Note: Descriptions are shown in the official language in which they were submitted.
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FORMULATION COMPONENTS RESISTANT TOWARDS DECOMPOSITION BY AROMATIZATION,
COMPOSITIONS AND LAUNDRY METHODS EMPLOYING SAME
Field of the Invention
This invention relates to formulation components such as bleach boosting
compounds
with increased stability, and compositions and laundry methods employing
bleach boosting
compounds with increased stability. More particularly, this invention relates
to quaternary imine
bleach boosters and/or oxaziridinium bleaching species, compositions and
laundry methods
employing quaternary imine bleach boosters and/or oxaziridinium bleaching
species.
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. 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, specifically
rubber hoses these appliances may contain. 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
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references, when combined with peroxygen compounds, undergo undesired
decomposition,
including the formation of an inactive, aromatic isoquinolinium, which causes
a reduction in
booster efficiency.
In light of the foregoing, researchers have been pursuing with vim and vigor
effective
bleach boosting agents that do not undergo decomposition.
Accordingly, the need remains for effective bleach boosting compounds and
compositions containing bleach boosting compounds which provide effective
bleaching even in
lower water temperatures and provide improved stability toward unwanted bleach
boosting
compound decomposition.
Summary of the Invention
This need is met by the present invention wherein longer lasting bleach
boosting
compounds, specifically bleach boosters and/or bleaching species, are
provided. The bleach
boosting compounds of the present invention provide superior bleaching
effectiveness even in
lower water temperatures as well as prevent unwanted decomposition.
A bleaching composition comprising a bleach boosting compound in conjunction
with or
without a peroxygen source, wherein said bleach boosting compound is selected
from the group
consisting of: (a) a bleach booster selected from the group consisting of
aryliminium cations,
aryliminium zwitterions, aryliminium polyions having a net charge of from
about +3 to about -3
and mixtures thereof; (b) a bleaching species selected from the group
consisting of oxaziridinium
cations, oxaziridinium zwitterions, oxaziridinium polyions having a net charge
of from about +3
to about -3 and mixtures thereof; and (c) mixtures thereof is provided in a
first embodiment.
In accordance with another embodiment of the present invention, a cationic or
zwitterionic laundry bleach boosting compound is provided.
In accordance with still another aspect of the present invention, a method for
laundering a
fabric in need of laundering comprising contacting the fabric with a laundry
solution having a
bleaching composition in accordance with the present invention as described
herein is provided.
In accordance with still yet another aspect of the present invention, a
laundry additive
product comprising a bleach boosting compound selected from the group
consisting of: (a) a
bleach booster selected from the group consisting of aryliminium cations,
aryliminium
zwitterions, aryliminium polyions having a net charge of from about +3 to
about -3 and mixtures
thereof; (b) a bleaching species selected from the group consisting of
oxaziridinium cations,
oxaziridinium zwitterions, oxaziridinium polyions having a net charge of from
about +3 to about -
3 and mixtures thereof; and (c) mixtures thereof is provided.
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Accordingly, it is an object of the present invention to provide: a bleach
boosting
compound which demonstrates improved performance even in lower temperature
solutions as
well as prevent unwanted aromatization; a bleaching composition including a
quaternary imine
bleach booster and/or an oxaziridinium bleaching species; a method for
laundering a fabric by
employing a quaternary imine bleach booster and/or an oxaziridinium bleaching
species; and a
laundry additive product having a quatemary imine bleach booster and/or an
oxaziridinium
bleaching species. 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.
Detailed Description of the Invention
The present invention discloses novel and highly useful bleach boosting
compounds
("bleach boosters", "bleaching species" and mixtures thereof), compositions,
and methods
employing the novel bleach boosting compounds. The bleach boosting compounds
of the present
invention provide increased bleaching effectiveness even in lower temperature
applications while
prevent unwanted decomposition by aromatization, resulting in improved
performance. The
bleach boosting compounds 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 prevention of aromatization.
DEFINITIONS
"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 (traderrgr3c OXONE) and their salts.
Bleach Boosters - The bleach boosters of the present invention are preferably
quatemary
imine bleach boosters. More preferably, the bleach boosters of the present
invention are selected
from the group consisting of aryliminium cations, aryliminium zwitterions,
and/or aryliminium
polyions having a net charge of from about +3 to about -3 and mixtures
thereof, wherein said
bleach boosters have the formulas [I] and [1I]:
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R1 R10 R9
R2 Rg
t R7
XO
~R6
R3
4 5
[I]
R Rl R10 R9
2 Rg
I t R7
R3 e
..o_7~
4 R5
[ll]
wherein t is 0 or 1; R1-R4 are substituted or unsubstituted radicals selected
from the group
consisting of H, alkyl, cycloalkyl, aryl, heterocyclic ring, nitro, halo,
cyano, sulfonato, sulfonato,
alkoxy, keto, carboxylic, and carboalkoxy radicals; any two vicinal Rl-R4 may
combine to form a
fused aryl, fused carbocyclic or fused heterocyclic ring; R5 is a substituted
or unsubstituted
radical selected from the group consisting of H, alkyl, cycloalkyl, alkaryl,
aryl, aralkyl,
heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic,
and carboalkoxy
radicals; R6 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 a radical
represented by the formula:
where Z- is covalently bonded to To, and Z- is selected from the group
consisting of
-C02-, -S03-, -OS03-, -SO2- and -OS02- and a is either I or 2; T. is selected
from the group
consisting of: (1) -(CH(R12))- or -(C(R12)2)- wherein R12 is independently
selected from H or
Cl-Cg alkyl; (2) -CH2(C6H4)-;
H H
-CHZ-C-CH2-
-CH2-C-CH2-
(3) I ; (4) OH (5) -(CH2)d(E)(CH2) f wherein d is from 2 to 8, f is from 1 to
3 and E is -C(O)O-;
(6) -C(O)NR13- wherein R13 is H or C1-C4 alkyl;
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H
-C-
(7) and
R16 R17
JX
R R15
(8)
wherein x is equal to 0 - 3; J, when present, is independently selected from
the group consisting of
-CR18R19-, -CR18R19CR20R21-, and -CR18R19CR20R21CR22R23-; R14-R23 are
substituted
or unsubstituted radicals selected from the linear or branched group
consisting of H, Cl-Clg
alkyls, cycloalkyls, alkaryls, aryls, aralkyls, alkylenes, heterocyclic rings,
alkoxys, arylcarbonyls,
carboxyalkyls and amide groups; wherein R7-RIO are substituted or
unsubstituted radicals
independently selected from the group consisting of H, linear or branched CI-
C12 alkyls,
alkylenes, alkoxys, aryls, alkaryls, aralkyls, cycloalkyls, and heterocyclic
rings, further provided
that when t is 0, neither R7 nor R8 can be H, and that when t is 1, either
both R7 and R8, or both
R9 and R10, are non-H; wherein any of R1 - RIO may be joined together with any
other of RI -
R 10 to fonm part of a common ring.
Preferred bleaching species include, but are not limited to: (1) oxaziridinium
cations of
fonrx.ila [III] as defined below wherein e is H or methyl, and e is selected
from the group of substituted or
unsubstituted radicals consisting of a linear or branched Cl-C14 alkyl, C3-C14
cycloalkyl, and
C6-C14 aryl; (2) oxaziridinium zwitterions of formula [IV] wherein R25 is H or
methyl, and R26
has the formula:
Preferred bleach boosters include, but are not limited to: (1) aryliminium
cations of
formula [I] wherein R5 is H or methyl, and R6 is selected from the group of
substituted or
unsubstituted radicals consisting of a linear or branched C1-C14 alkyl, C3-C14
cycloalkyl, and
C6-C 14 aryl; (2) aryliminium zwitterions of formula [II] wherein R5 is H or
methyl, and R6 has
the formula:
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where Z- is covalently bonded to To, and Z- is selected from the group
consisting of -C02-, -
SO3- and -OS03- and a is either 1 or 2; (3) aryliminium cations of formula [I]
wherein R6 is
selected from the group consisting of a linear or branched C1 - C14
substituted or unsubstituted
alkyl, or aryliminium zwitterions of formula [II] wherein R6 is a radical
represented by the
formula:
-To-(Z )a
wherein Z- is -C02-, -S03- or -OS03-, a is 1 and To is selected from the group
consisting of
R45
- (C)p-
R45
wherein p is an integer from 2 to 4, and R45 is independently selected from
the group consisting
of H and linear or branched C 1-C 1 g substituted or unsubstituted alkyl; and
(4) aryliminium
polyions having a net negative charge wherein R5 is H, Z- is -C02-,
-S03- or -OSO3-and a is 2.
More preferred bleach boosters include, but are not limited to: (1)
aryliminium cations of
formula [I] wherein R I- R5 are H, and R6 is linear or branched C I- C14
substituted or
unsubstituted alkyl; (2) aryliminium zwitterions of formula [II] wherein R1 -
R5 are H, and R6
has the formula:
-Tn-(Z )a
where Z- is covalently bonded to To, and Z- is selected from the group
consisting of -C02-, -S03-
and -OS03- and a is 1.
Furthermore, it is desirable that the aryliminium cations, aryliminium
zwitterions and aryliminium polyions having a net charge of from about +3 to
about -3, all of
formula [I] and [II] are geminally substituted. Geminally substituted bleach
boosters of the
present invention inhibit or prevent decomposition of the cations,
zwitterions, and polyions via
aromatization. The aromatization (decomposition) reaction of 6-membered ring
boosters 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:
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I~\
~ OH H OH
Step I I I Step 2 ~ I \ O+
-s
N\ N~
Active ~ OH Inactive
HO- H
Geminally substituted bleach boosters increase the turnover number of the
active bleach booster
by "blocking" the based-induced aromatization, as fully described above. Such
substitution,
without being limited by theory, may also inhibit or prevent decomposition of
the cations,
zwitterions, and polyions via other decomposition pathways. Other 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.
The quaternary imine bleach boosters 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
invention.
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.
The bleach activator may be selected from the group consisting of
tetraacetylethylenediamine, sodium octanoyloxybenzene sulfonate, sodium
nonanoyloxybenzene
sulfonate, sodium decanoyloxybenzene sulfonate, sodium lauroyloxybenzene
sulfonate, (6-
octanamido-caproyl)oxybenzenesulfonate, (6-nonanamido-
caproyl)oxybenzenesulfonate, (6-
decanamido-caproyl)
oxybenzenesulfonate, and mixtures thereof.
Preferred activators are selected from the group consisting of tetraacetyl
ethylene diamine
(TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-
chlorobenzoylcaprolactam,
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benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (NOBS),
phenyl
benzoate (PhBz), decanoyloxybenzenesulphonate (CIO-OBS), benzoylvalerolactam
(BZVL),
octanoyloxybenzenesulphonate (C8-OBS), perhydrolyzable esters, 4-[N-(nonaoyl)
amino
hexanoyloxy]-benzene sulfonate sodium salt (NACA-OBS) an example of which is
described in
U.S. Patent No. 5,523,434, lauroyloxybenzenesulfonate or
dodecanoyloxybenzenesulphonate
(LOBS or C12-OBS), 10-undecenoyloxybenzenesulfonate (UDOBS or CII-OBS with
unsaturation in the 10 position), and decanoyloxybenzoic acid (DOBA) and
mixtures thereof,
most 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.
Other 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 Wiiley 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 U.S. Patent No. 5,998,350.
Quaternary substituted bleach activators may also be included. The present
detergent
compositions preferably comprise a quaternary substituted bleach activator
(QSBA) or a
quatemary 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.
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-decanamidocaproyl)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 CfiH, ring to which is fused in
the 1,2-positions a
moiety --C(O)OC(Rl)=N-.
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
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from about 9.0 to about 10.5. Typically, for example, activators with electron-
withdrawing
moieties are used for near-neutral or sub-neutral 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 94-28 i 02 A) and acyl valerolactams (see
U.S. 5,503,639
Willey et al., issued April 2, 1996 ).
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 bleach boosters 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 Miracie 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 acid 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
acid has the general
formula:
O
11
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);
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(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 Bums 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
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.
The quatemary imine bleach booster of the present invention acts in
conjunction with a
peroxygen source to increase bleaching effectiveness. Without being bound by
theory, it is
believed that the bleach booster reacts with the peroxygen source to form a
more active bleaching
species, a quaternary oxaziridinium compound. The oxaziridinium compound has
an increased
activity at lower temperatures relative to the peroxygen compound. The
oxaziridinium compound
is represented by the formulas [III] and [IV]:
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R31 R30 R29
R32 R28
R27
t
N ~ XO
R33 1 ~ R26
34 250
[III]
R31 R30 R29
R3 Rzs
t R27
~To-Ga
R33 ~ N O ~
R34 R25~
[IV]
wherein t is 0 or 1; R31-R34 are substituted or unsubstituted radicals
selected from the group
consisting of H, alkyl, cycloalkyl, aryl, heterocyclic ring, nitro, halo,
cyano, sulfonato, alkoxy,
keto, carboxylic, and carboalkoxy radicals; any two vicinal R31-R34 may
combine to form a
fused aryl, fused carbocyclic or fused heterocyclic ring; R25 is a substituted
or unsubstituted
radical selected from the group consisting of H, alkyl, alkaryl, aryl,
aralkyl, heterocyclic ring,
nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy
radicals, and R26 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 a
radical represented by the
formula:
-TO-(Z )a
where Z- is covalently bonded to To, and Z- is selected from the group
consisting of
-CO2-, -S03-, -OS03-, -S02- and -OS02- and a is either 1 or 2; T. is selected
from the group
consisting of: (1) -(CH(R12))- or -(C(R12)2)- wherein R12 is independently
selected from H or
C I -Cg alkyl; (2) -CH2(C6H4)-;
H H
-CH2-C-CH2-
-CH2-C-CH2- 1
(3) ; (4) UH
(5) -(CH2)d(E)(CH2)f- wherein d is from 2 to 8, f is from 1 to 3 and E is -
C(O)O-;
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(6) -C(O)NR13- wherein R13 is H or C1-C4 alkyl;
H
I
-C-
(7) I ;and
R37 R38
JX
R 35 R36
wherein x is equal to 0 - 3; J, when present, is independently selected from
the group consisting of
-CR39R40-, -CR39R40CR41R42-, and -CR39R40CR41R42CR43R44-; R35-R44 are
substituted
or unsubstituted radicals selected from the linear or branched group
consisting of H, Cl-C18
alkyls, cycloalkyls, alkaryls, aryls, aralkyls, alkylenes, heterocyclic rings,
alkoxys, arylcarbonyls,
carboxyalkyls and amide groups; wherein R27-R30 are substituted or
unsubstituted radicals
independently selected from the group consisting of H, linear or branched C 1-
C 12 alkyls,
alkylenes, alkoxys, aryls, alkaryls, aralkyls, cycloalkyls, and heterocyclic
rings, further provided
that when t is 0, neither R27 nor R28 can be H, and that when t is 1, either
both R27 and R28, or
both R29 and R30, are non-H; wherein any of R25 - R34 may be joined together
with any other of
R25 - R34 to form part of a common ring. Furthermore, R25-R30 and R31-R34 may
be the same
as R5-R10 and Rl-R4, respectively, of the bleach booster of formulas [1] and
[II]. Such
oxaziridinium compounds can be produced from the quaternary imine of the
present invention
with the reactions:
RI R10 R9 RI R10 9
R2 R8 R2 R8
t R7 t R7
NO XO NO+ XD
R 3 R 6 R3 I R6
O
R4 R5 + RC03- 4 R4 R5 + RCOZ
[I] [III]
and
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WO 01/16273 PCT/US00/23315
R1 R10 R9 R1 R10 R9
R2 Rg R2 Rg
t R7 ~( t R7
N(D N O
R3 R3 I \
T T
o- O o-
4 5 4
R R S
+ RCO,- 4 R R +
RCO2-
[II] [IV]
Bleaching Species - The bleaching species (oxaziridiniums) may also be used
directly in
accordance with the present invention. The bleaching species of the present
invention are
preferably selected from the group consisting of oxaziridinium cations,
oxaziridinium zwitterions,
oxaziridinium polyions having a net charge of from about +3 to about -3, and
mixtures thereof,
said oxaziridinium compounds have the formulas [III] and [IV]:
R3 ~ R30 R29
R32 R2s
R27
t
I N XO
R33 I R26
R34 25~
[III]
and
R31 R30 R29
28
R27
R32 tN
\ R33 To-ZR[IV]
wherein t is 0 or 1; R31-R34 are substituted or unsubstituted radicals
selected from the group
consisting of H, alkyl, cycloalkyl, aryl, heterocyclic ring, nitro, halo,
cyano, sulfonato, alkoxy,
keto, carboxylic, and carboalkoxy radicals; any two vicinal R31-R34 may
combine to form a
fused aryl, fused carbocyclic or fused heterocyclic ring; R25 is a substituted
or unsubstituted
radical selected from the group consisting of H, alkyl, alkaryl, aryl,
aralkyl, heterocyclic ring,
nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy
radicals, and R26 may be
a substituted or unsubstituted, saturated or unsaturated, radical selected
from the group consisting
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WO 01/16273 PCT/US00/23315
of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, and a
radical represented by the
formula:
-TO-(Z )a
where Z- is covalently bonded to To, and Z- is selected from the group
consisting of
-C02-, -SO3-, -OS03-, -SO2- and -OS02- and a is either 1 or 2; T. is selected
from the group
consisting of: (1) -(CH(R12))- or -(C(R12)2)- wherein R12 is independently
selected from H or
CI-Cg alkyl; (2) -CH2(C6H4)-;
H H
-CH2-C-CH2-
-CH2-C-CH2-
(3) I ; (4) H
(5) -(CH2)d(E)(CH2) f= wherein d is from 2 to 8, f is from 1 to 3 and E is -
C(O)O-;
(6) -C(O)NR13- wherein R13 is H or CI-C4 alkyl;
H
-C-
(7) I ;and
R37 R38
JX
R 35 R36
wherein x is equal to 0 - 3; J, when present, is independently selected from
the group consisting of
-CR39R40-, -CR39R40CR4IR42-, and -CR39R40CR41R42CR43R44-; R35-R44 are
substituted
or unsubstituted radicals selected from the linear or branched group
consisting of H, C1-Cl8
alkyls, cycloalkyls, alkaryls, aryls, aralkyls, alkylenes, heterocyclic rings,
alkoxys, arylcarbonyls,
carboxyalkyls and amide groups; wherein R27-R30 are substituted or
unsubstituted radicals
independently selected from the group consisting of H, linear or branched C I-
C I 2 alkyls,
alkylenes, alkoxys, aryls, alkaryls, aralkyls, cycloalkyls, and heterocyclic
rings, further provided
that when t is 0, neither R27 nor R28 can be H, and that when t is 1, either
both R27 and R28, or
both R29 and R30, are non-H; wherein any of R25 - R34 may be joined together
with any other of
R25 - R34 to form part of a common ring. Furthermore, R25-R30 and R31-R34 may
be the same
as R5-R10 and R1-R4, respectively, of the bleach booster of formulas [I] and
[II].
Preferred bleaching species include, but are not limited to: (1) oxaziridinium
cations of
formula [III] wherein R25 is H or methyl, and R26 is selected from the group
of substituted or
unsubstituted radicals consisting of a linear or branched C I-C 14 alkyl, C3-C
14 cycloalkyl, and
14
CA 02381888 2004-09-30
C6-C14 aryl; (2) oxaziridinium zwitterions of formula [IV] wherein R25 is H or
methyl, and R26
has the formula:
-To-(Z )a
where Z- is covalently bonded to Ta, and Z- is selected from the group
consisting of -C02 ,-S03-
and -OS03- and a is either I or 2; (3) oxaziridinium cations of formula [Ilt]
wherein R26 is
selected from the group consisting of a linear or branched Cl - C14
substituted or unsubstituted
alkyl, or aryliminium oxaziridinium of formula [TV] wherein R26 is a radical
represented by the
formula:
~~Tn (Z./i
wherein Z- is -C02-, -SO3- or -OS03-, a is I and.lTa is selected from the
group consisting of
R45
1
-(C)p--
R45
wherein p is an integer from 2 to 4, and R45 is independently selected from
the group consisting
of H and linear or branched C1-C1g substituted or unsubstituted alkyl; and (4)
oxaziridinium
polyions having a net negative charge wherein R25 is H, Z- is -C02-,
-S03- or -OSO3-and a is 2.
The bleach boosting compounds of the present inventionmay 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 0.01% (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
bleach
boosting compound and/or bleaching species 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).
Preferably, the bleaching compositions of the present invention bieach
composition
comprise an amount of bleach boosting compound and/or bleaching species 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 bleach boosting compound
and/or
bleaching species, such that the resulting molar ratio of said peroxygen
compound to bleach
CA 02381888 2002-02-12
WO 01/16273 PCT/US00/23315
boosting compound and/or bleaching species 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 bleach boosting 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%
bleach boosting compound by weight results in a bleach boosting compound
concentration of 2
ppm. Similarly, a 3500 ppm wash solution of a product containing 0.2% bleach
boosting
compound by weight results in a bleach boosting compound concentration of 6.5
ppm.
The method for delivering bleach boosting compounds of the present invention
and the
method for delivering bleaching compositions (products) containing such bleach
boosting
compounds that are particularly useful in the methods of the present invention
are the bleach
boosting 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 bleach
boosting compound whose structures is defined herein and wherein said medium
contains active
oxygen from the peroxygen compound from about 0.05 to about 250 ppm per liter
of medium,
and said bleach boosting 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 bleach boosting 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 bleaching compositions of the present invention may be advantageously
employed in
laundry applications including, but not limited to, stain bleaching, dye
transfer inhibition, and
whitening, hard surface cleaning, automatic dishwashing applications, as well
as cosmetic
applications such as dentures, teeth, hair and skin. However, due to the
unique advantage of
increased bleaching effectiveness in lower temperature solutions, the bleach
boosting compounds
of the present invention are ideally suited for laundry applications such as
the bleaching of fabrics
through the use of bleach containing detergents or laundry bleach additives.
Furthermore, the
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CA 02381888 2002-02-12
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bleach boosting compounds of the present invention may be employed in both
granular and liquid
compositions.
Accordingly, the bleaching compositions of the present invention may include
various
additional ingredients which are desirable in laundry applications. Such
ingredients include
detersive surfactants, bleach catalysts, builders, chelating agents, enzymes,
polymeric soil release
agents, brighteners and various other ingredients. Compositions including any
of these various
additional ingredients preferably have a pH of from about 6 to about 12,
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 has a pH of
about 6 to about 12,
preferably from about 8 to about 10.5 in a 1% solution of the bleaching
composition.
In accordance with another aspect of the present invention, cationic or
zwitterionic
laundry bleach boosting compounds are provided. Such bleach boosting compounds
are
preferably selected from the group consisting of:
Rl R10 R9 RI RIO R9
R2 Rg R2 Rg
t R7 t R7
N0 Xe \ I ~ NO
R3 R6 R3 e
To-
4 5 4 5
[I] [II]
R3 ~ R30 R29 R31 R30 R29
32 R28 R32 R2a
R R27 ~ t R27
t o ~
33 I NO 26X R33 ~ NO ~
R I R To- 7a
34 25~ R34 25~
[III] [IV]
and mixtures thereof; wherein for formula [I] and [II] t is 0 or 1; Rl-R4 are
substituted or
unsubstituted radicals selected from the group consisting of H, alkyl,
cycloalkyl, aryl,
heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic,
and carboalkoxy
radicals; any two vicinal R1-R4 may combine to form a fused aryl, fused
carbocyclic or fused
heterocyclic ring; R5 is a substituted or unsubstituted radical selected from
the group consisting of
17
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WO 01/16273 PCT/US00/23315
H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, nitro, halo,
cyano, sulfonato, alkoxy,
keto, carboxylic, and carboalkoxy radicals; R6 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 a radical represented by the formula:
-T~ (Z )a
where Z- is covalently bonded to To, and Z- is selected from the group
consisting of
-C02-, -S03-, -OS03-, -S02- and -OS02- and a is either 1 or 2; To is selected
from the group
consisting of: (1) -(CH(R12))- or -(C(R12)2)- wherein R12 is independently
selected from H or
CI-Cg alkyl; (2) -CH2(C6H4)-;
H H
CH2-C-CH2- -CH2-C-CH2-
- ~
(3) ; (4) OH
(5) -(CH2)d(E)(CH2)f- wherein d is from 2 to 8, f is from 1 to 3 and E is -
C(O)O-;
(6) -C(O)NR13- wherein R13 is H or CI-C4 alkyl;
H
-c-
(7) I ;and
R16 R17
cJX
(8) R14 R15
wherein x is equal to 0 - 3; J, when present, is independently selected from
the group consisting of
-CR18RI9-, -CR18R19CR20R21-, and -CRI8RI9CR20R21CR22R23-; R14-R23 are
substituted
or unsubstituted radicals selected from the linear or branched group
consisting of H, CI-CIg
alkyls, cycloalkyls, alkaryls, aryls, aralkyls, alkylenes, heterocyclic rings,
alkoxys, arylcarbonyls,
carboxyalkyls and amide groups; wherein R7-RIO are substituted or
unsubstituted radicals
independently selected from the group consisting of H, linear or branched CI-
C12 alkyls,
alkylenes, alkoxys, aryls, alkaryls, aralkyls, cycloalkyls, and heterocyclic
rings, further provided
that when t is 0, neither R7 nor R8 can be H, and that when t is 1, either
both R7 and R8, or both
R9 and R10, are non-H; wherein any of RI - R10 may be joined together with any
other of RI -
RIO to form part of a common ring; andwherein for formulas [III] and [IV] t is
0 or 1; R31-R34
are substituted or unsubstituted radicals selected from the group consisting
of H, alkyl, cycloalkyl,
18
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WO 01/16273 PCT/US00/23315
aryl, heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto,
carboxylic, and carboalkoxy
radicals; any two vicinal R31-R34 may combine to form a fused aryl, fused
carbocyclic or fused
heterocyclic ring; R25 is a substituted or unsubstituted radical selected from
the group consisting
of H, alkyl, alkaryl, aryl, aralkyl, heterocyclic ring, nitro, halo, cyano,
sulfonato, alkoxy, keto,
carboxylic, and carboalkoxy radicals, and R26 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 a radical represented by the formula:
-T~--(Z )a
where Z- is covalently bonded to To, and Z- is selected from the group
consisting of
-C02-, -S03-, -OS03-, -S02- and -OS02- and a is either I or 2; T. is selected
from the group
consisting of: (1) -(CH(R12))- or -(C(R12)2)- wherein R12 is independently
selected from H or
C 1-C8 alkyl; (2) -CH2(C6H4)-;
H H
-CH2-C-CH2-
-CH2-C-CH2-
(3) 1 ; (4) H
(5) -(CH2)d(E)(CH2) f= wherein d is from 2 to 8, f is from 1 to 3 and E is -
C(O)O-;
(6) -C(O)NR13- wherein R 13 is H or C 1-C4 alkyl;
H
-C-
(7) I ;and
R37 R38
(8) R;;7c3JX
6
wherein x is equal to 0 - 3; J, when present, is independently selected from
the group consisting of
-CR39R40-, -CR39R40CR41R42-, and -CR39R40CR41R42CR43R44-; R35-R44 are
substituted
or unsubstituted radicals selected from the linear or branched group
consisting of H, C1-Cl8
alkyls, cycloalkyls, alkaryls, aryls, aralkyls, alkylenes, heterocyclic rings,
alkoxys, arylcarbonyls,
carboxyalkyls and amide groups; wherein R27-R30 are substituted or
unsubstituted radicals
independently selected from the group consisting of H, linear or branched C1-
C12 alkyls,
alkylenes, alkoxys, aryls, alkaryls, aralkyls, cycloalkyls, and heterocyclic
rings, further provided
that when t is 0, neither R27 nor R28 can be H, and that when t is 1, either
both R27 and R28, or
both R29 and R30, are non-H; wherein any of R25 - R34 may be joined together
with any other of
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CA 02381888 2002-02-12
WO 01/16273 PCT/US00/23315
R25 - R34 to form part of a common ring. 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 used
in this laundering
method preferably range from about 0 C to about 50 C. 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 ingredient
selected from
the group consisting of detersive surfactants, chelating agents, detersive
enzymes and mixtures
thereof. Preferably, the laundry solution has a pH of about 6 to about 12,
preferably from 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 a bleach boosting compound,
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.
It is desirable that the laundry additive product further includes a peroxygen
source, as
fully described above. The laundry additive product can also include powdered
or liquid
compositions containing a hydrogen peroxide source or a peroxygen source as
fully defined
above.
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
above.
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.
CA 02381888 2004-09-30
When the bleach boosting compounds of the present invention are other than an
aryliminium zwitterion or oxaziridinium zwitterion, a suitable bleach
compatible, charge-
balancing counterion is also present.
BLEACHING COMPOSITIONS COMPRISING BLEACH BOOSTING COMPOUNDS
In addition to the use of bleach boosting compounds discussed above, the
bleach boosting
compounds of the present invention may be employed in conjunction with or
without, preferably
with a peroxygen source in other bleaching compositions, regardless of their
form. For example,
the bleach boosting compounds may be employed in a laundry additive product.
In the bleaching
compositions of the present invention, the peroxygen source may be present in
levels of from
about 0.01% to about 60% by weight of the composition, and preferably from
about 1% to about
40% by weight of the composition. In a composition, the bleach boosting may be
present from
about 0.001% to about 10% by weight of the composition, and more preferably
from about
0.005% to about 5% by weight of the 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 bleach boosting compound
may be present
from about 0.00001 %(0.0001 ppm) to about 10% () 00 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%
bleach boosting compound by weight results in a bleach boosting compound
concentration of 2
ppm. Similarly, a 3500 ppm wash solution of a product containing 0.2% bleach
boosting
compound by weight results in a bleach boosting 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-$ M to 1.7 x 10'5M). Should a bleach
boosting compound of
higher m.w. be used in the bleaching compositions of the present invention,
the prefenred molar
concentration will remain unchanged, whereas the preferred weight
concentration (in ppm) will
21
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WO 01/16273 PCT/US00/23315
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 bleaching compositions of the present invention may be advantageously
employed in
laundry applications, hard surface cleaning, automatic dishwashing
applications, as well as
cosmetic applications such as dentures, teeth, hair and skin. However, due to
the unique
advantages of increased color safety and increased effectiveness in cold and
possibly warm water
solutions due to possible increased stability, the bleach boosting compounds
of the present
invention are ideally suited for laundry applications such as the bleaching of
fabrics through the
use of bleach-containing detergents or laundry bleach additives. Furthermore,
the bleach boosting
compounds of the present invention may be employed in both granular and liquid
compositions.
The bleach boosting compounds and bleaching composition comprising the bleach
boosting compounds can be used as antimicrobial agents and disinfectants.
Accordingly, the bleaching compositions of the present invention may include
various
additional ingredients which are desirable in laundry applications. Such
ingredients include
detersive surfactants, bleach catalysts, builders, chelating agents, enzymes,
polymeric soil release
agents, brighteners and various other ingredients. Compositions including any
of these various
additional ingredients preferably have a pH of from about 6 to about 12,
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 has a pH of
about 6 to about 12,
preferably from about 8 to about 10.5 in a 1% solution of the bleaching
composition.
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 ingredient
selected from
the group consisting of detersive surfactants, chelating agents, detersive
enzymes and mixtures
thereof. Preferably, the laundry solution has a pH of about 6 to about 12,
preferably from about 8
to about 10.5 in a 1% solution of the bleaching composition.
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WO 01/16273 PCT/US00/23315
In accordance with another aspect of the present invention, a laundry additive
product is
provided. The laundry additive product comprises an bleach boosting compound,
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 and medium temperature solution laundry
application.
It is desirable that the laundry additive product further includes a peroxygen
source, as
fully described above. The laundry additive product can also include powdered
or liquid
compositions containing a hydrogen peroxide source or a peroxygen source as
fully defined
above.
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
above.
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 peroxygen source; and
(b) an bleach boosting compounds;
wherein the bleach boosting compounds becomes active in a wash solution
containing said
bleaching composition a period of time after said peroxygen source becomes
active. The
peroxygen source, like discussed above, is preferably 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
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(ii) hydrogen peroxide sources selected from the group consisting of perborate
compounds, percarbonate compounds, perphosphate compounds and mixtures
thereof, and a
bleach activator.
Bleaching System - In addition to the bleach boosting 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
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 bleach bleach boosting compounds 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:
0
11
Y-R-C-O-OH
24
CA 02381888 2002-02-12
WO 01/16273 PCT/US00/23315
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
II
Y-(CH2)n-C-O-OH
where Y can be, for example, H, CH3, CH2C1, 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:
0
II
Y-C6H4-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.
CA 02381888 2004-09-30
Patent 4,634,551, issued January 6, 1987 to Bums 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. Hydrogen 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 Kirk
Othmer's Encyclopedia of Chemical Technology, 4th Ed (1992, John Wiley &
Sons), Vol. 4, pp.
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
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
26
CA 02381888 2004-09-30
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 (NOBS),
phenyl
benzoate (PhBz), decanoyloxybenzenesulphonate (C10-OBS), benzoylvalerolactam
(BZVL),
octanoyloxybenzenesulphonate (Cg-OBS), perhydrolyzable esters and mixtures
thereof, most
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 (NOBS), 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 C11-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 U.S. Patent No. 5,998,350.
The mole ratio of peroxygen bleaching compound (as AvO) 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 quatemary 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.
27
CA 02381888 2004-09-30
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(RI)=N-.
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-neutral 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).
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. 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 cations, 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.
28
CA 02381888 2004-09-30
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 Al, 549,272 Al, 544,440 A2, and 544,490
Al; 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,
Mn1V4(u-
0)6(1,4,7-triazacyclononane)4(CI04)4, MnIIIMnIV4(u-O)1(u-OAc)2-(1,4,7-
trimethyl-1,4,7-
triazacyclononane)2(CI04)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 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.
lnorg. Bioinorg.
Mech., (1983), 2, pages 1-94. The most preferred cobalt catalyst useful herein
are cobalt
pentaamine acetate salts having the formula [Co(NH3)5OAc] Ty, wherein "OAc"
represents an
acetate moiety and "Ty" is an anion, and especially cobalt pentaamine acetate
chloride,
[Co(NH3)5OAc]C12; as well as [Co(NH3)5OAc](OAc)2; [Co(NH3)5OAc](PF6)2;
[Co(NH3)5OAc](SO4); [Co(NH3)5OAc](BF4)2; and [Co(NH3)5OAc](NO3)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 lnorganic
Compounds, W.L. Jolly (Prentice-Hall; 1970), pp. 461-3; Inorg. Chem., 18, 1497-
1502 (1979);
InorQ. Chem., 21, 288 l-2885 (1982); lnorg. Chem., 18, 2023-2025 (1979);
Inorg. Synthesis, 173-
176 (1960); and Jouraal of Physical ChemistrX, 56 22-25 (1952).
29
CA 02381888 2004-09-30
iii. Transition Metal Complexes of Macropolycyclic Ri ig d Ligands -
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 I 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
been defined as the constrained converse of flexibility: see D.H. Busch.,
Chemical Reviews.,
(1993), 93, 847-860. 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 NI and N8 in the illustrative structure. By
comparison, a "same-
side" bridge, for example if one were to be introduced across NI and N12 in
1.1 1, would not be
sufficient to constitute a "cross-bridge" and accordingly would not be
preferred.
Suitable metals in the rigid ligand complexes include Mn(lI), Mn(III), Mn(IV),
Mn(V),
Fe(II), Fe(III), Fe(IV), Co(I), Co(II), Co(11I), Ni(I), Ni(II), Ni(III),
Cu(I), Cu(ll), 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
CA 02381888 2004-09-30
(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 Formula 1 and Formula 2 below, can be used.
(CH>
Formula 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 \
Formula 2
wherein m and n are integers from about I to 8, more preferably from I 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, 0, S or C.
Suitable MRL's are further nonlimitingly illustrated by the following
compound:
3
2 4
I r,"')
15",
14 N a N 6
13 12 b 8 7
N N
1~9
Formula 3
31
CA 02381888 2002-02-12
WO 01/16273 PCT/US00/23315
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 non-
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)
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).
(fl Other Bleach Catalysts - The compositions herein may comprise one or more
other
bleach catalysts. Preferred bleach catalysts are zwitterionic bleach
catalysts, which are described
in U.S. Patent No. 5,576,282 (especially 3-(3,4-dihydroisoquinolinium) propane
sulfonate. Other
bleach catalysts include cationic bleach catalysts are described in U.S.
Patent Nos. 5,360,569,
5,442,066, 5,478,357, 5,370,826, 5,482,515, 5,550,256, and WO 95/13351, WO
95/13352, and
WO 95/13353.
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,
32
CA 02381888 2004-09-30
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 bleach boosting, 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 bleach
boosting.
The period of time between the peracid becoming active in a wash solution and
the bleach
boosting compounds becoming active can be in the range of from about I second
to about 24
hours. Alternatively, since the bleach boosting compounds are relatively
stable in the wash
solution, the peracid can become active in the wash solution after the bleach
boosting compound
becomes active or available.
The purpose of a delayed addition bleaching composition (which may or may not
be used
in conjunction with this invention) is to allow the peracid to achieve maximum
bleaching
performance on a fabric in need of cleaning, such as a stained fabric, in a
wash solution prior to
the introduction of the bleach boosting compound. In other words, a bleaching
composition
comprising a bleach boosting compound which becomes active in a wash solution
after a fabric in
need of cleaning has been added to the wash solution. Methods for delayed
(controlled) addition
of bleach boosting compounds are more fully described in CA 2,382,280.
Alternatively, since the bleach boosting compounds can have increased
stability, a
bleaching composition comprising an bleach boosting compound which becomes
active in a wash
solution prior to a fabric in need of cleaning has been added to the wash
solution may be used.
The bleaching compositions of the present invention also preferably comprise,
in addition
to one or more bleach boosting compounds, described hereinbefore, one or more
cleaning adjunct
materials, preferably compatible with the bleach boosting(s) and/or any
enzymes present in the
33
CA 02381888 2004-09-30
bleaching composition. The term "compatible", as used herein, means the
bleaching composition
materials do not reduce the bleaching activity of the bleach boosting andlor
any enzymatic
activity of any enzyme present in the bleaching composition to such an extent
that the bleach
boosting and/or enzyme is not effective as desired during normal use
situations. The term
"cleaning adjunct materials", as used herein, means any liquid, solid or
gaseous material selected
for the particular type of bleaching composition desired and the form of the
product (e.g., liquid;
granule; powder; bar; paste; spray; tablet; gel; foam composition), which
materials are also
preferably compatible with the protease enzyme(s) and bleaching agent(s) used
in the
composition. Granular compositions can also be in "compact" form and the
liquid compositions
can also be in a "concentrated" form.
The specific selection of cleaning adjunct materials are readily made by
considering the
surface, item or fabric to be cleaned, and the desired form of the composition
for the cleaning
conditions during use (e.g., through the wash detergent use). Examples of
suitable cleaning
adjunct materials include, but are not limited to, surfactants, builders,
bleaches, bleach activators,
bleach catalysts, other enzymes; enzyme stabilizing systems, chelants, optical
brighteners, soil
release polymers, dye transfer agents, dispersants, suds suppressors, dyes,
perfumes, colorants,
filler salts, hydrotropes, photoactivators, fluorescers, fabric conditioners,
hydrolyzable surfactants,
preservatives, anti-oxidants, anti-shrinkage agents, anti-wrinkle agents,
germicides, fungicides,
color speckles, silvercare, anti-tarnish and/or anti-corrosion agents,
alkalinity sources, solubilizing
agents, carriers, processing aids, pigments and pH control agents as described
in U.S. Patent Nos.
5,705,464, 5,710,115, 5,698,504, 5,695,679, 5,686,014 and 5,646,101. Specific
bleaching
composition materials are exemplified in detail hereinafter.
Tf the cleaning adjunct materials are not compatible with an optional protease
variant(s) in the
bleaching compositions, then suitable methods of keeping the cleaning adjunct
materials and the
protease variant(s) separate (not in contact with each other) until
combination of the two
components is appropriate can be used. Suitable methods can be any method
known in the art,
such as gelcaps, encapulation, tablets, physical separation, etc.
Such bleaching compositions include detergent compositions for cleaning hard
surfaces,
unlimited in form (e.g., liquid, granular, paste, foam, spray, etc.);
detergent compositions for
cleaning fabrics, unlimited in form (e.g., granular, liquid, bar formulations,
etc.); dishwashing
compositions (unlimited in form and including both granular and liquid
automatic dishwashing);
oral bleaching compositions, unlimited in form (e.g., dentifrice, toothpaste
and mouthwash
formulations); and denture bleaching compositions, unlimited in form (e.g.,
liquid, tablet).
The fabric bleaching compositions of the present invention are mainly intended
to be used
in the wash cycle of a washing machine; however, other uses can be
contemplated, such as
34
CA 02381888 2004-09-30
pretreatment product for heavily-soiled fabrics, or soaking product; the use
is not necessarily
limited to the washing-machine context, and the compositions of the present
invention can be
used alone or in combination with compatible handwash compositions.
The bleaching compositions may include from about 1% to about 99.9% by weight
of the
composition of the cleaning adjunct materials.
As used herein, "non-fabric bleaching compositions" include hard surface
bleaching
compositions, dishwashing compositions, oral bleaching compositions, denture
bleaching
compositions and personal cleansing compositions.
When the bleaching compositions of the present invention are formulated as
compositions
suitable for use in a laundry machine washing method, the compositions of the
present invention
preferably contain both a surfactant and a builder compound and additionally
one or more
cleaning adjunct materials preferably selected from organic polymeric
compounds, bleaching
agents, enzymes, suds suppressors, dispersants, lime-soap dispersants, soil
suspension
and anti-redeposition agents and corrosion inhibitors. Laundry compositions
can also contain
softening agents, as additional cleaning adjunct materials.
The compositions of the present invention can also be used as detergent
additive products
in solid or liquid form. Such additive products are intended to supplement or
boost the
performance of conventional detergent compositions and can be added at any
stage of the
cleaning process.
When formulated as compositions for use in manual dishwashing methods the
compositions of the invention preferably contain a surfactant and preferably
other cleaning
adjunct materials selected from organic polymeric compounds, suds enhancing
agents, group II
metal ions, solvents, hydrotropes and additional enzymes.
If needed the density of the laundry detergent compositions herein ranges from
400 to
' 1200 g/ liter, preferably 500 to 950 g/liter of composition measured at 20
C.
The "compact" form of the bleaching compositions herein is best reflected by
density and,
in terms of composition, by the amount of inorganic filler salt; inorganic
filler salts are
conventional ingredients of detergent compositions in powder form; in
conventional detergent
compositions, the filler salts are present in substantial amounts, typically
17-35% by weight of the
total composition. In the compact compositions, the filler salt is present in
amounts not exceeding
15% of the total composition, preferably not exceeding 10%, most preferably
not exceeding 5%
by weight of the composition. The inorganic filler salts, such as meant in the
present
compositions are selected from the alkali and alkaline-earth-metal salts of
sulfates and chlorides.
A preferred filler salt is sodium sulfate.
CA 02381888 2002-02-12
WO 01/16273 PCT/US00/23315
Liquid bleaching compositions according to the present invention can also be
in a
"concentrated form", in such case, the liquid bleaching compositions according
the present
invention will contain a lower amount of water, compared to conventional
liquid detergents.
Typically the water content of the concentrated liquid bleaching composition
is preferably less
than 40%, more preferably less than 30%, most preferably less than 20% by
weight of the
bleaching composition.
Cleaning Adjunct Materials
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
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 - The compositions of the present invention preferably contain a
detersive
surfactant. The detersive surfactant is typically selected from the group
consisting of anionic,
nonionics, cationics, ampholytics, zwitterionics, and mixtures thereof. By
selecting the type and
amount of detersive surfactant, along with other adjunct ingredients disclosed
herein, the present
detergent compositions can be formulated to be used in the context of laundry
cleaning or in other
different cleaning applications, particularly including dishwashing. The
particular surfactants
used can therefore vary widely depending upon the particular end-use
envisioned. Suitable
surfactants are described below. Examples of suitable nonionic, anionic,
cationic amphoteric and
zwitterionic surfactants are given in "Surface Active Agents and Detergents"
(Vol. I and II by
Schwartz, Perry and Berch). A variety of such surfactants are also generally
disclosed in U.S.
36
CA 02381888 2002-02-12
WO 01/16273 PCT/US00/23315
Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23,
line 58 through
Column 29, line 23.
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.
Anionic Surfactants - Anionic surfactants useful in the present invention are
preferably
selected from the group consisting of, linear alkylbenzene sulfonate, alpha
olefin sulfonate,
paraffin sulfonates, alkyl ester sulfonates, alkyl sulfates, alkyl alkoxy
sulfate, alkyl sulfonates,
alkyl alkoxy carboxylate, alkyl alkoxylated sulfates, sarcosinates,
taurinates, and mixtures thereof.
An effective amount, typically from about 0.5% to about 90%, preferably about
5% to about 60%,
more preferably from about 10 to about 30%, by weight of anionic detersive
surfactant can be
used in the present invention.
Alkyl sulfate surfactants are another type of anionic surfactant of importance
for use herein.
In addition to providing excellent overall cleaning ability when used in
combination with
polyhydroxy fatty acid amides (see below), including good grease/oil cleaning
over a wide range
of temperatures, wash concentrations, and wash times, dissolution of alkyl
sulfates can be
obtained, as well as improved formulability in liquid detergent formulations
are water soluble
salts or acids of the formula ROSO3M wherein R preferably is a C10-C24
hydrocarbyl,
preferably an alkyl or hydroxyalkyl having a C I 0-C20 alkyl component, more
preferably a C 12-
C 1 g alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali (Group
IA) metal cation (e.g.,
sodium, potassium, lithium), substituted or unsubstituted ammonium cations
such as methyl-,
dimethyl-, and trimethyl ammonium and quaternary ammonium cations, e.g.,
tetramethyl-
ammonium and dimethyl piperdinium, and cations derived from alkanolamines such
as
ethanolamine, diethanolamine, triethanolamine, and mixtures thereof, and the
like. Typically,
alkyl chains of C12-16 are preferred for lower wash temperatures (e.g., below
about 50 C) and
C16-18 alkyl chains are preferred for higher wash temperatures (e.g., above
about 50 C).
Alkyl alkoxylated sulfate surfactants are another category of useful anionic
surfactant.
These surfactants are water soluble salts or acids typically of the formula
RO(A)mSO3M wherein
R is an unsubstituted C I 0-C24 alkyl or hydroxyalkyl group having a C I O-C24
alkyl component,
preferably a C 12-C20 alkyl or hydroxyalkyl, more preferably C I2-C 18 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, etc.), ammonium or
substituted-
ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated
sulfates are
37
CA 02381888 2004-09-30
contemplated herein. Specific examples of substituted ammonium cations include
methyl-,
dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as
tetramethyl-
ammonium, dimethyl piperidinium and cations derived from alkanolamines, e.g.
monoethanolamine, diethanolamine and triethanolamine, and mixtures thereof.
Exemplary
surfactants are C12-C18 alkyl polyethoxylate (1.0) sulfate, C12-C18 alkyl
polyethoxylate (2.25)
sulfate, C,Z-C18 alkyl polyethoxylate (3.0) sulfate, and C,Z-C,$ alkyl
polyethoxylate (4.0)
sulfate wherein M is conveniently selected from sodium and potassium.
Surfactants for use
herein can be made from natural or synthetic alcohol feedstocks. Chain lengths
represent
average hydrocarbon distributions, including branching.
Additionally and preferably, the surfactant may be a midchain branched alkyl
sulfate, midchain branched alkyl alkoxylate, or midchain branched alkyl
alkoxylate sulfate.
These surfactants are further described in WO 99/19434; WO 99/18929; WO
99/19435;
WO 99/18928; WO 99/19448; and WO 99/19449. Other suitable mid-chain branched
surfactants can be found in WO 97/39087; WO 97/39088; WO 97/39091; WO
98/23712;
WO 97/38972; WO 97/39089; and WO 97/39090. Mixtures of these branched
surfactants
with conventional linear surfactants are also suitable for use in the present
compositions.
Another preferred anionic surfactant are the so-called modified alkyl benzene
sulfonate surfactants, or MLAS. Some suitable MLAS surfactants, methods of
making them
and exemplary compositions are further described in WO 99/05243; WO 99/05242;
WO 99/05244; WO 99/05082; WO 99/05084; WO 99/05241; WO 99/07656; WO 00/23549
and WO 00/23548.
Examples of suitable anionic surfactants are given in "Surface Active Agents
and
Detergents" (Vol. I and II by Schwartz, Perry and Berch).
Nonionic Detergent Surfactants - Suitable nonionic detergent surfactants are
generally disclosed in U.S. Patent 3,929,678, Laughlin et al., issued December
30, 1975, at
column 13, line 14 through column 16, line 6. Exemplary, non-limiting classes
of useful
nonionic surfactants include: amine oxides, alkyl ethoxylate, alkanoyl glucose
amide, alkyl
betaines, sulfobetaine and mixtures thereof.
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CA 02381888 2002-02-12
WO 01/16273 PCT/US00/23315
Amine oxides are semi-polar nonionic surfactants and include water-soluble
amine oxides
containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2
moieties selected
from the group consisting of alkyl groups and hydroxyalkyl groups containing
from about 1 to
about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl
moiety of from about
10 to about 18 carbon atoms and 2 moieties selected from the group consisting
of alkyl groups
and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and
water-soluble
sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon
atoms and a moiety
selected from the group consisting of alkyl and hydroxyalkyl moieties of from
about 1 to about 3
carbon atoms.
Semi-polar nonionic detergent surfactants include the amine oxide surfactants
having the
formula
0
R3~OR4)xN~S)2
wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures
thereof containing from
about 8 to about 22 carbon atoms; R4 is an alkylene or hydroxyalkylene group
containing from
about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3;
and each R5 is an
alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or
a polyethylene
oxide group containing from about 1 to about 3 ethylene oxide groups. The R5
groups can be
attached to each other, e.g., through an oxygen or nitrogen atom, to form a
ring structure.
These amine oxide surfactants in particular include CIO-C18 alkyl dimethyl
amine oxides
and C8-C12 alkoxy ethyl dihydroxy ethyl amine oxides. Preferably the amine
oxide is present in
the composition in an effective amount, more preferably from about 0.1% to
about 20%, even
more preferably about 0.1% to about 15%, even more preferably still from about
0.5% to about
10%,by weight.
The polyethylene, polypropylene, and polybutylene oxide condensates of alkyl
phenols. In
general, the polyethylene oxide condensates are preferred. These compounds
include the
condensation products of alkyl phenols having an alkyl group containing from
about 6 to about 12
carbon atoms in either a straight chain or branched chain configuration with
the alkylene oxide.
In a preferred embodiment, the ethylene oxide is present in an amount equal to
from about 5 to
about 25 moles of ethylene oxide per mole of alkyl phenol. Commercially
available nonionic
surfactants of this type include Igepal CO-630, marketed by the GAF
Corporation; and Triton
X-45, X-114, X-100, and X-102, all marketed by the Rohm & Haas Company. These
compounds
are commonly referred to as alkyl phenol alkoxylates, (e.g., alkyl phenol
ethoxylates).
The condensation products of aliphatic alcohols with from about 1 to about 25
moles of
ethylene oxide. The alkyl chain of the aliphatic alcohol can either be
straight or branched,
39
CA 02381888 2002-02-12
WO 01/16273 PCT/US00/23315
n
primary or secondary, and generally contains from about 8 to about 22 carbon
atoms. Particularly
preferred are the condensation products of alcohols having an alkyl group
containing from about
to about 20 carbon atoms with from about 2 to about 18 moles of ethylene oxide
per mole of
alcohol. Examples of commercially available nonionic surfactants of this type
include Tergitol
5 15-S-9 (the condensation product of C11-C15 linear secondary alcohol with 9
moles ethylene
oxide), Tergitol 24-L-6 NMW (the condensation product of C 12-C 14 primary
alcohol with 6
moles ethylene oxide with a narrow molecular weight distribution), both
marketed by Union
Carbide Corporation; Neodol 45-9 (the condensation product of C14-C15 linear
alcohol with 9
moles of ethylene oxide), Neodol 23-6.5 (the condensation product of C 12-C
13 linear alcohol
10 with 6.5 moles of ethylene oxide), Neodol 45-7 (the condensation product
of C14-C15 linear
alcohol with 7 moles of ethylene oxide), Neodol 45-4 (the condensation
product of C14-C15
linear alcohol with 4 moles of ethylene oxide), marketed by Shell Chemical
Company, and
Kyro EOB (the condensation product of C13-C15 alcohol with 9 moles ethylene
oxide),
marketed by The Procter & Gamble Company. Other commercially available
nonionic
surfactants include Dobanol 91-8 marketed by Shell Chemical Co. and Genapol
UD-080
marketed by Hoechst. This category of nonionic surfactant is referred to
generally as "alkyl
ethoxylates."
The preferred alkylpolyglycosides have the formula
R20(CnH2n0)t(glycosyl)x
wherein R2 is selected from the group consisting of alkyl, alkyl-phenyl,
hydroxyalkyl,
hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain
from about 10 to
about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3,
preferably 2; t is from 0
to about 10, preferably 0; and x is from about 1.3 to about 10, preferably
from about 1.3 to about
3, most preferably from about 1.3 to about 2.7. The glycosyl is preferably
derived from glucose.
To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed
first and then
reacted with glucose, or a source of glucose, to form the glucoside
(attachment at the 1-position).
The additional glycosyl units can then be attached between their 1-position
and the preceding
glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominantly the 2-
position.
Fatty acid amide surfactants having the formula:
O
11
R6CN(R)2
wherein R6 is an alkyl group containing from about 7 to about 21 (preferably
from about 9 to
about 17) carbon atoms and each R7 is selected from the group consisting of
hydrogen, C1-C4
alkyl, C1-C4 hydroxyalkyl, and -(C2H4O)xH where x varies from about 1 to about
3.
CA 02381888 2002-02-12
WO 01/16273 PCT/US00/23315
Preferred amides are C8-C20 ammonia amides, monoethanolamides,
diethanolamides, and
isopropanolamides.
Preferably the nonionic surfactant, when present in the composition, is
present in an
effective amount, more preferably from about 0.1% to about 20%, even more
preferably about
0.1% to about 15%, even more preferably still from about 0.5% to about 10%,by
weight.
Polyhydroxy Fatty Acid Amide Surfactant - The detergent compositions hereof
may also
contain an effective amount of polyhydroxy fatty acid amide surfactant. By
"effective amount" is
meant that the formulator of the composition can select an amount of
polyhydroxy fatty acid
amide to be incorporated into the compositions that will improve the cleaning
performance of the
detergent composition. In general, for conventional levels, the incorporation
of about 1%, by
weight, polyhydroxy fatty acid amide will enhance cleaning performance.
The detergent compositions herein will typically comprise about 1% weight
basis,
polyhydroxy fatty acid amide surfactant, preferably from about 3% to about
30%, of the
polyhydroxy fatty acid amide. The polyhydroxy fatty acid amide surfactant
component comprises
compounds of the structural formula:
0
R2CNZ
R1
wherein: R1 is H, Cl-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a
mixture thereof,
preferably C I-C4 alkyl, more preferably C 1 or C2 alkyl, most preferably C I
alkyl (i.e., methyl);
and R2 is a C5-C31 hydrocarbyl, preferably straight chain C7-C19 alkyl or
alkenyl, more
preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight
chain C11-C15 alkyl
or alkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a
linear hydrocarbyl
chain with at least 3 hydroxyls directly connected to the chain, or an
alkoxylated derivative
(preferably ethoxylated or propoxylated) thereof. Z preferably will be derived
from a reducing
sugar in a reductive amination reaction; more preferably Z will be a glycityl.
Suitable reducing
sugars include glucose, fructose, maltose, lactose, galactose, mannose, and
xylose. As raw
materials, high dextrose corn syrup, high fructose corn syrup, and high
maltose corn syrup can be
utilized as well as the individual sugars listed above. These corn syrups may
yield a mix of sugar
components for Z. It should be understood that it is by no means intended to
exclude other
suitable raw materials. Z preferably will be selected from the group
consisting of -CH2-
(CHOH)ri CH2OH, -CH(CH2OH)-(CHOH)n-1-CH2OH, -CH2-(CHOH)2(CHOR')(CHOH)-
CH2OH, and alkoxylated derivatives thereof, where n is an integer from 3 to 5,
inclusive, and R'
is H or a cyclic or aliphatic monosaccharide. Most preferred are glycityls
wherein n is 4,
particularly -CH2-(CHOH)4-CH2OH.
41
CA 02381888 2004-09-30
R' can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-
hydroxy
ethyl, or N-2-hydroxy propyl.
R2-CO-N< can be, for example, cocamide, stearamide, oleamide, lauramide,
myristamide,
capricamide, palmitamide, tallowamide, etc.
Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl,
1-
deoxygalactityl, 1-deoxymannityl, I -deoxymaltotriotityl, etc.
Methods for making polyhydroxy fatty acid amides are known in the art. In
general, they
can be made by reacting an alkyl amine with a reducing sugar in a reductive
amination reaction to
form a corresponding N-alkyl polyhydroxyamine, and then reacting the N-alkyl
polyhydroxyamine with a fatty aliphatic ester or triglyceride in a
condensation/amidation step to
form the N-alkyl, N-polyhydroxy fatty acid amide product. Processes for making
compositions
containing polyhydroxy fatty acid amides are disclosed, for example, in G.B.
Patent Specification
809,060, published February 18, 1959, by Thomas Hedley & Co., Ltd., U.S.
Patent 2,965,576,
issued December 20, 1960 to E. R. Wilson, and U.S. Patent 2,703,798, Anthony
M. Schwartz,
issued March 8, 1955, and U.S. Patent 1,985,424, issued December 25, 1934 to
Piggott.
Diamines - The preferred liquid detergent compositions, such as light duty
liquid, LDL
compositions, useful in the methods of the present invention may further
comprise one or more
diamines, preferably an amount of diamine such that the ratio of anionic
surfactant present to the
diamine is from about 40 : 1 to about 2: 1. Said diamines provide for
increased removal of grease
and greasy food material while maintaining suitable levels of suds.
The diamines suitable for use in the compositions of the present invention
have the
formula:
R20 R20
~N-X-N ~
R20~ ~R20
wherein each R20 is independently selected from the group consisting of
hydrogen, C1-C4 linear
or branched alkyl, alkyleneoxy having the formula:
-(R21 p)YR22
wherein R21 is C2-C4 linear or branched alkylene, and mixtures thereof; R22 is
hydrogen, CI-C4
alkyl, and mixtures thereof; y is from 1 to about 10; X is a unit selected
from:
i) C3-C10 linear alkylene, C3-C10 branched alkylene, C3-C10 cyclic alkylene,
C3-
C 10 branched cyclic alkylene, an alkyleneoxyalkylene having the formula:
-(R21 p)yR21-
42
CA 02381888 2004-09-30
wherein R21 and y are the same as defined herein above;
ii) C3-C10 linear, C3-Clp branched linear, C3-CIO cyclic, C3-C10 branched
cyclic
alkylene, C6-C10 arylene, wherein said unit comprises one or more electron
donating or electron withdrawing moieties which provide said diamine with a
pKa greater than about 8; and
iii) mixtures of (i) and (ii)
provided said diamine has a pKa of at least about 8.
The preferred diamines of the present invention have a pKI and pK2 which are
each in
the range of from about 8 to about 11.5, preferably in the range of from about
8.4 to about 11,
more preferably from about 8.6 to about 10.75. For the purposes of the present
invention the term
"pKa" stands equally well for the terms "pKI" and "pK2" either separately or
collectively. The
term pKa as used herein throughout the present specification in the same
manner as used by those
of ordinary skill in the art. pKa values are readily obtained from standard
literature sources, for
example, "Critical Stability Constants: Volume 2, Amines" by Smith and Martel,
Plenum Press,
N.Y. and London, (1975).
As an applied definition herein, the pKa values of the diamines are specified
as being
measured in an aqueous solution at 250 C having an ionic strength of from
about 0.1 to about 0.5
M. As used herein, the pKa is an equilibrium constant dependent upon
temperature and ionic
strength, therefore, value reported by literature references, not measured in
the above described
manner, may not be within full agreement with the values and ranges which
comprise the present
invention. To eliminate ambiguity, the relevant conditions and/or references
used for pKa's of
this invention are as defined herein or in "Critical Stability Constants:
Volume 2, Amines". One
typical method of measurement is the potentiometric titration of the acid with
sodium hydroxide
and determination of the pKa by suitable methods as described and referenced
in "The Chemist's
Ready Reference Handbook" by Shugar and Dean, McGraw Hill, NY, 1990.
Preferred diamines for performance and supply considerations are 1,3-
bis(methylamino)cyclohexane, 1,3-diaminopropane (pKI=10.5; pK2=8.8), 1,6-
diaminohexane
(pK1=11; pK2=10), 1,3-diaminopentane (Dytek EP) (pKI=10.5; pK2=8.9), 2-methyl
1,5-
I'M
diaminopentane (Dytek A) (pK1=11.2; pK2=10.0). Other preferred materials are
the
primary/primary diamines having alkylene spacers ranging from C4-C8. In
general, primary
diamines are preferred over secondary and tertiary diamines.
The following are non-limiting examples of diamines suitable for use in the
present
invention.
1-N,N-dimethylamino-3-aminopropane having the formula:
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CA 02381888 2002-02-12
WO 01/16273 PCT/US00/23315
N--~-----~NHZ
1,6-diaminohexane having the formula:
H2N
NH2
1,3-diaminopropane having the formula:
H2N ,.~.NH2
2-methyl-1,5-diaminopentane having the formula:
H2N NH2
1,3-diaminopentane, available under the tradename Dytek EP, having the
formula:
H2N
NH2
1,3-diaminobutane having the formula:
H2N NH2 T'*'~ Jeffamine EDR 148, a diamine having an alkyleneoxy backbone,
having the formula:
H2N _--~O-,_~O_--~NH2
3-methyl-3-aminoethyl-5-dimethyl-l-aminocyclohexane (isophorone diamine)
having the
formula:
44
CA 02381888 2002-02-12
WO 01/16273 PCT/US00/23315
NH2
NH2
, and
1,3-bis(methylamino)cyclohexane having the formula:
CH2NH2
CHZNH2
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 50%, 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
aluniinosilicates. However, non-phosphate builders are required in some
locales. Importantly,
CA 02381888 2004-09-30
the compositions herein function surprisingly well even in the presence of the
so-called "weak"
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
SiO2:Na2O 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-Na2SiO5 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 NaMSixO2x+1-yH2O wherein M is sodium or hydro gen, 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
TM TM TM
layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the
alpha, beta and
gamma forms. As noted above, the delta-Na2SiO5 (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 Noverriber
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(zalO2)y]=xH2O
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-oceurring
aluminosilicates or synthetically derived. A method for producing
aluminosilicate ion exchange
materials is disclosed in U.S. 3,985,669, Krummel et a], 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:
Na12[(A102)12(SiO2)12]-xH2O
46
CA 02381888 2002-02-12
WO 01/16273 PCT/US00/23315
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 maleic 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 C5-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,
47
CA 02381888 2004-09-30
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 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., C12-C18 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-l-hydroxy-1,l-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.
Chelating 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 fonnation
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 [S,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.
48
CA 02381888 2004-09-30
Dye Transfer Inhibiting Agents - 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 European patent
application 719856.
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.
Dispersants - 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.
49
CA 02381888 2004-09-30
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 maleic 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 30ml 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 C16-C18 dimethyl amine oxide, C12-Cl8 alkyl
ethoxysulfates with an
average degree of ethoxylation of from 1-5, particularly C 12-C 15 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
trademarks
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.
CA 02381888 2004-09-30
Enzymes - The bleaching compositions can comprise in addition to an amylase
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, "manames" 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 trademark "SL" or the microencapsulated enzymes marketed by Novo Nordisk
under the
trademark "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,
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, B-glucanases, arabinosidases,
hyaluronidase, chondroitinase,
laccase, known amylases, mannanases, xyloglucanases and 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 optional
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 MAXAPEMO (protein engineered
Maxacal) from Gist-Brocades. Proteolytic enzymes also encompass modified
bacterial serine
proteases, such as those described in European Patent Application 251,446,
51
CA 02381888 2004-09-30
(particularly pages 17, 24 and 98), and which is called herein "Protease B",
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 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 piotease 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
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CA 02381888 2002-02-12
WO 01/16273 PCT/US00/23315
amino acid residue at one or more amino acid 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
Published Application
Nos. WO 99/20727, WO 99/20726, and WO 99/20723 all owned by The Procter &
Gamble
Company.
More preferably the protease variant includes a substitution set selected from
the group
consisting of:
12/76/ 103 / 104/ 13 0/222/245/261;
62/ 103/ 104/ 159/232/23 6/245/248/252;
62/ 103/ 104/ 159/213/232/23 6/245/248/252;
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/ 185/210/232/23 6/245/248/252;
68/103/104/159/210/232/236/245/248/252;
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CA 02381888 2002-02-12
WO 01/16273 PCT/US00/23315
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/ 15 9/23 0/23 6/245;
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;
103/104/13 1/15 9/232/236/245/248/252;
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/ 13 0T/222 S/245 R/261 D;
62D/ 103A/ 104I/ 15 9D/232 V/23 6H/245R/248D/252K;
62D/103A/1041/159D/213R/232V/236H/245R/248D/252K;
68A/103A/104I/159D/209W/232V/236H/245R;
68A/76D/103A/1041/ 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/1041/159D/230V/232V/236H/245R;
68A/103A/104I/159D/232V/236H/245R/257V;
68A/ 103A/ 104I/ 159D/213G/232 V/236H/245 R/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/1041/159D/210L/232V/236H/245R/248D/252K;
6 8 A/ 103 A/ 1041/ 15 9 D/213 G/23 2 V/2 3 6 H/24 5 R;
98L/103A/104I/ 159D/232V/236H/245R/248D/252K;
98L/ 102A/ 103A/ 104I/ 159D/212G/232 V/236H/245R/248D/252K;
101 G/103A/104I/159D/232V/236H/245R/248D/252K;
102A/103A/104I/159D/232V/236H/245R/248D/252K;
54
CA 02381888 2004-09-30
I 03A/ 104U 159D/230V/236H/245R;
103A/ 104I/ 159D/232 V/236H/245R/248D/252K;
1 03A/104U I 59D/217E/232V/236H/245R/248D/252K;
103A/1041/130G/ 159D/232 V/236H/245R/248D/252K;
103A/1041/13I V/159D/232V/236H/245R/248D/252K;
103A/104I/159D/213R/232V/236H/245R/248D/252K; and
1 03A/ 1041/ 159D/23 2 V/23 6H/245 R.
Most preferably the protease variant includes the substitution set
101/103/104/159/232/
236/245/248/252, preferably 101G/103A/1041/159D/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 U.S. 5,520,838. CarezymeTM and
CelluzymeTM
(Novo Nordisk A/S) are especially useful. See also WO 91/17243.
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,
WO 93/09224 and WO 97/30143. Also suitable is the laccase enzyme.
Preferred enhancers are substituted phenthiazine and phenoxasine 10-
Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4-carboxylic acid
(EPC), 10-
CA 02381888 2004-09-30
phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO
94/12621) and
substituted syringates (C3-C5 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 mark 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
MI 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 ((x and/or (3) 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 WO94/18314, 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.
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WO 01/16273 PCT/US00/23315
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 : P-mannosidase, EC 3.2.1.78 : Endo-1,4-(3-mannosidase,
referred therein
after as "mannanase" and EC 3.2.1.100 : 1,4-0-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 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.
57
CA 02381888 2004-09-30
Mannanases have been identified in several Bacillus organisms. For example,
Talbot et
al., Appl. Environ. Microbiol., Vol.56, No. 11, pp. 3505-3510 (1990) describes
a beta-mannanase
derived from Bacillus stearothermophilus in dimer 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 pl 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 pl of 5.3-5.4. JP-63056289 describes
the production of an
alkaline, thermostable beta-mannanase which hydrolyses beta-l,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 W097/1 1 1 64.
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. 1633 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.
1633 as described in
EP 1086211.
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
U.S. patent No. 6566114. More specifically, this mannanase is:
i) a polypeptide produced by Bacillus agaradhaerens, NCIMB 40482; or
58
CA 02381888 2004-09-30
ii) a polypeptide comprising an amino acid sequence as shown in positions 32-
343
of SEQ ID NO:2 as shown in U.S. patent No. 6566114; 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 No. 6566114;
(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
No. 6566114;
(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
I.nternational Recognition of
the Deposit of Microorganisms for the Purposes of Patent Procedure at the
Deutsche Sammlung
von Mikroorganismen und Zelikulturen GmbH, Mascheroder Weg lb, D-38124
Braunschweig,
Federal Republic of Gennany, 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 U.S. patent No. 6,060,299. 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. 6,060,299 or an analogue of
said
sequence; and/or
ii) a polypeptide comprising an amino acid sequence as shown SEQ ID NO:6 shown
in the U.S. patent No. 6,060,299; 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,
59
CA 02381888 2004-09-30
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 of:
(a) polynucleotide molecules encoding a polypeptide having mannanase
activity and comprising a sequence of nucleotides as shown in SEQ ID NO:5 as
shown in the U.S. patent No. 6,060,299;
(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 No. 6,060,299;
(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 EP 1086211. More
specifically,
this mannanase is:
i) a polypeptide produced by Bacillus sp. 1633;
ii) a polypeptide comprising an amino acid sequence as shown in positions
33-340 of SEQ ID NO:2 as shown in EP 1086211;
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
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: I from nucleotide
317 to nucleotide 1243 in EP 1086211;
(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 in EP 1086211;
(d) molecules complementary to (a), (b) or (c); and
CA 02381888 2004-09-30
(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
lnternational Recognition of the Deposit of Microorganisms for the Purposes of
Patent Procedure
at the Deutsche Sammlung von Mikroorganismen und Zelikulturen 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 EP 1086211. 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 NO:2as shown in EP 1086211;
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
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 EP 1086211;
(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 EP 1086211;
(d) molecules complementary to (a), (b) or (c); and
(e) degenerate nucleotide sequences of (a), (b), (c) or (d).
The plasmid pBXM1 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
Intemational Recognition of the Deposit of Microorganisms for the Purposes of
Patent Procedure
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WO 01/16273 PCT/US00/23315
at the Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH,
Mascheroder Weg lb,
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-p-D-glycosidic linkages present in any cellulosic material, such as
cellulose, cellulose
derivatives, lichenin, P-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 unit of endoglucanase activity (e.g. CMCU, AVIU, XGU or
BGU) is
defined as the production of 1 mol reducing sugar/min from a glucan
substrate, the glucan
substrate being, e.g., CMC (CMCU), acid swollen Avicell (AVIU), xyloglucan
(XGU) or cereal 0
-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: 5)
(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)
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WO 01/16273 PCT/US00/23315
(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: 15)
(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
ACCGGCTCCC AGTGCACTGG AGTCGACTCC TACAGCGGCG ACACCATCGC
TTGTCACACC
AGCAGGTCCT GGTCGGAGTA GCAGCAGCGT CAAGAGCTAT GCCAACG (SEQ ID
NO: 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 NO: 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
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CA 02381888 2002-02-12
WO 01/16273 PCT/US00/23315
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 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 5xSSC and prehybridizing
for 1 h at -40 C in a
solution of 5xSSC, 5xDenhardt'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 0-glucan and/or exhibits at the most 25% such as at the
most 10% or about
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WO 01/16273 PCT/US00/23315
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 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 0.00 1% 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
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WO 01/16273 PCT/US00/23315
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 Ingredients - 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,
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 of Cleaning - In addition to the methods for cleaning fabrics, dishes
and other
hard surfaces, and body parts by personal cleansing, described herein, the
invention herein also
encompasses a laundering pretreatment process for fabrics which have been
soiled or stained
comprising directly contacting said stains and/or soils with a highly
concentrated form of the
bleaching composition set forth above prior to washing such fabrics using
conventional aqueous
washing solutions. Preferably, the bleaching composition remains in contact
with the soil/stain
for a period of from about 30 seconds to 24 hours prior to washing the
pretreated soiled/stained
substrate in conventional manner. More preferably, pretreatment times will
range from about I to
180 minutes.
The following examples are meant to exemplify compositions of the present
invention,
but are not necessarily meant to limit or otherwise define the scope of the
invention.
In the following examples some abbreviations known to those of ordinary skill
in the art
are used, consistent with the disclosure set forth herein.
SYNTHESIS EXAMPLES
EXAMPLE I
Preparation of 1-(4,4-dimethyl-3,4-dihydroisoquinoline) decane-2-sulfate (7):
Step 1: Preparation of dimethylbenzylcyanide (2):
A 1 L three-necked round-bottom flask equipped with two addition funnels, a
side arm adapter,
ammonium hydroxide trap, reflux condenser, mechanical stirrer, thermometer and
adapter, and a
fritted gas diffuser is charged with dimethyl sulfoxide (200 mL) and chilled
in an ice bath.
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Methyl chloride gas is diffused into the dimethyl sulfoxide with stirring.
After 15 min, sodium
hydroxide (50% aqueous solution, 32.9 g) and benzylcyanide (1, 11.7 g, 1
equiv) are
simultaneously added as separate solutions via the two addition funnels at a
rate that does not
allow the temperature to go above 35 C. After complete addition of sodium
hydroxide and
benzylcyanide, the reaction is stirred at room temperature as the methyl
chloride continues to be
diffused into the solution. After 1 h, methyl chloride flow is stopped (38.8 g
total, 3.8 equiv) and
the reaction is extracted with toluene (3 x 100 mL) and ether (100 mL). The
combined organic
layers are washed with saturated sodium bicarbonate solution (2 x 100 mL),
brine (100 mL), dried
over sodium sulfate, and concentrated to give 2. The preparation is
represented by the following
reaction:
CN CN
2
Step 2: Preparation of 1-amino-2,2,dimethyl-2-phenylethane (3):
A 250 mL three-necked round-bottom flask equipped with pressure equalizing
drip funnel, argon
gas inlet and reflux condensers is charged with anhydrous diethyl ether (100
mL) and is cooled in
an ice bath. Lithium aluminum hydride powder (3.68 g, 2 equiv) is added slowly
to the reaction
mixture. Upon complete addition, dimethylbenzylcyanide (2, 7.00 g, 1 equiv) is
added dropwise
over fifteen min. The reaction is allowed to slowly warm to room temperature
overnight with
stirring. Water (7.0 mL) is added over 15 min followed by sodium hydroxide
(15% aqueous
solution, 7.0 mL). The mixture is stirred for approximately 1 h, and
additional water (21.0 mL) is
added. The reaction is diluted with diethyl ether (100 mL) and vacuum
filtered. The filter cake is
washed with diethyl ether (8 x 50 mL) and the combined organic layers are
dried over magnesium
sulfate, and concentrated under vacuum to give 3. The preparation is
represented by the
following reaction:
I CN
NH2
2 3
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Step 3: Preparation of 4,4-dimethyl-3,4-dihydroisoquinoline (4):
A 50 mL round-bottom flask equipped with magnetic stir bar and distillation
apparatus charged
with 1-amino-2,2-dimethyl-2-phenylethane (4.15 g, 1 equiv) and formic acid
(6.65 g, 3.5 equiv) is
stirred at 100 C for 1 h, at which time another portion of formic acid is
added (2 mL, 0.9 equiv).
After stirring for an additional 1 h, the mixture is heated to 200 C and
vacuum is applied. When
the unreacted formic acid and water are removed, the remaining oil, N-formyl-
(3,(3-dimethyl-(3-
phenethylamine, is cooled to room temperature.
A 100 mL round-bottom flask equipped with side arm adapter, addition funnel
and mechanical
stirrer is charged with polysulfuric acid (29.7g) and phosphorus pentoxide
(4.74 g). This mixture
is stirred and heated to 180 C for about 1 h, and cooled to about 150 C. The
N-formyl-(3,(3-
dimethyl-p-phenethylamine (5.31 g, 1 equiv) is melted and added as a stream to
the acid mixture.
The reaction is heated to 180 C and allowed to stir overnight. The reaction
mixture is cooled to
about 60 C and slowly mixed with ice water (250 mL). The diluted reaction
mixture is washed
with diethyl ether (2 x 100 mL). The aqueous solution is stirred and kept cool
in an acetone/dry
ice bath as a saturated aqueous solution of potassium hydroxide is added. When
the pH of the
mixture reaches 9, the mixture is extracted with diethyl ether (4 x 100 mL).
The organic layers
are washed with pH 10 buffer (200 mL), dried over magnesium sulfate, and
condensed under
vacuum to give 4. The preparation is represented by the following reaction:
QH2N
3 4
Step 4: Preparation of 1,2-decanediol cyclic sulfate (6):
A 500 mL three-necked round-bottom flask equipped with mechanical stirrer,
pressure equalizing
addition funnel, and reflux condenser is charged with 1,2-decanediol (5, 8.72
g, 50.0 mmol) and
50 mL of carbon tetrachloride. Upon dissolving of the 1,2-decanediol, thionyl
chloride (5.5 mL,
75 mmol) is added dropwise at room temperature, and the reaction is heated to
60 C. After 2 h,
the reaction is cooled via ice bath. Water (50 mL) and acetonitrile (75 mL)
are added.
Ruthenium chloride hydrate (0.131 g, 0.50 mmol) and sodium periodate (21.4 g,
100 mmol) are
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CA 02381888 2004-09-30
added and the reaction mixture is stirred at room temperature for I h. The
mixture is extracted
with diethyl ether (4 x 175 mL), the organic layers are washed with water (5 x
100 mL), saturated
sodium bicarbonate (3 x 100 mL), brine (2 x 100 mL), filtered through
Celite/silica gel, and dried
over magnesium sulfate. The clear liquid is concentrated to give 6, a clear
oil. The preparation is
represented by the following reaction:
0
O~II
OH S-p
HO -=~ O
5 6
Step 5: Preparation of 1-(4,4-dimethyl-3,4-dihydroisoquinoline) decane-2-
sulfate (7):
A 100 mL round-bottom flask equipped with magnetic stir bar is charged with
4,4-dimethyl-3,4-
dihydroisoquinoline (2.45 g, 15.4 mmol) and acetonitrile (15.2 mL). To this
solution is added in
one portion 1,2-decanediol cyclic sulfate (4, 3.78 g, 16.0 mmol). The reaction
mixture becomes
thick within 5 min and additional acetonitrile (60 mL) is added. The reaction
is stirred overnight.
The precipitate is collected, washed with acetone, and allowed to air dry to
give 7. The
preparation is represented by the following reaction:
SO
I~ -_~ ~I O+
4 7
EXAMPLE II
Preparation of 2,3,3-trimethyl-3,4-dihydroisoquinolinium tetrafluoroborate
(11):
Step 1: Preparation of N-formyl-a,a-dimethyl-(3-phenethylamine (9):
A I L three-necked round-bottom flask equipped with thermometer and adapter,
mechanical
stirrer, reflux condenser, ammonium hydroxide trap, and pressure equalizing
addition funnel is
charged with glacial acetic acid (83.0 mL), and is cooled in an ice bath.
Sodium cyanide(16.3 g, I
equiv) and a solution of concentrated sulfuric acid in acetic acid (160 g /
83.0 mL) are added at a
69
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rate slow enough to maintain a temperature of less than 20 C (CAUTION: Great
care must be
exercised to avoid contact with poisonous gas). 2-Methyl-l-phenyl-2-propanol
(8, 50.0 g, I
equiv) is slowly added to the reaction mixture, which is stirred overnight at
room temperature.
The solution is aerated with argon for 3 h, and poured into ice water (300
mL). A layer of oil
forms, and is separated and saved. The aqueous layer is neutralized to pH 7
with sodium
carbonate and extracted with diethyl ether (3 x 200 mL) The organic layers are
combined with
the previously separated oil, dried over magnesium sulfate, and concentrated
to give 9. The
preparation is represented by the following reaction:
--s
I OH N H
W
Y
8 9
O
Step 2: Pi-eparation of 2,3,3-trimethyl-3,4-dihydroisoquinolinium
tetrafluoroborate(10):
A I L three-necked round-bottom flask equipped with side arm adapter, addition
funnel and
mechanical stirrer is charged with polysulfuric acid (378 g) and phosphorus
pentoxide (60.4 g).
This mixture is stirred and heated to 180 C for about I h, and cooled to
about 150 C. The 1V-
formyl-a,a-dimethyl-p-phenethylamine is melted and added as a stream to the
acid mixture. The
reaction is heated to 180 C and allowed to stir ovemight. The reaction
mixture is cooled to about
100 C and slowly mixed with ice water (2 L). The diluted reaction mixture is
then filtered
through Celite . The filtrate is washed with diethyl ether (2 x 100 mL). The
aqueous solution is
stirred and kept cool in an acetone/dry ice bath as a saturated aqueous
solution of potassium
hydroxide is added When the pH of the mixture reaches 9, the mixture is
extracted with diethyl
ether (4 x 100 mL). The organic layers are washed with pH 10 buffer (200 mL),
dried over
magnesium sulfate, and condensed under vacuum to give 4. The preparation is
represented by the
following reaction:
CCWN H N
9 0 10
Step 3: Preparation of 3,3-dimethyl-3,4-dihydroisoquinoline tetrafluoroborate
(11):
CA 02381888 2004-09-30
A round-bottom flask equipped with magnetic stir bar at 0 C is charged with
trimethyloxonium
tetrafluoroborate (Meerwein salt, 1.13 g, 7.7 mmol) and methylene chloride (15
mL). To the
stirred solution is added a solution of 3,3-dimethyl-3,4-dihydroisoquine (1.11
g , 7.0 mmol) in
methylene chloride (40 mL) over a period of 5 min. The heterogeneous solution
is allowed to
warm to room temperature, and stirred overnight. The solution is concentrated,
and to the
resulting oil is added ethanol, resulting in crystallization to give 11. The
preparation is
represented by the following reaction:
I -> I o
N N\ BF
a
10 11
EXAMPLE III
Preparation of 1-(1,1-diphenyl-3-duryl pseudoisoindoline) hexane-2-sulfate
(15):
Step 1: Preparation of 1,1-diphenyl-3-duryl pseudoisoindole (12) is as
described in the art, as in
Fuson, R. C. et al. J. Org. Chem. 1951, 16, 648.
Step 2: Preparation of 1,2-hexanediol cyclic sulfate 14):
A 500 mL three-necked round-bottom flask equipped with mechanical stirrer,
pressure equalizing
addition funnel, and reflux condenser is charged with 1,2-hexanediol (13, 5.91
g, 50.0 mmol) and
50 mL of carbon tetrachloride. Upon dissolving of the 1,2-hexanediol, thionyl
chloride (5.5 mL,
75 mmol) is added dropwise at room temperature, and the reaction is heated to
60 C. After 2 h,
the reaction is cooled via ice bath. Water (50 mL) and acetonitrile (75 mL)
are added.
Ruthenium chloride hydrate (0.131 g, 0.50 mmol) and sodium periodate (21.4 g,
100 mmol) are
added and the reaction mixture is stirred at room temperature for 1 h. The
mixture is extracted
with diethyl ether (4 x 175 mL), the organic layers are washed with water (5 x
100 mL), saturated
sodium bicarbonate (3 x 100 mL), brine (2 x 100 mL), filtered through
Celitelsilica gel, and dried
over magnesium sulfate. The clear liquid is concentrated to give 7, a clear
oil. The preparation is
represented by the following reaction:
71
CA 02381888 2004-09-30
0
OH 0=S-O
HO
13 14
Step 3: Preparation of 1-(1,1-diphenyl-3-duryl pseudoisoindoline) hexane-2-
sulfate (15):
To a 200 mL round-bottom flask equipped with magnetic'stir bar is added l,1-
diphenyl-3-duryl
pseudoisoindole(12, 5.55 g, 20.0 mmol) and acetonitrile (30 mL). To this
solution is added in one
portion I,2-hexanediol cyclic sulfate (]4, 2.60 g, 22.0 mmol). The reaction
mixture becomes
thick within 5 min and additional acetonitrile (60 mL) is added. The reaction
is stirred ovecnight.
The precipitate is collected, washed with acetone, and allowed to air dry to
give 15. The
preparation is represented by the following reaction:
Ph Ph Ph Ph OSO3
N bo NG)
12 15 1 /
FORMULATION EXAMPLES
EXAMPLE IV
Bleaching detergent compositions having the form of granular laundry
detergents are
exemplified by the following formulations.
A B C D E
Bleach Boosting 0.05 0.01 0.13 0.04 0.07
Compound*
Conventional Activator 0.00 2.00 1.20 0.70 0.00
(NOBS)
Conventional Activator 3.00 0.00 2.00 0.00 0.00
(TAED)
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Conventional Activator 3.00 0.00 0.00 0.00 2.20
(NACA-OBS)
Sodium Percarbonate 5.30 0.00 0.00 4.00 0.00
Sodium Perborate 0.00 5.30 3.60 0.00 4.30
Monohydrate
Linear 12.00 0.00 12.00 0.00 21.00
Alkylbenzenesulfonate
C45AE0.6S 0.00 15.00 0.00 15.00 0.00
C2 Dimethylamine N-Oxide 0.00 2.00 0.00 2.00 0.00
C12 Coco Amidopropyl 1.50 0.00 1.50 0.00 0.00
Betaine
Palm N- Methyl Glucamide 1.70 2.00 1.70 2.00 0.00
C12 Dimethylhydroxyethyl- 1.50 0.00. 1.50 0.00 0.00
ammoniium Chloride
AE23-6.5T 2.50 3.50 2.50 3.50 1.00
C25E3S 4.00 0.00 4.00 0.00 0.00
Sodium Tripolyphosphate 25.00 25.00 15.00 15.00 25.00
Zeolite A 0.00 0.00 0.00 0.00 0.00
Acrylic Acid / Maleic Acid 0.00 0.00 0.00 0.00 1.00
Copolymer
Polyacrylic Acid, partially 3.00 3.00 3.00 3.00 0.00
neutralized
Soil Release Agent 0.00 0.00 0.50 0.40 0.00
Carboxymethylcellulose 0.40 0.40 0.40 0.40 0.40
Sodium Carbonate 2.00 2.00 2.00 0.00 8.00
Sodium Silicate 3.00 3.00 3.00 3.00 6.00
Sodium Bicarbonate 5.00 5.00 5.00 5.00 5.00
Savinase (4T) 1.00 1.00 1.00 1.00 0.60
Termamyl (60T) 0.40 0.40 0.40 0.40 0.40
Lipolase (100T) 0.12 0.12 0.12 0.12 0.12
Carezyme(5T) 0.15 0.15 0.15 0.15 0.15
Diethylenetriaminepenta 1.60 1.60 1.60 1.60 0.40
(methylenephosphonic
Acid)
Brightener 0.20 0.20 0.20 0.05 0.20
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Sulfonated Zinc 0.50 0.00 0.25 0.00 0.00
Phthalocyanine
Photobleach
MgSO4 2.20 2.20 2.20 2.20 0.64
Na2SO4 balance balance balance balance balance
* 1-(4,4-dimethyl-3,4-dihydroisoquinoline) decane-2-sulfate prepared according
to EXAMPLE I.
Any of the above compositions is used to launder fabrics at a concentration of
3500 ppm
in water, 25 C, and a 15:1 water:cloth ratio. The typical pH is about 9.5 but
can be can be
adjusted by altering the proportion of acid to Na- salt form of
alkylbenzenesulfonate.
EXAMPLE V
Bleaching detergent compositions having the form of granular laundry
detergents are
exemplified by the following formulations.
A B c D E
Bleach Boosting 0.26 0.38 0.04 0.03 0.01
Compound*
Conventional Activator 0.00 0.00 0.00 0.50 0.00
(NOBS)
Conventional Activator 1.80 1.00 2.50 3.00 1.00
(TAED)
Conventional Activator 3.00 0.00 0.00 2.50 0.00
(NACA-OBS)
Sodium Percarbonate 5.30 0.00 0.00 0.00 0.00
Sodium Perborate 0.00 9.00 17.60 9.00 9.00
Monohydrate
Linear 21.00 12.00 0.00 12.00 12.00
Alkylbenzenesulfonate
C45AEO.6S 0.00 0.00 15.00 0.00 0.00
C2 Dimethylamine N- 0.00 0.00 2.00 0.00 0.00
Oxide
C12 Coco Amidopropyl 0.00 1.50 0.00 1.50 1.50
Betaine
Palm N- Methyl Glucamide 0.00 1.70 2.00 1.70 1.70
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C12 1.00 1.50 0.00 1.50 1.50
Dimethylhydroxyethylamm
onium Chloride
AE23-6.5T 0.00 2.50 3.50 2.50 2.50
C25E3S 0.00 4.00 0.00 4.00 4.00
Sodium Tripolyphosphate 25.00 15.00 25.00 15.00 15.00
Zeolite A 0.00 0.00 0.00 0.00 0.00
Acrylic Acid / Maleic Acid 0.00 0.00 0.00 0.00 0.00
Copolymer
Polyacrylic Acid, partially 0.00 3.00 3.00 3.00 3.00
neutralized
Soil Release Agent 0.30 0.50 0.00 0.50 0.50
Carboxymethylcellulose 0.00 0.40 0.40 0.40 0.40
Sodium Carbonate 0.00 2.00 2.00 2.00 2.00
Sodium Silicate 6.00 3.00 3.00 3.00 3.00
Sodium Bicarbonate 2.00 5.00 5.00 5.00 5.00
Savinase (4T) 0.60 1.00 1.00 1.00 1.00
Termamyl (60T) 0.40 0.40 0.40 0.40 0.40
Lipolase (100T) 0.12 0.12 0.12 0.12 0.12
Carezyme(5T) 0.15 0.15 0.15 0.15 0.15
Diethylenetriaminepenta( 0.40 0.00 1.60 0.00 0.00
methylenephosphonic
Acid)
Brightener 0.20 0.30 0.20 0.30 0.30
Sulfonated Zinc 0.25 0.00 0.00 0.00 0.00
Phthalocyanine
Photobleach
MgSO4 0.64 0.00 2.20 0.00 0.00
Na2SO4 balance balance balance balance balance
* 1-(4,4-dimethyl-3,4-dihydroisoquinoline) decane-2-sulfate prepared according
to EXAMPLE I.
Any of the above compositions is used to launder fabrics at a concentration of
3500 ppm
in water, 25 C, and a 15:1 water:cloth ratio. The typical pH is about 9.5 but
can be can be
adjusted by altering the proportion of acid to Na- salt form of
alkylbenzenesulfonate.
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EXAMPLE VI
A bleaching detergent powder comprises the following ingredients:
Component Wei ng t %
Bleach Boosting Compound* 0.07
TAED 2.0
Sodium Perborate Tetrahydrate 10
C 12 linear alkyl benzene sulfonate 8
Phosphate (as sodium tripolyphosphate) 9
Sodium carbonate 20
Talc 15
Brightener, perfume 0.3
Sodium Chloride 25
Water and Minors Balance to 100%
* 1-(4,4-dimethyl-3,4-dihydroisoquinoline) decane-2-sulfate prepared according
to EXAMPLE I.
EXAMPLE VII
A laundry bar suitable for hand-washing soiled fabrics is prepared by standard
extrusion
processes and comprises the following:
Component Wei ng t %
Bleach Boosting Compound' 0.2
TAED 1.7
NOBS 0.2
Sodium Perborate Tetrahydrate 12
C12 linear alkyl benzene sulfonate 30
Phosphate (as sodium tripolyphosphate) 10
Sodium carbonate 5
Sodium pyrophosphate 7
Coconut monoethanolamide 2
Zeolite A (0.1-10 micron) 5
Carboxymethylcellulose 0.2
Polyacrylate (m.w. 1400) 0.2
Brightener, perfume 0.2
Protease 0.3
CaSO4 1
MgSO4 1
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Water 4
Fillerz Balance to 100%
' 1-(4,4-dimethyl-3,4-dihydroisoquinoline) decane-2-sulfate prepared according
to EXAMPLE I.
2 Can be selected from convenient materials such as CaCO3, talc, clay,
silicates, and the like.
Acidic fillers can be used to reduce pH.
EXAMPLE VIII
A laundry detergent composition suitable for machine use is prepared by
standard
methods and comprises the following composition:
Component Weight%
Bleach Boosting Compound* 0.82
TAED 7.20
Sodium Perborate Tetrahydrate 9.2
Sodium Carbonate 23.74
Anionic surfactant 14.80
Alumino Silicate 21.30
Silicate 1.85
Diethylenetriaminepentacetic acid 0.43
Polyacrylic acid 2.72
Brightener 0.23
Polyethylene glycol solids 1.05
Sulfate 8.21
Perfume 0.25
Water 7.72
Processing aid 0.10
Miscellaneous 0.43
* 1-(4,4-dimethyl-3,4-dihydroisoquinoline) decane-2-sulfate prepared according
to EXAMPLE I.
The composition is used to launder fabrics at a concentration in solution of
about 1000
ppm at a temperature of 20-40 C and a water to fabric ratio of about 20:1.
EXAMPLE IX
Component Weight%
Bleach Boosting Compound* 1.0
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WO 01/16273 PCT/US00/23315
TAED 10.0
Sodium Perborate Tetrahydrate 8.0
Sodium Carbonate 21.0
Anionic surfactant 12.0
Alumino Silicate 18.0
Diethylenetriaminepentacetic acid 0.3
Nonionic surfactant 0.5
Polyacrylic acid 2.0
Brightener 0.3
Sulfate 17.0
Perfume 0.25
Water 6.7
Miscellaneous 2.95
* 1-(4,4-dimethyl-3,4-dihydroisoquinoline) decane-2-sulfate prepared according
to EXAMPLE I.
The composition is used as a laundry auxiliary for laundering fabrics at a
concentration in
solution of about 850 ppm at a temperature of 20-40 C and a water to fabric
ratio of about 20:1.
While particular embodiments of the subject invention have been described, it
will be
obvious to those skilled in the art that various changes and modifications of
the subject invention
can be made without departing from the spirit and scope of the invention. It
is intended to cover,
in the appended claims, all such modifications that are within the scope of
the invention.
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. Patent
Nos. 5,691,297;
5,574,005; 5,569,645; 5,565,422; 5,516,448; 5,489,392; and 5,486,303.
In addition to the above examples, the bleach systems of the present invention
can be
formulated into any suitable laundry detergent composition, non-limiting
examples of which are
described in U.S. Patent Nos. 5,679,630; 5,565,145; 5,478,489; 5,470,507;
5,466,802; 5,460,752;
5,458,810; 5,458,809; and 5,288,431.
Having described the invention in detail with reference to preferred
embodiments and the
examples, 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.
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SEQUENCE LISTING
<110> The Procter & Gamble Company
<120> Formulation Components Resistant Towards Decomposition
by Aromatization, Compositions and Laundry Methods Employing Same
<130> 47534-NP
<140> CA 2,381,888
<141> 2000-08-25
<150> US 60/151,175
<151> 1999-08-27
<160> 18
<170> PatentIn 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 20
<210> 3
<211> 20
<212> DNA
79
CA 02381888 2002-08-26
<213> Aspergillus aculeatus
<400> 3
accccagccg accgattgtc 20
<210> 4
<211> 20
<212> DNA
<213> Aspergillus aculeatus
<400> 4
cttccttacc tcaccatcat 20
<210> 5
<211> 20
<212> DNA
<213> Aspergillus aculeatus
<400> 5
ttaacatctt ttcaccatga 20
<210> 6
<211> 20
<212> DNA
<213> Aspergillus aculeatus
<400> 6
agctttccct tctctccctt 20
<210> 7
<211> 28
<212> DNA
<213> Aspergillus aculeatus
<400> 7
gccaccctgg cttccgctgc cagcctcc 28
CA 02381888 2002-08-26
<210> 8
<211> 20
<212> DNA
<213> Aspergillus aculeatus
<400> 8
gacagtagca atccagcatt 20
<210> 9
<211> 20
<212> DNA
<213> Aspergillus aculeatus
<400> 9
agcatcagcc gctttgtaca 20
<210> 10
<211> 20
<212> DNA
<213> Aspergillus aculeatus
<400> 10
ccatgaagtt caccgtattg 20
<210> 11
<211> 20
<212> DNA
<213> Aspergillus aculeatus
<400> 11
gcactgcttc tctcccaggt 20
<210> 12
<211> 20
81
CA 02381888 2002-08-26
<212> DNA
<213> Aspergillus aculeatus
<400> 12
gtgggcggcc cctcaggcaa 20
<210> 13
<211> 20
<212> DNA
<213> Aspergillus aculeatus
<400> 13
acgctcctcc aattttctct 20
<210> 14
<211> 19
<212> DNA
<213> Aspergillus aculeatus
<400> 14
ggctggtagt aatgagtct 19
<210> 15
<211> 20
<212> DNA
<213> Aspergillus aculeatus
<400> 15
ggcgcagagt ttggccaggc 20
<210> 16
<211> 21
<212> DNA
<213> Aspergillus aculeatus
82
CA 02381888 2002-08-26
<400> 16
caacatcccc ggtgttctgg g 21
<210> 17
<211> 347
<212> DNA
<213> Aspergillus aculeatus
<400> 17
aaagattcat ttgtggacag tggacgttga tcgcacattg aaccaacccc agccgaccga 60
ttgtccttcc ttacctcacc atcatttaac atcttttcac catgaagctt tcccttctct 120
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 60
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
83
