Note: Descriptions are shown in the official language in which they were submitted.
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Laundry Detergent Composition Containing High
Level of Protease Enzyme
This invention relates to laundry detergent compositions having enhanced
whitening and stain removal benefits. More particularly, this invention
relates to laundry
detergent compositions containing among other components, a combination of an
endo-
cellulase enzyme, a protease enzyme and polyacrylate polymer, and which is
particularly
effective for providing enhanced whitening and stain removal benefits to
soiled fabrics.
Background of the Invention
Cellulase enzymes and protease enzymes are known components of laundry
detergent compositions which chemically decompose stains and provide improved
cleaning of washed fabrics. For example, U.S. Patent 5,858,948 describes
laundry
detergent compositions wherein the combination of a protease enzyme with a
modified
polyamine cotton soil release agent provides improved cleaning and soil
release benefits.
In U.S. Patent 5,707,950 the inclusion of lipase enzyme in combination with a
proteolytic enzyme and a surfactant is said to provide dingy soil clean-up and
whiteness
maintenance benefits. The protease enzymes are described as providing from
0.005 to 0.1
Anson units of activity per gram of composition.
In U.S. Statutory Invention Registration H1513 there is described a detergent
composition containing a defined fatty acid amide surfactant in combination
with oleoyl
sarcosinate to provide improved soil and stain removal from fabrics. Enzymes
selected
from among protease, cellulase and lipase enzymes are optional additives to
the detergent
composition to remove protein-based, carbohydrate-based or triglyceride-based
stains, as
well as for preventing dye transfer, and for fabric restoration.
Endo-type alkaline cellulases are a known class of cellulase enzyme which may
be
included as an ingredient in detergent compositions. Japanese Patent Abstracts
corresponding to JP 402255898A (10/16/1990) and JP 3612802760A (12/10/1986)
filed
in the name of Kao Corp. describe a bacterial strain capable of producing endo-
type
alkaline cellulase enzymes for use in detergent compositions.
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U.S. Patent 5,798,327 relates to an aqueous liquid detergent composition
containing a defined endoglucanase cellulase enzyme and a proteolytic enzyme.
The
resulting enzymatic detergent composition is said to provide in-wash stability
of the
cellulase enzyme.
While laundry detergent compositions containing protease, cellulase and/or
lipase
enzymes have been extensively described in the patent literature, there
remains a need in
the art for improving and enhancing the whitening and stain removal benefits
capable of
being provided to fabrics laundered with commercial detergent compositions
containing
enzymes for purposes of stain removal.
Summary of the Invention
In accordance with the present invention, there is provided a laundry
detergent
composition which provides enhanced whitening and stain removal benefits to
washed
laundry comprising:
a) from about 1 % to about 50%, by weight, of a surfactant or surfactant
mixture
selected from the group consisting of anionic and nonionic surfactants;
b) a protease enzyme in an amount sufficient to provide from at least about
0.030
to about 3.0 Kilo Novo Protease Units (KNPU) of activity of protease enzyme
per gram of detergent composition;
c) a cellulase enzyme of the endoglucanase type in an amount sufficient to
provide from about 0.5 to about 100 CMC units per gram of detergent
composition; said detergent composition being free of an endoglucanase
enzyme which is produced from Thermomonospora fusca; and
d) from about 0.5% to about 10%, by weight, of an acrylic acid-based polymer
or
copolymer in an amount effective to provide soil suspension and/or anti-
redeposition benefits in the wash bath.
In accordance with the process of the invention laundering of stained or
soiled
fabrics is effected by washing the fabrics to be laundered in an aqueous wash
solution
containing an effective amount of the above-described laundry detergent
composition.
The present invention is predicated on the discovery that the combination of
protease enzyme, endo-cellulase enzyme and acrylic acid-based polymer or
copolymer in
detergent composition in accordance with the invention provides surprisingly
effective
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stain removal and whitening significantly better than would be expected by the
levels of
enzyme in the composition itself. In particular, it has been discovered that
when protease
enzyme is provided in a detergent composition at a level greater than about
.06 Anson
units of activity per gram of composition, the resultant combination of
protease and endo-
cellulase enzyme provides a synergistic whitening effect in the presence of an
acrylate-
based polymer such as sodium polyacrylate.
One Novo Protease Units (NPU) is the amount of enzyme which hydrolyzes
casein at such a rate that the initial rate of formation of peptides/minute
corresponds to 1
micromole of glycine/minute. 1 KNPU (Kilo NPU) equals 1000 NPU.
For purposes of making comparisons, 3 KNPU are approximately equal to 1
Anson unit (AU). One KNPU corresponds to about 80,000 Alkaline Delft Units or
about
80 Properase Units (PU) or about 2.5 Genencor Subtilisin Units (GSU).
Detailed Description of Invention
The term "cellulase enzyme" as used in the present specification refers to
those
enzyme compositions derived from fungal sources or microorganisms genetically
modified so as to incorporate and express all or part of the cellulase genes
obtained from
a fungal source ("fungal cellulases") or bacterial sources of cellulase. Fungi
and bacteria
capable of providing cellulase enzymes which are useful in detergent
compositions are
well documented in the literature.
Cellulases are known to be comprised of several enzyme classifications having
different substrate specificity, enzymatic action patterns and the like. For
example,
cellulases can contain cellulase classifications which include endoglucanases
and exo-
cellobiohydrolases. For purposes of the present invention, the term "endo-
cellulase"
refers to those cellulase enzymes and enzyme-containing compositions which
comprise at
least 50% endoglucanase type components among other cellulose degrading
cellulase
components.
Most cellulases generally have their optimum activity in the acidic or neutral
pH
range although some fungal cellulases are known to possess significant
activity under
neutral and slightly alkaline conditions. Optimum activity of an enzyme is
ordinarily a
function of both pH and temperature.
The activity of endo-cellulase enzyme are generally measured using traditional
biochemical activity tests based on the ability of the cellulase enzyme in
question to
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hydrolyze soluble cellulose derivatives such as carboxymethylcellulose (CMC)
thereby
reducing the viscosity of CMC-containing solutions.
One carboxymethyl cellulose unit (CMCU) is the amount of enzyme which acts
on carboxymethyl cellulose (CM) to form sugars at such a rate that the rate of
formation
of glucose/minute corresponds to 1.0 micromoles/minute. One CMCU corresponds
to
one International Unit (ILJ).
For purposes of the present invention, the amount of endo-cellulose enzyme in
the
laundry detergent composition is from about 0.5 to about 100 CMC units per
gram of
composition. Preferred activity levels range from about 1 to 25 CMC units per
gram, and
most preferably from about 1 to 10 CMC units per gram.
The protease enzymes used in the compositions of the invention are present at
levels sufficient to provide at least about 0.030 to about 3.0 KNPU of
activity per gram of
composition, preferably from about 0.06 to about 0.5 KNPU per gram, and most
preferably from about 0.06 to about 0.1 KNPU per gram of composition. Protease
enzyme
may be of animal, vegetable or microorganism origin. Suitable proteolytic
include the
many species known to be adapted for use in detergent compositions. Especially
useful
commercial enzyme preparations for the present invention include Alcalase~,
Esperase~
and Savinase° sold by Novo Industries, Denmark, and Maxatase°,
Maxacal°, Purafect°,
and Properase° sold by Genecor International.
The acrylic acid-based polymers which are useful for the compositions of the
invention include the water-soluble salts of polymerized acrylic acid, such
as, for
example, the alkali metal, ammonium and substituted ammonium salts. Sodium
polyacrylate is particularly preferred. The average molecular weight of such
polymers
ranges from about 2,000 to about 10,000, preferably about 4,000 to about
7,000. Use of
polyacrylates of this type in detergent compositions is disclosed extensively
in the patent
literature such as, for example, in U.S. Patent No. 3,308,067.
Homopolymers or copolymers of acrylic acid or methacrylic acid or
hydroxyacrylic acid may be used. Sodium polyacrylate and sodium
polyhydroxyacrylate
are preferred homopolymers.
Acrylic/maleic-based copolymers may also be used. These copolymers include
the water-soluble salts of copolymers of acrylic acid and malefic acid. The
average
molecular weight of such copolymers ranges from about 2,000 to about 75,000.
While
the average molecular weight of the polymer can vary over a wide range, it is
preferably
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from 1,000 to about 500,000, more preferably from about 2,000 to about
250,000, and
most preferably from about 3,000 to 100,000. Terpolymers based on acrylic acid
may
also be useful. A preferred terpolymer for purposes of the invention is an
acrylic/maleic/vinyl acetate terpolymer having a molar ratio of about 45/50/5
and a
molecular weight of about 4,500. Molecular weights of such terpolymer may
range
advantageously from about 500 to about 100,000.
Any suitable nonionic detergent compound may be used as a surfactant in the
present compositions, with many members thereof being described in the various
annual
issues of Detergents and Emulsifiers, by John W. McCutcheon. Such volumes give
chemical formulas and trade names for commercial nonionic detergents marketed
in the
United States, and substantially all of such detergents can be employed in the
present
compositions. However, it is highly preferred that such nonionic detergent be
a
condensation product of ethylene oxide and higher fatty alcohol (although
instead of the
higher fatty alcohol, higher fatty acids and alkyl [octyl, nonyl and isooctyl]
phenols may
also be employed). The higher fatty moieties, such as the alkyls, of such
alcohols and
resulting condensation products, will normally be linear, of 10 to 18 carbon
atoms,
preferably of 10 to 16 carbon atoms, more preferably of 12 to 15 carbon atoms
and
sometimes most preferably of 12 to 14 carbon atoms. Because such fatty
alcohols are
normally available commercially only as mixtures, the numbers of carbon atoms
given are
necessarily averages but in some instances the ranges of numbers of carbon
atoms may be
actual limits for the alcohols employed and for the corresponding alkyls.
The ethylene oxide (Et0) contents of the nonionic detergents will normally be
in
the range of 3 to 15 moles of Et0 per mole of higher fatty alcohol, although
as much as
20 moles of Et0 may be present. Preferably such Et0 content will be 3 to 10
moles and
more preferably it will be 6 to 7 moles, e.g., 6.5 or 7 moles per mole of
higher fatty
alcohol (and per mole of nonionic detergent). As with the higher fatty
alcohol, the
polyethoxylate limits given are also limits on the averages of the numbers of
Et0 groups
present in the condensation product. Examples of suitable nonionic detergents
include
those sold by Shell Chemical Company under the trademark Neodol~, including
Neodol
25-7, Neodol 23-6.5 and Neodol 25-3.
Other useful nonionic detergent compounds include the alkylpolyglycoside and
alkylpolysaccharide surfactants, which are well known and extensively
described in the
art.
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Preferred alkyl polysaccharides for use herein are alkyl polyglucosides having
the
formula
RO(CnH2n0)r(Z)x
wherein Z is derived from glucose, R is a hydrophobic group selected from the
group
consisting of alkyl, alkylphenyl, hydroxyalkylphenyl, and mixtures thereof in
which said
alkyl groups contain from about 10 to 18, preferably from about 12 to about 14
carbon
atoms; n is 2 or 3 preferably, 2; r is from 0 to 10, preferably 0; and x is
from 1.5 to 8,
preferably from 1.5 to 4, most preferably from 1.6 to 2.7. To prepare these
compounds, a
long chain alcohol (R20H where R2 is an alkyl group of about C10 to Clg) can
be reacted
with glucose, in the presence of an acid catalyst to form the desired
glucoside.
Alternatively, the alkyl polyglucosides can be prepared by a two step
procedure in which
a short chain alcohol (R10H wherein R1 is an alkyl having from 1 to 6 carbon
atoms) is
reacted with glucose or a polyglucoside (x= 2 to 4) to yield a short chain
alkyl glucoside
(x = 1 to 4) which can in turn be reacted with a longer chain alcohol (R20H)
to displace
the short chain alcohol and obtain the desired alkyl polyglucoside. If this
two step
procedure is used, the short chain alkylglucoside content of the final alkyl
polyglucoside
material should be less than 50%, preferably less than 10%, more preferably
less than
about 5%, most preferably 0% of the alkyl polyglucoside.
The amount of unreacted alcohol (the free fatty alcohol content) in the
desired
alkyl polysaccharide surfactant is preferably less than about 2%, more
preferably less than
about 0.5% by weight of the total of the alkyl polysaccharide. For some uses
it is
desirable to have the alkyl monosaccharide content less than about 10%.
The term "alkyl polysaccharide surfactant" is intended to represent both the
preferred glucose and galactose derived surfactants and the less preferred
alkyl
polysaccharide surfactants. Throughout this specification, "alkyl
polyglucoside" is used
to include alkyl polyglycosides because the stereochemistry of the saccharide
moiety is
changed during the preparation reaction.
An especially preferred APG glycoside surfactant is Glucopon 625 CSUP
glycoside manufactured by the Henkel Corporation of Ambler, PA. Glucopon 625
CSUP
is a nonionic alkyl polyglycoside characterized by the formula:
CnH(2n+i)~(C6H10~5)xH
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wherein the alkyl chain length distribution is as follows: for n=10 (2%); n=12
(65%);
n=14 (21-28%); n=16 (4-8%) and n=18 (0.5%) and x (degree of polymerization) =
1.6.
Glucopon 625 CSUP has a pH of 11 to 11.5 (10% of Glucopon 625 in distilled
water); a
specific gravity at 25°C of 9.1 lbs./gallon; a calculated HLB of 12.1
and a Brookfield
viscosity at 35°C, 21 spindle, 5-10 RPM of 3,000 to 7,000 cps.
Among the anionic surface active agents useful in the present invention are
those
surface active compounds which contain an organic hydrophobic group containing
from
about 8 to 26 carbon atoms and preferably from about 10 to 18 carbon atoms in
their
molecular structure and at least one water-solubilizing group selected from
the group of
sulfonate, sulfate, carboxylate, phosphorate and phosphate so as to form a
water-soluble
detergent.
Examples of suitable anionic detergents include soaps, such as, the water-
soluble
salts (e.g., the sodium potassium, ammonium and alkanol-ammonium salts) of
higher
fatty acids or resin salts containing from about 8 to 20 carbon atoms and
preferably 10 to
18 carbon atoms. Particularly useful are the sodium and potassium salts of the
fatty acid
mixtures derived from coconut oil and tallow, for example, sodium coconut soap
and
potassium tallow soap.
The anionic class of detergents also includes the water-soluble sulfated and
sulfonated detergents having an aliphatic, preferably an alkyl radical
containing from
about 8 to 26, and preferably from about 12 to 22 carbon atoms. Examples of
the
sulfonated anionic detergents are the higher alkyl aromatic sulfonates such as
the higher
alkyl benzene sulfonates containing from about 10 to 16 carbon atoms in the
higher alkyl
group in a straight or branched chain, such as, for example, the sodium,
potassium and
ammonium salts of higher alkyl benzene sulfonates, higher alkyl toluene
sulfonates and
higher alkyl phenol sulfonates.
Other suitable anionic detergents are the olefin sulfonates including long
chain
alkene sulfonates, long chain hydroxyalkane sulfonates or mixtures of alkene
sulfonates
and hydroxyalkane sulfonates. The olefin sulfonate detergents may be prepared
in a
conventional manner by the reaction of S03 with long chain olefins containing
from
about 8 to 25, and preferably from about 12 to 21 carbon atoms, such olefins
having the
formula RCH=CHR1 wherein R is a higher alkyl group of from about 6 to 23
carbons and
RI is an alkyl group containing from about 1 to 17 carbon atoms, or hydrogen
to form a
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mixture of sultones and alkene sulfonic acids which is then treated to convert
the sultones
to sulfonates. Other examples of sulfate or sulfonate detergents are paraffin
sulfonates
containing from about 10 to 20 carbon atoms, and preferably from about 15 to
20 carbon
atoms. The primary paraffin sulfonates are made by reacting long chain alpha
olefins and
bisulfites.
Other suitable anionic detergents are sulfated ethoxylated higher fatty
alcohols of
the formula RO(C2H40)mS03M, wherein R is a fatty alkyl of from 10 to 18 carbon
atoms,
m is from 2 to 6 (preferably having a value from about 1/5 to 1/2 the number
of carbon
atoms in R) and M is a solubilizing salt-forming canon, such as an alkali
metal,
ammonium, lower alkylamino or lower alkanolamino, or a higher alkyl benzene
sulfonate
wherein the higher alkyl is of 10 to 15 carbon atoms. The proportion of
ethylene oxide in
the polyethoxylated higher alkanol sulfate is preferably 2 to 5 moles of
ethylene oxide
groups per mole of anionic detergent, with three moles being most preferred,
especially
when the higher alkanol is of 11 to 15 carbon atoms. A preferred
polyethoxylated alcohol
sulfate detergent is marketed by Shell Chemical Company as Neodol 25-3S.
The most highly preferred water-soluble anionic detergent compounds are the
ammonium and substituted ammonium (such as mono, di and tri ethanolamine),
alkali
metal (such as, sodium and potassium) and alkaline earth metal (such as,
calcium and
magnesium) salts of the higher alkyl benzene sulfonates, olefine sulfonates
and higher
alkyl sulfates. Among the above-listed anionics, the most preferred are the
sodium linear
alkyl benzene sulfonates (LABS), and especially those wherein the alkyl group
is a
straight chain alkyl radical of 12 or 13 carbon atoms.
Amphoteric or ampholytic detergents may be used, if desired, to supplement the
anionic and/or nonionic detergent in the composition of the invention.
Ampholytic
detergents are well known in the art and many operable detergents of this
class are
disclosed by A. M. Schwartz, J.W. Perry and J. Berch in "Surface Active Agents
and
Detergents," Interscience Publishers, N.Y., 1958, Vol. 2.
A preferred amphoteric surfactant is of the formula
R-(N-CH2CH~CH2)y-N-CHZCOOM
CH2COOM CH2COOM
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wherein R is an aliphatic hydrocarbonyl, perferably fatty alkyl or fatty
alkylene, of 16 to
18 carbon atoms, M is alkali metal, and y is 3 to 4. More preferably R is
tallowalkyl
(which is a mixture of stearyl, palmityl and oleyl in the proportions in which
they occur in
tallow), M is sodium and y is about 3.5, representing a mixture of about equal
parts of the
amphoteric surfactant wherein y is 3 and such amphoteric surfactant wherein y
is 4.
Among the more preferred amphoteric surfactants of this type is that available
commercially under the trade name Ampholak~'~' 7TX, which is obtainable from
Kenobel
AB, a unit of Nobel Industries, Sweden.
Builder materials may advantageously be included in the present compositions
and
may comprise any suitable water soluble or water insoluble builder, either
inorganic or
organic, providing that it is useful as a builder for the particular nonionic
or anionic
detergent compounds that may be employed. Such builders are well known to
those of
skill in the detergent art and include: alkali metal phosphates, such as
alkali metal
polyphosphates and pyrophosphates, including alkali metal tripolyphosphates;
alkali
metal silicates, including those of Na20:Si02 ratio in the range of 1:1.6 to
1:3.0,
preferably 1:2.0 to 1:2.8, and more preferably 1:2.35 or 1:2.4; alkali metal
carbonates;
alkali metal bicarbonates; alkali metal sesquicarbonates (which may be
considered to be a
mixture of alkali metal carbonates and alkali metal bicarbonates); alkali
metal borates,
e.g., borox; alkali metal citrates; alkali metal gluconates; alkali metal
nitrilotriacetates;
zeolites, preferably hydrated zeolites, such as hydrated Zeolite A, Zeolite X
and Zeolite
Y; and mixtures of individual builders within one or more of such types of
builders.
Preferably the builders will be sodium salts and will also be inorganic. A
highly preferred
non-phosphate mixed water soluble and water insoluble builder composition
comprises
carbonate, bicarbonate and zeolite builders. Phosphate-containing builder
systems will
usually be based on alkali metal (sodium) tripolyphosphate and silicate
builders, with
such silicate being in relatively minor proportion.
Zeolite A-type aluminosilicate builder, usually hydrated, with about 15 to 25%
of
water of hydration is particularly advantageous for the present invention.
Hydrated
zeolites X and Y may be useful too, as may be naturally occurring zeolites
that can act as
detergent builders. Of the various zeolite A products, zeolite 4A, a type of
zeolite
molecule wherein the pore size is about 4 Angstroms, is often preferred. This
type of
zeolite is well known in the art and methods for its manufacture are described
in the art
such as in U.S. Patent 3,114,603.
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The zeolite builders are generally of the formula
(Na~O)X ~ (A12O3)y ~ (SiO2)z ~ w H2O
wherein x is l, y is from 0.8 to 1.2, preferably about 1, z is from 1.5 to
3.5, preferably 2 or
3 or about 2, and w is from 0 to 9, preferably 2.5 to 6. The crystalline types
of zeolite
which may be employed herein include those described in "Zeolite Molecular
Series" by
Donald Breck, published in 1974 by John Wiley & Sons, typical commercially
available
zeolites being listed in Table 9.6 at pages 747-749 of the text, such Table
being
incorporated herein by reference.
The zeolite builder should be a univalent canon exchanging zeolite, i.e., it
should
be aluminosilicate of a univalent cation such as sodium, potassium, lithium
(when
practicable) or other alkali metal, or ammonium. A zeolite having an alkali
metal canon,
especially sodium, is most preferred, as is indicated in the formula shown
above. The
zeolites employed may be characterized as having a high exchange capacity for
calcium
ion, which is normally from about 200 to 400 or more milligram equivalents of
calcium
carbonate hardness per gram of the aluminosilicate, preferably 250 to 350 mg.
eg./g., on
an anhydrous zeolite basis.
Other components may be present in the detergent compositions to improve the
properties and in some cases, to act as diluents or fillers. Among the
suitable fillers, the
most preferred is sodium sulfate. Illustrative of suitable adjuvants are
enzymes
supplementary to the lipase which is an integral component of the present
compositions to
further promote cleaning of certain hard to remove stains from laundry or hard
surfaces.
Among enzymes, the proteolytic and amylolytic enzymes are most useful to
supplement
the lipase. Other useful adjuvants are foaming agents, such as lauric myristic
diethanolamide, when foam is desired, and anti-foams, when desired, such as
dimethyl
silicone fluids. Also useful are bleaches, such as sodium perborate, which may
be
accompanied by suitable activators) to promote bleaching actions in warm or
cold water.
Flow promoting agents, such as hydrated synthetic calcium silicate, which is
sold under
the trademark Microcel~ C, may be employed in relatively small proportions.
Other
adjuvants usually present in detergent compositions include fluorescent
brighteners, such
as stilbene brighteners, colorants such as dyes and pigments and perfume.
Examples
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The following compositions were prepared. Composition J was a composition of
the
invention containing polyacrylate, cellulase, and a high level of protease.
Compositions G and
K contained only components of the invention, with G having polyacrylate and
cellulase, but a
level of protease outside the invention, and K having protease and cellulase.
Example E was a
control composition with conventional levels of protease and other active
ingredients.
Component (wt. E G J K
%)
LAS~'~ 21.8 24.1 21.4 21.4
Sodium Tripolyphosphate18.2 25.6 20.6 18.6
Sodium Carbonate 10 11 8.5 11
Sodium Silicate 8.9 8.8 8.8 8.8
Optical Brightener0.04 0.04 0.05 0.05
Polyacrylate~4~ - 1.9 2.3
Protease~z~ 0.42 0.45 0.87 0.77
Endo-Cellulase~3~ 1.0 1.0 0.35
Clay 4.2 5.1 4.3 4.4
Perborate 2.1 1.9
Na Sulfate 31 11.6 23.6 28.4
Moisture 5.44 8.31 6.68 6.23
Total 100 100 100 100
~'~ Linear alkyl benzene sulfonate anionic surfactant.
~2~ The protease enzyme is Savinase 6T from Novo Nordisk Corp. The activity
corresponding to 0.42 wt. % as in
Composition E is 0.0252 KNPU per gram of composition.
~3~ The Endo - cellulose enzyme is KAC-500 from Kao Corp. The activity
corresponding to 1.0 wt% as in compositions G
and J is 5 CMC units per gram of composition.
~4~ Polyacrylate used was a copolymer of acrylic and malefic acids having a
molecular weight of about 20,000
The compositions were evaluated monadically by over 160 panelists per
formulation during a
five week period. Panelists evaluated sixteen cleaning and whitening
attributes versus the
control composition E. Statistically significant differences were obtained at
a 90 %
confidence level. Detailed results are provided below.
The panelists indicated that composition J of the invention provided
significant cleaning and
whitening benefits versus the control (Example E) for 15 of 16 attributes.
Compositions G
and K provided little or no noticeable benefit according to the panelists. A
synergy was
clearly demonstrated between the two enzymes when used in amounts according to
the
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invention in combination with polyacrylate to provide cleaning and whitening
benefits with
the use of composition J.
Panel Res onse
Summary
Type Composition Number of Winning
Attributes vs.
Control
Control E Control
Comparative G (Cellulase, Polyacrylate and 0
low level
Protease)
Com arative K (Protease, Cellulase) 3
Invention j J (Protease, Cellulase, Polyacrylate)15
12