most
preferably
from about 15% to about 25% of a sodium carbonate. It should be understood
that
additional starting detergent ingredients several of which are described
hereinafter may be
mixed into high speed mixer/densifier 10 without departing from the scope of
the invention.
However, it has been found that the surfactant paste 12 and the dry starting
detergent material 14 are continuously mixed within the ratio ranges described
herein so as
to ensure production of the desired free flowing, crisp, high density
detergent composition.
Preferably, the ratio of the surfactant paste 12 to the dry starting detergent
material 14 is
from about 1:10 to about 10:1, more preferably from about 1:4 to about 4:1
and, most
preferably from about 2:1 to about 2:3.
Also, it has been found that the first processing step can be successfully
completed,
under the process parameters described herein, in a high speed mixer/densifier
10 which
preferably is a Lddige CB mixer or similar brand mixer. These types of mixers
essentially
consist of a horizontal, hollow static cylinder having a centrally mounted
rotating shaft
around which several plough-shaped blades are attached. Preferably, the shaft
rotates at a
speed of from about 300 rpm to about 2500 rpm, more preferably from about 400
rpm to
about 1600 rpm. Preferably, the mean residence time of the detergent
ingredients in the
high speed mixer/densifier 10 is preferably in range from about 2 seconds to
about 45
seconds, and most preferably from about 5 seconds to about 15 seconds. The
mean
residence time can be conveniently and accurately measured by dividing the
tear weight of
the mixer/densifier by the throughput (e.g., kg/hr).
The resulting detergent agglomerates formed in the high speed mixer/densifier
10
are then fed into a lower or moderate speed mixer/densifier 16 during which
further
CA 02305324 2002-12-13
g
agglomeration and densification is carried forth. This particular moderate
speed
mixer/densifier 16 used in the present process should include liquid
distribution and
agglomeration toots so that both techniques can be carried forth
simultaneously. It is
TM
preferable to have the moderate speed mixerldensifier 16 to be, for example, a
Lodige KM
(Ploughshare) mixer, Drais~ K-T 160 mixer or similar brand mixer. The main
centrally
rotating shaft speed is from about 30 to about 160 rpm, more preferably from
about SO to
about 100 rpm. The mean residence time in the moderate speed mixer/densifier
16 is
preferably from about 0.25 minutes to about 1S minutes, most preferably the
residence time
is about O.S to about 10 minutes. This mean residence time also can be
conveniently and
accurately measured by dividing the tear weight of the mixer/densi~er at
steady state by the
throughput (e.g., kglhr). The liquid distribution is accomplished by cutters,
generally
smaller in size than the rotating shaft, which preferably operate at about
3600 rpm.
In accordance with the present process, the high speed mixer/densifer 10 and
moderate speed mixer/densifier 16 in combination preferably impart a requisite
amount of
energy to form the desired agglomerates. More particularly, the instant
process imparts
from about S x 1010 erg/kg to about 2 x I O I2 erg/kg at a rate of from about
3 x 108 erglkg-
sec to about 3 x 109 erg/kg-sec to form free flowing high density detergent
agglomerates.
The energy input and rate of input can be determined by calculations from
power readings
to the moderate speed mixer/densifier with and without granules, residence
time of the
granules in the mixer/densifier, and the mass of the granules in the
mixer/densifier. Such '
calculations are clearly within the scope of the skilled artisan.
The density of the resulting detergent agglomerates exiting the moderate speed
mixer/densifier 16 is at least 600 g/1, more preferably from about 700 g/1 to
albout 800 g/1.
Thereafter, the detergent agglomerates are dried in a fluid bed dryer 18 or
similar apparatus
to obtain the high density granular detergent composition which is ready for
packaging and
safe as a low dosage, compact detergent product at this point. The particle
porosity of the
resulting detergent agglomerates of the composition is preferably in a range
from about S%
to about 20%, more preferably at about 10%. As those skilled in the art will
readily
appreciate, a low porosity detergent agglomerate provides a dense or low
dosage detergent
product, to which the present process is primarily directed. In addition, an
attribute of
dense or densified detergent agglomerates is the relative particle size. The
present process
typically provides agglomerates having a median particle size of from about
400 microns to
about 700 microns, and more preferably from about 47S microns to about 600
microns. As
used herein, the phrase "median particle size" refers to individual
agglomerates and not
individual particles or detergent granules. The combination of the above-
referenced
porosity and particle size results in agglomerates having density values of
600 g/1 and
CA 02305324 2002-12-13
9
higher. Such a feature is especially useful in the production of low dosage
laundry
detergents as well as other granular compositions such as dishwashing
compositions.
Optional Process Steo "s
In an optional step of the present process, the detergent agglomerates exiting
the
fluid bed dryer 18 are further conditioned by cooling the agglomerates in a
fluid bed cooler
20 or similar apparatus as are well known in the art. Another optional process
step involves
adding a coating agent to improve flowability andlor minimize over
agglomeration of the
detergent composition in one or more of the following locations of 'the
instant process: (1)
the coating agent can be added directly after the fluid bed cooler 20 as shown
by coating
agent stream 22 (preferred); (2) the coating agent may be added between the
fluid bed dryer
18 and the fluid bed cooler 20 as shown by coating agent stream 24; (3) the
coating agent
may be added between the fluid bed dryer 18 and the moderate speed
mixer/densifier 16 as
shown by stream 26; and/or (4) the coating agent may be added directly to the;
moderate
speed mixer/densifier 16 and the fluid bed dryer 18 as shown.by stream 28. It
should be
understood that the coating agent can be added in any one or a combination of
streams 22,
24, 26, and 28 as shown in Fig. 1. The coating agent stream 22 is the most
preferred in the
instant process. See Capeci et al, U.S. Patent S,S I 6,448, issued May 14,
1996 and Capeci et
al, U.S. Patent 5,489,392, issued February 6, 1996.
The coating agent is preferably selected from the group consisting of
aluminosilicates, silicates, carbonates and mixtures thereof. The coating
agent can also be
the improved builder material described in more detail hereinafter'. However,
the coating
agent may be one or more combinations of the builder material,
aluminosilicates,
carbonates, silicates and the like. The coating agent not only enhances the
free flowability
of the resulting detergent composition which is desirable by consumers in that
it permits
easy scooping of detergent during use, but also serves to control
agglomeration by
preventing or minimizing over agglomeration, especially when added directly to
the
moderate speed mixer/densifier 16. As those skilled in the art are well
aware;, over
agglomeration can Lead to very undesirable flow properties and aesthetics of
the final
detergent product.
Optionally, the process comprises the step of spraying an additional binder in
one
or both of the mixer/densifiers 10 and 1 b. A binder is added for purposes of
enhancing
agglomeration by providing a "binding" or "sticking" agent for the detergent
components.
The binder is preferably selected from the group consisting of water, anionic;
surfactants,
nonionic surfactants, polyethylene glycol, polyvinyl pyrrolidone
polyacrylates, citric acid
and mixtures thereof. Other suitable binder materials including trtose listed
herein are
described in Beerse et aI, U.S. Patent No. 5,108,646 (Procter & Gamble Co.;l .
CA 02305324 2000-03-31
WO 99/19454 PCT/US98/21421
10
Other optional steps contemplated by the present process include screening the
oversized detergent agglomerates in a screening apparatus 30 which can take a
variety of
forms including but not limited to conventional screens chosen for the desired
particle size
of the finished detergent product. Other optional steps include conditioning
of the
detergent agglomerates by subjecting the agglomerates to additional drying.
Another optional step of the instant process entails finishing the resulting
detergent
agglomerates by a variety of processes including spraying and/or admixing
other
conventional detergent ingredients, collectively referenced as the finishing
step 32 in Fig. 1.
For example, the finishing step encompasses spraying perfumes, brighteners and
enzymes
onto the finished agglomerates to provide a more complete detergent
composition. Such
techniques and ingredients are well known in the art.
Preferably, the resulting detergent agglomerates produced by the process
embodiments described herein contain from about 20% to about 50% by weight of
the mid-
chain branched surfactant, from about 10% to about 65% of a detergent builder
such as
aluminosilicate, and optionally, up to about 40% by weight of sodium
carbonate. The
surfactant, builder, and carbonate levels can vary beyond those given here as
described
previously and hereinafter.
One or more spray drying techniques can be used alone, or in combination with
the
aforementioned agglomeration processes, to make detergent compositions
containing the
mid-chain branched surfactants in accordance with the instant invention. One
or more
spray-drying towers may be employed to manufacture granular laundry detergents
which
often have a density of about 500 g/1 or less. In this procedure, an aqueous
slurry of various
heat-stable ingredients in the final detergent composition are formed into
homogeneous
granules by passage through a spray-drying tower, using conventional
techniques, at
temperatures of about 175°C to about 225°C. If spray drying is
used as part of the overall
process herein, additional process steps as described herein can be optionally
used to obtain
the level of density (i.e., > 650 g/1) required by modern compact, low dosage
detergent
products.
For example, spray-dried granules from a tower can be densified further by
loading a
liquid such as water or a nonionic surfactant into the pores of the granules
and/or subjecting
them to one or more high speed mixer/densifiers. A suitable high speed
mixer/densifier for
this process is the aforementioned "LSdige CB 30" or "Lodige CB 30 Recycler"
which
comprises a static cylindrical mixing drum having a central rotating shaft
with
mixing/cutting blades mounted thereon. In use, the ingredients for the
detergent
composition are introduced into the drum and the shaft/blade assembly is
rotated at speeds
in the range of 100-2500 rpm to provide thorough mixing/densification. See
Jacobs et al,
CA 02305324 2002-12-13
11
U.S. Patent 5,149,455, issued September 22, 1992. Other such apparatus
includes the
devices marketed under the trade mark "Shugi Granulator" and under the
trademark "Drais
K-TTP 80).
Another process step which can be used to densify further spray-dried
l:ranules
involves grinding and agglomerating or deforming the spray-dried l;ranules in
a moderate
speed mixer/densifier so as to obtain particles having lower porosity.
Equipment such as
the aforementioned "Lodige KM" (Series 300 or 600) or "Lodige Ploughshare:"
mixerldensifiers are suitable for this process step. Other useful equipment
includes the
device which is available under the trademark "Drais K-T 160". This process
step which
employs a moderate speed mixer/densifier (e.g. Lodige KM) can be; used by
itself or
sequentially with the aforementioned high speed mixer/densifier {e.g. Lodige
CB) to
achieve the desired density. Other types of granules manufacturing apparatus
useful herein
include the apparatus disclosed in U.S. Patent 2,306,898, to G. L. Fleller,
December 29,
1942.
While it may be more suitable to use the high speed mixer/densifier followed
by the
low speed mixer/densifier, the reverse sequential mixer/densifier
configuration is also
contemplated by the invention. One or a combination of various parameters
including
residence times in the mixer/densifiers, operating temperatures of the
equipment,
temperature and/or composition of the granules, the use of adjunct ingredients
such as
liquid binders and flow aids, can be used to optimize densification of the
spray-dried
granules in the process of the invention. By way of example, see the processes
in Appel et
al, U.S. Patent 5,133,924, issued July 28, 1992 (spray-dried granules are
brought into a
deformable state prior to densification); Delwel et al, U.S. Patent 4,637,891,
issued January
20, 1987 {granulating spray-dried granules with a liquid binder and
aluminosiiicate); Kruse
et a1, U.S: Patent 4,726,908, issued February 23, 1988 (granulating spray-
dried granules
with a liquid binder and aluminosilicate); and, Bortolotti et al, U.S. Patent
5,160,657,
issued November 3, 1992 (coating densified spray-dried granules with a liquiid
binder and
aluminosilicate).
Admixing, Process
Specifically, other aspects of the process invention include admixing; the
builder
material with spray dried granules, agglomerates or combinations 'thereof.
This admixing
step may be enhanced by combining the granules, agglomerates, or combinations
thereof
with the builder material and a liquid binder as described previously in a
mixing drum or
other similar device. Optionally, the builder material may be coated with a
nonionic
surfactant or other liquid binder as described previously before the;
admixing: step so as to
preclude any deleterious interaction with the other detergent ingredients
(e.g. anionic
surfactants) prior to immersion in the washing solution (i.e. during;
processing and storage).
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12
This liquid binder (e.g. nonionic surfactant) coating also improves the flow
properties of
the detergent composition in which the builder material is included.
her processes
In yet another process embodiment, the high density detergent composition can
be
produced by feeding a liquid acid precursor of an anionic surfactant, such as
the mid-chain
branched surfactant described herein, an alkaline inorganic material (e.g.
sodium carbonate)
and optionally other detergent ingredients into a high speed mixer/densifier
(residence time
5-30 seconds) so as to form agglomerates containing a partially or totally
neutralized
anionic surfactant salt and the other starting detergent ingredients.
Subsequently, the
contents in the high speed mixer/densifier can be sent to a moderate speed
mixer/densifier
(e.g. Lodige KM) for further agglomeration resulting in the finished high
density detergent
composition. In another process embodiment, the surfactant paste is premixed
or extruded
in a mixing or extruding apparatus such as a twin-screw extruder (e.g., Werner
and
Pfleiderer. Continua Series) to structure the paste for easier agglomeration.
Additionally,
structuring agents such as polymers, sodium hydroxide, sodium chloride,
postassium
hydroxide silicates and the like can be used to render the paste more suitable
for loading
higher amounts of surfactant. See Aouad et al, U.S. Patent 5,451,354, issued
September 19,
1995.
Optionally, high density detergent compositions can be produced by blending
conventional or densified spray-dried detergent granules with detergent
agglomerates in
various proportions (e.g. a 60:40 weight ratio of granules to agglomerates)
produced by one
or a combination of the processes discussed herein. Additional adjunct
ingredients such as
enzymes, perfumes, brighteners and the like can be sprayed or admixed with the
agglomerates, granules or mixtures thereof produced by the processes discussed
herein.
Another process of the invention involves cooling a molten surfactant paste
containing the mid-chain branched surfactant and forming flakes on a chill
roll, after which
the flakes are ground to the desired particle size. The cooled flakes can be
dried further
using a rotary drum dryer.
y utfactant Paste
The viscoelastic surfactant paste used herein has viscoelastic fluid
properties which can
be described by a commonly used mathematical model that accounts for the shear
thinning nature
of the paste. The mathematical model is called the Power Law Model and is
described by the
following relation:
o. = Kyn
where 6 = Shear Stress (dynes/cm2), K = Consistency (Poise~secn-1 ), y = Shear
Rate (sec-1 ), and n
= Rate Index (dimensionless). The rate index n varies from 0 to 1. The closer
n is to 0, the more
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l3
shear thinning the fluid. The closer n is to 1, the closer it is to simple
Newtonian behavior, i.e.
constant viscosity behavior. K can be interpreted as the apparent viscosity at
a shear rate of 1 sec' 1
In this context, the viscoelastic surfactant paste used in the process has a
consistency K at
70°C of from about 50,000 to about 450,000 cPoise~secn-1 (500 to 2,500
Poise~secn-1 ), more
preferably from about 100,000 to about 195,000 cPoise~secn-1 (1,000 to 1,950
Poise~secn-I), and
most preferably from about 120,000 to about 180,000 cPoise~secn-1 (1,200 to
1,800 Poise~secn-1).
Preferably, the surfactant paste has a shear index n of from about 0.05 to
about 0.25, more
preferably from about 0.08 to about 0.20 and most preferably from about 0.10
to about 0.15.
The surfactant paste includes surfactant mixtures comprising mid-chain
branched
surfactant compounds as described herein before. In such compositions, certain
points of
branching (e.g., the location along the chain of the R, R1, and/or R2 moieties
in the above
formula) are preferred over other points of branching along the backbone of
the surfactant.
The formula below illustrates the mid-chain branching range (i.e., where
points of
branching occur), prefenred mid-chain branching range, and more preferred mid-
chain
branching range for mono-methyl branched alkyl Ab moieties useful according to
the
present invention.
CH3CH2CHZCH2CH2CH2(CH2) ~ _~CHzCH2CHZCH2CH2-
more preferred rang
preferred range
mid-chain branching ran
It should be noted that for the mono-methyl substituted surfactants these
ranges exclude the
two terminal carbon atoms of the chain and the carbon atom immediately
adjacent to the -X
- B group.
The formula below illustrates the mid-chain branching range, preferred mid-
chain
branching range, and more preferred mid-chain branching range for di-methyl
substituted
alkyl Ab moieties useful according to the present invention.
CH3CH2CH2CH2CHZCH2(CH2)o-6CH2CH2CH2CH2CH2 -
more preferred rang
preferred range
mid-chain branching range
The preferred branched surfactant compositions useful in cleaning compositions
according to the present invention are described in more detail hereinafter.
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14
The present invention branched surfactant compositions may comprise two or
more
mid-chain branched primary alkyl sulfate surfactants having the formula
R RI R2
CH3CH2(CH2)~,CH(CH2)xCH(CH2)yCH(CH2~OS03M
The surfactant mixtures of the present invention comprise molecules having a
linear primary alkyl sulfate chain backbone (i.e., the longest linear carbon
chain which
includes the sulfated carbon atom). These alkyl chain backbones comprise from
I2 to 19
carbon atoms; and further the molecules comprise a branched primary alkyl
moiety having
at least a total of 14, but not more than 20, carbon atoms. In addition, the
surfactant
mixture has an average total number of carbon atoms for the branched primary
alkyl
moieties within the range of from greater than 14.5 to about 17.5. Thus, the
present
invention mixtures comprise at least one branched primary alkyl sulfate
surfactant
compound having a longest linear carbon chain of not less than 12 carbon atoms
or more
than 19 carbon atoms, and the total number of carbon atoms including branching
must be at
least 14, and further the average total number of carbon atoms for the
branched primary
alkyl chains is within the range of greater than 14.5 to about 17.5.
For example, a C16 total carbon primary alkyl sulfate surfactant having 13
carbon
atoms in the backbone must have 1, 2, or 3 branching units (i.e., R, RI and/or
R2) whereby
total number of carbon atoms in the molecule is at least 16. In this example,
the C 16 total
carbon requirement may be satisfied equally by having, for example, one propyl
branching
unit or three methyl branching units.
R, R1, and R2 are each independently selected from hydrogen and Cl-C3 alkyl
(preferably hydrogen or CI-C2 alkyl, more preferably hydrogen or methyl, and
most
preferably methyl), provided R, R1, and R2 are not all hydrogen. Further, when
z is I, at
least R or R1 is not hydrogen.
Although for the purposes of the present invention surfactant compositions the
above formula does not include molecules wherein the units R, RI, and R2 are
all hydrogen
(i.e., linear non-branched primary alkyl sulfates), it is to be recognized
that the present
invention compositions may still further comprise some amount of linear, non-
branched
primary alkyl sulfate. Further, this linear non-branched primary alkyl sulfate
surfactant
may be present as the result of the process used to manufacture the surfactant
mixture
having the requisite one or more mid-chain branched primary alkyl sulfates
according to
the present invention, or for purposes of formulating detergent compositions
some amount
CA 02305324 2000-03-31
WO 99/19454 PCT/US98/21421
of linear non-branched primary alkyl sulfate may be admixed into the final
product
formulation.
Further it is to be similarly recognized that non-sulfated mid-chain branched
alcohol may comprise some amount of the present invention compositions. Such
materials
may be present as the result of incomplete sulfation of the alcohol used to
prepare the alkyl
sulfate surfactant, or these alcohols may be separately added to the present
invention
detergent compositions along with a mid-chain branched alkyl sulfate
surfactant according
to the present invention.
M is hydrogen or a salt forming cation depending upon the method of synthesis.
Examples of salt forming cations are lithium, sodium, potassium, calcium,
magnesium,
quaternary alkyl amines having the formula
R3
R6-N ~ R4
R5
wherein R3, R4, R5 and R6 are independently hydrogen, C I-C22 alkylene, C4-C22
branched alkylene, C1-C6 alkanol, CI-C22 alkenylene, C4-C22 branched
alkenylene, and
mixtures thereof. Preferred cations are ammonium (R3, R4, R5 and R6 equal
hydrogen),
sodium, potassium, mono-, dl-, and trialkanol ammonium, and mixtures thereof.
The
monoalkanol ammonium compounds of the present invention have R3 equal to C 1-
C6
alkanol, R4, R5 and R6 equal to hydrogen; dialkanol ammonium compounds of the
present
invention have R3 and R4 equal to C1-C6 alkanol, R5 and R6 equal to hydrogen;
trialkanol
ammonium compounds of the present invention have R3, R4 and R5 equal to C I-C6
alkanol, R6 equal to hydrogen. Preferred alkanol ammonium salts of the present
invention
are the mono-, dl- and tri- quaternary ammonium compounds having the formulas:
H3N+CH2CH20H, H2N+(CH2CH20H)2, HN+(CH2CH20H)3.
Preferred M is sodium, potassium and the C2 alkanol ammonium salts listed
above; most
preferred is sodium.
Further regarding the above formula, w is an integer from 0 to 13; x is an
integer
from 0 to 13; y is an integer from 0 to 13; z is an integer of at least 1; and
w + x + y + z is
an integer from 8 to 14.
The preferred surfactant mixtures of the present invention have at least
0.001%,
more preferably at least 5%, most preferably at least 20% by weight, of the
mixture one or
more branched primary alkyl sulfates having the formula
R1 R2
I I
CH3CH2(CH2)xCH(CH2)yCH(CH2)zOS03M
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16
wherein the total number of carbon atoms, including branching, is from I S to
18, and
wherein further for this surfactant mixture the average total number of carbon
atoms in the
branched primary alkyl moieties having the above formula is within the range
of greater
than 14.5 to about 17.5; R1 and R2 are each independently hydrogen or C 1-C3
alkyl; M is a
water soluble cation; x is from 0 to 1 I; y is from 0 to 11; z is at least 2;
and x + y + z is
from 9 to 13; provided RI and R2 are not both hydrogen. More preferred are
compositions
having at least 5% of the mixture comprising one or more mid-chain branched
primary
alkyl sulfates wherein x + y is equal to 9 and z is at least 2.
Preferably, the mixtures of surfactant comprise at least 5% of a mid chain
branched
primary alkyl sulfate having RI and R2 independently hydrogen, methyl,
provided R1 and
R2 are not both hydrogen; x + y is equal to 8, 9, or 10 and z is at least 2.
More preferably
the mixtures of surfactant comprise at least 20% of a mid chain branched
primary alkyl
sulfate having R1 and R2 independently hydrogen, methyl, provided R1 and R2
are not
both hydrogen; x + y is equal to 8,9, or 10 and z is at least 2.
Preferred detergent compositions according to the present invention, for
example
one useful for laundering fabrics, comprise from about 0.001 % to about 99% of
a mixture
of mid-chain branched primary alkyl sulfate surfactants, said mixture
comprising at least
about 5 % by weight of two or more mid-chain branched alkyl sulfates having
the formula:
CH3
CH3 (CH2)aCH (CHZ~CH2 OS03M
(i) ,
CH3 CH3
CH3 (CH2)dCH (CHZ)e CHCH2 OS03M
(II)
or mixtures thereof; wherein M represents one or more cations; a, b, d, and a
are integers,
a+b is from 10 to 16, d+e is from 8 to 14 and wherein further
when a + b = 10, a is an integer from 2 to 9 and b is an integer from 1 to 8;
when a + b = 11, a is an integer from 2 to 10 and b is an integer from 1 to 9;
when a + b = 12, a is an integer from 2 to 11 and b is an integer from 1 to
10;
when a + b = I 3, a is an integer from 2 to 12 and b is an integer from 1 to 1
I ;
when a + b = 14, a is an integer from 2 to 13 and b is an integer from 1 to
12;
when a + b = I5, a is an integer from 2 to 14 and b is an integer from 1 to
13;
when a + b = 16, a is an integer from 2 to I S and b is an integer from 1 to
14;
when d + a = 8, d is an integer from 2 to 7 and a is an integer from 1 to 6;
when d + a = 9, d is an integer from 2 to 8 and a is an integer from 1 to 7;
when d + a = 10, d is an integer from 2 to 9 and a is an integer from 1 to 8;
when d + a = 11, d is an integer from 2 to 10 and a is an integer from 1 to 9;
when d + a = 12, d is an integer from 2 to 11 and a is an integer from 1 to
10;
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WO 99/19454 PCT/US9$/21421
17
when d + a = 13, d is an integer from 2 to 12 and a is an integer from 1 to
11;
when d + a = 14, d is an integer from 2 to 13 and a is an integer from 1 to
12;
wherein further for this surfactant mixture the average total number of carbon
atoms in the
branched primary alkyl moieties having the above formulas is within the range
of greater
than 14.5 to about 17.5.
Further, the present invention surfactant composition may comprise a mixture
of
branched primary alkyl sulfates having the formula
R R1 R2
I 1 I
CH3CH2(CH2)wCH(CH2~CH(CH2)yCH(CHZ)ZOS03M
wherein the total number of carbon atoms per molecule, including branching, is
from 14 to
20, and wherein further for this surfactant mixture the average total number
of carbon
atoms in the branched primary alkyl moieties having the above formula is
within the range
of greater than 14.5 to about 17.5; R, R1, and R2 are each independently
selected from
hydrogen and C I-C3 alkyl, provided R, R1, and R2 are not all hydrogen; M is a
water
soluble cation; w is an integer from 0 to 13; x is an integer from 0 to 13; y
is an integer
from 0 to 13; z is an integer of at least 1; and w + x + y + z is from 8 to
14; provided that
when R2 is a C 1-C3 alkyl the ratio of surfactants having z equal to t to
surfactants having z
of 2 or greater is at least about 1:1, preferably at least about 1:5, more
preferably at least
about 1:10, and most preferably at least about 1:100. Also preferred are
surfactant
compositions, when R2 is a C 1-C3 alkyl, comprising less than about 20%,
preferably less
than 10%, more preferably less than S%, most preferably less than 1%, of
branched primary
alkyl sulfates having the above formula wherein z equals 1.
Preferred mono-methyl branched primary alkyl sulfates are selected from the
group
consisting of: 3-methyl pentadecanol sulfate, 4-methyl pentadecanol sulfate, 5-
methyl
pentadecanol sulfate, 6-methyl pentadecanol sulfate, 7-methyl pentadecanol
sulfate, 8-
methyl pentadecanol sulfate, 9-methyl pentadecanol sulfate, 10-methyl
pentadecanol
sulfate, 11-methyl pentadecanol sulfate, 12-methyl pentadecanol sulfate, I3-
methyl
pentadecanol sulfate, 3-methyl hexadecanol sulfate, 4-methyl hexadecanol
sulfate, 5-
methyl hexadecanol sulfate, 6-methyl hexadecanol sulfate, 7-methyl hexadecanol
sulfate, 8-
methyl hexadecanol sulfate, 9-methyl hexadecanol sulfate, 10-methyl
hexadecanol sulfate,
11-methyl hexadecanol sulfate, 12-methyl hexadecanol sulfate, 13-methyl
hexadecanol
sulfate, 14-methyl hexadecanol sulfate, and mixtures thereof.
Preferred di-methyl branched primary alkyl sulfates are selected from the
group
consisting of 2,3-methyl tetradecanol sulfate, 2,4-methyl tetradecanol
sulfate, 2,5-methyl
tetradecanol sulfate, 2,6-methyl tetradecanol sulfate, 2,7-methyl tetradecanol
sulfate, 2,8-
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18
methyl tetradecanol sulfate, 2,9-methyl tetradecanol sulfate, 2,10-methyl
tetradecanol
sulfate, 2,11-methyl tetradecanol sulfate, 2,12-methyl tetradecanol sulfate,
2,3-methyl
pentadecanol sulfate, 2,4-methyl pentadecanol sulfate, 2,5-methyl pentadecanol
sulfate,
2,6-methyl pentadecanol sulfate, 2,7-methyl pentadecanol sulfate, 2,8-methyl
pentadecanol
sulfate, 2,9-methyl pentadecanol sulfate, 2,10-methyl pentadecanol sulfate,
2,11-methyl
pentadecanol sulfate, 2,12-methyl pentadecanol sulfate, 2,13-methyl
pentadecanol sulfate,
and mixtures thereof.
The following branched primary alkyl sulfates comprising 16 carbon atoms and
having one branching unit are examples of preferred branched surfactants
useful in the
present invention compositions:
5-methylpentadecylsulfate having the formula:
OS03M
CH3
6-methylpentadecylsulfate having the formula
CH3
OS03M
7-methylpentadecylsulfate having the formula
OS03M
CH3
8-methylpentadecylsulfate having the formula
CH3
OS03M
9-methylpentadecylsulfate having the formula
~OS03M
CH3
10-methylpentadecylsulfate having the formula
CH3
OS03M
wherein M is preferably sodium.
'fhe following branched primary alkyl sulfates comprising 17 carbon atoms and
having two branching units are examples of preferred branched surfactants
according to the
present invention:
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19
2,5-dimethylpentadecylsulfate having the formula:
CH3
OS03M
CH3
2,6-dimethylpentadecylsulfate having the formula
- CH3 CH3
OS03M
2,7-dimethylpentadecylsulfate having the formula
CH3
OS03M
CH3
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2,8-dimethylpentadecylsulfate having the formula
CH3 CH3
OS03M
2,9-dimethylpentadecyisulfate having the formula
CH3
OS03M
CH3
2,10-dimethylpentadecylsulfate having the formula
CH3 CH3
OS03M
wherein M is preferably sodium.
The present invention branched surfactant compositions may comprise one or
more
mid-chain branched primary alkyl poiyoxyalkylene surfactants having the
formula
R R1 R2
I I I
CH3CH2(CH2)~,CH(CH2)xCH(CH2)yCH(CH2)Z(EO/PO)mOH
The surfactant mixtures of the present invention comprise molecules having a
linear primary polyoxyalkylene chain backbone (i.e., the longest linear carbon
chain which
includes the alkoxylated carbon atom). These alkyl chain backbones comprise
from 12 to
19 carbon atoms; and further the molecules comprise a branched primary alkyl
moiety
having at least a total of 14, but not more than 20, carbon atoms. In
addition, the surfactant
mixture has an average total number of carbon atoms for the branched primary
alkyl
moieties within the range of from greater than 14.5 to about 17.5. Thus, the
present
invention mixtures comprise at least one polyoxyalkylene compound having a
longest
linear carbon chain of not less than 12 carbon atoms or more than 19 carbon
atoms, and the
total number of carbon atoms including branching must be at least 14, and
further the
average total number of carbon atoms for the branched primary alkyl chains is
within the
range of greater than 14.5 to about 17.5.
For example, a C16 total carbon (in the alkyl chain) primary polyoxyalkylene
surfactant having 15 carbon atoms in the backbone must have a methyl branching
unit
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21
(either R, R1 or R2 is methyl) whereby the total number of carbon atoms in the
molecule is
16.
R, RI, and R2 are each independently selected from hydrogen and C1-C3 alkyl
(preferably hydrogen or C1-C2 alkyl, more preferably hydrogen or methyl, and
most
preferably methyl), provided R, R1, and R2 are not all hydrogen. Further, when
z is I, at
least R or R 1 is not hydrogen.
Although for the purposes of the present invention surfactant compositions the
above formula does not include molecules wherein the units R, R1, and R2 are
all hydrogen
(i.e., linear non-branched primary polyoxyalkylenes), it is to be recognized
that the present
invention compositions may still further comprise some amount of linear, non-
branched
primary polyoxyalkylene. Further, this linear non-branched primary
polyoxyalkylene
surfactant may be present as the result of the process used to manufacture the
surfactant
mixture having the requisite mid-chain branched primary polyoxyalkylenes
according to
the present invention, or for purposes of formulating detergent compositions
some amount
of linear non-branched primary polyoxyalkylene may be admixed into the final
product
formulation.
Further it is to be similarly recognized that non-alkoxylated mid-chain
branched
alcohol may comprise some amount of the present invention polyoxyalkylene-
containing
compositions. Such materials may be present as the result of incomplete
alkoxylation of
the alcohol used to prepare the polyoxyalkylene surfactant, or these alcohols
may be
separately added to the present invention detergent compositions along with a
mid-chain
branched polyoxyalkylene surfactant according to the present invention.
Further regarding the above formula, w is an integer from 0 to 13; x is an
integer
from 0 to 13; y is an integer from 0 to 13; z is an integer of at least 1; and
w + x + y + z is
an integer from 8 to 14.
EO/PO are alkoxy moieties, preferably selected from ethoxy, propoxy, and mixed
ethoxy/propoxy groups, more preferably ethoxy, wherein m is at least about 1,
preferably
within the range of from about 3 to about 30, more preferably from about 5 to
about 20, and
most preferably from about 5 to about 15. The (EO/PO)m moiety may be either a
distribution with average degree of alkoxylation (e.g., ethoxylation and/or
propoxylation)
corresponding to m, or it may be a single specific chain with alkoxylation
(e.g.,
ethoxylation and/or propoxylation) of exactly the number of units
corresponding to m.
The preferred surfactant mixtures of the present invention have at least
0.001%,
more preferably at least 5%, most preferably at least 20% by weight, of the
mixture one or
more mid-chain branched primary alkyl polyoxyalkylenes having the formula
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WO 99/19454 PCT/US98/21421
22
R1 R2
I I
CH3CH2(CH2~CH(CH2)yCH(CH2)z(EO/PO)mOH
wherein the total number of carbon atoms, including branching, is from 15 to
18, and
wherein further for this surfactant mixture the average total number of carbon
atoms in the
branched primary alkyl moieties having the above formula is within the range
of greater
than 14.5 to about 17.5; RI and R2 are each independently hydrogen or C1-C3
alkyl; x is
from 0 to 11; y is from 0 to I 1; z is at least 2; and x + y + z is from 9 to
13; provided RI
and R2 are not both hydrogen; and EO/PO are alkoxy moieties selected from
ethoxy,
propoxy, and mixed ethoxy/propoxy groups, more preferably ethoxy, wherein m is
at least
about 1, preferably within the range of from about 3 to about 30, more
preferably from
about 5 to about 20, and most preferably from about 5 to about 15. More
preferred are
compositions having at least 5% of the mixture comprising one or more mid-
chain
branched primary polyoxyalkylenes wherein z is at least 2.
Preferably, the mixtures of surfactant comprise at least 5%, preferably at
least
about 20%, of a mid. chain branched primary alkyl polyoxyaikylene having RI
and R2
independently hydrogen or methyl, provided RI and R2 are not both hydrogen; x
+ y is
equal to 8, 9 or 10 and z is at least 2.
Preferred detergent compositions according to the present invention, for
example
one useful for laundering fabrics, comprise from about 0.001% to about 99% of
a mixture
of mid-chain branched primary alkyl polyoxyalkylene surfactants, said mixture
comprising
at least about S % by weight of one or more mid-chain branched alkyl
polyoxyalkylenes
having the formula:
CH3
(1) CH3 (CHz)aCH (CHz~CH2 (EO/PO)mOH
CH3 CH3
CH3 (CH2)dCH (CH2)e CH CH2 (EO/PO)mOH
(II)
or mixtures thereof; wherein a, b, d, and a are integers, a+b is from 10 to
16, d+e is from 8
to 14 and wherein further
when a + b = 10, a is an integer from 2 to 9 and b is an integer from 1 to 8;
when a + b = 11, a is an integer from 2 to 10 and b is an integer from 1 to 9;
when a + b = 12, a is an integer from 2 to 1 I and b is an integer from 1 to
10;
when a + b = 13, a is an integer from 2 to 12 and b is an integer from 1 to
11;
when a + b = 14, a is an integer from 2 to 13 and b is an integer from 1 to
12;
when a + b = 15, a is an integer from 2 to 14 and b is an integer from 1 to
13;
when a + b = 16, a is an integer from 2 to 15 and b is an integer from 1 to
14;
when d + a = 8, d is an integer from 2 to 7 and a is an integer from 1 to 6;
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23
when d + a = 9, d is an integer from 2 to 8 and a is an integer from 1 to 7;
when d + a = 10, d is an integer from 2 to 9 and a is an integer from 1 to 8;
when d + a = 11, d is an integer from 2 to 10 and a is an integer from 1 to 9;
when d + a = 12, d is an integer from 2 to 11 and a is an integer from 1 to
10;
when d + a = 13, d is an integer from 2 to 12 and a is an integer from 1 to i
1;
when d + a = 14, d is an integer from 2 to 13 and a is an integer from 1 to
12;
and wherein further for this surfactant mixture the average total number of
carbon atoms in
the branched primary alkyl moieties having the above formulas is within the
range of
greater than 14.5 to about 17.5; and EO/PO are alkoxy moieties selected from
ethoxy,
propoxy, and mixed ethoxy/propoxy groups, wherein m is at least about 1,
preferably
within the range of from about 3 to about 30, more preferably from about 5 to
about 20, and
most preferably from about 5 to about 15.
Further, the present invention surfactant composition may comprise a mixture
of
branched primary alkyl polyoxyalkylenes having the formula
R R1 R2
I I I
CH3CH2(CH2)~,CH(CH2)XCH(CH2)yCH(CH2)Z(EO/PO)mOH
wherein the total number of carbon atoms per molecule, including branching, is
from 14 to
20, and wherein further for this surfactant mixture the average total number
of carbon
atoms in the branched primary alkyl moieties having the above formula is
within the range
of greater than 14.5 to about 17.5; R, RI, and R2 are each independently
selected from
hydrogen and C I-C3 alkyl, provided R, RI, and R2 are not all hydrogen; w is
an integer
from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z is
an integer of at
least 1; w + x + y + z is from 8 to 14; EO/PO are alkoxy moieties, preferably
selected from
ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein m is at least about
1,
preferably within the range of from about 3 to about 30, more preferably from
about 5 to
about 20, and most preferably from about 5 to about I5; provided that when R2
is CI-C3
alkyl the ratio of surfactants having z equal to 2 or greater to surfactants
having z of I is at
least about 1:1, preferably at least about I.5:1, more preferably at least
about 3: I, and most
preferably at least about 4:1. Also preferred are surfactant compositions when
R2 is CI-C3
alkyl comprising less than about 50%, preferably less than about 40%, more
preferably less
than about 25%, most preferably less than about 20%, of branched primary alkyl
polyoxyalkylene having the above formula wherein z equals I .
Preferred mono-methyl branched primary alkyl ethoxylates are selected from the
group consisting of: 3-methyl pentadecanol ethoxylate, 4-methyl pentadecanol
ethoxylate,
5-methyl pentadecanol ethoxylate, 6-methyl pentadecanol ethoxylate, 7-methyl
pentadecanol ethoxylate, 8-methyl pentadecanol ethoxylate, 9-methyl
pentadecanol
CA 02305324 2000-03-31
WO 99/19454 PCT/US98/21421
24
ethoxylate, 10-methyl pentadecanol ethoxylate, 11-methyl pentadecanol
ethoxylate, 12-
methyl pentadecanol ethoxylate, 13-methyl pentadecanol ethoxylate, 3-methyl
hexadecanol
ethoxylate, 4-methyl hexadecanol ethoxylate, 5-methyl hexadecanol ethoxylate,
6-methyl
hexadecanol ethoxylate, 7-methyl hexadecanol ethoxylate, 8-methyl hexadecanol
ethoxylate, 9-methyl hexadecanol ethoxylate, 10-methyl hexadecanol ethoxylate,
11-methyl
hexadecanol ethoxylate, 12-methyl hexadecanol ethoxylate, 13-methyl
hexadecanol
ethoxylate, 14-methyl hexadecanol ethoxylate, and mixtures thereof, wherein
the
compounds are ethoxylated with an average degree of ethoxylation of from about
5 to about
15.
Preferred di-methyl branched primary alkyl ethoxylates selected from the group
consisting of: 2,3-methyl tetradecanol ethoxylate, 2,4-methyl tetradecanol
ethoxylate, 2,5-
methyl tetradecanol ethoxylate, 2,6-methyl tetradecanol ethoxylate, 2,7-methyl
tetradecanol
ethoxylate, 2,8-methyl tetradecanol ethoxylate, 2,9-methyl tetradecanol
ethoxylate, 2,10-
methyl tetradecanol ethoxylate, 2,11-methyl tetradecanol ethoxylate, 2,12-
methyl
tetradecanol ethoxylate, 2,3-methyl pentadecanol ethoxylate, 2,4-methyl
pentadecanol
ethoxylate, 2,5-methyl pentadecanol ethoxylate, 2,6-methyl pentadecanol
ethoxylate, 2,7-
methyl pentadecanol ethoxylate, 2,8-methyl pentadecanol ethoxylate, 2,9-methyl
pentadecanol ethoxylate, 2,10-methyl pentadecanol ethoxylate, 2, l 1-methyl
pentadecanol
ethoxylate, 2,12-methyl pentadecanol ethoxylate, 2,13-methyl pentadecanol
ethoxylate, and
mixtures thereof, wherein the compounds are ethoxylated with an average degree
of
ethoxylation of from about 5 to about 15.
The present invention branched surfactant compositions may comprise one or
more
(preferably a mixture of two or more) mid-chain branched primary alkyl
alkoxylated
sulfates having the formula:
R Rl R2
I I I
CH3CH2(CH2h,~,CH(CH2)XCH(CH2)yCH(CH2)Z(EO/PO)m0 S03M
The surfactant mixtures of the present invention comprise molecules having a
linear primary alkoxylated sulfate chain backbone (i.e., the longest linear
carbon chain
which includes the alkoxy-sulfated carbon atom). These alkyl chain backbones
comprise
from 12 to 19 carbon atoms; and further the molecules comprise a branched
primary alkyl
moiety having at least a total of 14, but not more than 20, carbon atoms. In
addition, the
surfactant mixture has an average total number of carbon atoms for the
branched primary
alkyl moieties within the range of from greater than 14.5 to about 17.5. Thus,
the present
CA 02305324 2000-03-31
WO 99/19454 PCT/US98/21421
25
invention mixtures comprise at least one alkoxylated sulfate compound having a
longest
linear carbon chain of not less than 12 carbon atoms or more than 19 carbon
atoms, and the
total number of carbon atoms including branching must be at least 14, and
further the
average total number of carbon atoms for the branched primary alkyl chains is
within the
range of greater than 14.5 to about 17.5.
For example, a C16 total carbon (in the alkyl chain) primary alkyl alkoxylated
sulfate surfactant having 15 carbon atoms in the backbone must have a methyl
branching
unit (either R, R1 or R2 is methyl) whereby the total number of carbon atoms
in the
primary alkyl moiety of the molecule is 16.
R, R1, and R2 are each independently selected from hydrogen and CI-C3 alkyl
(preferably hydrogen or C 1-C2 alkyl, more preferably hydrogen or methyl, and
most
preferably methyl), provided R, R1, and R2 are not all hydrogen. Further, when
z is l, at
least R or R1 is not hydrogen.
Although for the purposes of the present invention surfactant compositions the
above formula does not include molecules wherein the units R, R1, and R2 are
all hydrogen
(i.e., linear non-branched primary alkoxylated sulfates), it is to be
recognized that the
present invention compositions may still further comprise some amount of
linear, non-
branched primary alkoxylated sulfate. Further, this linear non-branched
primary
alkoxylated sulfate surfactant may be present as the result of the process
used to
manufacture the surfactant mixture having the requisite mid-chain branched
primary
alkoxylated sulfates according to the present invention, or for purposes of
formulating
detergent compositions some amount of linear non-branched primary alkoxylated
sulfate
may be admixed into the final product formulation.
It is also to be recognized that some amount of mid-chain branched alkyl
sulfate
may be present in the compositions. This is typically the result of sulfation
of non-
alkoxylated alcohol remaining following incomplete alkoxylation of the mid-
chain
branched alcohol used to prepare the alkoxylated sulfate useful herein. It is
to be
recognized, however, that separate addition of such mid-chain branched alkyl
sulfates is
also contemplated by the present invention compositions.
Further it is to be similarly recognized that non-sulfated mid-chain branched
alcohol (including polyoxyalkylene alcohols) may comprise some amount of the
present
invention alkoxylated sulfate-containing compositions. Such materials may be
present as
the result of incomplete sulfation of the alcohol (alkoxylated or non-
alkoxylated) used to
prepare the alkoxylated sulfate surfactant, or these alcohols may be
separately added to the
present invention detergent compositions along with a mid-chain branched
alkoxylated
sulfate surfactant according to the present invention.
M is as described hereinbefore.
CA 02305324 2000-03-31
WO 99/19454 PCT/US98/21421
26
Further regarding the above formula, w is an integer from 0 to 13; x is an
integer
from 0 to 13; y is an integer from 0 to 13; z is an integer of at least 1; and
w + x + y + z is
an integer from 8 to 14.
EO/PO are alkoxy moieties, preferably selected from ethoxy, propoxy, and mixed
ethoxy/propoxy groups, wherein m is at least about 0.01, preferably within the
range of
from about 0.1 to about 30, more preferably from about 0.5 to about 10, and
most
preferably from about I to about 5. The (EO/PO)m moiety may be either a
distribution
with average degree of alkoxylation (e.g., ethoxytation and/or propoxylation)
corresponding to m, or it may be a single specific chain with alkoxylation
(e.g.,
ethoxylation and/or propoxylation) of exactly the number of units
corresponding to m.
The preferred surfactant mixtures of the present invention have at least
0.001%,
more preferably at least 5%, most preferably at least 20% by weight, of the
mixture one or
more mid-chain branched primary alkyl alkoxylated sulfates having the fonmula
R1 R2
I I
CH3CH2(CH2)xCH(CH2h,CH(CH2)z(EO/PO)m0 S03M
wherein the total number of carbon atoms, including branching, is from 15 to
18, and
wherein further for this surfactant mixture the average total number of carbon
atoms in the
branched primary alkyl moieties having the above formula is within the range
of greater
than 14.5 to about 17.5; R1 and R2 are each independently hydrogen or C 1-C3
alkyl; M is a
water soluble cation; x is from 0 to 11; y is from 0 to I 1; z is at least 2;
and x + y + z is
from 9 to 13; provided R1 and R2 are not both hydrogen; and EO/PO are alkoxy
moieties
selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein m is
at least
about 0.01, preferably within the range of from about 0.1 to about 30, more
preferably from
about 0.5 to about 10, and most preferably from about 1 to about 5. More
preferred are
compositions having at least 5% of the mixture comprising one or more mid-
chain
branched primary alkoxylated sulfates wherein z is at least 2.
Preferably, the mixtures of surfactant comprise at least 5%, preferably at
least
about 20%, of a mid chain branched primary alkyl alkoxylated sulfate having RI
and R2
independently hydrogen or methyl, provided R1 and R2 are not both hydrogen; x
+ y is
equal to 8, 9 or 10 and z is at least 2.
Preferred detergent compositions according to the present invention, for
example
one useful for laundering fabrics, comprise from about 0.001 % to about 99% of
a mixture
of mid-chain branched primary alkyl alkoxylated sulfate surfactants, said
mixture
comprising at least about 5 % by weight of one or more mid-chain branched
alkyl
alkoxylated sulfates having the formula:
CA 02305324 2000-03-31
WO 99/19454 PCTNS98/21421
27
CH3
CH3 (CH2)aCH (CH2~CH2 (EO/PO)m0 S03M
(I)
CH3 CH3
CN3 (CH2)dCH (CH2)e CH CHZ (EO/PO)m0 S03M
(II)
or mixtures thereof; wherein M represents one or more cations; a, b, d, and a
are integers,
a+b is from 10 to 16, d+e is from 8 to 14 and wherein further
when a + b = 10, a is an integer from 2 to 9 and b is an integer from 1 to 8;
when a + b = 11, a is an integer from 2 to 10 and b is an integer from 1 to 9;
when a + b = 12, a is an integer from 2 to 11 and b is an integer from 1 to
10;
when a + b = 13, a is an integer from 2 to 12 and b is an integer from 1 to
11;
when a + b = 14, a is an integer from 2 to 13 and b is an integer from 1 to
12;
when a + b = 15, a is an integer from 2 to 14 and b is an integer from 1 to
13;
when a + b = 16, a is an integer from 2 to 15 and b is an integer from 1 to
14;
when d + a = 8, d is an integer from 2 to 7 and a is an integer from 1 to 6;
when d + a = 9, d is an integer from 2 to 8 and a is an integer from 1 to 7;
when d + a = 10, d is an integer from 2 to 9 and a is an integer from I to 8;
when d + a = 1 I, d is an integer from 2 to 10 and a is an integer from 1 to
9;
when d + a = 12, d is an integer from 2 to 11 and a is an integer from 1 to
10;
when d + a = 13, d is an integer from 2 to 12 and a is an integer from 1 to
11;
when d + a = 14, d is an integer from 2 to 13 and a is an integer from 1 to
12;
and wherein further for this surfactant mixture the average total number of
carbon atoms in
the branched primary alkyl moieties having the above formulas is within the
range of
greater than 14.5 to about 17.5; and EO/PO are alkoxy moieties selected from
ethoxy,
propoxy, and mixed ethoxy/propoxy groups, wherein m is at least about 0.01,
preferably
within the range of from about 0.1 to about 30, more preferably from about 0.5
to about 10,
and most preferably from about 1 to about 5.
Further, the present-invention surfactant composition may comprise a mixture
of
branched primary alkyl alkoxylated sulfates having the formula
R Rl R2
I I I
CH3CH2(CH2)~,CH(CH2}xCH(CH2h,CH(CH2)z(EO/PO)m0 S03M
wherein the total number of carbon atoms per molecule, including branching, is
from 14 to
20, and wherein further for this surfactant mixture the average total number
of carbon
atoms in the branched primary alkyl moieties having the above formula is
within the range
of greater than 14.5 to about 17.5; R, R1, and R2 are each independently
selected from
hydrogen and C1-C3 alkyl, provided R, R1, and R2 are not all hydrogen; M is a
water
CA 02305324 2000-03-31
WO 99/19454 PCT/US98/21421
28
soluble cation; w is an integer from 0 to 13; x is an integer from 0 to 13; y
is an integer
from 0 to 13; z is an integer of at least I; w + x + y + z is from 8 to 14;
EO/PO are alkoxy
moieties, preferably selected from ethoxy, propoxy, and mixed ethoxy/propoxy
groups,
wherein m is at least about 0.01, preferably within the range of from about
0.1 to about 30,
more preferably from about 0.5 to about 10, and most preferably from about 1
to about 5;
provided that when R2 is C1-C3 alkyl the ratio of surfactants having z equal
to 2 or greater
to surfactants having z of 1 is at least about 1:1, preferably at least about
1.5:1, more
preferably at least about 3:1, and most preferably at least about 4:1. Also
preferred are
surfactant compositions when R2 is C1-C3 alkyl comprising less than about 50%,
preferably less than about 40%, more preferably less than about 25%, most
preferably less
than about 20%, of branched primary alkyl alkoxylated sulfate having the above
formula
wherein z equals 1.
Preferred mono-methyl branched primary alkyl ethoxylated sulfates are selected
from the group consisting of: 3-methyl pentadecanol ethoxylated sulfate, 4-
methyl
pentadecanol ethoxylated sulfate, 5-methyl pentadecanol ethoxylated sulfate, 6-
methyl
pentadecanol ethoxylated sulfate, 7-methyl pentadecanol ethoxylated sulfate, 8-
methyl
pentadecanol ethoxylated sulfate, 9-methyl pentadecanol ethoxylated sulfate,
10-methyl
pentadecanol ethoxylated sulfate, 11-methyl pentadecanol ethoxylated sulfate,
12-methyl
pentadecanol ethoxylated sulfate, 13-methyl pentadecanol ethoxylated sulfate,
3-methyl
hexadecanol ethoxylated sulfate, 4-methyl hexadecanol ethoxylated sulfate, 5-
methyl
hexadecanol ethoxylated sulfate, 6-methyl hexadecanol ethoxylated sulfate, 7-
methyl
hexadecanol ethoxylated sulfate, 8-methyl hexadecanol ethoxylated sulfate, 9-
methyl
hexadecanol ethoxylated sulfate, 10-methyl hexadecanol ethoxylated sulfate, 11-
methyl
hexadecanol ethoxylated sulfate, 12-methyl hexadecanol ethoxylated sulfate, 13-
methyl
hexadecanol ethoxylated sulfate, 14-methyl hexadecanol ethoxylated sulfate,
and mixtures
thereof, wherein the compounds are ethoxylated with an average degree of
ethoxylation of
from about 0.1 to about 10.
Preferred di-methyl branched primary alkyl ethoxylated sulfates selected from
the
group consisting of: 2,3-methyl tetradecanol ethoxylated sulfate, 2,4-methyl
tetradecanol
ethoxylated sulfate, 2,5-methyl tetradecanol ethoxylated sulfate, 2,6-methyl
tetradecano)
ethoxylated sulfate, 2,7-methyl tetradecanol ethoxylated sulfate, 2,8-methyl
tetradecanol
ethoxylated sulfate, 2,9-methyl tetradecanol ethoxylated sulfate, 2,10-methyl
tetradecanol
ethoxylated sulfate, 2,11-methyl tetradecanol ethoxylated sulfate, 2,12-methyl
tetradecanol
ethoxylated sulfate, 2,3-methyl pentadecanol ethoxylated sulfate, 2,4-methyl
pentadecanol
ethoxyiated sulfate, 2,5-methyl pentadecanol ethoxylated sulfate, 2,6-methyl
pentadecanol
ethoxyiated sulfate, 2,7-methyl pentadecanol ethoxylated sulfate, 2,8-methyl
pentadecanol
ethoxylated sulfate, 2,9-methyl pentadecanol ethoxylated sulfate, 2,10-methyl
pentadecanol
CA 02305324 2002-12-13
29
ethoxylated sulfate, 2,I 1-methyl pentadecanol ethoxylated sulfate, :Z,I2-
methyl
pentadecanol ethoxylated sulfate, 2,13-methyl pentadecanol ethoxytated
sulfate, and
mixtures thereof, wherein the compounds are ethoxylated with an average degree
of
ethoxylation of from about 0.1 to about 10.
The paste can include adjunct surfactants such as those selected from anionics
other
than BAS, nonionic, zwitterionic, ampholytic and cationic classes and
compatible mixtures
thereof. Detergent surfactants useful herein are described in U.S. Patent
3,664,961, Norris,
issued May 23, 1972, and in U.S. Patent 3,919,678, Laughlin et al., issued
December 30,
1975. Useful cationic surfactants also include those described in U.S. Patent
4,222,905,
Cockrell, issued September 16, 1980, and in U.S. Patent 4,239,659, Murphy,
issued
December 16, 1980.
The following are representative examples of adjunct detergent surfactants
useful
in the present surfactant paste. Water-soluble salts of the higher fatay
acids, i.e., "soaps",
are useful anionic surfactants in the compositions herein. This inchudes
alkali metal soaps
such as the sodium, potassium, ammonium, and alkyloiammonium salts of hil;her
fatty
acids containing from about 8 to about 24 carbon atoms, and preferably from
about 12 to
about 18 carbon atoms. Soaps can be made by direct saponification of fats and
oils or by
the neutralization of free fatty acids. Particularly useful are the sodium and
potassium salts
of the mixtures of fatty acids derived from coconut oil and tallow, i.e.,
sodium or potassium
tallow and coconut soap.
Additional anionic surfactants which suitable for use herein include the water-
soluble salts, preferably the alkali metal, ammonium and alkylolam.monium
salts, of
organic sulfuric reaction products having in their molecular structure a
straight-chain alkyl
group containing from about 10 to about 20 carbon atoms and a sulfonic acid or
sulfuric
acid ester group. (Included in the term "alkyl" is the alkyl portion of acyl
groups.)
Examples of this group of synthetic surfactants are the sodium and potassium
alkyl sulfates,
especially those obtained by sulfating the higher alcohols (C8-18 carbon
atoms) such as
those produced by reducing the glycerides of tallow or coconut oil; and the
sodium and
potassium alkylbenzene sulfonates in which the alkyl group contains from about
9 to about
15 carbon atoms, in straight chain, e.g., those of the type described in U.S.
Patents
2,220,099 and 2,477,383. Especially valuable are linear straight chain
alkylb~enzene
sulfonates in which the average number of carbon atoms in the alkyl group is
from about 11
to I3, abbreviated as CI 1-I3 LAS.
Other anionic surfactants suitable for use herein are the sodium alkyl
glyceryl ether
sulfonates, especially those ethers of higher aicohols derived from 'tallow
and coconut oil;
sodium coconut oil fatty acid monoglyceride suifonates and sulfates; sodium or
potassium
CA 02305324 2000-03-31
WO 99/19454 PCT/US98/21421
of ethylene oxide per molecule and wherein the alkyl groups contain from about
8 to about
12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether
sulfates
containing about 1 to about 10 units of ethylene oxide per molecule and
wherein the alkyl
group contains from about 10 to about 20 carbon atoms.
In addition, suitable anionic surfactants include the water-soluble salts of
esters of
alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the
fatty acid
group and from about 1 to 10 carbon atoms in the ester group; water-soluble
salts of
2-acyloxyalkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in
the acyl
group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl
ether sulfates
containing from about 10 to 20 carbon atoms in the alkyl group and from about
1 to 30
moles of ethylene oxide; water-soluble salts of olefin and paraffin sulfonates
containing
from about 12 to 20 carbon atoms; and beta-alkyloxy alkane sulfonates
containing from
about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon
atoms in the
alkane moiety.
Preferred adjunct anionic surfactants are C10-18 linear alkylbenzene sulfonate
and
C 10-18 alkyl sulfate. If desired, low moisture (less than about 25% water)
alkyl sulfate
paste can be the sole ingredient in the surfactant paste. Most preferred are C
10-18 alkyl
sulfates, linear or branched, and any of primary, secondary or tertiary. A
preferred
embodiment of the present invention is wherein the surfactant paste comprises
from about
20% to about 40% of a mixture of sodium C10-13 linear alkylbenzene sulfonate
and
sodium C12-16 alkyl sulfate in a weight ratio of about 2:1 to 1:2. Another
preferred
embodiment of the detergent composition includes a mixture of C 10-1 g alkyl
sulfate and
C10-18 alkyl ethoxy sulfate in a weight ratio of about 80:20.
Water-soluble nonionic surfactants are also useful in the instant invention.
Such
nonionic materials include compounds produced by the condensation of alkylene
oxide
groups (hydrophilic in nature) with an organic hydrophobic compound, which may
be
aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group
which is
condensed with any particular hydrophobic group can be readily adjusted to
yield a
water-soluble compound having the desired degree of balance between
hydrophilic and
hydrophobic elements.
Suitable nonionic surfactants include the polyethylene oxide condensates of
alkyl
phenols, e.g., the condensation products of alkyl phenols having an alkyl
group containing
from about 6 to 15 carbon atoms, in either a straight chain or branched chain
configuration,
with from about 3 to 12 moles of ethylene oxide per mole of alkyl phenol.
Included are the
water-soluble and water-dispersible condensation products of aliphatic
alcohols containing
from 8 to 22 carbon atoms, in either straight chain or branched configuration,
with from 3
to 12 moles of ethylene oxide per mole of alcohol.
CA 02305324 2002-12-13
31
An additional group of nonionics suitable for use herein are semi-polar
nonionic
surfactants which include water-soluble amine oxides containing one alkyl
moiety of from
abut 10 to 18 carbon atoms and two moieties selected from the group of alkyl
and
hydroxyalkyl moieties of from about 1 to about 3 carbon atoms; water-soluble
phosphine
oxides containing one alkyl moiety of about 10 to 18 carbon atoms and two
moieties
selected from the group consisting of alkyl groups and hydroxyalkyt groups
containing
from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one
alkyl moiety
of from about 10 to 18 carbon atoms and a moiety selected from the group
consisting of
alkyl and hydroxyalkyl moieties of from about I to 3 carbon atoms.
Preferred nonionic surfactants are of the formula RI(OC2H4)nOH, wherein R1 is
a
CIA C16 alkyl group or a C8 C12 alkyl phenyl group, and n is from 3 to about
80.
Particularly preferred are condensation products of C 12-C 15 alcohols with
from about 5 to
about 20 moles of ethylene oxide per mole of alcohol, e.g., C 12 C 13 alcohol
condensed with
about 6.5 moles of ethylene oxide per mole of alcohol.
Additional suitable nonionic surfactants include poiyhydroxy fatty acid
amides. Examples are N-methyl N-I-deoxyglucityl cocoamide and N-methyl. N-I-
deoxyglucityl oleamide. Processes for making polyhydroxy fatty acid amides are
known and
can be found in Wilson, U.S. Patent No. 2,965,576 and Schwartz, iJ.S. Patent
No. 2,703,798
Ampholytic surfactants include derivatives of aliphatic or aliphatic
derivatives of
heterocyclic secondary and tertiary amines in which the aliphatic moiety can
be straight
chain or branched and wherein one of the aliphatic substituents contains from
about 8 to 18
carbon atoms and at least one aliphatic substituent contains an anionic water-
aolubilizing
group.
Zwitterionic surfactants include derivatives of aliphatic, quaternary,
ammonium,
phosphonium, and sulfonium compounds in which one of the aliphatic
substil:uents contains
from about 8 to 18 carbon atoms.
Cationic surfactants can also be included in the present invention. Cationic
surfactants comprise a wide variety of compounds characterized by one or more
organic
hydrophobic groups in the cation and generally by a quaternary nitrogen
associated with an
acid radical. Pentavalent nitrogen ring compounds are also considered
quaternary nitrogen
compounds. Suitable anions are halides, methyl sulfate and hydroxide. Tertiary
amines
can have characteristics similar to cationic surfactants at washing solution
pH values less
than about 8.5. A more complete disclosure of these and other cationic
surfacaants useful
herein can be found in U.S. Patent 4,228,044, Cambre, issued October 14, 1980
.
CA 02305324 2002-12-13
32
Cationic surfactants are often used in detergent compositions to provide
fabric
softening and/or antistatic benefits. Antistatic agents which provide some
softening benefit
and which are preferred herein are the quaternary ammonium saltvc described in
U.S. Patent
3,936,537, Baskerville, Jr. et al., issued February 3, 1976.
CA 02305324 2002-12-13
33
Dry Starting Detergent Ingredients;
The compositions of the invention can contain all manner of organic, water-
soluble
detergent compounds, inasmuch as the builder material are compatiible with all
such
materials. In addition to a detersive surfactant, at least one suitable
adjunct detergent
ingredient is preferably included in the detergent composition. The: adjunct
detergent
ingredient is preferably selected from the group consisting of builders,
enzymes, bleaching
agents, bleach activators, suds suppressors, soil release agents, brighteners,
pE;rfumes,
hydrotropes, dyes, pigments, polymeric dispersing agents, pH controlling
agents, chelants,
processing aids, crystallization aids, and mixtures thereof. The following
list of detergent
ingredients and mixtures thereof which can be used in the compositions herein
is
representative of the detergent ingredients, but is not intended to be;
Limiting.
One or more builders can be used in conjunction with the builder material
described herein to further improve the performance of the compositions
described herein.
For example, the builder can be selected from the group consisting of
aluminosilicates,
crystalline layered silicates, MAP zeolites, citrates, amorphous silicates,
poiycarboxylates,
sodium carbonates and mixtures thereof. The sodium carbonate ingredient can
serve as the
inorganic alkaline material when a liquid acid precursor of the mid-chain
branched
surfactant is used. Other suitable auxiliary builders are described
hereinafter.
Preferred builders include aluminosilicate ion exchange materials and sodium
carbonate. The aiuminosilicate ion exchange materials used herein as a
detergent builder
preferably have both a high calcium ion exchange capacity and a high exchange
rate.
Without intending to be limited by theory, it is believed that such high
calcium ion
exchange rate and capacity are a function of several interrelated factors
which derive from
the method by which the aluminosilicate ion exchange material is produced. In
that regard,
the aluminosilicate ion exchange materials used herein are preferalbly
produced in
accordance with Corkill et al, U.S. Patent No. 4,b05,509 (Procter &i Gamble)..
Preferably, the aluminosilicate ion exchange material is in "sodium" form
since the
potassium and hydrogen forms of the instant alurninosilicate do ncrt exhibit
the as high of
an exchange rate and capacity as provided by the sodium form. Additionally,
the
aluminosilicate ion exchange material preferably is in over dried form so as
to facilitate
production of crisp detergent agglomerates as described herein. The
aluminosiiicate ion
exchange materials used herein preferably have particle size diameters which
optimize
their effectiveness as detergent builders. The term "particle size diameter"
as used herein
represents the average particle size diameter of a given aluminosilicate ion
exchange
material as determined by conventional analytical techniques, such as
microscopic
determination and scanning electron microscope (SEM). The preferred particle
size
CA 02305324 2002-12-13
34
diameter of the aluminosilicate is from about 0.1 micron to about RO microns.,
more
preferably from about 0.5 microns to about 9 microns. Most preferably, the
particle size
diameter is from about 1 microns to about 8 microns.
Preferably, the aluminosilicate ion exchange material has i:he formuha
Naz~~Al02)z~~si02)y]xH20
wherein z and y are integers of at least 6, the molar ratio of z to y is from
about 1 to about
and x is from about 10 to about 264. More preferably, the aluminosilicate lhas
the
formula
NaI2~tA102)12~~Si02)12~~20
wherein x is from about 20 to about 30, preferably about 27. These preferred
aluminosilicates are available commercially, for example under designations
Zeolite A,
Zeolite B and Zeolite X. Alternatively, naturally-occurring or synthetically
derived
aluminosilicate ion exchange materials suitable for use herein can be made as
described in
ICrummel et al, U.S. Patent No. 3,985,669 .
The aluminosilicates used herein are further characterized by their ion
exchange
capacity which is at least about 200 mg equivalent of CaCO3 hardnesslgram,
calculated on
an anhydrous basis, and which is preferably in a range from about 300 to 352
mg
equivalent of CaC03 hardness/gram. Additionally, the instant aluminosilicate
ion
exchange materials are still further characterized by their calcium ion
exchange rate which
is at least about 2 grains Ca~lgallon/minute/-gram/gallon, and more preferably
in a range
from about 2 grains Ca'~"~'/gallon/minute/-gram/gallon to about 6 grains
Ca'~'/gallon/minute/-gram/gallon .
In order to make the present invention more readily understood, reference is
made
to the following examples, which are intended to be illustrative only and not
intended to be
limiting in scope.
EXAMPLE I
This Example illustrates the process of the invention which produces free
flowing,
crisp, high density detergent composition. Two feed streams of various
detergent starting
ingredients are continuously fed, at a rate of 2800 kg/hr, into a Lodige CB-30
mixer/densifier, one of which comprises a surfactant paste containing
surfactant and water
and the other stream containing starting dry detergent material containing
aluminosilicate
and sodium carbonate. The rotational speed of the shaft in the Lodige CB-30
mixer/densifier is about 1400 rpm and the mean residence time is about 10
seconds. The
contents from the Lodige CB-30 mixer/densifer are continuously fed into a
Lodige KM 600
mixer/densifer for further agglomeration during which the mean residence time
is about 30
seconds. The resulting detergent agglomerates are then fed to a fluid bed
dn~er and then to
CA 02305324 2000-03-31
WO 99/19454 PCT/US9$/21421
a fluid bed cooler, the mean residence time being about 10 minutes and 15
minutes,
respectively. A coating agent, aluminosilicate, is fed after the Lodige KM 600
mixer/densifier to control and prevent over agglomeration. The detergent
agglomerates are
then screened with conventional screening apparatus resulting in a uniform
particle size
distribution. The composition of the detergent agglomerates exiting the fluid
bed cooler for
three process runs are set forth in Table I below:
TABLEI
Co~ % Weigh t l
ponent of Eeed
Tota
,
9
016.5 BAS 40.0 46.0 31.0
C14-15 AS - - 14.0
C12.3LAS 1.1 - -
Aluminosilicate 25.4 24.0 24.0
Sodium carbonate 26.3 24.0 24.0
Polyethylene glycol (MW 1.1 1.7 2.0
4000)
Misc. (water, etc.) ~ g~ ~,Q
100.0 100.0 100.0
Additional detergent ingredients including perfumes, enzymes, and other minors
are sprayed onto the agglomerates described above in the finishing step to
result in a
finished detergent composition. The relative proportions of the overall
finished detergent
composition produced by the process of instant process is presented in Table
II below:
TABLE 11
o1f° weiehtl
Component
C 16.SBAS, C 14-1 SAS and C 12.3 39.8
LAS 1
Neodol 23-6.52 3.0
C12-14 N-methyl glucamide 0.9
Polyacrylate (MW=4500) 3.0
Polyethylene glycol (MW=4000) 1.2
Sodium Sulfate 8.9
Aluminosilicate 2.8
Sodium carbonate 27.2
Protease enzyme 0.4
Amylase enzyme O.I
Lipase enzyme 0.2
Cellulase enzyme 0.1
CA 02305324 2000-03-31
WO 99/19454 PCT/US98/21421
36
Minors (water, perfume, etc.)
I 00.0
1 A mixture of a mid-chain branched C 16.5 alkyl sulfate ("BAS"), C 14_ 15
alkyl sulfate
("AS") and C12-13 linear alkylbenzene sulfonate ("LAS") surfactants.
2 C12-13 alkyl ethoxyiate (E0=6.5) commercially available from Shell Oil
Company.
The density of the resulting detergent composition is 796 g/1, the median
particle
size is 613 microns.
EXAMPLE II-III
Several detergent compositions made in accordance with the invention and
specifically for top-loading washing machines are exemplified below. The base
granule is
prepared by a conventional spray drying process in which the starting
ingredients are
formed into a slurry and passed though a spray drying tower having a counter
current
stream of hot air (200-300°C) resulting in the formation of porous
granules. The admixed
agglomerates are formed from two feed streams of various starting detergent
ingredients
which are continuously fed, at a rate of 1400 kg/hr, into a Lodige CB-30
mixer/densifier,
one of which comprises a surfactant paste containing surfactant and water and
the other
stream containing starting dry detergent material containing aluminosilicate
and sodium
carbonate. The rotational speed of the shaft in the Lodige CB-30
mixer/densifier is about
1400 rpm and the median residence time is about 5-10 seconds. The contents
from the
Lodige CB-30 mixer/densifier are continuously fed into a Lodige ICM-600
mixer/densifier
for further agglomeration during which the mean residence time is about 1-2
minutes. The
resulting detergent agglomerates are then fed to a fluid bed dryer and to a
fluid bed cooler
before being admixed with the spray dried granules. The remaining adjunct
detergent
ingredients are sprayed on or dry added to the blend of agglomerates and
granules.
II III
Base Granule
C 16.5 alkyl sulfate (mid-chain6.0 19.0
branched), Na
Aluminosilicate 1 S.0 2.0
Sodium sulfate 10.0 10.0
Sodium polyacrylate polymer 3.0 3.0
PolyethyleneGlycol (MW=4000)2.0 2.0
C12-13 linear alkylbenzene 6.0 6.0
sulfonate, Na
C14-15 alkyl ethoxylated 3.0 3.0
sulfate, Na
Sodium silicate 1.0 1.0
Brightener 246 0.3 0.3
Sodium carbonate 7.0 7.0
DTPA 1 0.5 0.5
CA 02305324 2002-12-13
37
~ldmi ed Agglomerates
C14-15 alkyl sulfate, Na 3.0 5.0
C12-13 linear alkylbenzene sulfonate, 1.0 2.0
Na
016.5 alkyl sulfate (mid-chain branched),3,0 7.0
Na
Sodium Carbonate 4.0 4.0
PolyethyleneGlycol (MW=4000) 1.0 I.O
Admix
C 12- I S alkyl ethoxylate (E0 = 7) 2.0 2.0
Perfume 0.3 0.3
Polyvinylpyrrolidone 0.5 0.5
Polyvinylpyridine N-oxide 0.5 0.5
Polyvinylpyrroiidone-polyvinylimidazole 0.5 0.5
Distearylamine & Cumene sulfonic acid 2.0 2.0
Soil Release Polymer 2 0.5 0.5
Lipolase Lipase {100.000 LUII)4 0.5 0.5
Termamyi amylase (60 ICNU/g)5 0.3 0.3
CAREZYME~ cellulase (1000 CEVU/g)4 0.3 0.3
Protease (40mg/g)5 0.5 0.5
NOBS 3 5.0 5.0
Sodium Percarbonate 12.0 12.0
Polydimethylsiloxane 0.3 0.3
Miscellaneous (water, etc.) balance baian~e_
Total I 100.0
00.0
I Diethylene Triamine Pentaacetic Acid
2Made according to U.S. Patent 5,415,807,sued
is May
16,
1995
to
Gosselink
et
al
3 Nonanoyloxybenzenesulfonate
4 Purchased from Novo Nordisk A/S
Purchased from Genencor
6 Purchased from Ciba-Geigy
Having thus described the invention i n it will be clear to those skilled
detail,in the
art that various changes may be made
without departing from the scope of
the invention
and the invention is not to be considered
limited to what is described in the
specification.
