Note: Descriptions are shown in the official language in which they were submitted.
CA 02363097 2003-05-23
METHOD OF REMOVING STAINS FROM A SURFACE
'T_FiCHNICAL FIELD
The present invention relates to methods of removing stains from a surface
using a
composition containing a specific combination of surfactants. Preferred
compositions used are
automatic dishwashing detergent compositions containing an oxygen bleaching
systems, further
preferably comprising bleach activators and/or metal-containing bleach
catalysts (e.g.,
manganese and/or selected cobaltJammonia catalysts), and detersive enzymes
(e.g., amylase;
protease).
BACKGROUND OF THE INVENTION
In household cleaning formulation, such as hard surface cleaning
compositions'(HSC)
and automatic dishwashing compositions (ADW), the problem of "red sauce
redeposition" is
well know. This is when a surface is cleaned, such as in an automatic
dishwasher, and the soil
redeposits back on to a surface that has just been cleaned, leaving the
surface stained and
unsightly. Once the stain has dried it effectively is a permanent addition to
the surface, and
virtually impossible to remove. This is especially true of hydrophobic
surfaces, for example
plastic. Numerous attempts have been made to deal with this deposition. This
"red sauce
redeposition" is caused by soils which contain tomato soils, such as lasagna,
carotene soils, such
as in cooked carrots, (also known as lycopene soils) and mixtures thereof.
One solution which has been attempted is the use of bleaches, to prevent the
formation
of the "red soil" stains and remove existing ones. However, the bleaches have
a minimal effect
on the existing stains and preventing the formation of more "red soil" stains.
Furthermore, some
bleaches while cleaning the surface better, only exacerbate the problem by
removing more soil
which is then more able to redeposit on to the surfaces to for "red sauce
redeposition".
Consequently, there remains the need for a way to prevent the formation of
this "red
sauce redeposition" by preventing the redeposition on to a surface of the "red
soil".
BACKGROUND ART
WO 94/22800, published October 13, 1994 by Olin Corporation, US patent
No. 5,912,218, issued July 15, 1999.
SUMMARY OF THE IIW~NT10N
It has now been surprisingly found that that methods using compositions
comprising an
oxide surfactant and specific nonionic surfactants prevent the redtposition of
"red soil", and
thereby preventing "red sauce redeposition" from occurring. This is surprising
considering that
oxide surfactant surfactants, such as amine oxide, are high sudsing
surfactants making them
unsuitable for use in situations which require low foam, such as in automatic
dishwashing
CA 02363097 2003-05-23
2
applications. It is this specific combination of oxide surfactant and specific
nonionic surfactants
in compositions which prevents the formation of "red sauce redeposition".
The present invention therefore encompasses a method for removing stains from
a surface
and preventing the redeposition of soil from a surface comprising the steps of
applying an
aqueous solution of a composition to a stained surface in need of stain
removal, wherein the
composition comprises:
(a) from about O.I% to about 15%, preferably from about 0.2% to about 10%,
more
preferably from about 0.5% to about 5%, weight of the composition of an oxide
surfactant, the oxide surfactant being selected from the group consisting of,
amine
oxides, phosphine oxides, sulfoxides and mixtures thereof;
(b) from about 0.1% to about 15%, preferably from about 0.2% to about 10%,
more .
preferably from about 0.5% to about 5%, by weight of the composition of one or
more low cloud point nonionic surfactants having a cloud point of less than
30°C the
nonionic surfactants are selected from the group consisting of ethoxylated-
propoxylated alcohol, capped poly(oxyalkylated) alcohols and mixtures thereof,
wherein said capped nonionic surfactant is substantially free of dimers and
trimers;
(c) optionally, from about 0.1% to about 40% by weight of the composition of
an
oxygen bleaching agent;
(d) optionally, from about 5% to about 90%, preferably from about 5% to about
75%,
more preferably from about 10% to about 50% by weight of the composition of a
builder; and
(e) adjunct materials, preferably automatic dishwashing detergent adjunct
materials
selected from the group consisting of enzymes, chelating agents, and mixtures
thereof;
wherein the weight ratio the nonionic surfactants to the oxide surfactant
being within the range
of from about 25:1 to about 1:5, preferably about 3:1 to about 15:1; the
stained surface is a
hydrophobic surface; the stains are selected from the group consisting of
tomato stains, carotene
stains, and mixtures thereof; and wherein the composition prevents
redeposition of the stains
once it has been removed from the stained surface. The composition may
comprise from
0.1% to 15%, by weight of the composition of one or more high cloud point
nonionic
surfactant having a cloud point of greater than 30°C.
The preferred compositions useful in the methods herein comprise a bleaching
system which is a source of hydrogen peroxide, preferably perborate and/or
percarbonate,
and preferably also comprise a cobalt-containing bleach catalyst or a
manganese-
containing bleach catalyst. Preferred cobalt-containing bleach catalysts have
the formula:
(C~~3)n(M)m~B)b)Tv
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3
wherein cobalt is in the +3 oxidation state; n is 4 or 5 (preferably 5); M is
one or more
ligands coordinated to the cobalt by one site; m is 0, 1 or 2 (preferably 1);
B is a ligand
coordinated to the cobalt by tW o sites; b is 0 or 1 (preferably 0), and when
b=0, then m+n = 6,
and when b=1, then m=0 and n=4; and T is one or more counteranions present in
a number y,
where y is an integer to obtain a charge-balanced salt (preferably y is 1 to
3; most preferably 2
when T is a -1 charged anion); and wherein further said catalyst has a base
hydrolysis rate
constant of less than 0.23 M-1 s-1 (25°C). Also, in another mode, the
compositions useful in the
methods of the present invention are those wherein the bleach catalyst is a
member selected from
the group consisting of manganese bleach catalysts, especially manganese
"TACN", as described
more fully hereinafter.
Additional bleach-improving materials can be present such as bleach activator
materials,
including tetraacetylethylenediamine ("TAED") and cationic bleach activators,
e.g., 6-
trimethylammoniocaproyl caprolactam, tosylate salt.
The preferred compositions useful in the methods herein further comprise a
protease
and/or amylase enzyme. Whereas conventional amylases such as TERMAMYL~ may be
used
with excellent results. Preferred compositions can use oxidative stability-
enhanced amylases.
Such an amylase is available from Novo Nordisk (described more fully in WO
94/02597,
published February 3, 1994) and from Genencor International (described more
fully in WO
94/18314, published August 18, 1994) Oxidative stability is enhanced by
substitution of the
methionine residue located in position 197 of B.Licheniformis or the
homologous position
variation of a similar parent amylase. Typical proteases include Esperase,
Savinase, and other
proteases as described hereinafter.
The present invention encompasses (but is not limited to) the use of granular-
form, fully-
formulated automatic dishwashing compositions in which additional ingredients,
including other
enzymes (especially proteases and/or amylases) are formulated.
All parts, percentages and ratios used herein are expressed as percent weight
unless
otherwise specified. All documents cited are, in relevant part, incorporated
herein by reference.
DETAILED DESCRIPTION OF THE INVENTION
Method of the present invention
It is preferred that the method of the present invention be performed in an
automatic
dishwasher, with the composition used being an ADW composition. However, the
composition
could also be a HSC composition and the method could be performed on a
hydrophobic surface
like a plastic cutting board, on a vinyl floor or on a kitchen counter top.
It is preferred that after the composition is applied to the stained surface
that the surface
is rinsed with water, more preferably, rinsed twice.
Stains
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4
The stains which the method of the present invention seek to remove and
prevent
redeposition are selected from tomato satins, carotene stains (also know as
lycopene stains) and
mixtures thereof. These soils are well know in the art to cause the "red soil
redeposition" which
causes the unsightly staining of hydrophobic surfaces.
Hydrophobic surface
Hydrophobic surfaces mean any surface which naturally repels water. The best
example
of this is plastic. In the method of the present invention the hydrophobic
surface is defined as
any hydrophobic surface which could suffer "red sauce redeposition" during
cleaning. This
would mean that if the method was performed in an automatic dishwasher, then
any possible
hydrophobic surface in the automatic dishwasher is meant. This would include
not only those
which are put in the dishwasher to be cleaned, such as plasticware, tableware,
plates, knives,
forks, spoons, cookware, ladles, spatulas, spoons, baby bottle, baby pacifies,
and other infant
feeding equipment, but also any of the internal surfaces of the automatic
dishwasher itself, such
as the dish racks, silverware racks, the sprayer arm, or even the internal
walls of the dishwasher.
Plastics, would include, but are not limited to, acrylates, methacrylates,
high density
polyethylene, PET, POET, PVC, melanine, and copolymers of these.
Compositions used in the method of the present invention
The compositions used in the present invention may be in any suitable form,
such as a
liquid, granule, powder, tablet, liqui-gel, gel, thixatropic liquid. It is
preferred that the
compositions used in the methods of the present invention be in the form of
automatic
dishwashing compositions (ADD). However, other compositions, such as hard
surface cleaning
compositions (HSC), can be used in the methods of the present invention.
The compositions used in the methods of the present invention comprise a mixed
surfactant system, and preferably also include builder, bleaching agent (such
as a source of
hydrogen peroxide) and/or detersive enzymes. Bleaching agents useful herein
include sources of
hydrogen peroxide, including any common hydrogen-peroxide releasing salt, such
as sodium
perborate, sodium percarbonate, and mixtures thereof. Also useful are sources
of available
oxygen such as persulfate bleach (e.g., OXONE, manufactured by DuPont). In the
preferred
embodiments, additional ingredients such as water-soluble silicates (useful to
provide alkalinity
and assist in controlling corrosion), dispersant polymers (which modify and
inhibit crystal
growth of calcium and/or magnesium salts), chelants (which control transition
metals), alkalis
(to adjust pH), and detersive enzymes (to assist with tough food cleaning,
especially of starchy
and proteinaceous soils), are present. Additional bleach-modifying materials
such as
conventional bleach activators (e.g. TAED and/or bleach catalysts) may be
added, provided that
any such bleach-modifying materials are delivered in such a manner as to be
compatible with the
purposes of the present invention. The present useful compositions may,
moreover, comprise
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one or more processing. aids, fillers, perfumes, conventional enzyme particle-
making materials
including enzyme cores or "nonpareils", as well as pigments, and the like.
In general, materials used for the production of the compositions used herein
are
preferably checked for compatibility with spotting/filming on glassware. Test
methods for
spotting/filming are generally described in the automatic dishwashing
detergent literature,
including DIN and ASTM test methods. Certain oily materials, especially at
longer chain
lengths, and insoluble materials such as clays, as well as long-chain fatty
acids or soaps which
form soap scum are therefore preferably limited or excluded from the instant
compositions.
Amounts of the essential ingredients can vary within wide ranges, however
preferred
automatic dishwashing detergent compositions herein (which typically have a 1%
aqueous
solution pH of above about 8, more preferably from about 9.5 to about 12, most
preferably from
about 9.5 to about 10.5) are those wherein there is present: from about 5% to
about 90%,
preferably from about 5% to about 75%, of builder; from about 0.1% to about
40%, preferably
from about 0.5% to about 30%, of bleaching agent; from about 0.1% to about
15%, preferably
from about 0.2% to about 10%, of the mixed surfactant system; from about
0.0001% to about
1%, preferably from about 0.001% to about 0.05%, of a metal-containing bleach
catalyst (most
preferred cobalt catalysts useful herein are present at from about 0.001% to
about 0.01%); and
from about 0.1% to about 40%, preferably from about 0.1% to about 20% of a
water-soluble
(two ratio) silicate. Such fully-formulated embodiments typically further
comprise from about
0.1% to about 15% of a polymeric dispersant, from about 0.01% to about 10% of
a chelant, and
from about 0.00001% to about 10% of a detersive enzyme, though further
additional or adjunct
ingredients may be present. The compositions used herein in granular form
typically limit water
content, for example to less than about 7% free water, for best storage
stability.
While the compositions useful in the methods of this invention (especially
those
comprising detersive enzymes) are substantially free of chlorine bleach. By
"substantially free"
of chlorine bleach is meant that the formulator does not deliberately add a
chlorine-containing
bleach additive, such as a dichloroisocyanurate, to the composition to be
used. However, it is
recognized that because of factors outside the control of the formulator, such
as chlorination of
the water supply, some non-zero amount of chlorine bleach may be present in
the wash liquor.
The term "substantially free" can be similarly constructed with reference to
preferred limitation
of other ingredients.
By "effective amount" herein is meant an amount which is sufficient, under
whatever
comparative test conditions are employed, to enhance cleaning of a soiled
surface. Likewise, the
term "catalytically effective amount" refers to an amount of metal-containing
bleach catalyst
which is sufficient under whatever comparative test conditions are employed,
to enhance
cleaning of the soiled surface. In automatic dishwashing, the soiled surface
may be, for
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example, a porcelain cup with tea stain, a porcelain cup with lipstick stain,
dishes soiled with
simple starches or more complex food soils, or a plastic spatula stained with
tomato soup. The
test conditions will vary, depending on the type of washing appliance used and
the habits of the
user. Some machines have considerably longer wash cycles than others. Some
users elect to use
warm water without a great deal of heating inside the appliance; others use
warm or even cold
water fill, followed by a warm-up through a built-in electrical coil. Of
course, the performance
of bleaches and enzymes will be affected by such considerations, and the
levels used in fully-
formulated detergent and cleaning compositions can be appropriately adjusted.
Surfactant System
Surfactants useful in the method of the present invention are desirably
included in the
present detergent compositions at levels of from about 0.1% to about 15% of
the composition.
In general, bleach-stable surfactants are preferred. The surfactant system
used may include
optional surfactants such as other nonionic surfactants, such as high cloud
point surfactants,
anionic surfactants, such as alkylethoxysulfates, zwitterionic surfactants,
such as betaines, and
mixtures thereof.
The essential surfactant system useful herein are mixtures of a low cloud
point nonionic
surfactant combined with an oxide surfactant in a weight ratio preferably
within the range of
from about 25:1 to about 1:5, preferably from about ??? to about ???, more
preferably from
about 3:1 to about 15:1.
Oxide Surfactant - The oxide surfactant is selected from the group consisting
of, amine oxides,
phosphine oxides, sulfoxides and mixtures thereof, with amine oxide being
preferred.
Preferred amine oxides have the formula
O
R3~OR4)xN~Rs)2
wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures
thereof containing from
about 8 to about 22 carbon atoms; R4 is an alkylene or hydroxyalkylene group
containing from
about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3;
and each RS 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.
Preferred phosphine oxides have the formula
O
R3~~R4)xP~RS)2
wherein R3, R4, x, and RS are as herein before defined.
Preferred sulfoxides have the formula
O
R3~~R4)xS~S)2
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7
wherein R3, R4, x, and RS are as herein before defined.
Essential nonionic surfactant - The one or more low cloud point nonionic
surfactants having a
cloud point of less than 30°C, are selected from the group consisting
of ethoxylated-
propoxylated alcohol, capped poly(oxyalkylated) alcohols and mixtures thereof;
wherein the
capped nonionic surfactant is substantially free of dimers and trimers.
Examples of suitable
surfactants are ethoxylated-propoxylated alcohol (e.g., Olin Corporation's
Poly-Tergent~ SLF-
18) and epoxy-capped poly(oxyalkylated) alcohols (e.g., Olin Corporation's
Poly-Tergent~ SLF-
18B series of nonionics, as described, for example, in WO 94/22800, published
October 13,
1994 by Olin Corporation).
As used herein, a "low cloud point" nonionic surfactant is defined as a
nonionic
surfactant system ingredient having a cloud point of less than 30°C,
preferably less than about
20°C, and more preferably less than about 10°C.
It is also preferred for purposes of the present invention that the low cloud
point
nonionic surfactant further have a hydrophile-lipophile balance ("HLB"; see
Kirk Othmer
hereinbefore) value within the range of from about 1 to about 10, preferably 3
to 8. Such
materials include, for example, ethoxylated-propoxylated alcohol (e.g., Olin
Corporation's Poly-
Tergent~ SLF-18), epoxy-capped poly(oxyalkylated) alcohols (e.g., Olin
Corporation's Poly-
Tergent~ SLF-18B series of nonionics, as described, for example, in WO
94/22800, published
October 13, 1994 by Olin Corporation), REVERSED PLURONIC~ 2582 and TETRONIC~
702.
Optional nonionic surfactant - The optional nonionic surfactant may be a low
cloud point
nonionic other than the essential low cloud point nonionics, high cloud point
nonionics and
mixtures thereof, with high cloud point being preferred.
Nonionic surfactants generally are well known, being described in more detail
in Kirk
Othmer's Encyclopedia of Chemical Technology, 3rd Ed., Vol. 22, pp. 360-379,
"Surfactants and
Detersive Systems", incorporated by reference herein. While a wide range of
nonionic
surfactants may be selected from for purposes of the mixed surfactant systems
useful in the
present invention ADD compositions, it is necessary that the surfactant system
comprise both a
low cloud point nonionic surfactants) and a charged surfactant as described as
follows. "Cloud
point", as used herein, is a well known property of nonionic surfactants which
is the result of the
surfactant becoming less soluble with increasing temperature, the temperature
at which the
appearance of a second phase is observable is referred to as the "cloud point"
(See Kirk Othmer,
pp. 360-362, hereinbefore).
Typical low cloud point nonionic surfactants include nonionic alkoxylated
surfactants,
especially ethoxylates derived from primary alcohol, and polyoxypropyl-
ene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverse block polymers.
CA 02363097 2003-05-23
Nonionic surfactants can optionally contain propyiene oxide in an amount up to
about
15% by weight. Other preferred nonionic surfactants can be prepared by the
processes described
in U.S. Patent 4,223,163, issued September 16, 1980, Builloty.
Low cloud point nonionic surfactants additionally comprise a polyoxyethyiene,
polyoxypropylene block polymeric compound. Block polyoxyethylene-
polyoxypropylene
polymeric compounds include those based on ethylene glycol, propylene glycol,
glycerol,
trimethylolpropane and ethylenediamine as initiator reactive hydrogen
compound. Certain of the
block polymer surfactant compounds designated PLURONICtO, REVERSED PLUROMC~,
and TETROMC~ by the BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable in
ADD
compositions of the invention. Preferred examples include REVERSED PLURONIC~
2582
and TETROMC~ 702, Such surfactants are typically useful herein as low cloud
point nonionic
surfactants.
As used herein, a "high cloud point" nonionic surfactant is defined as a
nonionic
surfactant system ingredient having a cloud point of greater than 40°C,
preferably greater than
about 50°C, and more preferably greater than about 60°C.
Preferably the nonionic surfactant
system comprises an ethoxylated surfactant derived from the reaction of a
monohydroxy alcohol
or alkylphenol containing from about 8 to about 20 carbon atoms, with from
about 6 to about 15
moles of ethylene oxide per mole of alcohol or alkyl phenol on an average
basis. Such high
cloud point nonionic surfactants include, for example, Tergitol 1559 (supplied
by Union
Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc), and Ncodol 91-8
(supplied by
Shell).
It is also preferred for purposes of the present invention that such high
cloud point
nonionic surfactants further have a hydrophile-lipophile balance ("HLB"; see
Kirk Othmer
hereinbefore) value within the range of from about 9 to about IS, preferably
11 to 15. Such
materials include, for example, Tergitol 1559 (supplied by Union Carbide),
Rhodasurf TMD 8.5
(supplied by Rhone Poulenc), and Neodol 91-8 (supplied by Shell).
Another preferred high cloud point nonionic surfactant is derived from a
straight or
preferably branched chain or secondary fatty alcohol containing from about 6
to about 20 carbon
atoms (C6-C2p alcohol), including secondary alcohols and branched chain
primary alcohols.
Preferably, high cloud point nonionic surfactants are branched or secondary
alcohol ethoxylates,
more preferably mixed C9/11 or C11l15 branched alcohol ethoxylates, condensed
with an
average of from about 6 to about 15 moles, preferably from about 6 to about 12
moles, and most
preferably from about 6 to about 9 moles of ethylene oxide per mole of
alcohol. Preferably the
ethoxylated nonionic surfactant so derived has a narrow ethoxyiate
distribution relative to the
average.
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Finally, if a high cloud point nonionic surfactant is also used, preferred
ratios of high
cloud point nonionic surfactant to the oxide surfactant are within the range
of from about 1:2 to
10:1, preferably 1:1 to 4:1, and it.is further to be recognized that the ratio
of low cloud point
nonionic surfactant to the combination of oxide surfactant and high cloud
point nonionic
surfactant is within the range of from about 20:1 to about 1:5. It is
preferred to use ADD
compositions comprising such mixed surfactant systems wherein the sudsing
(absent any
silicone suds controlling agent) is less than 2 inches, preferably less than 1
inch, determined as
follows.
Optional Anionic surfactant - While it is not preferred it is possible to
include in the
compositions used in the methods of the present invention an anionic
surfactant. When the
composition to be used is an ADD, the anionic surfactant is chosen from
alkylethoxycarboxylates, alkylethoxysulfates, with the degree of ethoxylation
greater than 3
(preferably 4 to 10; more preferably 6 to 8), and chain length in the range of
C8 to C16,
preferably 11-15. Additionally, branched alkylcarboxylates have been found to
be useful for the
purpose of the present invention when the branch occurs in the middle and the
average total
chain length is 10 to 18, preferably 12-16 with the side branch 2-4 carbons in
length. An
example is 2-butyloctanoic acid. The anionic surfactant is typically of a type
having good
solubility in the presence of calcium. Such anionic surfactants are further
illustrated by
sulfobetaines, alkyl(polyethoxy)sulfates (AES), alkyl (polyethoxy)carboxylates
(AEC), and short
chained C6-C 10 alkyl sulfates and sulfonates. Straight chain fatty acids have
been shown to be
ineffective due to their sensitivity to calcium.
Measuring Dishwasher Arm RPM Efficiency and Wash Suds Height:
The equipment useful for these measurements are: a Whirlpool Dishwasher (model
900)
equipped with clear plexiglass door, IBM computer data collection with Labview
and Excel
Software, proximity sensor (Newark Corp. - model 95F5203) using SCXI
interface, and a plastic
ruler.
The data is collected as follows. The proximity sensor is affixed to the
bottom
dishwasher rack on a metal bracket. The sensor faces downward toward the
rotating dishwasher
arm on the bottom of the machine (distance approximately 2 cm. from the
rotating arm). Each
pass of the rotating arm is measured by the proximity sensor and recorded. The
pulses recorded
by the computer are converted to rotations per minute (RPM) of the bottom arm
by counting
pulses over a 30 second interval. The rate of the arm rotation is directly
proportional to the
amount of suds in the machine and in the dishwasher pump (i.e., the more suds
produced, the
slower the arm rotation).
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The plastic ruler is clipped to the bottom rack of the dishwasher and extends
to the floor
of the machine. At the end of the wash cycle, the height of the suds is
measured using the
plastic ruler (viewed through the clear door) and recorded as suds height.
The following procedure is followed for evaluating ADD compositions for suds
production as well as for evaluating nonionic surfactant systems for utility
in such systems. (For
separate evaluation of nonionic surfactant systems, a base ADD formula, such
as Cascade
powder, is used along with the nonionic surfactants which are added separately
in glass vials to
the dishwashing machine.)
First, the machine is filled with water (adjust water for appropriate
temperature and
hardness) and proceed through a rinse cycle. The RPM is monitored throughout
the cycle
(approximately 2 min.) without any ADD product (or sufactants) being added (a
quality control
check to ensure the machine is functioning properly). As the machine begins to
fill for the wash
cycle, the water is again adjusted for temperature and hardness, and then the
ADD product is
added to the bottom of the machine (in the case of separately evaluated
surfactant systems, the
ADD base formula is first added to the bottom of the machine then the
surfactants are added by
placing the surfactant-containing glass vials inverted on the top rack of the
machine). The RPM
is then monitored throughout the wash cycle. At the end of the wash cycle, the
suds height is
recorded using the plastic ruler. The machine is again filled with water
(adjust water for
appropriate temperature and hardness) and runs through another rinse cycle.
The RPM is
monitored throughout this cycle.
An average RPM is calculated for the 1 st rinse, main wash, and final rinse.
The %RPM
efficiency is then calculated by dividing the average RPM for the test
surfactants into the
average RPM for the control system (base ADD formulation without the nonionic
surfactant
system). The RPM efficiency and suds height measurements are used to dimension
the overall
suds profile of the surfactant system.
Builders
Detergent builders other than silicates can optionally be included in the
compositions
used herein to assist in controlling mineral hardness. Inorganic as well as
organic builders can
be used. Builders are used in automatic dishwashing to assist in the removal
of particulate soils.
The level of builder can vary widely depending upon the end use of the
composition and
its desired physical form. The compositions will typically comprise at least
about 1% builder.
High performance compositions typically comprise from about S% to about 90%,
more typically
from about 5% to about 75% by weight, of the detergent builder. Lower or
higher levels of
builder, however, are not excluded.
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Inorganic or non-phosphate-containing detergent builders include, but are not
limited to,
phosphonates, phytic acid, silicates, carbonates (including bicarbonates and
sesquicarbonates),
sulfates, citrate, zeolite or layered silicate, and aluminosilicates.
Examples of carbonate builders are the alkaline earth and alkali metal
carbonates as
disclosed in German Patent Application No. 2,321,001 published on November 15,
1973.
Various grades and types of sodium carbonate and sodium sesquicarbonate may be
used, certain
of which are particularly useful as carriers for other ingredients, especially
detersive surfactants.
Aluminosilicate builders may be used in the present compositions though are
not
preferred for automatic dishwashing detergents. (See U.S. Pat. 4,605,509 for
examples of
preferred aluminosilicates.) 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: Na20~A1203~xSiOz~yH20 wherein z and y are integers of at
least 6, the
molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an
integer from about 15 to
about 264.
Useful aluminosilicate ion exchange materials are commercially available.
These
aluminosilicates can be crystalline or amorphous in structure and can be
naturally-occurring
aluminosilicates or synthetically derived. A method for producing
aluminosilicate ion exchange
materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued
October 12, 1976.
Preferred synthetic crystalline aluminosilicate ion exchange materials useful
herein are available
under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In
another
embodiment, the crystalline aluminosilicate ion exchange material has the
formula:
Nal2[(A102)12(Si02)12~'xH20 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.
Individual particles can desirably be even smaller than 0.1 micron to further
assist kinetics of
exchange through maximization of surface area. High surface area also
increases utility of
aluminosilicates as adsorbents for surfactants, especially in granular
compositions. Aggregates
of silicate or aluminosilicate particles may be useful, a single aggregate
having dimensions
tailored to minimize segregation in granular compositions, while the aggregate
particle remains
dispersible to submicron individual particles during the wash. As with other
builders such as
carbonates, it may be desirable to use zeolites in any physical or
morphological form adapted to
promote surfactant carrier function, and appropriate particle sizes may be
freely selected by the
formulator.
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,
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12
"polycarboxylate" 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 or "overbased".
When utilized in
salt form, alkali metals, such as sodium, potassium, and lithium, or
alkanolammonium salts are
preferred.
Included among the polycarboxylate builders are a variety of categories of
useful
materials. One important category of polycarboxylate builders encompasses the
ether
polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent
3,128,287, issued
April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18,
1972. See also
"TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May S,
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.
Other useful detergency builders include the ether hydroxypolycarboxylates,
copolymers
of malefic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy
benzene-2, 4, 6-
trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali
metal, ammonium and
substituted ammonium salts of polyacetic acids such as
ethylenediaminetetraacetic acid and
nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid,
succinic acid,
oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,
carboxymethyloxysuccinic acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly
sodium salt), are
polycarboxylate builders of particular importance for heavy duty laundry
detergent and
automatic dishwashing formulations due to their availability from renewable
resources and their
biodegradability. Citrates can also be used in combination with zeolite, the
aforementioned
BRITESIL types, and/or layered silicate builders. Oxydisuccinates are also
useful in such
compositions and combinations.
Also suitable in the compositions used in the present invention are the 3,3-
dicarboxy-4-
oxa-1,6-hexanedionates and the related compounds disclosed in U.S. Patent
4,566,984, Bush,
issued January 28, 1986. Useful succinic acid builders include the CS-C20
alkyl and alkenyl
succinic acids and salts thereof. A particularly preferred compound of this
type is
dodecenylsuccinic acid. Specific examples of succinate builders include:
laurylsuccinate,
myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-
pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred
builders of this group,
and are described in European Patent Application 86200690.5/0,200,263,
published November
5, 1986.
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13
Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226,
Crutchfield et al,
issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued March 7,
1967. See also U.S.
Patent 3,723,322.
Fatty acids, e.g., C12-Clg monocarboxylic acids, may 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 but are generally
not desired. Such use
of fatty acids will generally result in a diminution of sudsing in laundry
compositions, which
may need to be taken into account by the formulator. Fatty acids or their
salts are undesirable in
Automatic Dishwashing (ADD) embodiments in situations wherein soap scums can
form and be
deposited on dishware.
Where phosphorus-based builders can be used, 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-l,l-diphosphonate
and other
known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030;
3,422,021; 3,400,148
and 3,422,137) can also be used though such materials are more commonly used
in a low-level
mode as chelants or stabilizers.
Phosphate detergent builders for use in ADD compositions are well known. They
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). Phosphate builder sources are described in detail in Kirk
Othmer, 3rd
Edition, Vol. 17, pp. 426-472 and in "Advanced Inorganic Chemistry" by Cotton
and Wilkinson,
pp. 394-400 (John Wiley and Sons, Inc.; 1972).
Preferred levels of phosphate builders herein are from about 5% to about 90%,
preferably from about 5% to about 75%, more preferably from about 10% to about
50% by
weight of phosphate builder.
Bleaching Agents
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. An
"effective amount" of a
source of hydrogen peroxide is any amount capable of measurably improving
stain removal
(especially of tea stains) from soiled dishware compared to a hydrogen
peroxide source-free
composition when the soiled dishware is washed by the consumer in a domestic
automatic
dishwasher in the presence of alkali.
More generally a source of hydrogen peroxide herein is any convenient compound
or
mixture which under consumer use conditions provides an effective amount of
hydrogen
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peroxide. Levels may vary widely and are usually in the range from about 0.1%
to about 70%,
more typically from about 0.5% to about 30%, by weight of the compositions
used herein.
The preferred source of hydrogen peroxide used herein can be any convenient
source,
including hydrogen peroxide itself. For example, perborate, e.g., sodium
perborate (any hydrate
but preferably the mono- or tetra-hydrate), sodium carbonate peroxyhydrate or
equivalent
percarbonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or
sodium
peroxide can be used herein. Also useful are sources of available oxygen such
as persulfate
bleach (e.g., OXONE, manufactured by DuPont). Sodium perborate monohydrate and
sodium
percarbonate are particularly preferred. Mixtures of any convenient hydrogen
peroxide sources
can also be used.
A preferred percarbonate bleach comprises dry particles having an average
particle size
in the range from about 500 micrometers to about 1,000 micrometers, not more
than about 10%
by weight of said particles being smaller than about 200 micrometers and not
more than about
10% by weight of said particles being larger than about 1,250 micrometers.
Optionally, the
percarbonate can be coated with a silicate, borate or water-soluble
surfactants. Percarbonate is
available from various commercial sources such as FMC, Solvay and Tokai Denka.
While effective compositions useful herein may comprise only the mixed
surfactant
system and builder, useful fully-formulated compositions typically will also
comprise other
adjunct materials to improve or modify performance. These materials are
selected as
appropriate for the properties required of composition. For example, low
spotting and filming is
desired -- preferred compositions have spotting and filming grades of 3 or
less, preferably less
than 2, and most preferably less than 1, as measured by the standard test of
The American
Society for Testing and Materials ("ASTM") D3556-85 (Reapproved 1989)
"Standard Test
Method for Deposition on Glassware During Mechanical Dishwashing".
Adjunct Materials:
The compositions used in the methods of the present invention contain an
adjunct
material. It is preferred that the adjunct material be an ADD adjunct
material, as the preferred
form of the compositions used is as an ADD composition.
Detersive ingredients or adjuncts optionally included in the compositions can
include
one or more materials for assisting or enhancing cleaning performance,
treatment of the
substrate to be cleaned, or designed to improve the aesthetics of the
compositions. They are
further selected based on the form of the composition, i.e., whether the
composition is to be sold
as a liquid, paste (semi-solid), or solid form (including tablets and the
preferred granular forms
for the present compositions). Adjuncts which can also be included in
compositions of the
present invention, at their conventional art-established levels for use
(generally, adjunct
materials comprise, in total, from about 30% to about 99.9%, preferably from
about 70% to
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about 95%, by weight of the compositions), include other active ingredients
such as non-
phosphate builders, chelants, enzymes, suds suppressors, dispersant polymers
(e.g., from BASF
Corp. or Rohm & Haas), color speckles, silvercare, anti-tarnish and/or anti-
corrosion agents,
dyes, fillers, germicides, alkalinity sources, hydrotropes, anti-oxidants,
enzyme stabilizing
agents, perfumes, solubilizing agents, carriers, processing aids, pigments, pH
control agents,
and, for liquid formulations, solvents, as described in detail hereinafter.
1. Detersive En es
"Detersive enzyme", as used herein, means any enzyme having a cleaning, stain
removing or otherwise beneficial effect in a composition. Preferred detersive
enzymes are
hydrolases such as proteases, amylases and lipases. Highly preferred for
automatic dishwashing
are amylases and/or proteases, including both current commercially available
types and
improved types which, though more bleach compatible, have a remaining degree
of bleach
deactivation susceptibility.
In general, as noted, preferred compositions used herein comprise one or more
detersive
enzymes. If only one enzyme is used, it is preferably an amyolytic enzyme when
the
composition is for automatic dishwashing use. Highly preferred for automatic
dishwashing
compositions is a mixture of proteolytic enzymes and amyloytic enzymes. More
generally, the
enzymes to be incorporated include proteases, amylases, lipases, cellulases,
and peroxidases, as
well as mixtures thereof. Other types of enzymes may also be included. They
may be of any
suitable origin, such as vegetable, animal, bacterial, fungal and yeast
origin. However, their
choice is governed by several factors such as pH-activity and/or stability
optima, thermostability,
stability versus active detergents, builders, etc. In this respect bacterial
or fungal enzymes are
preferred, such as bacterial amylases and proteases, and fungal cellulases.
Enzymes are normally incorporated in the compositions used herein at levels
sufficient
to provide a "cleaning-effective amount". The term "cleaning-effective amount"
refers to any
amount capable of producing a cleaning, stain removal or soil removal effect
on substrates such
as fabrics, dishware and the like. Since enzymes are catalytic materials, such
amounts may be
very small. In practical terms for current commercial preparations, typical
amounts are up to
about 5 mg by weight, more typically about 0.01 mg to about 3 mg, of active
enzyme per gram of
the composition. Stated otherwise, the compositions herein will typically
comprise from about
0.001% to about 6%, preferably 0.01%-1% by weight of a commercial enzyme
preparation.
Protease enzymes are usually present in such commercial preparations at levels
sufficient to
provide from 0.005 to 0.1 Anson units (AU) of activity per gram of
composition. For automatic
dishwashing purposes, it may be desirable to increase the active enzyme
content of the
commercial preparations, in order to minimize the total amount of non-
catalytically active
materials delivered and thereby improve spotting/filming results.
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16
Suitable examples of proteases are the subtilisins which are obtained from
particular
strains of B. subtilis and B. licheniformis. Another suitable protease is
obtained from a strain of
Bacillus, having maximum activity throughout the pH range of 8-12, developed
and sold by
Novo Industries A/S as ESPERASE~. The preparation of this enzyme and analogous
enzymes
is described in British Patent Specification No. 1,243,784 of Novo.
Proteolytic enzymes suitable
for removing protein-based stains that are commercially available include
those sold under the
tradenames ALCALASE~ and SAVINASE~ by Novo Industries A/S (Denmark) and
MAXATASE~ by International Bio-Synthetics, Inc. (The Netherlands). Other
proteases
include Protease A (see European Patent Application 130,756, published January
9, 1985) and
Protease B (see European Patent Application Serial No. 87303761.8, filed April
28, 1987, and
European Patent Application 130,756, Bott et al, published January 9, 1985).
An especially preferred protease, referred to as "Protease D" is a carbonyl
hydrolase
variant having an amino acid sequence not found in nature, which is derived
from a precursor
carbonyl hydrolase by substituting a different amino acid for a plurality of
amino acid residues at
a position in said carbonyl hydrolase equivalent to position +76, preferably
also in combination
with one or more amino acid residue positions equivalent to those selected
from the group
consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128,
+135, +156,
+166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or
+274
according to the numbering of Bacillus amyloliquefaciens subtilisin, as
described in WO
95/10615 published April 20, 1995 by Genencor International.
Useful proteases are also described in PCT publications: WO 95/30010 published
November 9, 1995 by The Procter & Gamble Company; WO 95/30011 published
November 9,
1995 by The Procter & Gamble Company; WO 95/29979 published November 9, 1995
by The
Procter & Gamble Company.
Amylases suitable herein include, for example, a-amylases described in British
Patent
Specification No. 1,296,839 (Novo), RAPIDASE~, International Bio-Synthetics,
Inc. and
TERMAMYL~, Novo Industries.
Engineering of enzymes (e.g., stability-enhanced amylase) for improved
stability, e.g.,
oxidative stability is known. See, for example J.Biological Chem., Vol. 260,
No. 11, June 1985,
pp 6518-6521. "Reference amylase" refers to a conventional amylase inside the
scope of the
amylase component of this invention. Further, stability-enhanced amylases,
also within the
invention, are typically compared to these "reference amylases".
The present invention, in certain preferred embodiments, can makes use of
amylases
having improved stability in detergents, especially improved oxidative
stability. A convenient
absolute stability reference-point against which amylases used in these
preferred embodiments
of the instant invention represent a measurable improvement is the stability
of TERMAMYL~
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17
in commercial use in 1993 and available from Novo Nordisk A/S. This TERMAMYL~
amylase
is a "reference amylase", and is itself well-suited for use in the ADD
(Automatic Dishwashing
Detergent) compositions of the invention. Even more preferred amylases herein
share the
characteristic of being "stability-enhanced" amylases, characterized, at a
minimum, by a
measurable improvement in one or more of: oxidative stability, e.g., to
hydrogen
peroxide/tetraacetylethylenediamine in buffered solution at pH 9-10; thermal
stability, e.g., at
common wash temperatures such as about 60°C; or alkaline stability,
e.g., at a pH from about 8
to about 11, all measured versus the above-identified reference-amylase.
Preferred amylases
herein can demonstrate further improvement versus more challenging reference
amylases the
latter reference amylases being illustrated by any of the precursor amylases
of which preferred
amylases within the invention are variants. Such precursor amylases may
themselves be natural
or be the product of genetic engineering. Stability can be measured using any
of the art-disclosed
technical tests. See references disclosed in WO 94/02597, itself and documents
therein referred
to being incorporated by reference.
In general, stability-enhanced amylases respecting the preferred embodiments
of the
invention can be obtained from Novo Nordisk A/S, or from Genencor
International.
Preferred amylases herein have the commonality of being derived using site-
directed
mutagenesis from one or more of the Baccillus amylases, especialy the Bacillus
alpha-amylases,
regardless of whether one, two or multiple amylase strains are the immediate
precursors.
As noted, "oxidative stability-enhanced" amylases are preferred for use herein
despite
the fact that the invention makes them "optional but preferred" materials
rather than essential.
Such amylases are non-limitingly illustrated by the following:
(a) An amylase according to the hereinbefore incorporated WO/94/02597, Novo
Nordisk
A/S, published Feb. 3, 1994, as further illustrated by a mutant in which
substitution is made,
using alanine or threonine (preferably threonine), of the methionine residue
located in position
197 of the B.licheniformis alpha-amylase, known as TERMAMYL~, or the
homologous
position variation of a similar parent amylase, such as B. amyloliquefaciens,
B.subtilis, or
B.stearothermophilus;
(b) Stability-enhanced amylases as described by Genencor International in a
paper
entitled "Oxidatively Resistant alpha-Amylases" presented at the 207th
American Chemical
Society National Meeting, March 13-17 1994, by C. Mitchinson. Therein it was
noted that
bleaches in automatic dishwashing detergents inactivate alpha-amylases but
that improved
oxidative stability amylases have been made by Genencor from B.licheniformis
NCIB8061.
Methionine (Met) was identified as the most likely residue to be modified. Met
was substituted,
one at a time, in positions 8,15,197,256,304,366 and 438 leading to specific
mutants, particularly
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18
important being M197L and M197T with the M197T variant being the most stable
expressed
variant. Stability was measured in CASCADE~ and SUNLIGHT~;
(c) Particularly preferred herein are amylase variants having additional
modification in
the immediate parent available from Novo Nordisk A/S. These amylases do not
yet have a
tradename but are those referred to by the supplier as QL37+M197T.
Any other oxidative stability-enhanced amylase can be used, for example as
derived by
site-directed mutagenesis from known chimeric, hybrid or simple mutant parent
forms of
available amylases.
Cellulases usable in, but not preferred, for the present invention include
both bacterial or
fungal cellulases. Typically, they will have a pH optimum of between 5 and
9.5. Suitable
cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, issued
March 6, 1984,
which discloses fungal cellulase produced from Humicola insolens and Humicola
strain
DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas,
and cellulase
extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula
Solander). Suitable
cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-
2.247.832.
CAREZYME~ (Novo) is especially useful.
Suitable lipase enzymes for detergent use include those produced by
microorganisms of
the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed
in British
Patent 1,372,034. See also lipases in Japanese Patent Application 53,20487,
laid open to public
inspection on February 24, 1978. 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 commercial lipases include Amano-CES, lipases ex Chromobacter viscosum,
e.g.
Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available from
Toyo Jozo
Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S.
Biochemical Corp.,
U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
The
LIPOLASE~ enzyme derived from Humicola lanuginosa and commercially available
from
Novo (see also EPO 341,947) is a preferred lipase for use herein. Another
preferred lipase
enzyme is the D96L variant of the native Humicola lanuginosa lipase, as
described in WO
92/05249 and Research Disclosure No. 35944, March 10, 1994, both published by
Novo. In
general, lipolytic enzymes are less preferred than amylases and/or proteases
for automatic
dishwashing embodiments of the present invention.
Peroxidase enzymes can be used in combination with oxygen sources, e.g.,
percarbonate,
perborate, persulfate, hydrogen peroxide, etc. They are typically used for
"solution bleaching,"
i.e. to prevent transfer of dyes or pigments removed from substrates during
wash operations to
other substrates in the wash solution. Peroxidase enzymes are known in the
art, and include, for
example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro-
and bromo-
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19
peroxidase. Peroxidase-containing detergent compositions are disclosed, for
example, in PCT
International Application WO 89/099813, published October 19, 1989, by O.
Kirk, assigned to
Novo Industries A/S. The present invention encompasses peroxidase-free
automatic
dishwashing composition embodiments.
A wide range of enzyme materials and means for their incorporation into
synthetic
detergent compositions are also disclosed in U.S. Patent 3,553,139, issued
January 5, 1971 to
McCarty et al. Enzymes are further disclosed in U.S. Patent 4,101,457, Place
et al, issued July
18, 1978, and in U.S. Patent 4,507,219, Hughes, issued March 26, 1985. Enzymes
for use in
detergents can be stabilized by various techniques. Enzyme stabilization
techniques are
disclosed and exemplified in U.S. Patent 3,600,319, issued August 17, 1971 to
Gedge, et al, and
European Patent Application Publication No. 0 199 405, Application No.
86200586.5, published
October 29, 1986, Venegas. Enzyme stabilization systems are also described,
for example, in
U.S. Patent 3,519,570.
2. Enzyme Stabilizing System - The enzyme-containing compositions, especially
liquid
compositions, herein may comprise from about 0.001% to about 10%, preferably
from about
0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight of
an enzyme
stabilizing system. The enzyme stabilizing system can be any stabilizing
system which is
compatible with the detersive enzyme. Such stabilizing systems can comprise
calcium ion, boric
acid, propylene glycol, short chain carboxylic acid, boronic acid, and
mixtures thereof.
The stabilizing system of the compositions used herein may further comprise
from 0 to
about 10%, preferably from about 0.01% to about 6% by weight, of chlorine
bleach scavengers,
added to prevent chlorine bleach species present in many water supplies from
attacking and
inactivating the enzymes, especially under alkaline conditions. While chlorine
levels in water
may be small, typically in the range from about 0.5 ppm to about 1.75 ppm, the
available
chlorine in the total volume of water that comes in contact with the enzyme
during dishwashing
is relatively large; accordingly, enzyme stability in-use can be problematic.
Suitable chlorine scavenger anions are widely known and readily available, and
are
illustrated by salts containing ammonium cations with sulfite, bisulfate,
thiosulfite, thiosulfate,
iodide, etc. Antioxidants such as carbamate, ascorbate, etc., organic amines
such as
ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof,
monoethanolamine (MEA),
and mixtures thereof can likewise be used. Other conventional scavengers such
as bisulfate,
nitrate, chloride, sources of hydrogen peroxide such as sodium perborate
tetrahydrate, sodium
perborate monohydrate and sodium percarbonate, as well as phosphate, condensed
phosphate,
acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate,
etc., and mixtures thereof
can be used if desired. In general, since the chlorine scavenger function can
be performed by
several of the ingredients separately listed under better recognized
functions, (e.g., other
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components of the invention such as sodium perborate), there is no requirement
to add a separate
chlorine scavenger unless a compound performing that function to the desired
extent is absent
from an enzyme-containing embodiment of the invention; even then, the
scavenger is added only
for optimum results. Moreover, the formulator will exercise a chemist's normal
skill in avoiding
the use of any scavenger which is majorly incompatible with other ingredients,
if used. In
relation to the use of ammonium salts, such salts can be simply admixed with
the composition
but are prone to adsorb water and/or liberate ammonia during storage.
Accordingly, such
materials, if present, are desirably protected in a particle such as that
described in U.S. Patent
4,652,392, Baginski et al.
3. Optional Bleach Adjuncts
~) Bleach Activators -
Preferably, the peroxygen bleach component in the composition is formulated
with an
activator (peracid precursor). The activator is present at levels of from
about 0.01 % to about
15%, preferably from about 0.5% to about 10%, more preferably from about 1% to
about 8%, by
weight of the composition. Preferred activators are selected from the group
consisting of
tetraacetyl ethylene diamine (TAED), benzoylcaprolactam (BzCL), 4-
nitrobenzoylcaprolactam,
3-chlorobenzoylcaprolactam, benzoyloxybenzenesulphonate (BOBS),
nonanoyloxybenzene-
sulphonate (NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulphonate (C10-
OBS),
benzoylvalerolactam (BZVL), octanoyloxybenzenesulphonate (Cg-OBS),
perhydrolyzable esters
and mixtures thereof, most preferably benzoylcaprolactam and
benzoylvalerolactam.
Particularly preferred bleach activators in the pH range from about 8 to about
9.5 are those
selected having an OBS or VL leaving group.
Preferred bleach activators are those described in U.S. Patent 5,130,045,
Mitchell et al,
and 4,412,934, Chung et al, and copending patent applications U. S. Serial
Nos. 08/064,624,
08/064,623, 08/064,621, 08/064,562, 08/064,564, 08/082,270 and copending
application to M.
Burns, A. D. Willey, R. T. Hartshorn, C. K. Ghosh, entitled "Bleaching
Compounds Comprising
Peroxyacid Activators Used With Enzymes" and having U.S. Serial No. 08/133,691
(P&G Case
4890R), all of which are incorporated herein by reference.
The mole ratio of peroxygen bleaching compound (as Av0) to bleach activator in
the
present invention generally ranges from at least 1:1, preferably from about
20:1 to about 1:1,
more preferably from about 10:1 to about 3:1.
Quaternary substituted bleach activators may also be included. The present
detergent
compositions preferably comprise a quaternary substituted bleach activator
(QSBA) or a
quaternary substituted peracid (QSP); more preferably, the former. Preferred
QSBA structures
are further described in copending U.S. Serial No. 08/298,903, 08/298,650,
08/298,906 and
08/298,904 filed August 31, 1994, incorporated herein by reference.
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(b) Organic Peroxides especially Diacyl Peroxides - These 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.
(c) Metal-containing Bleach Catalysts:
The present invention methods may optionally utilize metal-containing bleach
catalysts
that are effective for use in ADD compositions. Preferred are manganese and
cobalt-containing
bleach catalysts.
One type of metal-containing bleach catalyst is a catalyst system comprising a
transition
metal cation of defined bleach catalytic activity, such as copper, iron,
titanium, ruthenium
tungsten, molybdenum, or manganese cations, an auxiliary metal cation having
little or no
bleach catalytic activity, such as zinc or aluminum cations, and a sequestrate
having defined
stability constants for the catalytic and auxiliary metal cations,
particularly
ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic
acid) and water-
soluble salts thereof. Such catalysts are disclosed in U.S. Pat. 4,430,243.
Other types of bleach catalysts include the manganese-based complexes
disclosed in
U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of theses
catalysts include
MnN2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(PF6)2 ("MnTACN"), Mn~2(u-
O)1(u-
OAc)2( 1,4,7-trimethyl-1,4,7-triazacyclononane)2-(C104)2, Mn~4(u-O)6( 1,4,7-
triazacyclononane)4-(C104)2, Mn~MnN4(u-O) 1 (u-OAc)2( 1,4,7-trimethyl-1,4,7-
triazacyclononane)2-(C104)3, and mixtures thereof. See also European patent
application
publication no. 549,272. Other ligands suitable for use herein include 1,5,9-
trimethyl-1,5,9-
triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-
triazacyclononane, and
mixtures thereof.
The bleach catalysts useful in automatic dishwashing compositions and
concentrated
powder detergent compositions may also be selected as appropriate for the
present invention.
For examples of suitable bleach catalysts see U.S. Pat. 4,246,612 and U.S.
Pat. 5,227,084.
See also U.S. Pat. 5,194,416 which teaches mononuclear manganese (IV)
complexes
such as Mn(1,4,7-trimethyl-1,4,7-triazacyclononane(OCH3)3-(PF6).
Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is
a water-
soluble complex of manganese (II), (III), and/or (IV) with a ligand which is a
non-carboxylate
polyhydroxy compound having at least three consecutive C-OH groups. Preferred
ligands
include sorbitol, iditol, dulsitol, mannitol, xylitol, arabitol, adonitol,
meso-erythr~itol, meso-
inositol, lactose, and mixtures thereof.
U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of
transition metals,
including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand. Said ligands
are of the formula:
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22
RZ R3
RL-N=C-B-C=N-R4
wherein R1, R2, R3, and R4 can each be selected from H, substituted alkyl and
aryl groups such
that each R1-N=C-R2 and R3-C=N-R4 form a five or six-membered ring. Said ring
can further
be substituted. B is a bridging group selected from O, S. CRSR6, NR~ and C=O,
wherein R5,
R6, and R~ can each be H, alkyl, or aryl groups, including substituted or
unsubstituted groups.
Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine,
imidazole, pyrazole, and
triazole rings. Optionally, said rings may be substituted with substituents
such as alkyl, aryl,
alkoxy, halide, and nitro. Particularly preferred is the ligand 2,2'-
bispyridylamine. Preferred
bleach catalysts include Co, Cu, Mn, Fe,-bispyridylmethane and -
bispyridylamine complexes.
Highly preferred catalysts include Co(2,2'-bispyridylamine)CI2,
Di(isothiocyanato)bispyridylamine-cobalt (II), trisdipyridylamine-cobalt(II)
perchlorate, Co(2,2-
bispyridylamine)202C104, Bis-(2,2'-bispyridylamine) copper(II) perchlorate,
tris(di-2-
pyridylamine) iron(II) perchlorate, and mixtures thereof.
Other examples include Mn gluconate, Mn(CF3S03)2, Co(NH3)SCI, and the
binuclear
Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including N4Mn~(u-
O)2MnIVN4)+and [Bipy2Mn~(u-O)2Mn~bipy2]-(C104)3.
The bleach catalysts may also be prepared by combining a water-soluble ligand
with a
water-soluble manganese salt in aqueous media and concentrating the resulting
mixture by
evaporation. Any convenient water-soluble salt of manganese can be used
herein. Manganese
(II), (III), (IV) and/or (V) is readily available on a commercial scale. In
some instances,
sufficient manganese may be present in the wash liquor, but, in general, it is
preferred to add Mn
cations in the compositions used to ensure its presence in catalytically-
effective amounts. Thus,
the sodium salt of the ligand and a member selected from the group consisting
of MnS04,
Mn(C104)2 or MnCl2 (least preferred) are dissolved in water at molar ratios of
ligand:Mn salt in
the range of about 1:4 to 4:1 at neutral or slightly alkaline pH. The water
may first be de-
oxygenated by boiling and cooled by spraying with nitrogen. The resulting
solution is
evaporated (under N2, if desired) and the resulting solids are used in the
bleaching and detergent
compositions herein without further purification.
In an alternate mode, the water-soluble manganese source, such as MnS04, is
added to
the bleach/cleaning composition used or to the aqueous bleaching/cleaning bath
which
comprises the ligand. Some type of complex is apparently formed in situ, and
improved bleach
performance is secured. In such an in situ process, it is convenient to use a
considerable molar
excess of the ligand over the manganese, and mole ratios of ligand:Mn
typically are 3:1 to 15:1.
The additional ligand also serves to scavenge vagrant metal ions such as iron
and copper,
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23
thereby protecting the bleach from decomposition. One possible such system is
described in
European patent application, publication no. 549,271.
While the structures of the bleach-catalyzing manganese complexes useful in
the present
invention have not been elucidated, it may be speculated that they comprise
chelates or other
hydrated coordination complexes which result from the interaction of the
carboxyl and nitrogen
atoms of the ligand with the manganese canon. Likewise, the oxidation state of
the manganese
cation during the catalytic process is not known with certainty, and may be
the (+II), (+~,
(+IV) or (+V) valence state. Due to the ligands' possible six points of
attachment to the
manganese cation, it may be reasonably speculated that mufti-nuclear species
and/or "cage"
structures may exist in the aqueous bleaching media. Whatever the form of the
active Mmligand
species which actually exists, it functions in an apparently catalytic manner
to provide improved
bleaching performances on stubborn stains such as tea, ketchup, coffee, wine,
juice, and the like.
Other bleach catalysts are described, for example, in European patent
application,
publication no. 408,131 (cobalt complex catalysts), European patent
applications, publication
nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455
(manganese/multidentate ligand catalyst), U.S. 4,711,748 and European patent
application,
publication no. 224,952, (absorbed manganese on aluminosilicate catalyst),
U.S. 4,601,845
(aluminosilicate support with manganese and zinc or magnesium salt), U.S.
4,626,373
(manganese/ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), German
Pat. specification
2,054,019 (cobalt chelant catalyst) Canadian 866,191 (transition metal-
containing salts), U.S.
4,430,243 (chelants with manganese cations and non-catalytic metal cations),
and U.S.
4,728,455 (manganese gluconate catalysts).
Preferred are cobalt (III) catalysts having the formula:
Co[(NH3)nM~mB~bT~tQqpp~ YY
wherein cobalt is in the +3 oxidation state; n is an integer from 0 to 5
(preferably 4 or 5; most
preferably 5); M' represents a monodentate ligand; m is an integer from 0 to 5
(preferably 1 or 2;
most preferably 1); B' represents a bidentate ligand; b is an integer from 0
to 2; T' represents a
tridentate ligand; t is 0 or 1; Q is a tetradentate ligand; q is 0 or 1; P is
a pentadentate ligand; p is
0 or 1; and n + m + 2b + 3t + 4q + Sp = 6; Y is one or more appropriately
selected counteranions
present in a number y, where y is an integer from 1 to 3 (preferably 2 to 3;
most preferably 2
when Y is a -1 charged anion), to obtain a charge-balanced salt, preferred Y
are selected from
the group consisting of chloride, iodide, I3-, formate, nitrate, nitrite,
sulfate, sulfite, citrate,
acetate, carbonate, bromide, PF6-, BF4-, B(Ph)4-, phosphate, phosphite,
silicate, tosylate,
methanesulfonate, and combinations thereof [optionally, Y can be protonated if
more than one
anionic group exists in Y, e.g., HP042-, HC03', H2P04-, etc., and further, Y
may be selected
from the group consisting of non-traditional inorganic anions such as anionic
surfactants, e.g.,
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linear alkylbenzene sulfonates (LAS), alkyl sulfates (AS),
alkylethoxysulfonates (AES), etc.,
and/or anionic polymers, e.g., polyacrylates, polymethacrylates, etc.]; and
wherein further at
least one of the coordination sites attached to the cobalt is labile under
automatic dishwashing
use conditions and the remaining coordination sites stabilize the cobalt under
automatic
dishwashing conditions such that the reduction potential for cobalt (III) to
cobalt (II) under
alkaline conditions is less than about 0.4 volts (preferably less than about
0.2 volts) versus a
normal hydrogen electrode.
Preferred cobalt catalysts of this type have the formula:
[Co~3)n(M~)m] Yy.
wherein n is an integer from 3 to S (preferably 4 or 5; most preferably 5); M'
is a labile
coordinating moiety, preferably selected from the group consisting of
chlorine, bromine,
hydroxide, water, and (when m is greater than 1) combinations thereof; m is an
integer from 1 to
3 (preferably 1 or 2; most preferably 1 ); m+n = 6; and Y is an appropriately
selected
counteranion present in a number y, which is an integer from 1 to 3
(preferably 2 to 3; most
preferably 2 when Y is a -1 charged anion), to obtain a charge-balanced salt.
The preferred cobalt catalyst of this type useful herein are cobalt pentaamine
chloride
salts having the formula [Co(NH3)SCl] Yy, and especially [Co(NH3)SCl]C12.
More preferred are the present invention compositions which utilize cobalt
(III) bleach
catalysts having the formula:
[Co(~3)n(M)m(B)b] TY
wherein cobalt is in the +3 oxidation state; n is 4 or 5 (preferably 5); M is
one or more ligands
coordinated to the cobalt by one site; m is 0, 1 or 2 (preferably 1); B is a
ligand coordinated to
the cobalt by two sites; b is 0 or 1 (preferably 0); and when b=0, then m+n =
6, and when b=1,
then m=0 and n=4; and T is one or more appropriately selected counteranions
present in a
number y, where y is an integer to obtain a charge-balanced salt (preferably y
is 1 to 3; most
preferably 2 when T is a -1 charged anion); and wherein further said catalyst
has a base
hydrolysis rate constant of less than 0.23 M-1 s-1 (25°C).
Preferred T are selected from the group consisting of chloride, iodide, I3-,
formate,
nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PFg-
, BF4-, B(Ph)4 ,
phosphate, phosphite, silicate, tosylate, methanesulfonate, and combinations
thereof.
Optionally, T can be protonated if more than one anionic group exists in T,
e.g., HP042-,
HC03-, H2P04-, etc. Further, T may be selected from the group consisting of
non-traditional
inorganic anions such as anionic surfactants (e.g., linear alkylbenzene
sulfonates (LAS), alkyl
sulfates (AS), alkylethoxysulfonates (AES), etc.) and/or anionic polymers
(e.g., polyacrylates,
polymethacrylates, etc.).
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The M moieties include, but are not limited to, for example, F-, 504-2, NCS-,
SCN-,
S203-2, NH3, P043-, and carboxylates (which preferably are mono-carboxylates,
but more than
one carboxylate may be present in the moiety as long as the binding to the
cobalt is by only one
carboxylate per moiety, in which case the other carboxylate in the M moiety
may be protonated
or in its salt form). Optionally, M can be protonated if more than one anionic
group exists in M
(e.g., HP042-, HC03-, H2P04-, HOC(O)CH2C(O)O-, etc.) Preferred M moieties are
substituted and unsubstituted C1-C30 carboxylic acids having the formulas:
RC(O)O-
wherein R is preferably selected from the group consisting of hydrogen and Cl-
C30 (preferably
C 1-C 1 g) unsubstituted and substituted alkyl, C6-C30 (preferably C6-C 1 g)
unsubstituted and
substituted aryl, and C3-C30 (preferably CS-C 1 g) unsubstituted and
substituted heteroaryl,
wherein substituents are selected from the group consisting of -NR'3, -NR'4+, -
C(O)OR', -OR', -
C(O)NR'2, wherein R' is selected from the group consisting of hydrogen and C1-
C6 moieties.
Such substituted R therefore include the moieties -(CH2)nOH and -(CH2)nNR'4+,
wherein n is
an integer from 1 to about 16, preferably from about 2 to about 10, and most
preferably from
about 2 to about 5.
Most preferred M are carboxylic acids having the formula above wherein R is
selected
from the group consisting of hydrogen, methyl, ethyl, propyl, straight or
branched C4-C12 alkyl,
and benzyl. Most preferred R is methyl. Preferred carboxylic acid M moieties
include formic,
benzoic, octanoic, nonanoic, decanoic, dodecanoic, malonic, malefic, succinic,
adipic, phthalic,
2-ethylhexanoic, naphthenoic, oleic, palmitic, triflate, tartrate, stearic,
butyric, citric, acrylic,
aspartic, fumaric, lauric, linoleic, lactic, malic, and especially acetic
acid.
The B moieties include carbonate, di- and higher carboxylates (e.g., oxalate,
malonate,
malic, succinate, maleate), picolinic acid, and alpha and beta amino acids
(e.g., glycine, alanine,
beta-alanine, phenylalanine).
Cobalt bleach catalysts useful herein are known, being described for example
along with
their base hydrolysis rates, in M. L. Tobe, "Base Hydrolysis of Transition-
Metal Complexes",
Adv. JI'lorQ. Bioinorg. Mech., (1983), 2, pages 1-94. For example, Table 1 at
page 17, provides
the base hydrolysis rates (designated therein as kOH) for cobalt pentaamine
catalysts complexed
with oxalate (kOH= 2.5 x 10-'1 M-1 s-1 (25°C)), NCS- (kOH= 5.0 x 10-4 M-
1 s-1 (25°C)),
formate (kOH= 5.8 x 10-'x' M-1 s-1 (25°C)), and acetate (kOH= 9.6 x 10-
'1 M-1 s-1 (25°C)). The
most preferred cobalt catalyst useful herein are cobalt pentaamine acetate
salts having the
formula [Co(NH3)SOAc] Ty, wherein OAc represents an acetate moiety, and
especially cobalt
pentaamine acetate chloride, [Co(NH3)SOAc]C12; as well as [Co(NH3)SOAc](OAc)2;
[Co(~3)SOAc](PF6)2~ [Co(~3)SOAc](S04)~ [Co~3)SOAc](BF4)2~ and
[Co(NH3)SOAc](N03)2.
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26
These cobalt catalysts are readily prepared by known procedures, such as
taught for
example in the Tobe article hereinbefore and the references cited therein, in
U.S. Patent
4,810,410, to Diakun et al, issued March 7,1989, J. Chem. Ed. (1989), 66 (12),
1043-45; The
Synthesis and Characterization of Inorganic Compounds, W.L. Jolly (Prentice-
Hall; 1970), pp.
461-3; Inor~. Chem., 18, 1497-1502 (1979); Inor~. Chem., 21, 2881-2885 (1982);
Inor~ Chem.,
18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of
Physical Chemistry, 56,
22-25 (1952).
These catalysts may be coprocessed with adjunct materials so as to reduce the
color
impact if desired for the aesthetics of the product, or to be included in
enzyme-containing
particles as exemplified hereinafter, or the compositions may be manufactured
to contain
catalyst "speckles".
As a practical matter, and not by way of limitation, the compositions used
herein can be
adjusted to provide on the order of at least one part per hundred million of
the active bleach
catalyst species in an 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 dishwashing
process, typical
automatic dishwashing 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 by weight
of the cleaning
compositions.
4. pH and Buffering Variation
Many compositions used herein will be buffered, i.e., they are relatively
resistant to pH
drop in the presence of acidic soils. However, other compositions herein may
have exceptionally
low buffering capacity, or may be substantially unbuffered. Techniques for
controlling or
varying pH at recommended usage levels more generally include the use of not
only buffers, but
also additional alkalis, acids, pH jump systems, dual compartment containers,
etc., and are well
known to those skilled in the art.
The preferred ADD compositions used herein comprise a pH-adjusting component
selected from water-soluble alkaline inorganic salts and water-soluble organic
or inorganic
builders. The pH-adjusting components are selected so that when the ADD is
dissolved in water
at a concentration of 1,000 - 10,000 ppm, the pH remains in the range of above
about 8,
preferably from about 9.5 to about 11. The preferred nonphosphate pH-adjusting
component of
the invention is selected from the group consisting of:
(i) sodium carbonate or sesquicarbonate;
(ii) sodium silicate, preferably hydrous sodium silicate having Si02:Na20
ratio of from
about 1:1 to about 2:1, and mixtures thereof with limited quantities of sodium
metasilicate;
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27
(iii) sodium citrate;
(iv) citric acid;
(v) sodium bicarbonate;
(vi) sodium borate, preferably borax;
(vii) sodium hydroxide; and
(viii) mixtures of (i)-(vii).
Preferred embodiments contain low levels of silicate (i.e. from about 3% to
about 10%
Si02).
Illustrative of highly preferred pH-adjusting component systems are binary
mixtures of
granular sodium citrate with anhydrous sodium carbonate, and three-component
mixtures of
granular sodium citrate trihydrate, citric acid monohydrate and anhydrous
sodium carbonate.
The amount of the pH adjusting component in the compositions used herein is
preferably
from about 1% to about SO%, by weight of the composition. In a preferred
embodiment, the pH-
adjusting component is present in the composition used herein in an amount
from about 5% to
about 40%, preferably from about 10% to about 30%, by weight.
For compositions used herein having a pH between about 9.5 and about 11 of the
initial
wash solution, particularly preferred ADD embodiments used herein comprise, by
weight of
ADD, from about 5% to about 40%, preferably from about 10% to about 30%, most
preferably
from about 15% to about 20%, of sodium citrate with from about 5% to about
30%, preferably
from about 7% to 25%, most preferably from about 8% to about 20% sodium
carbonate.
The essential pH-adjusting system can be complemented (i.e. for improved
sequestration
in hard water) by other optional detergency builder salts selected from
nonphosphate detergency
builders known in the art, which include the various water-soluble, alkali
metal, ammonium or
substituted ammonium borates, hydroxysulfonates, polyacetates, and
polycarboxylates.
Preferred are the alkali metal, especially sodium, salts of such materials.
Alternate water-
soluble, non-phosphorus organic builders can be used for their sequestering
properties.
Examples of polyacetate and polycarboxylate builders are the sodium,
potassium, lithium,
ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid;
nitrilotriacetic
acid, tartrate monosuccinic acid, tartrate disuccinic acid, oxydisuccinic
acid,
carboxymethoxysuccinic acid, mellitic acid, and sodium benzene polycarboxylate
salts.
(a) Water-Soluble Silicates
The compositions used herein may further comprise water-soluble silicates.
Water-
soluble silicates herein are any silicates which are soluble to the extent
that they do not
adversely affect spotting/filming characteristics of the ADD composition.
Examples of silicates are sodium metasilicate and, more generally, the alkali
metal
silicates, particularly those having a Si02:Na20 ratio in the range 1.6:1 to
3.2:1; and layered
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28
silicates, such as the layered sodium silicates described in U.S. Patent
4,664,839, issued May 12,
1987 to H. P. Rieck. NaSKS-6~ is a crystalline layered silicate marketed by
Hoechst
(commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, Na SKS-6
and other water-
soluble silicates useful herein do not contain aluminum. NaSKS-6 is the 8-
Na2Si05 form of
layered silicate and 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 preferred layered silicate for use
herein, but other
such layered silicates, such as those having the general formula
NaMSix02x+1'yH20 wherein
M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a
number from 0 to
20, preferably 0 can be used. Various other layered silicates from Hoechst
include NaSKS-5,
NaSKS-7 and NaSKS-11, as the a-, (3- and y- forms. 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.
Silicates particularly useful in (ADD) compositions used herein include
granular
hydrous 2-ratio silicates such as BRITESIL~ H20 from PQ Corp., and the
commonly sourced
BRITESIL~ H24 though liquid grades of various silicates can be used when the
ADD
composition has liquid form. Within safe limits, sodium metasilicate or sodium
hydroxide alone
or in combination with other silicates may be used in an ADD context to boost
wash pH to a
desired level.
6. Chelating Agents
The compositions used herein may also optionally contain one or more
transition-metal
selective sequestrants, "chelants" or "chelating agents", e.g., iron and/or
copper and/or
manganese chelating agents. Chelating agents suitable for use herein can be
selected from the
group consisting of aminocarboxylates, phosphonates (especially the
aminophosphonates),
polyfunctionally-substituted aromatic chelating agents, and mixtures thereof.
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 control iron, copper and manganese in washing solutions
which are known
to decompose hydrogen peroxide and/or bleach activators; other benefits
include inorganic film
prevention or scale inhibition. Commercial chelating agents for use herein
include the
DEQUEST~ series, and chelants from Monsanto, DuPont, and Nalco, Inc.
Aminocarboxylates useful as optional chelating agents are further illustrated
by
ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilo-
triacetates,
ethylenediamine tetraproprionates, triethylenetetraaminehexacetates,
diethylenetriamine-pentaacetates, and ethanoldiglycines, alkali metal,
ammonium, and
substituted ammonium salts thereof. In general, chelant mixtures may be used
for a combination
of functions, such as multiple transition-metal control, long-term product
stabilization, andlor
control of precipitated transition metal oxides and/or hydroxides.
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Polyfunctionally-substituted aromatic chelating agents are also useful in the
compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor
et al.
Preferred compounds of this type in acid form are dihydroxydisulfobenzenes
such as 1,2-
dihydroxy-3,5-disulfobenzene.
A highly preferred biodegradable chelator for use herein is ethylenediamine
disuccinate
("EDDS"), especially (but not limited to) the [S,S] isomer as described in
U.S. Patent 4,704,233,
November 3, 1987, to Hartman and Perkins. The trisodium salt is preferred
though other forms,
such as magnesium salts, may also be useful.
Aminophosphonates are also suitable for use as chelating agents in the
compositions of
the invention when at least low levels of total phosphorus are acceptable in
detergent
compositions, and include the ethylenediaminetetrakis (methylenephosphonates)
and the
diethylenetriaminepentakis (methylene phosphonates). Preferably, these
aminophosphonates do
not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
If utilized, chelating agents or transition-metal-selective sequestrants will
preferably
comprise from about 0.001% to about 10%, more preferably from about 0.05% to
about 1% by
weight of the compositions used herein.
7. Dispersant Polymer - Preferred compositions used herein may additionally
contain a
dispersant polymer. When present, a dispersant polymer in the compositions
used herein is
typically at levels in the range from 0 to about 25%, preferably from about
0.5% to about 20%,
more preferably from about 1 % to about 8% by weight of the composition used .
Dispersant
polymers are useful for improved filming performance of the present
compositions used,
especially in higher pH embodiments, such as those in which wash pH exceeds
about 9.5.
Particularly preferred are polymers which inhibit the deposition of calcium
carbonate or
magnesium silicate on dishware.
Dispersant polymers suitable for use herein are further illustrated by the
film-forming
polymers described in U.S. Pat. No. 4,379,080 (Murphy), issued Apr. 5, 1983.
Suitable polymers are preferably at least partially neutralized or alkali
metal, ammonium
or substituted ammonium (e.g., mono-, di- or triethanolammonium) salts of
polycarboxylic acids.
The alkali metal, especially sodium salts are most preferred. While the
molecular weight of the
polymer can vary over a wide range, it preferably is from about 1,000 to about
500,000, more
preferably is from about 1,000 to about 250,000, and most preferably,
especially if the
composition to be used is an ADD composition is for use in the method in a
North American
automatic dishwashing appliances, is from about 1,000 to about 5,000.
Other suitable dispersant polymers include those disclosed in U.S. Patent No.
3,308,067
issued March 7, 1967, to Diehl. Unsaturated monomeric acids that can be
polymerized to form
suitable dispersant polymers include acrylic acid, malefic acid (or malefic
anhydride), fumaric
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acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and
methylenemalonic acid.
The presence of monomeric segments containing no carboxylate radicals such as
methyl vinyl
ether, styrene, ethylene, etc. is suitable provided that such segments do not
constitute more than
about 50% by weight of the dispersant polymer.
Copolymers of acrylamide and acrylate having a molecular weight of from about
3,000 to
about 100,000, preferably from about 4,000 to about 20,000, and an acrylamide
content of less
than about 50%, preferably less than about 20%, by weight of the dispersant
polymer can also be
used. Most preferably, such dispersant polymer has a molecular weight of from
about 4,000 to
about 20,000 and an acrylamide content of from about 0% to about 15%, by
weight of the
polymer.
Particularly preferred dispersant polymers are low molecular weight modified
polyacrylate copolymers. Such copolymers contain as monomer units: a) from
about 90% to
about 10%, preferably from about 80% to about 20% by weight acrylic acid or
its salts and b)
from about 10% to about 90%, preferably from about 20% to about 80% by weight
of a
substituted acrylic monomer or its salt and have the general formula: -
[(C(R2)C(R1)(C(O)OR3)]
wherein the apparently unfilled valencies are in fact occupied by hydrogen and
at least one of
the substituents R1, R2, or R3, preferably R1 or R2, is a 1 to 4 carbon alkyl
or hydroxyalkyl
group; R1 or R2 can be a hydrogen and R3 can be a hydrogen or alkali metal
salt. Most
preferred is a substituted acrylic monomer wherein R1 is methyl, R2 is
hydrogen, and R3 is
sodium.
Suitable low molecular weight polyacrylate dispersant polymer preferably has a
molecular weight of less than about 15,000, preferably from about 500 to about
10,000, most
preferably from about 1,000 to about 5,000. The most preferred polyacrylate
copolymer for use
herein has a molecular weight of about 3,500 and is the fully neutralized form
of the polymer
comprising about 70% by weight acrylic acid and about 30% by weight
methacrylic acid.
Other suitable modified polyacrylate copolymers include the low molecular
weight
copolymers of unsaturated aliphatic carboxylic acids disclosed in U.S. Patents
4,530,766, and
5,084,535.
Agglomerated forms of the compositions used herein may employ aqueous
solutions of
polymer dispersants as liquid binders for making the agglomerate (particularly
when the
composition consists of a mixture of sodium citrate and sodium carbonate).
Especially preferred
are polyacrylates with an average molecular weight of from about 1,000 to
about 10,000, and
acrylate/maleate or acrylate/fumarate copolymers with an average molecular
weight of from
about 2,000 to about 80,000 and a ratio of acrylate to maleate or fumarate
segments of from
about 30:1 to about 1:2. Examples of such copolymers based on a mixture of
unsaturated mono-
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31
and dicarboxylate monomers are disclosed in European Patent Application No.
66,915,
published December 1 S, 1982.
Other dispersant polymers useful herein include the polyethylene glycols and
polypropylene glycols having a molecular weight of from about 950 to about
30,000 which can
be obtained from the Dow Chemical Company of Midland, Michigan. Such compounds
for
example; having a melting point within the range of from about 30°C to
about 100°C, can be
obtained at molecular weights of 1,450, 3;400, 4,500, 6,000, 7,400, 9,500, and
20,000. Such
compounds are formed by the polymerization of ethylene glycol or propylene
glycol with the
requisite number of moles of ethylene or propylene oxide to provide the
desired molecular
weight and melting point of the respective polyethylene glycol and
polypropylene glycol. The
polyethylene, polypropylene and mixed glycols are referred to using the
formula:
HO(CH2CH20)m(CH2CH(CH3)O)n(CH(CH3)CH20)oOH wherein m, n, and o are integers
satisfying the molecular weight and temperature requirements given above.
Yet other dispersant polymers useful herein include the cellulose sulfate
esters such as
cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate,
methylcellulose
sulfate, and hydroxypropylcellulose sulfate. Sodium cellulose sulfate is the
most preferred
polymer of this group.
Other suitable dispersant polymers are the carboxylated polysaccharides,
particularly
starches, celluloses and alginates, described in U.S. Pat. No. 3,723,322,
Diehl, issued Mar. 27,
1973; the dextrin esters of polycarboxylic acids disclosed in U.S. Pat. No.
3,929,107,
Thompson, issued Nov. 11, 1975; the hydroxyalkyl starch ethers, starch esters,
oxidized
starches, dextrins and starch hydrolysates described in U.S. Pat No.
3,803,285, Jensen, issued
Apr. 9, 1974; the carboxylated starches described in U.S. Pat. No. 3,629,121,
Eldib, issued Dec.
21, 1971; and the dextrin starches described in U.S. Pat. No. 4,141,841,
McDonald, issued Feb.
27, 1979. Preferred cellulose-derived dispersant polymers are the
carboxymethyl celluloses.
Yet another group of acceptable dispersants are the organic dispersant
polymers, such as
polyaspartate.
8. Material Care Agents - The compositions used herein may contain one or more
material
care agents which are effective as corrosion inhibitors and/or anti-tarnish
aids. Such materials
are preferred components of ADD compositions used herein especially in certain
European
countries where the use of electroplated nickel silver and sterling silver is
still comparatively
common in domestic flatware, or when aluminum protection is a concern and the
composition is
low in silicate. Generally, such material care agents include metasilicate,
silicate, bismuth salts,
manganese salts, paraffin, triazoles, pyrazoles, thiols, mercaptans, aluminium
fatty acid salts,
and mixtures thereof.
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32
When present, such protecting materials are preferably incorporated at low
levels, e.g.,
from about 0.01% to about 5% of the composition used. Suitable corrosion
inhibitors include
paraffin oil, typically a predominantly branched aliphatic hydrocarbon having
a number of
carbon atoms in the range of from about 20 to about S0; preferred paraffin oil
is selected from
predominantly branched C25..45 species with a ratio of cyclic to noncyclie
hydrocarbons of
about 32:68. A paraffin oil meeting those characteristics is sold by
Wintershall, Salzbergen,
Germany, under the trade name WINOG 70. Additionally, the addition of low
levels of bismuth
nitrate (i.e., Bi(N03)3) is also preferred.
Other corrosion inhibitor compounds include benzotriazole and comparable
compounds;
mercaptans or thiols including thionaphtol and thioanthranol; and finely
divided Aluminium
fatty acid salts, such as aluminium tristearate. The formulator will recognize
that such materials
will generally be used judiciously and in limited quantities so as to avoid
any tendency to
produce spots or films on glassware or to compromise the bleaching action of
the compositions.
For this reason, mercaptan anti-tarnishes which are quite strongly bleach-
reactive and common
fatty carboxylic acids which precipitate with calcium in particular are
preferably avoided.
9. Silicone and PhosQhate Ester Suds Suppressors - The compositions used in
the methods
of the invention can optionally contain an alkyl phosphate ester suds
suppressor, a silicone suds
suppressor, or combinations thereof. Levels in general are from 0% to about
10%, preferably,
from about 0.001% to about 5%. However, generally (for cost andlor deposition
considerations)
preferred compositions used herein do not comprise suds suppressors or
comprise suds
suppressors only at low levels, e.g., less than about 0.1% of active suds
suppressing agent.
Silicone suds suppressor technology and other defoaming agents useful herein
are
extensively documented in ''Defoaming, Theory and Industrial Applications",
Ed., P.R. Garrett,
Marcel Dekker, N.Y., 1973, ISBN 0-8247-8770-6. See
especially the chapters entitled "Foam control in Detergent Products" (Ferch
et al) and
"Surfactant Antifoams" (Blease et al). See also U.S. Patents 3,933,672 and
4,136,045. Highly
preferred silicone suds suppressors are the compounded types known for use in
laundry
detergents such as heavy-duty granules, although types hitherto used only in
heavy-duty liquid
detergents may also be incorporated in the instant compositions. For example,
polydimethylsiloxanes having trimethylsilyl or alternate endblocking units may
be used as the
silicone. These may be compounded with silica and/or with surface-active
nonsilicon
components, as illustrated by a suds suppressor comprising 12%
silicone/silica, 18% stearyl
alcohol and 70% starch in granular form. A suitable commercial source of the
silicone active
compounds is Dow Corning Coip.
If it is desired to use a phosphate ester, suitable compounds are disclosed in
U.S. Patent
3,314,891, issued April 18, 1967, to Schmolka et al. Preferred
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33
alkyl phosphate esters contain from 16-20 carbon atoms. Highly preferred alkyl
phosphate
esters are monostearyl acid phosphate or monooleyl acid phosphate, or salts
thereof, particularly
alkali metal salts, or mixtures thereof.
It has been found preferable to avoid the use of simple calcium-precipitating
soaps as
antifoams in the present compositions as they tend to deposit on the dishware.
Indeed,
phosphate esters are not entirely free of such problems and the formulator
will generally choose
to minimize the content of potentially depositing antifoams in the
compositions used.
10. Other Optional Adiuncts - Depending on whether a greater or lesser degree
of
compactness is required, filler materials can also be present in the
compositions used in the
methods herein. These include sucrose, sucrose esters, sodium sulfate,
potassium sulfate, etc., in
amounts up to about 70%, preferably from 0% to about 40% of the ADD
composition. Preferred
filler is sodium sulfate, especially in good grades having at most low levels
of trace impurities.
Sodium sulfate used herein preferably has a purity sufficient to ensure it is
non-reactive
with bleach; it may also be treated with low levels of sequestrants, such as
phosphonates or
EDDS in magnesium-salt form. Note that preferences, in terms of purity
sufficient to avoid
decomposing bleach, applies also to pH-adjusting component ingredients,
specifically including
any silicates used herein.
Although optionally present in the compositions used herein, the present
invention
encompasses embodiments which are substantially free from sodium chloride or
potassium
chloride.
Hydrotrope materials such as sodium benzene sulfonate, sodium toluene
sulfonate,
sodium cumene sulfonate, etc., can be present, e.g., for better dispersing
surfactant.
Bleach-stable perfumes (stable as to odor); and bleach-stable dyes such as
those disclosed
in U.S. Patent 4,714,562, Roselle et al, issued December 22, 1987 can also be
added to the
present compositions in appropriate amounts. Other common detergent
ingredients consistent
with the spirit and scope of the present invention are not excluded.
Since compositions used herein, especially the ADD compositions used herein,
can
contain water-sensitive ingredients or ingredients which can co-react when
brought together in
an aqueous environment, it is desirable to keep the free moisture content of
the compositions
used at a minimum, e.g., 7% or less, preferably 4% or less of the composition;
and to provide
packaging which is substantially impermeable to water and carbon dioxide.
Coating measures
have been described herein to illustrate a way to protect the ingredients from
each other and
from air and moisture. Plastic bottles, including refillable or recyclable
types, as well as
conventional barrier cartons or boxes are another. helpful means of assuring
maximum shelf
storage stability. As noted, when ingredients are not highly compatible, it
may further be
desirable to coat at least one such ingredient with a low-foaming nonionic
surfactant for
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34
protection. There are numerous waxy materials which can readily be used to
form suitable
coated particles of any such otherwise incompatible components; however, the
formulator
prefers those materials which do not have a marked tendency to deposit or form
films on dishes
including those of plastic construction.
Some preferred substantially chlorine bleach-free granular automatic
dishwashing
compositions for use in the methods of the invention are as follows: a
substantially chlorine-
bleach free automatic dishwashing composition comprising amylase (e.g.,
TERMAMYL~)
and/or a bleach stable amylase and a bleach system comprising a source of
hydrogen peroxide
selected from sodium perborate and sodium percarbonate and a cobalt catalyst
as defined herein.
There is also contemplated a substantially chlorine-bleach free automatic
dishwashing
composition comprising an oxidative stability-enhanced amylase and a bleach
system
comprising a source of hydrogen peroxide selected from sodium perborate and
sodium
percarbonate, a cobalt catalyst, and TAED or NOBS.
The following nonlimiting examples further illustrate compositions suitable
for use in the
methods of the present invention.
EXAMPLE 1
Automatic dishwashing compositions:
Ingredients: Weight%
A B
Sodium Tripolyphosphate (STPP) 24.0 45
Sodium carbonate 20.0 13.5
Hydrated 2.0r silicate 15 13.5
Poly-Tergent~ SLF-18B Nonionic 2.0 2.0
surfactant'l
C 13 Amine Oxide 1.0 1.0
Polymer 1 4.0 --
Protease (4% active) 0.83 0.83
Amylase (0.8% active) 0.5 0.5
Perborate monohydrate (15.5% 14.5 14.5
Active Av0)2
Cobalt catalyst3 0.008 --
Dibenzoyl Peroxide ( 18% active)4.4 4.4
Water, sodium sulfate and misc.Balance Balance
1 Terpolymer selected from either 60% acrylic acid/20% malefic acid/20% ethyl
acrylate, or
70% acrylic acid/10% malefic acid/20% ethyl acrylate.
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2 The Av0 level of the above formula is 2.2%.
3 Pentaammineacetatocobalt(III) nitrate prepared as described hereinbefore;
may be replaced by
MnTACN.
4 Epoxy-capped poly(oxyalkylated) alcohol of Example III of WO 94/22800
wherein 1,2-
epoxydodecane is substituted for 1,2-epoxydecane.
The following examples further illustrate phosphate built ADD compositions
which
contain a bleach/enzyme particle, but are not intended to be limiting thereof.
These
compositions are suitable for use in the methods of the present invention. All
percentages noted
are by weight of the finished compositions, other than the perborate
(monohydrate) component,
which is listed as AvO.
EXAMPLES 2 - 3
2 3
Catalystl 0.008 0.004
SavinaseTM 12T -- 1.1
Protease D 0.9 --
DuramylTM 1.5 0.75
STPP 31.0 30.0
Na2C03 20.0 30.5
Polymer2 4.0 --
Perborate (Av0) 2.2 0.7
Dibenzoyl Peroxide 0.2 0.15
2 R Silicate (Si02) 8.0 3.5
Paraffin 0.5 0.5
Benzotriazole 0.3 0.15
SLF-18 Nonionic surfactant31.0 1.0
C 13 Amine Oxide 1.0 1.0
Sodium Sulfate, Moisture ---------Balance----------
1 Pentaammineacetatocobalt (III) nitrate; may be replaced by MnTACN.
2 Polyacrylate or Acusol 480N or polyacrylate/polymethacrylate copolymers.
3 Supplied by Olin Corporation (cloud point=18°C).
4 An alkyl carboxy ethoxylate having an average of C13 alkyl and 6.5
ethoxylates.
In Compositions of Examples 2 and 3, respectively, the catalyst and enzymes
are
introduced into the compositions as 200-2400 micron composite particles which
are prepared by
spray coating, fluidized bed granulation, marumarizing, prilling or
flaking/grinding operations.
If desired, the protease and amylase enzymes may be separately formed into
their respective
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36
catalyst/enzyme composite particles, for reasons of stability, and these
separate composites
added to the compositions.
EXAMPLES 4 - 5
The following describes catalyst/enzyme particles (prepared by drum
granulation) for
use in the present invention compositions. For example 5, the catalyst is
incorporated as part of
the granule core, and for example 4 the catalyst is post added as a coating.
The mean particle
size is in the range from about 200 to 800 microns.
Catalyst/Enzyme Particles for Examples 4 and 5
4 S
Core
Cobalt Catalyst - 0.3
(PAC)
Amylase, commercial0.4 0.4
Fibrous Cellulose2.0 2.0
PVP 1.0 1.0
Sodium Sulphate 93.3 93.3
Coating
Titanium Dioxide 2.0 2.0
PEG 1.0 1.0
Cobalt Catalyst 0.3 -
(PAC)
Granular dishwashing detergents wherein Example 4 is a Compact product and
Example
is a Regular/Fluffy product are as follows:
4 5
Composite Particle 1.5 0.75
SavinaseTM 12T 2.2 -
Protease D -- 0.45
STPP 34.5 30.0
Na2C03 20.0 30.5
Acusol 480N 4.0 --
Perborate(Av0) 2.2 0.7
Dibenzoyl Peroxide 0.2 0.15
2 R Silicate(Si02) 8.0 3.5
Paraffin -- 0.5
Benzotriazole -- 0.15
SLF-18 Nonionic surfactant2.0 2.0
Tergitol 1 S S9 Nonionic 1.0 1.0
surfactant
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37
C 13 Amine Oxide 0.05 1.0
Sodium Sulphate, Moisture ---to balance-----
Other compositions herein are as follows:
EXAMPLES 6 - 9
6 7 8 9
STPP 34.4 34.4 34.4 34.4
Na2C03 20.0 30.0 30.5 30.5
Polymer3 4.0 -- -- 2.0
Perborate (Av0) 2.2 1.0 0.7 1.5
Catalystl 0.008 0.004 0.004 0.005
SavinaseTM 6.0T -- 2.02 2.02
Protease D 0.9 -- -- 0.05
DuramylTM 1.5 0.75 -- 0.05
TermamylTM 6.0T -- -- 1.0 0.02
Dibenzoyl Peroxide (active) 0.8 0.6 0.4 --
2 R Silicate (Si02) 8.0 6.0 4.0 5.0
SLF-18 Nonionic Surfactant 2.0 1.5 1.2 1.3
C12 phosphine oxide 0.5 -- 1.0 --
C12 sulfoxide -- 0.5 -- 1.0
Sodium Sulfate, Moisture -------------- Balance -------------------------------
---
lPentaamineacetatocobalt (III) nitrate; may be replaced by MnTACN.
2 May be replaced by 0.45 Protease D.
3 Polyacrylate or Acusol 480N.
In Compositions of Examples 6-8, respectively, the catalyst and enzymes are
introduced
into the final compositions as 200-2400 micron catalyst/enzyme composite
particles which are
prepared by spray coating, marumarizing, prilling or flaking/grinding
operations. If desired, the
protease and amylase enzymes may be separately formed into their respective
catalyst/enzyme
composite particles, for reasons of stability, and these separate composites
added to the
compositions.
EXAMPLES 10 - 12
11 12
STPP 31.0 31.0 31.0
Na2C03 20.0 20.0 20.0
Polymer3 4.0 4.0 4.0
Perborate (Av0) 2.2 2.2 2.2
Catalystl 0.008 -- 0.018
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38
SavinaseTM 6.0T2 2.0 2.0 2.0
TermamylTM 6.0T 1.0 1.0 1.0
TAED 2.0 -- 1.0
Cationic Activator'1 -- 2.0 --
2 R Silicate (Si02) 8.0 8.0 8.0
Metasilicate -- -- 2.5
016/18 dine Oxide 0.25 0.25 0.75
SLF-18 Nonionic surf. 0.5 1.0 1.5
Tergitol 1559 Nonionic surf. 1.0 1.0 0.75
Sodium Sulfate, Moisture --------------
Balance ---------------
lPentaamineacetatocobalt (III) nitrate;
may be replaced by MnTACN.
2 May be replaced by 0.45 Protease D.
3 Polyacrylate or Acusol 480N.
4 6-Trimethylammoniocaproyl caprolactam,
tosylate salt.
Example 13
Method of the present invention
Any of the foregoing ADD compositions can be used in the conventional manner
in an
automatic dishwashing machine to cleanse plasticware, dishware, glassware,
cooking/eating
utensils, and the like.
