U.S. patent application number 10/854695 was filed with the patent office on 2005-01-13 for color safe laundry methods employing cationic formulation components.
This patent application is currently assigned to The Procter & Gamble Company. Invention is credited to Dykstra, Robert Richard.
Application Number | 20050009719 10/854695 |
Document ID | / |
Family ID | 33455796 |
Filed Date | 2005-01-13 |
United States Patent
Application |
20050009719 |
Kind Code |
A1 |
Dykstra, Robert Richard |
January 13, 2005 |
Color safe laundry methods employing cationic formulation
components
Abstract
The present invention relates to cationic organic catalyst
compound bleach systems and methods for using such bleach systems
to increase color safety during laundering of fabrics, especially
colored fabrics. More particularly, this invention relates to
bleach systems comprising cationic, quarternary imine bleach
boosting compounds, cationic, quaternary oxaziridinium bleaching
species and mixtures thereof, and methods employing such bleach
systems in the laundering of fabrics, especially colored
fabrics.
Inventors: |
Dykstra, Robert Richard;
(Cleves, OH) |
Correspondence
Address: |
THE PROCTER & GAMBLE COMPANY
INTELLECTUAL PROPERTY DIVISION
WINTON HILL TECHNICAL CENTER - BOX 161
6110 CENTER HILL AVENUE
CINCINNATI
OH
45224
US
|
Assignee: |
The Procter & Gamble
Company
Cincinnati
OH
|
Family ID: |
33455796 |
Appl. No.: |
10/854695 |
Filed: |
May 26, 2004 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
10854695 |
May 26, 2004 |
|
|
|
10069630 |
Feb 26, 2002 |
|
|
|
10069630 |
Feb 26, 2002 |
|
|
|
PCT/US00/23320 |
Aug 25, 2000 |
|
|
|
60151110 |
Aug 27, 1999 |
|
|
|
Current U.S.
Class: |
510/310 |
Current CPC
Class: |
C11D 3/3927 20130101;
C11D 11/0017 20130101 |
Class at
Publication: |
510/310 |
International
Class: |
D06L 001/00 |
Claims
What is claimed is:
1. A bleach system for laundering fabrics in need of cleaning
comprising from about 0.001 ppm to about 1.4 ppm of a cationic
organic catalyst compound selected from the group consisting of: a)
aryliminium cations and aryliminium polyions, which have a net
charge of from about +3 to about -3, that are represented by the
formula [I]: 22where R.sup.2- and R.sup.3 are independently
selected from substituted or unsubstituted radicals selected from
the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl,
aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, sulfonato,
alkoxy, keto, carboxylic and carboalkoxy radicals; R.sup.1 is
R.sup.4 are independently selected from substituted or
unsubstituted, saturated or unsaturated radicals selected from the
group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl,
heterocyclic ring, silyl, nitro, halo, cyano, alkoxy, keto and
carboalkoxy radicals; and X.sup.- is a suitable charge-balancing
counterion and v is an integer from 1 to 3; b) oxaziridinium
cations and polyions, which have a net charge of from about +3 to
about -3, that are represented by the formula [III]: 23where
R.sup.2' and R.sup.3' are independently selected from substituted
or unsubstituted radicals selected from the group consisting of H,
alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring,
silyl, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic and
carboalkoxy radicals; R.sup.1' and R.sup.4' are indepedently
selected from the group consisting of substituted or unsubstituted,
saturated or unsaturated, H, alkyl, cycloalkyl, aryl, alkaryl,
aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, alkoxy, keto
and carboalkoxy radicals; and X.sup.- is a suitable
charge-balancing counterion and v is an integer from 1 to 3; and c)
mixtures thereof.
2. The bleach system according to claim 1 wherein said bleach
system further comprises from about 2.0 ppm to about 1200 ppm of
one or more peroxygen source.
3. The bleach system according to claim 1 wherein said bleach
system further comprises from about 0.5 ppm to about 300 ppm of one
or more peracids.
4. The bleach system according to claim 1 wherein said bleach
system further comprises from about 1.0 ppm to about 600 ppm of one
or more peroxygen compounds.
5. The bleach system according to claim 2 wherein said peroxygen
source is selected from the group consisting of: (a) 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; (b) hydrogen peroxide sources selected from the
group consisting of perborate compounds, percarbonate compounds,
perphosphate compounds and mixtures thereof; and a bleach
activator.
6. The bleach system according to claim 1 wherein said cationic
organic catalyst compound is present at a concentration of from
about 0.01 ppm to about 1.4 ppm.
7. The bleach system according to claim 6 wherein said cationic
organic catalyst compound is present at a concentration of from
about 0.1 ppm to about 1.0 ppm.
8. The bleach system according to claim 7 wherein said cationic
organic catalyst compound is present at a concentration of from
about 0.2 ppm to about 0.8 ppm.
9. The bleach system according to claim 8 wherein said cationic
organic catalyst compound is present at a concentration of from
about 0.3 ppm to about 0.7 ppm.
10. The bleach system according to claim 1 wherein said cationic
organic catalyst compound is selected from the group consisting of:
a) aryliminium cations and aryliminium polyions, which have a net
charge of from about +3 to about -3, that are represented by the
formula [XI]: 24where m is 1 to 3 when G is present and m is 1 to 4
when G is not present; and n is an integer from 0 to 4; each
R.sup.20 is independently selected from a substituted or
unsubstituted radical selected from the group consisting of H,
alkyl, cycloalkyl, aryl, fused aryl, heterocyclic ring, fused
heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto,
carboxylic, and carboalkoxy radicals, and any two vicinal R.sup.20
substituents may combine to form a fused aryl, fused carbocyclic or
fused heterocyclic ring; R.sup.18 may be a substituted or
unsubstituted radical selected from the group consisting of H,
alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring,
silyl, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic and
carboalkoxy radicals; R.sup.19 is a radical selected from the group
consisting of substituted or unsubstituted, saturated or
unsaturated, H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl and
heterocyclic ring; G is selected from the group consisting of: (1)
--O--; (2) --N(R.sup.23)--; and (3) --N(R.sup.23R.sup.24)--;
R.sup.21-R.sup.24 are substituted or unsubstituted radicals
independently selected from the group consisting of H, oxygen,
linear or branched C.sub.1-C.sub.12 alkyls, alkylenes, alkoxys,
aryls, alkaryls, aralkyls, cycloalkyls and heterocyclic rings;
provided that any of R.sup.18, R.sup.19, R.sup.20,
R.sup.21-R.sup.24 may be joined together with any other of
R.sup.18, R.sup.19, R.sup.20, R.sup.21-R.sup.24 to form part of a
common ring; any geminal R.sup.21-R.sup.22 may combine to form a
carbonyl; any vicinal R.sup.21-R.sup.24 may join to form
unsaturation; and wherein any one group of substituents
R.sup.21-R.sup.24 may combine to form a substituted or
unsubstituted fused unsaturated moiety; X.sup.- is a suitable
charge-balancing counterion and v is an integer from 1 to 3; b)
oxaziridinium cations and polyions, which have a net charge of from
about +3 to about -3, that are represented by formula [XIII]:
25wherein m is 1 to 3 when G is present and m is 1 to 4 when G is
not present; and n is an integer from 0 to 4; each R.sup.20' is
independently selected from a substituted or unsubstituted radical
selected from the group consisting of H, alkyl, cycloalkyl, aryl,
fused aryl, heterocyclic ring, fused heterocyclic ring, nitro,
halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy
radicals, and any two vicinal R.sup.20' substituents may combine to
form a fused aryl, fused carbocyclic or fused heterocyclic ring;
R.sup.18' may be a substituted or unsubstituted radical selected
from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl,
aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, sulfonato,
alkoxy, keto, carboxylic and carboalkoxy radicals; R.sup.19' may be
a substituted or unsubstituted, saturated or unsaturated, radical
selected from the group consisting of H, alkyl, cycloalkyl,
alkaryl, aryl, aralkyl and heterocyclic ring. G is selected from
the group consisting of: (1) --O--; (2) --N(R.sup.23')--; and (3)
--N(R.sup.23'R.sup.24')--; R.sup.21'-R.sup.24' are substituted or
unsubstituted radicals independently selected from the group
consisting of H, oxygen, linear or branched C.sub.1-C.sub.12
alkyls, alkylenes, alkoxys, aryls, alkaryls, aralkyls, cycloalkyls
and heterocyclic rings; provided that any of R.sup.18', R.sup.19',
R.sup.21'-R.sup.24' may be joined together with any other of
R.sup.18', R.sup.19', R.sup.21'-R.sup.24' to form part of a common
ring; any geminal R.sup.21'-R.sup.22' may combine to form a
carbonyl; any vicinal R.sup.21'-R.sup.24' may join to form
unsaturation; and wherein any one group of substituents
R.sup.21'-R.sup.24' may combine to form a substituted or
unsubstituted fused unsaturated moiety; and wherein any one group
of substituents R.sup.21'-R.sup.24' may combine to form a
substituted or unsubstituted fused unsaturated moiety; X.sup.- is a
suitable charge-balancing counterion and v is an integer from 1 to
3; and c) mixtures thereof.
11. The bleach system according to claim 10 wherein said cationic
organic catalyst compound is selected from the group consisting of:
(1) aryliminium cations or polyions of the formula [XI] wherein
R.sup.18 is H or methyl, and R.sup.19 is H or substituted or
branched C.sub.1-C.sub.18 alkyl or cycloalkyl; (2) oxaziridinium
cations or polyions of the formula [XIII] wherein R.sup.18' is H or
methyl, and R.sup.19' is H or substituted or branched
C.sub.1-C.sub.18 alkyl or cycloalkyl; and (3) mixtures thereof.
12. The bleach system according to claim 1 wherein said bleach
system further comprises a surfactant.
13. The bleach system according to claim 1 wherein said bleach
system further comprises an enzyme.
14. The bleach system according to claim 1 wherein said bleach
system further comprises a chelating agent.
15. The bleach system according to claim 2 wherein said peroxygen
source and said cationic organic catalyst compound are present in
said bleach system at a molar ratio of greater than 1:1.
16. The bleach system of claim 1 made by the process comprising: a)
providing a wash solution; and b) adding to said wash solution a
bleach composition comprising an amount of cationic organic
catalyst compound selected from the group consisting of: i)
aryliminium cations and aryliminium polyions, which have a net
charge of from about +3 to about -3, that are represented by the
formula [I]: 26 where R.sup.2 and R.sup.3 are independently
selected from substituted or unsubstituted radicals selected from
the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl,
aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, sulfonato,
alkoxy, keto, carboxylic and carboalkoxy radicals; R.sup.1 and
R.sup.4 are independently selected from substituted or
unsubstituted, saturated or unsaturated radicals selected from the
group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl,
heterocyclic ring, silyl, nitro, halo, cyano, alkoxy, keto and
carboalkoxy radicals; and X.sup.- is a suitable charge-balancing
counterion and v is an integer from 1 to 3; ii) oxaziridinium
cations and polyions, which have a net charge of from about +3 to
about -3, that are represented by the formula [III]: 27 where
R.sup.2' and R.sup.3' are independently selected from substituted
or unsubstituted radicals selected from the group consisting of H,
alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring,
silyl, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic and
carboalkoxy radicals; R.sup.1' and R.sup.4' are independently
selected from the group consisting of substituted or unsubstituted,
saturated or unsaturated, H, alkyl, cycloalkyl, aryl, alkaryl,
aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, alkoxy,
keto, and carboalkoxy radicals; and X.sup.- is a suitable
charge-balancing counterion and v is an integer from 1 to 3; and
iii) mixtures thereof. such that the resulting concentration of the
cationic organic catalyst compound in said wash solution is from
about 0.001 ppm to about 5 ppm.
17. A method for laundering a fabric in need of laundering, said
method comprises contacting said fabric with a laundry solution
having a bleach system according to claim 1.
18. The method according to claim 17 wherein said fabric is a
colored fabric.
19. The method according to claim 18 wherein said method is carried
out in an automatic washing machine.
20. A bleach system for laundering fabrics in need of cleaning
comprising a) a peroxygen source; and b) a cationic organic
catalyst compound selected from the group consisting of: i)
aryliminium cations and aryliminium polyions, which have a net
charge of from about +3 to about -3, that are represented by the
formula [I]: 28 where R.sup.2 and R.sup.3 are independently
selected from substituted or unsubstituted radicals selected from
the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl,
aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, sulfonato,
alkoxy, keto, carboxylic and carboalkoxy radicals; R.sup.1 and
R.sup.4 are independently selected from substituted or
unsubstituted, saturated or unsaturated radicals selected from the
group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl,
heterocyclic ring, silyl, nitro, halo, cyano, alkoxy, keto and
carboalkoxy radicals; and X.sup.- is a suitable charge-balancing
counterion and v is an integer from 1 to 3; ii) oxaziridinium
cations and polyions, which have a net charge of from about +3 to
about -3, that are represented by the formula [III]: 29 where
R.sup.2' and R.sup.3' are independently selected from substituted
or unsubstituted radicals selected from the group consisting of H,
alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring,
silyl, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic and
carboalkoxy radicals; R.sup.1' and R.sup.4' are independently
selected from the group consisting of substituted or unsubstituted,
saturated or unsaturated, H, alkyl, cycloalkyl, aryl, alkaryl,
aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, alkoxy, keto
and carboalkoxy radicals; and X.sup.- is a suitable
charge-balancing counterion and v is an integer from 1 to 3; and
iii) mixtures thereof. wherein said peroxygen source and said
cationic organic catalyst compound are present in said bleach
system at a molar ratio greater than 150:1.
21. The bleach system according to claim 20 wherein said peroxygen
source and said cationic organic catalyst compound are present in
said bleach system at a molar ratio of from about 30,000:1 to about
150:1.
22. The bleach system according to claim 21 wherein said peroxygen
source and said cationic organic catalyst compound are present in
said bleach system at a molar ratio of from about 20,000:1 to about
175:1.
23. The bleach system according to claim 22 wherein said peroxygen
source and said cationic organic catalyst compound are present in
said bleach system at a molar ratio of from about 10,000:1 to about
200:1.
24. The bleach system according to claim 23 wherein said peroxygen
source and said cationic organic catalyst compound are present in
said bleach system at a molar ratio of from about 5,000:1 to about
150:1.
25. A bleach system for laundering fabrics in need of cleaning
comprising a) a peracid; and b) a cationic organic catalyst
compound selected from the group consisting of: i) aryliminium
cations and aryliminium polyions, which have a net charge of from
about +3 to about -3, that are represented by the formula [I]: 30
where R.sup.2 and R.sup.3 are independently selected from
substituted or unsubstituted radicals selected from the group
consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl,
heterocyclic ring, silyl, nitro, halo, cyano, sulfonato, alkoxy,
keto, carboxylic and carboalkoxy radicals; R.sup.1 and R.sup.4 are
independently selected from substituted or unsubstituted, saturated
or unsaturated radicals selected from the group consisting of H,
alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring,
silyl, nitro, halo, cyano, alkoxy, keto and carboalkoxy radicals;
and X.sup.- is a suitable charge-balancing counterion and v is an
integer from 1 to 3; ii) oxaziridinium cations and polyions, which
have a net charge of from about +3 to about -3, that are
represented by the formula [III]: 31 where R.sup.2' and R.sup.3'
are independently selected from substituted or unsubstituted
radicals selected from the group consisting of H, alkyl,
cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring, silyl,
nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic and
carboalkoxy radicals; R.sup.1' and R.sup.4' are independently
selected from the group consisting of substituted or unsubstituted,
saturated or unsaturated, H, alkyl, cycloalkyl, aryl, alkaryl,
aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, alkoxy, keto
and carboalkoxy radicals; and X.sup.- is a suitable
charge-balancing counterion and v is an integer from 1 to 3; and
iii) mixtures thereof. wherein said peracid and said cationic
organic catalyst compound are present in said bleach system at a
molar ratio greater than 1:1.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to cationic organic catalyst
compound bleach systems and methods for using such bleach systems
to provide increased color safety during laundering of fabrics,
especially colored fabrics. More particularly, this invention
relates to bleach systems comprising cationic, quaternary imine
bleach boosting compounds, cationic, quaternary oxaziridinium
bleaching species and mixtures thereof, and methods employing such
bleach systems in the laundering of fabrics, especially colored
fabrics.
BACKGROUND OF THE INVENTION
[0002] 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.degree. C. are typically required for effectiveness of
an oxygen bleaching agent in solution.
[0003] 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.degree. C. to about 60.degree. C. In water
temperatures of less than about 40.degree. C., the peroxyacid
compound loses some of its bleaching effectiveness.
[0004] U.S. Pat. Nos. 5,576,282 and 5,817,614 both to Miracle et
al. disclose attempts at developing bleach systems comprising
cationic organic catalyst compounds which are effective in lower
temperature water conditions and are relatively safe on colors.
Although the bleach systems disclosed in this patent provide
enhanced color-safety over traditional organic catalyst bleach
systems, such as cationic, organic catalyst bleach systems examples
of which are disclosed in U.S. Pat. Nos. 5,360,568, 5,360,569,
5,370,826 and 5,482,515 all to Madison et al., consumers desire
more color-safe bleach products.
[0005] A serious disadvantage associated with methods of using
conventional organic catalysts, examples of which are described in
U.S. Pat. Nos. 5,360,568, 5,360,569 and 5,370,826 all to Madison et
al., and U.S. Pat. Nos. 5,576,282 and 5,817,614, both to Miracle et
al., is that such organic catalysts are used at too high an in-use
concentration. For example, the method used in U.S. Pat. No.
5,482,515 describes a method wherein the oxygen transfer agent (an
organic catalyst compound) is present from about 0.01 ppm to 300
ppm, with the preferred concentration range from 5 ppm to about 100
ppm per liter of medium. Such a concentration can result in
unacceptable color damage to fabric dyes. In addition, such a high
concentration can lead to too much available oxygen ("AvO")
consumption, leading to an altered performance profile (i.e.,
changing the balance between peracid bleaching and organic catalyst
bleaching). It may be possible to increase stain bleaching
performance with increased organic catalyst concentration but only
at the cost of dye damage and at some point the dye damage becomes
unacceptable. Accordingly, there is a need to maximize the ratio of
stain bleaching performance to dye damage of the organic catalyst
bleach systems.
[0006] In light of the foregoing, it is evident that there still
exists a need for cationic organic catalyst compound bleach systems
and laundry methods employing such cationic organic catalyst
compound bleach systems that provide effective bleaching in lower
temperature water conditions and provide superior color-safety
properties compared to the laundry methods employing the organic
catalyst bleach systems disclosed in the prior art, as discussed
above; and there is a need to maximize the ratio of stain bleaching
performance to dye damage of the organic catalyst bleach
systems.
SUMMARY OF THE INVENTION
[0007] The present invention fulfills the need discussed above. The
present invention provides cationic organic catalyst compound
bleach systems and methods for employing such cationic organic
catalyst compound bleach systems in the laundering of colored
fabric such that the bleach systems that provide acceptable color
safety on fabric dyes. Such cationic organic catalyst compounds and
bleach systems work best in lower wash temperatures less than
80.degree. C.
[0008] More particularly, this invention relates to cationic
organic catalyst compounds such as cationic, quaternary imine
bleach boosting compounds, cationic, quaternary oxaziridinium
bleaching species, bleach systems comprising such cationic organic
catalyst compounds and laundry methods employing such bleach
systems.
[0009] Nonlimiting examples of the benefits provided by the
cationic organic catalyst compounds and bleach systems employing
same include superior bleaching effectiveness even in lower
temperature water, and improved color safety.
[0010] In one aspect of the present invention, a cationic organic
catalyst bleach system which demonstrates effective bleaching in
lower water temperature and provides a superior color-safety
profile compared to the conventional organic catalyst bleach
systems is provided.
[0011] In accordance with another aspect of the present invention,
a cationic organic catalyst bleach system comprising one or more
cationic organic catalyst compounds, as described hereinafter, in
conjunction with or without a peroxygen source is provided.
[0012] In accordance with yet another aspect of the present
invention, a cationic organic catalyst bleach system comprising one
or more cationic organic catalyst compounds, as described
hereinafter, in conjunction with a peracid is provided.
[0013] In accordance with still yet another aspect of the present
invention, a method for laundering a fabric, especially a colored
fabric, in need of laundering comprising contacting the fabric with
a laundry solution comprising one or more cationic organic catalyst
compound bleach systems described herein is provided.
[0014] In accordance with even still yet another aspect of the
present invention, a bleach system of the present invention as made
by the process comprising:
[0015] a) providing a wash solution; and
[0016] b) adding to said wash solution a bleach composition
comprising an amount of cationic organic catalyst compound of the
present invention such that the resulting concentration of the
cationic organic catalyst compound in said wash solution is from
about 0.001 ppm to about 5 ppm, is provided.
[0017] Accordingly, it is an object of the present invention to
provide: cationic organic catalyst compound bleach systems, which
demonstrate improved performance even in lower temperature water
solutions and improved color safety; and a method for laundering a
fabric, especially a colored fabric, using one or more of the
cationic organic catalyst compound bleach systems described
herein.
[0018] 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.
[0019] All percentages, ratios and proportions herein are on a
weight basis unless otherwise indicated. All documents cited herein
are hereby incorporated by reference.
DETAILED DESCRIPTION OF THE INVENTION
[0020] The present invention discloses highly useful cationic
organic catalyst compounds, bleach systems comprising such cationic
organic catalyst compounds, and methods for laundering fabrics,
especially colored fabrics, employing such bleach systems.
[0021] The cationic organic catalyst compounds of the present
invention, and bleach systems comprising such cationic organic
catalyst compounds provide increased bleaching effectiveness in
lower temperature wash applications while providing improved color
safety, resulting in increased bleaching effectiveness and color
safety as compared to conventional cationic organic catalyst
compounds and cationic organic catalyst compound bleach systems.
The cationic organic catalyst compound bleach systems of the
present invention act in conjunction with or without, preferably
with, conventional peroxygen bleaching sources to provide the
above-mentioned increased bleaching effectiveness and superior
fabric color safety.
[0022] Definitions
[0023] "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).
[0024] "Peroxygen compounds" as used herein includes peracids and
peroxides (e.g., hydrogen peroxide, alkyl hydroperoxides, etc.
[0025] "Peracid" as used herein means a peroxyacid such as
peroxycarboxylic acid and/or peroxyrmonosulfuric acid (tradname
OXONE) and their salts.
[0026] "Cationic Organic Catalyst Compound" as used herein means
cationic organic catalyst compounds and/or polyions as described
hereinafter.
[0027] Cationic Organic Catalyst Compounds
[0028] The cationic organic catalyst compounds and bleach systems
comprising such cationic organic catalyst compounds of the present
invention bleach system preferably are employed in methods for
laundering fabrics, especially colored fabrics, in need of
laundering. Such methods typically encompass bleaching a stained
substrate, preferably a colored fabric, in an aqueous medium with a
peroxygen source and with a cationic organic catalyst compound
whose structure is as defined hereinafter wherein the aqueous
medium contains active oxygen from the peroxygen compound from
about 0.05 to about 250 ppm per liter of medium, and the cationic
organic catalyst compound from 0.001 ppm to about 1.4 ppm,
preferably from about 0.01 ppm to about 1.4 ppm, more preferably
from about 0.1 ppm to about 1.0 ppm, even more preferbly from about
0.2 ppm to about 0.8 ppm, and most preferably from about 0.3 ppm to
about 0.7 ppm.
[0029] In the bleaching systems of the present invention, when
present, the molar ratio of said peroxygen compound to cationic
organic catalyst compound is preferably greater than 1:1, more
preferably the molar ratio ranges 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.
[0030] The molar ratio of peroxygen compound to cationic organic
catalyst compound does influence the color safety properties of a
bleach system. However, the ppm concentration of the cationic
organic catalyst compound in the bleach system is the primary
factor in establishing the bleach systems' color safety
properties.
[0031] A product can deliver, for example, in an aqueous medium a 1
ppm concentration of a cationic organic catalyst compound with a
molecular weight of 300, and a 66 ppm concentration of NOBS (35 ppm
pernonanoic acid assuming 100% perhydrolysis) and a 66 ppm
concentration of percarbonate (21 ppm hydrogen peroxide) to give a
molar ratio of peroxygen compound to cationic organic catalyst
compound of 246:1. A product which delivers 240 ppm of TAED
(forming 160 ppm of peracetic acid) and 865 ppm of percarbonate
(forming 281 ppm of hydrogen peroxide) gives a molar ratio of
peroxygen compound to cationic organic catalyst of 3142:1. At 0.25
ppm of cationic organic catalyst compound, the molar ratio would be
12568:1.
[0032] In addition to the molar ratios of peroxygen compound to
cationic organic catalyst compound, the bleach systems of the
present invention can be characterized by the molar ratio of a
peracid to cationic organic catalyst compound. Preferably, the
molar ratio of peracid to cationic organic catalyst compound is
greater than 1:1, more preferably about 5,000:1 to about 5:1, still
even more preferably from about 2,000:1 to about 10:1, and even
from about 1,000:1 to 15:1.
[0033] The preferred molar ratios of peracid to cationic organic
catalyst compound vary with the wash conditions. For example, under
European wash conditions (typically comprising from about 4500 ppm
to 5000 ppm of detergent components in the wash water), the
preferred molar ratio of peracid to cationic organic catalyst
compound is from about 2,000:1 to about 150:1. Whereas, under North
American wash conditions (typically comprising from about 850 ppm
to about 1000 ppm of detergent components in the wash water), the
preferred molar ratio of peracid to cationic organic catalyst
compound is from about 150:1 to about 5:1.
[0034] Yet in addition to the molar ratios of peracid to cationic
organic catalyst compound, the bleach system of the present
invention can be characterized by the molar ratio of a hydrophobic
peracid to cationic organic catalyst compound, preferably a
hydrophobic cationic organic catalyst compound. Preferably the
molar ratio of the hydrophobic peracid to cationic organic catalyst
compound is from about 500:1 to about 15:1, more preferably about
350:1 to about 20:1, still even more preferably from about 200:1 to
about 25:1, and even more preferably from about 100:1 to about
35:1.
[0035] Preferably, the cationic organic catalyst compounds of the
present invention, more preferably the iminium-based cationic
organic catalyst compounds of the present invention, include, but
are not limited to, bleach boosting compounds.
[0036] I. Bleach Boosting Compounds--The bleach boosting compounds,
preferably iminium-based bleach boosting compounds, of the present
invention include, but are not limited to, aryliminium cations and
aryliminium polyions, which have a net charge of from about +3 to
about -3 and mixtures thereof.
[0037] Aryliminium Cations and Polyions--The aryliminium cations
and aryliminium polyions, which have a net charge of from about +3
to about -3, are represented by the formula [I]: 1
[0038] where R.sup.1-R.sup.3 are independently selected from
substituted or unsubstituted, saturated or unsaturated radicals
selected from the group consisting of H, alkyl, cycloalkyl, aryl,
alkaryl, aralkyl, heterocyclic ring, silyl, nitro, halo, cyano,
sulfonato, alkoxy, keto, carboxylic, and carboalkoxy radicals;
R.sup.4 is selected from substituted or unsubstituted, saturated or
unsaturated radicals selected from the group consisting of H,
alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring,
silyl, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and
carboalkoxy radicals; and X.sup.- is a suitable charge-balancing,
preferably bleach-compatible counterion; and v is an integer from 1
to 3.
[0039] Preferably, the aryliminium cations and aryliminium
polyions, which have a net charge of from about +3 to about -3, are
represented by the formula [XI]: 2
[0040] where m is 1 to 3 when G is present and m is 1 to 4 when G
is not present; and n is an integer from 0 to 4; each R.sup.20 is
independently selected from a substituted or unsubstituted radical
selected from the group consisting of H, alkyl, cycloalkyl, aryl,
fused aryl, heterocyclic ring, fused heterocyclic ring, nitro,
halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy
radicals, and any two vicinal R.sup.20 substituents may combine to
form a fused aryl, fused carbocyclic or fused heterocyclic ring;
R.sup.18 may be a substituted or unsubstituted radical selected
from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl,
aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, sulfonato,
alkoxy, keto, carboxylic, and carboalkoxy radicals; R.sup.19 is a
radical selected from the group consisting of substituted or
unsubstituted, saturated or unsaturated, H, alkyl, cycloalkyl,
alkaryl, aryl, aralkyl and heterocyclic ring; G is selected from
the group consisting of: (1) --O--; (2) --N(R.sup.23)--; and (3)
--N(R.sup.23R.sup.24)--; R.sup.21-R.sup.24 are substituted or
unsubstituted radicals independently selected from the group
consisting of H, oxygen, linear or branched C.sub.1-C.sub.12
alkyls, alkylenes, alkoxys, aryls, alkaryls, aralkyls, cycloalkyls,
and heterocyclic rings; provided that any of R.sup.18, R.sup.19,
R.sup.20, R.sup.21-R.sup.24 may be joined together with any other
of R.sup.18, R.sup.19, R.sup.20, R.sup.21-R.sup.24 to form part of
a common ring; any geminal R.sup.21-R.sup.22 may combine to form a
carbonyl; any vicinal R.sup.21-R.sup.24 may join to form
unsaturation; and wherein any one group of substituents
R.sup.21-R.sup.24 may combine to form a substituted or
unsubstituted fused unsaturated moiety; X.sup.- is a suitable
charge-balancing counterion, preferably a bleach-compatible
counterion; and v is an integer from 1 to 3.
[0041] More preferred, aryliminium cations and aryliminium
polyions, which have a net charge of from about +3 to about -3, as
represented by the formula [XI], include those of formula [XI]
where R.sup.18 is H or methyl and R.sup.19 is H or substituted or
unsubstituted, saturated or unsaturated C.sub.1-C.sub.14 alkyl.
[0042] II. Bleaching Species--The bleaching species
(oxaziridiniums) may also be used directly in accordance with the
present invention. The bleaching species of the present invention
include, but are not limited to, oxaziridinium cations and
oxaziridinium polyions, which have a net charge of from about +3 to
about -3 and mixtures thereof.
[0043] The aryliminium cations and/or aryliminium polyions of the
present invention act in conjunction with a peroxygen source, when
present, to increase bleaching effectiveness. Without being bound
by theory, it is believed that the aryliminium cations and/or
aryliminium polyions react with the peroxygen source to form a more
active bleaching species, a quaternary oxaziridinium compound, as
represented by the following reaction by way of example: 3
[0044] The cationic and/or polyion oxaziridinium compounds can have
an increased or preferred activity at lower temperatures relative
to the peroxygen compound.
[0045] Oxaziridinium Cations and Polyions--The oxaziridinium
cations and polyions, which have a net charge of from about +3 to
about -3, are represented by the formula [III]: 4
[0046] where R.sup.1'-R.sup.3' are independently selected from
substituted or unsubstituted radicals selected from the group
consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl,
heterocyclic ring, silyl, nitro, halo, cyano, sulfonato, alkoxy,
keto, carboxylic, and carboalkoxy radicals; R.sup.4' is a radical
selected from the group consisting of substituted or unsubstituted,
saturated or unsaturated, H, alkyl, cycloalkyl, aryl, alkaryl,
aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, sulfonato,
alkoxy, keto, carboxylic, and carboalkoxy radicals; and X.sup.- is
a suitable charge-balancing counterion, preferably a
bleach-compatible counterion; and v is an integer from 1 to 3.
[0047] Preferably, the oxaziridinium cations and polyions, which
have a net charge of from about +3 to about -3, are represented by
formula [XIII]: 5
[0048] For any structures that carry a net multiple charge,
suitable examples of anionic and cationic counterions include, but
are not limited to those described above.
[0049] Concentration of Organic Catalvst Compounds--The organic
catalyst compounds of the present invention may be added to a wash
solution in levels of from about 0.00001% (0.0001 ppm) to about 10%
(100 ppm) by weight of the composition, and preferably from about
0.0001% (0.001 ppm) to about 1% (10 ppm) by weight of the
composition, more preferably from about 0.001% (0.01 ppm) to about
0.5% (5 ppm), even more preferably from about 0.004% (0.04 ppm) to
about 0.25% (2.5 ppm). Most preferably from about 0.01% (0.1 ppm)
to about 0.1% (1 ppm).
[0050] The conversion values (in ppm) are provided for exemplary
purposes, based on an in-use product concentration of 1000 ppm. A
1000 ppm wash solution of a product containing 0.2% organic
catalyst compound by weight results in a organic catalyst compound
concentration of 2 ppm. Similarly, a 3500 ppm wash solution of a
product containing 0.2% organic catalyst compound by weight results
in a organic catalyst compound concentration of 6.5 ppm.
[0051] Decomposition of Organic Catalyst
[0052] The organic catalysts, specifically the bleach boosting
compounds of the present invention are susceptible to decomposition
by various decomposition pathways including, but not limited to,
the aromatization pathway. The aromatization (decomposition)
reaction of 6-membered ring boosters is well known in the art, as
exemplified, without being limited by theory, in Hanquet et al.,
Tetrahedron 1993, 49, pp. 423-438. 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.
[0053] Methods for Delayed (Controlled) Addition of Organic
Catalyst Compounds
[0054] It has surprisingly been found with organic catalyst
compounds of limited lifetime, that the addition of organic
catalyst compounds by a delivery means to a wash solution after a
fabric has been added to a wash solution, especially a wash
solution that contains a peroxygen source, provides enhanced
bleaching compared to the addition of such organic catalyst
compounds to the wash solution before a fabric has been added to
the wash solution. It is believed, without being limited by theory,
that the organic catalyst compound undergoes decomposition in the
wash solution prior to the introduction of the fabric load. One
method for improving the performance of organic catalyst compounds
is to delay the addition of the organic catalyst compound of the
present invention to the wash solution. Another method of improving
the performance of organic catalyst compounds is to use an organic
catalyst compound with increased stability to the wash conditions.
Methods for delayed (controlled) addition of organic catalyst
compounds are more fully described in copending and co-owned U.S.
Provisional Patent Application entitled "Controlled Availability of
Formulation Components, Compositions and Laundry Methods Employing
Same" filed Aug. 27, 1999 (P&G Attorney Docket Number
7749P).
[0055] Bleach Systems Comprising Cationic Organic Catalyst
Compounds
[0056] In addition to the use of cationic organic catalyst
compounds discussed above, the cationic organic catalyst compounds
of the present invention may be employed in conjunction with or
without, preferably with a peroxygen source in other bleach
systems, regardless of their form. For example, the cationic
organic catalyst compounds may be employed in a laundry additive
product. In the bleach systems of the present invention, the
peroxygen source may be present in levels of from about 0.1% 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
organic catalyst compound may be present from about 0.00001% to
about 10% by weight of the system, and preferably from about
0.0001% to about 1% by weight of the system, more preferably from
about 0.001% to about 0.5%, even more preferably from about 0.004%
to about 0.25%, most preferably from about 0.01% to about 0.1%.
[0057] The bleach systems 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 organic catalyst 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.
[0058] The cationic organic catalyst compounds and bleach systems
comprising the organic catalyst compounds can be used as
antimicrobial agents and disinfectants.
[0059] Accordingly, the bleach system systems 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 bleach system.
[0060] The bleach systems 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 8 to about 10.5 in a 1% solution of the bleach system.
[0061] In another embodiment of the present invention, a method for
laundering a fabric, especially a colored 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 bleach system
comprising one or more cationic organic catalyst compounds of the
present invention, as fully described herein. The water
temperatures preferably range from about 0.degree. C. to about
50.degree. C. or higher. The water to fabric ratio is preferably
from about 1:1 to about 15:1.
[0062] 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 bleach system.
[0063] The bleach systems of the present invention typically and
preferably 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:
[0064] (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
[0065] (ii) hydrogen peroxide sources selected from the group
consisting of perborate compounds, percarbonate compounds,
perphosphate compounds and mixtures thereof, and a bleach
activator.
[0066] 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 bleach
system comprising the bleaching agent-plus-bleach activator.
[0067] a. Preformed Peracids--The preformed peracid compound as
used herein is any convenient compound which is stable and which
under consumer use conditions provides an effective amount of
peracid anion. The organic catalysts of the present invention may
of course be used in conjunction with a preformed peracid compound
selected from the group consisting of percarboxylic acids and
salts, percarbonic acids and salts, perimidic acids and salts,
peroxymonosulfuric acids and salts, and mixtures thereof, examples
of which are described in U.S. Pat. No. 5,576,282 to Miracle et
al.
[0068] One class of suitable organic peroxycarboxylic acids have
the general formula: 6
[0069] 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.
[0070] 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: 7
[0071] where Y can be, for example, H, CH.sub.3, CH.sub.2Cl,
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: 8
[0072] wherein Y can be, for example, hydrogen, alkyl,
alkylhalogen, halogen, C(O)OH or C(O)OOH.
[0073] Typical monoperoxy acids useful herein include alkyl and
aryl peroxyacids such as:
[0074] (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);
[0075] (ii) aliphatic, substituted aliphatic and arylalkyl
monoperoxy acids, e.g. peroxylauric acid, peroxystearic acid,
N-nonanoylaminoperoxycaproic acid (NAPCA),
N,N-(3-octylsuccinoyl)aminoper- oxycaproic acid (SAPA) and
N,N-phthaloylaminoperoxycaproic acid (PAP);
[0076] (iii) amidoperoxyacids, e.g. monononylamide of either
peroxysuccinic acid (NAPSA) or of peroxyadipic acid (NAPAA).
[0077] Typical diperoxyacids useful herein include alkyl
diperoxyacids and aryldiperoxyacids, such as:
[0078] (iv) 1,12-diperoxydodecanedioic acid;
[0079] (v) 1,9-diperoxyazelaic acid;
[0080] (vi) diperoxybrassylic acid; diperoxysebacic acid and
diperoxyisophthalic acid;
[0081] (vii) 2-decyldiperoxybutane-1,4-dioic acid;
[0082] (viii) 4,4'-sulfonylbisperoxybenzoic acid.
[0083] Such bleaching agents are disclosed in U.S. Pat. No.
4,483,781, Hartman, issued Nov. 20, 1984, U.S. Pat. No. 4,634,551
to Burns et al., European Patent Application 0,133,354, Banks et
al. published Feb. 20, 1985, and U.S. Pat. No. 4,412,934, Chung et
al. issued Nov. 1, 1983. Sources also include
6-nonylamino-6-oxoperoxycaproic acid as fully described in U.S.
Pat. No. 4,634,551, issued Jan. 6, 1987 to Burns et al. Persulfate
compounds such as for example OXONE, manufactured commercially by
E.I. DuPont de Nemours of Wilmington, Del. can also be employed as
a suitable source of peroxymonosulfuric acid.
[0084] 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. Pat. 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.
[0085] Hydrogen peroxide sources are described in detail in the
herein incorporated Kirk Othmer's Encyclopedia of Chemical
Technology, 4th Ed (1992, John Wiley & Sons), Vol. 4, pp.
271-300 "Bleaching Agents (Survey)", and include the various forms
of sodium perborate and sodium percarbonate, including various
coated and modified forms.
[0086] 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.
[0087] 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.
[0088] 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.
[0089] b. Bleach Activators--Preferably, the peroxygen source in
the composition is formulated with an activator (peracid
precursor). The activator is present at levels of from about 0.01%,
preferably from about 0.5%, more preferably from about.1% to about
15%, preferably to about 10%, more preferably to about 8%, by
weight of the composition. A bleach activator as used herein is any
compound which when used in conjunction with a hydrogen peroxide
source leads to the in situ production of the peracid corresponding
to the bleach activator. Various non limiting examples of
activators are fully disclosed in U.S. Pat. No. 5,576,282, U.S.
Pat. No. 4,915,854 and U.S. Pat. No. 4,412,934. See also U.S. Pat.
No. 4,634,551 for other typical bleaches and activators useful
herein.
[0090] Preferred activators are selected from the group consisting
of tetaa acetyl ethylene diamine (TAED), benzoylcaprolactam (BzCL),
4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam,
benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate
(NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulphonate
(C.sub.10-OBS), benzoylvalerolactam (BZVL),
octanoyloxybenzenesulphonate (C.sub.8-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.
[0091] 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. Pat. No. 5,523,434,
lauroyloxybenzenesulphonate (LOBS or C.sub.12-OBS),
10-undecenoyloxybenzenesulphonate (UDOBS or C.sub.11-OBS with
unsaturation in the 10 position), and decanoyloxybenzoic acid
(DOBA).
[0092] Preferred bleach activators are those described in U.S. Pat.
No. 5,698,504 Christie et al., issued Dec. 16, 1997; U.S. Pat. No.
5,695,679 Christie et al. issued Dec. 9, 1997; U.S. Pat. No.
5,686,401 Willey et al., issued Nov. 11, 1997; U.S. Pat. No.
5,686,014 Hartshorn et al., issued Nov. 11, 1997; U.S. Pat. No.
5,405,412 Willey et al., issued Apr. 11, 1995; U.S. Pat. No.
5,405,413 Willey et al., issued Apr. 11, 1995; U.S. Pat. No.
5,130,045 Mitchel et al., issued Jul. 14, 1992; and U.S. Pat. No.
4,412,934 Chung et al., issued Nov. 1, 1983, and copending patent
applications U.S. Ser. Nos. 08 1709,072, 08/064,564, all of which
are incorporated herein by reference.
[0093] 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.
[0094] Quaternary substituted bleach activators may also be
included. The present bleach systems preferably comprise a
quaternary substituted bleach activator (QSBA) or a quaternary
substituted peracid (QSP); more preferably, the former. Preferred
QSBA structures are further described in U.S. Pat. No. 5,686,015
Willey et al., issued Nov. 11, 1997; U.S. Pat. No. 5,654,421 Taylor
et al., issued Aug. 5, 1997; U.S. Pat. No. 5,460,747 Gosselink et
al., issued Oct. 24, 1995; U.S. Pat. No. 5,584,888 Miracle et al.,
issued Dec. 17, 1996; and U.S. Pat. No. 5,578,136 Taylor et al.,
issued Nov. 26, 1996; all of which are incorporated herein by
reference.
[0095] Highly preferred bleach activators useful herein are
amide-substituted as described in U.S. Pat. No. 5,698,504, U.S.
Pat. No. 5,695,679, and U.S. Pat. No. 5,686,014 each of which are
cited herein above. Preferred examples of such bleach activators
include: (6-octanamidocaproyl) oxybenzenesulfonate,
(6-nonanamidocaproyl)oxybenzen- esulfonate, (6-decanamido
caproyl)oxybenzenesulfonate and mixtures thereof.
[0096] Other useful activators, disclosed in U.S. Pat. No.
5,698,504, U.S. Pat. No. 5,695,679, U.S. Pat. No. 5,686,014 each of
which is cited herein above and U.S. Pat. No. 4,966,723Hodge et
al., issued Oct. 30, 1990, include benzoxazin-type activators, such
as a C.sub.6H.sub.4 ring to which is fused in the 1,2-positions a
moiety --C(O)OC(R.sup.1).dbd.N--.
[0097] 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.
[0098] Acyl lactarn activators, as described in U.S. Pat. No.
5,698,504, U.S. Pat. No. 5,695,679 and U.S. Pat. No. 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. Pat. No. 5,503,639 Willey et al.,
issued Apr. 2, 1996 incorporated herein by reference).
[0099] d. Organic Peroxides, especially Diacyl Peroxides--In
addition to the bleaching agents described above, the bleach
systems of the present invention can optionally include organic
peroxides. Organic peroxides are extensively illustrated in Kirk
Othmer, Encyclopedia of Chemical Technology, Vol. 17, John Wiley
and Sons, 1982 at pages 27-90 and especially at pages 63-72, all
incorporated herein by reference. If a diacyl peroxide is used, it
will preferably be one which exerts minimal adverse impact on
spotting/filming.
[0100] e. Metal-containing Bleach Catalysts--The bleach systems can
also optionally include metal-containing bleach catalysts,
preferably manganese and cobalt-containing bleach catalysts.
[0101] 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. Pat. No. 4,430,243 Bragg, issued
Feb. 2, 1982.
[0102] 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. Pat.
No. 5,576,282 Miracle et al., issued Nov. 19, 1996; U.S. Pat. No.
5,246,621 Favre et al., issued Sep. 21, 1993; U.S. Pat. No.
5,244,594 Favre et al., issued Sep. 14, 1993; U.S. Pat. No.
5,194,416 Jureller et al., issued Mar. 16, 1993; U.S. Pat. No.
5,114,606 van Vliet et al., issued May 19, 1992; and European Pat.
App. Pub. Nos. 549,271 A1, 549,272 A1, 544,440 A2, and 544,490 A1;
Preferred examples of these catalysts include
Mn.sup.IV.sub.2(u-O).sub.3(-
1,4,7-trimethyl-1,4,7-triazacyclononane).sub.2-(PF.sub.6).sub.2,
Mn.sup.III.sub.2(u-O).sub.1(u-OAc).sub.2(1,4,7-trimethyl-1,4,7-triazacycl-
ononane).sub.2(CIO.sub.4).sub.2,
Mn.sup.IV.sub.4(u-O).sub.6(1,4,7-triazacy-
clononane).sub.4(CIO.sub.4).sub.4,
Mn.sup.IIIMn.sup.IV.sub.4(u-O).sub.1(u--
OAc).sub.2-(1,4,7-trimethyl-1,4,7-triazacyclononane).sub.2(CIO.sub.4).sub.-
3,
Mn.sup.IV(1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH.sub.3).sub.3(PF-
.sub.6), and mixtures thereof. Other metal-based bleach catalysts
include those disclosed in U.S. Pat. No. 4,430,243 included by
reference herein above and U.S. Pat. No. 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. Pat. No. 4,728,455 Rerek, issued Mar. 1, 1988; U.S. Pat. No.
5,284,944 Madison, issued Feb. 8, 1994; U.S. Pat. No. 5,246,612 van
Dijk et al., issued Sep. 21, 1993; U.S. Pat. No. 5,256,779
Kerschner et al., issued Oct. 26, 2993; U.S. Pat. No. 5,280,117
Kerschner et al., issued Jan. 18, 1994; U.S. Pat. No. 5,274,147
Kerschner et al., issued Dec. 28, 1993; U.S. Pat. No. 5,153,161
Kerschner et al., issued Oct. 6, 1992; and U.S. Pat. No. 5,227,084
Martens et al., issued Jul. 13, 1993.
[0103] ii. Cobalt Metal Complexes--Cobalt bleach catalysts useful
herein are known, and are described, for example, in U.S. Pat. No.
5,597,936 Perkins et al., issued Jan. 28, 1997; U.S. Pat. No.
5,595,967 Miracle et al., Jan. 21, 1997; U.S. Pat. No. 5,703,030
Perkins et al., issued Dec. 30, 1997; and M. L. Tobe, "Base
Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg.
Mech., (1983), 2, pages 1-94. The most preferred cobalt catalyst
useful herein are cobalt pentaamine acetate salts having the
formula [Co(NH.sub.3).sub.5OAc] T.sub.y, wherein "OAc" represents
an acetate moiety and "T.sub.y" is an anion, and especially cobalt
pentaamine acetate chloride, [Co(NH.sub.3).sub.5OAc]Cl.sub.2; as
well as [Co(NH.sub.3).sub.5OAc](OAc).sub.2;
[Co(NH.sub.3).sub.5OAc](PF.su- b.6).sub.2;
[Co(NH.sub.3).sub.5OAc](SO.sub.4); [Co(NH.sub.3).sub.5OAc](BF.-
sub.4).sub.2; and [Co(NH.sub.3).sub.5OAc](NO.sub.3).sub.2 (herein
"PAC").
[0104] These cobalt catalysts are readily prepared by known
procedures, such as taught for example in U.S. Pat. No. 5,597,936,
U.S. Pat. No. 5,595,967, U.S. Pat. No. 5,703,030, cited herein
above, the Tobe article and the references cited therein, and in
U.S. Pat. No. 4,810,410, to Diakun et al, issued Mar. 7, 1989, J.
Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis and
Characterization of Inorganic Compounds, W. L. Jolly
(Prentice-Hall; 1970), pp. 461-3; Inorg. Chem., 18, 1497-1502
(1979); Inorg. Chem., 2881-2885 (1982); Inorg. Chem., 18, 2023-2025
(1979); Inorg. Synthesis, 173-176 (1960); and Journal of Physical
Chemistry, 56, 22-25 (1952).
[0105] iii. Transition Metal Complexes of Macropolycyclic Rigid
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 1 ppb or more, for
example up to about 99.9%, more typically about 0.001 ppm or more,
preferably from about 0.05 ppm to about 500 ppm (wherein "ppb"
denotes parts per billion by weight and "ppm" denotes parts per
million by weight).
[0106] 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, incorporated by reference. More particularly,
"rigid" as used herein means that the MRL must be determinably more
rigid than a macrocycle ("parent macrocycle") which is otherwise
identical (having the same ring size and type and number of atoms
in the main ring) but lacking a superstructure (especially linking
moieties or, preferably cross-bridging moieties) found in the MRL's
. In determining the comparative rigidity of macrocycles with and
without superstructures, the practitioner will use the free form
(not the metal-bound form) of the macrocycles. Rigidity is
well-known to be useful in comparing macrocycles; suitable tools
for determining, measuring or comparing rigidity include
computational methods (see, for example, Zimmer, Chemical Reviews,
(1995), 95(38), 2629-2648 or Hancock et al., Inorganica Chimica
Acta, (1989), 164, 73-84.
[0107] 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
--CH.sub.2CH.sub.2-- moiety. It bridges N.sup.1 and N.sup.8 in the
illustrative structure. By comparison, a "same-side" bridge, for
example if one were to be introduced across N.sup.1 and N.sup.12 in
1.11, would not be sufficient to constitute a "cross-bridge" and
accordingly would not be preferred.
[0108] Suitable metals in the rigid ligand complexes include
Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV), Co(I),
Co(II), Co(III), Ni(I), Ni(II), Ni(III), Cu(I), Cu(II), Cu(III),
Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(II), V(I), 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.
[0109] More generally, the MRL's (and the corresponding
transition-metal catalysts) herein suitably comprise:
[0110] (a) at least one macrocycle main ring comprising four or
more heteroatoms; and
[0111] (b) a covalently connected non-metal superstructure capable
of increasing the rigidity of the macrocycle, preferably selected
from
[0112] (i) a bridging superstructure, such as a linking moiety;
[0113] (ii) a cross-bridging superstructure, such as a
cross-bridging linking moiety; and
[0114] (iii) combinations thereof.
[0115] The term "superstructure" is used herein as defined in the
literature by Busch et al., see, for example, articles by Busch in
"Chemical Reviews".
[0116] Preferred superstructures herein not only enhance the
rigidity of the parent macrocycle, but also favor folding of the
macrocycle so that it coordinates to a metal in a cleft. Suitable
superstructures can be remarkably simple, for example a linking
moiety such as any of those illustrated in FIG. 1 and FIG. 2 below,
can be used.
[0117] wherein n is an integer, for example from 2 to 8, preferably
less than 6, typically 2 to 4, or
[0118] wherein m and n are integers from about 1 to 8, more
preferably from 1 to 3; Z is N or CH; and T is a compatible
substituent, for example H, alkyl, trialkylammonium, halogen,
nitro, sulfonate, or the like. The aromatic ring in 1.10 can be
replaced by a saturated ring, in which the atom in Z connecting
into the ring can contain N, O, S or C.
[0119] Suitable MRL's are further nonlimitingly illustrated by the
following compound:
[0120] 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.
[0121] 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:
[0122]
Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(II)
[0123] Diaquo-5,
12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II)
Hexafluorophosphate
[0124]
Aquo-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecan-
e Manganese(III) Hexafluorophosphate
[0125]
Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(II) Tetrafluoroborate
[0126] Dichloro-5,12-dimethyl-1,5,8,12-tetraa
zabicyclo[6.6.2]hexadecane Manganese(III) Hexafluorophosphate
[0127] Dichloro-5,12-di-n-butyl-1,5,8,12-tetraza
bicyclo[6.6.2]hexadecane Manganese(II)
[0128]
Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane
Manganese(II)
[0129]
Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexade-
cane Manganese(II)
[0130]
Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexade-
cane Manganese(II)
[0131]
Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexade-
cane Manganese(II).
[0132] (f) Other Bleach Catalysts--The compositions herein may
comprise one or more other bleach catalysts. Preferred bleach
catalysts are cationic bleach catalysts, which are described in
U.S. Pat. No. 5,576,282 (especially 3-(3,4-dihydroisoquinolinium)
propane sulfonate. Other bleach catalysts include cationic bleach
catalysts are described in U.S. Pat. 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.
[0133] As a practical matter, and not by way of limitation, the
compositions and cleaning processes herein can be adjusted to
provide on the order of at least one part per hundred million of
the active bleach catalyst species in the aqueous washing medium,
and will preferably provide from about 0.01 ppm to about 25 ppm,
more preferably from about 0.05 ppm to about 10 ppm, and most
preferably from about 0.1 ppm to about 5 ppm, of the bleach
catalyst species in the wash liquor. In order to obtain such levels
in the wash liquor of an automatic washing process, typical
compositions herein will comprise from about 0.0005% to about 0.2%,
more preferably from about 0.004% to about 0.08%, of bleach
catalyst, especially manganese or cobalt catalysts, by weight of
the cleaning compositions.
[0134] 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.
[0135] Preferably, the bleach activator is selected from the group
consisting of hydrophobic bleach activators as disclosed
herein.
[0136] The purpose of such a bleach system is to mitigate unwanted
decomposition of the organic catalyst, and to allow the peracid to
achieve bleaching performance on a fabric in need of cleaning, such
as a stained fabric, in a wash solution prior to the availability
of the organic catalyst.
[0137] The period of time between the peracid becoming active in a
wash solution and the organic catalyst compounds becoming active
can be in the range of from about 1 second to about 24 hours.
Alternatively, since the organic catalyst compounds are relatively
stable in the wash solution, the peracid can become active in the
wash solution after the organic catalyst compound becomes active or
available.
[0138] The purpose of a delayed addition bleach system (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 organic catalyst compound. In
other words, a bleach system comprising an organic catalyst
compound which becomes active in a wash solution after a fabric in
need of cleaning has been added to the wash solution.
Alternatively, since the organic catalyst compounds can have
increased stability, a bleach system comprising an organic catalyst
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.
[0139] A preferred bleach system in accordance with the present
invention is a bleach system comprising:
[0140] (a) a peroxygen source; and
[0141] (b) a cationic organic catalyst compound;
[0142] wherein the cationic organic catalyst compound becomes
active in a wash solution containing said bleach system a period of
time after said peroxygen source becomes active. The peroxygen
source, like discussed above, is preferably selected from the group
consisting of:
[0143] (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
[0144] (ii) hydrogen peroxide sources selected from the group
consisting of perborate compounds, percarbonate compounds,
perphosphate compounds and mixtures thereof, and a bleach
activator.
[0145] The bleach systems of the present invention also preferably
comprise, in addition to one or more organic catalysts, described
hereinbefore, one or more cleaning adjunct materials, preferably
compatible with the organic catalyst(s) and/or any enzymes present
in the bleach system. The term "compatible", as used herein, means
the bleach system materials do not reduce the bleaching activity of
the organic catalyst and/or any enzymatic activity of any enzyme
present in the bleach system to such an extent that the organic
catalyst 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 bleach system 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.
[0146] 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. Pat. Nos. 5,705,464, 5,710,115, 5,698,504,
5,695,679, 5,686,014 and 5,646,101. Specific bleach system
materials are exemplified in detail hereinafter.
[0147] If the cleaning adjunct materials are not compatible with
the protease variant(s) in the bleach systems, 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.
[0148] Such bleach systems 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
bleach systems, unlimited in form (e.g., dentifrice, toothpaste and
mouthwash formulations); and denture bleach systems, unlimited in
form (e.g., liquid, tablet).
[0149] The fabric bleach systems 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 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.
[0150] The bleach systems may include from about 1% to about 99.9%
by weight of the composition of the cleaning adjunct materials.
[0151] As used herein, "non-fabric bleach systems" include hard
surface bleach systems, dishwashing compositions, oral bleach
systems, denture bleach systems and personal cleansing
compositions.
[0152] When the bleach systems 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,
additional 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.
[0153] 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.
[0154] 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.
[0155] If needed the density of the laundry detergent compositions
herein ranges from 400 to 1200 g/litter, preferably 500 to 950
g/litter of composition measured at 20.degree. C.
[0156] The "compact" form of the bleach systems 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.
[0157] Liquid bleach systems according to the present invention can
also be in a "concentrated form", in such case, the liquid bleach
systems according the present invention will contain a lower amount
of water, compared to conventional liquid detergents. Typically the
water content of the concentrated liquid bleach system is
preferably less than 40%, more preferably less than 30%, most
preferably less than 20% by weight of the bleach system.
[0158] Cleaning Adjunct Materials
[0159] While not essential for the purposes of the present
invention, several conventional adjuncts illustrated hereinafter
are suitable for use in the instant bleach systems 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 bleach system 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 bleach systems 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.
[0160] 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, cationics, 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 cationic
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. Pat. No.
3,929,678, issued Dec. 30, 1975 to Laughlin, et al. at Column 23,
line 58 through Column 29, line 23.
[0161] The surfactant is typically present at a level of from about
0.1%, preferably about 1%, more preferably about 5% by weight of
the bleach systems to about 99.9%, preferably about 80%, more
preferably about 35%, most preferably 30% about by weight of the
bleach systems.
[0162] 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.
[0163] 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
ROSO.sub.3M wherein R preferably is a C.sub.10-C.sub.24
hydrocarbyl, preferably an alkyl or hydroxyalkyl having a
C.sub.10-C.sub.20 alkyl component, more preferably a
C.sub.12-C.sub.18 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 C.sub.12-16 are preferred for
lower wash temperatures (e.g., below about 50.degree. C.) and
C.sub.16-18 alkyl chains are preferred for higher wash temperatures
(e.g., above about 50.degree. C.).
[0164] 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).sub.mSO.sub.3M
wherein R is an unsubstituted C.sub.10-C.sub.24 alkyl or
hydroxyalkyl group having a C.sub.10-C.sub.24 alkyl component,
preferably a C.sub.12-C.sub.20 alkyl or hydroxyalkyl, more
preferably C.sub.12-C.sub.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 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 C.sub.12-C.sub.18 alkyl
polyethoxylate (1.0) sulfate, C.sub.12-C.sub.18 alkyl
polyethoxylate (2.25) sulfate, C.sub.12-C.sub.18 alkyl
polyethoxylate (3.0) sulfate, and C.sub.12-C.sub.18 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.
[0165] 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 No. 60/061,971, Attorney
docket No 6881P Oct. 14, 1997, No. 60/061,975, Attorney docket No
6882P Oct. 14, 1997, No. 60/062,086, Attorney docket No 6883P Oct.
14, 1997, No. 60/061,916, Attorney docket No 6884P Oct. 14, 1997,
No. 60/061,970, Attorney docket No 6885P Oct. 14, 1997, No.
60/062,407, Attorney docket No 6886P Oct. 14, 1997,. Other suitable
mid-chain branched surfactants can be found in U.S. Patent
applications Ser. Nos. 60/032,035 (Docket No. 6401P), 60/031,845
(Docket No. 6402P), 60/031,916 (Docket No. 6403P), 60/031,917
(Docket No. 6404P), 60/031,761 (Docket No. 6405P), 60/031,762
(Docket No. 6406P) and 60/031,844 (Docket No. 6409P). Mixtures of
these branched surfactants with conventional linear surfactants are
also suitable for use in the present compositions.
[0166] 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 copending U.S. patent
applications Ser. Nos. 60/053,319 (Docket No. 6766P), 60/053,318
(Docket No. 6767P), 60/053,321 (Docket No. 6768P), 60/053,209
(Docket No. 6769P), 60/053,328 (Docket No. 6770P), 60/053,186
(Docket No. 6771P), 60/055,437 (Docket No. 6796P), 60/105,017
(Docket No. 7303P), and 60/104,962 (Docket No. 7304P).
[0167] Examples of suitable anionic surfactants are given in
"Surface Active Agents and Detergents" (Vol. I and II by Schwartz,
Perry and Berch).
[0168] Nonionic Detergent Surfactants--Suitable nonionic detergent
surfactants are generally disclosed in U.S. Pat. No. 3,929,678,
Laughlin et al., issued Dec. 30, 1975, at column 13, line 14
through column 16, line 6, incorporated herein by reference.
Exemplary, non-limiting classes of useful nonionic surfactants
include: amine oxides, alkyl ethoxylate, alkanoyl glucose amide,
alkyl betaines, sulfobetaine and mixtures thereof.
[0169] 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.
[0170] Semi-polar nonionic detergent surfactants include the amine
oxide surfactants having the formula 9
[0171] wherein R.sup.3 is an alkyl, hydroxyalkyl, or alkyl phenyl
group or mixtures thereof containing from about 8 to about 22
carbon atoms; R.sup.4 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 R.sup.5 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 R.sup.5 groups can be attached to each
other, e.g., through an oxygen or nitrogen atom, to form a ring
structure.
[0172] These amine oxide surfactants in particular include
C.sub.10-C.sub.18 alkyl dimethyl amine oxides and C.sub.8-C.sub.12
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.
[0173] 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.RTM. CO-630, marketed by the GAF
Corporation; and Triton.RTM. 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).
[0174] 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, 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 10 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.RTM. 15-S-9 (the
condensation product of C.sub.11-C.sub.15 linear secondary alcohol
with 9 moles ethylene oxide), Tergitol.RTM. 24-L-6 NMW (the
condensation product of C.sub.12-C.sub.14 primary alcohol with 6
moles ethylene oxide with a narrow molecular weight distribution),
both marketed by Union Carbide Corporation; Neodol.RTM. 45-9 (the
condensation product of C.sub.14-C.sub.15 linear alcohol with 9
moles of ethylene oxide), Neodol.RTM. 23-6.5 (the condensation
product of C.sub.12-C.sub.13 linear alcohol with 6.5 moles of
ethylene oxide), Neodol.RTM. 45-7 (the condensation product of
C.sub.14-C.sub.15 linear alcohol with 7 moles of ethylene oxide),
Neodol.RTM. 45-4 (the condensation product of C.sub.14-C.sub.15
linear alcohol with 4 moles of ethylene oxide), marketed by Shell
Chemical Company, and Kyro.RTM. EOB (the condensation product of
C.sub.13-C.sub.15 alcohol with 9 moles ethylene oxide), marketed by
The Procter & Gamble Company. Other commercially available
nonionic surfactants include Dobanol 91-8.RTM. marketed by Shell
Chemical Co. and Genapol UD -080.RTM. marketed by Hoechst. This
category of nonionic surfactant is referred to generally as "alkyl
ethoxylates."
[0175] The preferred alkylpolyglycosides have the formula
R.sup.2O(C.sub.nH.sub.2nO).sub.t(glycosyl).sub.x
[0176] wherein R.sup.2 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.
[0177] Fatty acid amide surfactants having the formula: 10
[0178] wherein R.sup.6 is an alkyl group containing from about 7 to
about 21 (preferably from about 9 to about 17) carbon atoms and
each R.sup.7 is selected from the group consisting of hydrogen,
C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 hydroxyalkyl, and
--(C.sup.2H.sub.4O).sub.xH where x varies from about 1 to about
3.
[0179] Preferred amides are C.sub.8-C.sub.20 ammonia amides,
monoethanolamides, diethanolamides, and isopropanolamides.
[0180] 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.
[0181] 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.
[0182] 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: 11
[0183] wherein: R.sup.1 is H, C.sub.1-C.sub.4 hydrocarbyl,
2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably
C.sub.1-C.sub.4 alkyl, more preferably C.sub.1 or C.sub.2 alkyl,
most preferably C.sub.1 alkyl (i.e., methyl); and R.sup.2 is a
C.sub.5-C.sub.31 hydrocarbyl, preferably straight chain
C.sub.7-C.sub.19 alkyl or alkenyl, more preferably straight chain
C.sub.9-C.sub.17 alkyl or alkenyl, most preferably straight chain
C.sub.11-C.sub.15 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 --CH.sub.2--(CHOH).sub.n--CH.sub.2O- H,
--CH(CH.sub.2OH)--(CHOH).sub.n-1--CH.sub.2OH,
--CH.sub.2--(CHOH).sub.2(- CHOR')(CHOH)--CH.sub.2OH, 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
--CH.sub.2--(CHOH).sub.4--CH.sub.2OH.
[0184] R' can be, for example, N-methyl, N-ethyl, N-propyl,
N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
[0185] R.sup.2--CO--N< can be, for example, cocamide,
stearamide, oleamide, lauramide, myristamide, capricamide,
palmitamide, tallowamide, etc.
[0186] Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl,
1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl,
1-deoxymaltotriotityl, etc.
[0187] 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 Feb. 18, 1959, by Thomas Hedley & Co., Ltd., U.S.
Pat. No. 2,965,576, issued Dec. 20, 1960 to E. R. Wilson, and U.S.
Pat. No. 2,703,798, Anthony M. Schwartz, issued Mar. 8, 1955, and
U.S. Pat. No. 1,985,424, issued Dec. 25, 1934 to Piggott, each of
which is incorporated herein by reference.
[0188] 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.
[0189] The diamines suitable for use in the compositions of the
present invention have the formula: 12
[0190] wherein each R.sup.20 is independently selected from the
group consisting of hydrogen, C.sub.1-C.sub.4 linear or branched
alkyl, alkyleneoxy having the formula:
--(R.sup.21O).sub.yR.sup.22
[0191] wherein R.sup.21 is C.sub.2-C.sub.4 linear or branched
alkylene, and mixtures thereof, R.sup.22 is hydrogen,
C.sub.1-C.sub.4 alkyl, and mixtures thereof; y is from 1 to about
10; X is a unit selected from:
[0192] i) C.sub.3-C.sub.10 linear alkylene, C.sub.3-C.sub.10
branched alkylene, C.sub.3-C.sub.10 cyclic alkylene,
C.sub.3-C.sub.10 branched cyclic alkylene, an alkyleneoxyalkylene
having the formula:
--(R.sup.21O).sub.yR.sup.21--
[0193] wherein R.sup.21 and y are the same as defined herein
above;
[0194] ii) C.sub.3-C.sub.10 linear, C.sub.3-C.sub.10 branched
linear, C.sub.3-C.sub.10 cyclic, C.sub.3-C.sub.10 branched cyclic
alkylene, C.sub.6-C.sub.10 arylene, wherein said unit comprises one
or more electron donating or electron withdrawing moieties which
provide said diamine with a pK.sub.a greater than about 8; and
[0195] iii) mixtures of (i) and (ii)
[0196] provided said diamine has a pK.sub.a of at least about
8.
[0197] The preferred diamines of the present invention have a
pK.sub.1 and pK.sub.2 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 "pK.sub.a" stands equally well
for the terms "pK.sub.1" and "pK.sub.2" either separately or
collectively. The term pK.sub.a as used herein throughout the
present specification in the same manner as used by those of
ordinary skill in the art. pK.sub.a 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).
[0198] As an applied definition herein, the pK.sub.a values of the
diamines are specified as being measured in an aqueous solution at
25.degree. C. having an ionic strength of from about 0.1 to about
0.5 M. As used herein, the pK.sub.a 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
pK.sub.a'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 pK.sub.a by suitable methods as
described and referenced in "The Chemist's Ready Reference
Handbook" by Shugar and Dean, McGraw Hill, N.Y., 1990.
[0199] Preferred diamines for performance and supply considerations
are 1,3-bis(methylamino)cyclohexane, 1,3-diaminopropane
(pK.sub.1=10.5; pK.sub.2=8.8), 1,6-diaminohexane (pK.sub.1=11;
pK.sub.2=10), 1,3-diaminopentane (Dytek EP) (pK.sub.1=10.5;
pK.sub.2=8.9), 2-methyl 1,5-diaminopentane (Dytek A)
(pK.sub.1=11.2; pK.sub.2=10.0). Other preferred materials are the
primary/primary diamines having alkylene spacers ranging from
C.sub.4-C.sub.8. In general, primary diamines are preferred over
secondary and tertiary diamines.
[0200] The following are non-limiting examples of diamines suitable
for use in the present invention.
[0201] 1-N,N-dimethylamino-3-aminopropane having the formula:
13
[0202] 1,6-diaminohexane having the formula: 14
[0203] 1,3-diaminopropane having the formula: 15
[0204] 2-methyl-1,5-diaminopentane having the formula: 16
[0205] 1,3-diaminopentane, available under the tradename Dytek EP,
having the formula: 17
[0206] 1,3-diaminobutane having the formula: 18
[0207] Jeffamine EDR 148, a diamine having an alkyleneoxy backbone,
having the formula: 19
[0208] 3-methyl-3-aminoethyl-5-dimethyl-1-aminocyclohexane
(isophorone diamine) having the formula: 20
[0209] 1,3-bis(methylamino)cyclohexane having the formula: 21
[0210] Additional Detergent Components
[0211] The following are non-limiting examples of additional
detergent components (adjunct ingredients) useful in the bleach
systems, 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.
[0212] Builders--The bleach systems 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.
[0213] 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.
[0214] Inorganic or P-containing detergent builders include, but
are not limited to, the alkali metal, ammonium and alkanolammonium
salts of polyphosphates (exemplified by the tripolyphosphates,
pyrophosphates, and glassy polymeric meta-phosphates),
phosphonates, phytic acid, silicates, carbonates (including
bicarbonates and sesquicarbonates), sulphates, and
aluminosilicates. However, non-phosphate builders are required in
some locales. Importantly, the compositions herein function
surprisingly well even in the presence of the so-called "weak"
builders (as compared with phosphates) such as citrate, or in the
so-called "underbuilt" situation that may occur with zeolite or
layered silicate builders.
[0215] Examples of silicate builders are the alkali metal
silicates, particularly those having a SiO.sub.2:Na.sub.2O ratio in
the range 1.6:1 to 3.2:1 and layered silicates, such as the layered
sodium silicates described in U.S. Pat. No. 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-Na.sub.2SiO.sub.5
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 NaMSi.sub.xO.sub.2x+1.y H.sub.2O wherein M is
sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and
y is a number from 0 to 20, preferably 0 can be used herein.
Various other layered silicates from Hoechst include NaSKS-5,
NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms. As noted
above, the delta-Na.sub.2SiO.sub.5 (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.
[0216] Examples of carbonate builders are the alkaline earth and
alkali metal carbonates as disclosed in German Patent Application
No. 2,321,001 published on Nov. 15, 1973.
[0217] 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:
[M.sub.z(zAlO.sub.2).sub.y].xH.sub.2O
[0218] 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.
[0219] Useful aluminosilicate ion exchange materials are
commercially available. These aluminosilicates can be crystalline
or amorphous in structure and can be naturally-occurring
aluminosilicates or synthetically derived. A method for producing
aluminosilicate ion exchange materials is disclosed in U.S. Pat.
No. 3,985,669, Krummel et al, issued Oct. 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:
Na.sub.12[(AlO.sub.2).sub.12(SiO.sub.2).sub.12].xH.sub.2O
[0220] 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.
[0221] 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.
[0222] Included among the polycarboxylate builders are a variety of
categories of useful materials. One important category of
polycarboxylate builders encompasses the ether polycarboxylates,
including oxydisuccinate, as disclosed in U.S. Pat No. 3,128,287
Berg, issued Apr. 7, 1964, U.S. Pat. No. 3,635,830 Lamberti et al.,
issued Jan. 18, 1972, and U.S. Pat. No. 3,936,448 Lamberti, issued
Feb. 3, 1976. See also "TMS/TDS" builders of U.S. Pat. No.
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. Pat. No.
3,923,679 Rapko, issued Dec. 2, 1975; U.S. Pat. No. 4,158,635
Crutchfield et al., issued Jun. 19, 1979; U.S. Pat. No. 4,120,874
Crutchfield et al., issued Oct. 17, 1978; and U.S. Pat. No.
4,102,903 Crutchfield et al., issued Jul. 25, 1978.
[0223] 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.
[0224] 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.
[0225] Also suitable in the bleach systems of the present invention
are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related
compounds disclosed in U.S. Pat. No. 4,566,984, Bush, issued Jan.
28, 1986. Useful succinic acid builders include the
C.sub.5-C.sub.20 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, myristylsuccinate, palmitylsuccinate,
2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the
like. Laurylsuccinates are the preferred builders of this group,
and are described in European Patent Application
86200690.5/0,200,263, published Nov. 5, 1986.
[0226] Other suitable polycarboxylates are disclosed in U.S. Pat.
No. 4,144,226, Crutchfield et al., issued Mar. 13, 1979 and in U.S.
Pat. No. 3,308,067, Diehl, issued March 7, 1967. See also Diehl
U.S. Pat. No. 3,723,322.
[0227] Fatty acids, e.g., C.sub.12-C.sub.18 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.
[0228] In situations where phosphorus-based builders can be used,
and especially in the formulation of bars used for hand-laundering
operations, the various alkali metal phosphates such as the
well-known sodium tripolyphosphates, sodium pyrophosphate and
sodium orthophosphate can be used. Phosphonate builders such as
ethane-1-hydroxy-1,1-diphosphon- ate and other known phosphonates
(see, for example, U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021;
3,400,148 and 3,422,137) can also be used.
[0229] Chelating Agents--The bleach systems 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 aromatic chelating agents and mixtures
therein, all as hereinafter defined. Without intending to be bound
by theory, it is believed that the benefit of these materials is
due in part to their exceptional ability to remove iron and
manganese ions from washing solutions by formation of soluble
chelates.
[0230] Examples of suitable chelating agents and levels of use are
described in U.S. Pat. Nos. 5,576,282 and 5,728,671.
[0231] A preferred biodegradable chelator for use herein is
ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer
as described in U.S. Pat. No. 4,704,233, Nov. 3, 1987, to Hartman
and Perkins.
[0232] 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.
[0233] If utilized, these chelating agents will generally comprise
from about 0.1% by weight of the bleach systems herein to about
15%, more preferably 3.0% by weight of the bleach systems
herein.
[0234] Dye Transfer Inhibiting Agents--The bleach systems 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.
[0235] 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.
[0236] 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.
[0237] 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.
[0238] In another embodiment, the cross-linked polymers entrap dyes
by swelling.
[0239] Suitable cross-linked polymers are described in the
co-pending European patent application 94870213.9.
[0240] Addition of such polymers also enhances the performance of
the enzymes within the bleach systems herein.
[0241] 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.
[0242] When present in the bleach systems 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 bleach systems to about 10%, more preferably about 2%, most
preferably about 1% by weight of the bleach systems.
[0243] Dispersants--The bleach systems 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.
[0244] 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.
[0245] 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.
[0246] 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.
[0247] 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 0.025 g of sodium oleate in 30 ml of water
of 333 ppm CaCo.sub.3 (Ca:Mg=3:2) equivalent hardness.
[0248] Surfactants having good lime soap peptiser capability will
include certain amine oxides, betaines, sulfobetaines, alkyl
ethoxysulfates and ethoxylated alcohols.
[0249] Exemplary surfactants having a LSDP of no more than 8 for
use in accord with the present invention include C.sub.16-C.sub.18
dimethyl amine oxide, C.sub.12-C.sub.18 alkyl ethoxysulfates with
an average degree of ethoxylation of from 1-5, particularly
C.sub.12-C.sub.15 alkyl ethoxysulfate surfactant with a degree of
ethoxylation of amount 3 (LSDP=4), and the C.sub.14-C.sub.15
ethoxylated alcohols with an average degree of ethoxylation of
either 12 (LSDP=6) or 30, sold under the tradenames Lutensol A012
and Lutensol A030 respectively, by BASF GmbH.
[0250] 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).
[0251] 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.
[0252] Enzymes--The bleach systems can comprise in addition to the
amylase of the present invention one or more detergent enzymes
which provide cleaning performance and/or fabric care benefits.
Such enzymes can include proteases, amylases, cellulases and
lipases. They may be incorporated into the non-aqueous liquid
bleach systems herein in the form of suspensions, "marumes" or
"prills". Another suitable type of enzyme comprises those in the
form of slurries of enzymes in nonionic surfactants, e.g., the
enzymes marketed by Novo Nordisk under the tradename "SL" or the
microencapsulated enzymes marketed by Novo Nordisk under the
tradename "LDP." Suitable enzymes and levels of use are described
in U.S. Pat. No. 5,576,282.
[0253] 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.
[0254] 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,
.beta.-glucanases, arabinosidases, hyaluronidase, chondroitinase,
laccase, known amylases, mannanases, xyloglucanases and mixtures
thereof. A preferred combination is a bleach system having a
cocktail of conventional applicable enzymes like protease, lipase,
cutinase and/or cellulase in conjunction with the amylase of the
present invention.
[0255] Examples of such suitable enzymes are disclosed in U.S. Pat.
Nos. 5,576,282, 5,728,671 and 5,707,950
[0256] 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.RTM. 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.RTM., DURAZYM.RTM. and
SAVINASE.RTM. from Novo and MAXATASE.RTM., MAXACAL.RTM.,
PROPERASE.RTM. and MAXAPEM.RTM. (protein engineered Maxacal) from
Gist-Brocades. Proteolytic enzymes also encompass modified
bacterial serine proteases, such as those described in European
Patent Application Serial Number 87 303761.8, filed Apr. 28, 1987
(particularly pages 17, 24 and 98), and which is called herein
"Protease B", and in European Patent Application 199,404, Venegas,
published Oct. 29, 1986, which refers to a modified bacterial
serine protealytic enzyme which is called "Protease A" herein. More
preferred is what is called herein "Protease C", which is a variant
of an alkaline serine protease from Bacillus in which lysine
replaced arginine at position 27, tyrosine replaced valine at
position 104, serine replaced asparagine at position 123, and
alanine replaced threonine at position 274. Protease C is described
in EP 90915958:4, corresponding to WO 91/06637, Published May 16,
1991. Genetically modified variants, particularly of Protease C,
are also included herein. See also a high pH protease from Bacillus
sp. NCIMB 40338 described in WO 93/18140 A to Novo. Enzymatic
detergents comprising protease, one or more other enzymes, and a
reversible protease inhibitor are described in WO 92/03529 A to
Novo. When desired, a protease having decreased adsorption and
increased hydrolysis is available as described in WO 95/07791 to
Procter & Gamble. A recombinant trypsin-like protease for
detergents suitable herein is described in WO 94/25583 to Novo.
[0257] In more detail, the protease referred to as "Protease D" is
a carbonyl hydrolase variant having an amino acid sequence not
found in nature, which is derived from a precursor carbonyl
hydrolase by substituting a different amino acid for a plurality of
amino acid residues at a position in said carbonyl hydrolase
equivalent to position +76, preferably also in combination with one
or more amino acid residue positions equivalent to those selected
from the group consisting of +99, +101, +103, +104, +107, +123,
+27, +105, +109, +126, +128, +135, +156, +166, +195 , +197, +204,
+206, +210, +216, +217, +218, +222, +260, +265, and/or 274 of
Bacillus amyloliquefaciens subtilisin, as described in WO 95/10615
published Apr. 20, 1995 by Genencor International. Also suitable
for the present invention are proteases described in patent
applications EP 251 446 and WO91/06637 and protease BLAP.RTM.
described in WO91/02792. The proteolytic enzymes are incorporated
in the bleach systems 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.
[0258] Useful proteases are also described in PCT publications: WO
95/30010 published Nov. 9, 1995 by The Procter & Gamble
Company; WO 95/30011 published Nov. 9, 1995 by The Procter &
Gamble Company; WO 95/29979 published Nov. 9, 1995 by The Procter
& Gamble Company.
[0259] Other particularly useful proteases are multiply-substituted
protease variants comprising a substitution of an amino acid
residue with another naturally occurring amino acid residue at an
amino acid residue position corresponding to position 103 of
Bacillus amyloliquefaciens subtilisin in combination with a
substitution of an amino acid residue with another naturally
occurring amino acid residue at one or more amino acid 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.
[0260] More preferably the protease variant includes a substitution
set selected from the group consisting of:
1 12/76/103/104/130/222/245/261;
62/103/104/159/232/236/245/248/252; 62/103/104/159/213/232/236/24-
5/248/252; 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; 68/103/104/159/183/232/23-
6/245/248/252; 68/103/104/159/185/232/236/245/248/252;
68/103/104/159/185/210/232/236/245/248/252;
68/103/104/159/210/232/236/245/248/252; 68/103/104/159/213/232/23-
6/245; 98/103/104/159/232/236/245/248/252;
98/102/103/104/159/212/232/236/245/248/252;
101/103/104/159/232/236/245/248/252; 102/103/104/159/232/236/245/-
248/252; 103/104/159/230/236/245; 103/104/159/232/236/245/-
248/252; 103/104/159/217/232/236/245/248/252;
103/104/130/159/232/236/245/248/252; 103/104/131/159/232/236/245/-
248/252; 103/104/159/213/232/236/245/248/252; and
103/104/159/232/236/245.
[0261] Still even more preferably the protease variant includes a
substitution set selected from the group consisting of:
2 12R/76D/103A/104T/130T/222S/245R/261D;
62D/103A/104I/159D/232V/236H/245R/248D/252K;
62D/103A/104I/159D/213R/232V/236H/245R/248D/252K;
68A/103A/104I/159D/209W/232V/236H/245R; 68A/76D/103A/104I/159D/21-
3R/232V/236H/245R/260A; 68A/103A/104I/159D/213E/232V/236H/245R/248-
D/252K; 68A/103A/104I/159D/183D/232V/236H/245R/248D/252K;
68A/103A/104I/159D/232V/236H/245R; 68A/103A/104I/159D/230V/232V/2-
36H/245R; 68A/103A/104I/159D/232V/236H/245R/257V;
68A/103A/104I/159D/213G/232V/236H/245R/248D/252K;
68A/103A/104I/159D/185D/232V/236H/245R/248D/252K;
68A/103A/104I/159D/185D/210L/232V/236H/245R/248D/252K;
68A/103A/104I/159D/210L/232V/236H/245R/248D/252K;
68A/103A/104I/159D/213G/232V/236H/245R; 98L/103A/104I/159D/232V/2-
36H/245R/248D/252K; 98L/102A/103A/104I/159D/212G/232V/236H/245R/24-
8D/252K; 101G/103A/104I/159D/232V/236H/245R/248D/252K;
102A/103A/104I/159D/232V/236H/245R/248D/252K;
103A/104I/159D/230V/236H/245R; 103A/104I/159D/232V/236H/245R/248D-
/252K; 103A/104I/159D/217E/232V/236H/245R/248D/252K;
103A/104I/130G/159D/232V/236H/245R/248D/252K;
103A/104I/131V/159D/232V/236H/245R/248D/252K;
103A/104I/159D/213R/232V/236H/245R/248D/252K; and
103A/104I/159D/232V/236H/245R.
[0262] Most preferably the protease variant includes the
substitution set 101/103/104/159/232/236/245/248/252, preferably
101G/103A/104I/159D/232V/- 236H/245R/248D/252K.
[0263] 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. Pat. No. 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.
[0264] Examples of such cellulases are cellulases produced by a
strain of Humicola insolens (Humicola grisea var. thermoidea),
particularly the Humicola strain DSM 1800.
[0265] Other suitable cellulases are cellulases originated from
Humicola insolens having a molecular weight of about 50 KDa, an
isoelectric point of 5.5 and containing 415 amino acids; and a
.sup.-43 kD 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 WO94/21801, Genencor,
published Sep. 29, 1994. Especially suitable cellulases are the
cellulases having color care benefits. Examples of such cellulases
are cellulases described in European patent application No.
91202879.2, filed Nov. 6, 1991 (Novo). Carezyme and Celluzyme (Novo
Nordisk A/S) are especially useful. See also WO91/17243.
[0266] Peroxidase enzymes are known in the art, and include, for
example, horseradish peroxidase, ligninase and haloperoxidase such
as chloro- and bromo-peroxidase. Peroxidase-containing bleach
systems are disclosed, for example, in U.S. Pat. Nos. 5,576,282,
5,728,671 and 5,707,950, PCT International Applications WO
89/099813, WO89/09813 and in European Patent application EP No.
91202882.6, filed on Nov. 6, 1991 and EP No. 96870013.8, filed Feb.
20, 1996. Also suitable is the laccase enzyme.
[0267] Preferred enhancers are substituted phenthiazine and
phenoxasine 10-Phenothiazinepropionicacid (PPT),
10-ethylphenothiazine-4-carboxylic acid (EPC),
10-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.
[0268] Said peroxidases are normally incorporated in the bleach
system at levels from 0.0001% to 2% of active enzyme by weight of
the bleach system.
[0269] Other preferred enzymes that can be included in the bleach
systems of the present invention include lipases. Suitable lipase
enzymes for detergent usage include those produced by
microorganisms of the Pseudomonas group, such as Pseudomonas
stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034.
Suitable lipases include those which show a positive immunological
cross-reaction with the antibody of the lipase, produced by the
microorganism Pseudomonas fluorescent IAM 1057. This lipase is
available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under
the trade name Lipase P "Amano," hereinafter referred to as
"Amano-P". Other suitable commercial lipases include Amano-CES,
lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan;
Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A.
and Disoynth Co., The Netherlands, and lipases ex Pseudomonas
gladioli. Especially suitable lipases are lipases such as M1
LIPASE.RTM. and LIPOMAX.RTM. (Gist-Brocades) and LIPOLASE.RTM. and
LIPOLASE ULTRA.RTM. (Novo) which have found to be very effective
when used in combination with the compositions of the present
invention.
[0270] 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 bleach
systems have been described in e.g. WO 88/09367 (Genencor).
[0271] The lipases and/or cutinases are normally incorporated in
the bleach system at levels from 0.0001% to 2% of active enzyme by
weight of the bleach system.
[0272] Known amylases (.alpha. and/or .beta.) can be included for
removal of carbohydrate-based stains. WO 94/02597, Novo Nordisk A/S
published Feb. 03, 1994, describes cleaning compositions which
incorporate mutant amylases. See also WO94/18314, Genencor,
published Aug. 18, 1994 and WO95/10603, Novo Nordisk A/S, published
Apr. 20, 1995. Other amylases known for use in bleach systems
include both .alpha.- and .beta.-Amylases. .alpha.-Amylases are
known in the art and include those disclosed in U.S. Pat. No.
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.RTM. described in WO 94/18314, published
Aug. 18, 1994 and WO96/05295, Genencor, published Feb. 22, 1996 and
amylase variants from Novo Nordisk A/S, disclosed in WO 95/10603,
published April 95.
[0273] Examples of commercial o-amylases products are
TERMAMYL.RTM., BAN.RTM., FUNGAMYL.RTM. and DURAMYL.RTM., all
available from Novo Nordisk A/S Denmark. WO95/26397 describes other
suitable amylases: .alpha.-amylases characterized by having a
specific activity at least 25% higher than the specific activity of
TERMAMYL.RTM. at a temperature range of 25.degree. C. to 55.degree.
C. and at a pH value in the range of 8 to 10, measured by the
Phadebas.RTM. .alpha.-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 WO95/35382.
[0274] 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:
.beta.-mannosidase, EC 3.2.1.78: Endo-1,4-.beta.-mannosidase,
referred therein after as "mannanase" and EC 3.2.1.100:
1,4-.beta.-mannobiosidase and mixtures thereof. (IUPAC
Classification-Enzyme nomenclature, 1992 ISBN 0-12-227165-3
Academic Press).
[0275] More preferably, the treating compositions of the present
invention, when a mannanase is present, comprise a
.beta.-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.
[0276] 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 .beta.-1,4-linked
mannose; glucomannans are polysaccharides having a backbone or more
or less regularly alternating .beta.-1,4 linked mannose and
glucose; galactomannans and galactoglucomannans are mannans and
glucomannans with .alpha.-1,6 linked galactose sidebranches. These
compounds may be acetylated.
[0277] 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 .alpha.-galactosidase and/or mannan acetyl esterases can be
further degraded to release free maltose by .beta.-mannosidase
and/or .beta.-glucosidase.
[0278] 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 pI of 4.8. JP-03047076 discloses a beta-mannanase
derived from Bacillus sp., having a molecular weight of 373 kDa
measured by gel filtration, an optimum pH of 8-10 and a pI of
5.3-5.4. JP-63056289 describes the production of an alkaline,
thermostable beta-mannanase which hydrolyses
beta-1,4-D-mannopyranoside bonds of e.g. mannans and produces
manno-oligosaccharides. JP-63036774 relates to the Bacillus
microorganism FERM P-8856 which produces beta-mannanase and
beta-mannosidase at an alkaline pH. JP-08051975 discloses alkaline
beta-mannanases from alkalophilic Bacillus sp. AM-001. A purified
mannanase from Bacillus amyloliquefaciens useful in the bleaching
of pulp and paper and a method of preparation thereof is disclosed
in WO 97/11164. WO 91/18974 describes a hemicellulase such as a
glucanase, xylanase or mannanase active at an extreme pH and
temperature. WO 94/25576 discloses an enzyme from Aspergillus
aculeatus, CBS 101.43, exhibiting mannanase activity which may be
useful for degradation or modification of plant or algae cell wall
material. WO 93/24622 discloses a mannanase isolated from
Trichoderna reseei useful for bleaching lignocellulosic pulps. An
hemicellulase capable of degrading mannan-containing hemicellulose
is described in WO91/18974 and a purified mannanase from Bacillus
amyloliquefaciens is described in WO097/11164.
[0279] 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 the co-pending Danish patent application
No. PA 1998 01340.
[0280] 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.
[0281] The alkaline mannanase from Bacillus agaradhaerens NICMB
40482 is described in the co-pending U.S. patent application Ser.
No. 09/111,256. More specifically, this mannanase is:
[0282] i) a polypeptide produced by Bacillus agaradhaerens, NCIMB
40482; or
[0283] 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
application Ser. No. 09/111,256; or
[0284] 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.
[0285] Also encompassed is the corresponding isolated polypeptide
having mannanase activity selected from the group consisting
of:
[0286] (a) polynucleotide molecules encoding a polypeptide having
mannanase activity and comprising a sequence of nucleotides as
shown in SEQ ID NO: 1 from nucleotide 97 to nucleotide 1029 as
shown in U.S. patent application Ser. No. 09/111,256;
[0287] (b) species homologs of (a);
[0288] (c) polynucleotide molecules that encode a polypeptide
having mannanase activity that is at least 70% identical to the
amino acid sequence of SEQ ID NO: 2 from amino acid residue 32 to
amino acid residue 343 as shown in U.S. patent application Ser. No.
09/111,256;
[0289] (d) molecules complementary to (a), (b) or (c); and
[0290] (e) degenerate nucleotide sequences of (a), (b), (c) or
(d).
[0291] The plasmid pSJ1678 comprising the polynucleotide molecule
(the DNA sequence) encoding said mannanase has been transformed
into a strain of the Escherichia coli which was deposited by the
inventors according to the Budapest Treaty on the International
Recognition of the Deposit of Microorganisms for the Purposes of
Patent Procedure at the Deutsche Sammlung von Mikroorganismen und
Zellkulturen GmbH, Mascheroder Weg 1b, D-38124 Braunschweig,
Federal Republic of Germany, on 18 May 1998 under the deposition
number DSM 12180.
[0292] A second more preferred enzyme is the mannanase from the
Bacillus subtilis strain 168, which is described in the co-pending
U.S. patent application Ser. No. 09/095,163. More specifically,
this mannanase is:
[0293] i) is encoded by the coding part of the DNA sequence shown
in SED ID No. 5 shown in the U.S. patent application Ser. No.
09/095,163 or an analogue of said sequence; and/or
[0294] ii) a polypeptide comprising an amino acid sequence as shown
SEQ ID NO:6 shown in the U.S. patent application Ser. No.
09/095,163; or
[0295] iii) an analogue of the polypeptide defined in ii) which is
at least 70% homologous with said polypeptide, or is derived from
said polypeptide by substitution, deletion or addition of one or
several amino acids, or is immunologically reactive with a
polyclonal antibody raised against said polypeptide in purified
form.
[0296] Also encompassed in the corresponding isolated polypeptide
having mannanase activity selected from the group consisting
of:
[0297] (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 application Ser.
No. 09/095,163
[0298] (b) species homologs of (a);
[0299] (c) polynucleotide molecules that encode a polypeptide
having mannanase activity that is at least 70% identical to the
amino acid sequence of SEQ ID NO: 6 as shown in the U.S. patent
application Ser. No. 09/095,163;
[0300] (d) molecules complementary to (a), (b) or (c); and
[0301] (e) degenerate nucleotide sequences of (a), (b), (c) or
(d).
[0302] A third more preferred mannanase is described in the
co-pending Danish patent application No. PA 1998 01340. More
specifically, this mannanase is:
[0303] i) a polypeptide produced by Bacillus sp. I633;
[0304] ii) a polypeptide comprising an amino acid sequence as shown
in positions 33-340 of SEQ ID NO:2 as shown in the Danish
application No. PA 1998 01340; or
[0305] 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 inununologically reactive with a
polyclonal antibody raised against said polypeptide in purified
form.
[0306] Also encompassed is the corresponding isolated
polynucleotide molecule selected from the group consisting of:
[0307] (a) polynucleotide molecules encoding a polypeptide having
mannanase activity and comprising a sequence of nucleotides as
shown in SEQ ID NO: 1 from nucleotide 317 to nucleotide 1243 the
Danish application No. PA 1998 01340;
[0308] (b) species homologs of (a);
[0309] (c) polynucleotide molecules that encode a polypeptide
having mannanase activity that is at least 65% identical to the
amino acid sequence of SEQ ID NO: 2 from amino acid residue 33 to
amino acid residue 340 the Danish application No. PA 1998
01340;
[0310] (d) molecules complementary to (a), (b) or (c); and
[0311] (e) degenerate nucleotide sequences of (a), (b), (c) or
(d).
[0312] The plasmid pBXM3 comprising the polynucleotide molecule
(the DNA sequence) encoding a mannanase of the present invention
has been transformed into a strain of the Escherichia coli which
was deposited by the inventors according to the Budapest Treaty on
the International Recognition of the Deposit of Microorganisms for
the Purposes of Patent Procedure at the Deutsche Sammlung von
Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg 1b, D-38124
Braunschweig, Federal Republic of Germany, on 29 May 1998 under the
deposition number DSM 12197.
[0313] A fourth more preferred mannanase is described in the Danish
co-pending patent application No. PA 1998 01341. More specifically,
this mannanase is:
[0314] i) a polypeptide produced by Bacillus sp. AAI 12;
[0315] ii) a polypeptide comprising an amino acid sequence as shown
in positions 25-362 of SEQ ID NO:2as shown in the Danish
application No. PA 1998 01341; or
[0316] 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 arnino acids, or is immunologically reactive with a
polyclonal antibody raised against said polypeptide in purified
form.
[0317] Also encompassed is the corresponding isolated
polynucleotide molecule selected from the group consisting of
[0318] (a) polynucleotide molecules encoding a polypeptide having
mannanase activity and comprising a sequence of nucleotides as
shown in SEQ ID NO: 1 from nucleotide 225 to nucleotide 1236 as
shown in the Danish application No. PA 1998 01341;
[0319] (b) species homologs of (a);
[0320] (c) polynucleotide molecules that encode a polypeptide
having mannanase activity that is at least 65% identical to the
amino acid sequence of SEQ ID NO: 2 from amino acid residue 25 to
amino acid residue 362 as shown in the Danish application No. PA
1998 01341;
[0321] (d) molecules complementary to (a), (b) or (c); and
[0322] (e) degenerate nucleotide sequences of (a), (b), (c) or
(d).
[0323] 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 International Recognition of the Deposit of Microorganisms for
the Purposes of Patent Procedure at the Deutsche Sammlung von
Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg 1b, D-38124
Braunschweig, Federal Republic of Germany, on 7 Oct. 1998 under the
deposition number DSM 12433.
[0324] 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-.beta.-D-glycosidic linkages present in any
cellulosic material, such as cellulose, cellulose derivatives,
lichenin, .beta.-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 .mu.mol reducing
sugar/min from a glucan substrate, the glucan substrate being,
e.g., CMC (CMCU), acid swollen Avicell (AVIU), xyloglucan (XGU) or
cereal .beta.-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 defmed as units/mg of
protein.
[0325] Suitable are enzymes exhibiting as its highest activity XGU
endoglucanase activity (hereinafter "specific for xyloglucan"),
which enzyme:
[0326] i) is encoded by a DNA sequence comprising or included in at
least one of the following partial sequences
3 (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) (l) 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
(SEQ ID NO:17) 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 or (r) CAGCATCTCC
ATTGAGTAAT CACGTTGGTG (SEQ ID NO:18) 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
[0327] or a sequence homologous thereto encoding a polypeptide
specific for xyloglucan with endoglucanase activity,
[0328] 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.
[0329] More specifically, as used herein the term "specific for
xyloglucan" means that the endoglucanse enzyme exhibits its highest
endoglucanase activity on a xyloglucan substrate, and preferably
less than 75% activity, more preferably less than 50% activity,
most preferably less than about 25% activity, on other
cellulose-containing substrates such as carboxymethyl cellulose,
cellulose, or other glucans.
[0330] 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 .beta.-glucan activity (XGU tBGU),
xyloglucan to carboxy methyl cellulose activity (XGU tCMCU), or
xyloglucan to acid swollen Avicell activity (XGU/AVIU), which is
preferably greater than about 50, such as 75, 90 or 100.
[0331] 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
5.times.SSC and prehybridizing for 1 h at -40.degree. C. in a
solution of 5.times.SSC, 5.times. Denhardt's solution, and 50 .mu.g
of denatured sonicated calf thymus DNA, followed by hybridization
in the same solution supplemented with 50 .mu.Ci 32-P-dCTP labeled
probe for 18 h at -40.degree. C. and washing three times in
2.times.SSC, 0.2% SDS at 40.degree. 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.
[0332] 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.
[0333] Furthermore, the endoglucanase specific for xyloglucan is
preferably substantially devoid of activity towards .beta.-glucan
and/or exhibits at the most 25% such as at the most 10% or about
5%, activity towards carboxymethyl cellulose and/or Avicell when
the activity towards xyloglucan is 100%. In addition, endoglucanase
specific for xyloglucan of the invention is preferably
substantially devoid of transferase activity, an activity which has
been observed for most endoglucanases specific for xyloglucan of
plant origin.
[0334] 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.
[0335] The xyloglucanase, when present, is incorporated into the
treating compositions of the invention preferably at a level of
from 0.0001% to 2%, more preferably from 0.0005% to 0.1%, most
preferred from 0.001% to 0.02% pure enzyme by weight of the
composition.
[0336] 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.
[0337] Said enzymes are normally incorporated in the bleach system
at levels from 0.0001% to 2% of active enzyme by weight of the
bleach system. 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).
[0338] Other suitable detergent ingredients that can be added are
enzyme oxidation scavengers. Examples of such enzyme oxidation
scavengers are ethoxylated tetraethylene polyamines.
[0339] A range of enzyme materials and means for their
incorporation into synthetic bleach systems is also disclosed in WO
93/07263 and WO 93/07260 to Genencor International, WO 89/08694 to
Novo, and U.S. Pat. No. 3,553,139, Jan. 5, 1971 to McCarty et al.
Enzymes are further disclosed in U.S. Pat. No. 4,101,457, Place et
al, Jul. 18, 1978, and in U.S. Pat. No. 4,507,219, Hughes, Mar. 26,
1985. Enzyme materials useful for liquid detergent formulations,
and their incorporation into such formulations, are disclosed in
U.S. Pat. No. 4,261,868, Hora et al, Apr. 14, 1981.
[0340] Enzyme Stabilizers--Enzymes for use in detergents can be
stabilized by various techniques. Enzyme stabilization techniques
are disclosed and exemplified in U.S. Pat. No. 3,600,319, Aug. 17,
1971, Gedge et al, EP 199,405 and EP 200,586, Oct. 29, 1986,
Venegas. Enzyme stabilization systems are also described, for
example, in U.S. Pat. No. 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.
[0341] Other Detergent Ingredients--The bleach systems 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. Pat. No.
5,576,282.
[0342] 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 bleach system set
forth above prior to washing such fabrics using conventional
aqueous washing solutions. Preferably, the bleach system 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 1 to 180 minutes.
[0343] 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.
[0344] In the following examples some abbreviations known to those
of ordinary skill in the art are used, consistent with the
disclosure set forth herein.
EXAMPLE I
[0345] Bleaching detergent compositions having the form of granular
laundry detergents are exemplified by the following
formulations.
4 A B C D E Organic Catalyst* 0.034 0.06 0.03 0.10 0.05
Conventional Activator 2.00 2.80 2.00 1.80 5.30 (NOBS) Conventional
Activator 0.00 0.00 0.60 0.00 0.00 (TAED) 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 0.00 2.00 0.00 2.00 0.00 N-Oxide C12 Coco Amidopropyl
1.50 0.00 1.50 0.00 0.00 Betaine Palm N-Methyl 1.70 2.00 1.70 2.00
0.00 Glucamide C12 1.50 0.00 1.50 0.00 0.00 Dimethylhydroxyethyl-
ammonium 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 25.00 25.00 15.00 15.00 25.00
Tripolyphosphate Acrylic Acid/ 0.00 0.00 0.00 0.00 1.00 Maleic Acid
Copolymer Polyacrylic Acid, 3.00 3.00 3.00 3.00 0.00 partially
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
Sulfonated Zinc 0.50 0.00 0.25 0.00 0.00 Phthalocyanine Photobleach
MgSO.sub.4 2.20 2.20 2.20 2.20 0.64 Na.sub.2SO.sub.4 balance
balance balance balance balance *Organic catalyst can be any of the
cationic organic catalysts described herein, preferably it is an
iminium-based organic catalyst, more preferably it is a
dihydroisoquinolinium-based organic catalyst.
[0346] Any of the above compositions can be used to launder fabrics
at a concentration of 3500 ppm in water, 25.degree. 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 II
[0347] Bleaching detergent compositions having the form of granular
laundry detergents are exemplified by the following
formulations.
5 A B C D E Organic Catalyst* 0.009 0.04 0.14 0.14 0.002
Conventional Activator (NOBS) 1.80 0.00 0.00 1.00 1.00 Conventional
Activator (TAED) 0.00 1.00 2.50 3.00 0.00 Sodium Percarbonate 5.30
0.00 0.00 0.00 0.00 Sodium Perborate Monohydrate 0.00 9.00 17.60
9.00 9.00 Linear Alkylbenzenesulfonate 21.00 12.00 0.00 12.00 12.00
C45AE0.6S 0.00 0.00 15.00 0.00 0.00 C2 Dimethylamine N-Oxide 0.00
0.00 2.00 0.00 0.00 C12 Coco Amidopropyl Betaine 0.00 1.50 0.00
1.50 1.50 Palm N-Methyl Glucamide 0.00 1.70 2.00 1.70 1.70 C12 1.00
1.50 0.00 1.50 1.50 Dimethylhydroxyethylammonium 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 Polyacrylic Acid,
partially neutralized 0.00 3.00 3.00 3.00 3.00 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 MgSO.sub.4 0.64 0.00 2.20 0.00 0.00
Na.sub.2SO.sub.4 balance balance balance balance balance *Organic
catalyst can be any of the cationic organic catalysts described
herein, preferably it is an iminium-based organic catalyst, more
preferably it is a dihydroisoquinolinium-based organic
catalyst.
[0348] Any of the above compositions can be used to launder fabrics
at a concentration of 3500 ppm in water, 25.degree. 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 III
[0349] A bleaching detergent powder in accordance with the present
invention comprises the following ingredients:
6 Component Weight % Organic Catalyst* 0.01 NOBS 2.0 Sodium
Perborate Tetrahydrate 10 C.sub.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% *Organic catalyst can be any of the cationic
organic catalysts described herein, preferably it is an
iminium-based organic catalyst, more preferably it is a
dihydroisoquinolinium-based organic catalyst.
EXAMPLE IV
[0350] A laundry bar suitable for hand-washing soiled fabrics is
prepared by standard extrusion processes and comprises the
following:
7 Component Weight % Organic Catalyst* 0.02 NOBS 1.7 TAED 0.2
Sodium Perborate Tetrahydrate 12 C.sub.12 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 CaSO.sub.4 1
MgSO.sub.4 1 Water 4 Filler.sup.2 Balance to 100% *Organic catalyst
can be any of the cationic organic catalysts described herein,
preferably it is an iminium-based organic catalyst, more preferably
it is a dihydroisoquinolinium-based organic catalyst. .sup.2Can be
selected from convenient materials such as CaCO.sub.3 ,talc, clay,
silicates, and the like. Acidic fillers can be used to reduce
pH.
EXAMPLE V
[0351] A laundry detergent composition suitable for machine use is
prepared by standard methods and comprises the following
composition:
8 Component Weight % Organic Catalyst* 0.3 TAED 10.0 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 Processing aid 0.10 Miscellaneous 0.43 Water Balance
*Organic catalyst can be any of the cationic organic catalysts
described herein, preferably it is an iminium-based organic
catalyst, more preferably it is a dihydroisoquinolinium-based
organic catalyst.
[0352] The composition can be used to launder fabrics at a
concentration in solution of about 1000 ppm at a temperature of
20-40.degree. C. and a water to fabric ratio of about 20:1.
EXAMPLE VI
[0353]
9 Component Weight % Organic Catalyst* 0.082 NOBS 7.20 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 Miscellaneous 2.95 Water Balance *Organic
catalyst can be any of the cationic organic catalysts described
herein, preferably it is an iminium-based organic catalyst, more
preferably it is a dihydroisoquinolinium-based organic
catalyst.
[0354] The composition can be used as a laundry auxiliary for
laundering fabrics at a concentration in solution of about 850 ppm
at a temperature of 5-50.degree. C. and a water to fabric ratio of
about 20:1.
EXAMPLE VII
[0355] A bleaching composition suitable for use in high suds
phosphate geographies has the formula:
10 Component A (% wt) B (% wt) Organic Catalyst* 0.02 0.018 NOBS
1.90 2.00 Sodium Perborate Tetrahydrate 2.25 3.00 Sodium Carbonate
13.00 13.00 Anionic surfactant 19.00 19.00 Cationic surfactant 0.60
0.60 Nonionic surfactant -- 0.40 Sodium Tripolyphosphate 22.50
22.50 Diethylenetriaminepentacetic acid 0.90 0.90 Acrylic
acid/Maleic acid copolymer 0.90 0.90 Carboxymethylcellulose 0.40
0.40 Protease 0.70 0.70 Amylase 0.36 0.36 Cellulase 0.35 0.35
Brightener 0.16 0.18 Magnesium sulfate 0.70 0.70 Water 3.0 1.0
Sodium sulfate Balance Balance *Organic catalyst can be any of the
cationic organic catalysts described herein, preferably it is an
iminium-based organic catalyst, more preferably it is a
dihydroisoquinolinium-based organic catalyst.
[0356] 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.
[0357] 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. Pat. Nos. 5,691,297;
5,574,005; 5,569,645; 5,565,422; 5,516,448; 5,489,392; and
5,486,303.
[0358] 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. Pat. 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.
[0359] 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.
Sequence CWU 1
1
18 1 21 DNA Aspergillus aculeatus 1 attcatttgt ggacagtgga c 21 2 20
DNA Aspergillus aculeatus 2 gttgatcgca cattgaacca 20 3 20 DNA
Aspergillus aculeatus 3 accccagccg accgattgtc 20 4 20 DNA
Aspergillus aculeatus 4 cttccttacc tcaccatcat 20 5 20 DNA
Aspergillus aculeatus 5 ttaacatctt ttcaccatga 20 6 20 DNA
Aspergillus aculeatus 6 agctttccct tctctccctt 20 7 28 DNA
Aspergillus aculeatus 7 gccaccctgg cttccgctgc cagcctcc 28 8 20 DNA
Aspergillus aculeatus 8 gacagtagca atccagcatt 20 9 20 DNA
Aspergillus aculeatus 9 agcatcagcc gctttgtaca 20 10 20 DNA
Aspergillus aculeatus 10 ccatgaagtt caccgtattg 20 11 20 DNA
Aspergillus aculeatus 11 gcactgcttc tctcccaggt 20 12 20 DNA
Aspergillus aculeatus 12 gtgggcggcc cctcaggcaa 20 13 20 DNA
Aspergillus aculeatus 13 acgctcctcc aattttctct 20 14 19 DNA
Aspergillus aculeatus 14 ggctggtagt aatgagtct 19 15 20 DNA
Aspergillus aculeatus 15 ggcgcagagt ttggccaggc 20 16 21 DNA
Aspergillus aculeatus 16 caacatcccc ggtgttctgg g 21 17 347 DNA
Aspergillus aculeatus 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 18 294 DNA Aspergillus aculeatus 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
* * * * *