Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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DETERGENT COMPOSITION CONTAINING
CYLINDRICALLY-SHAPED BLEACH ACTIVATOR EXTRUDATES
HAVING ENHANCED FLOWABILITY
FIELD OF THE INVENTION
The invention relates to detergent and bleaching compositions containing a
peroxygen bleaching system, said system comprising a peroxygen bleach and a
bleach activator comprising extrudate, said extrudate having increased
flowability.
The exturdate is substantially cylindrically-shaped and provides 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 large-
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
O
I I
R-C-L
wherein R is an alkyl group and L is a leaving group, have been disclosed in
the art.
Such bleach activators have typically been incorporated into detergent
products as an
admixed granule, 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 granule, agglomerate or other
particulate
foam of the bleach activator must be relatively large in comparison to the
other
detergent ingredients in a typicai granular detergent product. This, in turn,
causes
another problem associated with detergent product segregation 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 ingredients accumulate at or
near the
bottom of the box. Additionally, particle segregation 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 segregation
is
decreased 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 prior to packaging or
while
stored in the detergent product box. Additionally, it would be desirable to
have such
a detergent composition which also has acceptable physical properties, for
example,
acceptable flow properties for bulk handling of the composition as part of
large-scale
detergent manufacturing.
Yet another problem with the aforementioned bleach activators relates to the
inability to advertise the sanitization effects of the above-mentioned
bleach/bleach
activator systems on fabrics. Currently, most government regulation agencies
require
that sanitization advertising 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, agglomerate or other particle form of the bleach activator has
inhibited
such 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 bleach/bleach activator delivery during the laundering
process
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varied too widely to satisfy most governmental 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 physical properties, especially enhanced flowability which serves
to aid in
the processing of the detergent compositions. Yet another need in the art
remains for
such a detergent composition which has a more consistent bleach/bleach
activator
delivery.
SUMMARY OF THE INVENTION
The present invention relates to extrudates which comprise bleach activators
said extrudates having increased flowability. These extrudates are useful in
detergent
compositions containing a peroxygen bleaching compound which require the
bleach
activator in the form of substantially cylindrically-shaped extrudate having a
selected
relatively small particle size. The smaller sized bleach activator extrudates
unexpectedly remain stable over extended storage periods and reduce product
segregation in the detergent box in which they are contained as they more
closely
mirror the particle size of other conventional detergent ingredients. The
increase
flowability of the extrudates taken together with the particle size of the
extrudates
delivers enhanced sanitization effects to the laundered fabrics more
consistently.
The phrase "cylindrically-shaped extrudates" means an extruded particle
having a surface shape generated by a straight line moving parallel to a fixed
straight
line and intersecting a fixed planar closed curve. An "effective amount" of a
detergent 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. Examples of various microbes include germs,
bacteria,
viruses, parasites, and fi~ngi/spores. As used herein, "free water" level
means the
level on a percentage by weight basis of water in the detergent composition
which is
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.
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In accordance with one aspect of the present invention, a bleach containing
detergent composition is provided which comprises a bleach activator
extrudate, said
extrudate comprising:
a} from about 60% to about 95% by weight, of a bleach activator having
the formula:
O
I I
R-C-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 carbonyl carbon contains from about 6 to about 10
carbon atoms and L is a leaving group, the conjugate acid of which
has a pKa in the range of from about 6 to about 13;
b) from about 0.1% to about 40% by weight, of one or more. binder
materials; and
c) from about 0.5%, preferably from about 0.5% to about 10% by
weight, of a flowability enhancer;
said bleach activator extrudate is in the form of a substantially
cylindrically-
shaped extrudate having a mean extrudate length of from about 500 microns
to about 3500 microns and a mean extrudate diameter of from about 450
microns to about 850 microns.
Another aspect of the present invention provides a laundry detergent or
bleaching composition which utilizes said extrudate, said composition
comprising:
a) at least about 0.1% by weight of a peroxygen bleaching compound
capable of yielding hydrogen peroxide in an aqueous solution;
b) a bleach-containing extrudate comprising:
i) from about 60% to about 95% by weight, of a bleach activator
having the formula:
O
R-C-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 carbonyl carbon contains
from about 6 to about 10 carbon atoms and L is a leaving
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group, the conjugate acid of which has a pICa in the range of
from about 6 to about 13;
ii) from about 0.1 % to about 40% by weight, of one or more
binder materials; and
iii) from about 0.5% to about 10% by weight, of a flowability
enhancer;
wherein said bleach activator extrudate is in the form of a substantially
cylindrically-shaped extrudate having a mean extrudate length of from
about 500 microns to about 3500 microns and a mean extrudate
diameter of from about 450 microns to about 850 microns and
provided said extrudate comprises sufficient activator such that the
ratio of bleach activator to peroxygen bleaching compound is greater
than 1; and
c) the balance carriers and other adjunct ingredients.
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.
Accordingly, it is an object of the invention to provide a detergent
composition containing a 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.
All percentages and ratios used herein are expressed as percentages by weight
(anhydrous basis) unless otherwise indicated. All cited documents are
incorporated
herein by reference.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The detergent or bleaching compositions or the present invention comprise a
bleaching system having two essential components; a peroxygen bleach which is
capable of producing hydrogen peroxide as an aqueous solution, and a bleach
activator which enhances the formation of hydrogen peroxide by said peroxygen
bleach. The peroxygen bleach may be in any suitable form, for example, a
coated
particle, however, the bleach activator is in the form of a substantially
cylindrically-
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6
shaped extrudate, said extrudate comprising a flowability enhancer. The bleach
activator containing exturdate is formed using one or more flowability
enhancers
which act to prevent the extrudate particles from clumping or becoming
"sticky".
Typically, one or more binder materials are included in the bleach activator
extrudates including, but not limited to, palmitic acid, a detersive
surfactant,
polyethylene glycol and other fatty acids and polyacrylates.
The Peroxygen Bleaching Compound
The peroxygen bleaching systems useful herein are those capable of yielding
hydrogen peroxide in an aqueous liquor. These compounds are well known 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. Mixtures of two or more such bleaching compounds can also be used,
if
desired.
Preferred peroxygen 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
perbarate monohydrate and sodium percarbonate. 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
formation of higher levels of percarboxylic acid and, thus, enhanced surface
bleaching performance.
Highly 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%, 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
Beater than about 1.0, more preferably greater than about 1.5, and most
preferably
from about 2.0 to about 10. Preferably, the bleaching compositions herein
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comprise from about 0.5 to about 20, most preferably from about 1 to about 10,
wt%. of the peroxygen bleaching compound.
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
result
of a selected free water level as set forth herein.
Bleach Activator Comprising Extrudate
Flowability Enhancers
The bleach activator comprising extrudate of the present invention has
enhanced flowability and resistance to agglomeration or sticking. This
improvement
is achieved by the addition of one or more "dusting agents", "anti-
agglomeration
agents" or "flowability aids". Non-limiting examples of these flowability
enhancers
include alumino-silicates, magnesium silicates, fumed silica, pulverized
carbonate,
talc, corn starch, and the like. Any high surface are which is non-hydroscopic
is
suitable for use. For example, finely divided and pulverized sodium sulfate or
anhydrous magnesium sulfate.
Preferred flowability enhancers can be achieved by pulverizing zeolites, for
example zeolite A, zeolite X, or zeolite Y, and adding the required amount of
said
zeolite to the admixture prior to extrusion. The added benefit to the
formulator for
adding a material such as pulverized zeolite is that the material is useful as
a builder
once the extrudate is solublized in the laundry liquor.
Preferably the flowability enhancer has a particle size of less than 10 micron
(10 p.), more preferably from 1-10 p, most preferably from 3-5 ~,.
The flowability enhancer is present in the bleach activator comprising
extnadate at a level of from at least about 0.5%, preferably from about 0.5%
to about
10%, more preferably from about 2% to about 3% by weight, of the extrudate.
Preferred flow enhancers are selected from the group consisting of
aluminosilicates, silicas, crystalline layered silicates MAP zeolites,
citrates,
amorphous silicates, sodium carbonate, talc, corn starch, and mixtures
thereof.
Bleach Activators
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The bleach activator for the bleaching systems useful herein preferably has
the following structure:
O
I I
R-C-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
carbonyl
carbon contains from about 6 to about 10 carbon atoms and L is a leaving
group,
the conjugate acid of which has a pKa in the range of from about 4 to about
13,
preferably from about 6 to about 11, most preferably from about 8 to about 11.
L can be essentially any suitable leaving group. A leaving group is any group
that is displaced from the bleach activator as a consequence of the
nucleophilic
attack on the bleach activator by the perhydroxide anion. This, the
perhydrolysis
reaction, results in the formation of the percarboxylic acid. Generally, 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 group must be sufficiently reactive for the reaction to occur within the
optimum time frame (e.g., a wash cycle). However, if L is too reactive, this
activator will be difficult to stabilize. These characteristics are generally
paralleled
by the pKa of the conjugate acid of the leaving group, although exceptions to
this
convention are known.
Preferred bleach activators are those of the general formula:
5
Rl-N-O-R2-C-L or Rl-O-N-R2-O-L
wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms,
R2 is an alkylene containing from 1 to about 6 carbon atoms, RS is H or alkyl,
aryl,
or alkaryl containing from about 1 to about 10 carbon atoms, and L is selected
from the group consisting of
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9
R3Y R3
-p -O
Y
Y O
-N-C-R6-N~N
-O R3 U
I
Y
O
il
O O CH2 C
-N-C-CH-R4-O-C-R6-N ~C~NR4
R3 Y II
O
Y O
~C R3
-N~ ~ ~NR4 -O-CH=C-CH=CH2
C
II
O
Y R3
-O-CH=C-CH=CHZ , -O-C=CHR4 , and
O Y
-N -S-CH-R4
R3 O
wherein 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 -S03-M+, -COO-M+, -S04-M+, (-
N+R'3)X- and O+-N(R'3), wherein R' is an alkyl chain containing from about 1
to
about 4 carbon atoms, M is a cation 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 cation,
with
sodium and potassium being most preferred, and X is an anion selected from the
group consisting of halide, hydroxide, methylsulfate and acetate anions. More
preferably, Y is -S03-M+ and -COO-M+. It should be noted that bleach
activators
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with a leaving group that does not contain a solubilizing group should be well
dispersed in the bleach solution in order to assist in their dissolution.
Preferred is:
R3 Y
-~ o
wherein R3 is as defined above and Y is -S03-M+ or -COO-M+ 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 group consisting of
Y R3
-O ~ -O
and
Y
R3Y
-O
wherein R3 is as defined above, Y is -S03-M+ or -COO-M+ and M is as defined
above.
A preferred bleach activator is:
O
I
C~
0
I
N =C
R
wherein R is H, alkyl, aryl or alkaryl. This is described in U.S. Patent
4,966,723,
Hodge et al., incorporated by reference herein.
Preferred bleach activators are:
O O O
Rl O C-L or R2-C-O O C-L
wherein R1 is H or an alkyl group containing from about 1 to about 6 carbon
atoms
and R2 is an alkyl group containing from about 1 to about 6 carbon atoms and L
is
as defined above.
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Preferred bleach activators are also those of the above general formula
wherein L is as defined in the general formula, and R1 is H or an alkyl group
containing from about 1 to about 4 carbon atoms. Even more preferred are
bleach
activators of the above general formula wherein L is as defined in the general
formula and R1 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
O ~ R2y
-N-C-R, -O-C-R, -O
R2
I
Y Y
R2
-O -O
Y
R2 R2
-O-CH=C-CH-~H2, -O-C=CHR3 ,
O
I
CHZ C
-NwC/NH.
I
O
wherein R, R2, R3 and Y are as defined above.
Particularly preferred 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
including the carbonyl carbon is from about 6 to about 10 carbon atoms, and L
is
selected from the group consisting of:
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12
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-M+ wherein M is an alkali metal, ammonium or substituted
ammonium ration.
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
Y R2
-p -O Y and
R2Y
-O
wherein RZ is as defined above and Y is -S03M+ or -COO-M+ wherein M is as
defined above.
The most preferred bleach activators have the formula:
O
R-C-O O S03-M+
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 M is sodium or potassium.
Preferably, the bleach activator herein is sodium
nonanoyloxybenzenesulfonate (HOBS) or sodium benzoyloxybenzenesulfonate
(BOBS).
Further particularly preferred for use in the present invention bleaching
compositions are the following bleach activators which are particularly safe
for use
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 forming insoluble crystalline
solid
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13
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 O
R~-C-N-R2-C-L, R~-N-C-R2-C-L
Rs Rs
or mixtures thereof, wherein RI is an alkyl, aryl, or alkaryl group
containing from about 1 to about 14 carbon atoms, R2 is an alkylene,
arylene or alkarylene group containing from about 1 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:
O
~O
C-R
R4
Rs
wherein R1 is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3,
R4, and RS may be the same or different substituents selected from H,
halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkylamino,
COOR6 (wherein R6 is H or an alkyl group) and carbonyl functions;
c) N-acyl caprolactam bleach activators of the formula:
O
II
O C-C H2-C H2
R6-C-NBC -C H ~C H2
H2 2
wherein R6 is H or an alkyl, aryl, alkoxyaryl or alkaryl 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
activators are those of the above general formulas wherein R1 is an alkyl
group
containing from about 7 to about 10 carbon atoms and R2 contains from about 4
to
about S carbon atoms.
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Preferred bleach activators of type b) are those wherein R2, R3, R4, and RS
are H and R1 is a phenyl group.
The preferred acyl 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 group containing from 1 to 12 carbons, preferably from 6 to 12 carbon
atoms. In highly preferred embodiments, R6 is a member selected from the goup
consisting of phenyl, heptyl, octyl, nonyl, 2,4,4-trimethylpentyl, decenyl and
mixtures thereof.
Am~do Derived Bleach Activators - The bleach activators of type a) employed in
the present invention are amide substituted compounds of the general formulas:
0 0 0 O
R'~-C-N-R2-C-L, R~-N-C-R2-C-L
I I
R5 Rs
or mixtures thereof, wherein R1, R2 and RS are as defined above and L can be
essentially any suitable leaving group. Preferred bleach activators are those
of the
above general formula wherein R1, R2 and RS are as defined for the peroxyacid
and L is selected from the group consisting of
Y R3 R3Y
-O , -O ~ Y , and -O
a
-N-C-R - ~ -N-C-CH-R
R3 R3 Y
I
Y
R3 Y
-O-C H=C-C H=C H2 -O-C H=C-C H=C H2
H -0 Y O
-N C 2 C NR ~ /NR4
O-C R~ ~C/ 4 , NBC
p O
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IS
R3 O Y
-O-C=C HR4 , and -N-~-C H-R4
R3 O
and mixtures thereof, wherein RI is an alkyl, aryl, or alkaryl group
containing from
about 1 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 group.
The preferred solubilizing groups are -S03-M+, -CO -M+, -S04 M+,
N+(R3)43~ and O< N(R3)3 and most preferably -S03-M2+ and -C02-IvI+
wherein R3 is an alkyl chain containing from about 1 to about 4 carbon atoms,
M is
a cation 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 cation, 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 groups 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 group consisting of
Y R3 R3Y
-O ~ -O ~ Y , and -O
wherein R3 is as defined above and Y is -S03 M+ or -C02 M+ wherein M is as
defined above.
Another important class of bleach activators, including those of type b) and
type c), provide organic peracids as described herein by ring-opening as a
consequence of the nucleophilic attack on the carbonyl carbon of the cyclic
ring by
the perhydroxide anion. For instance, this ring-opening reaction in type c)
activators involves attack at the caprolactam ring carbonyl by hydrogen
peroxide or
its anion. Since attack of an acyl caprolactam by hydrogen peroxide or its
anion
occurs preferably at the exocyclic 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-type Bleach Activators - Such activator compounds disclosed by
Hodge include the activators of the benzoxazin-type, having the formula:
CA 02324397 2000-09-18
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16
O
II
O
0 ~c_R,
'N
including the substituted benzoxazins of the type
0
R3 ~O
R4 N C -R,
R5
wherein R1 is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R4, and
RS
may be the same or different substituents selected from H, halogen, alkyl,
alkenyl,
aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR6 (wherein R6 is H or an
alkyl
group) and carbonyl functions.
A preferred activator of the benzoxazin-type is:
0
II
I
NC
When the activators are used, optimum surface bleaching performance is
obtained with washing solutions wherein the pH of such solution is between
about
8.5 and 10.5 and preferably between 9.5 and 10.5 in order to facilitate the
perhydrolysis reaction. Such pH can be obtained with substances commonly
known as buffering agents, which are optional components of the bleaching
systems herein.
N-Acvl Caprolactam Bleach Activators - The N-acyl caprolactam bleach
activators
of type c) employed in the present invention have the formula:
O
II
6-O C-C H2-C H2
R C-N~ ,C H2
C H2-C H2
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing
from 1 to
12 carbons. Caprolactam activators wherein the R6 moiety contains at least
about
6, preferably from 6 to about 12, carbon atoms provide hydrophobic bleaching
which affords nucleophilic and body soil clean-up, as noted above. Caprolactam
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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.
Highly preferred N-acyl caprolactams are selected from the group consisting
ofbenzoyl caprolactam, octanoyl caprolactam, nonanoyl caprolactam, 3,5,5-
trimethylhexanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam,
and mixtures thereof. Methods for making N-acyl 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%, 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-safe, hydrophilic
activators
such 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.
Binders
The bleach activator comprising extrudates of the present invention comprise
from about 0.1% to about 40% by weight of one or more binders. Preferably
binders
include, but are not limited to, palmitic acid, detersive surfactants,
polyethylene
glycol, and fatty acids.
In a highly preferred embodiment of the invention, the substantially
cylindrically-
shaped extrudate comprises, by weight of the extrudate, 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% 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.
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
extrudates
gavitate or migrate toward the surface of the individual extrudate particles,
thereby
inhibiting excessive exposure of the bleach activator to environmental
conditions such
as heat and moisture prior to use. As a consequence, the bleach activator in
the
substantially cylindrically-shaped extrudates do not degrade and remain
stable, while
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18
also bearing a particle size closely mirroring the size of the other detergent
ingredients in the detergent composition. As mentioned, the added unanimity of
particle size renders the detergent composition less susceptible to product
segregation in the detergent box prior to use. As is known, product
segregation
occurs 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 substantially cylindrically-shaped extrudates have mean
extrudate length of from about 500 microns to about 3500 microns, more
preferably
from about 700 microns to about 3000 microns, and most preferably from about
900
microns to about 2500 microns. Preferably, the mean extrudate diameter is from
about 450 microns to about 850 microns, more preferably from about 500 microns
to
about 800 microns, and most preferably from about 550 microns to about 750
microns. The mean extrudate diameter can be measured in a variety of ways, one
of
which is to measure a representative sample of the extrudates using a
microscope and
determining the mean via calculation. The mean diameter can be determined
similarly
or via extrapolation from the extrusion die hole diameter.
The selected relatively smaller particle size and cylindrical shape of the
bleach
activator extrudates result in a more consistent delivery of activator to the
aqueous
laundering solution. Stated differently, the variation around the target level
of bleach
activator to be delivered to the wash solution is unexpectedly reduced as
result of
using the aforementioned substantially cylindrically-shaped extrudates.
Fortuitously,
this allows the detergent composition to deliver the bleach activator at a
more
consistent level to achieve sanitization effects on the laundered fabrics.
Most
governmental agencies require very little variation around bleach activator or
other
sanitizing 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
method 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 preferabiy reduced by
at
least about 99.9%. This sanitizing method is interchangeably used with
disinfecting,
antibacterial, germ killing, odor-causing germ killing methods in accordance
with the
invention.
Additionally, the specific bleach activator and peroxygen bleaching
composition in the detergent composition are preferably present at specific
molar
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19
ratios of hydrogen peroxide to bleach activator. Such compositions provide
extremely effective and efficient surface bleaching of textiles which thereby
remove
stains and/or 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 bleaching 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 and/or
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
carbonyl carbon. Without being bound by theory, it is believed that such
efficiency is
achieved because the bleach activators within the invention exhibit surface
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 generated 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, evolves a singlet oxygen which is believed to be the active
bleaching
component. It is theorized that the ringlet oxygen must be evolved at or near
the
textile surface in order to provide surface bleaching. Otherwise, the ringlet
oxygen
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 ringlet oxygen is more effciently 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 10
carbon
atoms. Such percarboxylic acids are surface active and, therefore, tend to be
concentrated 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
invention are extremely efficient because much lower levels, on a molar basis,
of such
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bleach activators are required to get the same level of surface bleaching
performance
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. S and 10.5 and preferably
between 9 and 10. It is preferred that such pH be greater 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 known as buffering agents, which are
optional
components of the bleaching compositions herein.
Adjunct Detergent Ingredients
Preferably, adjunct detergent ingredients selected from the group consisting
of enzymes, soil release agents, dispersing agents, optical brighteners, suds
suppressors, fabric softeners, enzyme stabilizers, perfumes, dyes, fillers,
dye transfer
inhibitors and mixtures thereof are included in the composition of the
invention.
The following are representative examples of the detergent surfactants useful
in the present detergent composition. When present, the detersive surfactants
comprise at least about 0.01% by weight, preferably from about 0.1% to about
60%,
more preferably from about 0.1% to about 30% by weight, of a detersive
surfactant
selected from the group consisting of anionic, cationic, nonionic,
zwitterionic,
ampholytic surfactants, and mixtures thereof. 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
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21
(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 fram 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 1 to 10 carbon atoms in the ester group;
water-soluble salts of 2-acyloxyalkane-1-sulfonic acids containing from about
2 to 9
carbon atoms in the aryl group and from about 9 to about 23 carbon atoms in
the
alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon
atoms in
the alkyl group and from about 1 to 30 moles of ethylene oxide; water-soluble
salts
of olefin and paraffin sulfonates containing from about 12 to 20 carbon atoms;
and
beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in
the
alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
Preferred essential anionic surfactants for the detergent composition are
C10-18 linear alkylbenzene sulfonate and C 10-18 alkyl sulfate. If desired,
low
moisture (less than about 25% water) alkyl sulfate paste can be the sole
ingredient in
the surfactant paste. Most preferred are C10-18 alkyl sulfates, linear or
branched,
and any of primary, secondary or tertiary. A preferred embodiment of the
present
invention is wherein the surfactant paste comprises from about 20% to about
40% of
a mixture of sodium C10-13 linear alkylbenzene sulfonate and sodium C12-16
alkyl
sulfate in a weight ratio of about 2:1 to 1:2.
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
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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 10 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.
Preferred nonionic surfactants are of the formula R1(OC2H4)nOH, wherein R1
is a C 1 a C 16 alkyl group or a C8-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-1-
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.
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Zwitterioruc 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.
In addition to a detersive surfactant, at least one suitable adjunct detergent
ingredient such as a builder is preferably included in the detergent
composition. 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. 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.
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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 1 microns to about 8 microns.
Preferably, the aluminosilicate ion exchange material has the formula
Naz~(~02)z~(Si02)yJxH20
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
aluminosilicate
has the formula
Nal2~(~02)12~(Si02)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, 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/gam, 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'~"~'/gallon/minute/-
gam/gallon, and more preferably in a range from about 2 grains
Ca'~'~/gallon/minute/-gam/gallon to about 6 grains Ca'~'+lgallon/minute/-
gam/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 1
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The following ingredients are added to a Littleford FM batch mixer: 81% of
sodium nonanoyloxybenzene sulfonate ("NOBS"); 6% of palmitic acid, 3% of
sodium
linear alkylbenzene sulfonate surfactant; 6% of polyethylene glycol (MW =
4000);
2% of Cg fatty acid, and 3% pulverized (3-5 micron) alumino silicate (zeolite
A).
The mixture is blended and fed to a lab extruder (Fuji Paudel Co. Ltd., Dome
Granulator, DG-L1) and extruded through dies having diameters of 350 microns,
500
microns; 700 microns and 890 microns, respectively. Each of the four different
diameter substantially cylindrically-shaped extrudates are sized to a mean
length of
2000 microns.
The following examples illustrate the use of the enhanced flowability bleach
activator comprising extrudates of the present invention.
TABLE I
weight
In redients 2 3 4 5
C12-16 linear alkylbenzene11.0 11.0 11.0 11.0
sulfonate
C 14-15 alkyl sulfate/C10.4 10.4 10.4 10.4
14-1 S
al 1 echo sulfate
Neodo123-6.51 2.2 2.2 2.2 2.2
Pol ac late =4500 3.0 3.0 3.0 3.0
Polyethylene glycol 1.2 1.2 1.2 1.2
=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 a a 0.4 0.4 0.4 0.4
Sodium erborate monoh 2.6 2.6 2.6 2.6
drate
Li ase a a 0.2 0.2 0.2 0.2
Cellulase a a 0.1 0.1 0.1 0.1
NOBS extrudates (500 6.0 - - -
micron
diameter
NOBS extrudates (700 - 6.0 - -
micron
diameter
NOBS extrudates (350 - - - 6.0
micron
diameter
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26
NOBS extrudates (890 - - 6.0 -
micron
diameter
Free water Z.0 2.0 2.0 2.0
Minors (bound water, ~ ~$
perfume,
etc.
100.0 100.0 100.0 100.0
1. C12-13 alkyl ethoxylate (EO=6.5) commercially available from Shell Oil
Company.
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.
