Note: Descriptions are shown in the official language in which they were submitted.
CA 02305351 2000-03-31
WO 99/19453 PCT/US98/21420
FIELD OF THE INVFNTTnN
The present invention generally relates to processes for producing a granular
detergent composition. More particularly, the invention is directed to
processes during
which a high density detergent composition is 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
alkoxylated 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 INV NTION
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/I 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 batch
process in which spray-dried or granulated detergent powders containing sodium
tripolyphosphate and sodium sulfate are densified and spheronized in a
Marumerizer~.
CA 02305351 2000-03-31
WO 99/19453 PC'f/US98/21420
This apparatus comprises a substantially horizontal, roughened, rotatabie
table positioned
within and at the base of a substantially vertical, smooth walled cylinder.
This process,
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. However, typical "post tower" processes have been
largely
unsuccessful in producing granular detergent products having acceptable flow
properties
and particle size regularity. Thus, there remains a need for a process which
produces a
compact granular detergent product having acceptable flow and particle size
properties (i.e.,
a more narrow particle size distribution).
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
compact granular detergent product having acceptable flow and particle size
properties (i.e.,
a more narrow particle size distribution). There is also a need in the art for
such a process
which includes 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.
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);
CA 02305351 2000-03-31
WO 99/19453 PCT/C1S98/21420
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).
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
commercial C 14/C 15 branched primary alkyl sulfate, namely LIAL 145 sulfate.
This is
believed to have 61% branching in the 2-position; 30% of this involves
branching with a
hydrocarbon chain having four or more carbon atoms. U.S. 3,480,556 describes
mixtures
of from I 0 to 90 parts of a straight chain primary alkyl sulfate and from 90
to 10 parts of a
beta branched (2-position branched) primary alcohol sulfate of formula:
R2
RICH CH2 OS03X
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.
Amer. 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 al., 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
isostearyl
CA 02305351 2000-03-31
WO 99/19453 PCT/US98/21420
4
alcohols and ethoxylated isostearyl alcohols 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. Varadaraj
et al., J.
Phys. Chem., Vol. 9S, (1991), pp 1671-1676 (which describes the surface
tensions of a
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 micelIar solutions of
surfactants
including branched alkyl sulfates).
"Linear Guerbet" alcohols are available from Henkel, e.g., EUTANOL G-16.
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 at elevated
temperatures
with constrained intermediate 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 temperatures 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.20-24
"Hydrophobic
groups and their sources"; pp 28-29 "Alcohols" , pp 34-3S "Primary Alkyl
Sulfates" and pp
3S-36 "Secondary Alkyl Sulfates"); and literature on "higher" or "detergent"
alcohols 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 86S-913 and
references
therein.
The present invention meets the aforementioned needs in the art by providing a
process which produces a compact granular detergent composition directly from
mid-chain
branched surfactants and other starting detergent ingredients. The mid-chain
branched
surfactants are mid-chain branched primary alkyl sulfate surfactants and mid-
chain
branched primary alkyl alkoxoxylated sulfate surfactants having an average of
greater than
14.5 carbon atoms. The process involves mixing a surfactant paste and drying
detergent
CA 02305351 2000-03-31
WO 99/19453 PCT/US98/21420
ingredients, spray drying the resulting slurry, compacting the spray dried
granules, grinding
and coating the granules to form the finished detergent product. The detergent
compositions resulting from the processes of the invention have acceptable
flow properties,
a narrow particle size distribution, and 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.
All percentages and ratios used herein are expressed as percentages by weight
(anhydrous basis) unless otherwise indicated. All documents are incorporated
herein by
reference. All viscosities referenced herein are measured at 70°C
(t5°C) and at shear rates
of about 10 to 100 sec-1.
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) continuously mixing a detergent surfactant paste and dry starting
detergent material
into a mixer to obtain a slurry, the surfactant paste containing mid-chain
branched
surfactant compounds of the formula:
Ab-X-B
wherein:
(a) Ab is a hydrophobic C9 to C22, total carbons in the moiety, preferably
from about C12
to about C 18, mid-chain branched alkyl moiety having: ( 1 ) 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
CI - 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 # 1 which is
attached to the - X - B moiety, to position w - 2 carbon, the terminal carbon
minus 2
carbons; and (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 hydophilic moiety selected
from sulfates,
sulfonates, amine oxides, polyoxyalkylene, alkoxylated sulfates, polyhydroxy
moieties,
phosphate esters, glycerol sulfonates, polygluconates, polyphosphate esters,
phosphonates,
sulfosuccinates, sulfosuccaminates, polyalkoxylated carboxylates, glucamides,
taurinates,
sarcosinates, glycinates, isethionates, dialkanolamides, monoalkanolamides,
monoalkanolamide sulfates, diglycolamides, diglycolamide sulfates, glycerol
esters,
glycerol ester sulfates, glycerol ethers, glycerol ether sulfates,
polyglycerol ethers,
polyglycerol ether sulfates, sorbitan esters, polyalkoxylated sorbitan esters,
ammonioalkanesuifonates, amidopropyl betaines, alkylated quats,
CA 02305351 2000-03-31
WO 99/19453 PCTNS98/21420
alkyated/polyhydroxyalkylated quats, alkylated quats,
alkylated/polyhydroxylated
oxypropyl quats, imidazolines, 2-yl-succinates, sulfonated alkyl esters, and
sulfonated fatty
acids; and (c) X is -CH2-; (B) spray drying the slurry to for spray dried
granules; (C)
compacting the spray dried granules in a compactor to form compacted granules;
(D)
grinding the compacted granules to form ground detergent particles; and (E)
coating the
detergent particles with a coating agent, thereby forming the high density
detergent
composition.
Accordingly, it is an object of the present invention to provide a process for
producing a compact granular detergent product having acceptable flow and
particle size
properties (i.e., a more narrow particle size distribution). It is also an
object of the
invention to provide such a process which includes a surfactant which exhibits
improved
cleaning performance over a wide variety of soils and stains. Also, it is an
object of the
invention to provide a process which is more efficient and economical to
facilitate large-
scale production of low dosage or compact detergents. 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 detailed description of the preferred
embodiment
and the appended claims.
BRIEF DESCRIPTION OF T D AWINC'.
FIG. 1 is a flow chart illustrating a preferred process in which the various
steps of
the process are serially positioned in accordance with the invention
The present process is used in the production of a compact granular detergent
composition using starting detergent ingredients including a mid-chain
branched surfactant
by way of a series of processing steps including a spray drying step and
additional "post-
tower" steps. By "post-tower" detergent granules, it is meant those detergent
granules
which have been processed through a conventional spray-drying tower or similar
apparatus.
Reference is now made to Fig. 1 which presents a flow chart illustrating the
process
and various embodiments thereof. In the first step of the process, the
invention entails
continuously mixing into a mixer or crutcher starting detergent ingredients
including a
surfactant paste which includes the mid-chain branched surfactant and a dry
starting
detergent materials, together which form a slurry 10. On a finished detergent
product basis,
the surfactant paste 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 surfactants one of which is the mid-chain branched surfactant
which is
described in detail hereinafter. Preferably, the dry starting detergent
material 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
CA 02305351 2000-03-31
WO 99/19453 PCT/US98/21420
about 10% to about 40%, preferably from about 15% to about 30% and, most
preferably
from about I S% 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 the mixer or crutcher without departing from the scope of the
invention.
The next step of the process involves spray drying 12 the slurry 10 by
inputted or
spraying the slurry into a spray drying tower or equivalent apparatus to form
spray dried
granules 14. The spray dried 14 granules have a density of from about 350 g/1
to about 550
g/1 as they exiting the spray drying step 12. 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.
Thereafter, the spray dried granules 14 are sent to compacting apparatus for
the
compaction step 16 of the process. In this step, the spray dried granules are
compacted to
form compacted granules 18 which have a density of from about 1000 g/1 to
about 1700 g/l.
The compacted granules 18 are sent to grinding apparatus for the grinding step
20 of the
process. Any known conventional compacting and grinding apparatus can be used
herein
In the grinding step 20, ground detergent particles 22 are formed. Optionally,
oversized
ground particles 24, typically having a median particle size greater than
about 1150
microns, can be recycled back to the grinding step 20 for additional grinding
to the desired
particle size.
The next step of the process entails a coating step 26 in which the ground
detergent
particles 22 are coated with a coating agent. The coating agent is preferably
selected from
the group consisting of aluminosilicates, silicates, carbonates and mixtures
thereof. 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. It
is preferable to conduct the coating step in a moderate speed mixer such as 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 50 to
about 100 rpm. The mean residence time in the moderate speed mixer is
preferably from
about 0.1 minutes to about 10 minutes, most preferably the residence time is
about 0.5
minutes to about 6 minutes. The mean residence time can be conveniently and
accurately
measured by dividing the tear weight of the mixer/densifier at steady state by
the
throughput (e.g., kg/hr).
Optionally, a liquid such as a nonionic surfactant can be inputted to the
moderate
speed mixer. The binder is preferably selected from the group consisting of
water, anionic
CA 02305351 2000-03-31
WO 99/19453 PCT/US98/21420
surfactants, nonionic surfactants, polyethylene glycol, polyvinyl pyrrolidone
polyacrylates,
citric acid and mixtures thereof. Other suitable binder materials including
those listed
herein are described in Beerse et al, U.S. Patent No. 5,108,646 (Procter &
Gamble Co.).
The liquid distribution is accomplished by cutters, generally smaller in size
than the
rotating shaft, which preferably operate at about 3600 rpm. Most preferably,
the coating
step 26 occurs in one ore more, preferably four, serially positioned mixers as
described
previously. The resulting high density detergent composition 28 exiting the
coating step 26
has a density of from about 650 g/I to about 950 g/l, more preferably from
about 700 g/I to
about 900 g/1.
Optionally, the last step of the process can be an admixing step 30 in which
admixing adjunct detergent ingredients to the high density detergent
composition 28.
Preferably, the adjunct detergent ingredients are selected from the group
consisting of
enzymes, detergent builders, bleaching agents, bleach activators, dyes, soil
release agents,
and mixtures thereof. By including the aforementioned adjunct ingredients, the
resulting
high density detergent composition 32 is fully formulated and ready for
commercially
marketing.
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 fonmula below illustrates the mid-chain branching range (i.e., where
points of
branching occur), preferred mid-chain branching range, and more preferred mid-
chain
branching range for mono-methyl branched alkyl Ab moieties useful according to
the
present invention.
CH3CH2CH2CH2CH2CH2(CH2)1_~CH2CH2CH2CH2CH2
more preferred ran
g
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.
CA 02305351 2000-03-31
WO 99/19453 PCT/US98/21420
9
CH3CH2CH2CH2CH2CH2(CH2)o-6CH2CH2CH2CH2CH2
more preferred ran
g
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.
The present invention branched surfactant compositions may comprise two or
more
mid-chain branched primary alkyl sulfate surfactants having the formula
R R1 R2
I I I
CH3CH2(CH2}~,~,CH(CH2~CH(CH2}yCH(CH2)ZOS03M
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 C 16 total carbon primary alkyl sulfate surfactant having 13
carbon
atoms in the backbone must have 1, 2, or 3 branching units (i.e., R, R1 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, Rl, and R2 are each independently selected from hydrogen and C1-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 I, at
least R or R1 is not hydrogen.
CA 02305351 2000-03-31
WO 99/19453 PCT/US98/Z1420
Although for the purposes of the present invention surfactant compositions the
above formula does not include molecules wherein the units R, Rl, 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
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
RS
wherein R3, R4, RS and R6 are independently hydrogen, C1-CZZ alkylene, C4-C22
branched alkylene, C 1-C6 alkanol, C 1-C22 alkenylene, C4-C22 branched
alkenylene, and
mixtures thereof. Preferred cations are ammonium (R3, R4, RS and R6 equal
hydrogen),
sodium, potassium, mono-, di-, and trialkanol ammonium, and mixtures thereof.
The
monoalkanol ammonium compounds of the present invention have R3 equal to C 1-
C6
alkanol, R4, RS and R6 equal to hydrogen; dialkanol ammonium compounds of the
present
invention have R3 and R4 equal to Cl-C6 alkanol, RS and R6 equal to hydrogen;
trialkanoi
ammonium compounds of the present invention have R3, R4 and RS equal to C 1-C6
alkanol, R6 equal to hydrogen. Preferred alkanol ammonium salts of the present
invention
are the mono-, di- and tri- quaternary ammonium compounds having the formulas:
H3N+CH2CH20H, H2N+(CH2CH2OH)2, HN+(CH2CH20H)3.
Preferred M is sodium, potassium and the C2 alkanol ammonium salts listed
above; most
preferred is sodium.
CA 02305351 2000-03-31
WO 99/19453 PCT/US98/21420
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 I; and
w + x + y + z is
an integer from 8 to i4.
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(CHZ)yCH(CHz)zOS03M
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 Ci-C3
alkyl; M is a
water soluble cation; x is from 0 to 11; y is from 0 to 11; z is at least 2;
and x + y + z is
from 9 to 13; provided R1 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 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.
More preferably
the mixtures of surfactant comprise at least 20% of a mid chain branched
primary alkyl
sulfate having RI and R2 independently hydrogen, 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 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 (CHZ)dCH (CH2)e CHCHZ 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 I
0;
CA 02305351 2000-03-31
WO 99/19453 PCT/US98/21420
12
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 I 5 and b is an integer from 1 to
14;
when d + a = 8, d is an integer from 2 to ? 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 = 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 I 2 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 I I
CH3CH2(CH2h,,,CH(CHZ~CH(CH2h,CH(CH2)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 C1-C3 alkyl, provided R, RI, 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 CI-C3 alkyl the ratio of surfactants having z equal to i 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 I-C3 alkyl, comprising less than about 20%,
preferably less
than 10%, more preferably less than 5%, 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, S-
methyl
pentadecanol sulfate, 6-methyl pentadecanol sulfate, 7-methyl pentadecanol
sulfate, 8-
methyl pentadecanol sulfate, 9-methyl pentadecanol sulfate, 10-methyl
pentadecanol
CA 02305351 2000-03-31
WO 99/19453 PCT/US98/21420
13
sulfate, 11-methyl pentadecanol sulfate, 12-methyl pentadecanol sulfate, 13-
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-
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-methyipentadecylsulfate having the formula
OS03M
CH3
8-methylpentadecylsulfate having the formula
CH3
OS03M
9-methylpentadecylsulfate having the formula
CA 02305351 2000-03-31
WO 99/19453 PCTNS98/21420
14
OS03M
CH3
10-methylpentadecylsulfate having the formula
CH3
OS03M
wherein M is preferably sodium.
The following branched primary alkyl sulfates comprising 17 carbon atoms and
having two branching units are examples of preferred branched surfactants
according to the
presentinvention:
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
2,8-dimethylpentadecylsulfate having the formula
CH3 CH3
OS03M
2,9-dimethylpentadecylsulfate having the formula
CH3
OS03M
CH3
CA 02305351 2000-03-31
WO 99/19453 PCT/US98/21420
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 polyoxyalkylene surfactants having the
formula
R Rl R2
CH3CH2(CH2h,~,CH(CH2)XCH(CH2h,CH(CH2)z(EO/PO)mOH
The surfactant mixtures of the present invention comprise molecules having a
linear primary polyoxyaikylene 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 C 16 total carbon (in the alkyl chain) primary polyoxyalkylene
surfactant having 1 S 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
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 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 polyoxyalkylenes), it is to be recognized
that the present
invention compositions may still further comprise some amount of linear, non-
branched
CA 02305351 2000-03-31
WO 99/19453 PCT/US98/21420
16
primary polyoxyalkylene. Further, this linear non-branched primary
poiyoxyalkylene
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 poiyoxyalkylene 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 polyoxyalkyiene 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
R1 R2
CH3CH2(CH2)xCH(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 CI-C3
alkyl; x is
from 0 to 11; 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; 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
CA 02305351 2000-03-31
WO 99/19453 PCT/US98/21420
17
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 polyoxyalkylene 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 5 % by weight of one or more mid-chain branched alkyl
polyoxyalkylenes
having the formula:
CH3
CH3 (CHZ)aCH (CH2~CH2 (EO/PO)mOH
(I)
CH3 CH3
CH3 (CHy)dCH (CH2)e CH CHZ (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 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 I to
13;
when a + b = 16, a is an integer from 2 to I 5 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 i 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 1 I 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 1,
preferably
CA 02305351 2000-03-31
WO 99/19453 PCT/US98/21420
18
within the range of from about 3 to about 30, more preferably from about S to
about 20, and
most preferably from about S to about IS.
Further, the present invention surfactant composition may comprise a mixture
of
branched primary alkyl polyoxyalkylenes having the formula
R Rl R2
CH3CH2(CH2)~,CH(CH2}xCH(CH2h,CH(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, R1, and R2 are each independently
selected from
hydrogen and C1-C3 alkyl, provided R, R1, 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
I,
preferably within the range of from about 3 to about 30, more preferably from
about S to
about 20, and most preferably from about S to about 1 S; provided that when R2
is C I-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 SO%, preferably less than about 40%, more
preferably less
than about 2S%, most preferably less than about 20%, of branched primary alkyl
polyoxyalkylene having the above formula wherein z equals 1.
Preferred mono-methyl branched primary alkyl ethoxylates are selected from the
group consisting of 3-methyl pentadecanol ethoxylate, 4-methyl pentadecanol
ethoxylate,
S-methyl pentadecanol ethoxylate, 6-methyl pentadecanol ethoxylate, 7-methyl
pentadecanol ethoxylate, 8-methyl pentadecanol ethoxylate, 9-methyl
pentadecanol
ethoxylate, 10-methyl pentadecanol ethoxylate, 1 I-methyl pentadecanol
ethoxylate, 12-
methyl pentadecanol ethoxylate, 13-methyl pentadecanol ethoxylate, 3-methyl
hexadecanol
ethoxylate, 4-methyl hexadecanol ethoxylate, S-methyl hexadecanol ethoxylate,
6-methyl
hexadecanol ethoxylate, 7-methyl hexadecanol ethoxylate, 8-methyl hexadecanol
ethoxylate, 9-methyl hexadecanol ethoxylate, 10-methyl hexadecanol ethoxylate,
I 1-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
S to about
1S.
CA 02305351 2000-03-31
WO 99/19453 PCT/US9$/21420
19
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
ethoxyiate, 2,10-
methyl tetradecanol ethoxylate, 2,11-methyl tetradecanol ethoxylate, 2,12-
methyl
tetradecanoi ethoxylate, 2,3-methyl pentadecanol ethoxylate, 2,4-methyl
pentadecanol
ethoxylate, 2,5-methyl pentadecanol ethoxylate, 2,6-methyl pentadecanol
ethoxylate, 2,7-
methyl pentadecanoi ethoxylate, 2,8-methyl pentadecanol ethoxylate, 2,9-methyl
pentadecanol ethoxylate, 2,10-methyl pentadecanol ethoxylate, 2,11-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 I5.
(31 Mid-chain Branched Primy Alkyl Alko~ylated Sulfate Surfactants
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 R1 R2
CH3CH2(CH2)~,CH(CH2~CH(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
invention mixtures comprise at least one alkoxyiated 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 C 16 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, RI or R2 is methyl) whereby the total number of carbon atoms
in the
primary alkyl moiety of the molecule is i6.
CA 02305351 2000-03-31
WO 99/19453 PCT/US98121420
R, R1, 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 RZ are not all hydrogen. Further, when
z is 1, 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 aikoxylation 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.
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 1 to about 5. The (EO/PO)m moiety may be either a
distribution
with average degree of alkoxylation (e.g., ethoxylation and/or propoxylation)
CA 02305351 2000-03-31
WO 99/19453 PCT/US98/21420
21
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 formula
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; R 1 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 11; 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 R1
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:
CH3
CH3 (CH2)aCH (CHZ~CH2 (EO/PO)m0 SO3M
(I) -
CH3 CH3
CH3 (CH2)dCH (CH2)e CH CH2 (EO/PO)m0 SO3M
(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 = I 1, a is an integer from 2 to 10 and b is an integer from I to
9;
CA 02305351 2000-03-31
WO 99/19453 PCTNS98/21420
22
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 I
1;
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 I 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 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
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 R1 R2
CH3CH2(CH2)ryCH(CHZ~CH(CH2h,CH(CH2~(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 fonmula is
within the range
of greater than 14.5 to about 17.5; R, RI, and R2 are each independently
selected fram
hydrogen and C1-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; 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 C 1-C3 alkyl the ratio of surfactants having z equal
to 2 or greater
to surfactants having z of 1 is at least about I:I, 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 C 1-C3 alkyl comprising less than about
50%,
CA 02305351 2000-03-31
WO 99/19453 PCT/US98/21420
23
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
tetradecanol
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
ethoxylated sulfate, 2,5-methyl pentadecanol ethoxylated sulfate, 2,6-methyl
pentadecanol
ethoxylated sulfate, 2,7-methyl pentadecanol ethoxylated sulfate, 2,8-methyl
pentadecanol
ethoxylated sulfate, 2,9-methyl pentadecanol ethoxylated sulfate, 2,10-methyl
pentadecanol
ethoxylated sulfate, 2,11-methyl pentadecanol ethoxylated sulfate, 2,12-methyl
pentadecanol ethoxylated sulfate, 2,13-methyl pentadecanol ethoxylated
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, Laughiin et al., issued
December 30,
1975, both of which are incorporated herein by reference. Useful cationic
surfactants also
CA 02305351 2000-03-31
WO 99/19453 PGTNS98/21420
24
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, both of which are
also
incorporated herein by reference.
The following are representative examples of adjunct detergent surfactants
useful
in the present surfactant paste. Water-soluble salts of the higher fatty
acids, i.e., "soaps",
are useful anionic surfactants in the compositions herein. This includes
alkali metal soaps
such as the sodium, potassium, ammonium, and alkylolammonium salts of higher
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 alkylolammonium
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
alkylbenzene
sulfonates in which the average number of carbon atoms in the alkyl group is
from about 11
to 13, abbreviated as C11-13 LAS.
Other anionic surfactants suitable for use herein are the sodium alkyl
glyceryl ether
sulfonates, especially those ethers of higher alcohols derived from tallow and
coconut oil;
sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or
potassium
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 I 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
CA 02305351 2000-03-31
WO 99/19453 PCT/US98/21420
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
CIO-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
CIO-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 C 12-16 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 10-18 alkyl
sulfate and
C 10-18 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.
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 hydroxyalkyl groups
containing
from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one
alkyl moiety
of from about I 0 to 18 carbon atoms and a moiety selected from the group
consisting of
alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.
CA 02305351 2000-03-31
WO 99/19453 PCT/US98/214Z0
26
Preferred nonionic surfactants are of the formula R1(OC2H4)nOH, wherein R1 is
a
C 1 ~ C 16 alkyl group or a Cg C 12 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 polyhydroxy fatty acid
amides.
Examples are N-methyl N-1-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, U.S. Patent No. 2,703,798, the
disclosures of
which are incorporated herein by, reference.
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-
solubilizing
group.
Zwitterionic surfactants include derivatives of aliphatic, quaternary,
ammonium,
phosphonium, and sulfonium compounds in which one of the aliphatic
substituents 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
surfactants useful
herein can be found in U.S. Patent 4,228,044, Cambre, issued October 14, 1980,
incorporated herein by reference.
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 salts described in
U.S. Patent
3,936,537, Baskerville, Jr. et al., issued February 3, 1976, the disclosure of
which is
incorporated herein by reference.
The compositions of the invention can contain all manner of organic, water-
soluble
detergent compounds, inasmuch as the builder material are compatible 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
CA 02305351 2000-03-31
WO 99/19453 PCT/US98/21420
27
ingredient is preferably selected from the group consisting of builders,
enzymes, bleaching
agents, bleach activators, suds suppressors, soil release agents, brighteners,
perfumes,
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,
polycarboxylates,
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 aluminosilicate 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 preferably produced
in
accordance with Corkill et al, U.S. Patent No. 4,605,509 (Procter & Gamble),
the
disclosure of which is incorporated herein by reference.
Preferably, the aluminosilicate ion exchange material is in "sodium" form
since the
potassium and hydrogen forms of the instant aluminosilicate do not 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
aiuminosilicate 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
diameter of the aluminosilicate is from about 0.1 micron to about 10 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 the formula
Naz~(A102)z.(Si02)y]xH20
CA 02305351 2000-03-31
WO 99/19453 PCT/US98/21420
28
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 has
the
formula
Nal2[(A102)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
ZeoIite 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
Krummel et al, U.S. Patent No. 3,985,669, the disclosure of which is
incorporated herein
by reference.
The aluminosilicates used herein are further characterized by their ion
exchange
capacity which is at least about 200 mg equivalent of CaC03 hardness/gram,
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 Cap-'~'/gallon/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
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 including a surfactant paste containing the mid-chain branched
surfactant and
water and the other stream containing starting dry detergent material
containing
aluminosilicate and sodium carbonate are fed to a crutcher for continuous
mixing, thus
forming a slurry. The slurry is fed to a conventional spray drying process in
which the
slurry is passed though a spray drying tower having a counter current stream
of hot air
(200-300°C) resulting in the formation of porous spray dried granules
having a density of
about 250 g/l. The spray dried granules are sent to a compactor (commercially
available
from the Sahut Company) which form compacted granules having a density of
about 1300
g/l. Subsequently and continuously, the compacted granules are sent to a
grinder to form
ground detergent particles having a density of about 700 g/l. The ground
detergent
particles, excluding oversized ground particles which recycled back to the
grinder, are fed
to the first of four serially positioned moderate speed mixers. Each of the
moderate speed
mixers are Lodige KM-600 mixers in which aluminosilicate is added to coat the
ground
CA 02305351 2000-03-31
WO 99/19453 PCT/US98/21420
29
detergent particles resulting in a high density detergent composition having a
density of 800
g/l. Admixed ingredients are added as the high density detergent composition
is passed
through a vertical mixer such as a Fukae mixer. The final composition of the
high density
detergent composition produced by the process is given below:
u~°
Base Granule
016.5 alkyl sulfate (mid-chain 14.1
branched), Na
Aluminosilicate 2,g
Sodium carbonate 16.6
C12-13 linear alkylbenzene sulfonate,4.2
Na
C14-15 alkyl sulfate, Na 9.9
Sodium silicate 12.0
Brightener 491 0.2
Brightener 1 0.1
Copolymer of Malefic and Acrylic 7.0
Acid
Co
tinQ
~ 3.3
C 12-15 alkyl ethoxylate (EO =
7)
Aluminosilicate 6.7
Sodium silicate 0.3
Silica 0.2
Meltose 0.3
Perfume 0.1
Perfume 0.3
Soil Release Polymer 2 0.3
Protease (40mg/g)3 0.2
NOBS 4 3.8
Sodium Perborate 3.5
Polydimethylsiloxane 2.0
Crystalline layered silicate 7.6
Miscellaneous (water, etc.) ]dance
Total 100.0
1 Purchased from Ciba-Geigy
2Made according to U.S. Patent 5,415,807, issued May 16, 1995 to Gosselink et
al
3 Purchased from Genencor
CA 02305351 2000-03-31
WO 99/19453 PCT/US98/21420
4 Nonanoyloxybenzenesulfonate, Na
Having thus described the invention in detail, it will be clear to those
skilled 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.
