CONTROLLED AVAILABILITY OF FORMULATION COMPONENTS, COMPOSITIONS AND LAUNDRY METHODS EMPLOYING SAME

DISPONIBILITE CONTROLEE DE COMPOSANTS DE FORMULATION, COMPOSITIONS ET PROCEDE DE BLANCHISSAGE UTILISANT CES PRODUITS

English Abstract

The present invention relates to a method for the controlled availability of
formulation components, such as organic catalysts, into a wash solution. More
particularly, the present invention relates to products and bleaching
compositions containing such formulation components and laundry methods
employing such formulation components.

French Abstract

L'invention concerne un procédé pour la disponibilité contrôlée de composants de formulation, tels que des catalyseurs organiques, dans une solution de lavage. Plus particulièrement, l'invention concerne des produits et des compositions de blanchiment contenant de tels composants de formulation, ainsi que des procédés de blanchissage utilisant de tels composants de formulation.

Claims

WHAT IS CLAIMED IS:
1. A method for laundering comprising contacting a fabric in need of cleaning
with an
organic catalyst by a controlled availability method.
2. The method according to Claim 1 wherein said organic catalyst is selected
from the group
consisting of:
a) aryliminium cations and aryliminium polyions, which have a net charge of
from
about +3 to about -3, that are represented by the formula [I]:
<IMG>
where R2 and R3 are independently selected from substituted or unsubstituted
radicals selected
from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl,
heterocyclic ring, silyl,
nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy
radicals; R1 and R4 are
selected from substituted or unsubstituted, saturated or unsaturated radicals
selected from the
group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic
ring, silyl, nitro, halo,
cyano, alkoxy, keto and carboalkoxy radicals; and X- is a suitable charge-
balancing counterion;
and v is an integer from 1 to 3;
b) aryliminium zwitterions, which have a net charge of from about +3 to about -
3,
that are represented by the formula [II]:
<IMG>
where R5-R7 are independently selected from substituted or unsubstituted
radicals selected from
the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl,
heterocyclic ring, silyl, nitro,
halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy radicals;
also present in this
formula is the radical represented by the formula:
77

<IMG>
where Z p- is covalently bonded to T o, and Z p- is selected from the group
consisting of
-CO2-, -SO3-, -OSO3-, -SO2- and -OSO2- and p is either 1, 2 or 3; T o is
selected from the group
consisting of substituted or unsubstituted, saturated or unsaturated alkyl,
cycloalkyl, aryl, alkaryl,
aralkyl, and heterocyclic ring;
c) modified amines, which have a net charge of from about -3 to about +3, that
are
represented by formulas [V] and [VI]:
<IMGS>
where R9-R10 are independently selected from substituted or unsubstituted
radicals selected from
the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl,
heterocyclic ring, silyl, vitro,
halo, cyano, sulfonato; alkoxy, keto, carboxylic, and carboalkoxy radicals and
anionic and/or
cationic charge carrying radicals; R8 and R11, when present, are radicals
selected from the group
consisting of substituted or unsubstituted, saturated or unsaturated H, alkyl,
cycloalkyl, aryl,
alkaryl, aralkyl, heterocyclic ring, silyl, vitro, halo, cyano, alkoxy, keto
and carboalkoxy radicals
and anionic and/or cationic charge carrying radicals; R12 is a leaving group,
the protonated form
of which has a pK a value (H2O reference) that falls within the following
range: 37 > pK a > -2;
with the proviso that any R8-R12, when present, may combine to form a fused
aryl, fused
carbocyclic or fused heterocyclic ring; and the radical represented by the
formula:
<IMG>
where ZP- is covalently bonded to T o, and Z p- is selected from the group
consisting of
-CO2-, -SO3-, -OSO3-, -SO2- and -OSO2- and p is either 1, 2 or 3; T o is
selected from the group
consisting of substituted or unsubstituted, saturated or unsaturated alkyl,
cycloalkyl, aryl, alkaryl,
aralkyl, and heterocyclic ring;
d) modified amine oxides, which have a net charge of from about -3 to about
+3,
that are represented by formulas [VII]-[X]:
78

<IMGS>
where R9-R10 are independently selected from substituted or unsubstituted
radicals selected from
the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl,
heterocyclic ring, silyl, nitro,
halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy radicals and
anionic and/or
cationic charge carrying radicals; R8 and R11 are radicals selected from the
group consisting of
substituted or unsubstituted, saturated or unsaturated H, alkyl, cycloalkyl,
aryl, alkaryl, aralkyl,
heterocyclic ring, silyl, nitro, halo, cyano, sulfonato, alkoxy, keto,
carboxylic, and carboalkoxy
radicals and anionic and/or cationic charge carrying radicals; R12 is a
leaving group, the
protonated form of which has a pK a value (H2O reference) that falls within
the following range:
37 > pK a > -2; with the proviso that any R8-R12, when present, may combine to
form a fused
aryl, fused carbocyclic or fused heterocyclic ring; and also present in this
formula is the radical
represented by the formula:
<IMG>
where Z P- is covalently bonded to T o, and Z p- is selected from the group
consisting of
-CO2-, -SO3-, -OSO3-, -SO2- and -OSO2- and p is either 1, 2 or 3; T o is
selected from the group
consisting of substituted or unsubstituted, saturated or unsaturated alkyl,
cycloalkyl, aryl, alkaryl,
aralkyl, and heterocyclic ring;
e) sulfonimines, phosphonimines, N-acylimines and thiodiazole dioxides that
are
represented by the formulas [XXIa], [XXIb], [XXII] and [XXIII], respectively:
79

<IMGS>
where R41-R44, when present, are independently selected from substituted or
unsubstituted,
saturated or unsaturated radicals selected from the group consisting of H,
alkyl, cycloalkyl, aryl,
alkaryl, aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, sulfonato,
alkoxy, keto, carboxylic, and
carboalkoxy radicals; provided that any of R41-R44 may be joined together with
any other R41-
R44 to form part of a common ring, including a fused aryl, fused carbocyclic
or fused
heterocyclic ring;
f) oxaziridinium canons and polyions, which have a net charge of from about +3
to
about -3, that are represented by the formula [III]:
<IMG>
where R2'-R3' are independently selected from substituted or unsubstituted
radicals selected from
the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl,
heterocyclic ring, silyl, nitro,
halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy radicals;
R1' and R4' are
radicals selected from the group consisting of substituted or unsubstituted,
saturated or
unsaturated, H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring,
silyl, nitro, halo, cyano,
alkoxy, keto and carboalkoxy radicals; and X- is a suitable charge-balancing
counterion,
preferably a bleach-compatible counterion;
g) oxaziridinium zwitterions, which have a net charge of from about +3 to
about -3,
that are represented by formula [IV]:
<IMG>

where R5'-R7' are independently selected from substituted or unsubstituted
radicals selected from
the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl,
heterocyclic ring, silyl, nitro,
halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy radicals;
also present in this
formula is the radical represented by the formula:
<IMG>
where Z'p- is covalently bonded to T'o, and Z'p is selected from the group
consisting of -CO2-, -
SO3-, -OSO3-, -SO2- and -OSO2- and p is either 1, 2 or 3; T'o is selected from
the group
consisting of substituted or unsubstituted, saturated or unsaturated alkyl,
cycloalkyl, aryl, alkaryl,
aralkyl, and heterocyclic ring;
h) oxaziridine sulfonimines [XXIVa], phosphonimines [XXIVb], N-acylimines
[XXV]
and thiodiazole dioxides [XXVI] and [XXVII] are represented as follows:
<IMGS>
where R41'-R44', when present, are independently selected from substituted or
unsubstituted
radicals selected from the group consisting of H, alkyl, cycloalkyl, aryl,
alkaryl, aralkyl,
heterocyclic ring, silyl, nitro, halo, cyano, sulfonato, alkoxy, keto,
carboxylic, carboalkoxy
radicals, provided that any of R41'-R44' may be joined together with any other
R41'-R44' to form
part of a common ring, including a fused aryl, fused carbocyclic or fused
heterocyclic ring; and.
i) mixtures thereof.
81

3. The method according to Claim 2 wherein the organic catalyst is selected
from the group
consisting of:
a) aryliminium canons and aryliminium polyions, which have a net charge of
from
about +3 to about -3, that are represented by the formula [XI]:
<IMG>
where m is 1 to 3 when G is present and m is 1 to 4 when G is not present; and
n is an integer
from 0 to 4; each R20 is independently selected from a substituted or
unsubstituted radical
selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused aryl,
heterocyclic ring,
fused heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto,
carboxylic, and carboalkoxy
radicals, and any two vicinal R20 substituents may combine to form a fused
aryl, fused
carbocyclic or fused heterocyclic ring; R18 may be a substituted or
unsubstituted radical selected
from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl,
heterocyclic ring, silyl,
nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy
radicals; R19 is a radical
selected from the group consisting of substituted or unsubstituted, saturated
or unsaturated, H,
alkyl, cycloalkyl, alkaryl, aryl, aralkyl and heterocyclic ring; G is selected
from the group
consisting of: (1) -O- ; (2) -N(R23)-; and (3) -N(R23R24)-; R21-R24 are
substituted or
unsubstituted radicals independently selected from the group consisting of H,
oxygen, linear or
branched C1-C12 alkyls, alkylenes, alkoxys, aryls, alkaryls, aralkyls,
cycloalkyls, and
heterocyclic rings; provided that any of R18, R19, R20, R21 -R24 may be joined
together with any
other of R18, R19, R20, R21-R24 to form part of a common ring; any geminal R21-
R22 may
combine to form a carbonyl; any vicinal R21-R24 may join to form unsaturation;
and wherein any
one group of substituents R21-R24 may combine to form a substituted or
unsubstituted fused
unsaturated moiety; X- is a suitable charge-balancing counterion; and v is an
integer from 1 to 3;
b) aryliminium zwitterions, which have a net charge of from about +3 to about -
3,
that are represented by the formula [XII]:
82

<IMG>
where m is 1 to 3 when G is present and m is 1 to 4 when G is not present; and
n is an integer
from 0 to 4; each R26 is independently selected from a substituted or
unsubstituted radical
selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused aryl,
heterocyclic ring,
fused heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto,
carboxylic, and carboalkoxy
radicals, and any two vicinal R26 substituents may combine to form a fused
aryl, fused
carbocyclic or fused heterocyclic ring; R25 may be a substituted or
unsubstituted radical selected
from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl,
heterocyclic ring, silyl,
nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy
radicals; also present in
this formula is the radical represented by the formula:
<IMG>
where Z p- is covalently bonded to T o, and Z p- is selected from the group
consisting of
-CO2-, -SO3-, -OSO3-, -SO2- and -OSO2- and p is either 1, 2 or 3; T o is
selected from the group
consisting of:
<IMG>
wherein q is an integer from 1 to 8; R29 is independently selected from
substituted or
unsubstituted radicals selected from the group consisting of linear or
branched H, alkyl,
cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxy,
arylcarbonyl, carboxyalkyl
and amide groups; G is selected from the group consisting of: (1) -O- ; (2) -
N(R30)-; and (3)
N(R30R31)-; R27, R28, R30 and R31 are substituted or unsubstituted radicals
independently
selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl,
aryl, aralkyl,
alkylenes, heterocyclic ring, alkoxys, arylcarbonyl groups, carboxyalkyl
groups and amide
groups; any of R25, R26, R27, R28, R30 and R31 may be joined together with any
other of R25,
R26, R27, R28, R30 and R31 to form part of a common ring; any geminal R27 -
R28 may
83

combine to form a carbonyl; any vicinal R27 - R31 may join to form
unsaturation; and wherein
any one group of substituents R27 - R31 may combine to form a substituted or
unsubstituted
fused unsaturated moiety;
c) modified amines that are represented by the formulas [XV] and [XVI]:
<IMGS>
where m is 1 to 3 when G is present and m is 1 to 4 when G is not present; and
n is an integer
from 0 to 4; R34 is a radical selected from the group consisting of
substituted or unsubstituted,
saturated or unsaturated hydroxy, perhydroxy, alkoxy, peralkoxy, carboxylic,
percarboxylic,
sulfonato and persulfonato radicals, each R35 is independently selected from a
substituted or
unsubstituted radical selected from the group consisting of H, alkyl,
cycloalkyl, aryl, fused aryl,
heterocyclic ring, fused heterocyclic ring, nitro, halo, cyano, sulfonato,
alkoxy, keto, carboxylic,
and carboalkoxy radicals, and any two vicinal R35 substituents may combine to
form a fused aryl,
fused carbocyclic or fused heterocyclic ring; R32 may be a substituted or
unsubstituted radical
selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl,
aralkyl, heterocyclic ring,
silyl, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and
carboalkoxy radicals; R33 may
be a substituted or unsubstituted, saturated or unsaturated, radical selected
from the group
consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring,
and also present in this
formula is the radical represented by the formula:
<IMG>
where Z p- is covalently bonded to T o, and Z p, is selected from the group
consisting of
-CO2-, -SO3-, -OSO3-, -SO2- and -OSO2-, and a is either 1, 2 or 3; To is
selected from the group
consisting of:
<IMG>

wherein q is an integer from 1 to 8; R38 is independently selected from
substituted or
unsubstituted radicals selected from the group consisting of linear or
branched H, alkyl,
cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxy,
arylcarbonyl, carboxyalkyl
and amide groups; G is selected from the group consisting of: (1) -O- ; (2) -
N(R39)-; and (3)
N(R39R40); R36, R37, R39 and R40 are substituted or unsubstituted radicals
independently
selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl,
aryl, aralkyl,
alkylenes, heterocyclic ring, alkoxys, arylcarbonyl groups, carboxyalkyl
groups and amide
groups; any of R32, R33, R34, R35, R36, R37, R39 and R40 may be joined
together with any
other of R32, R33, R34, R35, R36, R37, R39 and R40 to form part of a common
ring; any
geminal R36 - R37 may combine to form a carbonyl; any vicinal R36, R37, R39
and R40 may join
to form unsaturation; and wherein any one group of substituents R36, R37, R39
and R40 may
combine to form a substituted or unsubstituted fused unsaturated moiety;
d) modified amine oxides that are represented by formulas [XVII]-[XX]:
<IMGS>
where m is 1 to 3 when G is present and m is 1 to 4 when G is not present; and
n is an integer
from 0 to 4; R34 is a radical selected from the group consisting of
substituted or unsubstituted,
saturated or unsaturated hydroxy, perhydroxy, alkoxy, peralkoxy, carboxylic,
percarboxylic,
sulfonato and persulfonato radicals; each R35 is independently selected from a
substituted or
unsubstituted radical selected from the group consisting of H, alkyl,
cycloalkyl, aryl, fused aryl,
heterocyclic ring, fused heterocyclic ring, nitro, halo, cyano, sulfonato,
alkoxy, keto, carboxylic,
and carboalkoxy radicals, and any two vicinal R35 substituents may combine to
form a fused aryl,

fused carbocyclic or fused heterocyclic ring; R32 may be a substituted or
unsubstituted radical
selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl,
aralkyl, heterocyclic ring,
silyl, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and
carboalkoxy radicals; R33 may
be a substituted or unsubstituted, saturated or unsaturated, radical selected
from the group
consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring,
and also present in this
formula is the radical represented by the formula:
<IMG>
where Z p- is covalently bonded to T o, and Z p- is selected from the group
consisting of
-CO2-, -SO3-, -OSO3-, -SO2- and -OSO2-, and a is either 1, 2 or 3; T o is
selected from the group
consisting of:
<IMG>
wherein q is an integer from 1 to 8; R38 is independently selected from
substituted or
unsubstituted radicals selected from the group consisting of linear or
branched H, alkyl,
cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxy,
arylcarbonyl, carboxyalkyl
and amide groups; G is selected from the group consisting of: (1) -O- ; (2) -
N(R39)-; and (3) -
N(R39R40)-; R36, R37, R39 and R40 are substituted or unsubstituted radicals
independently
selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl,
aryl; aralkyl,
alkylenes, heterocyclic ring, alkoxys, arylcarbonyl groups, carboxyalkyl
groups and amide
groups; any of R32, R33, R34, R35, R36, R37, R39 and R40 may be joined
together with any
other of R32, R33, R34, R35, R36, R37, R39 and R40 to form part of a common
ring; any
geminal R36- R37 may combine to form a carbonyl; any vicinal R36, R37, R39 and
R40 may join
to form unsaturation; and wherein any one group of substituents R36, R37, R39
and R40 may
combine to form a substituted or unsubstituted fused unsaturated moiety;
e) sulfonimines [XXVIIIa], phosphonimines [XXVIIIb], N-acylimines [XXIX] are
represented as follows:
86

<IMGS>
wherein each R46 is independently selected from a substituted or unsubstituted
radical selected
from the group consisting of H, alkyl, cycloalkyl, aryl, fused aryl,
heterocyclic ring, fused
heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic,
and carboalkoxy
radicals, and any two vicinal R46 substituents may combine to form a fused
aryl, fused
carbocyclic or fused heterocyclic ring; R45 may be a substituted or
unsubstituted radical selected
from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl,
heterocyclic ring, silyl,
nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy
radicals; G, when present,
is selected from the group consisting of: (1) -O- ; (2) -N(R47)-; and (3) -
N(R47R48)-; R47-R48
are substituted or unsubstituted radicals independently selected from the
group consisting of H,
oxygen, linear or branched C1-C12 alkyls, alkylenes, alkoxys, aryls, alkaryls,
aralkyls,
cycloalkyls, and heterocyclic rings;
f) oxaziridinium canons and polyions, which have a net charge of from about +3
to
about -3, that are represented by formula [XIII]:
<IMG>
wherein m is 1 to 3 when G is present and m is 1 to 4 when G is not present;
and n is an integer
from 0 to 4; each R20' is independently selected from a substituted or
unsubstituted radical
selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused aryl,
heterocyclic ring,
fused heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto,
carboxylic, and carboalkoxy
radicals, and any two vicinal R20' substituents may combine to form a fused
aryl, fused
carbocyclic or fused heterocyclic ring; R18' may be a substituted or
unsubstituted radical selected
from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl,
heterocyclic ring, silyl,
nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy
radicals; R19' may be a
87

substituted or unsubstituted, saturated or unsaturated, radical selected from
the group consisting of
H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl and heterocyclic ring. G is
selected from the group
consisting of: (1) -O- ; (2) -N(R23')-; and (3) -N(R23'R24')-; R21'-R24' are
substituted or
unsubstituted radicals independently selected from the group consisting of H,
oxygen, linear or
branched C1-C12 alkyls, alkylenes, alkoxys, aryls, alkaryls, aralkyls,
cycloalkyls, and
heterocyclic rings; provided that any of R18', R19', R21'-R24' may be joined
together with any
other of R18', R19', R21'-R24' to form part of a common ring; any geminal R21'
- R22' may
combine to form a carbonyl; any vicinal R21' - R24' may join to form
unsaturation; and wherein
any one group of substituents R21' - R24' may combine to form a substituted or
unsubstituted
fused unsaturated moiety; and wherein any one group of substituents R21' -
R24' may combine to
form a substituted or unsubstituted fused unsaturated moiety; X- is a suitable
charge-balancing
counterion; and v is an integer from 1 to 3;
g) oxaziridinium zwitterions, which have a net charge of from about +3 to
about -3,
that are represented by formula [XIV]:
<IMG>
wherein m is 1 to 3 when G is present and m is 1 to 4 when G is not present;
and n is an integer
from 0 to 4; each R26' is independently selected from a substituted or
unsubstituted radical
selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused aryl,
heterocyclic ring,
fused heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto,
carboxylic, and carboalkoxy
radicals, and any two vicinal R26' substituents may combine to form a fused
aryl, fused
carbocyclic or fused heterocyclic ring; R25' may be a substituted or
unsubstituted radical selected
from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl,
heterocyclic ring, silyl,
nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy
radicals; the radical
represented by the formula:
<IMG>
where Z'p is covalently bonded to T'o, and Z'p is selected from the group
consisting of -CO2-, -
SO3-, -OSO3-, -SO2' and -OSO2-, and a is either 1 or 2; T'o is selected from
the group consisting
of
88

<IMG>
wherein q is an integer from 1 to 8; R29~ is independently selected from
substituted or
unsubstituted radicals selected from the group consisting of linear or
branched H, alkyl,
cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxy,
arylcarbonyl, carboxyalkyl
and amide groups; G is selected from the group consisting of: (1) -O- ; (2) -
N(R30')-; and (3) -
N(R30~R31')-; R27', R28', R30' and R31, are substituted or unsubstituted
radicals independently
selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl,
aryl, aralkyl,
alkylenes, heterocyclic ring, alkoxys, arylcarbonyl groups, carboxyalkyl
groups and amide
groups; any of R25', R26', R27', R28', R30' and R31' may be joined together
with any other of
R25', R26', R27', R28', R30' and R31, to form part of a common ring; any
geminal R27'- R28'
may combine to form a carbonyl; any vicinal R27'- R31' may join to form
unsaturation; and
wherein any one group of substituents R27'- R31' may combine to form a
substituted or
unsubstituted fused unsaturated moiety;
h) oxaziridine sulfonimines [XXXIa], phosphonimines [XXXIb], N-acylimines
[XXXII]
are represented as follows:
<IMGS>
wherein each R46' is independently selected from a substituted or
unsubstituted radical selected
from the group consisting of H, alkyl, cycloalkyl, aryl, fused aryl,
.heterocyclic ring, fused
heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic,
and carboalkoxy
radicals, and any two vicinal R46' substituents may combine to form a fused
aryl, fused
carbocyclic or fused heterocyclic ring; R45' may be a substituted or
unsubstituted radical selected
from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl,
heterocyclic ring, silyl;
nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy
radicals; G, when present,
89

is selected from the group consisting of: (1) -O- ; (2) -N(R47')-; and (3) -
N(R47'R48')-; R47'-
R48' are substituted or unsubstituted radicals independently selected from the
group consisting of
H, oxygen, linear or branched C1-C12 alkyls, alkylenes, alkoxys, aryls,
alkaryls, aralkyls,
cycloalkyls, and heterocyclic rings; and
i) mixtures thereof.
4. The method according to Claim 1 wherein said fabric comprises a stain.
5. A bleaching composition comprising
(a) a peroxygen source; and
(b) an organic catalyst;
wherein the organic catalyst becomes available in a wash solution containing
said bleaching
composition by a controlled availability method.
6. The bleaching composition according to Claim 5 wherein said peroxygen
source is
selected from the group consisting of:
(i) preformed peracid compounds selected from the group consisting of
percarboxylic acids and salts, percarbonic acids and salts, perimidic acids
and salts,
peroxymonosulfuric acids and salts, and mixtures thereof, and
(ii) hydrogen peroxide sources selected from the group consisting of perborate
compounds, percarbonate compounds, perphosphate compounds and mixtures
thereof, and a
bleach activator.
7. The bleaching composition according to Claim 6 wherein said peroxygen
source is
selected from hydrogen peroxide sources selected from the group consisting of
perborate
compounds, percarbonate compounds, perphosphate compounds and mixtures
thereof, and a
bleach activator.
8. The bleaching composition according to Claim 7 wherein said bleach
activator is selected
from the group consisting of hydrophobic bleach activators.
9. The bleaching composition according to Claim 7 wherein said bleach
activator is selected
from the group consisting of tetraacetyl ethylene diamine (TAED),
benzoylcaprolactam (BzCL),
4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam,
benzoyloxybenzenesulphonate (BOBS),
nonanoyloxybenzenesulphonate (NOBS), phenyl benzoate (PhBz),
90

decanoyloxybenzenesulphonate (C10-OBS), benzoylvalerolactam (BZVL),
octanoyloxybenzenesulphonate (C8-OBS), perhydrolyzable esters, 4-[N-(nonanoyl)
amino
hexanoyloxy]-benzene sulfonate sodium salt (NACA-OBS),
lauryloxybenzenesulphonate (LOBS
or C12-OBS), 10-undecenoyloxybenzenesulfonate (UDOBS or C11-OBS with
unsaturation in the
position), decanoyloxybenzoic acid (DOBA) and mixtures thereof.
10. The bleaching according to Claim 5 wherein said organic catalyst is
selected from the
group consisting of:
a) aryliminium canons and aryliminium polyions, which have a net charge of
from
about +3 to about -3, that are represented by the formula [I]:
<IMG>
where R1-R2 are independently selected from substituted or unsubstituted
radicals selected from
the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl,
heterocyclic ring, silyl, nitro,
halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy radicals; R1
and R4 are selected
from substituted or unsubstituted, saturated or unsaturated radicals selected
from the group
consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring,
silyl, nitro, halo, cyano,
alkoxy, keto and carboalkoxy radicals; and X- is a suitable charge-balancing
counterion; and v is
an integer from 1 to3;
b) aryliminium zwitterions, which have a net charge of from about +3 to about -
3,
that are represented by the formula [II]:
<IMG>
where R5-R7 are independently selected from substituted or unsubstituted
radicals selected from
the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl,
heterocyclic ring, silyl, nitro,
91

halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy radicals;
also present in this
formula is the radical represented by the formula:
<IMG>
where Z p- is covalently bonded to T o, and Z p- is selected from the group
consisting of
-CO2-, -SO3-, -OSO3-, -SO2- and -OSO2- and p is either 1, 2 or 3; T o is
selected from the group
consisting of substituted or unsubstituted, saturated or unsaturated alkyl,
cycloalkyl, aryl, alkaryl,
aralkyl, and heterocyclic ring;
c) modified amines, which have a net charge of from about -3 to about +3, that
are
represented by formulas [V] and [VI]:
<IMGS>
where R9-R10 are independently selected from substituted or unsubstituted
radicals selected from
the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl,
heterocyclic ring, silyl, nitro,
halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy radicals and
anionic and/or
cationic charge carrying radicals; R8 and R11, when present, are radicals
selected from the group
consisting of substituted or unsubstituted, saturated or unsaturated H, alkyl,
cycloalkyl, aryl,
alkaryl, aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, sulfonato,
alkoxy, keto, carboxylic, and
carboalkoxy radicals and anionic and/or cationic charge carrying radicals; R12
is a leaving group,
the protonated form of which has a pK.alpha. value (H2O reference) that falls
within the following
range: 37 > pK.alpha. > -2; with the proviso that any R8-R12, when present,
may combine to form a
fused aryl, fused carbocyclic or fused heterocyclic ring; and the radical
represented by the
formula:
<IMG>
where Z p is covalently bonded to T o, and Z p- is selected from the group
consisting of
92

-CO2-, -SO3-, -OSO3-, -SO2- and -OSO2- and p is either 1, 2 or 3; T o is
selected from the group
consisting of substituted or unsubstituted, saturated or unsaturated alkyl,
cycloalkyl, aryl, alkaryl,
aralkyl, and heterocyclic ring;
d) modified amine oxides, which have a net charge of from about -3 to about
+3,
that are represented by formulas [VII]-[X]:
<IMGS>
where R9-R10 are independently selected from substituted or unsubstituted
radicals selected from
the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl,
heterocyclic ring, silyl, nitro,
halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy radicals and
anionic and/or
cationic charge carrying radicals; R8 and R11 are radicals selected from the
group consisting of
substituted or unsubstituted, saturated or unsaturated H, alkyl, cycloalkyl,
aryl, alkaryl, aralkyl,
heterocyclic ring, silyl, nitro, halo, cyano, alkoxy, keto and carboalkoxy
radicals and anionic
and/or cationic charge carrying radicals; R12 is a leaving group, the
protonated form of which has
a pK.alpha. value (H2O reference) that falls within the following range: 37 >
pK.alpha. > -2; with the
proviso that any R8-R12, when present, may combine to form a fused aryl, fused
carbocyclic or
fused heterocyclic ring; and also present in this formula is the radical
represented by the formula:
<IMG>
where Z p is covalently bonded to T o, and Z p is selected from the group
consisting of
-CO2-, -SO3-, -OSO3-, -SO2- and -OSO2- and p is either 1, 2 or 3; T o is
selected from the group
consisting of substituted or unsubstituted, saturated or unsaturated alkyl,
cycloalkyl, aryl, alkaryl,
aralkyl, and heterocyclic ring;
93

e) sulfonimines, phosphonimines, N-acylimines and thiodiazole dioxides that
are
represented by the formulas [XXIa], [XXIb], [XXII] and [XXIII], respectively:
<IMGS>
where R41-R44, when present, are independently selected from substituted or
unsubstituted,
saturated or unsaturated radicals selected from the group consisting of H,
alkyl, cycloalkyl; aryl,
alkaryl, aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, sulfonato,
alkoxy, keto, carboxylic, and
carboalkoxy radicals; provided that any of R41-R44 may be joined together with
any other R41-
R44 to form part of a common ring, including a fused aryl, fused carbocyclic
or fused
heterocyclic ring;
f) oxaziridinium cations and polyions, which have a net charge of from about
+3 to
about -3, that are represented by the formula [III]:
<IMG>
where R2'-R3' are independently selected from substituted or unsubstituted
radicals selected from
the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl,
heterocyclic ring, silyl, nitro,
halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy radicals;
R1' and R4' are
radicals selected from the group consisting of substituted or unsubstituted,
saturated or
unsaturated, H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring,
silyl, nitro, halo, cyano,
alkoxy, keto and carboalkoxy radicals; and X- is a suitable charge-balancing
counterion; and v is
an integer from 1 to 3;
g) oxaziridinium zwitterions, which have a net charge of from about +3 to
about -3,
that are represented by formula [IV]:
94

<IMG>
where R5'-R7' are independently selected from substituted or unsubstituted
radicals selected from
the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl,
heterocyclic ring, silyl, nitro,
halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy radicals;
also present in this
formula is the radical represented by the formula:
<IMG>
where Z'p is covalently bonded to T'o, and Z'p is selected from the group
consisting of -CO2-, -
SO3-, -OSO3-, -SO2- and -OSO2- and p is either 1, 2 or 3; T'o is selected from
the group
consisting of substituted or unsubstituted, saturated or unsaturated alkyl,
cycloalkyl, aryl, alkaryl,
aralkyl, and heterocyclic ring;
h) oxaziridine sulfonimines [XXIVa], phosphonimines [XXIVb], N-acylimines
[XXV] and thiodiazole dioxides [XXVI] and [XXVII] are represented as follows:
<IMGS>
where R41'-R44', when present, are independently selected from substituted or
unsubstituted radicals selected from the group consisting of H, alkyl,
cycloalkyl, aryl, alkaryl,
aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, sulfonato, alkoxy,
keto, carboxylic,
95

carboalkoxy radicals, provided that any of R41'-R44' may be joined together
with any other R41'-
R44' to form part of a common ring, including a fused aryl, fused carbocyclic
or fused
heterocyclic ring;i) mixtures thereof.
11. The bleaching composition according to Claim 10 wherein the organic
catalyst is selected
from the group consisting of:
a) aryliminium canons and aryliminium polyions, which have a net charge of
from
about +3 to about -3, that are represented by the formula [XI]:
<IMG>
where m is 1 to 3 when G is present and m is 1 to 4 when G is not present; and
n is an integer
from 0 to 4; each R20 is independently selected from a substituted or
unsubstituted radical
selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused aryl,
heterocyclic ring,
fused heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto,
carboxylic, and carboalkoxy
radicals, and any two vicinal R20 substituents may combine to form a fused
aryl, fused
carbocyclic or fused heterocyclic ring; R18 may be a substituted or
unsubstituted radical selected
from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl,
heterocyclic ring, silyl,
nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy
radicals; R19 is a radical
selected from the group consisting of substituted or unsubstituted, saturated
or unsaturated, H,
alkyl, cycloalkyl, alkaryl, aryl, aralkyl and heterocyclic ring; G is selected
from the group
consisting of: (1) -O- ; (2) -N(R23)-; and (3) -N(R23R24)-; R21-R24 are
substituted or
unsubstituted radicals independently selected from the group consisting of H,
oxygen, linear or
branched C1-C12 alkyls, alkylenes, alkoxys, aryls, alkaryls, aralkyls,
cycloalkyls, and
heterocyclic rings; provided that any of R18, R19, R20, R21-R24 may be joined
together with any
other of R18, R19, R20, R21-R24 to form part of a common ring; any geminal R21-
R22 may
combine to form a carbonyl; any vicinal R21-R24 may join to form unsaturation;
and wherein any
one group of substituents R21-R24 may combine to form a substituted or
unsubstituted fused
unsaturated moiety; X- is a suitable charge-balancing counterion; and v is an
integer from 1 to 3;
b) aryliminium zwitterions, which have a net charge of from about +3 to about -
3,
that are represented by the formula [XII]:
96

<IMG>
where m is 1 to 3 when G is present and m is 1 to 4 when G is not present; and
n is an integer
from 0 to 4; each R26 is independently selected from a substituted or
unsubstituted radical
selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused aryl,
heterocyclic ring,
fused heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto,
carboxylic, and carboalkoxy
radicals, and any two vicinal R26 substituents may combine to form a fused
aryl, fused
carbocyclic or fused heterocyclic ring; R25 may be a substituted or
unsubstituted radical selected
from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl,
heterocyclic ring, silyl,
nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy
radicals; also present in
this formula is the radical represented by the formula:
<IMG>
where Z p- is covalently bonded to T o, and Z p- is selected from the group
consisting of
-CO2-, -SO3-, -OSO3-, -SO2- and -OSO2- and p is either 1, 2 or 3; T o is
selected from the group
consisting of:
<IMG>
wherein q is an integer from 1 to 8; R29 is independently selected from
substituted or
unsubstituted radicals selected from the group consisting of linear or
branched H, alkyl,
cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxy,
arylcarbonyl, carboxyalkyl
and amide groups; G is selected from the group consisting of (1) -O- ; (2) -
N(R30)-; and (3)
N(R30R31)-; R27, R28, R30 and R31 are substituted or unsubstituted radicals
independently
selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl,
aryl, aralkyl,
alkylenes, heterocyclic ring, alkoxys, arylcarbonyl groups, carboxyalkyl
groups and amide
groups; any of R25, R26, R27, R28, R30 and R31 may be joined together with any
other of R25,
97

R26, R27, R28, R30 and R31 to form part of a common ring; any geminal R27 -
R28 may
combine to form a carbonyl; any vicinal R27 - R31 may join to form
unsaturation; and wherein
any one group of substituents R27 - R31 may combine to form a substituted or
unsubstituted
fused unsaturated moiety;
c) modified amines that are represented by the formulas [XV] and [XVI]:
<IMGS>
where m is 1 to 3 when G is present and m is 1 to 4 when G is not present; and
n is an integer
from 0 to 4; R34 is a radical selected from the group consisting of
substituted or unsubstituted,
saturated or unsaturated hydroxy, perhydroxy, alkoxy, peralkoxy, carboxylic,
percarboxylic,
sulfonato and persulfonato radicals; each R35 is independently selected from a
substituted or
unsubstituted radical selected from the group consisting of H, alkyl,
cycloalkyl, aryl, fused aryl,
heterocyclic ring, fused heterocyclic ring, nitro, halo, cyano, sulfonato,
alkoxy, keto, carboxylic,
and carboalkoxy radicals, and any two vicinal R35 substituents may combine to
form a fused aryl,
fused carbocyclic or fused heterocyclic ring; R32 may be a substituted or
unsubstituted radical
selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl,
aralkyl, heterocyclic ring,
silyl, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and
carboalkoxy radicals; R33 may
be a substituted or unsubstituted, saturated or unsaturated, radical selected
from the group
consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring,
and also present in this
formula is the radical represented by the formula:
<IMG>
where Z p- is covalently bonded to T o, and Z p is selected from the group
consisting of
-CO2-, -SO3-, -OSO3-, -SO2- and -OSO2-, and a is either 1, 2 or 3; T o is
selected from the group
consisting of:
98

<IMG>
wherein q is an integer from 1 to 8; R38 is independently selected from
substituted or
unsubstituted radicals selected from the group consisting of linear or
branched H, alkyl,
cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxy,
arylcarbonyl, carboxyalkyl
and amide groups; G is selected from the group consisting of: (1) -O- ; (2) -
N(R39)-; and (3) -
N(R39R40)-; R36, R37, R39 and R40 are substituted or unsubstituted radicals
independently
selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl,
aryl, aralkyl,
alkylenes, heterocyclic ring, alkoxys, arylcarbonyl groups, carboxyalkyl
groups and amide
groups; any of R32, R33, R34, R35, R36, R37, R39 and R40 may be joined
together with any
other of R32, R33, R34, R35, R36, R37, R39 and R40 to form part of a common
ring; any
geminal R36- R37 may combine to form a carbonyl; any vicinal R36, R37, R39 and
R40 may join
to form unsaturation; and wherein any one group of substituents R36, R37, R39
and R40 may
combine to form a substituted or unsubstituted fused unsaturated moiety;
d) modified amine oxides that are represented by formulas [XVII]-[XX]:
<IMGS>
where m is 1 to 3 when G is present and m is 1 to 4 when G is not present; and
n is an integer
from 0 to 4; R34 is a radical selected from the group consisting of
substituted or unsubstituted,
saturated or unsaturated hydroxy, perhydroxy, alkoxy, peralkoxy, carboxylic,
percarboxylic,
99

sulfonato and persulfonato radicals; each R35 is independently selected from a
substituted or
unsubstituted radical selected from the group consisting of H, alkyl,
cycloalkyl, aryl, fused aryl,
heterocyclic ring, fused heterocyclic ring, nitro, halo, cyano, sulfonato,
alkoxy, keto, carboxylic,
and carboalkoxy radicals, and any two vicinal R35 substituents may combine to
form a fused aryl,
fused carbocyclic or fused heterocyclic ring; R32 may be a substituted or
unsubstituted radical
selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl,
aralkyl, heterocyclic ring,
silyl, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and
carboalkoxy radicals; R33 may
be a substituted or unsubstituted, saturated or unsaturated, radical selected
from the group
consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring,
and also present in this
formula is the radical represented by the formula:
<IMG>
where Z p- is covalently bonded to T o, and Z p- is selected from the group
consisting of
-CO2-, -SO3-, -OSO3-, -SO2-, and -OSO2-, and a is either 1, 2 or 3; T o is
selected from the group
consisting of:
<IMG>
wherein q is an integer from 1 to 8; R38 is independently selected from
substituted or
unsubstituted radicals selected from the group consisting of linear or
branched H, alkyl,
cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxy,
arylcarbonyl, carboxyalkyl
and amide groups; G is selected from the group consisting of: (1) -O- ; (2) -
N(R39)-; and (3) -
N(R39R40)-; R36, R37, R39 and R40 are substituted or unsubstituted radicals
independently
selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl,
aryl, aralkyl,
alkylenes, heterocyclic ring, alkoxys, arylcarbonyl groups, carboxyalkyl
groups and amide
groups; any of R32, R33, R34, R35, R36, R37, R39 and R40 may be joined
together with any
other of R32, R33, R34, R35, R36, R37, R39 and R40 to form part of a common
ring; any
geminal R36- R37 may combine to form a carbonyl; any vicinal R36, R37, R39 and
R40 may join
to form unsaturation; and wherein any one group of substituents R36, R37, R39
and R40 may
combine to form a substituted or unsubstituted fused unsaturated moiety;
100

e) sulfonimines [XXVIIIa], phosphonimines [XXVIIIb], N-acylimines [XXIX] are
represented as follows:
<IMGS>
wherein each R46 is independently selected from a substituted or unsubstituted
radical selected
from the group consisting of H, alkyl, cycloalkyl, aryl, fused aryl,
heterocyclic ring, fused
heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic,
and carboalkoxy
radicals, and any two vicinal R46 substituents may combine to form a fused
aryl, fused
carbocyclic or fused heterocyclic ring; R45 may be a substituted or
unsubstituted radical selected
from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl,
heterocyclic ring, silyl,
nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy
radicals; G, when present,
is selected from the group consisting of: (1) -O- ; (2) -N(R47)-; and (3) -
N(R47R48)-; R47-R48
are substituted or unsubstituted radicals independently selected from the
group consisting of H,
oxygen, linear or branched C1-C12 alkyls, alkylenes, alkoxys, aryls, alkaryls,
aralkyls,
cycloalkyls, and heterocyclic rings; and n is an integer from 0 to 4;
f) oxaziridinium cations and polyions, which have a net charge of from about
+3 to
about -3, that are represented by formula [XIII]:
<IMG>
wherein m is 1 to 3 when G is present and m is 1 to 4 when G is not present;
and n is an integer
from 0 to 4; each R20' is independently selected from a substituted or
unsubstituted radical
selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused aryl,
heterocyclic ring,
fused heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto,
carboxylic, and carboalkoxy
radicals, and any two vicinal R20' substituents may combine to form a fused
aryl, fused
101

carbocyclic or fused heterocyclic ring; R18' may be a substituted or
unsubstituted radical selected
from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl,
heterocyclic ring, silyl,
nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy
radicals; R19' may be a
substituted or unsubstituted, saturated or unsaturated, radical selected from
the group consisting of
H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl and heterocyclic ring. G is
selected from the group
consisting of: (1) -O- ; (2) -N(R23')-; and (3) -N(R23'R24')-; R21'-R24' are
substituted or
unsubstituted radicals independently selected from the group consisting of H,
oxygen, linear or
branched C1-C12 alkyls, alkylenes, alkoxys, aryls, alkaryls, aralkyls,
cycloalkyls, and
heterocyclic rings; provided that any of R18', R19', R21'-R24' may be joined
together with any
other of R18', R19', R21'-R24' to form part of a common ring; any geminal R21'
- R22' may
combine to form a carbonyl; any vicinal R21' - R24' may join to form
unsaturation; and wherein
any one group of substituents R21' - R24' may combine to form a substituted or
unsubstituted
fused unsaturated moiety; and wherein any one group of substituents R21' -
R24' may combine to
form a substituted or unsubstituted fused unsaturated moiety; X- is a suitable
charge-balancing
counterion; and v is an integer from 1 to 3;
g) oxaziridinium zwitterions, which have a net charge of from about +3 to
about -3,
that are represented by formula [XIV]:
<IMG>
wherein m is 1 to 3 when G is present and m is 1 to 4 when G is not present;
and n is an integer
from 0 to 4; each R26' is independently selected from a substituted or
unsubstituted radical
selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused aryl,
heterocyclic ring,
fused heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto,
carboxylic, and carboalkoxy
radicals, and any two vicinal R26' substituents may combine to form a fused
aryl, fused
carbocyclic or fused heterocyclic ring; R25' may be a substituted or
unsubstituted radical selected
from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl,
heterocyclic ring, silyl,
nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy
radicals; the radical
represented by the formula:
<IMG>
102

where Z'p- is covalently bonded to T'o, and Z'p is selected from the group
consisting of -CO2-, -
SO3-, -OSO3-, -SO2- and -OSO2-, and a is either 1 or 2; T'o is selected from
the group consisting
of:
<IMG>
wherein q is an integer from 1 to 8; R29' is independently selected from
substituted or
unsubstituted radicals selected from the group consisting of linear or
branched H, alkyl,
cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxy,
arylcarbonyl, carboxyalkyl
and amide groups; G is selected from the group consisting of: (1) -O- ; (2) -
N(R30')-; and (3) -
N(R30'R31')-; R27', R28', R30' and R31' are substituted or unsubstituted
radicals independently
selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl,
aryl, aralkyl,
alkylenes, heterocyclic ring, alkoxys, arylcarbonyl groups, carboxyalkyl
groups and amide
groups; any of R25', R26', R27', R28', R30' and R31' may be joined together
with any other of
R25', R26', R27', R28', R30' and R31' to form part of a common ring; any
geminal R27'- R28'
may combine to form a carbonyl; any vicinal R27'- R31' may join to form
unsaturation; and
wherein any one group of substituents R27'- R31' may combine to form a
substituted or
unsubstituted fused unsaturated moiety;
h) oxaziridine sulfonimines [XXXIa], phosphonimines [XXXIb], N-acylimines
[XXXII] are represented as follows:
<IMGS>
wherein each R46' is independently selected from a substituted or
unsubstituted radical selected
from the group consisting of H, alkyl, cycloalkyl, aryl, fused aryl,
heterocyclic ring, fused
heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic,
and carboalkoxy
radicals, and any two vicinal R46' substituents may combine to form a fused
aryl, fused
103

carbocyclic or fused heterocyclic ring; R45' may be a substituted or
unsubstituted radical selected
from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl,
heterocyclic ring, silyl,
nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy
radicals; G, when present,
is selected from the group consisting of: (1) -O- ; (2) -N(R47')-; and (3) -
N(R47'R48')-; R47'-
R48' are substituted or unsubstituted radicals independently selected from the
group consisting of
H, oxygen, linear or branched C1-C12 alkyls, alkylenes, alkoxys, aryls,
alkaryls, aralkyls,
cycloalkyls, and heterocyclic rings; and n is an integer from 0 to 4; and
i) mixtures thereof.
12. The bleaching composition according to Claim 5 wherein said bleaching
compound
further comprises one or more of the following detergent components selected
from the group
consisting of: surfactants, solvents, buffers, enzymes, soil release agents,
clay soil removal
agents, dispersing agents, brighteners, suds suppressors, fabric softeners,
suds organic catalysts,
enzyme stabilizers, builders, chelants, other bleaching agents, including
metal catalysts, other
organic catalysts, dyes, dye transfer inhibiting agents, perfumes and mixtures
thereof.
13. A product comprising an organic catalyst, the product further including
instructions for
using said compound to clean a fabric in need of cleaning, the instructions
including the step of
contacting said fabric with a wash solution comprising the product wherein the
organic catalyst
becomes available in said wash solution by a controlled availability method.
14. The product according to Claim 13 wherein said product is a laundry
detergent.
15. The product according to Claim 13 wherein said product is a laundry
additive.
16. A modified amine compound selected from the group consisting of
modified amine oxides having the general formula [VII] - [X]:
<IMGS>
104

<IMGS>
where R8-R10 are independently selected from substituted or unsubstituted
radicals selected from
the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl,
heterocyclic ring, silyl, nitro,
halo, cyano, alkoxy, keto, carboalkoxy radicals and anionic and/or cationic
charge carrying
radicals; R11, when present, is a radical selected from the group consisting
of substituted or
unsubstituted, saturated or unsaturated H, alkyl, cycloalkyl, aryl, alkaryl,
aralkyl, heterocyclic
ring, silyl, nitro, halo, cyano, alkoxy, keto, carboalkoxy radicals and
anionic and/or cationic
charge carrying radicals; R12 is a leaving group, the protonated form of which
has a pK.alpha.value
(H2O reference) that falls within the following range: 37 > pK.alpha. > -2;
with the proviso that any
R8-R12, when present, may combine to form a fused aryl, fused carbocyclic or
fused heterocyclic
ring.
17. The modified amine compound according to Claim 16 wherein R11 is
represented by the
formula:
<IMG>
where Z p- is covalently bonded to T o, and Z p- is selected from the group
consisting of
-CO2-, -SO3-, -OSO3-, -SO2- and -OSO2- and p is either 1, 2 or 3; T o is
selected from the group
consisting of substituted or unsubstituted, saturated or unsaturated alkyl,
cycloalkyl, aryl, alkaryl,
aralkyl, and heterocyclic ring.
18. The modified amine compound according to Claim 18 wherein for R12, the
pK.alpha. value is
greater than 3 and less than 23.
19. The modified amine compound according to Claim 17 wherein for R12, the
pK.alpha. value is
greater than 9 and less than 21.
20. The modified amine compound according to Claim 18 wherein for R12, the
pK.alpha. value is
greater than 11 and less than 17.
105

21. The modified amine compound according to Claim 16 wherein R12 is selected
from the
group consisting of substituted or unsubstituted, saturated or unsaturated
hydroxy, perhydroxy,
alkoxy and peralkoxy radicals.
22. The modified amine compound according to Claim 21 wherein said R12 is
selected from
the group consisting of hydroxy or perhydroxy.
23. The modified amine compound according to Claim 16 wherein said modified
amine
compound has the general formula [XVII] - [XX].
<IMGS>
where m is 1 to 3 when G is present and m is 1 to 4 when G is not present; and
n is an integer
from 0 to 4; R34 is a leaving group, the protonated form of which has a
pK.alpha.value (H2O
reference) that falls within the following range: 37 > pK.alpha. > -2; each
R35 is independently
selected from a substituted or unsubstituted radical selected from the group
consisting of H, alkyl,
cycloalkyl, aryl, fused aryl, heterocyclic ring, fused heterocyclic ring,
nitro, halo, cyano,
sulfonato, alkoxy, keto, carboxyl, and carboalkoxy radicals, and any two
vicinal R35 substituents
may combine to form a fused aryl, fused carbocyclic or fused heterocyclic
ring; R32 may be a
substituted or unsubstituted radical selected from the group consisting of H,
alkyl, cycloalkyl,
alkaryl, aryl, aralkyl, heterocyclic ring, silyl, nitro, halo, cyano,
sulfonato, alkoxy, keto, carboxyl,
and carboalkoxy radicals; R33 may be a substituted or unsubstituted, saturated
or unsaturated,
106

radical selected from the group consisting of H, alkyl, cycloalkyl, alkaryl,
aryl, aralkyl,
heterocyclic ring, including anionic and/or cationic charge carrying radicals.
24. The modified amine compound according to Claim 23 wherein R33 is
represented by the
formula:
<IMG>
where Z p- is covalently bonded to T o, and Z p- is selected from the group
consisting of
-CO2-, -SO3-, -OSO3-, -SO2- and -OSO2-, and p iseither 1, 2 or 3; T o is
selected from the group
consisting of:
<IMG>
wherein q is an integer from 1 to 8; R38 is independently selected from
substituted or
unsubstituted radicals selected from the group consisting of linear or
branched H, alkyl,
cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxy,
arylcarbonyl, carboxyalkyl
and amide groups; G is selected from the group consisting of: (1) -O- ; (2) -
N(R39)-; and (3) -
N(R39R40)-; R36, R37, R39 and R40 are substituted or unsubstituted radicals
independently
selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl,
aryl, aralkyl,
alkylenes, heterocyclic ring, alkoxys, arylcarbonyl groups, carboxyalkyl
groups and amide
groups; any of R32, R33, R34, R35, R36, R37, R39 and R40 may be joined
together with any
other of R32, R33, R34, R35, R36, R37, R39 and R40 to form part of a common
ring; any
geminal R36- R37 may combine to form a carbonyl; any vicinal R36, R37, R39 and
R40 may join
to form unsaturation; and wherein any one group of substituents R36, R37, R39
and R40 may
combine to form a substituted or unsubstituted fused unsaturated moiety.
25. The modified amine compound according to Claim 23 wherein for R34, the
pK.alpha. value is
greater than 3 and less than 23.
26. The modified amine compound according to Claim 25 wherein for R34, the
pK.alpha. value is
greater than 11 and less than 17.
107

27. The modified amine compound according to Claim 23 wherein R34 is selected
from the
group consisting of substituted or unsubstituted, saturated or unsaturated
hydroxy, perhydroxy,
alkoxy and peralkoxy radicals.
28. The modified amine compound according to Claim 27 wherein R34 is selected
from the
group consisting of hydroxy or perhydroxy radicals.
29. The modified amine compound according to Claim 16 wherein said modified
amine
compound has the general formula [XV] - [XVI].
<IMGS>
where m is 1 to 3 when G is present and m is 1 to 4 when G is not present; and
n is an integer
from 0 to 4; R34 is a leaving group, the protonated form of which has a pK
.alpha. value (H2O
reference) that falls within the following range: 20 > pK .alpha. > 10; each
R35 is independently
selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused aryl,
heterocyclic ring,
fused heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto,
carboxyl, and carboalkoxy
radicals, and any two vicinal R35 substituents may combine to form a fused
aryl, fused
carbocyclic or fused heterocyclic ring; R32 is a radical selected from the
group consisting of H or
Me; R33 is a substituted or unsubstituted, saturated or unsaturated, radical
selected from the group
consisting of C3 - C18 alkyl, C3 - C18 cycloalkyl and anionic and/or cationic
charge-carrying
radicals.
30. The modified amine compound according to Claim 29 wherein R33 is
represented by the
formula:
<IMG>
here Z p is covalently bonded to T o, and Z p is selected from the group
consisting of
108

-CO2-, -SO3-, -OSO3-, -SO2- and -OSO2-, and p iseither 1, 2 or 3; T o is
selected from the group
consisting of:
<IMG>~
wherein q is an integer from 1 to 8; R38 is independently selected from
substituted or
unsubstituted radicals selected from the group consisting of linear or
branched H, alkyl,
cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxy,
arylcarbonyl, carboxyalkyl
and amide groups; G is selected from the group consisting of: (1) -O- ; (2) -
N(R39)-; and (3) -
N(R39R40)-; R36, R37, R39 and R40 are substituted or unsubstituted radicals
independently
selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl,
aryl, aralkyl,
alkylenes, heterocyclic ring, alkoxys, arylcarbonyl groups, carboxyalkyl
groups and amide
groups; any of R32, R33, R34, R35, R36, R37, R39 and R40 may be joined
together with any
other of R32, R33, R34, R35, R36, R37, R39 and R40 to form part of a common
ring; when G is
present, any geminal R36- R37 may combine to form a carbonyl; any vicinal R36,
R37, R39 and
R40 may join to form unsaturation; and wherein any one group of substituents
R36, R37, R39 and
R40 may combine to form a substituted or unsubstituted fused unsaturated
moiety.
31. The modified amine compound according to Claim 29 wherein R34 is selected
from the
group consisting of hydroxy or perhydroxy radicals.
32. A bleaching composition comprising a modified amine compound in
conjunction with or
without a peroxygen source, wherein said modified amine compound is selected
from the group
consisting of modified amines having the general formula [V] and/or [VI],
modified amine oxides
having the general formula [VII] - [X], and mixtures thereof:
<IMGS>
109

<IMGS>
where R8-R10 are independently selected from substituted or unsubstituted
radicals selected from
the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl,
heterocyclic ring, silyl, nitro,
halo, cyano, alkoxy, keto, carboalkoxy radicals and anionic and/or cationic
charge carrying
radicals; R11, when present, is a radical selected from the group consisting
of substituted or
unsubstituted, saturated or unsaturated H, alkyl, cycloalkyl, aryl, alkaryl,
aralkyl, heterocyclic
ring, silyl, nitro, halo, cyano, alkoxy, keto, carboalkoxy radicals and
anionic and/or cationic
charge carrying radicals; R12 is a leaving group, the protonated form of which
has a pK .alpha. value
(H2O reference) that falls within the following range: 37 > pK .alpha. > -2;
with the proviso that any
R8-R12, when present, may combine to form a fused aryl, fused carbocyclic or
fused heterocyclic
ring.
33. The bleaching composition according to Claim 32 wherein R11 is represented
by the
formula:
<IMG>
where Z p is covalently bonded to T o, and Z p is selected from the group
consisting of
-CO2-, -SO3-, -OSO3-, -SO2- and -OSO2- and p is either 1, 2 or 3; T o is
selected from the group
consisting of substituted or unsubstituted, saturated or unsaturated alkyl,
cycloalkyl, aryl, alkaryl,
aralkyl, and heterocyclic ring.
110~

34. The bleaching composition according to Claim 32 wherein for R12, the pK
.alpha. value is
greater than 3 and less than 23.
35. The bleaching composition according to Claim 34 wherein for R12, the pK
.alpha. value is
greater than 9 and less than 21.
36. The bleaching composition according to Claim 35 wherein for R12, the pK
.alpha. value is
about greater than 11 and about less than 17.
37. The bleaching composition according to Claim 32 wherein R12 is selected
from the group
consisting of substituted or unsubstituted, saturated or unsaturated hydroxy,
perhydroxy, alkoxy
and peralkoxy radicals.
38. The bleaching composition according to Claim 37 wherein R12 is selected
from the group
consisting of hydroxy or perhydroxy radicals.
39. The bleaching composition according to Claim 32 wherein said modified
amine
compound comprises from about 0.001% to about 10% by weight of said
composition, and said
peroxygen source, when present, comprises from about 0.01 % to about 60% by
weight of said
composition.
40. The bleaching composition according to Claim 32 wherein said peroxygen
source, when
present, is selected from the group consisting of:
(a) preformed peracid compounds selected from the group consisting of
percarboxyl
acids and salts, percarbonic acids and salts, perimidic acids and salts,
peroxymonosulfuric acids
and salts, and mixtures thereof;
(b) hydrogen peroxide sources selected from the group consisting of perborate
compounds, percarbonate compounds, perphosphate compounds and mixtures
thereof; and a
bleach activator.
41. A bleaching composition wherein said modified amine compound has the
general formula
[XV] - [XX].
111

<IMGS>
where m is 1 to 3 when G is present and m is 1 to 4 when G is not present; and
n is an integer
from 0 to 4; R34 is a leaving group, the protonated form of which has a pK
.alpha. value (H2O
reference) that falls within the following range: 37 > pK .alpha. > -2; each
R35 is independently
selected from a substituted or unsubstituted radical selected from the group
consisting of H, alkyl,
cycloalkyl, aryl, fused aryl, heterocyclic ring, fused heterocyclic ring,
nitro, halo, cyano,
sulfonato, alkoxy, keto, carboxyl, and carboalkoxy radicals, and any two
vicinal R35 substituents
may combine to form a fused aryl, fused carbocyclic or fused heterocyclic
ring; R32 may be a
substituted or unsubstituted radical selected from the group consisting of H,
alkyl, cycloalkyl,
alkaryl, aryl, aralkyl, heterocyclic ring, silyl, nitro, halo, cyano,
sulfonato, alkoxy, keto, carboxyl,
and carboalkoxy radicals; R33 may be a substituted or unsubstituted, saturated
or unsaturated,
radical selected from the group consisting of H, alkyl, cycloalkyl, alkaryl,
aryl, aralkyl,
heterocyclic ring, including anionic and/or cationic charge carrying radicals.
42. The bleaching composition according to Claim 41 wherein R33 is represented
by the
formula:
112

<IMG>
where Z p is covalently bonded to T o, and Z p- is selected from the group
consisting of
-CO2-, -SO3-, -OSO3-, -SO2- and -OSO2-, and p iseither 1, 2 or 3; T o is
selected from the group
consisting of:
<IMG>
wherein q is an integer from 1 to 8; R38 is independently selected from
substituted or
unsubstituted radicals selected from the group consisting of linear or
branched H, alkyl,
cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxy,
arylcarbonyl, carboxyalkyl
and amide groups; G is selected from the group consisting of: (1) -O- ; (2) -
N(R39)-; and (3) -
N(R39R40)-; R36, R37, R39 and R40 are substituted or unsubstituted radicals
independently
selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl,
aryl, aralkyl,
alkylenes, heterocyclic ring, alkoxys, arylcarbonyl groups, carboxyalkyl
groups and amide
groups; any of R32, R33, R34, R35, R36, R37, R39 and R40 may be joined
together with any
other of R32, R33, R34, R35, R36, R37, R39 and R40 to form part of a common
ring; any
geminal R36- R37 may combine to form a carbonyl; any vicinal R36, R37, R39 and
R40 may join
to form unsaturation; and wherein any one group of substituents R36, R37, R39
and R40 may
combine to form a substituted or unsubstituted fused unsaturated moiety.
43. The bleaching composition according to Claim 41 wherein for R34, the pK
.alpha. value is
greater than 3 and less than 23.
44. The bleaching composition according to Claim 43 wherein for R34, the pK
.alpha. value is
greater than 11 and less than 17.
45. The bleaching composition according to Claim 41 wherein R34 is selected
from the group
consisting of substituted or unsubstituted, saturated or unsaturated hydroxy,
perhydroxy, alkoxy
and peralkoxy radicals.
113

46. The bleaching composition according to Claim 45 wherein R34 is selected
from the group
consisting of hydroxy or perhydroxy radicals.
47. The bleaching composition according to-Claim 32 wherein said bleaching
composition
further comprises one or more of the following detergent components selected
from the group
consisting of: surfactants, solvents, buffers, enzymes, soil release agents,
clay soil removal
agents, dispersing agents, brighteners, suds suppressors, fabric softeners,
suds boosters, enzyme
stabilizers, builders, chelants, other bleaching agents, dyes, dye transfer
inhibiting agents,
perfumes and mixtures thereof.
48. The bleaching composition according to Claim 47 wherein said bleaching
composition
further comprises a surfactant.
49. The bleaching composition according to Claim 48 wherein said surfactant is
a branched
surfactant.
50. The bleaching composition according to Claim 49 wherein said branched
surfactant is a
mid-chain branched surfactant.
51. The bleaching composition according to Claim 48 wherein said surfactant is
an anionic
surfactant.
52. The bleaching composition according to Claim 41 wherein said bleaching
composition
further comprises a chelating agent.
53. The bleaching composition according to Claim 41 wherein said bleaching
composition
further comprises other bleaching agents selected from the group consisting of
perborates,
percarbonates, perphosphates and mixtures thereof.
54. The bleaching composition according to Claim 53 wherein said bleaching
composition
further comprises a bleach activator.
55. The bleaching composition according to Claim 54 wherein said bleach
activator is
selected from the group consisting of hydrophobic bleach activators.
114

56. The bleaching composition according to Claim 55 wherein said hydrophobic
bleach
activators are selected from the group consisting of tetraacetyl ethylene
diamine (TAED),
benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-
chlorobenzoylcaprolactam,
benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (NOBS),
phenyl
benzoate (PhBz), decanoyloxybenzenesulphonate (C10-OBS), benzoylvalerolactam
(BZVL),
octanoyloxybenzenesulphonate (C8-OBS), perhydrolyzable esters, 4-[N-(nonanoyl)
amino
hexanoyloxy]-benzene sulfonate sodium salt (NACA-OBS),
lauryloxybenzenesulphonate (LOBS
or C12-OBS), 10-undecenoyloxybenzenesulfonate (UDOBS or C11-OBS with
unsaturation in the
position), decanoyloxybenzoic acid (DOBA) and mixtures thereof.
57. The bleaching composition according to Claim 41 wherein said bleaching
composition
further comprises an enzyme.
58. The bleaching composition according to Claim 57 wherein said enzyme is
selected from
the group consisting of cellulases, lipases, amylases, phospholipases,
proteases, peroxidases and
mixtures thereof.
59. A method for laundering a fabric in need of cleaning, said method
comprises contacting
said fabric with a laundry solution having a bleaching composition according
to Claim 32.
60. A laundry additive product comprising a modified amine compound selected
from the
group consisting of modified amine compounds having the general formula [V] -
[X], and
mixtures thereof:
<IMGS>
115

<IMGS>
where R8-R10 are independently selected from substituted or unsubstituted
radicals selected from
the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl,
heterocyclic ring, silyl, nitro,
halo, cyano, alkoxy, keto, carboalkoxy radicals and anionic and/or cationic
charge carrying
radicals; R11, when present, is a radical selected from the group consisting
of substituted or
unsubstituted, saturated or unsaturated H, alkyl, cycloalkyl, aryl, alkaryl,
aralkyl, heterocyclic
ring, silyl, nitro, halo, cyano, alkoxy, keto, carboalkoxy radicals and
anionic and/or cationic
charge carrying radicals; R12 is a leaving group, the protonated form of which
has a pK .alpha. value
(H2O reference) that falls within the following range: 37 > pK .alpha. > -2;
with the proviso that any
R8-R12, when present, may combine to form a fused aryl, fused carbocyclic or
fused heterocyclic
ring.
61. The laundry additive product according to Claim 60 wherein R11 is
represented by the
formula:
<IMG>
where Z p is covalently bonded to T o, and Z p is selected from the group
consisting of
-CO2-, -SO3-, -OSO3-, -SO2- and -OSO2- and p is either 1, 2 or 3; T o is
selected from the group
consisting of substituted or unsubstituted, saturated or unsaturated alkyl,
cycloalkyl, aryl, alkaryl,
aralkyl, and heterocyclic ring.
62. The laundry additive product according to Claim 60, wherein said laundry
additive
product is in a dosage form selected from the group consisting of a pill,
tablet, caplet, gelcap or
other single dosage form.
116

63. The laundry additive product according to Claim 60 wherein said laundry
additive
product further includes a suitable carrier.
117~

Description

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
CONTROLLED AVAILABILITY OF FORMULATION COMPONENTS,
COMPOSITIONS AND LAUNDRY METHODS EMPLOYING SAME
Field of the Invention
The present invention relates to a method for the controlled availability of
formulation
components, such as organic catalysts, into a wash solution. More
particularly, the present
invention relates to products and bleaching compositions containing such
formulation
components and laundry methods employing such formulation components.
Background of the Invention
Oxygen bleaching agents have become increasingly popular in recent years in
household
and personal care products to facilitate stain and soil removal. Bleaches are
particularly desirable
for their stain-removing, dingy fabric cleanup, whitening and sanitization
properties, as well as for
dye transfer inhibition. Oxygen bleaching agents have found particular
acceptance in laundry
products such as detergents, in automatic dishwashing products and in hard
surface cleansers.
Oxygen bleaching agents, however, are somewhat limited in their effectiveness.
Some frequently
encountered disadvantages include color damage on fabrics and damage to
laundry appliances. In
addition, oxygen bleaching agents tend to be extremely temperature rate
dependent. Thus, the
colder the solution in which they are employed, the less effective the
bleaching action.
Temperatures in excess of 60 °C are typically required for
effectiveness of an oxygen bleaching
agent in solution.
To solve the aforementioned temperature rate dependency, a class of compounds
known
as "bleach activators" has been developed. Bleach activators, typically
perhydrolyzable acyl
compounds having a leaving group such as oxybenzenesulfonate, react with the
active oxygen
group, typically hydrogen peroxide or its anion, to form a more effective
peroxyacid oxidant. It is
the peroxyacid compound which then oxidizes the stained or soiled substrate
material. However,
bleach activators are also somewhat temperature dependent. Bleach activators
are more effective
at warm water temperatures of from about 40 °C to about 60 °C.
In water temperatures of less
than about 40 °C, the peroxyacid compound loses some of its bleaching
effectiveness.
Attempts have been made as disclosed in U.S. Patent Nos. 5,360,568, 5,360,569
and
5,370,826 all to Madison et al. to develop a bleach system which is effective
in lower temperature
water conditions. However, the dihydroisoquinolinium bleach boosters disclosed
in these
references, when combined with peroxygen compounds, undergo undesired
decomposition,
particularly when in the presence of wash solution components.
1

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
U.S. Patent Nos. 5,576,282 and 5,817,614 both to Miracle et al. disclose
additional
attempts at developing a bleach system comprising organic catalysts which is
effective in lower
temperature water conditions and is safe on colors.
However, the prior art has failed to teach or disclose the delayed
(controlled) addition of
formulation components, such as organic catalysts, in accordance with the
present invention.
In light of the foregoing, researchers have been pursuing a method to mitigate
(or control)
the decomposition of the organic catalyst, particularly prior to contact with
the oxidizable stain.
Accordingly, the need remains for an effective method to deliver organic
catalysts and
compositions containing organic catalysts which provide effective bleaching
even in lower water
temperatures, provides improved stability toward unwanted organic catalyst
decomposition, and
maximizes peracid performance early in the wash cycle.
Summary of the Invention
This need is met by the present invention wherein methods to deliver organic
catalysts,
specifically bleach boosting compounds, bleaching species, modified amines,
modified amine
oxides, sulfonimines, phosphonimines, N-acylimines and/or thiodiazole dioxides
are provided.
Nonlimiting examples of the benefits provided by the methods for delivering
organic
catalysts of the present invention include: superior bleaching effectiveness
even in lower water
temperatures; avoidance of decomposition of organic catalysts which typically
occurs during the
premix period prior to addition of fabrics in need of cleaning (i.e., stained
fabrics); permitting
peracid to perform bleaching on stained fabrics in need of cleaning prior to
delivery of organic
catalysts in order to maximize peracid concentration with stains on fabrics;
and decrease of
peracid concentration via bleaching, thus reducing the rate of organic
catalyst decomposition by
excess peracid present in the wash solution.
In one aspect of the present invention, a method for laundering a fabric in
need of
cleaning comprising delivering an organic catalyst by a controlled
availability method as defined
by Test Protocols I, II and/or III, disclosed hereinafter, in conjunction with
or without, preferably
with, a peroxygen source to a wash solution containing the fabric, is
provided.
In another aspect of the present invention, a bleaching composition comprising
an organic
catalyst capable of becoming available (chemically available to interact with
other compounds) by
a controlled availability method as defined by Test Protocols I, II and/or
III, disclosed hereinafter,
to perform bleaching when delivered to a wash solution, in conjunction with or
without,
preferably with, a peroxygen source, is provided.
In still yet another aspect of the present invention, a product comprising an
organic
catalyst capable of becoming available (chemically available to interact with
other compounds) by
2

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
a controlled availability method as defined by Test Protocols I, II and/or
III, disclosed hereinafter,
to perform bleaching in the form of dye transfer inhibition when delivered to
a wash solution, in
conjunction with or without, preferably with, a peroxygen source is provided.
In yet another aspect of the present invention, a product comprising an
organic catalyst
capable of becoming available (chemically available to interact with other
compounds) by a
controlled availability method as defined by Test Protocols I, II and/or III,
disclosed hereinafter,
to perform bleaching when delivered to a wash solution, in conjunction with or
without,
preferably with, a peroxygen source, the product further including
instructions for using the
organic catalyst to clean a fabric in need of cleaning, the instructions
including the step of
delivering an amount of the product comprising the organic catalyst, in
conjunction with or
without a peroxygen source, to a wash solution containing the fabric such that
at least a majority
of said organic catalyst is delivered by a delivery means to the wash solution
after the fabric is
added to the wash solution is provided.
It has been surprisingly found that an organic catalyst being available
(chemically
available to interact with other compounds) by a controlled availability
method as defined by Test
Protocols I, II and/or III, disclosed hereinafter, in a wash solution
containing a peroxygen source
and a fabric in need of cleaning provides enhanced bleaching performance
compared to an
organic catalyst being instantaneously available (chemically available to
interact with other
compounds) in the wash solution.
By controlling the availability of the organic catalysts of the present
invention in a wash
solution containing a peroxygen source and a fabric by a controlled
availability method as defined
in Test Protocols I, II and/or III, disclosed hereinafter, the peroxygen
source/peracid can bleach
during the early part of the wash cycle when its concentration is the highest,
and at the same time
the exposure of the organic catalysts to the highest peroxygen source/peracid
concentration can be
avoided thus, reducing organic catalyst decomposition. The organic catalysts
can then become
available (chemically available to interact with other compounds, i.e.,
peracid) by a controlled
availability method as defined by Test Protocols I, II and/or III, as
disclosed hereinafter. Once
available in the wash solution, the organic catalysts can react with the
remaining available peracid
to form the oxygen transfer agents (bleaching species) which can oxidize
stains. This results in
the added benefits of the peroxygen source/peracid and the organic catalyst
being optimized.
Without being bound by theory, the organic catalysts, particularly the bleach
boosting compounds react with a peroxygen source, preferably a peracid, to
form the oxygen
transfer agents (bleaching species). Various decomposition pathways can lead
to
the decomposition of either the bleach boosting compound or the oxygen
transfer agent, leading
to decomposition products which can also react with the peroxygen
source/peracid.
3

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
Accordingly, controlling the availability of the organic catalysts, and thus
controlling the
timing of the contact between the organic catalysts and any peroxygen
sources/peracids in a wash
solution allows such peroxygen sources/peracids present in the wash solution
to perform
maximum bleaching on select stains of a fabric prior to coming into contact
with the organic
catalysts.
Under typical wash conditions, since the peracid reacts with stain slower than
the oxygen
transfer agent, there is often available oxygen in the form of peracid present
at the end of the wash
cycle. The available oxygen at the end of the wash cycle is at a lower
concentration, which
results in a lower bleaching rate, and upon completion of the wash, it results
in the wasting of the
remaining peracid. Actually, as the wash cycle proceeds, the concentration
(after perhydrolysis is
complete) begins to decrease due to the peracid bleaching stains and soils.
The bleaching done by
the peracid is relatively slow (from a kinetic point of view, especially at
lower wash bath
temperatures), and it is necessary to maximize the wash time and maximize the
concentration of
the peracid to maximize stain removal. It is important and necessary to allow
a high peracid
concentration to work on certain oxidizable stains, and then allow the organic
catalyst to work on
a complimentary set of oxidizable stains. It is known that peracids react
rapidly with the organic
catalysts which forms a bleaching species, which then reacts rapidly with
oxidizable stains.
Accordingly, it is an object of the present invention to provide: a method for
delivering
an organic catalyst by a controlled availability method as defined in Test
Protocols I, II and/or III,
which demonstrates improved performance even in lower temperature solutions as
well as being
able to mitigate (or control) unwanted decomposition and to maximize peracid
performance early
in the wash cycle; a method for laundering a fabric in need of cleaning by
delivering an organic
catalyst in a controlled availability method as defined in Test Protocols I,
II and/or III, disclosed
hereinafter, to a wash solution containing the fabric; a bleaching composition
comprising an
organic catalyst capable of becoming available by a controlled availability
method as defined by
Test Protocols I, II and/or III, disclosed hereinafter; and a product
comprising an organic catalyst
capable of becoming available by a controlled availability method as defined
by Test Protocols I,
II and/or III, disclosed hereinafter, to a wash solution already containing a
fabric in need of
cleaning. These, and other objects, features and advantages of the present
invention will be
recognized by one of ordinary skill in the art from the following description
and the appended
claims.
All percentages, ratios and proportions herein are on a weight basis unless
otherwise
indicated. All documents cited herein are hereby incorporated by reference.
Detailed Descr~tion of the Invention
4

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
The present invention discloses novel and highly useful methods for delivering
organic
catalyst compounds, also referred to as organic catalysts ("bleach boosting
compounds",
"bleaching species", "modified amines", "modified amine oxides", sulfonimines,
phosphinimines,
thiodiazole dioxides and mixtures thereof), by a controlled availability
method as defined in Test
Protocols I, II and/or III, disclosed hereinafter, to a wash solution
containing a fabric in need of
cleaning (i.e., stained/soiled fabric).
The controlled availability methods for delivering organic catalysts of the
present
invention provide increased bleaching effectiveness even in lower temperature
applications while
being able to mitigate (or control) unwanted decomposition. As a result, the
organic catalysts and
methods of using same in accordance with the present invention result in
superior mitigation of
unwanted decomposition, which leads to increased catalytic efficiency, which
leads to increased
bleaching, and thus enhanced performance. Further, the organic catalysts and
methods of using
same in accordance with the present invention maximize peracid performance
early in the wash
cycle, resulting in improved overall performance. The controlled availability
methods as defined
1 S in Test Protocols I, II and/or III, disclosed hereinafter, permit the
organic catalysts to become
chemically available to interact with other compounds in a wash solution in a
controlled (less than
total amount of organic catalyst becoming available at one time) rather than a
lump sum (total
amount of organic catalyst becoming available at one time) manner.
DEFINITIONS
"Becoming Available" means herein, becoming chemically available to interact
with
other compounds.
"Peroxygen source" as used herein means materials that generate peroxygen
compounds,
which can include the peroxygen compounds themselves. Examples include, but
are not limited
to, bleach activators, peracids, percarbonate, perborate, hydrogen peroxide,
bleach boosting
compounds, and/or bleaching species (e.g., oxaziridiniums).
"Peroxygen compounds" as used herein includes peracids and peroxides (e.g.,
hydrogen
peroxide, alkyl hydroperoxides, etc.
"Peracid" as used herein means a peroxyacid such as peroxycarboxylic acid
and/or
peroxymonosulfuric acid (tradname OXONE) and their salts.
The methods for delivering organic catalysts of the present invention act in
conjunction
with or without, preferably with conventional peroxygen bleaching sources, to
provide the above-
mentioned increased bleaching effectiveness and superior mitigation of
unwanted decomposition.
ORGANIC CATALYST COMPOUNDS
Nonlimiting examples of organic catalyst compounds, such as bleach boosting
and
bleaching species compounds are described in U.S. Patent Nos. 5,041,232,
5,045,223, 5,047,163,
5

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
5,310,925, 5,413,733, 5,360,568, 5,482,515, 5,550,256, 5,360,569, 5,478,357,
5,370,826,
5,442,066, 5,576,282, 5,760,222, 5,753,599, 5,652,207 and 5,817,614, PCT
Published
Applications WO 98/23602, WO 95/13352, WO 95/13353, WO 95/13351, WO 97/06147
and
WO 98/23717, and EP 728 182.
The organic catalyst compounds of the present invention and bleaching
compositions
(products) containing such organic catalyst compounds that are particularly
useful in the methods
of the present invention are the organic catalyst compounds and compositions
containing same
that satisfy the conditions outlined in Test Protocols I, II and/or III,
disclosed hereinafter.
Preferably, the organic catalyst compounds of the present invention, more
preferably the
iminium-based organic catalyst compounds of the present invention, include,
but are not limited
to, bleach boosting compounds, modified amines, modified amine oxides,
sulfonimines,
phosphinimes, thiodiazole dioxides and mixtures thereof.
I Bleach Boosting Compounds - The bleach boosting compounds, preferably
iminium
based bleach boosting compounds, of the present invention include, but are not
limited to,
aryliminium cations, aryliminium polyions, which have a net charge of from
about +3 to about -3,
and aryliminium zwitterions, which have a net charge of from about +3 to about
-3.
A preferred organic catalyst in accordance with the present invention and for
use in the
bleaching compositions of the present invention is a bleach boosting compound
selected from
aryliminium zwitterions or its oxaziridinium bleaching species because unlike
aryliminium
cations and/or oxaziridinium cations, the zwitterions provide effective
bleaching without resulting
in unacceptable level of color damage on fabrics.
a. _Aryliminium Canons and Polyions - The aryliminium cations and
aryliminium polyions, which have a net charge of from about +3 to about -3,
are represented by
the formula [I]:
i
. Ra
R3
[I]
where R2 and R3 are independently selected from substituted or unsubstituted,
saturated or
unsaturated radicals selected from the group consisting of H, alkyl,
cycloalkyl, aryl, alkaryl,
aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, sulfonato, alkoxy,
keto, carboxylic, and
carboalkoxy radicals; R1 and R4 are selected from substituted or
unsubstituted, saturated or
6

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
unsaturated radicals selected from the group consisting of H, alkyl,
cycloalkyl, aryl, alkaryl,
aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, alkoxy, keto and
carboalkoxy radicals; and X-
is a suitable charge-balancing, preferably bleach-compatible counterion; and v
is an integer from
1 to 3.
Preferably, the aryliminium canons and aryliminium polyions, which have a net
charge of
from about +3 to about -3, are represented by the formula [XI]:
R22
/ G R2 i
~2o n ~ ~ ~XOw
\ i ~~Ri9
Ri g
[XI]
where m is 1 to 3 when G is present and m is 1 to 4 when G is not present; and
n is an integer
from 0 to 4; each R20 is independently selected from a substituted or
unsubstituted radical
selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused aryl,
heterocyclic ring,
fused heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto,
carboxylic, and carboalkoxy
radicals, and any two vicinal R20 substituents may combine to form a fused
aryl, fused
carbocyclic or fused heterocyclic ring; R18 may be a substituted or
unsubstituted radical selected
from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl,
heterocyclic ring, silyl,
nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy
radicals; R19 is a radical
selected from the group consisting of substituted or unsubstituted, saturated
or unsaturated, H,
alkyl, cycloalkyl, alkaryl, aryl, aralkyl and heterocyclic ring; G is selected
from the group
consisting o~ (1) -O- ; (2) -N(R23)-; and (3) -N(R23R24)-; R21-R24 are
substituted or
unsubstituted radicals independently selected from the group consisting of H,
oxygen, linear or
branched C1-C12 alkyls, alkylenes, alkoxys, aryls, alkaryls, aralkyls,
cycloalkyls, and
heterocyclic rings; provided that any of R18, R19, R20, R21_R24 may be joined
together with any
other of Rlg, R19, R20, R21-R24 to form part of a common ring; any geminal R21-
R22 may
combine to form a carbonyl; any vicinal R21-R24 may join to form unsaturation;
and wherein any
one group of substituents R21-R24 may combine to form a substituted or
unsubstituted fused
unsaturated moiety; X- is a suitable charge-balancing counterion, preferably a
bleach-compatible
counterion; and v is an integer from 1 to 3.
More preferred, aryliminium canons and aryliminium polyions, which have a net
charge
of from about +3 to about -3, as represented by the formula [XI], include
those of formula [XI]
7

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
where R1g is H or methyl and R19 is H or substituted or unsubstituted,
saturated or unsaturated
C 1 ' C 14 alkyl.
b. Aryliminium Zwitterions - The aryliminium zwitterions, which have a net
charge of
from about +3 to about -3, are represented by the formula [II]:
Rs
R6 N O
R~
[II]
where RS-R~ are independently selected from substituted or unsubstituted
radicals selected from
the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl,
heterocyclic ring, silyl, nitro,
halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy radicals;
also present in this
formula is the radical represented by the formula:
- T ~O
0
where ZP is covalently bonded to To, and ZP is selected from the group
consisting of
-C02-, -S03-, -OS03-, -S02- and -OS02- and p is either 1, 2 or 3; Ta is
selected from the group
consisting of substituted or unsubstituted, saturated or unsaturated alkyl,
cycloalkyl, aryl, alkaryl,
aralkyl, and heterocyclic ring.
Preferably, the aryliminium zwitterions, which have a net charge of from about
+3 to
about -3, are represented by the formula [XII]:
R2s
G~ R2~
~26 I L~m
n ~ ~ o\ To ~O
RZs
[XII]
where m is 1 to 3 when G is present and m is 1 to 4 when G is not present; and
n is an integer
from 0 to 4; each R26 is independently selected from a substituted or
unsubstituted radical
selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused aryl,
heterocyclic ring,
fused heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto,
carboxylic, and carboalkoxy
8

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
radicals, and any two vicinal R26 substituents may combine to form a fused
aryl, fused
carbocyclic or fused heterocyclic ring; R25 may be a substituted or
unsubstituted radical selected
from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl,
heterocyclic ring, silyl,
nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy
radicals; also present in
this formula is the radical represented by the formula:
- T -Zp0
°
where ZP is covalently bonded to To, and ZP is selected from the group
consisting of
-C02-, -S03-, -OS03-, -S02- and -OS02- and p is either 1, 2 or 3; To is
selected from the group
consisting of:
R29
-~C)q
R29
wherein q is an integer from 1 to 8; R29 is independently selected from
substituted or
unsubstituted radicals selected from the group consisting of linear or
branched H, alkyl,
cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxy,
arylcarbonyl, carboxyalkyl
and amide groups; G is selected from the group consisting of: (1) -O- ; (2) -
N(R30)-; and (3) -
N(R30R31)-; R27~ R28~ R30 and R31 are substituted or unsubstituted radicals
independently
selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl,
aryl, aralkyl,
alkylenes, heterocyclic ring, alkoxys, arylcarbonyl groups, carboxyalkyl
groups and amide'
groups; any of R25, R26, R27~ R28~ R30 and R31 may be joined together with any
other of R25,
R26~ R27~ R28~ R30 and R31 to form part of a common ring; any geminal R27 -
R28 may
combine to form a carbonyl; any vicinal R27 - R31 may join to form
unsaturation; and wherein
any one group of substituents R27 - R31 may combine to form a substituted or
unsubstituted
fused unsaturated moiety.
More preferred aryliminium zwitterions, which have a net charge of from about
+3 to
about -3, as represented by the formula [XII], include those of formula [XII]
where R25 is H or
methyl, and for the radical represented by the formula:
- ,T -Zp0
°
ZP is -C02-, -S03- or -OS03-, and p is 1 or 2, even more preferably Zp is -S03-
or -OS03- and
p is 1.
9

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
II Modified Amine/Amine Oxide Compounds - The modified amine and/or amine
oxide
compounds of the present invention include, but are not limited to, modified
amines and modified
amine oxides having a net charge of from about +3 to about -3.
a. Modified Amines - The modified amines are represented by formulas [V] and
[VI]:
R8 R8
R N~RI1 Ro N~T-
Rl ~ R ~z o
Ri z R
[V] [VI]
where R9-R1~ are independently selected from substituted or unsubstituted
radicals selected from
the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl,
heterocyclic ring, silyl, nitro,
halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy radicals and
anionic and/or
cationic charge carrying radicals; R8 and R11, when present, are radicals
selected from the group
consisting of substituted or unsubstituted, saturated or unsaturated H, alkyl,
cycloalkyl, aryl,
alkaryl, aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, alkoxy, keto
and carboalkoxy radicals
and anionic and/or cationic charge carrying radicals; Rl2 is a leaving group,
the protonated form
of which has a pKa value (H20 reference) that falls within the following
range: 37 > pKa > -2;
with the proviso that any R8-R12, when present, may combine to form a fused
aryl, fused
carbocyclic or fused heterocyclic ring; and also present in this formula is
the radical represented
by the formula:
- T -Zp0
0
where Zp is covalently bonded to To, and ZP is selected from the group
consisting of
-C02-, -S03-, -OS03-, -S02- and -OS02- and p is either 1, 2 or 3; To is
selected from the group
consisting of substituted or unsubstituted, saturated or unsaturated alkyl,
cycloalkyl, aryl, alkaryl,
aralkyl, and heterocyclic ring.
Preferably, the modified amines are represented by the formulas [XV] and
[XVI]:

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
37 R37
G R36 / G R36
~35 ~ rn35 n ~ ~m
N~ R33
R32 X R32~34 To
IR34 R
[XV] [XVI]
where m is 1 to 3 when G is present and m is 1 to 4 when G is not present; and
n is an integer
from 0 to 4; R34 is a radical selected from the group consisting of
substituted or unsubstituted,
saturated or unsaturated hydroxy, perhydroxy, alkoxy, peralkoxy, carboxylic,
percarboxylic,
sulfonato, and persulfonato radicals; each R35 is independently selected from
a substituted or
unsubstituted radical selected from the group consisting of H, alkyl,
cycloalkyl, aryl, fused aryl,
heterocyclic ring, fused heterocyclic ring, nitro, halo, cyano, sulfonato,
alkoxy, keto, carboxylic,
and carboalkoxy radicals, and any two vicinal R35 substituents may combine to
form a fused aryl,
fused carbocyclic or fused heterocyclic ring; R32 may be a substituted or
unsubstituted radical
selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl,
aralkyl, heterocyclic ring,
silyl, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and
carboalkoxy radicals; R33 may
be a substituted or unsubstituted, saturated or unsaturated, radical selected
from the group
consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring,
and also present in this
formula is the radical represented by the formula:
- T -Zp0
0
where ZP is covalently bonded to To, and ZP is selected from the group
consisting of
-C02-, -S03-, -OS03-, -S02- and -OS02-, and p is either 1, 2 or 3; To is
selected from the group
consisting o~
R38
-~C)q
R38
wherein q is an integer from 1 to 8; R38 is independently selected from
substituted or
unsubstituted radicals selected from the group consisting of linear or
branched H, alkyl,
cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxy,
arylcarbonyl, carboxyalkyl
and amide groups; G is selected from the group consisting of: (1) -O- ; (2) -
N(R39)-; and (3)
11

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
N(R39R40)_; R36~ R37~ R39 and R40 are substituted or unsubstituted radicals
independently
selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl,
aryl, aralkyl,
alkylenes, heterocyclic ring, alkoxys, arylcarbonyl groups, carboxyalkyl
groups and amide
groups; any of R32, R33, R34~ R35~ R36~ R37~ R39 and R40 may be joined
together with any
other of R32, R33, R34~ R35~ R36~ R37~ R39 and R40 to form part of a common
ring; any
geminal R36- R37 may combine to form a carbonyl; any vicinal R36, R37, R39 and
R40 may join
to form unsaturation; and wherein any one group of substituents R36, R37, R39
and R40 may
combine to form a substituted or unsubstituted fused unsaturated moiety.
Examples of such modified amines include, but are not limited to those with an
R34 radical
selected from the group consisting of substituted or unsubstituted, saturated
or unsaturated
hydroxy, perhydroxy, alkoxy, peralkoxy, carboxyl, percarboxyl, sulfonato and
persulfonato
radicals.
Preferably, the R34 radical is selected from the group consisting of
substituted or
unsubstituted, saturated or unsaturated hydroxy, perhydroxy, alkoxy and
peralkoxy radicals. The
following examples are meant to exemplify such modified amines of the present
invention, but
are not necessarily meant to limit or otherwise define the scope of the
invention.
Me0
OS03H ~ 1
N
N\ ~ N Me0 ~ \
OH OH OEt
t-Bu
N~ Ph N~~ SO~
t-Bu
Me OOH OH
O O
~OH
\ SO~
12

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
More preferably, for the modified amines represented by the formulas [XV] and
[XVI],
R34 is a leaving group, the protonated form of which has a pKa value (H20
reference) that fall
within the following range: 30 > pKa > 0; more preferably 23 > pKa > 3; even
more preferably 21
> pKa > 9; most preferably 17 > pKa > 11.
Preferably, for the modified amines represented by the formulas [XV] and
[XVI], R12 is
selected from the group consisting of substituted or unsubstituted, saturated
or unsaturated
hydroxy, perhydroxy, alkoxy and peralkoxy radicals. More preferably, for the
modified amines
represented by the formulas [XV] and [XVI] wherein said R12 is selected from
the group
consisting of hydroxy or perhydroxy.
Even more preferred modified amines, as represented by the formulas [XV] and
[XVI],
include those modified amines having a net charge of about +1 to about -1
where R32 is H or Me;
R34 is a radical selected from the group consisting of hydroxy and perhydroxy
radicals; R35 is
independently selected from the group consisting of H, alkyl, nitro, halo,
sulfonato, alkoxy,
carboxyl and carboalkoxy radicals and/or ZP is -C02-, -S03- or -OS03-.
For the modified amines, R12 is a leaving group (LG), the protonated form of
which has a
pKa value (H20 reference) that fall within the following range: 37 > pKa > -2;
preferably 30 >
pKa > 0; more preferably 23 > pKa > 3; even more preferably 17 > pKa > 11;
most preferably
R12 is a leaving group consisting of substituted or unsubstituted, saturated
or unsaturated
hydroxy, perhydroxy, alkoxy and peralkoxy radicals; and any Rg-R12 may combine
to form a
fused aryl, fused carbocyclic or fused heterocyclic ring.
b. Modified Amine Oxides - The modified amine oxides of the present invention
are
represented by formulas [VII]-[X]:
Rg
O
R9 ON ~ O R9 ~N ~ 0
R~ o~ ~ Ri i Ri o~2 w To ~O
' 12
R R
[VII] [VIII]
Rs Rg
R9 ~~0~~4 R9 ~~O~DO
Rl o~ ~ Rl 1 Ri o~2 \ To
'12
R R
[IX] [X]
13

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
where R8-R10 are independently selected from substituted or unsubstituted
radicals selected from
the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl,
heterocyclic ring, silyl, nitro,
halo, cyano, sulfonato, alkoxy, keto, carboxyl, and carboalkoxy radicals and
anionic and/or
cationic charge carrying radicals; R11 is a radical selected from the group
consisting of
substituted or unsubstituted, saturated or unsaturated H, alkyl, cycloalkyl,
aryl, alkaryl, aralkyl,
heterocyclic ring, silyl, nitro, halo, cyano, sulfonato, alkoxy, keto,
carboxyl, and carboalkoxy
radicals and anionic and/or cationic charge carrying radicals; R12 is a
leaving group, the
protonated form of which has a pKavalue (H20 reference) that falls within the
following range:
37 > pKa > -2; with the proviso that any Rg-R12, when present, may combine to
form a fused
aryl, fused carbocyclic or fused heterocyclic ring; and also present in this
formula is the radical
represented by the formula:
- T -Zp0
0
where Zp is covalently bonded to To, and ZP is selected from the group
consisting of
-C02-, -S03-, -OS03-, -S02- and -OS02- and p is either 1, 2 or 3; To is
selected from the group
consisting of substituted or unsubstituted, saturated or unsaturated alkyl,
cycloalkyl, aryl, alkaryl,
aralkyl, and heterocyclic ring.
Preferably, for the modified amine oxides represented by the formulas [VII] -
[X], R12 is
a leaving group, the protonated form of which has a pKa value (H20 reference)
that fall within
the following range: 30 > pKa > 0; more preferably 23 > pKa > 3; even more
preferably 21 > pKa
> 9; most preferably 17 > pKa > 11.
Preferably, for the modified amine oxides represented by the formulas [VII] to
[X], R12
is selected from the group consisting of substituted or unsubstituted,
saturated or unsaturated
hydroxy, perhydroxy, alkoxy and peralkoxy radicals. More preferably, for the
modified amine
oxides represented by the formulas [VII] to [X], R12 is selected from the
group consisting of
hydroxy or perhydroxy.
Also preferably, the modified amine oxides are represented by formulas [XVII]-
[XX]:
R3~ R37
G R36 / G~ R36
~3s ~ ~m ~35 I m
n ~ O+N_00 n ~ O+N-OO
R32~ ~R33 R32
' IR34 R34
[XVII] [XVIII]
14

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
R3~ R3~
/ G mR3 ~p 35 / G~mR3 ~O
~35 I / /
n ~ ~ n ~ O+
\ ON-O \ N-O O
~ 33 32
R32 i34 R R R34 T
R
[XIX] [XX]
S where m is 1 to 3 when G is present and m is 1 to 4 when G is not present;
and n is_an integer
from 0 to 4; R34 is a radical selected from the group consisting of
substituted or unsubstituted,
saturated or unsaturated hydroxy, perhydroxy, alkoxy, peralkoxy, carboxyl,
percarboxyl,
sulfonato, persulfonato radicals; each R35 is independently selected from a
substituted or
unsubstituted radical selected from the group consisting of H, alkyl,
cycloalkyl, aryl, fused aryl,
heterocyclic ring, fused heterocyclic ring, nitro, halo, cyano, sulfonato,
alkoxy, keto, carboxyl,
and carboalkoxy radicals, and any two vicinal R35 substituents may combine to
form a fused aryl,
fused carbocyclic or fused heterocyclic ring; R32 may be a substituted or
unsubstituted radical
selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl,
aralkyl, heterocyclic ring,
silyl, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxyl, and carboalkoxy
radicals; R33 may be
a substituted or unsubstituted, saturated or unsaturated, radical selected
from the group consisting
of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, and also
present in this formula is
the radical represented by the formula:
- T -Zp0
0
where ZP is covalently bonded to To, and ZP is selected from the group
consisting of
-C02', -S03', -OS03', -S02' and -OS02', and p iseither 1, 2 or 3; To is
selected from the group
consisting of:
R38
-~C)q
R38
wherein q is an integer from 1 to 8; R38 is independently selected from
substituted or
unsubstituted radicals selected from the group consisting of linear or
branched H, alkyl,
cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxy,
arylcarbonyl, carboxyalkyl

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
and amide groups; G is selected from the group consisting of: (1) -O- ; (2) -
N(R39)-; and (3) -
N(R39R4~)-; R36, R37~ R39 and R4~ are substituted or unsubstituted radicals
independently
selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl,
aryl, aralkyl,
alkylenes, heterocyclic ring, alkoxys, arylcarbonyl groups, carboxyalkyl
groups and amide
groups; any of R32, R33, R34~ R35~ R36~ R37~ R39 and R4~ may be joined
together with any
other of R32, R33, R34~ R35~ R36~ R37~ R39 and R4~ to form part of a common
ring; any
geminal R36- R37 may combine to form a carbonyl; any vicinal R36, R37, R39 and
R4~ may join
to form unsaturation; and wherein any one group of substituents R36, R37, R39
and R4~ may
combine to form a substituted or unsubstituted fused unsaturated moiety;
Examples of such modified amine oxides include, but are not limited to those
with an R34
radical selected from the group consisting of substituted or unsubstituted,
saturated or unsaturated
hydroxy, perhydroxy, alkoxy, peralkoxy, carboxyl, percarboxyl, sulfonato and
persulfonato
radicals.
Preferably, the R34 radical is selected from the group consisting of
substituted or
unsubstituted, saturated or unsaturated hydroxy, perhydroxy, alkoxy and
peralkoxy radicals.
/O ~ I ~ ~OS03H
O
N ~ N
O
OH OH
Me0 / / I t-Bu p
p O
O ~ N ~ Ph N'~ SO~
Me0 \ O+~ O t-Bu ~0
OEt Me OOH OH
0 ~ 00
t-Bu00 O
OH
More preferably, for the modified amine oxides represented by the formulas
[XVII] and
[XX], R34 is a leaving group, the protonated form of which has a pKa value
(H20 reference) that
16

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
fall within the following range: 30 > pKa > 0; more preferably 23 > pKa > 3;
even more
preferably 21 > pKa > 9; most preferably 17 > pKa > 11.
Preferably, for the modified amine oxides represented by the formulas [XVII]
to [XX],
R34 is selected from the group consisting of substituted or unsubstituted,
saturated or unsaturated
hydroxy, perhydroxy, alkoxy and peralkoxy radicals. More preferably, for the
modified amine
oxides represented by the formulas [XVII] to [XX], R34 is selected from the
group consisting of
hydroxy or perhydroxy.
Even more preferred modified amine oxides, as represented by the formulas
[XVII] and
[XX], include those modified amine oxides having a net charge of about +1 to
about -1 where
R32 is H or Me; R34 is a radical selected from the group consisting of hydroxy
and perhydroxy
radicals; R35 is independently selected from the group consisting of H, alkyl,
vitro, halo,
sulfonato, alkoxy, carboxyl and carboalkoxy radicals and/or ZP is -C02-, -S03-
or -OS03-.
For the modified amine oxides, R12 is a leaving group (LG), the protonated
form of
which has a pKa value (H20 reference) that fall within the following range: 37
> pKa > -2;
preferably 30 > pKa > 0; more preferably 23 > pKa > 3; even more preferably 17
> pKa > 11;
most preferably R12 is a leaving group consisting of substituted or
unsubstituted, saturated or
unsaturated hydroxy, perhydroxy, alkoxy and peralkoxy radicals; and any Rg-R12
may combine
to form a fused aryl, fused carbocyclic or fused heterocyclic ring.
Nonlimiting examples of suitable modified amine compounds (modified amines
and/or
modified amine oxides) (and the pKa (H20 reference) value of the protonated
form of R12) in
accordance with the present invention include, but are not limited to:
00
~503~
CH3
O O
pKa=-0.25 pKa=4.76
o Ph
N I
/ CH3 Nwt_Bu
N O~ ~ I ~-OpEtO OEt
CH3 S O HOO ~ t-Bu O O
17

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
pKa ~ 10. S pKa ~ 11.6 pKa ~ 13
00
\/
N-
/ Ph N
Ph ~N/
~ ~ 00 \
Me3Si/ I
Ot-Bu NHPh
pKa~15.7 pKa~20 pKa~28 pKa~37
S
The modified amine compounds of the present invention act in conjunction with
the
peroxygen source to provide a more effective bleaching system. Peroxygen
sources are well-
known in the art and the peroxygen source employed in the present invention
may comprise any
of these well known sources, including peroxygen compounds as well as
compounds which under
consumer use conditions provide an effective amount of peroxygen in situ. The
peroxygen source
may include a hydrogen peroxide source, the in situ formation of a peracid
anion through the
reaction of a hydrogen peroxide source and a bleach activator, preformed
peracid compounds or
mixtures of suitable peroxygen sources.' Of course, one of ordinary skill in
the art will recognize
that other sources of peroxygen may be employed without departing from the
scope of the
1 S invention. Preferably, the peroxygen source is an organic and/or an
inorganic peracid.
IV. Sulfonimines Phosphonimines N-Acylimines Thiodiazole Dioxides - The
sulfonimines, phosphonimines, N-acylimines and thiodiazole dioxides of the
present invention are
represented by the formulas [XXIa], [XXIb], [XXII] and [XXIII],
respectiRv421y.
,_N
~ S02
R43
R42 N R42 Nw 44 R42 N R44 R41 N
~ SO2R44 ~ P02R
R43 R R43 O R
[XXIa] [XXIb] [XXII] [XXIII]
where R41-R44, when present, are independently selected from substituted or
unsubstituted,
saturated or unsaturated radicals selected from the group consisting of H,
alkyl, cycloalkyl, aryl,
alkaryl, aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, sulfonato,
alkoxy, keto, carboxylic, and
carboalkoxy radicals; provided that any of R41-R44 may be joined together with
any other R41-
R44 to form part of a common ring, including a fused aryl, fused carbocyclic
or fused
heterocyclic ring.
18

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
II Bleaching Species - The bleaching species (oxaziridiniums, oxaziridines)
may also be
used directly in accordance with the present invention. The bleaching species
of the present
invention include, but are not limited to, oxaziridinium cations,
oxaziridinium polyions, which
have a net charge of from about +3 to about -3, oxaziridinium zwitterions,
which have a net
charge of from about +3 to about -3, oxaziridine sulfonimines, oxaziridine
phosphonimines,
oxaziridine thiodiazole dioxides, and mixtures thereof.
The organic catalysts, especially the aryliminium cations, aryliminium
polyions,
aryliminium zwitterions, sulfonimines, phosphonimines, thiodiazole dioxides of
the present
invention act in conjunction with a peroxygen source, when present to increase
bleaching
effectiveness. Without being bound by theory, it is believed that the organic
catalysts react with
the peroxygen source to form a more active bleaching species, a quaternary
oxaziridinium and/or
oxaziridine compounds, as represented by the following reaction by way of
example:
R R O
2 ~ ~ ~ R2, O ~ N p 4, X + O
R' /_N ~ R4 + RCO~ ~ ~ R RC02
R3 R3,
42 42' O ~ N
R ~N ~ S02R44 + RCO~ ~ R ~ ~ SO2R44~ + RCO
R43 R43'
R42 N R44 + RCOO ~ R42' O~N R44 + RCO
3
~3 R43
R O
The oxaziridinium and/or oxaziridine compounds can have an increased or
preferred
activity at lower temperatures relative to the peroxygen compound.
a. Oxaziridinium Cations and Polyions - The oxaziridinium canons and polyions,
which
have a net charge of from about +3 to about -3, are represented by the formula
[III]:
R~, O
R2, N O+ ~X w
~~.R4
~3, O
R
[III]
19

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
where R2~ - R3~ are independently selected from substituted or unsubstituted
radicals selected
from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl,
heterocyclic ring, silyl,
nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy
radicals; R1~ and R4~ are
radicals selected from the group consisting of substituted or unsubstituted,
saturated or
unsaturated, H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring,
silyl, nitro, halo, cyano,
alkoxy, keto and carboalkoxy radicals; and X- is a suitable charge-balancing
counterion,
preferably a bleach-compatible counterion; and v is an integer from 1 to 3.
Preferably, the oxaziridinium cations and polyions, which have a net charge of
from
about +3 to about -3, are represented by formula [XIII]:
R22,
G~ R2 n
2o I L~Tm
(R ~n ~ O+NI ~ R19'
Rl8p CX°)~
[XIII]
wherein m is 1 to 3 when G is present and m is 1 to 4 when G is not present;
and n is an integer
from 0 to 4; each R20' is independently selected from a substituted or
unsubstituted radical
selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused aryl,
heterocyclic ring,
fused heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto,
carboxylic, and carboalkoxy
radicals, and any two vicinal R20' substituents may combine to form a fused
aryl, fused
carbocyclic or fused heterocyclic ring; R1 g~ may be a substituted or
unsubstituted radical selected
from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl,
heterocyclic ring, silyl,
nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy
radicals; R19~ may be a
substituted or unsubstituted, saturated or unsaturated, radical selected from
the group consisting of
H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl and heterocyclic ring. G is
selected from the group
consisting of: (1) -O- ; (2) -N(R23')-; and (3) -N(R23'R24')-; R21'_R24' are
substituted or
unsubstituted radicals independently selected from the group consisting of H,
oxygen, linear or
branched C1-C12 alkyls, alkylenes, alkoxys, aryls, alkaryls, aralkyls,
cycloalkyls, and
heterocyclic rings; provided that any of R1 g', R19', R21'-R24' may be joined
together with any
other of R18', R19', R21'_R24' to form part of a common ring; any geminal R21'
- R22' may
combine to form a carbonyl; any vicinal R21' - R24' may join to form
unsaturation; and wherein
any one group of substituents R21' - R24' may combine to form a substituted or
unsubstituted
fused unsaturated moiety; and wherein any one group of substituents R21 ~ -
R24' may combine to

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
form a substituted or unsubstituted fused unsaturated moiety; X- is a suitable
charge-balancing
counterion, preferably a bleach-compatible counterion; and v is an integer
from 1 to 3.
More preferred oxaziridinium cations and oxaziridinium polyions, which have a
net
charge of from about +3 to about -3, as represented by the formula [XIII],
include those of
formula [XIII] where RIg~ is H or methyl, and RI9~ is H or substituted or
unsubstituted, saturated
or unsaturated, C I - C 14 alkyl and cycloalkyl.
b. Oxaziridinium Zwitterions - The oxaziridinium zwitterions, which have a net
charge
of from about +3 to about -3, are represented by formula [IV]:
5'
R
R6, N O O
To- Z~P
~, O
R
[IV]
where R5~-R~~ are independently selected from substituted or unsubstituted
radicals selected from
the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl,
heterocyclic ring, silyl, nitro,
halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy radicals;
also present in this
formula is the radical represented by the formula:
-To~Q
where Z'P is covalently bonded to T'o, and Z'P is selected from the group
consisting of -C02-, -
S03-, -OS03-, -S02- and -OS02- and p is either 1, 2 or 3; T'o is selected from
the group
consisting of substituted or unsubstituted, saturated or unsaturated alkyl,
cycloalkyl, aryl, alkaryl,
aralkyl, and heterocyclic ring.
Preferably, the oxaziridinium zwitterions, which have a net charge of from
about +3 to
about -3, are represented by formula [XIV]:
R2s'
G~ R2~'
[R26'~
\ ON\T/Z,pO
R2sp
[xlv]
wherein m is 1 to 3 when G is present and m is 1 to 4 when G is not present;
and n is an integer
from 0 to 4; each R26' is independently selected from a substituted or
unsubstituted radical
21

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused aryl,
heterocyclic ring,
fused heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto,
carboxylic, and carboalkoxy
radicals, and any two vicinal R26' substituents may combine to form a fused
aryl, fused
carbocyclic or fused heterocyclic ring; R25' may be a substituted or
unsubstituted radical selected
from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl,
heterocyclic ring, silyl,
nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy
radicals; and also present
in this formula is the radical represented by the formula:
O
-To Z'p
where Z'P is covalently bonded to T'o, and Z'p is selected from the group
consisting of -C02-, -
S03-, -OS03-, -S02- and -OS02-, and a is either 1 or 2; T'o is selected from
the group consisting
of:
R29'
yC)q-
R29'
wherein q is an integer from 1 to 8; R29~ is independently selected from
substituted or
unsubstituted radicals selected from the group consisting of linear or
branched H, alkyl,
cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxy,
arylcarbonyl, carboxyalkyl
and amide groups; G is selected from the group consisting of: (1) -O- ; (2) -
N(R30~)-; and (3) -
N(R30~R31')-; R27'~ R28'~ R30' and R31~ are substituted or unsubstituted
radicals independently
selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl,
aryl, aralkyl,
alkylenes, heterocyclic ring, alkoxys, arylcarbonyl groups, carboxyalkyl
groups and amide
groups; any of R25~, R26', R27'~ R28'~ R30' and R31~ may be joined together
with any other of
R25'~ R26'~ R27'~ R28'~ R30' and R31~ to form part of a common ring; any
geminal R27~ - R28'
may combine to form a carbonyl; any vicinal R27~ - R31' may join to form
unsaturation; and
wherein any one group of substituents R27~ - R31' may combine to form a
substituted or
unsubstituted fused unsaturated moiety.
More preferred aryliminium zwitterions, which have a net charge of from about
+3 to
about -3, as represented by the formula [XIV], include those of formula [XIV]
where R25~ is H or
methyl, and for the radical represented by the formula:
22

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
.O
-To Zp
Z'P is -C02-, -503- or -OS03-, and p is 1 or 2.
c) Oxaziridine Sulfonimines Phosphonimines N-Acylimines, Thiodiazole Dioxides -
The oxaziridine sulfonimines [XXIVa], phosphonimines [XXIVb], N-acylimines
[XXV] and
thiodiazole dioxides [XXVI] and [XXVII] are represented as follows:
R42' O\Nw 44' R4z~ O\N~SO R44~ R42~ O~N R44
S02R
43' 43'
R43 R R O
[XXIVa] [XXIVb] [XXV]
R42, O~N\ R42, O~N\
502 ~ 502
R43' ~ R43'
R41' N R4 i' N
~O
R44~ R44
[XXVI] [XXVII]
where R41'-R44', when present, are independently selected from substituted or
unsubstituted
radicals selected from the group consisting of H, alkyl, cycloalkyl, aryl,
alkaryl, aralkyl,
heterocyclic ring, silyl, nitro, halo, cyano, sulfonato, alkoxy, keto,
carboxylic, carboalkoxy
radicals, provided that any of R41'-R44' may be joined together with any other
R41'-R44' to form
part of a common ring, including a fused aryl, fused carbocyclic or fused
heterocyclic ring.
Suitable examples of X-, an anionic counterion, include, but are not limited
to: BFQ ,
OTS-, and other anionic counterions disclosed in WO 97/06147, WO 95/13352, WO
95/13353,
WO 95/13351, WO 98/23717, U.S. Patent Nos. 5,360,568, 5,360569, 5,482,515,
5,550,256,
5,478,357, 5,370,826, 5,442,066, EP 728 182 B1 and UK 1 215 656. Preferably,
the anionic
counterion is bleach-compatible.
For any structures that carry no net charge, no counterions are associated
with the
compound.
For any structures that carry a net negative charge, suitable examples of X+,
a cationic
counterion include, but are not limited to Na+, K+, H+.
23

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
For any structures that carry a net multiple charge, suitable examples of
anionic and
cationic counterions include, but are not limited to those described above.
Other Ora,anic Catalyst Compounds - In addition to the bleach boosting
compounds,
bleaching species and modified amines and amine oxides disclosed above,
organic catalyst
compounds can be any compound known in the art that is capable of reacting
with a peracid to
form an oxygen transfer agent (a bleach).
Concentration of Organic Catalyst Compounds - The organic catalyst compounds
of the present
invention may be added to a wash solution in levels of from about 0.00001 %
(0.0001 ppm) to
about 10% (100 ppm) by weight of the composition, and preferably from about
0.0001% (0.001
ppm) to about 2% (20 ppm) by weight of the composition, more preferably from
about 0.005%
(0.05 ppm) to about 0.5% (5 ppm), even more preferably from about 0.01% (0.1
ppm) to about
0.2% (2 ppm). Most preferably from about 0.02% (0.2 ppm) to about 0.1 % ( 1
ppm).
Preferably, the bleaching compositions of the present invention bleach
composition comprise an amount of organic catalyst compound such that the
resulting
concentration of the bleach boosting compound in a wash solution is from about
0.001 ppm to
about 5 ppm.
Further, preferably the bleach compositions of the present invention comprise
an amount
of peroxygen compound, when present, and an amound of organic catalyst
compound, such that
the resulting molar ratio of said peroxygen compound to organic catalyst
compound in a wash
solution is preferably greater than 1:1, more preferably greater than 10:1,
even more preferably
greater than 50:1. The preferred molar ratio ranges of peroxygen compound to
cationic organic
catalyst compound range from about 30,000:1 to about 10:1, even more
preferably from about
10,000:1 to about 50:1, yet even more preferably from about 5,000:1 to about
100:1, still even
more preferably from about 3,500:1 to about 150:1.
The conversion values (in ppm) are provided for exemplary purposes, based on
an in-use
product concentration of 1000 ppm. A 1000 ppm wash solution of a product
containing 0.2%
organic catalyst compound by weight results in a organic catalyst compound
concentration of 2
ppm. Similarly, a 3500 ppm wash solution of a product containing 0.2% organic
catalyst .
compound by weight results in a organic catalyst compound concentration of 6.5
ppm.
The method for delivering organic catalyst compounds of the present invention
and the
method for delivering bleaching compositions (products) containing such
organic catalyst
compounds that are particularly useful in the methods of the present invention
are the organic
catalyst compounds and compositions containing same that satisfy the preferred
method for
bleaching a stained substrate in an aqueous medium with a peroxygen source and
with an organic
catalyst compound whose structures is defined herein and wherein said medium
contains active
24

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
oxygen from the peroxygen compound from about 0.05 to about 250 ppm per liter
of medium,
and said organic catalyst compound from 0.001 ppm to about 5 ppm, preferably
from about 0.01
ppm to about 3 ppm, more preferably from about 0.1 ppm to about 2 ppm, and
most preferably
from about 0.2 ppm to about 1 ppm.
Such a preferred method for bleaching a stained substrate in an aqueous medium
with a
peroxygen source and with an organic catalyst compound is of particular value
for those
applications in which the color safety of the stained substrate in need of
cleaning is a concern. In
such applications the preferred embodiment (e.g., 0.01 ppm to about 3 ppm) is
of particular
importance in terms of achieving acceptable fabric color safety. For other
applications in which
color safety of the stained substrate in need of cleaning is of less concern,
a higher in-use
concentration may be preferred.
DECOMPOSITION OF ORGANIC CATALYSTS
The organic catalysts, specifically the bleach boosting compounds of the
present
invention are susceptible to decomposition by various decomposition pathways
including, but not
limited to, the aromatization pathway. The aromatization (decomposition)
reaction : of 6
membered ring bleach boosting compounds is well known in the art, as
exemplified, without
being limited by theory, in Hanquet et al., Tetrahedron 1993, 49, pp. 423-438
and as set forth
below:
OH H OH
/ / H / \
Ste 1 / I ~ Step 2
~ N~ ~ \ ~ NO+ p \ ~IV~\ ~ \ I ~ N ~
\ ~\
H Inactive
Active
HO-H Ot
her means of decomposition include, but are not limited to, attack on the
bleach boosting
compound and/or on the bleaching species by nucleophiles, including but not
limited to attack by
hydroxide anion, perhydroxide anion, carboxylate anion, percarboxylate anion
and other
nucleophiles present under in-wash conditions. For example, and without
intending to be
bound by theory, the decomposition reaction of a 6-membered ring
oxaziridinium, the overall
process of which can lead to reduced bleaching efficiency, is exemplified as
set forth below:
/ / o
NO ~ \ ~ \
~I\ 1 0
NuO~~o Nu
METHODS FOR CONTROLLED AVAILABILITY OF ORGANIC CATALYSTS

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
It has been surprisingly found that an organic catalyst being available under
a controlled
availability method as defined in Test Protocols I, II and/or III, as
disclosed hereinafter, provides
enhanced bleaching performance compared to an organic catalyst being available
in a non-
controlled availability method as defined in Test Protocols I, II and/or III,
as disclosed hereinafter,
in the wash solution containing the fabric. Furthermore, it has been found
that an organic catalyst
being available under a controlled availability method as defined in Test
Protocols I, II and/or III,
as disclosed hereinafter, in a wash solution containing a peracid and a fabric
in need of cleaning
provides enhanced bleaching performance compared to an organic catalyst being
available in a
non-controlled availability method as defined in Test Protocols I, II and/or
III, as disclosed
hereinafter in the wash solution containing the fabric.
Any suitable means and/or method for delivering the organic catalysts of the
present
invention by a controlled availability method as defined in Test Protocols I,
II and/or III, as
disclosed hereinafter, can be used in accordance with the present invention.
Nonlimiting examples of delivery means and/or methods that fall within the
scope of the
present invention follow.
Delivery Means - A delivery means in accordance with the present invention can
be any
means that is capable of controlling the availability of an organic catalyst
of the present invention
such that the organic catalyst is made available in the wash solution by a
controlled availability
method as defined in Test Protocols I, II and/or III, as disclosed
hereinafter.
Suitable delivery means include, but are not limited to, adding a controlled
release
material, such as an encapsulate or agglomerate or other type of controlled
release material,
containing an organic catalyst of the present invention wherein the controlled
release material
controls the availability of the organic catalyst such that the organic
catalyst is made available in
the wash solution by a controlled availability method as defined in Test
Protocols I, II and/or III,
as disclosed hereinafter. Preferably, the controlled release material controls
the availability of the
organic catalyst until after a peroxygen source, if any, has been released and
preferably, has had
time to perform bleaching and/or after the fabric has been added to the wash
solution.
Adding Encapsulated Organic Catalyst - As discussed above, another suitable
delivery
means in accordance with the present invention is to add encapsulated organic
catalysts, with or
without detergent components, to a wash solution, prior to or after a
peroxygen source, if any, has
been added to the wash solution and/or prior to or after a fabric in need of
cleaning has been
added to the wash solution. Encapsulated organic catalysts can include, but
are not limited to,
bleaching compositions that contain the organic catalyst of the present
invention, wherein the
bleaching compositions resist the release of a majority of the amount of
organic catalyst to a wash
solution until after a peroxygen source, if any, has been released and
preferably, has had time to
26

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
perform bleaching and/or until after a fabric in need of cleaning has been
added to the wash
solution. For example, if the encapsulated organic catalyst are added to a
wash solution prior to
the addition of a fabric in need of cleaning to the wash solution, then the
encapsulated organic
catalyst resists release of the organic catalyst until after the fabric is
added to the wash solution.
Typically, this time period ranges from about 2 minutes, more preferably 1
minute, more
preferably 1 second to about 10 minutes, preferably 7 minutes, more preferably
5 minutes.
However, in rare occasions this time period can range up to 24 hours or more.
On the other hand, if the encapsulated organic catalysts are added to a wash
solution
containing a fabric in need of cleaning, then the encapsulated organic
catalysts preferably resist
release of the organic catalysts until after any peracid present in the wash
solution has performed
bleaching of the fabric. Typically, this time period ranges from about 2
minutes, more preferably
1 minute, more preferably 1 second to about 10 minutes, preferably 7 minutes,
more preferably 5
minutes.
Any suitable encapsulation material known to those of ordinary skill in the
art can be
used. Examples of such suitable encapsulating materials for encapsulating the
organic catalyst of
the present invention include, but are not limited to, microspheres made from
plastics, such as
thermoplastics, acrylonitrile, methacrylonitrile, polyacrylonitrile,
polymethacrylonitrile
and mixtures thereof; and/or silicaceous materials such as glass. Commercially
available
microspheres are available from Expancel of Sweden (an Akzo Nobel company)
under
the trademark EXPANCEL~; PQ Corp. under the trade names PM 6545, PM 6550, PM
7220, PM 7228, EXTENDOSPHERES~, LUXSIL~, Q-CEL~, SPHERICEL~; and
Malinckrodt under the trademark ALBUMEX~.
Other suitable encapsulating materials include biopolymers, such as starch,
and
polyethylene glycols and paraffin waxes as described in U.S. Patent No.
5,703,034 to Offshack et
al. owned by The Procter & Gamble Company.
The encapsulated organic catalysts comprise one or more of the organic
catalysts of the
present invention and can optionally comprise one or more of the following
detergent
components: filler salts, surfactants, other bleaching agents, enzymes,
preferably bleach-stable
enzymes, chelants, builders, dye transfer inhibiting agents, perfumes, fabric
softening agents, soil
release agents, and brighteners.
A nonlimiting example of a suitable form for the encapsulated organic catalyst
is a
gelcap.
Agglomerates Containing Organic Catalyst - As discussed above, yet another
suitable
delivery means in accordance with the present invention is to add an
agglomerate containing the
organic catalyst of the present invention to a wash solution prior to or after
a peroxygen source, if
27

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
any, has been added to the wash solution and/or prior to or after a fabric in
need of cleaning has
been added to the wash solution. Agglomerated organic catalysts can include,
but are not limited
to, bleaching compositions that contain the organic catalyst of the present
invention, wherein the
bleaching compositions resist the release of a majority of the amount of
organic catalyst to a wash
S solution until after a peroxygen source, if any, has been released and
preferably, has had time to
perform bleaching and/or until after a fabric in need of cleaning has been
added to the wash
solution.
For example, if the agglomerate containing an amount of an organic catalyst is
added to a
wash solution prior to the addition of a fabric in need of cleaning to the
wash solution, then the
agglomerate resists release of the organic catalyst until after the fabric is
added to the wash
solution. Typically, this time period ranges from about 2 minutes, more
preferably 1 minute,
more preferably 1 second to about 10 minutes, preferably 7 minutes, more
preferably 5 minutes.
However, in rare occasions this time period can range up to 24 hours or more.
On the other hand, if the agglomerate containing an amount of an organic
catalyst is
added to a wash solution after a fabric in need of cleaning has been added to
the wash solution,
then the agglomerate preferably resists release of the organic catalyst until
after any peracid
present in the wash solution has performed bleaching of any stains on the
fabric. Typically, this
time period ranges from about 2 minutes, more preferably 1 minute, more
preferably 1 second to
about 10 minutes, preferably 7 minutes, more preferably 5 minutes.
Any suitable agglomerating material known to those of ordinary skill in the
art can be
used. Examples of suitable agglomerating materials for agglomerating the
organic catalyst of the
present invention include, but are not limited to, solid, water-soluble
ionizable materials such as
organic acids, organic and inorganic acid salts and mixtures thereof. Examples
of such
agglomerating materials are described in U.S. Patent Nos. 5,540,855 to
Baillely et al. and
5,482,642 to Agar et al., both owned by The Procter & Gamble Company.
The agglomerate containing the organic catalyst comprise one or more of the
organic
catalyst of the present invention and can optionally comprise one or more of
the following
detergent components: filler salts, surfactants, other bleaching agents,
enzymes, preferably
bleach-stable enzymes, chelants, builders, dye transfer inhibiting agents,
perfumes, fabric
softening agents, soil release agents, and brighteners.
BLEACHING COMPOSITIONS COMPRISING ORGANIC CATALYST
In addition to the encapsulates and agglomerates discussed above, the organic
catalysts of
the present invention may be employed in conjunction with a peroxygen source
in other bleaching
compositions, regardless of their form. For example, the organic catalysts may
be employed in a
laundry additive product.
28

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
The bleach boosting compounds of the present invention may be employed in
conjunction
with or without, preferably with a peroxygen source in a bleaching
composition. In the bleaching
compositions of the present invention, the peroxygen source may be present in
levels of from
about 0.1 % ( 1 ppm) to about 60% (600 ppm) by weight of the composition, and
preferably from
about 1% (10 ppm) to about 40% (400 ppm) by weight of the composition, and the
organic
catalyst compound may be present from about 0.00001 % (0.0001 ppm) to about
10% ( 100 ppm)
by weight of the composition, and preferably from about 0.0001 % (0.001 ppm)
to about 2% (20
ppm) by weight of the composition, more preferably from about 0.005% (0.05
ppm) to about
0.5% (5 ppm), even more preferably from about 0.01% (0.1 ppm) to about 0.2% (2
ppm). Most
preferably from about 0.02% (0.2 ppm) to about 0.1% (1 ppm).
The conversion values (in ppm) are provided for exemplary purposes, based on
an in-use
product concentration of 1000 ppm. A 1000 ppm wash solution of a product
containing 0.2%
organic catalyst compound by weight results in a organic catalyst compound
concentration of 2
ppm. Similarly, a 3500 ppm wash solution of a product containing 0.2% organic
catalyst
compound by weight results in a organic catalyst compound concentration of 6.5
ppm.
The preferred bleach boosting compound concentration is based on a bleach
boosting
compound molecular weight of about 300 grams/mole, although bleach boosting
compounds can
preferably have molecular weights of from about 150 to 1000 grams/mole, or
even higher for
oligomeric or polymeric bleach boosting compounds. For example, in the
bleaching compositions
of the present invention, when the bleach boosting compound is present more
preferably from
about 0.005% (0.05 ppm) to about 0.5% (5 ppm), the molar (M) concentration of
bleach boosting
compound will range from 1.7 x 10-8 M to 1.7 x 10-5M). Should an organic
catalyst compound
of higher m.w. be used in the bleaching compositions of the present invention,
the preferred molar
concentration will remain unchanged, whereas the preferred weight
concentration (in ppm) will
increase accordingly. For example, a bleach boosting compound with a molecular
weight of
about 600 grams/mole would be present more preferably from about 0.01 % (0.1
ppm) to about
1.0% ( 10 ppm). For oligomeric or polymeric bleach boosting compounds, the
more preferred
molar concentration will be based on the monomeric unit associated with the
iminium or
oxaziridinium active site.
The method for delivering organic catalyst compounds of the present invention
and the
method for delivering bleaching compositions (products) containing such
organic catalyst
compounds that are particularly useful in the methods of the present invention
are the organic
catalyst compounds and compositions containing same that satisfy the preferred
method for
bleaching a stained substrate in an aqueous medium with a peroxygen source and
with an organic
catalyst compound whose structures is defined herein and wherein said medium
contains active
29

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
oxygen from the peroxygen compound from about 0.05 to about 250 ppm per liter
of medium,
and said organic catalyst compound from 0.001 ppm to about 5 ppm, preferably
from about 0.01
ppm to about 3 ppm, more preferably from about 0.1 ppm to about 2 ppm, and
most preferably
from about 0.2 ppm to about 1 ppm.
S Such a preferred method for bleaching a stained substrate in an aqueous
medium with a
peroxygen source and with an organic catalyst compound is of particular value
for those
applications in which the color safety of the stained substrate in need of
cleaning is a concern. In
such applications the preferred embodiment (e.g., 0.01 ppm to about 3 ppm) is
of particular
importance in terms of achieving acceptable fabric color safety. For other
applications in which
color safety of the stained substrate in need of cleaning is of less concern,
a higher in-use
concentration may be preferred.
The organic catalysts of the present invention particularly useful in the
bleaching
compositions of the present invention preferably are capable of becoming
available in a wash
solution comprising the bleaching compositions containing the organic catalyst
by a controlled
availability method as defined in Test Protocols I, II and/or III, disclosed
hereinafter. The organic
catalysts can inherently be capable of becoming available in a wash solution
containing the
organic catalysts by a controlled availability method as defined in Test
Protocols I, II and/or III,
disclosed hereinafter. Alternatively, the bleaching compositions containing
the organic catalysts
may be prepared in such a way that the organic catalysts become available in a
wash solution
containing the bleaching compositions by a controlled availability method as
defined in Test
Protocols I, II and/or III, disclosed hereinafter.
The bleaching compositions of the present invention may be advantageously
employed in
laundry applications, hard surface cleaning, automatic dishwashing
applications, whitening and/or
bleaching applications associated with wood pulp and/or textiles,
antimicrobial and/or disinfectant
applications, as well as cosmetic applications such as dentures, teeth, hair
and skin. However, due
to the unique advantages of both increased effectiveness in lower temperature
solutions and the
superior mitigation of unwanted decomposition of the organic catalysts, the
organic catalysts of
the present invention are ideally suited for laundry applications such as the
bleaching of fabrics
and/or the bleaching of dyes (e.g., dye transfer inhibition) through the use
of bleach containing
detergents or laundry bleach additives. Furthermore, the organic catalyst of
the present invention
may be employed in granular, powder, bar, paste, foam, gel and liquid
compositions.
Accordingly, the bleaching compositions of the present invention may include
various
additional detergent components which are desirable in laundry applications.
Such components
include, but are not limited to, detersive surfactants, other bleaching agents
including other bleach
catalysts, builders, chelating agents, enzymes, polymeric soil release agents,
brighteners and

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
various other detergent components. Compositions including any of these
various additional
detergent components preferably have a pH of from about 6 to about 12, more
preferably from
about 8 to about 10.5 in a 1% solution of the bleaching composition.
The bleaching compositions preferably include at least one detersive
surfactant, at least
one chelating agent, at least one detersive enzyme and preferably have a pH of
from about 6 to
about 12, more preferably from about 8 to about 10.5 in a 1 % solution of the
bleaching
composition.
It is desirable that the bleaching composition further includes a peroxygen
source, as fully
described below. The bleaching composition can also include powdered or liquid
compositions
containing a hydrogen peroxide source or a peroxygen source as fully defined
below.
If the bleaching composition includes a hydrogen peroxide source, it is
desirable that the
laundry additive product further includes a bleach activator, as fully
described below.
In another embodiment of the present invention, a method for laundering a
fabric in need
of laundering is provided. The preferred method comprises contacting the
fabric with a laundry
solution. The fabric may comprise most any fabric capable of being laundered
in normal
consumer use conditions. The laundry solution comprises a bleaching
composition, as fully
described herein. The water temperatures preferably range from about 0
°C to about 50 °C or
higher. The water to fabric ratio is preferably from about 1:1 to about 15:1.
The laundry solution may further include at least one additional detergent
component
selected from the group consisting of detersive surfactants, other bleaching
agents, chelating
agents, detersive enzymes and mixtures thereof. Preferably, the laundry
solution has a pH of
about 8 to about 10.5 in a 1 % solution of the bleaching composition.
In accordance with another aspect of the present invention, a laundry additive
product is
provided. The laundry additive product comprises an organic catalyst, as fully
described above.
Such a laundry additive product would be ideally suited for inclusion in a
wash process when
additional bleaching effectiveness is desired. Such instances may include, but
are not limited to,
low-temperature solution laundry application.
The organic catalysts of the present invention particularly useful in the
laundry additive
products of the present invention preferably are capable of becoming available
in a wash solution
comprising the laundry additive products containing the organic catalysts by a
controlled
availability method as defined in Test Protocols I, II and/or III, disclosed
hereinafter. The organic
catalysts can inherently be capable of becoming available in a wash solution
containing the
organic catalysts by a controlled availability method as defined in Test
Protocols I, II and/or III,
disclosed hereinafter. Alternatively, the laundry additive products containing
the organic
catalysts may be prepared in such a way that the organic catalysts become
available in a wash
31

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
solution containing the laundry additive products by a controlled availability
method as defined in
Test Protocols I, II and/or III, disclosed hereinafter.
It is desirable that the laundry additive product further includes a peroxygen
source, as
fully described below. The laundry additive product can also include powdered
or liquid
compositions containing a hydrogen peroxide source or a peroxygen source as
fully defined
below.
Furthermore, if the laundry additive product includes a hydrogen peroxide
source, it is
desirable that the laundry additive product further includes a bleach
activator, as fully described
below.
Preferably, the laundry additive product is packaged in dosage form for
addition to a
laundry process where a source of peroxygen is employed and increased
bleaching effectiveness
is desired. Such single dosage form may comprise a pill, tablet, gelcap or
other single dosage unit
such as pre-measured powders or liquids. A filler or carrier material may be
included to increase
the volume of composition if desired. Suitable filler or carrier materials may
be selected from but
not limited to various salts of sulfate, carbonate and silicate as well as
talc, clay and the like.
Filler or carrier materials for liquid compositions may be water or low
molecular weight primary
and secondary alcohols including polyols and diols. Examples include methanol,
ethanol,
propanol and isopropanol. Monohydric alcohols may also be employed. The
compositions may
contain from about 5% to about 90% of such materials. Acidic fillers can be
used to reduce pH.
A preferred bleaching composition is a bleaching composition comprising:
(a) a bleaching system comprising a peroxygen source; and
(b) an organic catalyst;
wherein the organic catalyst becomes available in a wash solution containing
said bleaching
composition by a controlled availability method as defined in Test Protocols
I, II and/or III.
Bleaching Sstem - In addition to the organic catalyst of the present
invention, the
bleaching compositions of the present invention preferably comprise a
bleaching system.
Bleaching systems typically comprise a peroxygen source. Peroxygen sources are
well-known in
the art and the peroxygen source employed in the present invention may
comprise any of these
well known sources, including peroxygen compounds as well as compounds which
under
consumer use conditions provide an effective amount of peroxygen in situ. The
peroxygen source
may include a hydrogen peroxide source, the in situ formation of a peracid
anion through the
reaction of a hydrogen peroxide source and a bleach activator, preformed
peracid compounds or
mixtures of suitable peroxygen sources. Of course, one of ordinary skill in
the art will recognize
32

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
that other sources of peroxygen may be employed without departing from the
scope of the
invention. Preferably, the peroxygen source is selected from the group
consisting of:
(i) preformed peracid compounds selected from the group consisting of
percarboxylic
acids and salts, percarbonic acids and salts, perimidic acids and salts,
peroxymonosulfuric acids
and salts, and mixtures thereof, and
(ii) hydrogen peroxide sources selected from the group consisting of perborate
compounds, percarbonate compounds, perphosphate compounds and mixtures
thereof, and a
bleach activator.
When present, peroxygen sources (peracids and/or hydrogen peroxide sources)
will
typically be at levels of from about 1%, preferably from about 5% to about
30%, preferably to
about 20% by weight of the composition. If present, the amount of bleach
activator will typically
be from about 0.1%, preferably from about 0.5% to about 60%, preferably to
about 40% by
weight, of the bleaching composition comprising the bleaching agent-plus-
bleach activator.
a. Preformed Peracids - The preformed peracid compound as used herein is any
convenient compound which is stable and which under consumer use conditions
provides an
effective amount of peracid anion. The organic catalysts of the present
invention may of course
be used in conjunction with a preformed peracid compound selected from the
group consisting of
percarboxylic acids and salts, percarbonic acids and salts, perimidic acids
and salts,
peroxymonosulfuric acids and salts, and mixtures thereof, examples of which
are described in
U.S. Patent No. 5,576,282 to Miracle et al.
One class of suitable organic peroxycarboxylic acids have the general formula:
O
Y-R-C-O-OH
wherein R is an alkylene or substituted alkylene group containing from 1 to
about 22 carbon
atoms or a phenylene or substituted phenylene group, and Y is hydrogen,
halogen, alkyl, aryl,
C(O)OH or -C(O)OOH.
Organic peroxyacids suitable for use in the present invention can contain
either one or
two peroxy groups and can be either aliphatic or aromatic. When the organic
peroxycarboxylic
acid is aliphatic, the unsubstituted peracid has the general formula:
O
Y-(CH2)n C-O-OH
where Y can be, for example, H, CH3, CH2CI, C(O)OH, or C(O)OOH; and n is an
integer from 0
to 20. When the organic peroxycarboxylic acid is aromatic, the unsubstituted
peracid has the
general formula:
33

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
O
Y-C~-C-O-OH
wherein Y can be, for example, hydrogen, alkyl, alkylhalogen, halogen, C(O)OH
or C(O)OOH.
Typical monoperoxy acids useful herein include alkyl and aryl peroxyacids such
as:
(i) peroxybenzoic acid and ring-substituted peroxybenzoic acid, e.g. peroxy-a
naphthoic acid, monoperoxyphthalic acid (magnesium salt hexahydrate), and o
carboxybenzamidoperoxyhexanoic acid (sodium salt);
(ii) aliphatic, substituted aliphatic and arylalkyl monoperoxy acids, e.g.
peroxylauric
acid, peroxystearic acid, N-nonanoylaminoperoxycaproic acid (NAPCA), N,N-(3
octylsuccinoyl)aminoperoxycaproic acid (SAPA) and N,N-
phthaloylaminoperoxycaproic
acid (PAP);
(iii) amidoperoxyacids, e.g. monononylamide of either peroxysuccinic acid
(NAPSA)
or of peroxyadipic acid (NAPAA).
Typical diperoxyacids useful herein include alkyl diperoxyacids and
aryldiperoxyacids,
such as:
(iv) 1,12-diperoxydodecanedioic acid;
(v) 1,9-diperoxyazelaic acid;
(vi) diperoxybrassylic acid; diperoxysebacic acid and diperoxyisophthalic
acid;
(vii) 2-decyldiperoxybutane-1,4-dioic acid;
(viii) 4,4'-sulfonylbisperoxybenzoic acid.
Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued
November
20, 1984, U.S. Patent 4,634,551 to Burns et al., European Patent Application
0,133,354, Banks et
al. published February 20, 1985, and U.S. Patent 4,412,934, Chung et al.
issued November 1,
1983. Sources also include 6-nonylamino-6-oxoperoxycaproic acid as fully
described in U.S.
Patent 4,634,551, issued January 6, 1987 to Burns et al. Persulfate compounds
such as for
example OXONE, manufactured commercially by E.I. DuPont de Nemours of
Wilmington, DE
can also be employed as a suitable source of peroxymonosulfuric acid.
b. Hydr~en Peroxide Sources - The hydrogen peroxide source may be any suitable
hydrogen peroxide source and present at such levels as fully described in U.S.
Patent No.
5,576,282. For example, the hydrogen peroxide source may be selected from the
group consisting
of perborate compounds, percarbonate compounds, perphosphate compounds and
mixtures
thereof.
Hydrogen peroxide sources are described in detail in the herein incorporated
Kirk
Othmer's Encyclopedia of Chemical Technology, 4th Ed (1992, John Wiley &
Sons), Vol. 4, pp.
34

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
271-300 "Bleaching Agents (Survey)", and include the various forms of sodium
perborate and
sodium percarbonate, including various coated and modified forms.
The preferred source of hydrogen peroxide used herein can be any convenient
source,
including hydrogen peroxide itself. For example, perborate, e.g., sodium
perborate (any hydrate
S but preferably the mono- or tetra-hydrate), sodium carbonate peroxyhydrate
or equivalent
percarbonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or
sodium peroxide
can be used herein. Also useful are sources of available oxygen such as
persulfate bleach (e.g.,
OXONE, manufactured by DuPont). Sodium perborate monohydrate and sodium
percarbonate
are particularly preferred. Mixtures of any convenient hydrogen peroxide
sources can also be
used.
A preferred percarbonate bleach comprises dry particles having an average
particle size in
the range from about 500 micrometers to about 1,000 micrometers, not more than
about 10% by
weight of said particles being smaller than about 200 micrometers and not more
than about 10%
by weight of said particles being larger than about 1,250 micrometers.
Optionally, the
percarbonate can be coated with a silicate, borate or water-soluble
surfactants. Percarbonate is
available from various commercial sources such as FMC, Solvay and Tokai Denka.
Compositions of the present invention may also comprise as the bleaching agent
a
chlorine-type bleaching material. Such agents are well known in the art, and
include for example
sodium dichloroisocyanurate ("NaDCC"). However, chlorine-type bleaches are
less preferred for
compositions which comprise enzymes.
b. Bleach Activators - Preferably, the peroxygen source in the composition is
formulated with an activator (peracid precursor). The activator is present at
levels of from about
0.01%, preferably from about 0.5%, more preferably from about 1% to about 15%,
preferably to
about 10%, more preferably to about 8%, by weight of the composition. A bleach
activator as
used herein is any compound which when used in conjunction with a hydrogen
peroxide source
leads to the in situ production of the peracid corresponding to the bleach
activator. Various non
limiting examples of activators are fully disclosed in U.S. Patent No.
5,576,282, U.S. Patent
4,915,854 and U.S. Patent 4,412,934. See also U.S. 4,634,551 for other typical
bleaches and
activators useful herein.
Preferred activators are selected from the group consisting of tetraacetyl
ethylene diamine
(TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-
chlorobenzoylcaprolactam,
benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (HOBS),
phenyl
benzoate (PhBz), decanoyloxybenzenesulphonate (C10-OBS), benzoylvalerolactam
(BZVL),
octanoyloxybenzenesulphonate (Cg-OBS), perhydrolyzable esters and mixtures
thereof, most

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
preferably benzoylcaprolactam and benzoylvalerolactam. Particularly preferred
bleach activators
in the pH range from about 8 to about 9.5 are those selected having an OBS or
VL leaving group.
Preferred hydrophobic bleach activators include, but are not limited to,
nonanoyloxybenzenesulphonate (HOBS), 4-[N-(nonanoyl) amino hexanoyloxy]-
benzene
sulfonate sodium salt (NACA-OBS) an example of which is described in U.S.
Patent No.
5,523,434, lauroyloxybenzenesulphonate- (LOBS or C12-OBS), 10-
undecenoyloxybenzenesulfonate (UDOBS or CI I-OBS with unsaturation in the 10
position), and
decanoyloxybenzoic acid (DOBA).
Preferred bleach activators are those described in U.S. 5,698,504 Christie et
al., issued
December 16, 1997; U.S. 5,695,679 Christie et al. issued December 9, 1997;
U.S. 5,686,401
Willey et al., issued November 11, 1997; U.S. 5,686,014 Hartshorn et al.,
issued November 11,
1997; U.S. 5,405,412 Willey et al., issued April 11, 1995; U.S. 5,405,413
Willey et al., issued
April 11, 1995; U.S. 5,130,045 Mitchel et al., issued July 14, 1992; and U.S.
4,412,934 Chung et
al., issued November 1, 1983, and copending patent applications U. S. Serial
Nos. 08/709,072,
08/064,564, all of which are incorporated herein by reference.
The mole ratio of peroxygen bleaching compound (as Av0) to bleach activator in
the
present invention generally ranges from at least 1:1, preferably from about
20:1, more preferably
from about 10:1 to about 1:1, preferably to about 3:1.
Quaternary substituted bleach activators may also be included. The present
bleaching
compositions preferably comprise a quaternary substituted bleach activator
(QSBA) or a
quaternary substituted peracid (QSP); more preferably, the former. Preferred
QSBA structures
are further described in U.S. 5,686,015 Willey et al., issued November 11,
1997; U.S. 5,654,421
Taylor et al., issued August 5, 1997; U.S. 5,460,747 Gosselink et al., issued
October 24, 1995;
U.S. 5,584,888 Miracle et al., issued December 17, 1996; and U.S. 5,578,136
Taylor et al., issued
November 26, 1996; all of which are incorporated herein by reference.
Highly preferred bleach activators useful herein are amide-substituted as
described in
U.S. 5,698,504, U.S. 5,695,679, and U.S. 5,686,014 each of which are cited
herein above.
Preferred examples of such bleach activators include: (6-octanamidocaproyl)
oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamido
caproyl)oxybenzenesulfonate and mixtures thereof.
Other useful activators, disclosed in U.S. 5,698,504, U.S. 5,695,679, U.S.
5,686,014
each of which is cited herein above and U.S. 4,966,723Hodge et al., issued
October 30, 1990,
include benzoxazin-type activators, such as a C6H4 ring to which is fused in
the 1,2-positions a
moiety --C(O)OC(Rl)=N-.
36

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
Depending on the activator and precise application, good bleaching results can
be
obtained from bleaching systems having with in-use pH of from about 6 to about
13, preferably
from about 9.0 to about 10.5. Typically, for example, activators with electron-
withdrawing
moieties are used for near-neutral or sub-neutial pH ranges. Alkalis and
buffering agents can be
used to secure such pH.
Acyl lactam activators, as described in U.S. 5,698,504, U.S. 5,695,679 and
U.S.
5,686,014, each of which is cited herein above, are very useful herein,
especially the acyl
caprolactams (see for example WO 94-28102 A) and acyl valerolactams (see U.S.
5,503,639
Willey et al., issued April 2, 1996 incorporated herein by reference).
d. Organic Peroxides especially Diacyl Peroxides - In addition to the
bleaching agents
described above, the bleaching compositions of the present invention can
optionally include
organic peroxides. Organic peroxides are extensively illustrated in Kirk
Othmer, Encyclopedia of
Chemical Technology, Vol. 17, John Wiley and Sons, 1982 at pages 27-90 and
especially at pages
63-72, all incorporated herein by reference. If a diacyl peroxide is used, it
will preferably be one
which exerts minimal adverse impact on spotting/filming.
e. Metal-containing Bleach Catalysts - The bleaching compositions can also
optionally
include metal-containing bleach catalysts, preferably manganese and cobalt-
containing bleach
catalysts.
One type of metal-containing bleach catalyst is a catalyst system comprising a
transition
metal cation of defined bleach catalytic activity, such as copper, iron,
titanium, ruthenium
tungsten, molybdenum, or manganese canons, an auxiliary metal cation having
little or no bleach
catalytic activity, such as zinc or aluminum cations, and a sequestrate having
defined stability
constants for the catalytic and auxiliary metal cations, particularly
ethylenediaminetetraacetic
acid, ethylenediaminetetra (methylenephosphonic acid) and water-soluble salts
thereof. Such
catalysts are disclosed in U.S. 4,430,243 Bragg, issued February 2, 1982.
i. Manganese Metal Complexes - If desired, the compositions herein can be
catalyzed by means of a manganese compound. Such compounds and levels of use
are well
known in the art and include, for example, the manganese-based catalysts
disclosed in U.S.
5,576,282 Miracle et al., issued November 19, 1996; U.S. 5,246,621 Favre et
al., issued
September 21, 1993; U.S. 5,244,594 Favre et al., issued September 14, 1993;
U.S. 5,194,416
Jureller et al., issued March 16, .1993; U.S. 5,114,606 van Vliet et al.,
issued May 19, 1992; and
European Pat. App. Pub. Nos. 549,271 A1, 549,272 A1, 544,440 A2, and 544,490
A1; Preferred
examples of these catalysts include MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-
triazacyclononane)2-
(pF6)2~ MnIII2(u-O)1(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2(C104)2,
MnIV4(u-
O)6(1,4,7-triazacyclononane)4(C104)4, MnIIIMnIV4(u-O)1(u-OAc)2_(1,4,7-
trimethyl-1,4,7-
37

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
triazacyclononane)2(C104)3, MnIV(1,4,7-trimethyl-1,4,7-triazacyclononane)-
(OCH3)3(PF6),
and mixtures thereof. Other metal-based bleach catalysts include those
disclosed in U.S.
4,430,243 included by reference herein above and U.S. 5,114,611 van Kralingen,
issued May 19,
1992. The use of manganese with various complex ligands to enhance bleaching
is also reported
in the following: U.S. 4,728,455 Rerek, issued March 1, 1988; U.S. 5,284,944
Madison, issued
February 8, 1994; U.S. 5,246,612 van Dijk et al., issued September 21, 1993;
U.S. 5,256,779
Kerschner et al., issued October 26, 2993; U.S. 5,280,117 Kerschner et al.,
issued January 18,
1994; U.S. 5,274,147 Kerschner et al., issued December 28, 1993; U.S.
5,153,161 Kerschner et
al., issued October 6, 1992; and U.S. 5,227,084 Martens et al., issued July
13, 1993.
ii. Cobalt Metal Complexes - Cobalt bleach catalysts useful herein are known,
and are described, for example, in U.S. 5,597,936 Perkins et al., issued
January 28, 1997; U.S.
5,595,967 Miracle et al., January 21, 1997; U.S. 5,703,030 Perkins et al.,
issued December 30,
1997; and M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv.
Inorg. BioinorQ.
Mech., (1983), 2, pages 1-94. The most preferred cobalt catalyst useful herein
are cobalt
pentaamine acetate salts having the formula [Co(NH3)50Ac] Ty, wherein "OAc"
represents an
acetate moiety and "Ty" is an anion, and especially cobalt pentaamine acetate
chloride,
[Co(NH3)50Ac]C12; as well as [Co(NH3)50Ac](OAc)2; [Co(NH3)50Ac](PF6)2;
[Co(NH3)50Ac](504); [Co(NH3)50Ac](BF4)2; and [Co(NH3)50Ac](N03)2 (herein
"PAC").
These cobalt catalysts are readily prepared by known procedures, such as
taught for
example in U.S. 5,597,936, U.S. 5,595,967, U.S. 5,703,030, cited herein above,
the Tobe article
and the references cited therein, and in U.S. Patent 4,810,410, to Diakun et
al, issued March
7,1989, J. Chem. Ed. ( 1989), 66 ( 12), 1043-45; The Synthesis and
Characterization of Inorganic
Compounds, W.L. Jolly (Prentice-Hall; 1970), pp. 461-3; Inor . Chem., 18, 1497-
1502 (1979);
Inorg. Chem., 21, 2881-2885 (1982); InorQ. Chem., 18, 2023-2025 (1979); Inorg.
Synthesis, 173-
176 (1960); and Journal of Physical Chemistry, 56, 22-25 (1952).
iii. Transition Metal Complexes of Macropolycyclic RigLd Li~ands -
Compositions herein may also suitably include as bleach catalyst a transition
metal complex of a
macropolycyclic rigid ligand. The phrase "macropolycyclic rigid ligand" is
sometimes
abbreviated as "MRL" in discussion below. The amount used is a catalytically
effective amount,
suitably about 1 ppb or more, for example up to about 99.9%, more typically
about 0.001 ppm or
more, preferably from about 0.05 ppm to about 500 ppm (wherein "ppb" denotes
parts per billion
by weight and "ppm" denotes parts per million by weight).
Suitable transition metals e.g., Mn are illustrated hereinafter.
"Macropolycyclic" means a
MRL is both a macrocycle and is polycyclic. "Polycyclic" means at least
bicyclic. The term
"rigid" as used herein herein includes "having a superstructure" and "cross-
bridged". "Rigid" has
38

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
been defined as the constrained converse of flexibility: see D.H. Busch.,
Chemical Reviews.,
(1993), 93, 847-860, incorporated by reference. More particularly, "rigid" as
used herein means
that the MRL must be determinably more rigid than a macrocycle ("parent
macrocycle") which is
otherwise identical (having the same ring size 'and type and number of atoms
in the main ring) but
lacking a superstructure (especially linking moieties or, preferably cross-
bridging moieties) found
in the MRL's. In determining the comparative rigidity of macrocycles with and
without
superstructures, the practitioner will use the free form (not the metal-bound
form) of the
macrocycles. Rigidity is well-known to be useful in comparing macrocycles;
suitable tools for
determining, measuring or comparing rigidity include computational methods
(see, for example,
Zimmer, Chemical Reviews, (1995), 95(38), 2629-2648 or Hancock et al.,
Inorganica Chimica
Acta, ( 1989), 164, 73-84.
Preferred MRL's herein are a special type of ultra-rigid ligand which is cross-
bridged. A
"cross-bridge" is nonlimitingly illustrated in 1.11 hereinbelow. In 1.11, the
cross-bridge is a -
CH2CH2- moiety. It bridges N1 and N8 in the illustrative structure. By
comparison, a "same-
side" bridge, for example if one were to be introduced across N1 and N12 in
1.11, would' not be
sufficient to constitute a "cross-bridge" and accordingly would not be
preferred.
Suitable metals in the rigid ligand complexes include Mn(II), Mn(III), Mn(IV),
Mn(V),
Fe(II), Fe(III), Fe(IV), Co(I), Co(II), Co(III), Ni(I), Ni(II), Ni(III),
Cu(I), Cu(II), Cu(III), Cr(II),
Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), V(IV), V(V), Mo(IV), Mo(V), Mo(VI),
W(IV), W(V),
W(VI), Pd(II), Ru(II), Ru(III), and Ru(IV). Preferred transition-metals in the
instant transition-
metal bleach catalyst include manganese, iron and chromium.
More generally, the MRL's (and the corresponding transition-metal catalysts)
herein
suitably comprise:
(a) at least one macrocycle main ring comprising four or more heteroatoms; and
(b) a covalently connected non-metal superstructure capable of increasing the
rigidity of the
macrocycle, preferably selected from
(i) a bridging superstructure, such as a linking moiety;
(ii) a cross-bridging superstructure, such as a cross-bridging linking moiety;
and
(iii) combinations thereof.
The term "superstructure" is used herein as defined in the literature by Busch
et al., see,
for example, articles by Busch in "Chemical Reviews".
Preferred superstructures herein not only enhance the rigidity of the parent
macrocycle,
but also favor folding of the macrocycle so that it coordinates to a metal in
a cleft. Suitable
superstructures can be remarkably simple, for example a linking moiety such as
any of those
illustrated in Fig. 1 and Fig. 2 below, can be used.
39

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
(C
2
Fig. 1
wherein n is an integer, for example from 2 to 8, preferably less than 6,
typically 2 to 4, or
T
(CH2) ~(CH2)n
Z
Fig. 2
wherein m and n are integers from about 1 to 8, more preferably from 1 to 3; Z
is N or CH; and T
is a compatible substituent, for example H, alkyl, trialkylammonium, halogen,
nitro, sulfonate, or
the like. The aromatic ring in 1.10 can be replaced by a saturated ring, in
which the atom in Z
connecting into the ring can contain N, O, S or C.
Suitable MRL's are further nonlimitingly illustrated by the following
compound:
3
n5,
2 4
l4 N a N 6
13 12 b 8
/N N
11~ 9
Fig. 3
This is a MRL in accordance with the invention which is a highly preferred,
cross-
bridged, methyl-substituted (all nitrogen atoms tertiary) derivative of
cyclam. Formally, this
ligand is named 5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane using
the extended von
Baeyer system. See "A Guide to IUPAC Nomenclature of Organic Compounds:
Recommendations 1993", R. Panico, W.H. Powell and J-C Richer (Eds.), Blackwell
Scientific
Publications, Boston, 1993; see especially section R-2.4.2.1.
Transition-metal bleach catalysts of Macrocyclic Rigid Ligands which are
suitable for use
in the invention compositions can in general include known compounds where
they conform with
the definition herein, as well as, more preferably, any of a large number of
novel compounds
expressly designed for the present laundry or cleaning uses, and rion-
limitingly illustrated by any
of the following:
Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
Hexafluorophosphate
Aquo-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(III)
Hexafluorophosphate
Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Tetrafluoroborate
Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(III)
Hexafluorophosphate
Dichloro-5,12-di-n-butyl-1,5,8,12-tetraaza bicyclo[6.6.2]hexadecane
Manganese(II)
Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza- bicyclo[6.6.2]hexadecane
Manganese(II)
Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane
Manganese(II)
Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza- bicyclo[6.6.2]hexadecane
Manganese(II).
As a practical matter, and not by way of limitation, the compositions and
cleaning
processes herein can be adjusted to provide on the order of at least one part
per hundred million of
the active bleach catalyst species in the aqueous washing medium, and will
preferably provide
from about 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm to
about 10 ppm,
and most preferably from about 0.1 ppm to about 5 ppm, of the bleach catalyst
species in the wash
liquor. In order to obtain such levels in the wash liquor of an automatic
washing process, typical
compositions herein will comprise from about 0.0005% to about 0.2%, more
preferably from
about 0.004% to about 0.08%, of bleach catalyst, especially manganese or
cobalt catalysts, by
weight of the cleaning compositions.
Preferably, the peroxygen source is selected from hydrogen peroxide sources
selected
from the group consisting of perborate compounds, percarbonate compounds,
perphosphate
compounds and mixtures thereof, and a bleach activator.
Preferably, the bleach activator is selected from the group consisting of
hydrophobic bleach
activators as disclosed herein.
The purpose of such a bleaching composition is to mitigate unwanted
decomposition of
the organic catalyst, and to allow the peracid to achieve bleaching
performance on a fabric in need
of cleaning, such as a stained fabric, in a wash solution prior to the
availability of the organic
catalyst.
DETERGENT COMPONENTS
While not essential for the purposes of the present invention, several
conventional
adjuncts illustrated hereinafter are suitable for use in the instant bleaching
compositions and may
be desirably incorporated in preferred embodiments of the invention, for
example to assist or
enhance cleaning performance, for treatment of the substrate to be cleaned, or
to modify the
41

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
aesthetics of the bleaching composition as is the case with perfumes,
colorants, dyes or the like.
The precise nature of these additional components, and levels of incorporation
thereof, will
depend on the physical form of the composition and the nature of the cleaning
operation for
which it is to be used. Unless otherwise indicated, the bleaching compositions
of the invention
may for example, be formulated as granular or powder-form all-purpose or
"heavy-duty" washing
agents, especially laundry detergents; liquid, gel or paste-form all-purpose
washing agents,
especially the so-called heavy-duty liquid types; liquid fine-fabric
detergents; hand dishwashing
agents or light duty dishwashing agents, especially those of the high-foaming
type; machine
dishwashing agents, including the various tablet, granular, liquid and rinse-
aid types for
household and institutional use; liquid cleaning and disinfecting agents,
including antibacterial
hand-wash types, laundry bars, mouthwashes, denture cleaners, car or carpet
shampoos, bathroom
cleaners; hair shampoos and hair-rinses; shower gels and foam baths and metal
cleaners; as well
as cleaning auxiliaries such as bleach additives and "stain-stick" or pre-
treat types.
Surfactants - Preferably, the bleaching compositions according to the present
invention
comprise a surfactant or surfactant system wherein the surfactant can be
selected from nonionic
and/or anionic and/or cationic surfactants and/or ampholytic and/or
zwitterionic and/or semi-polar
nonionic surfactants.
The surfactant is typically present at a level of from about 0.1 %, preferably
about 1 %,
more preferably about 5% by weight of the bleaching compositions to about
99.9%, preferably
about 80%, more preferably about 35%, most preferably 30% about by weight of
the bleaching
compositions.
The surfactant can be nonionic, anionic, ampholytic, zwitterionic, or
cationic. Mixtures
of these surfactants can also be used. Preferred bleaching compositions
comprise anionic
surfactants or mixtures of anionic surfactants with other surfactants,
especially nonionic
surfactants.
The surfactant is preferably formulated to be compatible with enzyme
components
present in the composition. In liquid or gel compositions the surfactant is
most preferably
formulated such that it promotes, or at least does not degrade, the stability
of any enzyme in these
compositions.
Nonlimiting examples of suitable nonionic, anionic, cationic, ampholytic,
zwitterionic
and semi-polar nonionic surfactants are disclosed in U.S. Patent Nos.
5,707,950 and 5,576,282.
Additional examples of suitable surfactants can be found in McCutcheon's
EMULSIFIERS AND
DETERGENTS, North American Edition, 1997, McCutcheon Division, MC Publishing
Company, in U.S. Patent Nos. 3,929,678 and 4,259,217; in the series
"Surfactant Science",
Marcel Dekker, Inc., New York and Basel; in "Handbook of Surfactants", M.R.
Porter, Chapman
42

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
and Hall, 2nd Ed., 1994; in "Surfactants in Consumer Products", Ed. J. Falbe,
Springer-Verlag,
1987; and "Surface Active Agents and Detergents" (Vol. I and II by Schwartz,
Perry and Berch).
Highly preferred nonionic surfactants are polyhydroxy fatty acid amide
surfactants of the
formula:
R2 - C(O) - N(R1 ) - Z,
wherein R1 is H, or R1 is C1_4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl
or a mixture
thereof, R2 is CS_31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a
linear hydrocarbyl
chain with at least 3 hydroxyls directly connected to the chain, or an
alkoxylated derivative
thereof. Preferably, R1 is methyl, R2 is a straight C11-15 alkyl or C16-18
alkyl or alkenyl chain
such as coconut alkyl or mixtures thereof, and Z is derived from a reducing
sugar such as glucose,
fructose, maltose, lactose, in a reductive amination reaction.
Highly preferred anionic surfactants include alkyl alkoxylated sulfate
surfactants hereof
are water soluble salts or acids of the formula RO(A)mS03M wherein R is an
unsubstituted C10-
C24 alkyl or hydroxyalkyl group having a C 1 p-C24 alkyl component, preferably
a C 12-C20 alkyl
or hydroxyalkyl, more preferably C 12-C 1 g alkyl or hydroxyalkyl, A is an
ethoxy or propoxy unit,
m is greater than zero, typically between about 0.5 and about 6, more
preferably between about
0.5 and about 3, and M is H or a cation which can be, for example, a metal
cation (e.g., sodium,
potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-
ammonium cation.
Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are
contemplated herein.
When included therein, the bleaching compositions, especially laundry
detergent
compositions, of the present invention typically comprise from about 1 %, more
preferably about
3% by weight of such anionic surfactants to about 40%, more preferably about
20% by weight of
such anionic surfactants.
Highly preferred cationic surfactants are the water-soluble quaternary
ammonium
compounds useful in the present composition having the formula
R 1 R2R3 ~N+X_
wherein R1 is Cg-C16 alkyl, each of R2, R3 and R4 is independently C1-C4
alkyl, C1-C4
hydroxy alkyl, benzyl, and -(C2H40)xH where x has a value from 2 to 5, and X
is an anion. Not
more than one of R2, R3 or R4 should be benzyl.
When included therein, the bleaching compositions of the present invention
typically
comprise from about 0.2%, more preferably about 1% by weight of such cationic
surfactants to
about 25%, more preferably about 8% by weight of such cationic surfactants.
When included therein, the bleaching compositions of the present invention
typically
comprise from about 0.2%, more preferably about 1 % by weight of such
ampholytic surfactants to
about 15%, more preferably about 10% by weight of such ampholytic surfactants.
43

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
When included therein, the bleaching compositions of the present invention
typically
comprise from about 0.2%, more preferably about 1% by weight of such
zwitterionic surfactants
to about 15%, more preferably about 10% by weight of such zwitterionic
surfactants.
When included therein, the bleaching compositions of the present invention
typically
comprise from about 0.2%, more preferably 1% by weight of such semi-polar
nonionic surfactants
to about 15%, more preferably about 10% by weight of such semi-polar nonionic
surfactants.
The bleaching compositions of the present invention can also comprise from
about
0.001% to about 100% of one or more (preferably a mixture of two or more) mid-
chain branched
surfactants, preferably mid-chain branched alkyl alkoxy alcohols having the
formula:
R R1 R2
I ~ I
CH3CH2(CH2)~,,CH(CHZ),~CH(CHZ)yCH(CH2)Z(EO/PO)n,OH
mid-chain branched alkyl sulfates having the formula:
R R1 R2
I I I
CH3CH2(CHz)~,,CH(CHZ),~CH(CHZ)yCH(CH2)ZOS03M
and mid-chain branched alkyl alkoxy sulfates having the formula:
R R1 R2
I I
CH3CH2(CHz)",CH(CHZ),~CH(CHz)yCH(CHZ)~(EO/PO)a,OS03M
wherein the total number of carbon atoms in the branched primary alkyl moiety
of these formulae
(including the R, R1, and R2 branching, but not including the carbon atoms
which comprise any
EO/PO alkoxy moiety) is from 14 to 20, and wherein further for this surfactant
mixture the
average total number of carbon atoms in the branched primary alkyl moieties
having the above
formula is within the range of greater than 14.5 to about 17.5 (preferably
from about 15 to about
17); R, R1, and R2 are each independently selected from hydrogen, C1-C3 alkyl,
and mixtures
thereof, preferably methyl; provided R, R1, and R2 are not all hydrogen and,
when z is 1, at least
R or R1 is not hydrogen. M is a water soluble cation and may comprises more
than one type of
cation, for example, a mixture of sodium and potassium. The index w is an
integer from 0 to 13;
x is an integer from 0 to 13; y is an integer from 0 to 13; z is an integer of
at least 1; provided w +
x + y + z is from 8 to 14. E0 and PO represent ethyleneoxy units and
propyleneoxy units having
the formula:
IH3 IH3
-CHCHZO- or -CHZCHO
respectively, however, other alkoxy units inter alia 1,3-propyleneoxy, butoxy,
and mixtures
thereof are suitable as alkoxy units appended to the mid-chain branched alkyl
moieties.
The mid-chain branched surfactants are preferably mixtures which comprise a
surfactant
system. Therefore, when the surfactant system comprises an alkoxylated
surfactant, the index m
indicates the average degree of alkoxylation within the mixture of
surfactants. As such, the index
44

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
m is at least about 0.01, preferably within the range of from about 0.1, more
preferably from
about 0.5, most preferably from about 1 to about 30, preferably to about 10,
more preferably to
about 5. When considering a mid-chain branched surfactant system which
comprises only
alkoxylated surfactants, the value of the index m represents a distribution of
the average degree of
alkoxylation corresponding to m, or it may be a single specific chain with
alkoxylation (e.g.,
ethoxylation and/or propoxylation) of exactly the number of units
corresponding to m.
The preferred mid-chain branched surfactants of the present invention which
are suitable
for use in the surfactant systems of the present invention have the formula:
i H3
CH3(CHZ)aCH(CHZ)bCH2(EO/PO)a,OS03M
or the formula:
H3 CH3
CH3(CH2)dCH(CH2)eCHCH2(EO/PO)n,OS03M
wherein a, b, d, and a are integers such that a + b is from 10 to 16 and d + a
is from 8 to 14; M is
selected from sodium, potassium, magnesium, ammonium and substituted ammonium,
and
mixtures thereof.
The surfactant systems of the present invention which comprise mid-chain
branched
surfactants are preferably formulated in two embodiments. A first preferred
embodiment
comprises mid-chain branched surfactants which are formed from a feedstock
which comprises
25% or less of mid-chain branched alkyl units. Therefore, prior to admixture
with any other
conventional surfactants, the mid-chain branched surfactant component will
comprise 25% or less
of surfactant molecules which are non-linear surfactants.
A second preferred embodiment comprises mid-chain branched surfactants which
are
formed from a feedstock which comprises from about 25% to about 70% of mid-
chain branched
alkyl units. Therefore, prior to admixture with any other conventional
surfactants, the mid-chain
branched surfactant component will comprise from about 25% to about 70%
surfactant molecules
which are non-linear surfactants.
The surfactant systems of the bleaching compositions of the present invention
can also
comprise from about 0.001%, preferably from about 1%, more preferably from
about 5%, most
preferably from about 10% to about 100%, preferably to about 60%, more
preferably to about
30% by weight, of the surfactant system, of one or more (preferably a mixture
of two or more)
mid-chain branched alkyl arylsulfonate surfactants, preferably surfactants
wherein the aryl unit is
a benzene ring having the formula:

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
R1RZL R3
M q .~-
C b
SO3
- a
wherein L is an acyclic hydrocarbyl moiety comprising from 6 to 18 carbon
atoms; R', RZ, and R'
are each independently hydrogen or C,-C3 alkyl, provided R' and R2 are not
attached at the
terminus of the L unit; M is a water soluble canon having charge q wherein a
and b are taken
together to satisfy charge neutrality.
ADDITIONAL DETERGENT COMPONENTS
The following are non-limiting examples of additional detergent components
(adjunct
ingredients) useful in the bleaching compositions, especially laundry
detergent compositions, of
the present invention, said adjunct ingredients include builders, optical
brighteners, soil release
polymers, dye transfer agents, dispersants, enzymes, suds suppressers, dyes,
perfumes, colorants,
filler salts, hydrotropes, photoactivators, fluorescers, fabric conditioners,
hydrolyzable
surfactants, preservatives, anti-oxidants, chelants, stabilizers, anti-
shrinkage agents, anti-wrinkle
agents, germicides, fungicides, anti corrosion agents, and mixtures thereof.
Builders - The bleaching compositions of the present invention preferably
comprise one
or more detergent builders or builder systems. When present, the compositions
will typically
comprise at least about 1% builder, preferably from about 5%, more preferably
from about 10%
to about 80%, preferably to about 50%, more preferably to about 30% by weight,
of detergent
builder.
The level of builder can vary widely depending upon the end use of the
composition and
its desired physical form. When present, the compositions will typically
comprise at least about
1% builder. Formulations typically comprise from about 5% to about SO%, more
typically about
5% to about 30%, by weight, of detergent builder. Granular formulations
typically comprise
from about 10% to about 80%, more typically from about 15% to about-50% by
weight, of the
detergent builder. Lower or higher levels of builder, however, are not meant
to be excluded.
Inorganic or P-containing detergent 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 sesquicarbonates),
sulphates, and
aluminosilicates. However, non-phosphate builders are required in some
locales. Importantly,
the compositions herein function surprisingly well even in the presence of the
so-called "weak"
46

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
builders (as compared with phosphates) such as citrate, or in the so-called
"underbuilt" situation
that may occur with zeolite or layered silicate builders.
Examples of silicate builders are the alkali metal silicates, particularly
those having a
Si02:Na20 ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the
layered sodium
silicates described in U.S. 4,664,839 Rieck, issued May 12, 1987. NaSKS-6 is
the trademark for
a crystalline layered silicate marketed by Hoechst (commonly abbreviated
herein as "SKS-6").
Unlike zeolite builders, the Na SKS-6 silicate builder does not contain
aluminum. NaSKS-6 has
the delta-Na2Si05 morphology form of layered silicate. It can be prepared by
methods such as
those described in German DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly
preferred
layered silicate for use herein, but other such layered silicates, such as
those having the general
formula NaMSix02x+1'YH20 wherein M is sodium or hydrogen, x is a number from
1.9 to 4,
preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein.
Various other
layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-1 l, as the
alpha, beta and
gamma forms. As noted above, the delta-Na2Si05 (NaSKS-6 form) is most
preferred for use
herein. Other silicates may also be useful such as for example magnesium
silicate, which can
serve as a crispening agent in granular formulations, as a stabilizing agent
for oxygen bleaches,
and as a component of suds control systems.
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 15,
1973.
Aluminosilicate builders are useful in the present invention. Aluminosilicate
builders are
of great importance in most currently marketed heavy duty granular detergent
compositions, and
can also be a significant builder ingredient in liquid detergent formulations.
Aluminosilicate
builders include those having the empirical formula:
[Mz(zA102)y]~xH20
wherein z and y are integers of at least 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 15 to about 264.
Useful aluminosilicate ion exchange materials are commercially available.
These
aluminosilicates can be crystalline or amorphous in structure and can be
naturally-occurring
aluminosilicates or synthetically derived. A method for producing
aluminosilicate ion exchange
materials is disclosed in U.S. 3,985,669, Krummel et al, issued October 12,
1976. Preferred
synthetic crystalline aluminosilicate ion exchange materials useful herein are
available under the
designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an
especially preferred
embodiment, the crystalline aluminosilicate ion exchange material has the
formula:
Nal2[(A102)12(Si02)12~~xH20
47

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
wherein x is from about 20 to about 30, especially about 27. This material is
known as Zeolite A.
Dehydrated zeolites (x = 0 - 10) may also be used herein. Preferably, the
aluminosilicate has a
particle size of about 0.1-10 microns in diameter.
Organic detergent builders suitable for the purposes of the present invention
include, but
are not restricted to, a wide variety of polycarboxylate compounds. As used
herein, "poly
carboxylate" refers to compounds having a plurality of carboxylate groups,
preferably at least 3
carboxylates. Polycarboxylate builder can generally be added to the
composition in acid form,
but can also be added in the form of a neutralized salt. When utilized in salt
form, alkali metals,
such as sodium, potassium, and lithium, or alkanolammonium salts are
preferred.
Included among the polycarboxylate builders are a variety of categories of
useful mate-
rials. One important category of polycarboxylate builders encompasses the
ether polycarboxy-
lates, including oxydisuccinate, as disclosed in U.S. 3,128,287 Berg, issued
April 7, 1964, U.S.
3,635,830 Lamberti et al., issued January 18, 1972, and U.S. 3,936,448
Lamberti, issued
February 3, 1976. See also "TMS/TDS" builders of U.S. 4,663,071 Bush et al.,
issued May 5,
1987. Suitable ether polycarboxylates also include cyclic compounds,
particularly alicyclic
compounds, such as those described in U.S. 3,923,679 Rapko, issued December 2,
1975; U.S.
4,158,635 Crutchfield et al., issued June 19, 1979; U.S. 4,120,874 Crutchfield
et al., issued
October 17, 1978; and U.S. 4,102,903 Crutchfield et al., issued July 25, 1978.
Other useful detergency builders include the ether hydroxypolycarboxylates,
copolymers
of malefic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy
benzene-2, 4, 6
trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali
metal, ammonium and
substituted ammonium salts of polyacetic acids such as ethylenediamine
tetraacetic acid and
nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid,
succinic acid, oxydisuccinic
acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,
carboxymethyloxysuccinic acid, and
soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly
sodium salt), are
polycarboxylate builders of particular importance for heavy duty liquid
detergent formulations
due to their availability from renewable resources and their biodegradability.
Citrates can also be
used in granular compositions, especially in combination with zeolite and/or
layered silicate
builders. Oxydisuccinates are also especially useful in such compositions and
combinations.
Also suitable in the bleaching compositions of the present invention are the
3,3-dicar-
boxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S.
4,566,984, Bush,
issued January 28, 1986. Useful succinic acid builders include the CS-C20
alkyl and alkenyl
succinic acids and salts thereof. A particularly preferred compound of this
type is
dodecenylsuccinic acid. Specific examples of succinate builders include:
laurylsuccinate,
48

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-
pentadecenylsuccinate,
and the like. Laurylsuccinates are the preferred builders of this group, and
are described in
European Patent Application 86200690.5/0,200,263, published November 5, 1986.
Other suitable polycarboxylates are disclosed in U.S. 4,144,226, Crutchfield
et al., issued
March 13, 1979 and in U.S. 3,308,067, Diehl, issued March 7, 1967. See also
Diehl U.S. Patent
3,723,322.
Fatty acids, e.g., C 12-C 1 g monocarboxylic acids, can also be incorporated
into the
compositions alone, or in combination with the aforesaid builders, especially
citrate and/or the
succinate builders, to provide additional builder activity. Such use of fatty
acids will generally
result in a diminution of sudsing, which should be taken into account by the
formulator.
In situations where phosphorus-based builders can be used, and especially in
the for-
mulation of bars used for hand-laundering operations, the various alkali metal
phosphates such as
the well-known sodium 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.
Chelatin~Agents - The bleaching compositions herein may also optionally
contain one or
more iron and/or manganese chelating agents. Such chelating agents can be
selected from the
group consisting of amino carboxylates, amino phosphonates, polyfunctionally-
substituted aro-
matic chelating agents and mixtures therein, all as hereinafter defined.
Without intending to be
bound by theory, it is believed that the benefit of these materials is due in
part to their exceptional
ability to remove iron and manganese ions from washing solutions by formation
of soluble
chelates.
Examples of suitable chelating agents and levels of use are described in U.S.
Pat. Nos.
5,576,282 and 5,728,671.
A preferred biodegradable chelator for use herein is ethylenediamine
disuccinate
("EDDS"), especially the [5,S] isomer as described in U.S. Patent 4,704,233,
November 3, 1987,
to Hartman and Perkins.
The compositions herein may also contain water-soluble methyl glycine diacetic
acid
(MGDA) salts (or acid form) as a chelant or co-builder useful with, for
example, insoluble
builders such as zeolites, layered silicates and the like.
If utilized, these chelating agents will generally comprise from about 0.1 %
by weight of
the bleaching compositions herein to about 15%, more preferably 3.0% by weight
of the
bleaching compositions herein.
49

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
Dye Transfer Inhibiting- AA~ents - The bleaching compositions of the present
invention
may also include one or more compounds, dye transfer inhibiting agents, for
inhibiting dye
transfer from one fabric to another of solubilized and suspended dyes
encountered during fabric
laundering and conditioning operations involving colored fabrics.
Suitable polymeric dye transfer inhibiting agents include, but are not limited
to,
polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-
vinylpyrrolidone
and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or
mixtures thereof.
Examples of such dye transfer inhibiting agents are disclosed in U.S. Pat.
Nos. 5,707,950 and
5,707,951.
Additional suitable dye transfer inhibiting agents include, but are not
limited to, cross-
linked polymers. Cross-linked polymers are polymers whose backbone are
interconnected to a
certain degree; these links can be of chemical or physical nature, possibly
with active groups on
the backbone or on branches. Cross-linked polymers have been described in the
Journal of
Polymer Science, volume 22, pages 1035-1039.
In one embodiment, the cross-linked polymers are made in such a way that they
form a
three-dimensional rigid structure, which can entrap dyes in the pores formed
by the three-
dimensional structure.
In another embodiment, the cross-linked polymers entrap dyes by swelling.
Suitable cross-linked polymers are described in the co-pending European patent
application 94870213.9.
Addition of such polymers also enhances the performance of the enzymes within
the
bleaching compositions herein.
The dye transfer inhibiting agents have the ability to complex or adsorb
fugitive dyes
wash out of dyed fabrics before the dyes have the opportunity to become
attached to other articles
in the wash.
When present in the bleaching compositions herein, the dye transfer inhibiting
agents are
present at levels from about 0.0001%, more preferably about 0.01%, most
preferably about 0.05%
by weight of the bleaching compositions to about 10%, more preferably about
2%, most
preferably about 1 % by weight of the bleaching compositions.
Disnersants - The bleaching compositions of the present invention can also
contain
dispersants. Suitable water-soluble organic salts are the homo- or co-
polymeric acids or their salts,
in which the polycarboxylic acid comprises at least two carboxyl radicals
separated from each
other by not more than two carbon atoms.

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
Polymers of this type are disclosed in GB-A-1,596,756. Examples of such salts
are
polyacrylates of MW 2000-5000 and their copolymers with malefic anhydride,
such copolymers
having a molecular weight of from 1,000 to 100,000.
Especially, copolymer of acrylate and methylacrylate such as the 480N having a
molecular weight of 4000, at a level from 0.5-20% by weight of composition can
be added in the
detergent compositions of the present invention.
The compositions of the invention may contain a lime soap peptiser compound,
which has
a lime soap dispersing power (LSDP), as defined hereinafter of no more than 8,
preferably no
more than 7, most preferably no more than 6. The lime soap peptiser compound
is preferably
present at a level from 0% to 20% by weight.
A numerical measure of the effectiveness of a lime soap peptiser is given by
the lime soap
dispersant power (LSDP) which is determined using the lime soap dispersant
test as described in
an article by H.C. Borghetty and C.A. Bergman, J. Am. Oil. Chem. Soc., volume
27, pages 88-90,
(1950). This lime soap dispersion test method is widely used by practitioners
in this art field being
referred to, for example, in the following review articles; W.N. Linfield,
Surfactant science Series,
Volume 7, page 3; W.N. Linfield, Tenside surf. det., volume 27, pages 159-163,
(1990); and M.K.
Nagarajan, W.F. Masler, Cosmetics and Toiletries, volume 104, pages 71-73,
(1989). The LSDP
is the % weight ratio of dispersing agent to sodium oleate required to
disperse the lime soap
deposits formed by 0.025g of sodium oleate in 30m1 of water of 333ppm CaCo3
(Ca:Mg=3:2)
equivalent hardness.
Surfactants having good lime soap peptiser capability will include certain
amine oxides,
betaines, sulfobetaines, alkyl ethoxysulfates and ethoxylated alcohols.
Exemplary surfactants having a LSDP of no more than 8 for use in accord with
the
present invention include C 16-C 1 g dimethyl amine oxide, C 12-C 1 g alkyl
ethoxysulfates with an
average degree of ethoxylation of from 1-5, particularly C12-C15 alkyl
ethoxysulfate surfactant
with a degree of ethoxylation of amount 3 (LSDP=4), and the C14-C15
ethoxylated alcohols with
an average degree of ethoxylation of either 12 (LSDP=6) or 30, sold under the
tradenames
Lutensol A012 and Lutensol A030 respectively, by BASF GmbH.
Polymeric lime soap peptisers suitable for use herein are described in the
article by M.K.
Nagarajan, W.F. Masler, to be found in Cosmetics and Toiletries, volume 104,
pages 71-73,
(1989).
Hydrophobic bleaches such as 4-[N-octanoyl-6-aminohexanoyl]benzene sulfonate,
4-[N-
nonanoyl-6-aminohexanoyl]benzene sulfonate, 4-[N-decanoyl-6-
aminohexanoyl]benzene
sulfonate and mixtures thereof; and nonanoyloxy benzene sulfonate together
with hydrophilic /
hydrophobic bleach formulations can also be used as lime soap peptisers
compounds.
51

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
Enzymes - The bleaching compositions can comprise in addition to the amylase
of the
present invention one or more detergent enzymes which provide cleaning
performance and/or
fabric care benefits. Such enzymes can include proteases, amylases, cellulases
and lipases. They
may be incorporated into the non-aqueous liquid bleaching compositions herein
in the form of
suspensions, "marumes" or "prills". Another suitable type of enzyme comprises
those in the form
of slurries of enzymes in nonionic surfactants, e.g., the enzymes marketed by
Novo Nordisk under
the tradename "SL" or the microencapsulated enzymes marketed by Novo Nordisk
under the
tradename "LDP." Suitable enzymes and levels of use are described in U.S. Pat.
No. 5,576,282.
Enzymes added to the compositions herein in the form of conventional enzyme
prills are
especially preferred for use herein. Such prills will generally range in size
from about 100 to
1,000 microns, more preferably from about 200 to 800 microns and will be
suspended throughout
the non-aqueous liquid phase of the composition. Prills in the compositions of
the present
invention have been found, in comparison with other enzyme forms, to exhibit
especially
desirable enzyme stability in terms of retention of enzymatic activity over
time. Thus,
1 S compositions which utilize enzyme prills need not contain conventional
enzyme stabilizing such
as must frequently be used when enzymes are incorporated into aqueous liquid
detergents.
Examples of suitable enzymes include, but are not limited to, hemicellulases,
peroxidases,
proteases, cellulases, xylanases, lipases, phospholipases, esterases,
cutinases, pectinases,
keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases,
pullulanases,
tannases, pentosanases, malanases, f3-glucanases, arabinosidases,
hyaluronidase, chondroitinase,
laccase, and known amylases, or mixtures thereof. A preferred combination is a
bleaching
composition having a cocktail of conventional applicable enzymes like
protease, lipase, cutinase
and/or cellulase in conjunction with the amylase of the present invention.
Examples of such suitable enzymes are disclosed in U.S. Patent Nos. 5,576,282,
5,728,671 and 5,707,950
Suitable proteases are the subtilisins which are obtained from particular
strains of B.
subtilis and B. licheniformis (subtilisin BPN and BPN'). One suitable protease
is obtained from a
strain of Bacillus, having maximum activity throughout the pH range of 8-12,
developed and sold
as ESPERASE~ by Novo Industries A/S of Denmark, hereinafter "Novo". The
preparation of
this enzyme and analogous enzymes is described in GB 1,243,784 to Novo. Other
suitable
proteases include ALCALASE~, DURAZYM~ and SAVINASE~ from Novo and
MAXATASE~~ MAXACAL~, PROPERASE~ and MAXAPEM~ (protein engineered
Maxacal) from Gist-Brocades. Proteolytic enzymes also encompass modified
bacterial serine
proteases, such as those described in European Patent Application Serial
Number 87 303761.8,
filed April 28, 1987 (particularly pages 17, 24 and 98), and which is called
herein "Protease B",
52

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
and in European Patent Application 199,404, Venegas, published October 29,
1986, which refers
to a modified bacterial serine protealytic enzyme which is called "Protease A"
herein. More
preferred is what is called herein "Protease C", which is a variant of an
alkaline serine protease
from Bacillus in which lysine replaced arginine at position 27, tyrosine
replaced valine at position
104, serine replaced asparagine at position 123, and alanine replaced
threonine at position 274.
Protease C is described in EP 90915958:4, corresponding to WO 91/06637,
Published May 16,
1991. Genetically modified variants, particularly of Protease C, are also
included herein. See also
a high pH protease from Bacillus sp. NCIMB 40338 described in WO 93/18140 A to
Novo.
Enzymatic detergents comprising protease, one or more other enzymes, and a
reversible protease
inhibitor are described in WO 92/03529 A to Novo. When desired, a protease
having decreased
adsorption and increased hydrolysis is available as described in WO 95/07791
to Procter &
Gamble. A recombinant trypsin-like protease for detergents suitable herein is
described in WO
94/25583 to Novo.
In more detail, the protease referred to as "Protease D" is a carbonyl
hydrolase variant
having an amino acid sequence not found in nature, which is derived from a
precursor carbonyl
hydrolase by substituting a different amino acid for a plurality of amino acid
residues at a position
in said carbonyl hydrolase equivalent to position +76, preferably also in
combination with one or
more amino acid residue positions equivalent to those selected from the group
consisting of +99,
+101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166,
+195, +197,
+204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to
the numbering
of Bacillus amyloliquefaciens subtilisin, as described in WO 95/10615
published April. 20, 1995
by Genencor International. Also suitable for the present invention are
proteases described in
patent applications EP 251 446 and W091/06637 and protease BLAP~ described in
W091/02792. The proteolytic enzymes are incorporated in the bleaching
compositions of the
present invention a level of from 0.0001% to 2%, preferably from 0.001% to
0.2%, more
preferably from 0.005% to 0.1% pure enzyme by weight of the composition.
Useful proteases are also described in PCT publications: WO 95/30010 published
November 9, 1995 by The Procter & Gamble Company; WO 95/30011 published
November 9,
1995 by The Procter & Gamble Company; WO 95/29979 published November 9, 1995
by The
Procter & Gamble Company.
Other particularly useful proteases are multiply-substituted protease variants
comprising a substitution of an amino acid residue with another naturally
occurring
amino acid residue at an amino acid residue position corresponding to position
103 of
Bacillus amyloliquefaciens subtilisin in combination with a substitution of an
amino acid
residue with another naturally occurring amino acid residue at one or more
amino acid
53

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
residue positions corresponding to positions 1, 3, 4, 8, 9, 10, 12, 13, 16,
17, 18, 19, 20,
21, 22, 24, 27, 33, 37, 38, 42, 43, 48, 55, 57, 58, 61, 62, 68, 72, 75, 76,
77, 78, 79, 86, 87,
89, 97, 98, 99, 101, 102, 104, 106, 107, 109, 111, 114, 116, 117, 119, 121,
123, 126, 128,
130, 131, 133, 134, 137, 140, 141, 142, 146, 147, 158, 159, 160, 166, 167,
170, 173, 174,
177, 181, 182, 183, 184, 185, 188, 192, 194, 198, 203, 204, 205, 206, 209,
210, 211, 212,
213, 214, 215, 216, 217, 218, 222, 224, 227, 228, 230, 232, 236, 237, 238,
240, 242, 243,
244, 245, 246, 247, 248, 249, 251, 252, 253, 254, 255, 256, 257, 258, 259,
260, 261, 262,
263, 265, 268, 269, 270, 271, 272, 274 and 275 of Bacillus amyloliquefaciens
subtilisin;
wherein when said protease variant includes a substitution of amino acid
residues at
positions corresponding to positions 103 and 76, there is also a substitution
of an amino
acid residue at one or more amino acid residue positions other than amino acid
residue
positions corresponding to positions 27, 99, 101, 104, 107, 109, 123, 128,
166, 204, 206,
210, 216, 217, 218, 222, 260, 265 or 274 of Bacillus amyloliquefaciens
subtilisin and/or
multiply-substituted protease variants comprising a substitution of an amino
acid residue
with another naturally occurring amino acid residue at one or more amino acid
residue
positions corresponding to positions 62, 212, 230, 232, 252 and 257 of
Bacillus
amyloliquefaciens subtilisin as described in PCT Patent Publication Nos. WO
99/20727,
WO 99/20726 and WO 99/20723 all filed on October 23, 1998 by The Procter &
Gamble
Company. More preferably the protease variant includes a substitution set
selected from the
group consisting of:
12/76/ 103/ 104/ 130/222/245/261;
62/103/104/159/232/236/245/248/252;
62/103/104/159/213/232/236/245/248/252;
62/101/103/104/159/212/213/232/236/245/248/252;
68/103/104/159/232/236/245;
68/103/104/159/230/232/236/245;
68/103/104/159/209/232/236/245;
68/103/104/159/232/236/245/257;
68/76/103/104/159/213/232/236/245/260;
68/103/104/159/213/232/236/245/248/252;
68/103/104/159/183/232/236/245/248/252;
68/103/104/159/185/232/236/245/248/252;
68/103/104/159/185/210/232/236/245/248/252;
68/103/104/159/210/232/236/245/248/252;
54

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
68/103/104/159/213/232/236/245;
98/103/104/159/232/236/245/248/252;
98/102/103/104/159/212/232/236/245/248/252;
101/103/104/159/232/236/245/248/252;
102/103/104/159/232/236/245/248/252;
103/104/159/230/236/245;
103/104/159/232/236/245/248/252;
103/104/159/217/232/236/245/248/252;
103/104/130/159/232/236/245/248/252;
103/104/131/159/232/236/245/248/252;
103/104/159/213/232/236/245/248/252; and
103/104/159/232/236/245.
Still even more preferably the protease variant includes a substitution set
selected from the group
consisting of:
12R/76D/103A/104T/130T/2225/245R/261 D;
62D/103A/104I/159D/232V/236H/245R/248D/252K;
62D/103A/104I/159D/213R/232V/236H/245R/248D/252K;
68A/103A/104I/159D/209W/232V/236H/245R;
68A/76D/103A/104I/159D/213R/232V/236H/245R/260A;
68A/103A/104I/159D/213E/232V/236H/245R/248D/252K;
68A/103A/104I/159D/183D/232V/236H/245R/248D/252K;
68A/103A/104I/159D/232V/236H/245R;
68A/103A/104I/159D/230V/232V/236H/245R;
68A/103A/104I/159D/232V/236H/245R/257V;
68A/103A/104I/159D/213G/232V/236H/245R/248D/252K;
68A/103A/104I/159D/185D/232V/236H/245R/248D/252K;
68A/103A/104I/159D/185D/210L/232V/236H/245R/248D/252K;
68A/103A/ 104I/ 159D/21 OL/232V/236H/245R/248D/252K;
68A/103A/104I/159D/213G/232V/236H/245R;
98L/103A/104I/159D/232V/236H/245R/248D/252K;
98L/102A/103A/104I/159D/212G/232V/236H/245R/248D/252K;
101 G/103A/104I/159D/232V/236H/245R/248D/252K;
102A/103A/104I/159D/232V/236H/245R/248D/252K;

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
103A/104I/159D/230V/236H/245R;
103A/104I/159D/232V/236H/245R/248D/252K;
103A/104I/159D/217E/232V/236H/245R/248D/252K;
103A/104I/1306/159D/232V/236H/245R/248D/252K;
103A/104I/131 V/159D/232V/236H/245R/248D/252K;
103A/104I/159D/213R/232V/236H/245R/248D/252K; and
103A/104I/159D/232V/236H/245R.
Most preferably the protease variant includes the substitution set
101/103/104/159/232/
236/245/248/252, preferably lOIG/103A/104I/159D/232V/236H/245R/248D/252K.
The cellulases usable in the present invention include both bacterial or
fungal cellulase.
Preferably, they will have a pH optimum of between 5 and 9.5. Suitable
cellulases are disclosed in
U.S. Patent 4,435,307, Barbesgoard et al, which discloses fungal cellulase
produced from
Humicola insolens. Suitable cellulases are also disclosed in GB-A-2.075.028;
GB-A-2.095.275
and DE-OS-2.247.832.
Examples of such cellulases are cellulases produced by a strain of Humicola
insolens
(Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800.
Other suitable cellulases are cellulases originated from Humicola insolens
having a
molecular weight of about 50KDa, an isoelectric point of 5.5 and containing
415 amino acids; and
a "43kD endoglucanase derived from Humicola insolens, DSM 1800, exhibiting
cellulase activity;
a preferred endoglucanase component has the amino acid sequence disclosed in
PCT Patent
Application No. WO 91/17243. Also suitable cellulases are the EGIII cellulases
from
Trichoderma longibrachiatum described in W094/21801, Genencor, published
September 29,
1994. Especially suitable cellulases are the cellulases having color care
benefits. Examples of
such cellulases are cellulases described in European patent application No.
91202879.2, filed
November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A/S) are
especially useful.
See also W091/17243.
Peroxidase enzymes are known in the art, and include, for example, horseradish
peroxidase, ligninase and haloperoxidase such as chloro- and bromo-peroxidase.
Peroxidase
containing bleaching compositions are disclosed, for example, in U.S. Patent
Nos. 5,576,282,
5,728,671 and 5,707,950, PCT International Applications WO 89/099813,
W089/09813 and in
European Patent application EP No. 91202882.6, filed on November 6, 1991 and
EP No.
96870013.8, filed February 20, 1996. Also suitable is the laccase enzyme.
Preferred enhancers are substituted phenthiazine and phenoxasine 10-
Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4-carboxylic acid
(EPC), 10-
56

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO
94/12621) and
substituted syringates (C3-CS substituted alkyl syringates) and phenols.
Sodium percarbonate or
perborate are preferred sources of hydrogen peroxide.
Said peroxidases are normally incorporated in the bleaching composition at
levels from
0.0001 % to 2% of active enzyme by weight of the bleaching composition.
Other preferred enzymes that can be included in the bleaching compositions of
the present
invention include lipases. Suitable lipase enzymes for detergent usage include
those produced by
microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC
19.154, as
disclosed in British Patent 1,372,034. Suitable lipases include those which
show a positive
immunological cross-reaction with the antibody of the lipase, produced by the
microorganism
Pseudomonas fluorescent IAM 1057. This lipase is available from Amano
Pharmaceutical Co.
Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter
referred to as "Amano-
P". Other suitable commercial lipases include Amano-CES, lipases ex
Chromobacter viscosum,
e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co.,
Tagata, Japan;
Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth
Co., The
Netherlands, and lipases ex Pseudomonas gladioli. Especially suitable lipases
are lipases such as
M1 LIPASE~ and LIPOMAX~ (Gist-Brocades) and LIPOLASE~ and LIPOLASE
ULTRA~(Novo) which have found to be very effective when used in combination
with the
compositions of the present invention.
Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special
kind of
lipase, namely lipases which do not require interfacial activation. Addition
of cutinases to
bleaching compositions have been described in e.g. WO 88/09367 (Genencor).
The lipases and/or cutinases are normally incorporated in the bleaching
composition at
levels from 0.0001 % to 2% of active enzyme by weight of the bleaching
composition.
Known amylases (a and/or f3) can be included for removal of carbohydrate-based
stains.
WO 94/02597, Novo Nordisk A/S published February 03, 1994, describes cleaning
compositions
which incorporate mutant amylases. See also W094/18314, Genencor, published
August 18, 1994
and W095/10603, Novo Nordisk A/S, published April 20, 1995. Other amylases
known for use
in bleaching compositions include both a- and [3-amylases. a-Amylases are
known in the art and
include those disclosed in US Pat. 5,003,257; EP 252,666; WO 91/00353; FR
2,676,456; EP
285,123; EP 525,610; EP 368,341; and British Patent Specification No.
1,296,839 (Novo). Other
suitable amylase are stability-enhanced amylases including PURAFACT OX AM~
described in
WO 94/18314, published August 18, 1994 and W096/05295, Genencor, published
February 22,
1996 and amylase variants from Novo Nordisk A/S, disclosed in WO 95/10603,
published April
95.
57

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
Examples of commercial a-amylases products are TERMAMYL~, BAN~,
FUNGAMYL~ and DURAMYL~, all available from Novo Nordisk A/S Denmark.
W095/26397 describes other suitable amylases : a-amylases characterized by
having a specific
activity at least 25% higher than the specific activity of TERMAMYL~ at a
temperature range of
25°C to 55°C and at a pH value in the range of 8 to 10, measured
by the Phadebas~ a-amylase
activity assay. Other amylolytic enzymes with improved properties with respect
to the activity
level and the combination of thermostability and a higher activity level are
described in
W095/35382.
The compositions of the present invention may also comprise a mannanase
enzyme. Preferably, the mannanase is selected from the group consisting of:
three
mannans-degrading enzymes : EC 3.2.1.25 : ~3-mannosidase, EC 3.2.1.78 : Endo-
1,4-(3
mannosidase, referred therein after as "mannanase" and EC 3.2.1.100 : 1,4-(3
mannobiosidase and mixtures thereof. (IUPAC Classification- Enzyme
nomenclature,
1992 ISBN 0-12-227165-3 Academic Press).
~ More preferably, the treating compositions of the present invention, when a
mannanase is present, comprise a [3-1,4-Mannosidase (E.C. 3.2.1.78) referred
to as
Mannanase. The term "mannanase" or "galactomannanase" denotes a mannanase
enzyme
defined according to the art as officially being named mannan endo-1,4-beta-
mannosidase and having the alternative names beta-mannanase and endo-1,4-
mannanase
and catalysing the reaction: random hydrolysis of 1,4-beta-D- mannosidic
linkages in
mannans, galactomannans, glucomannans, and galactoglucomannans.
In particular, Mannanases (EC 3.2.1.78) constitute a group of polysaccharases
which degrade mannans and denote enzymes which are capable of cleaving polyose
chains containing mannose units, i.e. are capable of cleaving glycosidic bonds
in
mannans, glucomannans, galactomannans and galactogluco-mannans. Mannans are
polysaccharides having a backbone composed of (3-1,4- linked mannose;
glucomannans
are polysaccharides having a backbone or more or less regularly alternating (3-
1,4 linked
mannose and glucose; galactomannans and galactoglucomannans are mannans and
glucomannans with a-1,6 linked galactose sidebranches. These compounds may be
acetylated.
The degradation of galactomannans and galactoglucomannans is facilitated by
full
or partial removal of the galactose sidebranches. Further the degradation of
the acetylated
mannans, glucomannans, galactomannans and galactogluco-mannans is facilitated
by full
or partial deacetylation. Acetyl groups can be removed by alkali or by mannan
acetylesterases. The oligomers which are released from the mannanases or by a
58

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
combination of mannanases and a-galactosidase and/or mannan acetyl esterases
can be
further degraded to release free maltose by (3-mannosidase and/or (3-
glucosidase.
Mannanases have been identified in several Bacillus organisms. For example,
Talbot et al., Appl. Environ. Microbiol., Vo1.56, No. 11, pp. 3505-3510 (1990)
describes
a beta-mannanase derived from Bacillus stearothermophilus in dimes form having
molecular weight of 162 kDa and an optimum pH of 5.5-7.5. Mendoza et al.,
World J.
Microbiol. Biotech., Vol. 10, No. 5, pp. 551-555 (1994) describes a beta-
mannanase
derived from Bacillus subtilis having a molecular weight of 38 kDa, an optimum
activity
at pH 5.0 and 55C and a pI of 4.8. JP-03047076 discloses a beta-mannanase
derived from
Bacillus sp., having a molecular weight of 373 kDa measured by gel filtration,
an
optimum pH of 8-10 and a pI of 5.3-5.4. JP-63056289 describes the production
of an
alkaline, thermostable beta-mannanase which hydrolyses beta-1,4-D-
mannopyranoside
bonds of e.g. mannans and produces manno-oligosaccharides. JP-63036774 relates
to the
Bacillus microorganism FERM P-8856 which produces beta-mannanase and beta-
mannosidase at an alkaline pH. JP-08051975 discloses alkaline beta-mannanases
from
alkalophilic Bacillus sp. AM-001. A purified mannanase from Bacillus
amyloliquefaciens
useful in the bleaching of pulp and paper and a method of preparation thereof
is disclosed
in WO 97/11164. WO 91/18974 describes a hemicellulase such as a glucanase,
xylanase
or mannanase active at an extreme pH and temperature. WO 94/25576 discloses an
enzyme from Aspergillus aculeatus, CBS 101.43, exhibiting mannanase activity
which
may be useful for degradation or modification of plant or algae cell wall
material. WO
93/24622 discloses a mannanase isolated from Trichoderma reseei useful for
bleaching
lignocellulosic pulps. An hemicellulase capable of degrading mannan-containing
hemicellulose is described in W091/18974 and a purified mannanase from
Bacillus
amyloliquefaciens is described in W097/11164.
Preferably, the mannanase enzyme will be an alkaline mannanase as defined
below, more preferably, a mannanase originating from a bacterial source.
Especially, the
laundry detergent composition of the present invention will comprise an
alkaline
mannanase selected from the mannanase from the strain Bacillus agaradhaerens
NICMB
40482; the mannanase from Bacillus subtilis strain 168, gene yght; the
mannanase from
Bacillus sp. I633 and/or the mannanase from Bacillus sp. AAI12. Most preferred
mannanase for the inclusion in the detergent compositions of the present
invention is the
mannanase enzyme originating from Bacillus sp. I633 as described in the co-
pending
Danish patent application No. PA 1998 01340.
59

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
The terms "alkaline mannanase enzyme" is meant to encompass an enzyme
having an enzymatic activity of at least 10%, preferably at least 25%, more
preferably at
least 40% of its maximum activity at a given pH ranging from 7 to 12,
preferably 7.5 to
10.5.
The alkaline mannanase from Bacillus agaradhaerens NICMB 40482 is described
in the co-pending U.S. patent application serial No. 09/111,256. More
specifically, this
mannanase is:
i) a polypeptide produced by Bacillus agaradhaerens, NCIMB 40482; or
ii) a polypeptide comprising an amino acid sequence as shown in positions
32-343 of SEQ ID N0:2 as shown in U.S. patent application serial No.
09/111,256; or
iii) an analogue of the polypeptide defined in i) or ii) which is at least 70%
homologous with said polypeptide, or is derived from said polypeptide by
substitution, deletion or addition of one or several amino acids, or is
immunologically reactive with a polyclonal antibody raised against said
polypeptide in purified form.
Also encompassed is the corresponding isolated polypeptide having mannanase
activity
selected from the group consisting of:
(a) polynucleotide molecules encoding a polypeptide having mannanase
activity and comprising a sequence of nucleotides as shown in SEQ ID
NO: 1 from nucleotide 97 to nucleotide 1029 as shown in U.S. patent
application serial No. 09/111,256;
(b) species homologs of (a);
(c) polynucleotide molecules that encode a polypeptide having
mannanase activity that is at least 70% identical to the amino acid
sequence of SEQ ID NO: 2 from amino acid residue 32 to amino acid
residue 343 as shown in U.S. patent application serial No. 09/111,256;
(d) molecules complementary to (a), (b) or (c); and
(e) degenerate nucleotide sequences of (a), (b), (c) or (d).
The plasmid pSJ1678 comprising the polynucleotide molecule (the DNA
sequence) encoding said mannanase has been transformed into a strain of the
Escherichia
coli which was deposited by the inventors according to the Budapest Treaty on
the
International Recognition of the Deposit of Microorganisms for the Purposes of
Patent
Procedure at the Deutsche Sammlung von Mikroorganismen and Zellkulturen GmbH,

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
Mascheroder Weg 1b, D-38124 Braunschweig, Federal Republic of Germany, on 18
May
1998 under the deposition number DSM 12180.
A second more preferred enzyme is the mannanase from the Bacillus subtilis
strain 168, which is described in the co-pending U.S. patent application
serial No.
09/095,163. More specifically, this mannanase is:
i) is encoded by the coding part of the DNA sequence shown in SED ID No.
5 shown in the U.S. patent application serial No. 09/095,163 or an
analogue of said sequence; and/or
ii) a polypeptide comprising an amino acid sequence as shown SEQ ID N0:6
shown in the U.S. patent application serial No. 09/095,163; or
iii) an analogue of the polypeptide defined in ii) which is at least 70%
homologous with said polypeptide, or is derived from said polypeptide by
substitution, deletion or addition of one or several amino acids, or is
immunologically reactive with a polyclonal antibody raised against said
polypeptide in purified form.
Also encompassed in the corresponding isolated polypeptide having mannanase
activity
selected from the group consisting o~
(a) polynucleotide molecules encoding a polypeptide having
mannanase activity and comprising a sequence of nucleotides as shown in
SEQ ID N0:5 as shown in the U.S. patent application serial No.
09/095,163
(b) species homologs of (a);
(c) polynucleotide molecules that encode a polypeptide having
mannanase activity that is at least 70% identical to the amino acid
sequence of SEQ ID NO: 6 as shown in the U.S. patent application serial
No. 09/095,163;
(d) molecules complementary to (a), (b) or (c); and
(e) degenerate nucleotide sequences of (a), (b), (c) or (d).
A third more preferred mannanase is described in the co-pending Danish patent
application No. PA 1998 01340. More specifically, this mannanase is:
i) a polypeptide produced by Bacillus sp. I633;
ii) a polypeptide comprising an amino acid sequence as shown in
positions 33-340 of SEQ ID N0:2 as shown in the Danish application No.
PA 1998 01340; or
61

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
iii) an analogue of the polypeptide defined in i) or ii) which is at least
65% homologous with said polypeptide, is derived from said polypeptide
by substitution, deletion or addition of one or several amino acids, or is
immunologically reactive with a polyclonal antibody raised against said
polypeptide in purified form.
Also encompassed is the corresponding isolated polynucleotide molecule
selected from
the group consisting of:
(a) polynucleotide molecules encoding a polypeptide having mannanase
activity and comprising a sequence of nucleotides as shown in SEQ ID
NO: 1 from nucleotide 317 to nucleotide 1243 the Danish application No.
PA 1998 01340;
(b) species homologs of (a);
(c) polynucleotide molecules that encode a polypeptide having
mannanase activity that is at least 65% identical to the amino acid
sequence of SEQ ID NO: 2 from amino acid residue 33 to amino acid
residue 340 the Danish application No. PA 1998 01340;
(d) molecules complementary to (a), (b) or (c); and
(e) degenerate nucleotide sequences of (a), (b), (c) or (d).
The plasmid pBXM3 comprising the polynucleotide molecule (the DNA
sequence) encoding a mannanase of the present invention has been transformed
into a
strain of the Escherichia coli which was deposited by the inventors according
to the
Budapest Treaty on the International Recognition of the Deposit of
Microorganisms for
the Purposes of Patent Procedure at the Deutsche Sammlung von Mikroorganismen
and
Zellkulturen GmbH, Mascheroder Weg 1b, D-38124 Braunschweig, Federal Republic
of
Germany, on 29 May 1998 under the deposition number DSM 12197.
A fourth more preferred mannanase is described in the Danish co-pending patent
application No. PA 1998 01341. More specifically, this mannanase is:
i) a polypeptide produced by Bacillus sp. AAI 12;
ii) a polypeptide comprising an amino acid sequence as shown in
positions 25-362 of SEQ ID N0:2as shown in the Danish application No.
PA 1998 O 1341; or
iii) an analogue of the polypeptide defined in i) or ii) which is at least
65% homologous with said polypeptide, is derived from said polypeptide
by substitution, deletion or addition of one or several amino acids, or is
62

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
immunologically reactive with a polyclonal antibody raised against said
polypeptide in purified form.
Also encompassed is the corresponding isolated polynucleotide molecule
selected from
the group consisting of
(a) polynucleotide molecules encoding a polypeptide having mannanase
activity and comprising a sequence of nucleotides as shown in SEQ ID
NO: 1 from nucleotide 225 to nucleotide 1236 as shown in the Danish
application No. PA 1998 01341;
(b) species homologs of (a);
(c) polynucleotide molecules that encode a polypeptide having
mannanase activity that is at least 65% identical to the amino acid
sequence of SEQ ID NO: 2 from amino acid residue 25 to amino acid
residue 362 as shown in the Danish application No. PA 1998 01341;
(d) molecules complementary to (a), (b) or (c); and
(e) degenerate nucleotide sequences of (a), (b), (c) or (d).
The plasmid pBXM 1 comprising the polynucleotide molecule (the DNA
sequence) encoding a mannanase of the present invention has been transformed
into a
strain of the Escherichia coli which was deposited by the inventors according
to the
Budapest Treaty on the International Recognition of the Deposit of
Microorganisms for
the Purposes of Patent Procedure at the Deutsche Sammlung von Mikroorganismen
and
Zellkulturen GmbH, Mascheroder Weg 1b, D-38124 Braunschweig, Federal Republic
of
Germany, on 7 October 1998 under the deposition number DSM 12433.
The mannanase, when present, is incorporated into the treating compositions of
the present invention preferably at a level of from 0.0001 % to 2%, more
preferably from
0.0005% to 0.1 %, most preferred from 0.001 % to 0.02% pure enzyme by weight
of the
composition.
The compositions of the present invention may also comprise a xyloglucanase
enzyme. Suitable xyloglucanases for the purpose of the present invention are
enzymes
exhibiting endoglucanase activity specific for xyloglucan, preferably at a
level of from
about 0.001% to about 1%, more preferably from about 0.01% to about 0.5%, by
weight
of the composition. As used herein, the term "endoglucanase activity" means
the
capability of the enzyme to hydrolyze 1,4-(3-D-glycosidic linkages present in
any
cellulosic material, such as cellulose, cellulose derivatives, lichenin, (3-D-
glucan, or
xyloglucan. The endoglucanase activity may be determined in accordance with
methods
known in the art, examples of which are described in WO 94/14953 and
hereinafter. One
63

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
unit of endoglucanase activity (e.g. CMCU, AVIU, XGU or BGU) is defined as the
production of 1 pmol reducing sugar/min from a glucan substrate, the glucan
substrate
being, e.g., CMC (CMCU), acid swollen Avicell (AVID), xyloglucan (XGU) or
cereal (3-
glucan (BGU). The reducing sugars are determined as described in WO 94/14953
and
hereinafter. The specific activity of an endoglucanase towards a substrate is
defined as
units/mg of protein.
Suitable are enzymes exhibiting as its highest activity XGU endoglucanase
activity (hereinafter "specific for xyloglucan"), which enzyme:
i) is encoded by a DNA sequence comprising or included in at least one of the
following partial sequences
(a) ATTCATTTGT GGACAGTGGA C (SEQ ID No: 1)
(b) GTTGATCGCA CATTGAACCA (SEQ ID NO: 2)
(c) ACCCCAGCCG ACCGATTGTC (SEQ ID NO: 3)
(d) CTTCCTTACC TCACCATCAT (SEQ ID NO: 4)
(e) TTAACATCTT TTCACCATGA (SEQ ID NO: S)
(f) AGCTTTCCCT TCTCTCCCTT (SEQ ID NO: 6)
(g) GCCACCCTGG CTTCCGCTGC CAGCCTCC (SEQ ID NO: 7)
(h) GACAGTAGCA ATCCAGCATT (SEQ ID NO: 8)
(i) AGCATCAGCC GCTTTGTACA (SEQ ID NO: 9)
(j) CCATGAAGTT CACCGTATTG (SEQ ID NO: 10)
(k) GCACTGCTTC TCTCCCAGGT (SEQ ID NO: 11)
(1) GTGGGCGGCC CCTCAGGCAA (SEQ ID NO: 12)
(m) ACGCTCCTCC AATTTTCTCT (SEQ ID NO: 13)
(n) GGCTGGTAG TAATGAGTCT (SEQ ID NO: 14)
(o) GGCGCAGAGT TTGGCCAGGC (SEQ ID NO: 1 S)
(p) CAACATCCCC GGTGTTCTGG G (SEQ ID NO: 16)
(q) AAAGATTCAT TTGTGGACAG TGGACGTTGA TCGCACATTG
AACCAACCCC AGCCGACCGA
TTGTCCTTCC TTACCTCACC ATCATTTAAC ATCTTTTCAC CATGAAGCTT
TCCCTTCTCT
CCCTTGCCAC CCTGGCTTCC GCTGCCAGCC TCCAGCGCCG CACACTTCTG
CGGTCAGTGG
GATACCGCCA CCGCCGGTGA CTTCACCCTG TACAACGACC TTTGGGGCGA
GACGGCCGGC
64

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
ACCGGCTCCC AGTGCACTGG AGTCGACTCC TACAGCGGCG ACACCATCGC
TTGTCACACC
AGCAGGTCCT GGTCGGAGTA GCAGCAGCGT CAAGAGCTAT GCCAACG(SEQ
ID N0:17) or
(r) CAGCATCTCC ATTGAGTAAT CACGTTGGTG TTCGGTGGCC CGCCGTGTTG
CGTGGCGGAG
GCTGCCGGGA GACGGGTGGG GATGGTGGTG GGAGAGAATG TAGGGCGCCG
TGTTTCAGTC
CCTAGGCAGG ATACCGGAAA ACCGTGTGGT AGGAGGTTTA TAGGTTTCCA
GGAGACGCTG
TATAGGGGAT AAATGAGATT GAATGGTGGC CACACTCAAA CCAACCAGGT
CCTGTACATA
CAATGCATAT ACCAATTATA CCTACCAAAA AAAAAAAAAA AAAAAAAAAA
AAAA (SEQ ID N0:18)
or a sequence homologous thereto encoding a polypeptide specific for
xyloglucan with
endoglucanase activity,
ii) is immunologically reactive with an antibody raised against a highly
purified
endoglucanase encoded by the DNA sequence defined in i) and derived from
Aspergillus
aculeatus, CBS 101.43, and is specific for xyloglucan.
More specifically, as used herein the term "specific for xyloglucan" means
that
the endoglucanse enzyme exhibits its highest endoglucanase activity on a
xyloglucan
substrate, and preferably less than 75% activity, more preferably less than
50% activity,
most preferably less than about 25% activity, on other cellulose-containing
substrates
such as carboxymethyl cellulose, cellulose, or other glucans.
Preferably, the specificity of an endoglucanase towards xyloglucan is further
defined as a relative activity determined as the release of reducing sugars at
optimal
conditions obtained by incubation of the enzyme with xyloglucan and the other
substrate
to be tested, respectively. For instance, the specificity may be defined as
the xyloglucan
to (3-glucan activity (XGU/BGU), xyloglucan to carboxy methyl cellulose
activity
(XGU/CMCU), or xyloglucan to acid swollen Avicell activity (XGU/AVIU), which
is
preferably greater than about 50, such as 75, 90 or 100.
The term "derived from" as used herein refers not only to an endoglucanase
produced by strain CBS 101.43, but also an endoglucanase encoded by a DNA
sequence
isolated from strain CBS 101.43 and produced in a host organism transformed
with said
DNA sequence. The term "homologue" as used herein indicates a polypeptide
encoded by

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
DNA which hybridizes to the same probe as the DNA coding for an endoglucanase
enzyme specific for xyloglucan under certain specified conditions (such as
presoaking in
SxSSC and prehybridizing for 1 h at -40°C in a solution of SxSSC,
SxDenhardt's solution,
and 50 ~g of denatured sonicated calf thymus DNA, followed by hybridization in
the
same solution supplemented with 50 ~Ci 32-P-dCTP labeled probe for 18 h at -
40°C and
washing three times in 2xSSC, 0.2% SDS at 40°C for 30 minutes). More
specifically, the
term is intended to refer to a DNA sequence which is at least 70% homologous
to any of
the sequences shown above encoding an endoglucanase specific for xyloglucan,
including
at least 75%, at least 80%, at least 85%, at least 90% or even at least 95%
with any of the
sequences shown above. The term is intended to include modifications of any of
the
DNA sequences shown above, such as nucleotide substitutions which do not give
rise to
another amino acid sequence of the polypeptide encoded by the sequence, but
which
correspond to the codon usage of the host organism into which a DNA construct
comprising any of the DNA sequences is introduced or nucleotide substitutions
which do
give rise to a different amino acid sequence and therefore, possibly, a
different amino
acid sequence and therefore, possibly, a different protein structure which
might give rise
to an endoglucanase mutant with different properties than the native enzyme.
Other
examples of possible modifications are insertion of one or more nucleotides
into the
sequence, addition of one or more nucleotides at either end of the sequence,
or deletion of
one or more nucleotides at either end or within the sequence.
Endoglucanase specific for xyloglucan useful in the present invention
preferably
is one which has a XGU/BGU, XGU/CMU and/or XGU/AVIU ratio (as defined above)
of more than 50, such as 75, 90 or 100.
Furthermore, the endoglucanase specific for xyloglucan is preferably
substantially
devoid of activity towards (3-glucan and/or exhibits at the most 25% such as
at the most
10% or about 5%, activity towards carboxymethyl cellulose and/or Avicell when
the
activity towards xyloglucan is 100%. In addition, endoglucanase specific for
xyloglucan
of the invention is preferably substantially devoid of transferase activity,
an activity
which has been observed for most endoglucanases specific for xyloglucan of
plant origin.
Endoglucanase specific for xyloglucan may be obtained from the fungal species
A. aculeatus, as described in WO 94/14953. Microbial endoglucanases specific
for
xyloglucan has also been described in WO 94/14953. Endoglucanases specific for
xyloglucan from plants have been described, but these enzymes have transferase
activity
and therefore must be considered inferior to microbial endoglucanses specific
for
xyloglucan whenever extensive degradation of xyloglucan is desirable. An
additional
66

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
advantage of a microbial enzyme is that it, in general, may be produced in
higher
amounts in a microbial host, than enzymes of other origins.
The xyloglucanase, when present, is incorporated into the treating
compositions of
the invention preferably at a level of from 0.0001 % to 2%, more preferably
from
0.0005% to 0.1 %, most preferred from 0.001 % to 0.02% pure enzyme by weight
of the
composition.
The above-mentioned enzymes may be of any suitable origin, such as vegetable,
animal,
bacterial, fungal and yeast origin. Purified or non-purified forms of these
enzymes may be used.
Also included by definition, are mutants of native enzymes. Mutants can be
obtained e.g. by
protein and/or genetic engineering, chemical and/or physical modifications of
native enzymes.
Common practice as well is the expression of the enzyme via host organisms in
which the genetic
material responsible for the production of the enzyme has been cloned.
Said enzymes are normally incorporated in the bleaching composition at levels
from
0.0001 % to 2% of active enzyme by weight of the bleaching composition. The
enzymes can be
added as separate single ingredients (prills, granulates, stabilized liquids,
etc. containing one
enzyme ) or as mixtures of two or more enzymes ( e.g. cogranulates).
Other suitable detergent ingredients that can be added are enzyme oxidation
scavengers.
Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene
polyamines.
A range of enzyme materials and means for their incorporation into synthetic
bleaching
compositions is also disclosed in WO 93/07263 and WO 93/07260 to Genencor
International,
WO 89/08694 to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al.
Enzymes are
further disclosed in U.S. 4,101,457, Place et al, July 18, 1978, and in U.S.
4,507,219, Hughes,
March 26, 1985. Enzyme materials useful for liquid detergent formulations, and
their
incorporation into such formulations, are disclosed in U.S. 4,261,868, Hora et
al, April 14, 1981.
Enzyme Stabilizers - Enzymes for use in detergents can be stabilized by
.various
techniques. Enzyme stabilization techniques are disclosed and exemplified in
U.S. 3,600,319,
August 17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986,
Venegas. Enzyme
stabilization systems are also described, for example, in U.S. 3,519,570. A
useful Bacillus, sp.
AC13 giving proteases, xylanases and cellulases, is described in WO 9401532 to
Novo. The
enzymes employed herein can be stabilized by the presence of water-soluble
sources of calcium
and/or magnesium ions in the finished compositions which provide such ions to
the enzymes.
Suitable enzyme stabilizers and levels of use are described in U.S. Pat. No.
5,576,282.
Other Detergent In,~redients - The bleaching compositions herein may also
optionally contain one or more of the following: polymeric dispersing agents,
clay
soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes,
perfumes,
67

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
structure elasticizing agents, fabric softeners, carriers, hydrotropes,
processing aids
and/or pigments. Suitable examples of such other detergent ingredients and
levels of
use are found in U.S. Patent No. 5,576,282.
METHODS FOR LAUNDERING FABRICS
The organic catalysts and compositions containing same of the present
invention may be
used in essentially any washing or cleaning methods, including soaking
methods, pretreatment
methods and methods with rinsing steps for which a separate rinse aid
composition may be added.
The method for laundering fabrics described herein preferably comprises
contacting
fabrics with a laundering solution comprising an organic catalyst (in neat or
in bleaching
composition form) which becomes available in the laundering solution by a
controlled availability
method as defined in Test Protocols I, II and/or III. Optionally, but
preferably the laundering
solution comprises a peroxygen source.
The method of the invention is conveniently carried out in the course of the
cleaning process. The method of cleaning is preferably carried out at
5°C to 95°C, especially
between 10°C and 60°C. The pH of the laundering solution is
preferably from 7 to 11.
ORGANIC CATALYST PRODUCT
The organic catalysts and/or bleaching compositions of the present invention
may be
employed in various products for use in the laundering process.
In a preferred embodiment, a product comprising the organic catalyst and/or
bleaching
compositions containing the organic catalyst of the present invention wherein
the organic catalyst
becomes available in a wash solution containing the product by a controlled
availability method
as defined in Test Protocols I, II and/or III, as disclosed hereinafter, is
provided. The product
further includes instructions for using the organic catalyst and/or bleaching
composition to clean a
fabric in need of cleaning, preferably a stained fabric. The instructions
include the step of
delivering an amount of the product comprising the organic catalyst and/or
bleaching
composition, in conjunction with or without a peroxygen source, to a wash
solution containing the
fabric such that the organic catalyst becomes available in the wash solution
by a controlled
availability method as defined in Test Protocols I, II and/or III, as
disclosed hereinafter.
DETERMINATION OF CONTROLLED AVAILABILITY OF ORGANIC CATALYST
To facilitate the determination of whether an organic catalyst or a bleaching
composition
of the present invention or a product comprising an organic catalyst or
bleaching composition of
the present invention falls within the scope of this invention, three test
protocols, Test Protocols I,
II and III are provided below.
68

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
Only if Case I1 for Protocol I, Case II l for Protocol II and Case III1 for
Protocol III are
satisfied, does the organic catalyst-containing product (OCCP) not fall within
the boundaries of
this invention.
OCCP
TESTPROTOCOLI
General / Parameters: All solutions are maintained at 25 °C.
Adjustments of pH as required are
accomplished using either sodium carbonate or sulfuric acid as appropriate.
All solutions are
continuously stirred at 250 rpm, except small (1-5 mL) dye bleaching solution
(DBS) aliquots
removed to measure absorbance. Absorbance values are measures at the ~,max of
the reference
dye solution (RDS).
A test run is performed to determine if either of the parameters, dbleach or
~'"OCCP~ need to be
reset from their default values.
dbleach is a parameter in the final test protocol describing the time that
elapses between the
formation of the dye bleaching solution (DBS) and data acquisition. The
default value of the
parameter dbleach is 1 min, but may be defined as a longer time according to
Case I below.
wOCCP is a parameter in the final test protocol describing the weight of
organic catalyst-
containing product (OCCP) used to form the organic catalyst-containing product
solution
(OCCPS). The default value of the parameter is 1.00 grams, but may be defined
as a lesser
quantity or weight according to Case II below.
CDS is the concentrated dye solution, defined as a 300 ppm solution of
Amaranth dye (Aldrich )
in deionized water at pH 10.
OCCP is a fully formulated organic catalyst-containing product (as defined
hereinabove) in which
the organic catalyst may be present with various adjunct ingredients.
OCCPS is the organic catalyst-containing product solution prepared by
dissolving 1.00 g of an
organic catalyst-containing product (OCCP) in 1.0 L of 25 °C deionized
water, the pH of which
has been previously adjusted such that the final solution has a pH between 9.9
and 10.1.
69

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
DBS is the dye bleaching solution formed from the addition of a 100 mL aliquot
of the OCCPS to
mL of CDS.
Determination of Amax. 100 mL of deionized water at pH 10 is added to 10 mL of
CDS. The
5 absorbance of the resulting homogeneous reference dye solution (RDS)
determined by UV-
Visible Spectroscopy at the 7~max (approximately 518 nm) is Amax
Aliquot removal times: the times for aliquot removal from the OCCPS include
both fixed (tf) and
duration defined (tdd). The values of t f are 0.5, 1.5, 2.5 and 3.5 minutes.
The values of tdd are
10 0.25D, O.SOD and 0.75D, wherein D is the recommended duration of the wash.
Duration defined
aliquots for which tdd is less than 5 minutes need not be taken. For the
purposes of this test, D
can be no less than 5 minutes nor no greater than 16 hours. If no wash
duration is recommended
by the manufacturer of the OCCP, then D is set to 20 minutes. For example, if
the wash period is
60 minutes, the tdd required in addition to the t f are 15, 30 and 45 minutes.
For a 12 minute wash
period, the data points required are those associated with aliquot removals at
0.5, 1.5, 2.5,3.5, 6
and 9 minutes.
The test is performed vide infra using the default values of dbleach and
wOCCP~ From among all
fixed and duration defined aliquots, identify the one aliquot, Q, which gives
rise to the smallest
measured absorbance, Amin. The time (tf or tdd) at which Q is removed from the
OCCPS is
defined as tQ. Note by definition that this is the same point that shows the
greatest 8A (Amax -
Amin). Three cases exist, depending upon the value of Amim
Case 1: If Amin > 0.9 Amax, rerun the test to reset the value of dbleach~ In
this new test, the
aliquot removed at tQ is treated as before except it is stirred for additional
1 min increments until
such time as the absorbance Amin _< 0.9 Amax. The minimum number of minutes of
DBS stirring
required to satisfy the absorbance condition defines the new dbleach for the
final test protocol
implementation. If, however, a dbleach heater than 30 minutes is required
[i.e., if 10% bleaching
is not achieved in 30 minutes, even at the point where 8A is greatest (when
the organic catalyst is
present in its highest concentration)], the OCCP is not shown by Protocol I to
be within the
boundaries of this invention, however, the OCCP may be found to fall within
the boundaries of
this invention by Protocol II and/or Protocol III.
Case 2: If Amin < 0.25 Amax, rerun the test to reset the value of wOCCP~ The
OCCPS is
prepared from 50% of the default quantity of the OCCP. This process is
repeated only until the

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
absorbance condition described in Case 3 is met (e.g., reduce OCCP from 1.0 g
to 0.5 g, then if
necessary from 0.5 g to 0.25 g, etc.).
Case 3: If 0.25 Amax ~ Amin ~ 0.9 Amax, the test run serves as the final test
protocol
implementation. Under these conditions, dbleach and wOCCP do not need to be
changed from
the default values used.
Test protocol I: The initial step is the preparation of the OCCPS as
described. The time at which
the OCCP is added to the deionized water to form the OCCPS is set to t = 0. At
each of the
aliquot removal times (tf or tdd), a 100 mL aliquot of the OCCPS is withdrawn,
immediately
filtered during the period from t = (tf or tdd) to t = (tf or tdd + 0.25 min)
to remove undissolved
OCCP, and the filtrate added all at once at t = (t f or tdd + 0.50 min) to
10.0 mL of CDS. A 1-5
mL aliquot, C, of the resulting DBS is withdrawn immediately prior to the
absorbance
determination (data acquisition). Absorbance of C is measured at the 7~max at
the conclusion of
dbleach~
The time at which the absorbance determination (data acquisition) of aliquot C
is measured is
defined as tC. Therefore, it is required that tC = (t f or tdd) + 0.50 min +
dbleach~ The absorbance
value measured at tC is defined as At(C). The symbol 8At(C) is defined as Amax
- ~'t(C)~ For
example, if the wash period is 12 minutes, the value of dbleach is 1 minute,
and the aliquot
removals times are 0.5, 1.5, 2.5, 3.5, 6 and 9 minutes, then the data
acquisition times (tC) are 2, 3,
4, 5, 7.5 and 10.5 minutes.
The value tCa is any data acquisition time, tC, acquired prior to any other
data acquisition time,
tC~. Therefore, tCa < tCa. The absorbance at tCa is At(C)a; the absorbance at
tC~ is At(C)~.
Two cases exist, depending upon the values of At(C)a and At(C)~.
Case I1: If any At(C)~ < any At(C)a, and by definition 8At(C)(3 > SAt(C)a~
then a controlled
availability organic catalyst-containing product (OCCP) is indicated, and thus
the controlled
availability organic catalyst-containing product falls within the boundaries
of this invention.
Example of Case I1 for a 20 minute wash cycle:
71

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
t tC Amax At(C) b At(C) % t.2
dye 1.1 --o- At(c)
1.o
n n 1 ~n ~ ~~ 0.9
0.5 2 1.20 1.00 0.20 83
1.5 3 1.20 0.84 0.36 71 ~ o.~
2.5 4 1.20 0.70 0.50 58 N o.6
3.5 5 1.20 0.67 0.53 56 Q o.s
S 6.5 1.20 0.72 0.48 60 0.4
0.3
11.5 1.20 0.78 0.42 65
0.2
16.5 1.20 0.83 0.37 69 0.1
o.o
0 2 4 6 8 10 12 14 16 18 20
Time (min)
Case I2: If each At(C)a >_ each At(C)a, and by definition 8At(C)~ _< 8At(C)a,
then a controlled
availability organic catalyst-containing product (OCCP) is not indicated by
Protocol I, however,
S the OCCP may be found to fall within the boundaries of this invention by
Test Protocol II and/or
Test Protocol III. By way of example, this can occur for a non- controlled
availability organic
catalyst-containing product (OCCP), in which the OCCP fully dissolves in the
OCCPS prior to
the first t f, such that subsequent values of At(C) will remain constant.
Decomposition of the
organic catalyst over time in the OCCPS (which leads to less dye consumption
in the DBS over
10 time) results in each At(C)R being > each At(C)a
Example of Case I2 for a 20 minute wash cycle:
72

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
1.2
I.1
1.0 °'""
0.9
~, 0.8 -~ At(C)
U
0.7 Amax = 1.2
0 0.6
Q 0.5
0.4
0.3
0.2
0.1
0.0
0 2 4 6 8 10 12 14 16 18 20
Time (min)
TEST PROTOCOL II
General / Parameters / Protocol: Same as defined from Test Protocol I with the
following
additions.
OCSP is the organic catalyst-segregated product prepared by reformulating the
OCCP without the
organic catalyst and then adding the organic catalyst to the reformulated
product, such that the
overall composition of the OCSP is the same as the OCCP.
OCSPS is the organic catalyst-segregated product solution prepared by
dissolving 1.00 g of an
organic catalyst-segregated product (OCSP) in 1 L of 25 °C deionized
water, the pH of which has
been previously adjusted such that the final solution has a pH between 9.9 and
10.1.
wOCSP is a parameter in the final test protocol describing the weight of
organic catalyst-
segregated product (OCSP) used to form the organic catalyst-segregated product
solution
(OCSPS). The default value of the parameter is 1.00 grams, but may be defined
as a lesser
quantity or weight according to Case II below.
DBS2 is the dye bleaching solution formed from the addition of a 100 mL
aliquot of the OCSPS
to 10 mL of CDS.
Aliquot removal times from the OCSPS are the same as from the OCCPS, as
described earlier.
73

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
Test protocol II: The initial step is the completion of Protocol I as
described. The same
procedure is repeated (except that OCSP replaces OCCP) using the same dbleach
as defined in
Protocol I. The time at which the OCSP is added to the deionized water to form
the OCSPS is set
to t = 0. At each of the aliquot removal times (tf or tdd), a 100 mL aliquot
of the OCSPS is
withdrawn, immediately filtered during the period from t = (t f or tdd) to t =
(tf or tdd + 0.25 min)
to remove undissolved OCSP, and the filtrate added all at once at t = (tf or
tdd + 0.50 min) to 10.0
mL of CDS. A 1-5 mL aliquot, S, of the resulting DBS2 is withdrawn immediately
prior to the
absorbanee determination (data acquisition). Absorbance of S is measured at
the Amax at the
conclusion of dbleach~
The time at which the absorbance determination (data acquisition) of aliquot S
is measured is
defined as tS. Therefore, it is required that tS = (t f or tdd) + 0.50 min +
dbleach = tC~ The
absorbance value measured at tS is defined as At(S). The symbol 8At(S) is
defined as Amax -
At(S). For example, if the wash period is 12 minute, the value of dbleach's 1
minute, and the
aliquot removals times are 0.5, 1.5, 2.5, 3.5, 6 and 9 minutes, then the data
acquisition times (tS)
are 2, 3, 4, 5, 7.5 and 10.5 minutes.
Two cases exist, depending upon the values of At(C) and At(S) for tS = tC:
Case II1: If at least one At(S) < At(C)~ and by definition 8At(S) > 8At(C),
then a controlled
availability organic catalyst-containing product (OCCP) is indicated, and,the
OCCP falls within
the boundaries of this invention.
Example of Case II1 for a 20 minute wash cycle:
74

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
i.2 qmax = 1.2
1.1 ° qt(C) . BCPS
v
1.0 ~ v
0.9
d.......... ......... o.....................o
y 0.8
U p~L7"'
0.7 qt~S) ; gSPS
0 0.6
N
a o.s
0.4
0.3
0.2
0.1
0.0
0 2 4 6 8 10 12 14 16 18 20
Time (min)
More preferably, for Protocol II, even if in at least one instance, 1.2 x
At(S) < At(C), then a
controlled availability organic catalyst-containing product (OCCP) is
indicated, and the OCCP
falls within the boundaries of this invention.
10
Case II2: If each At(S) ? At(C), and by definition 8At(S) <_ 8At(C), then a
controlled
availability organic catalyst-containing product (OCCP) is not indicated by
Protocol II, however,
the OCCP may be found to fall within the boundaries of this invention by Test
Protocol I and/or
Test Protocol IILOCCP
TEST PROTOCOL III
20
General / Parameters / Protocol: Same as defined from Test Protocol I with the
following
additions. Peracetic acid, 32 wt% solution in dilute acetic acid available
from Aldrich.
OCCPS' in Protocol III is the organic catalyst-containing product solution
prepared by dissolving
1.00 g of an organic catalyst-containing product (OCCP) in 1 L of 25 °C
deionized water
containing 100 mg of peracetic acid (based on 100% activity), the pH of which
has been
previously adjusted such that the final solution has a pH between 9.9 and
10.1.
Test protocol III: All steps are as in Protocol I except that OCCPS' is used
in place of OCCPS.
Case III1: If any At(C)a < any At(C)a, and by definition 8At(C)~ > 8At(C)a,
then a controlled
availability organic catalyst-containing product (OCCP) is indicated, and thus
the controlled
availability organic catalyst-containing product falls within the boundaries
of this invention.

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
Case III2: If each At~C)a >_ each At~C)a, and by definition BAt~C)~ <_
BAt~C)a, then a controlled
availability organic catalyst-containing product (OCCP) is not indicated by
Protocol III, however,
the OCCP may be found to fall within the boundaries of this invention by Test
Protocol I and/or
Test Protocol II.
The compositions of the present invention can be suitably prepared by any
process chosen
by the formulator, non-limiting examples of which are described in U.S.
5,691,297 Nassano et al.,
issued November 11, 1997; U.S: 5,574,005 Welch et al., issued November 12,
1996; U.S.
5,569,645 Dinniwell et al., issued October 29, 1996; U.S. 5,565,422 Del Greco
et al., issued
October 15, 1996; U.S. 5,516,448 Capeci et al., issued May 14, 1996; U.S.
5,489,392 Capeci et
al., issued February 6, 1996; U.S. 5,486,303 Capeci et al., issued January 23,
1996 all of which
are incorporated herein by reference.
In addition to the above embodiments, the organic catalysts of the present
invention can
be formulated into any suitable laundry detergent composition, non-limiting
examples of which
are described in U.S. 5,679,630 Baeck et al., issued October 21, 1997; U.S.
5,565,145 Watson et
al., issued October 15, 1996; U.S. 5,478,489 Fredj et al., issued December 26,
1995; U.S.
5,470,507 Fredj et al., issued November 28, 1995; U.S. 5,466,802 Panandiker et
al., issued
November 14, 1995; U.S. 5,460,752 Fredj et al., issued October 24, 1995; U.S.
5,458,810 Fredj et
al., issued October 17, 1995; U.S. 5,458,809 Fredj et al., issued October 17,
1995; U.S. 5,288,431
Huber et al., issued February 22, 1994 all of which are incorporated herein by
reference.
Having described the present invention in detail with reference to preferred
embodiments,
it will be clear to those skilled in the art that various changes and
modifications 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.
76

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
SEQUENCE LISTING
<110> The Procter & Gamble Company
Dykstra, Robert
Miracle, Gregory
<120> Controlled Availability of Formulation Components, Compositi
ons and Laundry Methods Employing Same
<130> 7749X
<150> 60/151,002
<151> 1999-08-27
<150> 60/151,004
<151> 1999-08-27
<160> 18
<170> Patentln version 3.0
<210> 1
<211> 21
<212> DNA
<213> Aspergillus aculeatus
<400> 1
attcatttgt ggacagtgga c
21
<210> 2
<211> 20
<212> DNA
<213> Aspergillus aculeatus
<400> 2
gttgatcgca cattgaacca
<210> 3
<211> 20
<212> DNA
<213> Aspergillus aculeatus
<400> 3
accccagccg accgattgtc
Page 1

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
<210> 4
<211> 20
<212> DNA
<213> Aspergillus aculeatus
<400>
cttccttacc tcaccatcat
<210> 5
<211> 20
<212> DNA
<213> Aspergillus aculeatus
<400> 5
ttaacatctt ttcaccatga
<210> 6
<211> 20
<212> DNA
<213> Aspergillus aculeatus
<400> 6
agctttccct tctctccctt
<210> 7
<211> 28
<212> DNA
<213> Aspergillus aculeatus
<400> 7
gccaccctgg cttccgctgc cagcctcc
28
<210> 8
<211> 20
<212> DNA
<213> Aspergillus aculeatus
Page 2

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
<400> 8
gacagtagca atccagcatt
<210> 9
<211> 20
<212> DNA
<213> Aspergillus aculeatus
<400> 9
agcatcagcc gctttgtaca
<210>10
<211>20
<212>DNA
<213>Aspexgillus aculeatus
<400> 10
ccatgaagtt caccgtattg
<210>11
<211>20
<212>DNA
<213>Aspergilius aculeatus
<400> 11
gcactgcttc tctcccaggt
<210>12
<211>20
<212>DNA
<213>Aspergillus aculeatus
<400> 12
gtgggcggcc cctcaagcaa
<210> 13
<211> 20
<212> DNA
Page 3

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
<213> Aspergillus aculeatus
<400> 13
acgctcctcc aattttctct
<210> 14
<211> 19
<212> DNA
<213> Asperaillus aculeatus
<400> 14
ggctggtagt aatgagtct
19
<210> 15
<211> 20
<212> DNA
<213> Aspergillus aculeatus
<400> 15
ggcgcagagt ttggccaggc
<210> 16
<211> 21
<212> DNA
<213> Aspergillus aculeatus
<400> 16
caacatcccc ggtgttctgg g
21
<210> 17
<211> 347
<212> DNA
<213> Aspergillus aculeatus
<400> 17
aaagattcat ttgtggacag tggacgttga tcgcacattg aaccaacccc agccgaccga
ttgtccttcc ttacctcacc atcatttaac atcttttcac catgaagctt tcccttctct
120
Page 9

CA 02382280 2002-02-13
WO 01/16263 PCT/US00/23323
cccttgccac cctggcttcc gctgccagcc tccagcgccg cacacttctg cggtcagtgg
180
gataccgcca ccgccggtga cttcaccctg,tacaacgacc tttggggcga gacggccggc
240
accggctccc -agtgcactgg agtcgactcc tacagcggcg acaccatcgc ttgtcacacc
300
agcaggtcct ggtcggagta gcagcagcgt caagagctat gccaacg
347
<210> 18
<211> 294
<212> DNA
<213> Aspergillus aculeatus
<400> 18
cagcatctcc attgagtaat cacgttggtg ttcggtggcc cgccgtgttg cgtggcggag
gctgccggga -gacgggtggg gatggtggtg ggagagaatg tagggcgccg tgtttcagtc
120
cctaggcagg ataccggaaa accgtgtggt aggaggttta taggtttcca ggagacgctg
180
tataggggat aaatgagatt gaatggtggc cacactcaaa ccaaccaggt cctgtacata
240
caatgcatat accaattata cctaccaaaa aaaaaaaaaa aaaaaaaaaa aaaa
294
Page 5