Note: Descriptions are shown in the official language in which they were submitted.
CA 02311378 2002-12-13
DETERGENT COMPOSTTION CONTAINING OPTIMALLY SIZED
BLEACH ACTIVATOR PARTICLES
FIELD OF THE INVENTION
The invention relates to a detergent composition containing a peroxygen
bleaching compound and bleach activator particles having a selected particle
size
for improved stability and performance.
BACKGROUND OF THE INVENTION
As is known, surface bleaching of textiles is bleaching wherein the bleaching
mechanism takes place on the textile surface and, thereby, removes stains
and/or
soils. Typical bleaching compositions contain peroxygen bleaches capable of
yielding
hydrogen peroxide in aqueous solutions and bleach activators to enhance bleach
performance. It has long been known that peroxygen bleaches are effective for
stain
and/or soil removal from textiles, but that they are also extremely
temperature
dependent. Such bleaches are essentially only practicable and/or effective in
bleaching solutions, i.e., a bleach and water mixture, wherein the solution
temperature is above about 60°C. At bleach solution temperatures of
about 60°C,
peroxygen bleaches are only partially effective and, therefore, in order to
obtain a
desirable level of bleaching performance extremely high levels of peroxygen
bleach
must be added to the system. This is economically impracticable for largo-
scale
commercialization of modern detergent products. As the bleach solution
temperature
is lowered below 60°C, peroxygen bleaches are rendered ineffective,
regardless of the
level of peroxygen bleach added to the system. The temperature dependence of
peroxygen bleaches is significant because such bleaches are commonly used as a
detergent adjuvant in textile wash processes that utilize an automatic
household
washing machine at wash water temperatures below 60°C. Such wash
temperatures
are utilized because of textile care and energy considerations. As a
consequence of
such a wash process, there has been much industrial research to develop
substances,
generally referred to as bleach activators, that render peroxygen bleaches
effective at
bleach solution temperatures below 60°C.
Numerous substances have been disclosed in the art as effective bleach
activators. For example, bleach activators having the general formula
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2
R-C-L
wherein R is an alkyl goup and L is a leaving goup, have been disclosed in the
art.
Such bleach activators have typically been incorporated into detergent
products as an
admixed ganule, agglomerate or other type of particle. However, one problem
with
such bleach activators is maintaining the stability of the activator prior to
use by the
consumer. The bleach activator granule or agglomerate has a tendency to
degrade
over time which is exacerbated by exposure to environmental effects such as
heat and
humidity. As a consequence of this, the ganule, agglomerate or other
particulate
form of the bleach activator must be relatively large in comparison to the
other
detergent ingedients in a typical granular detergent product. This, in turn,
causes
another problem associated with detergent product segegation in that the
larger
bleach activator particles tend to accumulate at or near the top of the
detergent box
while relatively smaller particle sized detergent ingedients accumulate at or
near the
bottom of the box. Additionally, particle segegation occurs during the
detergent
manufacturing process, leading to increased box to box variability for the
detergent
active ingredients. The net result of such an undesirable product segegation
is
dac~ased performance since the user scoops the product from the top to the
bottom
and each scoop has a disproportionate amount of bleach activator or other
detergent
ingredient, and similarly, the performance of product from different boxes is
affected
by variance in the detergent composition. Thus, it would be desirable to have
a
detergent composition containing a bleach activator which has improved
stability
prior to use, and which does not significantly segregate poor to packaging or
while
stored in the detergent producx box. Additionally, it would be desirable to
have such
a detergent composition which also has acceptable physical properties, for
example,
acceptable Bow properties for bulk handling of the composition as part of
largo-scale
detergent manufacturing.
Yet another problem with the aforementioned bleach activators relates to the
inability to advertise the sanitization effects of the above-mentioned
bleacldbleach
activator systems on fabrics. Currently, most governmem regulation agencies
require
that sanitization add claims for fabric care can only be made if a relatively
high
level of microbes are consistently removed from the laundered fabrics as a
result of
using the bleach-containing detergent product. In the past, however, the
relatively
large granule, agglomd ate or other particle form of the bleach activator has
inhibited
tech sanitization advertising claims in that the product segregation effects
of such
larger particles prevented the consistent removal of high levels of microbes
from the
laundered fabrics. The bleaclJbleach activator delivery during the laundering
process
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3
varied too widely to satisfy most govennmental agency requirements for
sanitization
advertising claims. It would therefore be desirable to have a bleach-
containing
composition detergent which can be used to sanitize fabrics.
Accordingly, there remains a need in the art to have detergent composition
containing a bleach activator which has improved stability prior to use. Also,
there is
a need in the art for a detergent composition containing a bleach activator
which does
not significantly segregate while stored in the detergent product box and has
acceptable physics! properties. Yet another need in the art remains for such a
detergent composition which has a more consistent bleachlbleach activator
delivery.
BACKGRO~ ART
The following references relate to detergent compositions comaining bleach
activators and/or antimicrobials: U.S. Patent 4,412,934 to Chung et al
(Procter &
Gamble); U.S. Patent 5,021,182 to Jentsch (Roman A. Epp); U.S. Patent
5,489,434
to Oaken et al (Ecolab) and U.S. Patent 4,422,950 to Kemper et al (Lever
Brothers
Company).
SII~.(ARY nF THE INVENTION
The invention provides a detergent composition containing a peroxygen
bleaching compound a~ a bleach activator in the form of particles, preferably
in the
form of substeulbaliy cylindrically shaped exaudates, having a selected
relatively
small particle size. The smaller sized bleach activator particles unexpectedly
remain
stable over extended storage periods and reduce product segrega'on in the
detergent
box in which they are co»tainod as they more closely mirror the particle size
of other
conventional detergent ingnoaients. Additionally, the bleach activator
particles have
acceptable flow properties and allow the detergent composition to deliver
sanitization
effects to the launder ed fabrics more consistently.
As used herein, the tam "particles" refer to agglomerates, flakes, extrudates,
or other shaped particles. The phrase "cylindrically shaped extrudates" means
an
extruded particle having a stuface shape ~ by a straight line moving parallel
to a faced straight line and intaaecxing a fixed planar dosed cxuve. An
"effective
amount" of a d~ergent composition containing a bleach activator is any amount
capable of measurably improving both soil removal from and sanitization of the
fabric
when it is washed by the consumer. In general, this amount may vary quite
widely.
As used herein, the terms "disinfecting", "disinfection", "antibacterial",
"germ kill",
and "sanitization" are intended to mean killing microbes commonly found in and
on
fabrics requiring laundering. Fxampies of various microbes include germs,
bacteria,
viruses, parasites, and fungi/spores. As used ha~ein, "free water" level means
the
level on a pa centage by weight basis of water in the detergent composition
which is
CA 02311378 2002-12-13
4
not bound up or in another detergent ingredient such as zeolite; it is the
water level in
excess of any water entrained in, adsorbed in, or otherwise bound up in other
detergent
ingredients.
In accordance with one aspect of the invention, a bleach-containing detergent
composition is provided. The detergent composition comprises: (a) a
particulate
peroxygen bleaching compound capable of yielding hydrogen peroxide in an
aqueous
solution; (b) a bleach activator which is nonanoyloxybenzene sulfonate,
wherein the molar
ratio of hydrogen peroxide yielded by (a) to bleach activator (b) is greater
than 1.0, and
said bleach activator is in the form of substantially cylindrically-shaped
extrudate having a
mean extrudate length of from 500 microns to 3500 microns and a mean extrudate
diameter of from 450 microns to 850 microns, said extrudate containing less
than 3% free
moisture, and wherein the particle size of said peroxygen belaching compound
closely
mirrors that of said bleach activator.
In accordance with another aspect of the invention, a method of using the
detergent
composition to sanitize fabrics is provided. The method comprises the step of
contacting
said fabrics with an effective amount of a detergent composition as described
herein in an
aqueous solution to sanitize the fabrics. All percentages and ratios used
herein are
expressed as percentages by weight (anhydrous basis) unless otherwise
indicated.
Accordingly, it is an object of the invention to provide a detergent
composition
containing bleach activator particles which have good stability prior to use
and acceptable
physical properties. It is also an object of the invention to provide a
detergent composition
containing a bleach activator which does not significantly segregate while
stored in the
detergent product box. Another object of the invention is to provide such a
detergent
product which can be used to sanitize fabrics. 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.
DETAILED DESCR1PT10N OF THE PREFERRED EMBODIMENT
The detergent composition of the invention essentially comprises two
components, namely, a peroxygen bleaching compound and a bleach activator in
the form
of particles having a specified mean particle diameter. In a preferred mode,
the particles
are in substantially cylindrically-shape extrudate form. Preferably, the
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peroxygen bleaching compound is capable of yielding hydrogen peroxide in an
aqu~us solution. The detergent composition of the invention is unexpectedly
stable
with respect to the bleach activator in terms of maintaining or not degrading
over
extended storage periods prior to use. Preferably, one or more binder
materials are
included in the bleach activator particles or extrudates including, but not
limited to,
palmitic acid, a detersive surfactant, polyethylene glycol and other fatty
acids and
poiyacrylates.
While not intending to be bound by theory, it is believed that by selecting a
particle size as described herein, the binder materials in the specific
particles or
extrudates gravitate or migrate toward the surface of the individual
particles, thereby
inhibiting excessive exposure of the bleach activator to envrrotunental
conditions such
as heat and moisture prior to use. As a consequence, the bleach activator
particles
including those that are substantially cylindrically-shaped exttudates do not
degrade
and remain stable, while also beating a particle size closely mirroring the
size of the
other detergent ingredients in the detergent composition. As mentioned, the
added
unanimity of particle size rends the detergent composition less susceptible to
product segregation in the detergent box prior to use. As is known, product
segegation oaxns during handling, transporting, and storing the detergent
composition prior to use; the vibrating, shaking and otherwise movement of the
detergent product box causes the composition to segregate by particle size.
The
detergent composition of the present invention reduces this problem via a
selected
choice of particle size and shape.
In that regard, the mean particle diameta~ of the particles are from about 200
microns to about 2000 microns, more preferably from about 300 microns to about
I000 micxons, and most preferably from about 350 microns to about 750 microns.
More preferably, she particles are substantially cylindrically-shaped
exttudates having
a mean exttudate length of from about 500 micxons to about 3500 microns, snore
preferably from about 700 microns to about 3000 microns, and most preferably
from
about 900 microns to about 2500 microns. Preferably, the mean extcudate
diameter
is from about 450 microns to about 850 rnicxons, more preferably from about
500
microns to about 800 microns, and most preferably from about 550 microns to
about
750 microns. The mean particle and extrudate diameters can be min a variety
of ways, one of which is to measure a representative sample of the extrudates
using a
microscope and dexamining the mean via calculation. The mean diameter can be
determined similarly or via extrapolation from the extrusion die hole
diameter.
To yield acceptable flow properties for bulk handling of the particles, a
finely
divided inorganic powder may be added as a flow aid to the surface of the
particles.
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6
This flow aid includes, but is not limited to, finely divided
aluminositicates, silicas,
crystalline layered silicates, MAP zeolites, citrates, amorphous silicates,
sodium
carbonate, and mixtures thereof. It is preferable for the level of the flow
aid to be
from about 0.1% to about 10'/0, more preferably from about 1% to about 7%, and
most preferably from about 1.5% to about 5% by weight of the detergent
composition. The most preferable flow aid is aluminosilicate.
The peroxygen bleaching compound is preferably selected from the group
consisting of sodium perborate monohydrate, sodium perborate tetrahydrate,
sodium
carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea
peroxyhydrate,
sodium peroxide and mixtures thereof. It is preferable for the detergent
composition
of the invention to contain less than about 3%, more preferably less than
about 2.5%,
and most preferably less than about 2% by weight of free water. While not
wishing
to be bound by theory, it is believed that by maintaining this relatively low
level of
free water in the composition, the propensity of the bleach activator to
degrade via
hydrolysis prior to use is lowered. Thus, the stability of the bleach
activator is
enhanced and prolonged even further as a re~lt of a selected free water level
as set
forth herein.
The selected relatively smaller particle size the bleach activator particles,
especially the cylindrically-shaped extrudates, result in a more consistent
delivery of
activator to the aqueous laundering solution. Stated differa~tly, the
variation around
the target level of bleach activator to be delivered to the wash solution is
unexpectedly reduced as result of using the aforeme~ioned substantially
cylindrically-shapod extrudatee;. Fortuitously, this allows the detergent
composition
to deliver the bleach activator at a more consistent level to achieve
sanitization effects
on the lauadexed fabrics. Moat governmental agencies require very fittle
variation
amend bleach activator or other sanitiang agent target levels in order for
sanitization
advertising claims to be legally made to the public. Thus, the invention also
provides
a suitable and convenient nartlwd of sanitizing fabrics which may be suitable
for
public advertising. Preferably, the number of microbes present on said fabrics
is
reduced by at least about 50%, more preferably reduced by at least about 90%,
and
most preferably reduced by at least about 99.9%. This sanitizing method is
interchangeably used with disirifeaing, antibacterial, germ killing, odor-
causing germ
killing methods in accordance with the invention.
Additionally, the speaflc bleach activator and peroxygen bleaching
composition in the detergent composition are preferably present at specific
molar
ratios of hydrogen peroxide to bleach activator. Such compositions provide
extremely effective and efficient surface bleaching of textiles which thereby
remove
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7
stains andlor soils from the textiles. Such compositions are particularly
effective at
removing dingy soils from textiles. Dingy soils are soils that build up on
textiles after
numerous cycles of usage and washing and, thus, result in a white textile
having a
gray tint. These soils tend to be a blend of particulate and greasy materials.
The
removal of this type of soil is sometimes referred to as "dingy fabric clean
up". The
bleach-containing detergent compositions of this invention provide such
bleaching
over a wide range of bleach solution temperatures. Such bleachung is obtained
in
bleach solutions wherein the solution temperature is at least about
5°C. Without the
bleach activator, such peroxygen bleaches would be ineffective andlor
impracticable
at temperatures below about 60°C.
Much lower levels of the bleach activators within the invention are required,
on a molar basis, to achieve the same level of surface bleaching performance
that is
obtained with similar bleach activators containing only from about 2 to about
5
carbon atoms in the longest linear alkyl chain extending from and including
the
carbomrl carbon. Without being bound by theory, it is believed that such
efficiency is
achieved because the bleach activators within the invention exhibit s<uface
activity.
This can be explained as follows. The bleaching mechanism generally, and the
surface bleaching mechanism in particular, are not completely understood.
However,
it is generally believed that the bleach activator undergoes nucleophilic
attack by a
perhydroxide anion, which is ga~erated from the hydrogen peroxide evolved by
the
peroxygen bleach, to form a percarboxylic acid. This reaction is commonly
referred
to as perhydrolysis. The percarboxylic acid then forms a reactive dimer with
its anion
which, in turn, evohres a singlet oxygen which is believed to be the active
bleaching
component. It is theorized that the singlet oxygen must be evolved at or near
the
textile surface in order to provide surface bleaching. Otherwise, the singlet
oxyg~
will provide bleaching, but not at the textile surface. Such bleaching is
known as
solution bleaching, i.e., the bleaching of soils in the bleach solution.
To ensure that the singlet oxygen is more effiaently evolved at the textile
surface, it is essential that the longest linear alkyl chain extending from
and including
the carbonyl carbon of the percarboxylic acid have from about 6 to about 12
carbon
atoms. Such percarboxylic acids are surface active and, therefore, term to be
concernrated at the textile surface. Percarboxylic acids containing fewer
carbon
atoms in such alkyl chain have similar redox potentials, but do not have the
ability to
concentrate at the textile surface. Therefore, the bleach activators within
the
inve~ion are extremely effcient because much lower levels, on a molar basis,
of such
bleach activators are required to get the same level of surface bleaching
performance
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as with similar bleach activators containing fewer carbon atoms in such an
alkyl
chain, which are not within the invention.
Optimum surface bleaching performance is obtained with bleaching solutions
wherein the pH of such solution is between about 8.5 and 10.5 and preferably
between 9 and 10. It is preferred that such pH be geater than 9 not only to
optimize
surface bleaching performance, but also to prevent the bleaching solution from
having
an undesirable odor. It has been observed that once the pH of the bleaching
solution
drops below 9, the bleaching solution has an undesirable odor. Such pH can be
obtained with substances commonly iuwwn as buffering agents, which are
optional
components of the bleaching compositions herein.
In a highly preferred embodiment of the invention, the substantially
cylindrically shaped extrudate comprises, by weight of the extnrdate, from
about
60% to about 95% of a bleach activator, from about 0.1% to about 10% of
palmitic
acid, from about 0.1% to about 10'/0 of a detersive surfactant, from about
0.1% to
about 10% of polyethylene glycol, and from about 0.1% to about 10% of fatty
acid.
The bleach activator for the bleaching systems useful herein preferably has
the following shucdwe:
O
R~-L
wherein R is an alkyl group containing from about 5 to about 18 carbon atoms
wherein the longest linear alkyl chain extending from and including the
carbomrl
carbon contains from about 6 to about 12 carbon atoms and L is a leaving
group,
the conjugate acid of which has a pKo in the range of from about 4 to about
13,
preferably from about 6 to about 1 I, most preferably from about 8 to about
11.
L can be esse~iaily any suitable leaving group. A leaving group is any goup
that is displaced from the bleach for as a consequence of the nucioophilic
attack on the bleach activator by the pefiydroxide anion. This, the
perhydrolysis
r~cxion, ruts in the formation of the p~rboxylic acid. Gaierally, for a group
to be a suitable leaving group it must exert an electron attracting effect.
This
facilitates the nucleophilic attach by the perhydroxide anion.
The L goup must be sufficiently reactive for the reaction to occur within the
optinwm time frame (e.g., a wash cycle). However, if L is too reactive, this
activator will be diflxcuh to stabilize. These characteristics are generally
paralleled
by the pKa of the conjugate acid of the leaving group, although exceptions to
this
com~ion are known.
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Preferred bleach activators are those of the general formula:
RS O RS O
R1-N ~-RZ-C-L or Rl ~-N-R2-C-L
wherein Rl is an alkyl group containing from about 6 to about 12 carbon atoms,
R2 is an alkylene containing from 1 to about b carbon atoms, RS is H or
allcyl, aryl,
or alkaryl containing from about 1 to about 10 carbon atoms, and L is selected
from the group consisting of
R3Y R3
-O -O
O
-N-C-R6-N~~ N
R3 U
I
Y
-N-C-CH
R3 Y
Y P
R3
-Nw ~NR4 -O-CH~-CH~CH2
R3
-O-CH ~ H~HZ -O-C=cHR4 and
> >
O Y
-N-If -CH.--R4
R3
vvhd~in R6 is an alkylene, arylene, or alkarylene group containing from about
1 to
about 14 carbon atoms, R3 is an alkyl chain containing from about 1 to about 8
carbon atoms, R4 is H or R3, and Y is H or a solubilizing group. Y is
preferably
selected from the group consisting of -S03M", -COOM'~, -CO~i, -COZM", -SO,~
CA 02311378 2002-12-13
1U
M+, (-N+R'3)X' and Ot-N(R'3), wherein R' is an alkyl chain containing from
about
I to about 4 carbon atoms, M is a ration which provides solubility to the
bleach
activator and X is an anion which provides solubility to the bleach activator.
Preferably, M is an alkali metal, ammonium or substituted ammonium ration,
with
sodium and potassium being most preferred, and X is an anion selected from the
goup consisting of halide, hydroxide, methylsulfate and acetate anions. More
preferably, Y is -S03-M', -C02H and -COOM'. It should be noted that bleach
activators with a leaving group that does not contain a solubilizing goup
should be
well dispersed in the bleach solution in order to assist in their dissolution.
Preferred
is:
R3Y
-O
wherein R3 is as defined above and Y is -S03M' or -COOZvi' wherein M is as
defined above.
Especially preferred bleach activators are those wherein Rl is a linear alkyl
chain containing from about 6 to about 12 carbon atoms, R2 is a linear
alkylene
chain containing from about 2 to about 6 carbon atoms, RS is H, and L is
selected
from the goup consisting of
Y R3
-O ~ -p
and
R3Y
-O
wherein R3 is as defined above, Y is -S03M' or -COOM' and M is as defined
above.
A preferred bleach activator is:
O
I)
C~
O ~CI -R,
'N
wherein R1 is H, alkyl, aryl or alkaryl. This is described in U.S. Patent
4,966,723,
Hodge et al.
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11
Preferred bleach activators are:
O O
Rl II _L or R2 ~-O I I-L
0 0
wherein Rl is H or an alkyl group containing from about 1 to about 6 carbon
atoms
and R2 is an alkyl goup containing from about 1 to about 6 carbon atoms and L
is
as defined above.
Preferred bleach activators are also those of the above general formula
wherein L is as defined in the general formula, and Rl is H or an alkyl group
containing from about 1 to about 4 carbon atoms. Even more prefernod are
bleach
activators of the above general formula wherein L is as defined in the genera!
formula and Rl is a H.
More preferred bleach activators are those of the above general formula
wherein R is a linear alkyl chain containing from about 5 to about 9 and
preferably
from about 6 to about 8 carbon atoms and L is selected from the group
consisting
of
R2Y
_N~_~ ~ -
I »'' U
R2
I
Y Y
R2
-O -O
Y ,
R2 R2
-O--CH~--CH--EH2, -O~~CHR3,
_"~~,
wherein R, R2, R3 and Y are as definod above.
Particularly prefer ed bleach activators are those of the above general
formula wherein R is an alkyl group containing from about 5 to about 12 carbon
atoms wherein the longest linear portion of the alkyl chain extending from and
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12
including the carbonyl carbon is from about 6 to about 12 carbon atoms, and L
is
selected from the goup consisting of
Y R2
-O ~ -O Y and
R2Y
-O
herein R2 is an alkyl chain containing from about 1 to about 8 carbon atoms,
and Y
is -S03M' or -COO~t' wherein M is an alkali metal, ammonium or substituted
ammonium canon.
Especially preferred bleach activators are those of the above general formula
wherein R is a linear alkyl chain containing from about 5 to about 9 and
preferably
from about 6 to about 8 carbon atoms and L is selected from the group
consisting
of
R2
-O Y -O Y and
> >
'O a RAY
wherein RZ is as defined above and Y is -SOalVt", -COO'M~, or -COzH, wherein M
is as defined above.
The most prefarod bleach activators have the formula:
O
R-C- O SO~~''
whd~ein R is a linear alkyl chain containing from about 5 to about 9 and
preferably
from about 6 to about 8 carbon atoms and M is sodium or potassium. Preferably,
the bleach activator herein is sodium nonanoyloxybenzenesulfonate (NOBS),
sodium benzoyloxybenzenesulfonate (BOBS), sodium iauroyloxybenzene sulfonate
(LOBS) or pare-decanoyloxybenzoic acid (DOBA).
Further particularly preferred for use in the present invention bleaching
compositions are the following bleach activators which are particularly safe
for use
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13
with machines having natural rubber parts. This is believed to be the result
of not
producing oily diacylperoxide (DAP) species by the perhydrolysis reaction of
these
amido acid-derived bleach activators, but rather foaming insoluble crystalline
solid
DAP's. These solids are believed to not form a coating film and thus natural
rubber
parts are not exposed to DAP's for extended periods of time. These preferred
bleach activators are members selected from the group consisting of
a) a bleach activator of the general formula:
O O ~ O
R'~-C-N-R2-C-L, R'~-N-C-RZ-C-L
R5 R5
or mixtures thereof; wherein R1 is an alkyl, aryl, or alkaryl group
containing from about 1 to about I4 carbon atoms, R2 is an alkylene,
arylene or alkarylene group containing from about I to about 14
carbon atoms, RS is H or an alkyl, aryl, or alkaryl group containing
from about 1 to about 10 carbon atoms, and L is a leaving group;
b) benzoxazin-type bleach activators of the general formula:
6C--R~
wherein Rl is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3,
R4, and RS may be the same or different subsdtue~ts selected from H,
COOR6 (wharein R6 is H or an alkyl group) and carbonyl functions;
c) N-acyl caprolactam bleach activators of the formula:
0
O ~-CH2-CH ;
Rg-C-N~C~~~~CH2
wherein R6 is H or an alkyl, aryl, alkoxyaryl or alkaryi group
containing from 1 to 12 carbons; and
d) mixtures of a), b) and c).
Preferred bleach activators of type a) are those wherein RI is an alkyl group
containing from about 6 to about 12 carbon atoms, R2 contains from about 1 to
about 8 carbon atoms, and RS is H or methyl. Particularly preferred bleach
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14
activators are those of the above general formulas wherein R1 is an alkyl goup
containing from about 7 to about 10 carbon atoms and R2 contains from about 4
to
about 5 carbon atoms.
Preferred bleach activators of type b) are those wherein R2, R3, R4, and RS
are H and Rl is a phenyl goup.
The preferred aryl moieties of said N-acyl caprolactam bleach activators of
type c) have the formula R6-CO' wherein R6 is H or an alkyl, aryl, alkoxyaryl,
or
alkaryl goup containing from 1 to 12 carbons, preferably from 6 to 12 carbon
atoms. In highly preferr~ embodiments, R6 is a member selected from the goup
consisting of phenyl, heptyl, octyl, nonyl, 2,4,4-trimethylpentyl, decenyl and
mixtures thereof.
Amide Derived,Bleach Actiyators - The bleach activators oftype a) employed in
the present invention are amide substituted compounds of the general formulas:
R'E-C-N-R2-C-L, R'~--N~-R2 ~-L
IR'~ Rs
or mixtures thereof wherein R1, R2 and R$ are as defined above and L can be
essentially any suitable leaving group. Preferred bleach activators are those
of the
above general formula wheran Rl, R2 and RS are as defined for the peroxyacid
and L is selected from the group consisting of
Y R3 RaY
Y , and
O O
-N-C-R' -N N -N~-CH-R4 ,
R3 ~ ~ , ~a Y
I
Y
R3 Y
I I
-O-CHI-CI-~CHZ -O-CI~C-CH=CH2
_p~_.R~
CA 02311378 2000-OS-23
WO 99127061 PCT/US98119999
IS
3
R ~ Y
-O-C=C HR4 , and -N-~-C H-R4
R3 O
and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl goup containing
from
about I to about 14 carbon atoms, R3 is an alkyl chain containing from 1 to
about
8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing goup.
The preferred solubilizing goups are -SO -M+, -CO -M+, -SO -M+,
-N+(R3)4X- and O<--N(R3)3 and most preferab y -S03-M~ and -C02~1VI+
wherein R3 is an alkyl chain containing from about 1 to about 4 carbon atoms,
M is
a ration which provides solubility to the bleach activator and X is an anion
which
provides solubility to the bleach activator. Preferably, M is an alkali metal,
ammonium or substituted ammonium canon, with sodium and potassium being
most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.
It
should be noted that bleach activators with a leaving group that does not
contain a
solubilizing goups should be well dispersed in the bleaching solution in order
to
assist in their dissolution.
Preferred bleach activators are those of the above general formula wherein L
is selected from the goup consisting of
R3
-O Y -O ~ Y -O R3Y
' , and
wherein R3 is as defined above and Y is -S03'~VI+, -C02-lvi+, or -COI, wherein
M is as defined above.
Another important class of bleach activators, including those of type b) and
type c), Provide organic pera~ds as described herein by ring-opening as a
consoquence of the nucdeophilic attack on the carbonyl carbon of the cyclic
ring by
the perhydroxide anion. For instance, this ring-opening reaction in type c)
activators irrvolves attack at the caprolactam ring carbonyl by hydrogen
peroxide or
its anion. Since attack of an aryl caprolactam by hydrogen peroxide or its
anion
occurs preferably at the exocyciic carbonyl, obtaining a significant fraction
of ring-
opening may require a catalyst. Another example of ring-opening bleach
activators
can be found in type b) activators, such as those disclosed in U.S. Patent
4,966,723, Hodge et al, issued Oct. 30, 1990.
Benzoxazin-t<me Bleach Activators - Such activator compounds disclosed by
Hodge include the activators of the benzoxazin-type, having the formula:
CA 02311378 2000-OS-23
WO 99/27061 PCTIUS98/19999
16
O
~,C-R~
'N
including the substituted benzoxazins of the type
R2
C~
,Q
R4 N
wherein R1 is H, alkyl, alkaryl, aryl, arylallcyl, and wherein R2, R3, R4, and
RS
may be the same or differed substituents selectcd from H, halogen, alkyl,
alkenyl,
aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR6 (whercin R6 is H or an
alkyl
group) and carbonyl functions.
A preferred activator of the benzoxazin-type is:
o~.,~-~o
When the activators are used, optimum surface bleaching performance is
obtained with washing solutions whcrein the pH of such solution is betwetn
about
8.5 and 10.5 and preferably betwecn 9.5 and 10.5 in order to facilitate the
perhydrolysis reaction. Such pH can be obtainod with substances commonly
known as buffering agents, which are optional components of the bleaching
systans herein.
]~T-Acvl r~ylBleach Activators - The N-acyl caprolactam bleach activators
of type c) employed in the presait invention have the formula:
O
O ~-CHZ--Chi \
Rs-C-~CH2-CH2~CH2
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl goup containing from
1 to
12 carbons. Caprolactam activators wherein the R6 moiety contains at least
about
b, preferably from 6 to about 12, carbon atoms provide hydrophobic bleaching
which affords nucleophilic and body soil clean-up, as noted above. Caprolactam
*rB
CA 02311378 2000-OS-23
WO 99127061 PCT/US98/19999
17
activators wherein R6 comprises from 1 to about 6 carbon atoms provide
hydrophilic bleaching species which are particularly efficient for bleaching
beverage
stains. Mixtures of hydrophobic and hydrophilic caprolactams, typically at
weight
ratios of 1:5 to 5:1, preferably 1:1, can be used herein for mixed stain
removal
benefits.
ITlghly preferred N-aryl caprolactams are selected from the group consisting
of benzoyl caprolactam, octanoyl caprolactam, nonanoyl caprolactam, 3,5,5-
trimethylhexanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam,
and mixtures thereof. Methods for making N-aryl caprolactams are well known in
the art.
Contrary to the teachings of U.S. Pat. 4,545,784, the bleach activator is
preferably not absorbed onto the peroxygen bleaching compound. To do so in the
presence of other organic detersive ingredients could cause safety problems.
The bleach activators of type a), b) or c) will comprise at least about 0.1%,
preferably from about 0.1 % to about 50~/0, more preferably from about 1 % to
about 30%, most preferably from about 3% to about 25%, by weight of bleaching
system or detergent composition.
The preferred amido-derived and caprolactam bleach activators herein can
also be used in combination with rubber-safe, enzyme-safer hydrophilic
activators
tech as TAED, typically at weight ratios of amido-derived or caprolactam
activators:TAED in the range of 1:5 to 5:1, preferably about 1:1.
The Peroxv~;en Bleaching Com~und
The peroxygen bleaching systems useful heran are those capable of yielding
hydrogen peroxide in an aqueous liquor. These compounds are well lrnown in the
art and include hydrogen peroxide and the alkali metal peroxides, organic
peroxide
bleaching compounds such as urea peroxide, and inorganic persalt bleaching
compounds, such as the alkali metal perborates, percarbonates, perphosphates,
and
the like. ll~~xtures of two or more such bleaching compounds can also be used,
if
desir ad.
Preferred pexoxygen bleaching compounds include sodium perborate,
commercially available in the form of mono-, tri-, and tetra hydrate, sodium
pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium percarbonate, and
sodium peroxide. Particularly preferred are sodium perborate tetrahydrate,
sodium
perborate monohydrate and sodium pacarbonate. Percarbonate is especially
preferred because it is very stable during storage and yet still dissolves
very quickly
in the bleaching liquor. It is believed that such rapid dissolution results in
the
CA 02311378 2000-OS-23
WO 99127061 PCT/US98/19999
18
formation of higher levels of percarboxylic acid and, thus, enhanced surface
bleaching performance.
I-bghly preferred percarbonate can be in uncoated or coated form. The
average particle size of uncoated percarbonate ranges from about 400 to about
1200 microns, most preferably from about 400 to about 600 microns. If coated
percarbonate is used, the preferred coating materials include mixtures of
carbonate
and sulphate, silicate, borosilicate, or fatty carboxylic acids.
The peroxygen bleaching compound will comprise at least about 0.1%,
preferably from about 1% to about 75%, more preferably from about 3% to about
40'/0, most preferably from about 3% to about 25%, by weight of bleaching
system
or detergent composition. The weight ratio of bleach activator to peroxygen
bleaching compound in the bleaching system typically ranges from about 2:1 to
1:5.
Preferred ratios range from about 1:1 to about 1:3. The molar ratio of
hydrogen
peroxide yielded by the peroxygen bleaching compound to the bleach activator
is
greater than about 1.0, more preferably greater than about 1.5, and most
preferably
from about Z.0 to about 10. Preferably, the bleaching compositions herein
comprise from about 0.5 to about 20, most preferably from about 1 to about 10,
wt.% of the peroxygen bleaching compound.
The bleach activatorlbleachirig compound systems herein are useful per se as
blue. However, such bleaching systems are espeaaily useful in compositions
which can comprise various detersive adjuncts such as surfactants, builders
and the
like.
Preferably, adjunct detergent ingrodients sdec~ed from the group c~nsistirtg
of ~ soil rdeaae agents, dispes~ng agems, optical brightalers, ands
suppressors, fabric softeners, enzyme ~abiliz~s, perfumes, dyes, fillers, dye
inln'bitors and mixtures thereof are included in the composition of the
invention. The
following are representative acamplaa of the d~ga~t surl~~ants useful in the
pr~a~rt detergent composition. 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
aikylolammonium
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
sapon>Scation of fats and oils or by the neutralization of Eros fatty acids.
Particularly
useful are the sodium and potassium salts of the mixtures of fatty acids
derived from
cocomm~t oil and tallow, i.e., sodium or potassium tallow and coconut soap.
CA 02311378 2000-OS-23
WO 99/27061 PCTNS98/19999
19
Additional anionic surfactants which suitable for use herein include the water-
soluble salts, preferably the alkali metal, ammonium and allcylolammonium
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 giycerides 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 alkylbanzene sulfonates in which the average number
of
carbon atoms in the alkyl group is from about 11 to 13, abbreviated as 011-13
L~
anionic its suitable for use herein are the sodium alkyl glyceryl
ether sulfonates, G~poaauy those ethers of higher alcohols derived from tallow
and
coconut oil; sodium coconut oil fatty sect monoglycaide sulfonates and
sulfates;
sodium or potassium of ethylene oxide per molecule and wha~ein the atlryt
groups
contain from about 8 to about 12 carbon atoms; and sodium or potassium salts
of
alkyl ethylene oxide ether containing about 1 to about 10 u~ts of ethylene
oxide per molecule and wheran the alkyl group contains from about 10 to about
20
carbon atoms.
In addition, suitable anionic surfruxants 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-acyloxya>fau~e-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 containing from about 10 to 20 carbon atoms in
the alkyl group and from about I to 30 moles of ethyl~e oxide; water-soluble
salts
of olefin and paraffin a~lfonates containing from about 12 to 20 carbon atoms;
and
beta alkyloxy alkane suifonatea 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 a~sential aniorbe surfactants for the detergent composition are
010-18 ~~ ~e neonate and 010.18 alkyl sulfate. If desired, low
moisture (less than about 25% water) alkyl sulfate paste can be the sole
ingredient in
the surfa~ant paste. Most preferred arc 010-18 ~~'l sulfates, linear or
branched,
and any of prur>aiy, secondary or tertiary. A preferred embodiment of the
present
ion is wherein the surfactant paste comprises from about 20~/o to about 40'/0
of
CA 02311378 2002-12-13
20
a mixture of sodium C10-13 linear alkylbenzene sulfonate and sodium C12-16 ~'1
sulfate in a weight ratio of about 2:1 to 1:2.
Water-soluble nonionic surfactants are also useful in the instant invention.
Such nonionic materials include compounds produced by the condensation of
alkylene oxide goups (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 goup
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 goup 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 10 to 18 carbon atoms and
a
moiety selected from the goup consisting of alkyl and hydroxyalkyl moieties of
from
about 1 to 3 carbon atoms.
Preferred nonionic surfactants are of the fonmula Rl(OC2H4)nOH, wherein Rl
is a C 10-C 16 alkyl goup or a C8-C 12 alkyl phenyl goup, and n is from 3 to
aboitt 80.
Particularly preferred are condensation products of C 12-C 15 alcohols wtth
from about 5
to about 20 moles of ethylene oxide per mole of alcohol, e.g., C 12-C 13
~c°h°l
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-1-
deoxygluatyl
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 .
CA 02311378 2002-12-13
21
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 I8 carbon atoms and at least one aliphatic substituent contains an
anionic
water-solubilizing goup.
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 goups in the ration 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.
Cationic surfactants are often used in detergent compositions to provide
fabric softening and/or antistatic benefits. Antistatic agentswhich 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 .
In addition to a detersive surfactant, at least one suitable adjunct detergent
ingedient such as a builder is preferably included in the detergent
composition. For
example, the builder can be selected from the goup consisting of
aluminosilicates,
crystalline layered silicates, MAP zeolites, citrates, amorphous silicates, .
polycarboxylates, sodium carbonates and mixtures thereof. 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 firnction 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.
CA 02311378 2002-12-13
22
4,605,509 (Procter & Gamble),
Preferably, the aluminosilicate ion exchange material is in "sodium" form
since the potassium and hydrogen forms of the instant aluminosiGcate 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 aluminosilicate 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 I microns to about 8 microns.
Preferably, the aluminosilicate ion exchange material has the formula
Nazl(AJ02)z.(SiO~,JxH20
wherein z and y are integers of at least 6, the molar ratio of z to y is from
about 1 to
about 5 and x is from about 10 to about 264. More preferably, the
aluminosdicate
has the formula
Na 12[(AIO~ 12~(Si~ 12J~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, ZeoGte 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 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
Ca'i";'/gallon/minuteJ-
gram/gaUon, and more preferably in a range from about 2 grains
Ca'f'+/gallon/nunute!-gam/gallon to about 6 gains Ca~"'~/gallon/minuteJ-
gam/gallon
CA 02311378 2002-12-13
23
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.
Exam len s I-IV
TM
The following ingredients are added to a Littleford FM batch mixer: 83% of
sodium nonanoyloxybenzene sulfonate ("HOBS"); 6% of palmitic acid, 3% of
sodium
linear alkylbenzene sulfonate surfactant; 6% of polyethylene glycol (MW =
4000);
and 2% of Cg fatty acid. The mixture is blended and fed to a lab extruder
(Fuji
TM
Paudel Co. Ltd., Dome Granulator, DG-LI) and extruded through dies having
diameters of 350 microns, 500 microns, 700 microns and 890 microns,
respectively.
Each of the four di8'erent diameter substantially cylindrically-shaped
extrudates are
sized to a mean length of 2000 microns and blended into a bleach-containing
detergent composition having the following formula:
Component ~, ~,I ~ ~V
C12-16 ~~' Kyle I I.0 1 I.0 1 I.0 11.0
sulfonate
C 14-15 ~Yl sulfateJC 1,~ I 5 10.4 10.4 10.4 10.4
atlcyl ethoxy sulfate
Neodo123-6.51 2.2 2.2 2.2 2.2
Polyacrylate (MW=4500) 3.0 3.0 3.0 3.0
Polyethylene glycol 1.2 1.2 1.2 1.2
(MW-4000)
Sodium Sulfate . - 10.5 10.5 10.5 10.5
Aluminosilicate 26.6 26.6 26.6 26.6
Sodium carbonate 21.0 21.0 21.0 21.0
Protease enzyme 0.4 0.4 0.4 0.4
Sodium perborate monohydrate 2.6 2.6 2.6 2.6
Lipase enzyme 0.2 0.2 0.2 0.2
Cellulase enzyme 0.1 0.1 0.1 0.1
NOBS extrudates (S00 micron 6.0 - - -
diameter)
NOBS extnrdates (700 micron - 6.0 - -
diameter)
NOBS extrudates (350 micron - - - 6.0
diameter)
NOBS extrudates (890 micron - - 6.0 -
diameter)
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WO 99/27061 PCT/US98I19999
24
Free water 2.0 2.0 2.0 2.0
Minors (bound water, perfume, ~ ~,$ ~,$
etc.)
100.0 100.0 100.0 100.0
1 C12-13 dkYl ethoxylate (E0=6.5) commercially available from Shell Oil
Company.
Each of the Example I, B, III and IV compositions are tested for bleach
activator storage stability and product segregation tendency according to the
following test method described in detail hereinafter.
For the storage stability test, fight samples of 20 grams of the compositions
exemplified above are individually placid into separate glass jars and sealed.
Each of
the four sets of glass jars are mixed by rotating the jars in planetary
motion. The jars
are then opened and placed in a controlled environment room maintained at
80°F
(26.7°C) and 60'/o relative humidity. Each weds, starting with week 0
and ending at
weds 8, the convents of the jars are analyzed for bleach activator (e.g.,
NOBS) level,
and using regression analysis, the complete aet of data is converted to a
bleach
activator level remaining in the stored product. In this test, good stability
is indicated
why the bleach activator level remaining in the stored product is at least
90'/0 of the
starting level.
For determining the product segregation tendency, the following procedure is
condudad.
S~p~tion Tendency Test
I . Two funnels aro set up on a ring stand with the stem on top such that
is a-distan<x of 37 em betv~neen the-neck of the top fiumd and the
bottom of the lower firnnd a~ there is enough space to position a small
jar under the lower funnel;
2. Add 100 grams of the detergent composition to the jar, seal the jar and
rotate it in a plan~ary motion to mix thoroughly the coMa~ts;
3. Stopper the top fimnd and pour the jar contents in the top fuzmd;
4. Stopper the bottom fiumd, and remove the stopper from the top funnel to
allow contents to flow into bottom funnel;
S. Tare an dnpty jar on a wdgh scale and allow the contems from the funnel
to flow into the jar until the weight is 25 grams;
6. Repeat 5 two more times and allow the remaining contents to flow into a
fourth jar,
7. Analyze the bleach activator level in each jar,
CA 02311378 2002-12-13
8. The Coning Index (CI) = 100x(highest activator level - lowest activator
level)/mean activator level, wherein the higher the CI, the greater the
segregation tendency.
In the segregation test, a Coning Index (Cn of Beater than 80 is considered
unacceptable and indicates excessive product segegation potential. The results
of
the stability and segegation tendency indicate that Examples I and II having
mean
extrudate diameters within the scope of invention unexpectedly have good
activator
stability and less product segregation tendency. Comparative Example III
having a
mean extrudate diameter outside the scope of the invention has an unacceptable
segegation potential, and comparative Example IV also having a mean extrudate
diameter outside the scope of the invention has unacceptable bleach activator
storage
stability.
Examnles V-VII
As in Examples I-IV described above, NOBS extrudates are prepared in the
same manner except the extrudates have a mean diameter of 850 microns.
TM
Thereafter, three batches ofNOBS extrudates are Bound in a Quadro CO-I1~11 to
form extrudates having a mean length of 4000 microns (Example V), 2000 microns
(Example Vn and 1000 microns (Ex$mple VIl), respectively. Each batch is
blended
into a bleach-containing detergent composition as exemplified in above in
Examples
I-IV. The activator stability and segegation tendency tests are conducted as
in
Examples I-IV. The results indicate that Examples VI and VII which are within
the
scope of the invention all unexpectedly have excellent stability and product
segregation properties; whereas comparative Example V having a mean extrudate
length outside the invention has an unacceptable segegation potential.
~g~nles VIII-X
As in Examples I-IV described above, sodium lauroyloxybenz~ne sulfonate
("i,OBS") extrudates are prepared, in the same manner as Example I and are
contained in identical formulas as Example I except NOBS is replaced with
LOBS.
Thereafter, three batches of LOBS extrudates are Bound in a Quadro CO-I~11 to
form extrudates having a mean length of 4000 microns (Example VIII), 2000
microns
(Example D~ and 1000 micxons (Example X), respectively. Each batch is blended
into a bleach-containing detergent composition as exemplified in above in
Examples
I-IV. The activator stability and segegation tendency tests are conducted as
in
Examples I-IV. The results indicate that Examples IX and X which are within
the
scope of the invention all unexpectedly have excellent stability and product
segegation properties, whereas comparative Example VBI having a mean extrudate
length outside the invention has an unacceptable segregation potential.
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WO 99/27061 PCT/US98/19999
26
Exam2es XI-XIII
As in Examples I-IV described above, pare-decanoyloxybenzoic acid
("DOBA") extrudates are prepared in the same manner as E~uample I and are
contained in ide~ical formulas as Example I except NOBS is replaced with DOBA.
Thereafter, three batches of DOBA cxtrudatcs are ground in a Quadro CO-Nfill
to
form extrudates having a mean length of 4004 microns (Example XI), 2000
microns
(Example XII) and 1000 microns (Example 30II), respectively. Each batch is
blended into a bieach-containing detergent composition as exemplified in above
in
Examples I-IV. The activator stability and sermon tendency tests are conducted
as in Examples I-IV. The resuhs indicate that Examples 3~ and 3~ which are
within the scope of the invention all unexpectedly have excellent stability
and product
segregation Properties, whereas comparative Example XI having a mean extrudate
length outside the invention has an unaccxptable segregation potential.
Synthesis of Lauroyloxy>x~xnesulfonate, Sodium Salt (LOBS)
i ~.
Q i .. i
8 ~ 1
A 2 L three-necked round-bottomed Bask is » with a mechanical stirner, re8ux
conda~ser, and gas inlet tube. The Bask is charged with lauroyl d~loride (~,
Aldrich,
96g, 0.44 mol), tolu~e (500 mL), and anhydrous phenol sulfonate (~,, 78g, 0.40
men. With stirring under argon the reacxion mixture is heated to re8ux for 16
his.
After coolir4g to room tentperaturo the mixt~ue is dilutal with diethyl ether
(500 mL),
and the procipitated solids are co>>ected by filtration, wasl~d with
additional diethyl
ether, and .air dried. The dry solids are titrated with refiuxing methanol
(750 mL).
After cooling to room temperature, filtering, and dr»ng, 1258 (83% of theory)
of
lauroyrloxybd~esulfonate, sodium sah (LOBS, ~, is obtained.
CA 02311378 2000-OS-23
WO 99/Z7061 PCTIUS98/19999
27
Example XV
Synthesis of p-Decanoyloxybenzoic Acid (DOBA)
0
o al
O O OOH
1. NaOH
d ~ ~ ( 2 hlCl
4
A 2 L beaker is fitted with a mechanics! stirrer, pH electrode, and
temperature prod.
The beaker is charged with p-hydroxybenzoic acid (5, Aldrich, 1388, 1.0 mol)
and
1N sodium hydroxide (1.0 L, 1.0 mol), resulting in a solution having a pH of
11.2.
This solution is cooled to 10° C and docanoyl chloride (ø~ Aldtich,
95g, 0.5 mol)
dissolved in 250 mL of diethyl ethar is added dropwise at 0- I S° C
over a period of 15
min while mainta;ning the pH at 10 with concurrent addition of 50% sodium
hydroxide solution. ARer completion of addition of the decnnoyl chloride the
solution pH is 10.1 and the solution tempaature was 10° C. Stirring is
continued at
pH 10 and 10° C for 10 minutes following completion of addition. The pH
of the
reacxion mixture is then adjusted to 3 with conca~rated HCI, and the
precipitated
solids collaxed by filtration and air dried to yield 180 g of crude product.
Raxys~allization from 900 mL of 95% ethanol afforded 38g (40% of theory) of p-
decanoyloxybenaoic aad (DOBA, ~, mp 125-129° C. Analysis of this
product by
I~TI~ indicated a purity of 93%, with the rernaind~ being 4-hydroxybenzoic
acid.
Having thus de:aibed the imr~ion in detail, it will be clear to those skilled
in
the art that various 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
apeafication.
