BLEACHING COMPOSITIONS COMPRISING PEROXYACID ACTIVATORS HAVING AMIDE MOIETIES

COMPOSITIONS DE BLANCHIMENT RENFERMANT DES ACTIVATEURS A BASE DE PEROXYACIDE RENFERMANT DES FRACTIONS D'AMIDE

English Abstract

The present invention relates to a method of cleaning fabrics in washing machines which have parts made of natural rubber using
laundry detergents comprising amido-derived bleaching activators and a source of hydrogen peroxide such that said natural lubber parts of
said machines are substantially undamaged by products of the perhydrolysis reaction between the activator and hydrogen peroxide.

French Abstract

L'invention se rapporte à un procédé pour nettoyer les textiles dans des machines à laver qui comportent des pièces en caoutchouc naturel, à l'aide de détergents pour lessives comprenant des adjuvants de blanchiment dérivés d'amides ainsi qu'une source de peroxyde d'hydrogène, de sorte que les pièces en caoutchouc naturel des machines à lavers ne soient pas endommagées par les produits de la réaction de perhydrolyse entre l'adjuvant et le peroxyde d'hydrogène.

Claims

-23-
1. A bleaching system comprising a peroxygen bleaching compound, preferably
selected from the group consisting of perborate salts and percarbonate salts,
and
a bleach activator system selected from the group consisting of:
I)
a) a bleach activator of formula i):
<IMG>, <IMG>
or mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group
containing from 1 to 14 carbon atoms, R2 is an alkylene, arylene or
alkarylene group containing from 1 to 14 carbon atoms, R5 is H or an
alkyl, aryl, or alkaryl group containing from 1 to 10 carbon atoms, and L
is a leaving group; or mixture of a bleach activator of formula i) with a
bleach activator of formula ii):
<IMG>
wherein R1 is H, alkyl, alkaryl, aryl, aralkyl, and wherein R2, R3, R4, and
R5 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; and
b) a nonamido-derived hydrophilic bleach activator, and
II)
a) a bleach activator of formula ii), and
b) a non-amido-derived hydrophilic bleach activator of the N-acyl
caprolactam type.

-23a-
2. A composition according to Claim 1 wherein R1 is an alkyl group containing
from about 7 to about 10 carbon atoms, R2 contains from about 4 to about 5
carbon atoms, and L is selected from the group consisting of:
<IMG>, <IMG> , and <IMG>
wherein R3 is an alkyl chain containing from about 1 to about 8 carbon atoms,
Y
is -SO3-M+ or -CO2-M+ wherein M is sodium or potassium.

-24-
3. A composition according to Claim 1 wherein the hydrophilic bleach
activator is a N-aryl caprolactam activator wherein the aryl moiety has
the formula R1-CO- wherein R1 contains 6 or less carbon atoms.
4. A composition according to Claim 3 wherein the hydrophilic
caprolactam bleach activator is benzoyl caprolactam.
5. A composition according to Claim 1 wherein the bleach activator is
<IMG>.
6. A composition according to Claim 1 wherein the hydrophilic bleach
activator is tetraacetyl ethylene diamine.
7. A composition according to Claim 1 wherein the the peroxygen
bleaching compound is selected from perborate salts and percarbonate
salts.
8. A composition according to Claim 1 which additionally comprises a
chelant.
9. A composition according to Claim 8 wherein the chelant is an
ethylenediamine disuccinate chelant or an aminophosphonate chelant.
10. A composition according to Claim 1 in the form of a laundry detergent
which additionally comprises. detersive surfactants, builders and
detersive adjunct ingredients.
11. A method for cleaning fabrics in an automatic washing machine having
parts made of natural rubber which is susceptible to oxidative
degradation, said method comprising agitating said fabrics in said
machine in an aqueous liquor comprising a bleaching system according

-25-
to Claim 1, such that said natural rubber parts of said machine are
substantially undamaged by the bleaching system.
12. A method according to Claim 11 wherein the bleaching system
comprises a bleach activator which reacts in said aqueous liquor to
yield a peroxyacid of the general formulae:
<IMG>, <IMG>
wherein R1 is an alkyl, aryl, or alkaryl group containing from about 1 to
shout 14 carbon atoms, R2 is an alkylene, arylene or alkarylene group
containing from about 1 to about 14 carbon atoms, and R5 is H or an
alkyl, aryl, or alkaryl goup containing from about 1 to about 10 carbon
atoms.
13. A method according to Claim 12 wherein said aqueous liquor further
comprises conventional detergent ingredients; said bleaching system
comprising:
a) at least about 0.1%, by weight, of a peroxygen bleaching
compound capable of yielding hydrogen peroxide in an aqueous liquor;
and
b) at least about 0.1%, by weight, of a bleach activator selected
from the goup consisting of:
<IMG>,~~<IMG>
or mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group
containing from about 1 to about 14 carbon atoms, R2 is an alkylene,
arylene or alkarylene goup containing from about 1 to about 14 carbon
atoms, R5 is H or an alkyl, aryl, or alkaryl goup containing from about
1 to about 10 carbon atoms, and L is a leaving goup; and

-26-
<IMG>~
wherein R1 is H, alkyl, alkaryl, aryl, aralkyl, and wherein R2, R3, R4,
and R5 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,
such that the molar ratio of hydrogen peroxide yielded by a) to bleach
activator b) is greater than about 1Ø
14. A method according to Claim 13 wherein R1 is an alkyl group
containing from about 6 to about 12 carbon atoms, R2 contains from
about 1 to about 8 carbon atoms, and R5 is H or methyl.
15. A method according to Claim 14 wherein R1 is an alkyl group
containing from about 7 to about 10 carbon atoms and R2 contains
from about 4 to about 5 carbon atoms.
16. A method according to Claim 13 wherein L is selected from the group
consisting of:
<IMG>, <IMG> , and <IMG>
<IMG>, <IMG> , <IMG> ,

-27-
<IMG>, ~~<IMG>,
<IMG>, <IMG>, ~<IMG>,
<IMG>, and ~<IMG>
and mixtures thereof, wherein R1 is as defined in Claim 1, 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.
17. A method according to Claim 16 wherein Y is selected from the group
consisting of: -SO3-M+, -CO2-M+, -SO4-M+, -N+(R3)4X- and
0<-N(R3)3 and mixtures thereof wherein R3 is an alkyl chain containing
from 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.
18. A method according to Claim 16 wherein L is selected from the group
consisting of:
<IMG>, <IMG>, and <IMG>
wherein R3 is an alkyl chain containing from about 1 to about 8 carbon
atoms, Y is -SO3-M+ or -CO2-M+ wherein M is sodium or potassium.

-28-
19. A method according to Claim 13 wherein the bleach activator is
<IMG>.
20. A method according to Claim 13 wherein the conventional detergent
ingredients comprise from about 5% to about 80%, by weight, of a
detersive surfactant.
21. A method according to Claim 20 wherein the conventional detergent
ingredients further comprise from about 5% to about 80%, by weight,
of a detersive builder and from 0% to about 20%, by weight, of
conventional detersive adjunct materials.
22. A method according to Claim 13 wherein the peroxygen bleaching
compound is selected from the group consisting of sodium perborate
monohydrate, sodium percarbonate, sodium perborate tetrahydrate,
sodium pyrophosphate peroxy-hydrate, urea peroxy-hydrate, sodium
peroxide and mixtures thereof.
23. A composition according to Claim 1 wherein said bleach activators are
in particulate form.
24. A composition according to Claim 23 wherein said bleach activator
particle comprises shout 40% to about 60%, by weight, of a 1:1
mixture of (6-octanamidocaproyl)oxybenzenesulfonate and
(6-decanamidocaproyl)oxybenzenesulfonate; about 20% to about 40%, by
weight, citric acid; and about 15% to about 30%, by weight, tallow
alcohol ethoxylate nonionic surfactant.
25. A composition according to Claim 23 wherein said bleach activator
particle comprises about 65% benzoyl caprolactam, about 7%
aluminium silicate, about 15% sodium carbonate, about 9%
polyacrylate poymer, and about 4% linear alkyl sulfonate.

-29-
26. A composition according to Claim 23 wherein said particle comprises
about 80% benzoyl caprolactam and about 20% tallow alcohol
ethoxylate nonionic surfactant.

Description

WO 94/28104 PCT/US94I05370
~i6~z~~
BLEACHING COMPOS1~TIONS COMPRISING
PEROXYACm ACTIVATORS HAVING AMIDE MOIETIES
FIELD OF THE i)NVENTION
The present invention relates t~p laundry detergents with activated
bleaching systems.
BACKGROUND OF '~''1~ INVENTION
It has long been known that peroprygen bleaches are effective for stain
and/or soil removal from fabrics, but that such bleaches are temperature
dependent. At a wash liquor temperatuire of 60°C) peroxygen bleaches
are
only partially effective As the wash liquor temperature is lowered below
60°C, peroxygen bleaches become relatilvely ineffective. As a
consequence)
there has been a substantial amount of industrial research to develop
bleaching
=0 rystems which contain an activator that readers peroxygen bleaches
effective at
wash liquor temperatures below 60°C.
Numerous substances have been d~ixlosed in the art as effective bleach
activators. One widely-used bleach activator is tetraacetyl ethylene diamine
(TAED). TA>:D provides effective hydrophilic cleaning especially on beverage
:5 stains) but has limited performance on idingy) yellow stains such as those
resulting from body oils Another tyke of activator) such as nonanoyl
oxybenzenesulfonate (HOBS) and other ~etivators which generally comprise
long chain alkyl moieties, is hydrophobic in nature and provides excellent
performance on dingy stains However, 'many of the hydrophobic activators
30 developed thus far can promote damage tip natural rubber parts used in
certain
washing machines Because of these negative effects on washing machine
parts) the selection of such detergent-addled bleaching systems has long bren
limited. This is especially true for Eurolpean detergentJbleaches, since many
washing machines manufactured in Europt~ have been equipped with key parts)
35 such as sump hoses and motor gaskets)'' made of natural rubber. A need_
therefore) exists for a bleaching system iwhich provides dingy soil clean up

WO 94/28104 PCT/US94/05370
without substantially damaging the n~ktural rubber parts found in washing
machines.
It has now been determined that in conventional bleaching systems)
typically comprising a hydrophobic bleach activator and a source of hydrogen
peroxide, the activator undergoes perhydrolysis to form a peroxyacid bleaching
agent. A by-product of the perhydiolysis reaction between such bleach
activators and hydrogen peroxide is a Idiacylperoxide (DAP) species. It has
now further beat discovaod that thpe DAP's derived from hydrophobic
bleaching activators tend to be insoluble) poorly dispersible) oily materials
0 which form a residue which can deposit on the natural rubber machine parts
that are exposed to the wash liquor. Ttue oily DAP residue can form a film on
the natural rubber parts and promote free radical and peroxide damage to the
rubber) which eventually leads to failure; of the parts. This is particularly
true
of rubber parts which have prolonged exposure to the wash liquor) such as
sump hoses.
By the present invention, it has now been discovered that the class of
hydrophobic bleach activators derived from amido acids forms hydrophobic
amido peracids upon perhydrolysis without the production of harmful) oily
DAP's. Without limiting the invention i herein, it is believed that the DAP's
=o produced by the perhydrolysis reactioln of the amido acid-derived bleach
activators are insoluble crystalline soiid~. Such solid DAP's do not form a
coating film. Accordingly, the natural nrbber machine parts are not exposed to
the DAP's for extended periods of time artd remain substantially undamaged by
the bleaching system of the present invention.
The present invention thus soNves the long-standing need for an
eH'ective hydrophobic bleaching system .which does not promote free radical
and peroxide damage to natural rubber parts in washing machines. The
invention provides a method of cleaning fabrics with a bleaching system in
washing machines which have parts mode of natural rubber such that the
natural rubber is substantially undamagedby the bleaching system.
3o BACKGROLiND ART ,
U.S. Patent 4,634,551) Burns et ~1) issued January 6) 1987, discloses
amido peroxyacid bleaching compounds and their precursors of the type ,
employed in the present invention. See also, U.S. Patent 4,852,989, Burns et
al, issued August 1, 1989, and U.S. Paterwt 4,966,723) Hodge et al, issued
Oct.
30) 1990.

WO 94/28104 ~ ' PCT/US94/05370
3
SUMMARY OF TlE-iE INVENTION
The present invention relates ~to a method for cleaning fabrics in
automatic washing machines having patrts made of natural rubber which is
susceptible to oxidative degradation. The method comprises agitating fabrics
in said washing machine in an aqueous jliquor comprising a bleaching system
comprising a bleach activator which reacts with a source of peroxide its said
aqueous liquor to yield a peroxyac~d without the formation of oily
diarylperoxide (DAP) such that said natural rubber parts are substantially
undamaged by the by-products of said reaction.
The amido-derived peroxyacids ;generated by the reaction are of the
general formulas:
O 0 O O
R~-C-N-RZ-C-OOH , R~--N-C-R2-C-OOH
Rs Rs
wherein R 1 is an alkyl) aryl, or alkaryl grpup containing from about 1 to
about
14 carbon atoms) R2 is an alkylene) arylene or alkarylene group containing
from about I to about 14 carbon atoms, alnd RS is H or an alkyl, aryl, or
alkaryl
goup containing from about 1 to about 10 carbon atoms.
2o The bleaching rystem of said method comprises:
a) at least about 0.1~/0, preferably from about 1% to about 75%) by
weight) of a peroxygen bleaching compound capable of yielding hydrogen
peroxide in an aqueous liquor; and
b) at least about 0.1 ~/., preferabl;w from about 0.1 % to about 50%, by
weight) of a bleach activator selected fronp the group consisting of:
z5
i)
O O , '- 0 2-O
R'--C-N-RZ-C-L, R N-C-R C-L
RS Rs
30 or mixtures thereof, wherein R 1' is an alkyl) aryl) or alkaryl group
containing from about 1 to about 14 carton atoms) RZ is an alkylene, arylene
or alkarylene group containing from abou~l 1 to about 14 carbon atoms) RS is H
or an alkyl) aryl, or alkaryl goup containpng from about 1 to about 10 carbon
atoms, and L is a leaving group; '

WO 94/28104 PCT/US94/05370
4
2~1fi1~1~
ii)
0
R3 ~O
I
~ , C -R~
R4 N
Rs
wherein RI is H) alkyl) alkaryl) aryl, aralkyl) and wherein R2, R3, R4,
and RS may be the same or different substituents selected from H, halogen,
1 o alkyl) alkenyl, aryl, hydroxyl) alkoxyl) amino) alkylamino) COOR6 (wherein
R6
is H or an alkyl group) and carbonyl functions; and
iii) mixtures of i) and ii).
Preferably the molar ratio of hydrogen peroxide yielded by a) to bleach
activator b) is greater than about 1Ø Most preferably) the molar ratio of
hydrogen peroxide yielded by a) to bleach activator b) is at least about 1.5.
The invention also encompasses laundry compositions in granular) paste)
liquid)
or bar form which comprise the aforesaid bleaching system together with
detersive ingredients which are present in the composition at the levels
indicated hereinafter.
Preferred bleach activators of type b)i) are those wherein R 1 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 of type b)i) are those of the above general formulas
wherein,
R 1 is an alkyl goup containing from about 7 to about 10 carbon atoms and R2
2 5 contains from about 4 to 5 carbon atoms.
Preferred bleach activators of type b)ii) are those wherein R2, R3, R4)
and RS are H and R 1 is a phenyl group.
The peroxygen bleaching compound can be any peroxide source and is
preferably a member selected from the group consisting of sodium perborate
monoh'ydrate) sodium perborate tetrahydrate, sodium percarbonate, sodium
pyrophosphate peroxyhydrate) urea peroxyhydrate) sodium peroxide and
mixtures thereof. Highly preferred peroxygen bleaching compounds are
selected from the group consisting of sodium perborate monohydrate) sodium
perborate tetrahydrate, sodium percarbonate and mixtures thereof. The most
highly preferred peroxygen bleaching compound is sodium percarbonate.

CA 02161211 1999-06-04
n ..
-5-
The bleach activators herein can also be used in combination with rubber-safe,
hydrophilic activators such as TAED, typically at weight ratios of amido-
derived
activators:TAED in the range of 1:5 to 5:1, preferably about 1:1. Another
important class
of rubber-safe, hydrophilic activators comprise the N-acyl caprolactam
activators
wherein the acyl moiety has the formula Rl-CO- wherein Rl contains 6 or less
carbon
atoms. Highly preferred hydrophilic caprolactam activators include formyl
caprolactam,
acetyl caprolactam, and benzoyl caprolactam.
The method of cleaning fabrics comprises agitating fabrics in said washing
machine in an aqueous liquor comprising a detergent composition which
comprises at
least about 300 ppm of conventional detergent ingredients, at least about 25
ppm of the
bleaching compound and at least about 25 ppm of a bleach activator.
Preferably, the
liquor comprises from about 900 ppm to about 20,000 ppm of conventional
detergent
ingredients, from about 100 ppm to about 25,000 ppm of the bleaching compound
and
from about 100 ppm to about 2,500 ppm of a bleach activator. The method can be
successfully carried out at temperatures below about 60°C but, of
course, is quite
effective and is still safe to rubber parts at laundry temperatures up to the
boil.
The conventional detergent ingredients employed in fully formulated detergent
compositions provided herein can comprise from about 1 % to about 99.8%,
preferably
from about 5% to about 80%, of a detersive surfactant. Optionally, detergent
compositions can comprise from about 5% to about 80% of a detersive builder.
Other
optional detergent ingredients are also encompassed by the fully-formulated
detergentJbleach compositions provided by this invention.
All percentages, ratios, and proportions are by weight, unless otherwise
specified.
DETAILED DESCRIPTION OF THE INVENTION
The invention relates to a method for cleaning fabrics in automatic washing
machines
having parts made of natural rubber which is susceptible to oxidative
degradation. The
bleaching system used in this invention is safe to natural rubber machine
parts and to
other natural rubber articles which are exposed to the bleaching system,
including fabrics
containing natural rubber and natural rubber elastic materials. The bleaching
system
employed in the present invention provides effective and efficient surface
bleaching of
fabrics which thereby removes stains and/or soils, including "dingy" soils,
from the

WO 94/28104 PCT/US94/05370
~I~f~~l
fabrics. Dingy soils are soils that buildup on fabrics after numerous cycles
of
usage and washing and, thus) eventuallyi cause white fabrics to have a gray or
yellow tint. These soils tend to be a blend of particulate and greasy
materials.
The removal of this type of soil is some~Gimes referred to as "dingy fabric
clean
up'.
The bleaching systems and ';activators herein afford additional
advantages in that, unexpextexlly) they ate safer to fabrics and cause less
color
damage than other activators when uiaed in the manner provided by this
invention.
t o The bleaching mechanism and, in particular) the surface bleaching
mechanism are not completely understoiod. However) it is generally believed
that the bleach activator undergoes n~~cleophilic attack by a perhydroxide
anion, which is generated from the hydrogen peroxide evolved by the
peroxygen bleach) to form a peroxycarb~I~xylic acid. This reaction is commonly
referred to as perhydrolysis.
It is also believed, that the blea~th activators within the invention can
render peroxygen bleaches more efficient even at wash liquor temperatures
wherein bleach activators are not neces;kary to activate the bleach, i.e.,
above
about 60oC. Therefore) with bleach systems of the invention, less peroxygen
bleach is requirexi to get the same level ~pf surface bleaching performance as
is
obtained with the peroxygen bleach alone.
The Bleach Activator
The hydrophobic bleach activat~prs employed with this invention are
amide substituted compounds of the genyral formulas:
:s RFC-N-R~-C-L
I , R N C-R C-L
Rs Rs
or mixtures thereof) wherein R 1, R2, and RS are as defined hereinabove and L
~n 'essentially any suitable leaving grc>up. A leaving group is any group that
is displaced from the bleaching activator as a consequence of the nucleophilic
attack on the bleach activator by the perhydroxide anion. This, the
perhydrolysis reaction) results in the foilmation of the peroxycarboxylic
acid.
Generally, for a group to be a suitable having group it must exert an electron
attracting effect. It should also form a stiable entity so that the rate of
the back

~161~~ :~
WO 94/28104 PCT/US94/05370
~1
reaction is negligible. This facilitates the nucleophilic attack by the perhy-
droxide anion.
The L group must be sufficienr<ly 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 difficullt to stabilize for use in a
bleaching
composition. These characteristics are ;;generally paralleled by the pKa of
the
conjugate acid of the leaving group, altluough exceptions to this convention
are
known. Ordinarily) leaving groups that exhibit such behavior are those in
which their conjugate aad has a pKa in yhe range of from about 4 to about 13)
o preferably from about 6 to about 1 l and'; most preferably from about 8 to
about
I1
Preferred bleach activators are ; those of the above general formula
wherein Rl) RZ and RS are as defined! for the peroxyacid and L is selected
from the group consisting of
Y R~ R3Y
-Y , and
O O
-N- II -R~ II
C -N N -N-C -C H-R,
Ra ' ~ ~ R3 Y ,
I
Y
Y
2 5 -p-C H=C -C H=C Hz -O-i~C H=C -C H=C H2
O C ~ Y 0
,~ ~--C,
-O-C-R' -N~C~NFI~ , 'N~C/N~
II II
O O
3
R O Y
-O-C=C HR, ( and -N-S-C H-R4
R3 O

WO 94/28104 PCT/US94/05370
yl~ X211
and mixtures thereof, wherein R 1 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 solubiliung groups are -S03-M+) -CO -M+,-S04 -M+,
-N+(R3)47~ and O<-N(R3)3 and most preferably -S03-M~ and -C02-M+
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 ration, with sodium and potassium
t o 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 solubiliz~ng groups should be well disperxd in the bleaching.
solution in order to assist in their dissolution.
Preferred bleach activators are thox of the above general formula
wherein L is xlected from the group consisting of:
Y R3 R3Y
-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 which provide organic
peracids as described herein ring-opens as a consequence of., the nucleophilic
attack on the carbonyl carbon of the cyclic ring by the perhydroxide anion.
This ring-opening reaction involves attack at the ring carbonyl by hydrogen
2 5 peroxide or its anion Examples of ring-opening bleach activators can be
found
in U.S. Patent 4,966,723) Hodge et al, issued Oct. 30) 1990.
Such activator compounds disclosed by Hodge include the activators of
the benzoxazin-type) having the formula:
O
C
O
of
,~~-R,
N
including the substituted benaoxaz~ns of the type

WO 94/28104 ~ i PCTlUS94/05370
.o
o '-
~N4C
wherein R 1 is H, alkyl) alkaryl, aryl, aral~Cyl, and wherein R2) R3) R4, and
RS
may be the same or different substituqnts selected from H) halogen, alkyl,
alkenyl, aryl) hydroxyl) alkoxyl) amino, a~kyl-amino) COOR6 (wherein R6 is H
0 or an alkyl group) and carbonyl functions
A preferred activator of the benzc~xavn-type is:
II
C
I;
is o
0
N
The bleach activators employed herein will comprise at least about
0. I %, preferably from about 0.1 % to about 50%, more preferably from about
1% to about 30%, most preferably from out 3% to about 25%) by weight of
20 the bleaching system or detergent composlNnon.
When the activators are used, op>~imum surface bleaching performance
is obtained with washing solutions whereiln the pH of such solution is between
about 8.5 and 10.5 and preferably betwejen 9.5 and 10.5 in order to facilitate
the perhydrolysis reaction. Such pH can b~ obtained with substances commonly
25 known as buffering agents) which are olptional components of the bleaching
systems herein.
The Peroxygen Bleaching Compound
The bleaching systems, wherein thie bleach activator is used, also have
as an essential component a peroxygen bileach capable of releasing hydrogen
30 peroxide in aqueous solution.
The peroxygen bleaching systems; useful herein are those capable of
yielding hydrogen peroxide in an aqueousE liquor. These compounds are well
known in the an and include hydrogen perioxide and the alkali metal peroxides)
organic peroxide bleaching compounds such as urea peroxide, and inorganic
35 persalt bleaching compounds, such its the alkali metal perborates)

WO 94/28104 f.' ~ ~ ~2 ~ PCT/US94/05370
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 foam of mono-) tri-, and tetra-hydrate, sodium
5 percarbonate) sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and
sodium peroxide. Particularly preferred are sodium perborate tetrahydrate,
sodium perborate monohydrate and sodium percarbonate. Sodium
pacarbonate 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
t 0 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 siu 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. I %)
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 the
10 bleaching rystem or detergent composition.
The weight ratio of bleach activator to peroxygen bleaching compound
in the bleaching system ranges form about 2:1 to about 1:5. In preferred
embodiments) the ratio ranges from about 1:1 to about I :3.
The bleach activator/bleaching compound rystems herein are uxful pcr
2 5 x as bleaches. However, such bleaching rystems are especially useful in
compositions which can comprix various detersive adjuncts such as sur
factants, builders, enzymes, and the like as disclosed hereinafter.
petersive Surfactant
The amount of detersive surfactant included in the fully-formulated
30 detergent compositions afforded by the present invention can vary from
about
1% to about 99.8% by weight of detergent composition depending upon the
particular surfactants used and the effects desired. Preferably) the detersive
surfactants comprise from about 5% to about 80% by weight of the
composition.
35 The detersive surfactant can be nonionic, anionic) ampholytic,
zwitterionic, or cationic. Mixtures of these surfactants can also be used.

WO 94/28104 ~~ ~ ~ ~~ ~ ~ PCT/US94/05370
11
Preferred detergent compositions corr~prise anionic detersive surfactants or
mixtures of anionic surfactants with ;other surfactants, especially nonionic
surfactants.
Nonlimiting exaJnples of suil~factants useful herein include the
conventional C 11-C 18 alkyl benzene slulfonates and primary) secondary, and
random alkyl sulfates) the C 1 ~-C 18 all~yl aJkoxy sulfates, the C 10-C 18
alkyl
polyglycosides and their correspondiyg sulfated polyglycosides) C 12-C 18
alpha-sulfonated fatty acid esters) C 12-'C 18 alkyl and alkyl phenol
alkoxylates
(especially ethoxylates and mixed ethpxylpropoxy), C 12-C 18 betaines and
sulfobetaines ("sultaines"), C 1 p-C 18 amine oxides) and the like. Other
conven-
tional useful surfactants are listed in sta.n~dard texts.
One particular class of adjunct nonionic surfactants especially useful
herein comprises the polyhydroxy fatty ajcid amides of the formula:
i5 2,;,0 R
(1) R vC-N-Z
wherein: R 1 is H, C 1-Cg hydrocart~yl) ;~-hydroxyethyl, 2-hydroxypropyl) or a
mixture thereof) preferably C 1-C4 alkyl,! more preferably C 1 or C2 alkyl)
most
preferably C 1 alkyl (i.e., methyl); and jR2 is a CS-C32 hydrocarbyl moiety)
preferably straight chain C~-C I 9 alkyl ~, or alkenyl) more preferably
straight
chain C9-C I ~ alkyl or aJkenyl) most pref~Crably straight chain C 11-C 19
alkyl or
aJkenyl, or mixture thereof; and Z is a pa~yhydroxyhydrocarbyl moiety having a
linear hydrocarbyl chain with at least 2.(in the case of glyceraldehyde) or at
least 3 hydroxyls (in the case of other rj~ducing sugars) directly connected
to
the chain, or an alkoxylated derivative (preferably ethoxylated or
propoxylated)
thereof. Z preferably will be derived f~om a reducing sugar in a reductive
amination reaction; more preferably Z is~ a glycityl moiety. Suitable reducing
sugars include glucose, fructose, maltose, lactose) galactose) mannose) and
xyiose) a well as glyceraldehyde. As nor materials) high dextrose corn syrup,
high fructose corn syrup, and high maJtosle corn syrup can be utilized as well
as
the individual sugars listed above. These; corn syrups may yield a mix of
sugar
components for Z. It should be understood that it is by no means intended to
exclude other suitable raw materials. Z', preferably will be selected from the
group consisting of -CH2-(CHOH)n-C~H20H) -CH(CH20H)-(CHOH)n-1-
-CH20H, -CH2-(CHOH)2(CHOR')(CHI~H)-CH20H) where n is an integer
from 1 to 5, inclusive) and R' is H or a cyclic mono- or poly- saccharide, and

WO 94/28104 PCT/US94/05370
zml~~~
12
alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4
particularly -CH2-(CHOH)4-CH20H.
In Formula (I), R1 can be) for example) N-methyl, N-ethyl, N-propyl)
N-isopropyl) N-butyl) N-isobutyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
For highest sudsing, R I is preferably methyl or hydroxyalkyl. If lower
sudsing
is desired) R1 is preferably C2-C8 alkyl) especially n-propyl) iso-propyl,
n-butyl, iso-butyl, pentyl) hexyl and 2-ethyl hexyl.
R2-CO-N~ can be) for example) cocamide) stearamide, oleamide)
Isuramide) myristamide, capricamide, palmitamide) tallowamide) etc.
l0 ~sive Builders
Optional detergent ingredients employed in the present invention
contain inorganic and/or organic detersive builders to assist in mineral
hardness
control. If used) these builders comprise from about 5% to about 80% by
weight of the detergent compositions.
Inorganic detersive builders include) but are not limited to, the alkali
metal) ammonium and alkanolammonium salts of polyphosphates (exemplified
by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-
phosphates), phosphonates, phytic acid) silicates, carbonates (including
bicarbonates and sesquicartionates)) sulphates) and aluminosilicates. However)
10 non-phosphate builders are required in some locales.
Examples of silicate builders are the alkali metal silicates) particularly
those having a Si02:Na20 ratio in the range 1.6:I to 3.2:1 and layered
silicates) such as the layered sodium silicates described in U.S. Patent
4,664,839, issued May 12, 1987 to H. P. Rieck, available from Hoechst under
the trademark'SKS'; SKS-b is an especially preferred layered silicate builder.
Carbonate builders, especially a finely ground calcium carbonate with
surface area greater than 10 m2/g, are preferred builders that can be used in
granular compositions The density of such alkali metal carbonate built
detergents can be in the range of 450-850 g/I with the moisture content
preferably below 4~/..
Examples of carbonate builders are the alkaline earth and alkali metal
carbonates as disclosed in German Patent Application No. 2,321,001 published
on November l5) 1973.
Aluminosilicate builders are especially useful in the present invention.
Preferred aluminosilicates are zeolite builders which have the formula:
NaZI(A102)Z (Si02)y)'xH20

~~s~ ~r~
WO 94/28104 ~ PCT/US94/05370
13
wherein z and y are integers of at leas~l 6, the molar ratio of z to y is in
the
range from 1.0 to about 0.5, and x is an integer from about l5.to about 264.
Useful aluminosilicate ion extchange materials are commercially
available. These aluminosiiicates can b~~ crystalline or amorphous in
structure
and can be naturally-occurring alurtuinosilicates or synthetically derived.
Methods for producing aluminosilicate iion exchange materials are disclosed in
U.S. Patent 3,985,669) Krummel) et all) issued October 12, 1976) and U.S.
Patent 4,605,509) Corkill) et al) issued Aug. 12, 1986. Preferred synthetic
crystalline aluminosilicate ion exchanger materials useful herein are
available
t o under the designations Zeolite A) Zeolite P (B), (including those
disclosed in
EPO 384,070)) and Zeolite X. Prefer~ly, the aluminosilicate has a particle
size of about 0.1-10 microns in diameter;
Organic detersive builders suitable for the purposes of the present
invention include, but are not restricted' to) a wide variety of
polycarboxylate
compounds) such as ether polycarbo;irylates) including oxydisuccinate) as
disclosed in Berg) U.S. Patent 3) 128,287 issued April 7) 1964) and Lamberti
et
al) U.S. Patent 3,635,830) issued lanu~ry 18, 1972. See also "TMSrfDS"
builders of U.S. Patent 4,663,071) issued to Bush et al) on May 5) 1987.
Other useful detersive builders include the ether hydroxypolycar
boxylates, copolymers of malefic anhydride with ethylene or vinyl methyl
ether)
l ) 3) 5-trihydroxy beruene-2) 4, 6-trisulphonic acid) and carboxymethyl
oxysuccinic acid, the vuious alksli ~ metal, ammonium and substituted
ammonium salts of polyscetic acids ~ sucph as ethylenediamine tetraacetic acid
and nitrilotriacetic acid, as well as pdlycartioxylates such as mellitic acid)
succinic acid) oxydisuccinic acid, polymjlleic acid) benzene 1,3,5-
tticarboxylic
acid) carboxymethyloxysuccinic acid) ands soluble salts thereof.
Citrate builders, a g., citric acid jand soluble salts thereof (particularly
sodium salt), are preferred polycarboxyl~ate builders that can also be used in
granular compositions, especially in co~Inbination with zeolite and/or layered
3o silicate builders.
Also suitable in the detergent conhpositions of the present invention are
the 3,3-dicarboxy-4-oxa-1,6-hexanodio~Ittes and the related compounds
disclosed in U.S. Patent 4,566,984) Bush; issued January 28) 1986.
In situations where phosphorus-based builders can be used) and
especially in the formulation of bars used for hand-laundering operations) the
various alkali metal phosphates such as the well-known sodium

WO 94/28104 a PCT/US94/05370
~ 161 ~ ~. ~-
14
tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be
used. Phosphonate builders such as ethane-1-hydroxy-1) 1-diphosphonate and
other known phosphonates (see) for example) U.S. Patents 3,159,581;
3,213,030; 3,422,021; 3,400) 148 and 3,422) 137) can also be used.
Optional Detersive Ad,'ui nets
As a preferred embodiment) the conventional detergent ingredients
employed herein can be selected from typical detergent composition
components such as detersive surfactants and detersive builders. Optionally)
the detergent ingedients can include one or more other detersive adjuncts or
other materials for assisting or enhancing cleaning performance, treatment of
the wbstrate to be cleaned, or to modify the aesthetics of the detergent
composition. Usual detersive adjuncts of detergent compositions include the.
ingedients set forth in U.S. Pat. No. 3,936,537) Baskerville et al. Adjuncts
which can also be included in detergent compositions employed in the present
invention, in their conventional art-established levels for use (generally
from
0% to about 20°/. of the detergent ingedients) preferably from about
0.5% to
about 10%), include enzymes) especially proteases, lipases) and cellulases,
color speckles, wds boosters) wds suppressors) antitarnish and/or
anticorrosion agents, soil-wspending agents, soil release agents) dyes)
fillers,
optical brighteners, germicides, alkalinity sources) hydrotropes)
antioxidants)
enzyme stabiliang agents) perfumes) solvents) solubilizing agents) clay soil
removaUanti-redeposition agents) polymeric dispersing agents,_processing aids)
fabric softening components, static control agents, etc.
Bleach systems optionally, but preferably) will also comprise a chelant
which not only enhances bleach stability by scavenging heavy metal ions which
tend to decompose bleaches, but also assists in the removal of polyphenolic
stains such as tea stains, and the like. Various chelants, including the amino
phosphonates) available as DEQUEST from Monsanto, the nitrilotriacetates,
the hydroxyethyl-ethylenediamine triacetates, and the like) are known for such
use. Preferred biodegradable) non-phosphorus chelants include ethylene-
diamine diwccinate ("EDDS"; set U.S. Patent 4,704,233) Hartman and
Perkins)) ethylenediamine-N,N-diglutamate (EDDG) and 2-hydroxypro-
pylenediamine-N,N-diwccinate (I~DDS) compounds. Such chelants can be
used in their alkali or alkaline earth metal salts) typically at levels from
about
0. I % to about 10°/, of the present compositions.

WO 94/28104 ~ .~ ~ ~ ~ I 1'CT/US94/05370
Optionally, the detergent compositions employed herein can comprise,
in addition to the bleaching system of that present invention) one or more
other
conventional bleaching agents) activator.i, or stabilizers which do not react
with
or otherwise harm natural nrbber. In general) the formulator will ensure that
the bleach compounds used are compittible with the detergent formulation.
Conventional tesu) such as tests of bleach activity on storage in the presence
of
the separate or fully-formulated ingredients, can be used for this purpose.
Specific examples of optional blekch activators for incorporation in this
invention include tetraacetyl ethylerpe diamine (TAED) and N-acyl
t o uprolactams. Highly preferred N-t<cyl caprolactams include benzoyl
caprolactam and those wherein the acy~ moieties have the formula R I -CO-
wherein R I is H or an alkyl, aryl) arkaryll) or alkoxyaryl group containing
from
I to 12 carbon atoms, preferably 1 to 6 Gltrbon atoms.
Such bleaching compounds and agents can be optionally included in
detergent compositions in their conveytional art-established levels of use)
generally from 0% to about 15%, by weight of detergent composition.
Bleaching activators of the invention are especially useful in
conventional laundry detergent compositiions such as those typically found in
granular detergents or laundry bars. U.~G. Patent 3) 178,370, Okenfuss) issued
April 13) 1965, describes laundry detergent bars and processes for making
them. Philippine Patent 13,778, Andersen) issued Sept. 23, 1980, describes
synthetic detergent laundry bars. Methods for making laundry detergent bars
by various extrusion methods are well kndwn in the art.
The following examples are given to further illustrate the present
invention) but are not intended to be limitijng thereof.
FX~MP E I
Synthesis of (6-Nonanamidocaproyl)oxyb~tnzenesulfonate (NACA-OBS).
6-Nonanamidocaproic Acid (NAC'~A,) - The reaction is carried out in a
12L 3-necked flask equipped with a '~ thermometer) addition funnel and
mechanical stirrer. To a solution madet from 2128 (5.3 moles) of sodium
hydroxide and 6L of water (cooled to rocarr temperature) is added 694.38 (5.3
moles) of 6-aminocaproic acid. This mixture is cooled to 10°C and a
solution
of 694.38 (5.~ moles) of nonanoyl chloride in I L of ether is added in a slow
stream (about 2.5 hours) keeping the temperature at 10-15°C. During the
addition, and subsequently until acidification) the reaction is maintained at
pH
11-12 by periodic addition of 50% NaOH, ARer the addition is complete, the

WO 94/28104 ~) PCT/US94/05370
16
reaction is stirred for another 2 hours at 10°C and allowed to come to
room
temperature before acidification to pH 1 with conc. HCI. The precipitated
product is vacuum filtered) the filter cake is washed twice with 8L portions
of
water and the product air dried overnight. It is then suspended in 3L of
hexane) filtered and washed with an additional 3L of hexane. The product is
then vacuum dried overnight (50°C) 1 mm) to give 1354 g (94%) of NACA.
Acid Chloride (NACA-CIl - The reaction is carried out in a SL,
3-necked flask equipped with an addition funnel, mechanical stirrer and argon
sweep. To a susperuion of 5428 (2.0 moles) of NACA in 2L of toluene is
added (in a slow stream over 30 minutes) 476 g (4.0 moles) of thionyl
chloride.
This mixture is stirred at room temperature for four hours during which time
the solids dissolve. The solution is partially evaporated (30°C) 10 mm)
to
remove any excess thionyl chloride leaving 905g of NACA-CUtoluene solution
(contains approximately 2 moles of NACA-CI). An IR spectrum confirms
conversion of COOH to COCI.
(6-Nonanamidocapro I~xYbenzenesulfonate yACA-OBS) - The
reactor is a 12L, 3-necked flask equipped with a condenser) mechanical stirrer
and static argon supply. To the reactor are added 647g of the above
NACA-CUtoluene solution ( I 43 moles), 6L of toluene and 310.8g ( 1.43
moles) of disodium p-phenolsulfonate (disodium p-phenolsulfonate is
previously prepared and dried in a vacuum oven before use ( 1 I 0°C)
0.1 mm hg)
18 hours). This mixture is refluxed for 18 hours. After cooling to room
temperature, the product is collected on a Buchner funnel and dried to give
725g of rnrde solids. The crude is taken up in 7L of refluxing 87:13 (v,v)
2 5 methanoUwater) filtered hot and allowed to recrystallize at room
temperature.
The resulting precipitate is filtered and vacuum dried (50°C, 0.1 mm)
for 18
hours to give 4108 (64% based on NACA) of light tan product. A trace of
unreacted phenolsulfonate is indicated by the small doublets at 6.75 and 7.55
ppm in the 1 H spectrum Otherwise, the spectra are consistent with expected
structure and no other impurities are evident.
EXAMPLE 11
A granular detergent compositions is prepared comprising the following
ingredients.
m n nt Wei h8 t
C 12 linear alkyl benzene sulfonate 22
Phosphate (as sodium tripolyphosphate) 30

WO 94/28104 PCT/US94/05370
'~1.6~.~1~
Sodium carbonate 14
Sodium silicate 3
Sodium percartionate 5
Ethylenediamine disuccinate cheliant (EDDS) 0.4
Sodium sulfate 5.5
(6-Nonanamidocaproyl)oxybenz~~nesulfonate 5
Minors, filler' and water Balance to 100%
'Can be selected from convenient materiuaals such as CaC03, talc) clay)
silicates)
and the like.
In testing the bleaching performance and effect on natural rubber
washing machine parts) the following test method is used:
Aqueous crutcher mixes of heat and alkali stable components of the
detergent compositions are prepared anjd spray-dried. The other ingredients
are admixed so that the composition cokrtains the ingredients tabulated at the
levels shown.
The detergent granules with blea~eh activator are added together with 5
Ib. (2.3 kg) of previously laundered fat~rics) including natural rubber
articles
such as elastic fabrics, to an automatic washing machine equipped with a
natural rubber sump hose. Actual weighty of detergent and bleach activator are
taken to provide a 950 ppm concenyration of the former and 50 ppm
concentration of the latter in the 17 gallon (65 1) water-fill machine. The
water
used has 7 grains/gallon hardness and ~a; pH of 7 to 7.5 prior to (about 9 to
about 10.5 aRa) addition of the detergent and bleaching system.
The fabrics are laundered at 35°C~ (95°F) for a full cycle
(12 min.) and
rinsed at 21 oC (70oF). The IaunderinB~ method is repeated for 2,000 wash
cycles without rupture of) or significant dlamage to) the natural rubber pans,
or
damage to the natural rubber articles.
EXAMPI;.E III
A granular detergent composition is prepared comprising the following
ingredients.
n n , Weightht%
Anionic alkyl sulfate 7
Nonionic surfactant
Zeolite (0. I - I 0 micron) I p
Trisodium citrate 2
SKS-6 silicate builder I p

X161211
WO 94/28104 PCT/US94/05370
18
Acrylaie maleate polymer 4
(6-Nonanamidocaproyl~xybenzenesulfonate 5
Sodium percarbonate 15
Sodium carbonate 5
Ethylenediamine disuccinate chelant (EDDS) 0.4
Suds suppresser 2
E~~' 1. 5
Soil release agent 0.2
Minors) filler" and water Balance to 100%
' 1: I :1 mixture of proteax) lipax) and cellulase.
"Can be xleaed from convenient materials such as CaC03) talc, clay,
silicates) and the like.
In testing the bleaching performance and effect on natural rubber
washing machine parts) the following test method is used:
Aqueous rnrtcher mixes of heat and alkali stable components of the
detergent composition are prepared and spray-dried. the other ingredients are
admixed so that the composition contains the ingredients tabulated at the
levels
shown.
The detergent granules with bleach activator are added via the
dispensing drawer together with 5 Ib. (2.3 kg) of previously laundered fabrics
to an automatic washing machine equipped with a natural rubber sump hose.
Actual weights of detergent and bleach activator are taken to provide a 8,000
ppm concentration of the former and 400 ppm concentration of the latter in the
17 1 water-fill machine. The water used has 7 grains/gallon hardness and a pH
of 7 to 7.5 prior to (about 9 to about 10.5 at3er) addition of the detergent
and
bleaching rystem.
The fabrics are laundered at 40oC ( 104oF) for a full cycle (40 min. ) and
rinxd at 21 oC (70oF). The laundering method is repeated for 2,000 wash
rycles without rupture of, or significant damage to) the natural nrbber parts.
3o EXAMPLE IV
A detergent composition is prepared by a procedure identical to that of
Example III, with the single exception that an equivalent amount of
nonanoyloxybenzenesulfonate (HOBS) is substituted for the (6-Nonanamido-
caproyl)oxybenzenesulfonate bleach activator in Example III. The laundering
method of Example III is repeated for 1200 cycles at about which time the
natural rubber sump hex ruptures.

PCT/US94/05370
WO 94/28104
19
EXAIyC LE V
A detergent composition is prepared by a procedure identical to that of
Example III, with the single exception that an equivalent amount of
benzoyloxybenzenesulfonate (BOBS) i:p substituted for the (6-Nonanamido-
caproyl~xybenzenesulfonate bleach activator in Example III. The laundering
method of Example III is repeated fore 1200 cycles at about which time the
natural rubber sump hose ruptures.
E_~LE VI
A detergent composition is prepared by a procedure identical to that of
Example III) with the exceptions that ~: I S% of a l : l mixture of
tetraacetyl
ethylene diamine and (6-Nonanamidbcaproyl)oxybenzenesulfonate bleach
activator is substituted for the bleach acitivator in Example III and the
amount
of sodium percarbonate is 30%. The Maundering method of Example III is
repeated for 2,000 rycles without rupt~rre of) or significant damage to, the
natural rubber parts.
EXAMP E VI1
A detergent composition is prepared by a procedure identical to that of
Example III, with the single exception ~khat I S% of a l : l mixture of
benzoyl
caprolactam and (6-Nonanamidocaproyl;'oxybenzenesulfonate is substituted for
2o the bleach activator in Example III and the amount of sodium percarbonate
is
30%. The laundering method of Exar~tple 1II is repeated for 2,000 cycles
without rupture of, or significant damaged to, the natural rubber parts.
EXAMPI~,E V111
A detergent composition is prepared by a procedure identical to that of
.5 Example III, with an equivalent amolunt of a benzoxazin-type bleaching
activator, as disclosed in U.S. Pstent 4,9166,723, Hodge et al, is substituted
for
the bleach activator in Example III. Thy laundering method of Example III is
repeated for 2,000 rycles without ruptjure of, or significant damase to) the
natural rubber parts.
3o EXAMP E tX
A detergent composition is prepared by a procedure identical to that of
Example III) with the single exception tlhat 6% of a 1:1 mixture of (6-Nonan-
amidocaproyl)oxybenzenesulfonate and ~k benzoxazin-type bleaching activator,
as disclosed in U.S Patent 4,966,723) H~pdge et al) is substituted for the
bleach
35 activator in Example 111. The laundering. method of Example III is repeated
for

WO 94/28104 ~ PCT/US94105370
:~1~ ~.'~
2,000 cycles without rupture of) or significant damage to, the natural rubber
parts.
~, LE X
A detergent composition is preps~red by a procedure identical to that of
5 Example III) with the single exception t~tat 6% of a 1:1 mixture of
tetraacetyl
ethylene diamine and a benzoxazin-typie bleaching activator, as disclosed in
U.S. Patent 4,966,723, Hedge et al) is ,substituted for the bleach activator
in
Example III. The laundering method of Example III is repeated for 2,000
cycles without rupture of) or significant yamage to) the natural rubber parts.
10 Method of Processing 'the Bleach Activators
The bleach activators may be plrocessed with a range of organic and
inorganic substance to achieve a rapid dispersion in the bleaching Liquor and
to
insure good stability in the detergent ccbmposition. The bleach activators are
preferably employed in partiarlate form. i
15 An example of preferred caproluactam bleach activator particles is an
agglomerate of about 65%) by weight,, benzoyl caprolactam; about 7% of a
builder, such as aluminium silicate; about 15% sodium carbonate; about 9%
dispersant, such as a polyacrylate poly~tner; and about 4% of a solubilizing
agent) such as a linear alkyl sulfonatie. Another example of a preferred
20 caprolactam bleach activator particle is ~n agglomerate of about 80% to
about
85%, by weight, benioyl aprolactam ~ and about 15% to about 20% of a
binder) such as tallow alcohol ethoxylate~) preferably TAE25.
An example of a preferred ar~ido-derived bleach activator particle
comprises a 1:1:1 mixture of (6-octanajmidocaproyl)oxybenzenesulfonate) (6
decanamidocaproyl~xyben~enesulfonate~) and citric acid powder. The mixture
is intimately mixed in a food mixer for 5~-10 minutes. To the resultant
mixture
is added tallow alcohol ethoxylate (TAE~25) nonionic surfactant at SOo C until
granules are formed. Typically successful granulations are achieved with a
ratio of bleach aaivator/citric acid solid mixtures:nonionic binding agent of
3.5:1. The resultant granules) ellipsodia~I and spherical in shape) are white
and
free flowing.
A typical particle composition i~~ about 40% to about 60%) preferably
about 55%) by weight, of the bleach ac>Givator or mixture of bleach
activators;
about 20% to about 40%) preferably ab6ut 25%, by weight, of citric acid; and
about 15% to about 30%) preferably ab~put 20%, by weight of TAE25 binding
agent. Alternatively, a 2:1 mixtmre of (6-decanamidocaproyl)oxyben-

~16~.2:~1
WO 94/28104 PCT/US94105370
21
zenesulfonate and citric acid powder. may be used. In this case, the
composition on the granule is SS% bleayh activator, 2S% citric acid, and 20%
TAE2S binding agent. Other preferred organic binding agents include anionic
surfactants (C 12 linear alkyl benzene ,~ulfonates)) polyethylene glycols) and
TAESO.
The particle size of the resulting granules may be varied according to
the desired performanceJstability. Fine panicles (<2S0 um) show improved
solubility) though coarse particles (>~ 180 um) are more stable at high
temperatures/moist environment. A tylpically preferred particle size range is
2S4-1180 um; particles conforming to thus specification show excellent
stability
end solubility. v
~XAMP~LE XI
A laundry bar suitable for hand~~washing soiled fabrics is prepared by
standard extrusion processes and comprises the following:
m n n Weir
C 12 linear alkyl benzene sulfonate 30
Phosphate (as sodium tripolypho;sphate) 7
Sodium carbonate 2S
Sodium pyrophosphate 7
Coconut monoethanolamide 2
Zeolite A (0.1-10 micron) S
Carboxymethylcellulose 0.2
Ethylenediamine disuccinate chel,itnt (EDDS) 0.4
Polyacrylate (m.w. 1400) 0.2
2 S (6-Nonanamidocaproyl)~xybenzelnesulfonateS
Sodium percarbonate' S
Brightener, perfume 0.2
Protease 0.3
CaS04 1
MgS04 1
Water 4
Filler" Balance to 100%
'Average particle size of 400 to 1200 miicrons.
"Can be selected from convenient nitaterials such as CaC03) talc) clay)
silicates, and the like

WO 94/28104 v ~ PCT/US94/05370
~~~~~1~
22
The detergent laundry bars acre processed in conventional soap or
detergent bar making equipment as cpmmonly used in the art: Testing is
conducted following the testing mettwods in Example II. The laundering
method is repeated for 2,000 wash cycles without rupture of) or significant
damage to, the natural rubber parts) or namage to the natural rubber articles.