Note: Descriptions are shown in the official language in which they were submitted.
21~7658
WO 94/10284 PCI`/US93/09930
GRANULAR DETERGENTS W~TH PROTEASE ÉNZYME AND BLEACH
TECHNICAL FIELD
The present invention relates to granular detergent
compositions comprising certain levels of bleaching agent,
protease enzyme, and detergent surfactant. The bleaching agent is
substantially water-insoluble organic peroxyacid or a combination
of certain bleach activators and peroxygen bleaching compound
capable of yielding hyJ.Ggen peroxide.
BACKGROUND OF THE ~NVENTION
It has been found that certain levels of substantially
water-insoluble peroxyacid bleaches, and/or bleach
activators/peroxygen bleaching compounds, can be used with certain
levels of protease enzyme ln granular detergent compositions to
obtain surprisingly effecttve cleaning. The combined effect of
the peroxyacid, which bleaches, and the protease, which hydrolyzes
protein based stains, is greater in this granular detergent
composition than expected, especially in light of the fact that
bleach is known to oxidize enzymes. ~ithout meaning to be bound
by theory, it is believed that at these levels, there is a synergy
between the peroxyacid and the protease so that the combined
cleaning effect of the two is greater than the additive effect of
each one separately.
EP O 359 087~ publlshed March 21, 1990, describes an
activated oxidant system for in situ generatlon of peracid in
aqueous media comprising protease and a specified ester substrate,
along with a source of peroxygen.
WO 94/10284 PCI`/US~3/0993
21~7658 - 2 -
U.S. Patent 3,974, 082, Weyn, issued August 10, 1976,
describes a bleaching composition and method utilizing a
percompound, an acyl-alkyl ester, and an ester-hydrolyzing enzyme.
SUMMARY OF THE INVENTION
This invention relates to granular detergent compositions
which provide especially effective surface cleaning of textiles.
This invention also relates to methods for cleaning fabrics using
such detergent compositions.
The granular detergent compositions of this invention
comprise:
a) a bleaching agent which either is from 0.5% to 20% of an
organic peroxyacid or is a combination of from 0.5% to
20% of a bleach activator and a peroxygen compound
capable of yielding hydrogen peroxide that can react
with the activator to form an organic peroxyacid in situ
in a bleaching solution formed from the composition;
b) from about 0.064 to about 0.64 mg of active protease
enzyme per gram of composition wherein the protease
enzyme is present in an amount sufficient to provide a
- ratio of mg of active protease per 100 grams of
composition to ppm theoretical Available 2 Of the
peroxyacid ranging from about 1:1 to about 20:1; and
c) from about lX to about 40% by weight of the composition
of a detergent surfactant which can be anionic,
nonionic, ampholytic or zwitterionic surfactants or
combinations thereof.
The peracid which is in the composition, or which is formed
by the combination of activator and peroxygen compound, has a
corresponding carboxylic acid that has a Hydrophobic-Lipophilic
Balance value which ranges from about 3 to about 6.5. When the
composition utilizes a combination of activator and peroxygen
compound, the molar ratio of hydrogen peroxide yielded by the
peroxygen compound to the activator is greater than about 1.5.
Furthermore, when such an activator/peroxygen compound combination
is utilized, the activator can have the formula:
2147658
WO 94/10284 PCI`/US93/09930
- 3 -
(I) 0
Il
R - C - L;
(II) R5 0 0
l 11 11
R1 - N - C - R2 - C - L; or
(III) R5 0
Il l 11
R1 - C - N - R2 - C - L;
wherein R is an alkyl group containing from about 5 to about 18
carbon atoms wherein the longest linear alkyl chain extending from
and including the carbonyl carbon contains from about 6 to about
10 carbon atoms; Rl is an alkyl group containing from about 6 to
about 12 carbon atoms; R2 is an alkylene containing from 1 to
about 6 carbon atoms; R5 is H or alkyl, aryl, or alkaryl
containing from about 1 to about lC carbon atoms; and L is a
leaving group, the conjugate acid of which has a PKa in the range
of from about 6 to about 13.
DETAILED DESCRIPTION OF THE INVENTION
The granular detergent compositions herein (see above
summary) are preferably nonphosphate granular (powder) laundry
detergents which contain both bleach and enzyme for good cleaning
of soiled laundry. For purposes of this invention, the term
"granular" refers to detergent compositions in any suitable solid
form, e.g., granules, powders, agglomerates, laundry bars, etc.
Granular laundry detergent compositions herein provide
effective and efficient surface cleaning of textiles, particularly
grass stains, over a wide range of laundry washing temperatures.
Laundry wash solutions are preferably at temperatures between
about 5-C and about 80-C, preferably between about 10-C and about
60-C, for this cleaning benefit.
A. Bleachinq Aqent
The granular detergent compositions herein contain a
bleaching agent, which preferably comprises from about 0.5 to
WO 94~10284 PCI'/US93/0993
21~7658 4.
about 20 wt.% of the;det~ergent composition. The bleaching agent
is either a substantially insoluble, preferably solid, organic
peroxyacid, or a bleach activator and a peroxygen bleaching
compound capable of yielding hydrogen peroxide, or a combination
of both.
1. Bleach Activator and PeroxYqen Bleaching ComDound
The bleach activator has the following structure:
o
Il
R - C - L
wherein R is an alkyl group containing from about 5 to about 18
carbon atoms wherein the longest linear alkyl chain extending from
and including the carbonyl carbon contains from about 6 to about
10 carbon atoms and L is a leaving group, the conjugate acid of
which has a Pka in the range of from about 6 to about 13,
preferably from about 7 to about 11, most preferably from about 8
to about 11.
L can be essentially any suitable leaving group. A leaving
group is any group that is displaced from the bleach activator as
a consequence of the nucleophilic attack on the bleach activator
by the perhydroxide anion. This, the perhydrolysis reaction,
results in the formation of the percarboxylic acid. Generally,
for a group to be a suitable leaving group it must exert an
electron attracting effect. This facilitates the nucleophilic
attack by the perhydroxide anion.
The L group must be sufficiently reactive for the reaction to
occur within the optimum time frame (e.g., a wash cycle).
However, if L is too reactive, this activator will be difficult to
stabilize. These characteristics are generally paralleled by the
pKa of the conjugate acid of the leaving group, although
exceptions to this convention are known.
Preferred bleach activators are those of the general formula:
R5 0 0 0 R5 0
l 11 11 11 1 11
Rl - N - C - R2 - C - L or Rl - C - N - R2 - C - L
wherein Rl is an alkyl group containing from about 6 to about 12
carbon atoms, R2 is an alkylene containing from 1 to about 6
WO 94/10284 2 1 4 765 8 PCI`/US93/09930
- 5 -
carbon atoms, RS is H or alkyl-, aryl, or alkaryl containing from
about 1 to about 10 carbon atoms, and L is selected from the group
consisting of:
R3Y ~ 3
- N - C - R6 ~ \ ~
13
y
Il
O O CH2 C~
Il 11 / \
- N - C - CH -R4 - O - C - R6 ~ / R4
R3 Y C
o
Y O
11
IR3
- ~ ~ R4, - O - CH - C - CH - CH2
o
Y IR3
- O - CH ~ C - CH - CH2, - O - C ~ CHR4, and
W O 94/10284 ` ~ PcT/uss3/o993~
2147658 - 6 -
O y ~,~
~ 'J:. :.;
- N - S - CH - R4
l 11
R3 o
wherein R6 is an alkylene, arylene, or alkarylene group containing
from about 1 to about 14 carbon atoms, R3 is an alkyl chain
containing from about 1 to about 8 carbon atoms, R4 is H or R3,
and Y is H or a solubilizing group. Y is preferably selected from
the group consisting of --S03-M+, --COO-M+, --S04-M+, (--N+R'3)X-
and O`N(R'3), wherein R' is an alkyl chain containing from about 1
to about 4 carbon atoms, M is a cation which provides solubility
to the bleach activator and X is an anion which provides
solubility to the bleach activator. Preferably, M is an alkali
metal, ammonium or substituted ammonium cation, with sodium and
potassium being most preferred, and X is an anicn selected from
the group consisting of halide, hydroxide, methylsulfate and
acetate anions. More preferably, Y is --S03-M+ and --COO-M+. It
should be noted that bleach activators with a leaving group that
does not contain a solubilizing group should be well dispersed in
the bleach solution in order to assist in their dissolution.
Preferred is:
_", R3Y
wherein R3 is as defined above and Y is --S03-M+ or --COO-M+
wherein M is as defined above.
Especially preferred bleach activators are those wherein Rl
is a linear alkyl chain containing from about 6 to about 12 carbon
atoms, R2 is a linear alkylene chain containing from about 2 to
about 6 carbon atoms, R5 is H, and L is selected from the group
consisting of:
Y /R3 R3Y
- O ~ - O ~ Y and - ~
W o 94/10284 2 1 ~ 76 5 8 PCr/US93/09930
wherein R3 is as defined above, Y is --S03-M+ or --COO-M+ and M is
as defined above.
A preferred bleach activator is:
Il
~C
~ N
wherein R is H, alkyl, aryl or alkaryl. This is described in U.S.
Patent 4,966,723, Hodge et al, incorporated by reference herein.
Preferred bleach activators are:
O O O
R ~ C - L or R2-C- O ~ C - L
wherein Rl is H or an alkyl group containing from about 1 to about
6 carbon atoms and R2 is an alkyl group containing from about 1 to
about 6 carbon atoms and L is as defined above.
Preferred bleach activators are also those of the above
general formula wherein L is as defined in the general formula,
and Rl is H or an alkyl group containing from about 1 to about 4
carbon atoms, and R2 is an alkyl group containing from about 1 to
about 4 carbon atoms.
Even more preferred are bleach activators of the above
general formula wherein L is as defined in the general formula and
Rl is a H.
A more preferred bleach activator is:
o
Il
R - C - L
More preferred bleach activators are those of the above
general formula wherein R is a linear alkyl chain containing from
about 5 to about 9 and preferabiy from about 6 to about 8 carbon
atoms and L is selected from the group consisting of:
WO 94/10284 - PCr/US93/0993'
2147658 - 8 -
R2Y ~ R2 IY
~(,'~`~' ~)
y
Il
O O CH2--C
Il 11 / \
- N - C - R, - O - C - R, - N\ NH
\/
R2 C
11
Y O
R2 R2
- O - CH - C - CH - CH2, - O - C - CHR3,
wherein R, R2, R3 and Y are as defined above.
Particularly preferred bleach activators are those of the
above general formula wherein R is an alkyl group containing from
about 5 to about 12 carbon atoms wnerein the longest linear
portion of the alkyl chain extending from and including the
carbonyl carbon is from about 6 to about 10 carbon atoms, and L is
selected from the group consisting of:
Y R2 R2Y
- O ~ , - ~ Y, and - O ~
wherein R2 is an alkyl chain containing from about 1 to about 8
carbon atoms, and Y is --SO-3M+ or --COO-M+ wherein M is an alkali
metal, ammonium or substituted ammonium cation.
Especially preferred bleach activators are those of the above
general formula wherein R is a linear alkyl chain containing from
about 5 to about 9 and preferably from about 6 to about 8 carbon
atoms and L is selected from the group consisting of:
W O 94/10284 2 1 4 7 6 5 8 PCr/US93/09930
g ~.
~ ~ Y, and ~ ~ R2Y
wherein R2 is as defined above and Y is --50-3M+ or --COO-M+
wherein M is as defined above.
The most preferred bleach activators have the formula:
o
Il
R- C- ~ S03-M+
wherein R is a linear alkyl chain containing from about 5 to about
9 and preferably from about 6 to about 8 carbon atoms and M is
sodium or potassium.
The level of bleach activator within the compositions of the
invention is preferably from about 0.5 to about 20, more
preferably from about 1 to about 10, most preferably from about 2
to about 7, wt.% of the composition.
The bleaching mechanism generally, and the surface bleaching
mechanism in particular, are not completely understood. However,
it is generally believed that the bleach activator undergoes
nucleophilic attack by a perhydroxide anion, which is generated
from the hydrogen peroxide evolved by the peroxygen bleach, to
form a peroxycarboxylic acid. This reaction is commonly referred
to as perhydrolysis.
When the activators are used, optimum surface bleaching
performance is obtained with wash solutions wherein the pH of such
solution is between about 8.5 and 10.5 and preferably between 9.5
and 10.5 in order to facilitate the perhydrolysis reaction. Such
pH can be obtained with substances commonly known as buffering
agents, which are optional components of the bleaching
compositions herein.
Preferably, the bleach activator herein is sodium nonanoyl-
oxybenzenesulfonate (NOBS) or sodium benzoyloxybenzenesulfonate
(BOBS).
The molar ratio of hydrogen peroxide yielded by the peroxygen
bleaching compound to the bleach activator is greater than about
1.5, preferably from about 2.0 to about 10. Preferably, the
WO 94~10284 PCI`/US~3/0993'
21~76~8 - lo-
detergent compositions herein cnmprise from about 0.5 to about 20,
most preferably from about l-to about 10, wt.% of the peroxygen
bleaching compound.
Salts of perborate and percarbonate are preferred peroxygen
bleaching compounds for use herein. Sodium perborate and sodium
carbonate peroxyhydrate are most preferred.
It is preferred that peroxyacids are formed in situ in the
laundry wash water by the combination of the peroxygen bleaching
compound and the bleaching activator.
2. PeroxYacid
The peroxyacid herein comprises from about 0.5 to about 20,
preferably from about 1 to about 10, most preferably from about 2
to about 7, wt.~ of the detergent composition.
Preferred organic peroxyacids are selected from the group
consisting of 4-nonylamino-4-oxoperoxybutyric acid; 6-(nonyl-
amino)-6- oxoperoxycaproic acid; 1,12-diperoxydodecanedioic acid,;
heptyl sulfonylperpropionic acid; decylsulphonyl perpropionic
acid; and heptyl-, octyl-, nonyl-, decyl-sulphonylperbutyric
acids; and mixtures thereof.
Of the organic peroxyacids, amidoperoxyacids (amide
substituted peroxycarboxylic acids) are preferred. Suitable
amidoperoxyacids for use herein are described in U.S. Patents
4,634,551 and 4,686,063, both Burns et al, issued January 6, 1987
and August 11, 1987, respectively, both incorporated herein by
reference. Suitable amidoperoxyacids are of the formula:
R1 - NH - C - R2 - C - OOH or R1-C-NH-R2-C-OOH
Il 11 11 11
O O O O
wherein Rl is an alkyl group containing from about 6 to about 12
carbon atoms, and R2 is an alkylene group containing from 1 to
about 6 carbon atoms. Preferably, R1 is an alkyl group containing
from about 8 to about 10 carbon atoms, and R2 is an alkylene group
containing from about 2 to about 4.
Also suitable for use herein are peroxyfumarates, which are
described in U.S. Patent 4,852,989, Burns et al, issued August 1,
1989, incorporated herein by reference, and sulfone peroxyacids
(sulfone peroxycarboxylic acids), which are described in U.S.
W094/10284 21 176S8 PCI/US93/09930
- 11 -
Patents 4,758,369, 4,824,591, and 5,004,558, all Dryoff et al,
issued July 19, 1988, April 25, 1989, and April 2, 1991,
respectively, all incorporated herein by reference.
Example I of U.S. Patent 4,686,063 contains one description
of the synthesis of NAPSA, from column 8, line 40 to Column 9,
line 5, and NAP M , from column 9, line 15 to column 9, line 65.
At the end of the amidoperoxyacid synthesis, the reaction is
quenched with water, filtered, washed with water to remove some
excess sulfuric acid (or other strong acid with which the
peroxyacid was made), and filtered again.
The amidoperoxyacid wet cake thus obtained can be contacted
with a phosphate buffer solution at a pH between about 3.5 and 6,
preferably between about 4 and 5, according to U.S. Patent
4,909,953, Sadlowski et al, issued March 2C, 1990, which is
incorporated herein by reference.
Other agents for storage stabilization or exotherm control
can be added to the amidoperoxyacid before incorporation into the
final product. For example, boric acid, an exotherm control agent
disclosed in U.S. Patent 4,686,063, Burns, issued August 11, 1987
and incorporated herein, can be mixed with the amidoperoxyacid
(which has been washed in phosphate buffer) in about a 2:1
peracid:boric acid ratio. The phosphate buffer washed
amidoperoxyacid can also be mixed with appropriate amounts of
dipicolinic acid and tetrasodium pyrophosphate, a chelating
stabilization system. Chelants can optionally be included in the
phosphate buffer before contact with the wet cake.
The wet cake is preferably made up of particles with an
average particle diameter of from about 0.1 to about 260 microns,
preferably from about 10 to about 100 microns, and most preferably
from about 30 to about 60 microns. Small particle size NAPM
crystals are desired herein. See U.S. Patent 5,055,218, Getty et
al, issued October 8, 1991, which is incorporated herein by
reference.
NAP M filter cake herein is preferably washed twice in
phosphate buffer. It has been found that two successive phosphate
buffer washes lend optimal stability to NAPM .
2 1 4 7 6 ~ 8 12 - PCI/US93/0993
Particulate (solid), organic peroxyacids with a theoretical
AvO (available oxygen) of between about 3 and about 12, most
preferably between 5 and 7, are preferred.
Most preferred for use her~i~n`is NAPM . Another name for the
nonylamide of peroxyadipic _cid (~NAPAA~) is 6-(nonylamino)-6-
oxoperoxycaproic acid. The chemical formula for NAP M is:
H O O
l 11 11
CH3(CH2)8N C (CH2)4COOH
The molecular weight of NAP M is 287.4.
Detergent compositions and bleaching compositions containing
NAP M provide extremely effective and efficient surface bleaching
of textiles. Stains and/or soils are removed from the textiles.
These compositions are particularly effective at removing dingy
soils from textiles.
NAPM's polar amide or substituted amide moiety results in a
peroxyacid which has a very low vapor pressure and thus possesses
a low odor profile as well as excellent bleaching performance. It
is believed that the polarity of the amide group results in a
reduction of vapor pressure of the peroxyacid, and an increase in
melting point.
NAPM can be used directly as a bleaching agent. It has a
reduced vapor pressure and a good odor profile in laundry
applications.
NAP M can be prepared by, for example, first reacting N MM
(monononyl amide of adipic acid), sulfuric acid, and hydrogen
peroxide. The reaction product is quenched by addition to ice
water followed by filtration, washing with distilled water, and
final suction filtration to recover the wet cake. Washing can be
continued until the pH of the filtrate is neutral.
It is also preferred that the NAPM pH (10X solids in water)
be between about 4.2 and 4.8. Surprisingly~ this pH results in
more thermally stable particles.
While not wishing to be bound by theory, the present
invention is based on the use of relatively hydrophobic
(lipophilic) peracids (from activators or as preformed
peroxyacids) which are thought to concentrate at the soil/fabric
21476~8
WO 94/10284 ` PC~/US93/09930
- 13 -
interface and enhance the performance benefits from protease
enzymes. A method that can be used to characterize the selected
peroxyacids (from activators or as preformed peroxyacids) which
are useful in the present invention is the "H.L.B. Scale~ such as
that described in Davies, J.T., Proc. 2nd Internat. Congr. Surface
Activitv 1, 426, Butterworths, London (1957), incorporated herein
by reference. Such an H.L.B. Scale (Hydrophilic-Lipophilic
Balance) has been used in the study of surface-active agents
(surfactants) as a means to relate the distribution of a
surface-active agent between a hydrophilic (water-like) and a
lipophilic (oil-like) phase. In this manner, H.L.B. values can be
used as an indication of the lipophilic (hydrophobic) character of
the active bleaching species in the wash (i.e., the ability of the
peroxyacid to partition out of the wash liquor and concentrate at
the soil/fabric interface).
Set forth hereinafter in Table A are H.L.B. values which have
been calculated for selected peroxyacids (as the corresponding
carboxylic acids). The equation used to calculate the H.L.B.
values can be set forth as:
HLB 8 Sum (Hydrophilic Group Numbers) - Sum (Hydrophobic
Group Numbers) + 7.
The values for the Hydrophilic Group Numbers are [-C(O)OH &
-N(H)C(0)--2.1] and the values for the Hydrophobic Group Numbers
are [aliphatic/aromatic carbon - 0.475 ~ aliphatic carbon atoms
between polar groups are 1/2 the value of an aliphatic carbon in a
hydrocarbon chain - (0.475)/2]. For reference, an H.L.B. value >7
indicates that the material is preferentially water soluble and an
H.L.B. value <7 indicates increasing surface-activity and
hydrophobicity.
TABLE A
H.L.B. Values Provided bY Various Peroxvacids
H.L.B.
Activator/Preformed Abbrevi- Corresponding
PeroxYacid ation PeroxYacidCarboxvlic Acid
Tetra Acetyl TAED CH3C(O)OOH 8.6
Ethylene Diamine
~ 94/1~4 214~58 PCI`/US~3/099^
- 14 -
DiPeroxyDodecane DPDDA HOO(O)C(CH2)10- 6.5
Dioic Acid C(O)OOH
Nonyl Amide of Peroxy NAPSA CH3(CH2)gN(H)C(0)- 6.4
Succinic Acid (CH2)2C(O)OOH
BenzoylOxyBenzene BOBS ~C6HsC(O)OOH 6.3
Sulfonate
Nonyl Amide of Peroxy NAPAA CH3(CH2)gN(H)C(0)- 6.0
Adipic Acid (cH2)4c(o)ooH
NonanoylOxyBenzene NOBS CH3(CH2)7C(O)OOH 5.3
Sulfonate
~ecanoylOxyBenzene DOBS CH3(CH2)8C()H 4.8
Sulfonate
PerLauric Acid PLA CH3(CH2)10C(O)OOH 3.9
A preferred range of H.L.B. values (as the carboxylic acid
for the peroxyacids of the present invention (whether added
directly or generated in situ) ranges from about 3.0 to about 6.5.
A more preferred range of H.L.B. values (as the carboxylic acid)
for the peroxyacids useful in the present invention (whether added
directly or generated in situ) range from about 4.0 to 6.5. The
most preferred range of H.L.B. values (as the carboxylic acid) for
the peroxyacids of the present invention (whether added directly
as generated in situ) ranges from about 4.0 to about 6Ø
B. Protease Enzvmes
The detergent compositions of the present invention also
comprise from about 0.064 to about 0.64, preferably from about
0.096 to about 0.32, mg of active protease enzyme per gram of
composition.
Mixtures of proteolytic enzyme (protease) are also included.
The proteolytic enzyme can be of animal, vegetable or
microorganism (preferred) origin. More preferred is serine
proteolytic enzyme of bacterial origin. Purified or nonpurified
forms of this enzyme may be used. Proteolytic enzymes produced by
chemically or genetically modified mutants are included by
definition, as are close structural enzyme variants.
Suitable proteases include Alcalase, Esperase0, Savinase0
(preferred); Maxatasee, Maxacal~ (preferred), and Maxapem 150
(protein engineered Maxacal0); and subtilisin BPN and BPN'
WO 94/10284 2 1 4 7 6 5 8 PCI/US93/09930
- 15 -
~preferred); which are commercially available. Also suitable are
modified bacterial serine proteases, such as those described in
European Patent Application Serial Number 87 303761.8, filed April
28, 1987 (particularly pages 17, 24 and 98), and which is called
herein "Protease Bn, and in European Patent Application 199,404,
Venegas, published October 29, 1986, which refers to a modified
bacterial serine proteolytic enzyme which is called "Protease A"
herein. Most preferred is what is called herein "Protease C",
which is a triple variant of an alkaline serine protease from
Bacillus in which 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,
which is incorporated herein by reference. Genetically modified
variants, particularly of Protease C, are also included herein.
Preferred proteolytic enzymes, then, are selected from the
group consisting of Savinase~, Maxacal~, BPN', Protease A,
Protease B, Protease C, and mixtures thereof. Protease B and
Protease C are most preferred. Bacterial serine protease enzymes
obtained from Bacillus subtilis and/or Bacillus licheniformis are
preferred.
The enzymes of the present invention provide effective and
efficient removal of stains and/or soils on textiles. The enzymes
are particularly efficient at removing protein based stains and/or
soils from textiles. While not wishing to be bound by theory, it
is believed that surface active bleaches are required since the
enzymes of the present invention remove stains and/or soils from
the fabric surface, thereby reducing the stain and/or soils load
at the fabric surface and resulting in efficient use of both
bleach and enzyme.
Since the improved cleaning performance provided by the
present invention is believed to result from a synergistic effect
WO 94/10284 PCI'/US93/099?
21~76S8 - 16 -
between a relatively hydrophobic peracid and protease enzymes, it
is possible to express the preferred concentrations of protease
enzyme and peroxyacid (whether ;added directly or generated in
situ) as a range of ratios a~s~well as concentration ranges for the
protease and bleach individuàlly. A preferred manner of
expressing this ratio is [mg active protease per 100 grams of
composition/ppm Active Oxygen (ppm Av02) from the peroxyacid in
the wash liquor] and will be referred to as the Enzyme to Bleach
ratio (E/B ratio). The preferred range for the ratio of active
protease to peroxyacid Av02 (E/B) is from about 1 to about 20.
C. Deterqent Surfactant
The compositions of this invention also include from about 1
to about 40 weight X of peroxyacid-stable, water-soluble detergent
surfactant selected from the group consisting of anionics,
nonionics, zwitterionics, ampholytics, and mixtures thereof. From
about 2 to about 25 weight % of detergent surfactant is preferred
and from about 5 to about 15 weight % is most preferred. Anionic
surfactant is preferred and salts of Cll l3 linear alkyl benzene
sulfonate, Clz 16 alkyl sulfate and/or methyl ester sulfonates are
more preferred. From about 2 to about 25 wt. Z of sodium C12 13
linear alkyl benzene sulfonate and sodium C14 15 alkyl sulfate are
most preferred.
Detergent surfactants useful herein are listed in U.S.
Patents 3,664,961, Norris, issued May 23, 1972, and 3,919,678,
Laughlin et al, issued December 30, 1975, both incorporated herein
by reference. The following are representative examples of
detergent surfactants useful in the present compositions.
Water-soluble salts of the higher fatty acids, i.e., ~soapsn,
are useful anionic surfactants in the compositions herein. This
includes alkali metal soaps such as the sodium, potassium,
ammonium, and alkylammonium salts of higher fatty acids containing
from about 8 to about 24 carbon atoms, and preferably from about
12 to about 18 carbon atoms. Soaps can be made by direct
saponification of fats and oils or by the neutralization of free
fatty acids. Particularly useful are the sodium and potassium
salts of the mixtures of fatty acids derived from coconut oil and
tallow, i.e., sodium or potassium tallow and coconut soap.
2147fi58O 94/10284 PCI`/US93/09930
- 17 -
Useful anionic surfactants also include the water-soluble
salts, preferably the alkali metal, ammonium and alkylolammonium
salts, of organic sulfuric reaction products having in their
molecular structure an alkyl group containing from about 10 to
about 20 carbon atoms and a sulfonic acid or sulfuric acid ester
group. (Included in the term ~alkyl~ is the alkyl portion of acyl
groups.) Examples of this group of synt~etic surfactants are the
sodium and potassium alkyl sulfates, especially those obtained by
sulfating the higher alcohols (Cg-C1g carbon atoms) such as those
produced by reducing the glycerides of tallow or coconut oil; and
the sodium and potassium alkylbenzene sulfonates in which the
alkyl group contains from about 9 to about 15 carbon atoms, in
straight chain or branched chain configuration, e.g., those of the
type described in U.S. Patents 2,220,099 and 2,477,383.
Especially valuable are linear straight chain alkylbenzene
sulfonates in which the average number of carbon atoms in the
alkyl group is from about 11 to 13, abbreviated as Cll l3LAS.
Other anionic surfactants herein are the sodium alkyl
glyceryl ether sulfonates, especially those ethers of higher
alcohols derived from tallow and coconut oil; sodium coconut oil
fatty acid monoglyceride sulfonates and sulfates; sodium or
potassium salts of alkyl phenol ethylene oxide ether sulfates
containing from about 1 to about 10 units of ethylene oxide per
molecule and wherein the alkyl groups contain from about 8 to
about 12 carbon atoms; and sodium or potassium salts of alkyl
ethylene oxide ether sulfates containing about 1 to about 10 units
of ethylene oxide per molecule and wherein the alkyl group
contains from about 10 to about 20 carbon atoms.
Other useful anionic surfactants herein include the
water-soluble salts of esters of alpha-sulfonated fatty acids
containing from about 6 to 20 carbon atoms in the fatty acid group
and from about 1 to 10 carbon atoms in the ester group;
water-soluble salts of 2-acyloxyalkane-1-.ulfonic acids containing
from about 2 to 9 carbon atoms in the acyl group and from about 9
to about 23 carbon atoms in the alkane moiety; water-soluble salts
of olefin and paraffin sulfonates containing from about 12 to 20
carbon atoms; and beta-alkyloxy alkane sulfonates containing from
WO 94/10284 PCI'/US~3/099~
21476S8 - 18-
about 1 to 3 carbon atoms in the alkyl group and from about 8 to
20 carbon atoms in the alkane moiety.
Water-soluble nonionic surfactants are also useful in the
compositions of the invention. ~Such nonionic materials include
compounds produced by the condé~sation of alkylene oxide groups
(hydrophilic in nature) wi,tn an organic hydrophobic compound,
which may be aliphatic or alkyl aromatic in nature. The length of
the polyoxyalkylene group which is condensed with any particular
hydrophobic group can be readily adjusted to yield a water-soluble
compound having the desired degree of balance between hydrophilic
and hydrophobic elements.
Suitable nonionic surfactants include the polyethylene oxide
condensates of alkyl phenols, e.g., the condensation products of
alkyl phenols having an alkyl group containing from about 6 to 15
carbon atoms, in either a straight chain or branched
configuration, with from 3 to 12 moles of ethylene oxide per mole
of alkyl phenol.
Preferred nonionics are the water-soluble and
water-dispersible condensation products of aliphatic alcohols
containing from 8 to 22 carbon atoms, in either straight chain or
branched configuration, with from 3 to 12 moles of ethylene oxide
per mole of alcohol. Particularly preferred are the condensation
products of alcohols having an alkyl group containing from about 9
to 15 carbon atoms with from about 4 to 8 moles of ethylene oxide
per mole of alcohol.
Semi-polar nonionic surfactants include water-soluble amine
oxides containing one alkyl moiety of from about 10 to 18 carbon
atoms and two moieties selected from the group of alkyl and
hydroxyalkyl moieties of from about 1 to about 3 carbon atoms;
water-soluble phosphine oxides containing one alkyl moiety of
about 10 to 18 carbon atoms and two moieties selected from the
group consisting of alkyl groups and hydroxyalkyl groups
containing from about 1 to 3 carbon atoms; and water-soluble
sulfoxides containing one alkyl moiety of from about 10 to 18
carbon atoms and a moiety selected from the group consisting of
alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.
WO 94/10284 2 I 4 7 6 5 8 PCT/US93/09930
- 19 -
Ampholytic surfactants include derivatives of aliphatic or
aliphatic derivatives of heterocyclic secondary and tertiary
amines in which the aliphatic moiety can be straight chain or
branched and wherein one of the aliphatic substituents contains
from about 8 to 18 carbon atoms and at least one aliphatic
substituent contains an anionic water-solubilizing group.
Zwitterionic surfactants include derivatives of aliphatic,
quaternary, ammonium, phosphonium, and sulfonium compounds in
which one of the aliphatic substituents contains from about 8 to
18 carbon atoms.
D. Optional DeterqencY Builder
From 1 to about 80, preferably about 20 to about 70, weight
of detergency builder can optionally be, and preferably is,
included herein. Inorganic as well as organic builders can be
used.
Inorganic detergency 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 aluminosili-
cates. Borate builders, as well as builders containing
borate-forming materials that can produce borate under detergent
storage or wash conditions (hereinafter, collectively "borate
builders~), can also be used. Preferably, non-borate builders are
used in the compositions of the invention intended for use at wash
conditions less than about 50-C, especially less than about 40-C.
Examples of silicate builders are the alkali metal silicates,
particularly those having a SiO2:Na20 ratio in the range 1.6:1 to
3.2:1 and layered silicates, such as the layered sodium silicates
described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P.
Rieck, incorporated herein by reference. However, other silicates
may also be useful.
Examples of carbonate builders are the alkaline earth and
alkali metal carbonates, including sodium carbonate and
sesquicarbonate and mixtures thereof with ultra-fine calcium
carbonate as disclosed in German Patent Application No. 2,321,001
WO 94/10284 PCr/US93/0993'
21l7fi~i8 - 20 -
published on November 15, 1973, the disclosure of which is
incorporated herein by reference.
Aluminosilicate builders are useful in the present invention.
Aluminosilicate builders include those having the empirical
formula:
MZ~zA~o2-ysio2)
wherein M is sodium, potassium, ammonium ~or substituted ammonium,
z is from about 0.5 to about 2; and y is 1; this material having a
magnesium ion exchange capacity of at least about 50 milligram
equivalents of CaC03 hardness per gram of anhydrous
aluminosilicate. Preferred aluminosilicates are zeolite builders
which have the formula:
Naz[(A102)z (Sio2)y]-xH2o
wherein z and y are integers of at least 6, the molar ratio of z
to y is in the range from 1.0 to about 0.5, and x is an integer
from about 15 to about 264. Preferred synthetic crystalline
aluminosilicate ion exchange materials useful herein are available
under the designations Zeolite A, Zeolite P (B), and Zeolite X.
Specific examples of polyphosphates are the alkali metal
tripolyphosphates, sodium, potassium and ammonium pyrophosphate,
sodium and potassium and ammonium pyrophosphate, sodium and
potassium orthophosphate, sodium polymeta phosphate in which the
degree of polymerization ranges from about 6 to about 21, and
salts of phytic acid.
Organic detergent builders preferred for the purposes of the
present invention include polycarboxylate compounds which have 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.
One important category of polycarboxylate builders
encompasses the ether polycarboxylates. Examples of useful ether
polycarboxylates include oxydisuccinate, as disclosed in Berg,
U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al.,
WO 94/10284 2 1 g 7 6~ 8 PCI'/US93/09930
- 21 -
U.S. Patent 3,635,830, issued January 18, 1972, both of which are
incorporated herein by reference.
A specific type of ether polycarboxylates useful as builders
in the present invention also include those having the general
formul 2:
CH(A)(COOX)-CH(COOX)-O-CH(COOX)-CH(COOX)(B)
wherein A is H or OH; B is H or -O-CH(COOX)-CH2(COOX); and X is H
or a salt-forming cation. Suitable examples of these builders are
disclosed in U.S. Patent 4,663,071, issued to Bush et al., on May
5, 1987.
Suitable ether polycarboxylates also include cyclic
compounds, particularly alicyclic compounds, such as those
described in U.S. Patents 3,923,679; 3,835,163; 4,158,635;
4,120,874 and 4,102,903, all of which are incorporated herein by
reference.
Other useful detergency builders include the ether
hydroxypolycarboxylates and the copolymers of maleic anhydride
with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2,
4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid.
Organic polycarboxylate builders also include the various
alkali metal, ammonium and substituted ammonium salts of
polyacetic acids. Examples include the sodium, potassium,
lithium, ammonium and substituted ammonium salts of
ethylenediamine tetraacetic acid, and nitrilotriacetic acid.
Also included are polycarboxylates such as mellitic acid,
succinic acid, oxydisuccinic acid, polymaleic acid, benzene
1,3,5-tricarboxylic acid, and carboxymethyloxysuccinic acid, and
soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof
(particularly sodium salt), are polycarboxylate builders which can
also be used in granular compositions.
Other carboxylate builders include the carboxylated
carbohydrates disclosed in U.S. Patent 3,723,322, Diehl, issued
March 28, 1973, incorporated herein by reference.
Also suitable in the detergent compositions of the present
invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the
related compounds disclosed in U.S. Patent 4,566,984, Bush, issued
2 1 ~ 7 6 ~ 8 - 22 - PCI'/US~3/099?
January 28, 1986j incorporated herein by reference. Useful
succinic acid builders include the Cs-C20 alkyl succinic acids and
salts thereof. The succinate builders are preferably used in the
form of their water-soluble salts, including the sodium,
potassium, ammonium and alkanolammonium salts.
Examples of useful builders also include sodium and potassium
carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclo-
hexane-hexacarboxylate, cis-cyclopentane-tetracarboxylate, water-
soluble polyacrylates, and the copolymers of maleic anhydride with
vinyl methyl ether or ethylene.
Other suitable polycarboxylates are the polyacetal car-
boxylates disclosed in U.S. Patent 4,144,226, Crutchfield et al.,
issued March 13, 1979, incorporated herein by reference.
Polycarboxylate builders are also disclosed in U.S. Patent
3,308,067, Diehl, issued March 7, 1967, incorporated herein by
reference. Such materials include the water-soluble salts of
homo- and copolymers of aliphatic carboxylic acids such as maleic
acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid,
citraconic acid and methylenemalonic acid.
Other organic builders known in the art can also be used.
For example, monocarboxylic acids, and soluble salts thereof,
having long chain hydrocarbyls can be utilized. These would
include materials generally referred to as ~soaps.~ Chain lengths
of C1o-C20 are typically utilized. The hydrocarbyls can be
saturated or unsaturated.
Preferably the detergency builder herein is selected from the
group consisting of the salts, preferably the sodium salt, of
carbonate, silicate, sulfate, phosphate, aluminosilicate, and
citric acid and mixtures thereof.
E. Second EnzYme
Optional, and preferred, ingredients include second enzymes,
particularly peroxidase, cellulase, and mixtures thereof. By
"second enzyme~ is meant one or more enzymes in addition to
protease which are also added to the composition.
The amount of second enzyme used in the composition varies
according to the type of enzyme and the use intended. In general,
from about 0.0001 to about 1.0, more preferably about 0.001 to
WO 94/10284 21 g 7~ 5 8 PCI`/US93/09930
about 0.5, weight % of the composition on an active basis of these
second enzymes are preferably used.
Purified or nonpurified forms of these enzymes may be used.
Enzymes produced by chemically or genetically modified mutants are
included by definition, as are close structural enzyme variants.
F. Other Inqredients
Other ingredients suitable for use in the present
compositions, such as water, perfume, brightener, conditioners
such as fumed silica, polyethylene glycol, dyes and colorants, and
peroxyacids, can be included. Preferred ingredients are from
about 0.5 to about 5 wt.% of the composition of polyethylene
glycol (preferably with molecular weight between S,000 and 10,000,
most preferably 8,000), from about 0.01 to about 0.7 wt.% of
fluorescent whitening and/or brightening agents, and from about
0.01 to about 1.0 wt.% of perfume.
The detergent compositions of the present invention do not
need to contain quaternary ammonium salts to delay active oxygen
production or to achieve suitably high levels of active oxygen in
bleaching solution. Accordingly, such compositions may be
substantially free of quaternary ammonium salts.
The granular detergent composition is added to the wash,
usually at levels of 1/4 to 1 cup.
This invention most preferably provides a nonphosphate
granular laundry detergent composition comprising, by weight of
the composition:
a. from about 2 to about 7 weight X of
nonanoyloxybenzenesulfonate (NOBS) and from about 2 to about 7
weight % of sodium perborate;
b. from about 0.096 to about 0.32 of active Protease C per
gram of composition; and
c. from about 2 to about 25 weight % of sodium C12-13
linear alkyl benzene sulfonate and sodium C14 15 alkyl sulfate.
This invention further provides a method for cleaning fabrics
in the wash by contacting the fabrics with a wash solution which
contains an effective amount of the detergent compositions
hereinbefore described.
WO 94/10284 P~/US93/0993'
2147 65 8 - 24` - `
Agitation is preferably provided in the washing machine for
good cleaning. Washing is preferably followed by drying the wet
fabric in a conventional clothes dryer. An effective amount of
the granular detergent composition in the washing machine is
preferably from about 500 to about 7000 ppm, more preferably from
about 1000 to about 3000 ppm.
The following examples illustrate the compositions of the
present invention, but are not necessarily meant to limit or
otherwise define the scope of the invention.
All parts, percentages and ratios used herein are by weight
unless otherwise specified.
EXAMPLE I
The wash performance of several proteases are evaluated in
the presence of a n-nonanoyloxybenzenesulfonate (NOBS)/sodium
perborate (PBl) bleach system in non-phosphate detergent granules
prepared according to the following composition:
Material Wt.%
Sodium C11 13 linear alkyl benzene sulfonate 15.33
Sodium C14 15 alkyl sulfate 6.57
Sodium aluminosilicate 31.52
Sodium carbonate 12.93
Sodium sulfate, moisture, and miscellaneous 30.92
The following proteases are added to the bleach-containing
detergent granules at a level of 64 mg active enzyme per 100 gram
of product: Maxacal~ ex IBIS; a triple variant of an alkaline
serine protease from Bacillus in which tyrosine replaced valine at
position 104, serine replaced asparagine at position 123, and
alanine replaced threonine at position 274 (described in EP
90915958:4) hereinafter referred to as Protease C; and a variant
of Protease C hereinafter referred to as Protease Cl.
The bleaching performance of n-nonanoyloxybenzenesulfonate
and the enzymatic performance of protease are determined in a
series of experiments comparing the fabric whitening and stain
removal of a treatment containing alkaline detergent granules
(composition above) alone, with a treatment containing the
detergent granules plus peroxyacid, with a treatment containing
21~7fi58
WO 94/10284 PCr/US93/09930
- 25 -
detergent granules plus protease, with a treatment containing
detergent granules plus peroxyacid plus protease.
Thus, to each of four top-loading automatic washing machines
is added 5 lbs. of naturally soiled ballast fabrics and 64 liters
of 95-F city water having a hardness of 6 gr/gal. To one machine
is added 87 9 of detergent granules only. To the second machine
is added 87 9 of detergent granules and sufficient NOBS/PBl to
result in an available oxygen (Av02) level of 4.2 ppm in the wash
solution. To the third machine is added 87 9 detergent granules
and protease at a level of 64 mg of active enzyme per 100 9 of the
final product. To the fourth machine is added 87 9 detergent
granules and the same amount of bleach and protease as in the
second and third machine, respectively. The E/B ratio for each of
the treatments is 15.2.
To each of the above wash solutions is added two sets of
naturally soiled white fabrics and two sets of artificially
stained swatches. The washing machines are then allowed to
complete their normal washing and rinsing cycles, and the ballast
and test fabrics are dryer dried. This procedure is repeated four
times, using different sets of ballast fabrics, naturally soiled
white fabrics and artificially stained swatches for each
replicate.
After completion of the four replicates, the fabrics and
swatches are arranged under suitable lighting for comparison of
soil and stain removal. Three qualified graders compare the
extent of removal of the soils and stains using the following
scale:
0: no difference between two swatches
1: thought to be a difference
2: certain of a difference
3: certain of a large difference
4: certain of a very large difference
By this grading the naturally soiled white fabrics are
compared for improvement in whiteness, and the artificially
stained swatches are compared for removal of the stain. The
grades obtained are then averaged and normalized to yield the
WO 97461~ - 26 - PCT/US93/O99?
results. The wash performance data on grass stain is shown in
Table 1.
Table 1
Treatment and Average Relative Grade
A ff C D
No Protease Bqeach Protease Bleach +
Protease No Bleach onlv onlv Protease
Maxacal O.OO 0.88 3.00 4.25 s
Protease C O.OO 0.82 2.67 4.20 s
Protease Cl O.OO 1.18 1.86 4.04 s
s - statistically significant difference (confidence level of
95%) relative to all other treatments.
This data shows unexpected synergy between bleach and
protease on cleaning of grass stain. All the proteases tested
exhibited more performance benefit than the added single
contributions of bleach and protease would predict, as Table lA
shows.
Table lA
~ D
Maxacal 3.88 4.25S
Protease C 3.59 4.20S
Protease Cl 3.04 4.04S
EXAMPLE II
In this example, proteases at a level of 32 mg active enzyme
per 100 9 of the bleach-containing detergent product are tested as
in Example I. The E/B ratio for these treatments is 7.6. Once
again, an unexpected synergy exists between bleach (NOBS/PBl) and
protease on grass stain. The results are shown in Table 2.
Table 2
Treatment and Average Relative Grade
A ~ C D
No Protease Bleach Protease Bleach +
Protease No Bleach onlv onlv Protease
Maxacal O.OO 1.25 2.53 4.57 s
Protease C O.OO 1.47 2.10 4.04 s
Protease Cl 0.00 1.10 2.75 4.43 s
W O 94/10284 2 1 4 7 6 5 8 PCI'/US93/09930
s - statistically significant difference (confidence level of
95%) relative to all other treatments.
Table 2A
B+C D
Maxacal 3.78 4.57s
Protease A 3.57 4.04s
Protease B 3.85 4.43s
Table 2A shows that, according to this wash performance test,
the bleach + protease sample (D) performs significantly better
than the added single contributions of the bleach sample (B) and
the protease sample (C) for the proteases tested.
EXAMPLE III
Several proteases were tested in the presence of different
bleach systems in the same detergent composition as Example I.
Protease C at a level of 32 mg active enzyme per 100 9 of the
final product is tested in the presence of
benzoyloxybenzenesulfonate (BOBSJ/PB1 and tetra acetyl ethylene
diamine (TAED)/PB1 bleach systems (E/B ratio of 7.6J. Protease C
is also tested at a level of 6.4 mg active enzyme per 100 9 of the
final product in the presence of the nonyl amide of monoperoxy
adipic acid (NAPM ) (E/B ratio of 1.5). Protease C1 is evaluated
in the presence of NAPM at a level of 64 mg active enzyme per 100
g of the product (E/B ratio of 15.2). In this testing, a
sufficiènt amount of bleach is added to result in an available
oxygen level of 4.2 ppm. Performance data on grass stain is
presented in Table 3.
Table 3
Treatment and Average Relative Grade
Q B C D
No Protease Bleach Protease Bleach +
Protease No Bleach onlv onlv Protease
Protease C/BOBS 0.00 0.09 1.48 2.08 s
Protease C/TAED 0.00 0.35 2.09 2.31
Protease C/NAP M 0.00 0.86 2.44 3.68 s
Protease C1/NAP M0.00 0.80 2.00 3.14 s
WO 94/10284 PCI`/US93/099?
21476~8 - 28 -
s ~ statistically significant difference (confidence level of
95%) relative to all other treatments.
The data shows ~h-at~ an unexpected synergy exists between
bleach and protease under these conditions, except for the
TAED/PB1 bleach system.
Table 3A
B+C D
Maxacal/BOBS 1.57 2.08s
Protease C/TAED 2.44 2.31
Protease C/NAP M 3.30 3.68s
Protease C1/NAP M 2.803.14s
Table 3A shows that, according to this wash performance test,
the bleach and protease sample (D) performs significantly better
than the additive contributions of the bleach sample (B) (except
TAED) plus the protease sample (C) for the proteases tested.
EXAMPEE IV
Protease C is tested at a level of 12.8 mg active enzyme per
100 9 of the product (same procedure and same detergent
composition as in Example ~) in a reduced NOBS/PB1 level (2.7 ppm
AvO) and at a lower temperature. The E/B ratio for this example
is 4.7. The wash performance is carried out at 70-F and 8 gr/gal
hardness. The results are reported in Table 4.
Table 4
Treatment and Averaqe Relative Grade
A ~ C
No Protease Bleach Protease Bleach +
Stains No Bleach onlv onlv Protease
Grass 0.00 1.34 1.28 3.39 s
Gravy 0.00 0.00 -0.13 0.74 s
Betacarotene0.00 1.61 -0.50 2.49 s
s - statistically significant difference (confidence level of
95%) relative to all other treatments
Once again, the data shows that an unexpected synergy exists
between protease and bleach (at this reduced bleach level) on
grass, gravy and betacarotene stains as shown in Table 4.
W 0 94/10284 2 1 4 7~`~ 8 ~ PCI/US93/09930
- 29 -
Table 4A
Stains B+C D
Grass 2.62 3.39s
Gravy -0.13 0.74s
Betacarotene 1.11 2.49s
Table 4A shows that, according to this wash performance test,
the bleach and protease sample (D) performs significantly better
than the additive contributions of the bleach sample (B) plus the
protease sample (C).
Other proteases such as Protease B, Maxacal, and BPN' can be
interchanged with Protease C. Protease levels can be varied
between about 0.064 and about 0.64 mg of active enzyme per gram of
composition.
Other bleaching agents can be interchanged with NOBS, such as
BOBS, NAP M , the nonylamide of peroxysuccinic acid (NAPSA), and
the phenyl sulfonate salt of 6-nonylamino-6-oxycaproicacid and
other NAPAA-like activators. The level of bleaching agent can be
varied between about 0.5 and about 20 wt % of the composition.
Sodium carbonate peroxyhydrate can be used instead of sodium
perborate in an amount between about 0.5 and about 20 weight % of
the composition.
EXAMPLE V
A composition of the present invention is as follows:
Material Wt %
Sodium Cll-Cl3 linear alkylbenzene sulfonate 10.36
Sodium C14-Cls alkyl sulfate 2.96
Sodium C14-Cls alkyl ethoxy sulfate 1.48
Sodium aluminosilicate 21.30
Sodium carbonate 25.30
Citric acid 3.00
Sodium n-nonanoyloxybenzene sulfonate 4.73
Sodium perborate monohydrate 3.54
Protease C 0.11*
Polyethyleneglycol 1.06
Sodium polyacrylate 2.72
~vo 94t102~ 214~658 PCI'/US93/099.
- 30 -
Sodium silicate 1.85
Fluorescent whitening agent, moisture, misc. 11 . 97
*denotes mg of active enzyme per gram of composition
Other bleaching agents can be substituted for NOBS, such as
BOBS, NAP M , and NAPSA (all defined above). Other proteases such
as Protease B, Maxacal and BPN' can be substituted for Protease
C.
EXAMPLE VI
A laundry bar suitable for hand-washing soild fabrics is
prepared by standard extrusion processes and comprises the
following:
ComDonent Wt %
C12 linear alkylbenzene sulfonate 30
Phosphate (as sodium tripolyphosphate 7
Sodium carbonate 25
Sodium pyrophosphate 7
Coconut monoethanolamide 2
Zeolite A (0.1-10 micron) 5
Carboxymethylcellulose 0.2
Polyacrylate (m.w. 1400) 0.2
Sodium n-nonanoyloxybenzene sulfonate 5
Sodium percarbonate 5
Brightener, perfume 0.2
Protease C 0.3*
Lipase (as LIPOLASEJ~ 0.3
CaS04
MgS04
Water 4
Filler** Balance to 100%
*denotes mg of active enzyme per gram of composition
**Can be selected from convenient materials such as CaC03, talc,
clay, silicates, and the like.
The detergent laundry bars are processed in conventional soap
or detergent bar making equipment as commonly used in the art.
