Note: Descriptions are shown in the official language in which they were submitted.
2130~6~
~~ 93/18129 ~ PCI'/US93/0189
LOW-DOSAGE AUTOMATIC DISHWASHING DETERGENT
WITH MONOPERSULFATE AND ENZYMES
TECHNICAL FIELD
The present invention is in the field of solid-form automatic
dishwashing detergents. More specifically, the invention relates
to nonphosphated (i.e., substantially free from inorganic
phosphate builder salts) low-dosage forms of such compositions
wherein there is present a beverage stain-removing amount of a
monopersulfate salt. Granular and tabletted forms of the
compositions are encompassed, as is a method of washing domestic
tableware, such as dishes, glassware, cups and flatware, with the
compositions here provided.
BACKGROUND OF THE INVENTION
Automatic dishwashing detergents (ADD's) used for washing
tableware in the home or institutionally in machines especially
designed for the purpose have long been known. The particular
requirements of cleansing tableware and leaving it in a sanitary,
essentially spotless, residue-free state has indeed resulted in so
many particular ADD compositions that the body of art pertaining
thereto is now recognized as quite distinct from other cleansing
product arts. British Patents 1,325,645; 1,527,706; and
1,381,187; European Patent Application EP-A 82,564; and U.S.
Patents 4,427,417i 4,436,642; and 4,539,144 describe various
aspects of ADD's, their components and their manufacture.
In recent times, there has been a renewed interest among
consumers in effective, economical cleansing products, especially
laundry detergents, using smaller amounts of chemicals and
packaging for a diminished environmental impact. In light of
legislation and current environmental trends, such products are
desirably substantially free of inorganic phosphate builder salts.
In addition, such compositions are desirably free of chlorine
bleach and "inert" filler ingredients such as sodium sulfate.
Unfortunately, low-dosage nonphosphated ADD products may be
made available to the consumer with a promise of effectiveness but
in technical terms sacrificing efficacy, especially owing to the
loss of phosphate and chlorine mainstay ingredients. Indeed,
WO 93/18129 213 0 4 6 a PCr/US93/0189'-
there does not currently appear to be a commercial low-dosage,
nonphosphated ADD product which is economical and at the same time
free from end-result shortcomings, such as relatively poor stain
removal as compared with the same technology incorporated in
regular-dosage nonphosphated formulas. Without being limited by
theory, we believe stain removal shortcomings in particular are
due to commercial perborate- and perborate-plus-activator ADD
products relying quite heavily on a robust product matrix, which
is lost in low-dosage product forms unless very expensive high
levels of nonphosphorus builder are utilized.
In the course of exploratory studies to address this problem
and secure improved low-dosage nophosphated compositions which are
both economical and effective, it has been discovered that
perborate, perborate-with-activator (such as tetraacetylethylene-
diamine) and others among the conventional oxygen bleachtechnologies are relatively intolerant of significant reductions
in levels of alkaline ingredients, builders and "inert" fillers
(which actually function as electrolytes), all seemingly vital to
successfully arriving at low-dosage forms of the ADD products.
Moreover, these shortcomings are especially apparent when the
compact-form ADD is used under "stressed" conditions, such as is
frequently the case in high-hardness areas or among economy-minded
consumers who use products sparingly.
One way round the problem would be to use chlorine bleaches,
meaning chlorine-containing compounds which release hypochlorite
when dissolved in water; but chlorine bleach limits the formulator
since it is incompatible with many desirable components of
nonphosphated ADD's, such as enzymes and many nonphosphorus
builders and surfactants.
Accordingly, it is an object of the present invention to
provide new and improved low-dosage ADD compositions. Such
compositions are nonphosphated compositions, i.e., they are
substantially free from, and unreliant on inorganic phosphate
builders. The compositions herein are also free of chlorine
bleach. More specifically, it is an object herein to provide
low-dosage solid-form ADD's, especially granules, formulated with
monopersulfate ("MPS") salts for highly effective removal of
stains from tableware, especially beverage stains such as tea, tea
~ 93/18129 2 1 3 0 ~ 6 ~ P~us93/0l895
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with milk, or coffee, from cups and mugs. Dosages, that is to say
usage levels of ADD in automatic dishwashing appliances, are
generally from about 25%-70Yo, more typically from about 50%-60% of
the dosage of a conventional phosphated, chlorine-bleach contain-
ing automatic dishwashing detergent. Another object herein is toprovide a method for washing tableware in home or institutional
automatic dishwashing appliances, especially in home appliances,
using compositions provided herein at the specific dosage levels
further detailed hereinafter.
The unique MPS-containing compositions herein provide
numerous advantages in addition to compactness and stain-removal
efficacy with economy. These include material protection via a
reduced tendency to etch glass and tableware, excellent spotless-
ness and lack of filming, high water solubility and elimination of
undissolved product residue, and the ability to remove proteina-
ceous food residues from articles such as pots and pans.
BACKGROUND ART
Monopersulfate salts, such as the potassium, sodium, and
magnesium salts, as well as binary and ternary mixed salts of
monopersulfate with alkali metal sulfates and/or bisulfates, are
generally known from the literature. One such salt, sold as OXONE
(registered trademark of DuPont), has been variously described in
the literature as a mixture of potassium monopersulfate with
potassium sulfate and potassium bisulfate, or as a "triple salt"
having specific stoichiometry. The use of monopersulfate salts
such as OXONE has previously been described. See: U.S. Patents
3,049,495; 3,556,711; 3,558,497; 3,732,170; 3,805,809; 3,819,828;
3,945,937; 4,127,496; 5,041,232; 5,045,223; 5,047,163; European
Patent Applications EP-A 135,226; EP-A 239,379; and EP-A 400,858;
Japanese JP 58180420 A2; and South African ZA 8,301,869. Monoper-
sulfate salts are chemically different from peroxydisulfate salts,
such as potassium peroxydisulfate K2S20~. Indeed, peroxydisulfate
alone is not effective in the instant invention.
SUMMARY OF THE INVEN~ION
ComPositions - The present invention encompasses low-dosage
granular automatic dishwashing detergent compositions, in solid
form, e.g., as granules or tablets, which are substantially free
of inorganic phosphate builders, substantially free of chlorine
WO 93/18129 2 1 3 0 ~ 6 S PCI'/US93/01895
bleach, and preferably substantially free of inert fillers such as
sodium sulfate, comprising:
(a) monopersulfate salt in an amount sufficient to provide
from about 0.18~. to about 1.3% by weight, more
preferably from about 0.36% to about 1.1%, most
preferably from about 0.54% to about 0.9% by weight of
the composition of Available Oxygen (this corresponds to
the amount of monopè:rsulfate salt required to establish
a usage level of Avàilable Oxygen of from about 5 ppm to
about 35 ppm, more preferably from about 10 ppm to about
30 ppm, most preferably from about 15 ppm to about 25
ppm);
(b) detersive enzyme in an amount sufficient to provide from
about 0.01% to about 0.5%, more preferably from about
0.02% to about 0.2% of the composition, of active enzyme
(this corresponds to the amount of detersive enzyme
required to establish a usage level of active enzyme of
from about 0.5 ppm to about S ppm);
(c) from about 0.1X to about 10% by weight of the composi-
tion of an organic dispersant; (this ingredient is
typically a water-soluble or water-dispersible poly-
electrolyte capable of inhibiting the precipitation of
water hardness salts; such dispersants include the
sodium polyacrylates, mono- and dicarboxy starches and
the like);
(d) pH adjusting agent in an amount sufficient to establish
a usage pH in the range from about 8 to about 11,
preferably from about 9.5 to about 10.5, at typical
composition usage levels of from about 1500 ppm to about
4000 ppm, more preferably from about 2000 ppm to about
3000 ppm, in water; (pH adjusting agent will typically
comprise (i) from 0% to about 30%, more preferably from
about 5% to about 25%, most preferably from about 8% to
about 20% of the composition of a carbonate ingredient
and (ii) from 0% to about 35%, more preferably from
about 4% to about 25%, most preferably from about 6% to
about 15% of a water-soluble silicate ingredient; always
subject to the provision that the sum of the levels of
''IO 93/18129 2 1 3 0 4 6 ~ P~/US93/0l895
pH-adjusting agent components (i) and (ii) is greater
than zero. The carbonate ingredient is typically
selected from the group consisting of: sodium carbonate,
sodium bicarbonate, sodium sesquicarbonate, potassium
carbonate, potassium bicarbonate and potassium
sesquicarbonate and mixtures thereof; more preferably
this first component of the pH adjusting agent is
selected from the group consisting of sodium carbonate,
sodium bicarbonate, sodium sesquicarbonate and mixtures
thereof. The water-soluble silicate ingredient is
typically selected from the group consisting of hydrous
sodium and potassium silicates having a SiO2:M20 ratio
in the range from about 1.6 to about 3, more preferably
from about 2 to about 2.4 wherein M represents sodium or
potassium).
Preferred embodiments of the invention comprise compositions
having the above components (a) through (d) plus one or more of
the following optional ingredients; in certain highly preferred
embodiments of the invention, all of the optional ingredients are
present at non-zero levels:
(e) from 0% to about 1.5%, more preferably from about 0.1%
to about 0.5% by weight of the composition of a chlorine
bleach scavenger; (when present, the chlorine bleach
scavenger is typically sodium perborate, preferably in
the monohydrate form);
(f) from 0% to about 40X, more preferably from about 5% to
about 30% by weight of the composition of a weak non-
phosphorus builder; (when present, this builder is
preferably selected from organic carboxylate builders
having molecular weight of below about 600; more
preferably the weak nonphosphorus builder is selected
from the group consisting of an alkali metal salt of one
or more of: citrate, tartrate succinates, glycerol
succinates, carboxymethyloxysuccinate and glucohepton-
ate; most preferably this builder is sodium citrate in
the trisodium, dihydrate form although citric acid may
be equally useful in the lower-pH embodiments);
WO 93/18129 2 1~ 0 4 6 ~ PCI /US93/01895
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(g) from 0% to about 4% by weight of the composition, more
preferably from about 0.1% to about 2%, most preferably
from about 0.2% to about 0.7% by weight of the composi-
tion, of a bleach stabilizer; (when present, the bleach
stabilizer is preferably selected from the group con-
sisting of organic nitrogen-containing sequestrants and
organic phosphorus-containing sequestrants, more prefer-
ably the bleach stabilizer is selected from the group
consisting of organic nitrogen-containing sequestrants.
Especially preferred nitrogen-containing sequestrants
are ethylenediamine disuccinate, 1,2-oxoethanediyl-
bis(aspartate) and diethylenetriaminepentacetate in acid
or, more preferably, sodium-salt form); and
(h) from about OYO to about 10% by weight, more preferably
from about 1% to about 7%, most preferably from about 2%
to about 5% of the composition of a low-sudsing surfact-
ant. (When present, the low-sudsing surfactant is
typically one known for use in ADD's and is selected
from low-sudsing nonionic surfactants, low-sudsing
anionic surfactants and their mixtures; and mixtures of
higher-sudsing surfactants with a conventional suds-
suppressor such as a silicone/silica mixture).
Method - The invention also encompasses a method for cleaning
dishware, and the like, comprising in an automatic dishwashing
appliance containing domestic tableware, such as flatware, cups
and mugs, glassware, dinner plates and/or pots and pans, a step of
washing said tableware by contact with an aqueous bath comprising
from about 1500 ppm to about 4000 ppm, more preferably from about
2000 ppm to about 3000 ppm, of the instant composition. Prefer-
ably the appliance is a commercial domestic automatic dishwasher
and there will be two such steps in sequence, with one or more
rinse steps, in which no composition is dispensed, intervening
between the said washing steps. Temperatures in the method can
vary quite widely, but in accordance with normal practice, hot
water preheated outside the appliance and having a temperature in
the range from about lOO-F (37.8-C) to about 150-F (65.6-C) may be
used; alternatively, and depending on the power output of the
heating coil which may be present in the appliance, cold water
213046~
'''O 93/18129 - PCI'/US93/0189~
fill, such as at a temperature of from about 40-F (4.4-C) to about
80-F (26.7 C), can be used and the water is heated in the
appliance to temperatures of about 150-F (65.6-C), or higher. In
a preferred embodiment of the method, a washing step is followed
by several rinse steps during which a conventional rinse agent may
be dispensed to aid sheeting and drying action.
Units - All percentages, ratios and proportions herein are by
weight, unless otherwise noted. When percentages are quoted
without any particular indication as to whether the ADD composi-
tions, their aqueous solutions at usage level, or percentages of
components such as water in raw materials are intended, such
percentages should be taken to refer to percentages by weight of
the fully-formulated automatic dishwashing detergent. The abbre-
viation "ppm" refers to "parts by million". When "ppm" is used
without indicating whether the ADD compositions or their aqueous
solutions are intended, "ppm" should be taken to refer to usage-
level parts by million of the indicated ingredient or composition
in wash water.
DETAILED DESCRIPTION OF THE INVENTION
The present invention employs ingredients which are generally
known in the art, but which are combined in a unique manner herein
to provide important cleaning benefits in an automatic dishwashing
detergent context. More specifically, the combination of the
ingredients in the manner disclosed hereinafter allows the formula-
tion of what might be referred to as "low dosage" or "compact"
automatic dishwashing detergent compositions which are character-
ized by the fact that they contain lesser volumes of ingredients
than conventional, granular dishwashing detergents now being sold,
yet perform well under a wide variety of conditions. ~hese lesser
volumes are achieved without it being essential to resort to
densification. ("Densification" or "densified", as distinct from
"compaction" or "compact" as used herein, refers to a process
involving physically compressing the product by the application of
pressure). Since excessive densification tends to adversely
affect ADD solubility and since solubility of ADD's is prized by
the consumer owing to the avoidance of undissolved detergent
residues. the invention brings with it solubility advantages.
Densities of typical compositions herein are in the range from
Wog3,l8l29 2~-3046~ PCI/US93/01895
- 8
about 0.7 g/cm3 to about 1.2 g/cm3, more preferably from about 0.8
g/cm3 to about 1.1 g/cm3. In light of the reduced volume and
excellent solubility, the consumer is afforded more convenient
compositions which, as used in properly functioning automatic
dishwashing appliances, do not leave unsightly residues of
undissolved detergent.
The compositions herein are formulated to be substantially
free of inorganic phosphate salts (phosphate builders) and are
substantially free of chlorine bleaches.
While it may be thought that the selection of non-chlorine
bleaches for use in compositions of the present type is a roùtine
affair, the selection of monopersulfate salts (sometimes known as
monoperoxysulfate salts) from among the many known oxygen bleaches
(e.g., perborate, percarbonate, peroxydisulfate, organic peracids,
perborate-with-activator and the like) takes into consideration
various factors designed to provide optimum cleaning performance
in the present compositions. Without being bound by theory,
optimum stain removal performance by low-dosage ADD's in the
absence of conventional chlorine bleaches requires an oxygen
bleaching species to be present throughout the washing operation.
In a low-dosage ADD composition, this bleach at usage levels of
only a few ppm to a few tens of ppm Available Oxygen in the wash
water must operate at much lower electrolyte, hydroxide ion/pH
adjusting agent and builder levels, as compared with the levels
afforded by conventional dosage ADD's. It is now surprisingly
revealed that of the known oxygen bleaches, monopersulfate salts
do exceptionally well in this regard. Moreover high wash water
temperatures or dispersed soils from the tableware can rapidly
consume Available Oxygen, thereby preventing bleach from reaching
and acting on the stained tableware. Again, it transpires that
monopersulfate is effective for stain-removal in low-dosage ADD's
while at the same time being relatively resistant to such causes
of wasteful decomposition when formulated and used in accordance
with the invention. In particular circumstances known as
"stressed usage conditions", referring to high domestic water
hardness, sparing use of ADD, excessively high or low wash
temperatures and the like, monopersulfate salts as formulated
' '0 93/181 29 2 13 0 ~ 6 ~ PCI /US93/01 89~
herein are believed to provide superior stain removal results as
compared with other conventional oxygen bleaches otherwise
similarly formulated.
MonoPersulfate Salts - Monopersulfate salts (MPS bleach)
employed herein comprise compounds which dissociate in water to
provide monopersulfate species such as HSOs~ or the corresponding
dianion or radical anions. Such salts are illustrated by potas-
sium monopersulfate, sodium monopersulfate, magnesium monopersul-
fate, and tetra-alkylammonium monopersulfates such as tetrabutyl-
ammonium monopersulfate. A long-known and readily commercially
available monopersulfate salt employed herein is a "triple salt".
Commmercial compositions comprising this salt are available under
the tradename OXONE, from DuPont. OXONE has the Chemical Abstracts
Registry Number 37222-66-5 and is in the form of a stable, free-
flowing powder which comprises 2~HSOs.K2SO~.KHSO4. Since thissalt is the most readily available, it is used in many preferred
embodiments of this invention. The lower molecular weight (and
thus more mass-efficient) MPS salts are desirably used for low-
dosage ADD compositions of the invention, but these salts are not
commonly available in bulk, and must be made by conventional
literature methods. Chemical practitioners will of course be
aware that cations accompanying the monopersulfate can conveni-
ently be exchanged by metathesis. Yet another approach is to ship
bulk liquid stock of a solution of sodium or potassium monopersul-
fate, and, subject to the normal safety procedures for oxidants ofthis general type, dry or otherwise convert it adjacent the ADD
manufacturing facility to whatsoever convenient solid form is
desired.
Available OxYqen - ~Available Oxygen" as defined herein
refers to percentage by weight of titratable O (not ~2)~ inclusive
only of titratable O from monopersulfate salts and specifically
exclusive of titratable O from any active oxygen-containing
chlorine bleach scavenger which may be used. Titration may be
done using any convenient literature method for the determination
of MPS bleaches, such as iodometric methods. See, for example,
Skoog and West, Fundamentals of Analytical Chemistry, Holt,
Rinehart, 1976, pages 362-369 and 748-751.
WO93/18129 2130 465 PCI/US93/0189~
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Conversion between Available Oxygen (AvO) and percentage of
monopersulfate salt in any given composition is illustrated in the
case of the pure monopersulfate triple salt 2KHSOs-KHSO4-K2SO4 as
follows:
triple salt molecular weight = 614.74 g/mol;
mass fraction of Active Oxygen in pure triple salt
32/614.74; where 32 corresponds with two moles of Available O per
mole of the triple salt in accordance with the presence of two
moles of potassium monopersulfate in the triple salt formula;
percentage of Available Oxygen in the pure triple salt =
(32/614.74)*100 = 5.21% AvO.
Let us say, for example, that a given ADD composition in
accordance with the invention has a percentage of Available Oxygen
of 0.78%
Then the percentage by weight of monopersulfate triple salt
that it contains, assuming the salt is pure, is given by:
0.78/0.0521 = 14.97%
Similar conversions apply to any other composition in accord-
ance with the invention, requiring only that the appropriate
molecular weight of the monopersulfate salt be used. It will
naturally be appreciated that commercial-grade monopersulfate
salts can be used, such as OXONE triple salt formulated with
commercial stabilizers and the like, in which case conversion from
analyzed % AvO to percentage by weight of commercial-grade OXONE
in the composition will include an assay factor. It has been
found that commercial OXONE typically contains only about 88
percent by weight of the pure triple salt, accordingly a percent-
age by weight of the commercial sample will be increased by the
assay factor: taking the above-given illustration, if the analyzed
Available Oxygen in the composition was 0.78%, the content of 88%
commercial OXONE would be:
(0.78/0.0521)*1/0.88 = 17.01% where 0.88 is the assay factor.
For simplicity, OXONE percentages other than in the detailed
Examples are given on a pure basis herein, unless otherwise
specifically indicated. Typically, the compositions herein will
comprise from about l~o to about 9.5% by weight of MPS (as HSOs-),
which translates into about 3% to about 25% by weight OXONE, dry
basis as the pure triple salt.
21 30465
Detersive EnzYme - The enzymes employed in the present
compositions are of types well-known in the art. Such enzymes are
commonly available in "prill" form. A prill is a fabricated
particle containing varying proportions of active enzyme, inactive
enzyme, and supporting materials which serve to stabilize the active
enzyme during storage. For this reason, the levels of enzyme in the
instant compositions are specified on the basis of active enzyme
content. Assays may be carried out using any of the standard
methods available from the enzyme suppliers. It is essentially
immaterial to know the precise nature and level of the inactive
components of the prill, except that it has been discovered that
overly high levels of inactive enzyme and prill ingredients, e.g.,
above about 8X by weight of the fully-formulated ADD composition,
actually tend to have adverse effects on the filming characteristics
of the ADD; such levels should preferably be avoided.
Suitable enzymes herein comprise proteolytic enzymes well-
known in the art. Proteolytic enzymes such as SAVINASE~. ESPERASE~
and ALCALASE~, sold by NOVO Industries, Copenhagen, Denmark, are
particularly useful herein, sine proteolytic enzymes serve to
attack, degrade and remove various protein residues from the
tableware being cleaned. Moreover, it has been discovered that in
combination with oxygen bleach, such proteolytic enzymes, or their
variants engineered for greater oxygen bleach stability, work
exceptionally well for the removal of tea-with-milk stains from cups
and mugs.
Amylase enzymes can also be used, either in combination with
proteases in an optional, but preferred mode, or singly. in the
compositions of the invention. Amylase sold by NOVO under the name
TERMAMYL is a typical example.
Enzyme activity and enzyme activity measurement are described
in detail in the following publications: "Enzyme Nomenclature
Recommendations (1972) of the International Union of Pure and
Applied Chemistry and the International Union of Biochemistry", 2nd
Reprint, 1975, ISBN 0-444-41139-9 and Publications B259c (Alcalase),
B260c (Esperase) and B274c (Termamyl~), all published March 1988 by
Novo Industri A/S, Novo Allé, 2880 Bagsvaerd, Denmark~
W O 93/18129 ~ ~ 3 0 4 ~ S P ~ /US93/0189
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Orqanic DisPersant - As noted hereinabove, the present
compositions contain organic dispersant which overcomes the
problem of unsightly films which form on china and especially on
glassware due to calcium- or ~agnesium-hardness-induced precipita-
tion of pH-adjusting agents~ especially carbonates, used herein.
The organic dispersants herein are used at levels of at least
about 0.1%, typically from about 1% to about 10%, most preferably
from about 1% to about 7% of the automatic dishwashing composi-
tion. Such organic dispersants are preferably water-soluble
sodium polycarboxylates. ("Polycarboxylate" dispersants herein
generally contain truly polymeric numbers of carboxylate groups,
e.g., 8 or more, as distinct from carboxylate builders, sometimes
called "polycarboxylates" in the art when, in fact, they have
relatively low numbers of carboxylate groups such as four per
molecule.) The organic dispersants are known for their ability to
disperse or suspend calcium and magnesium "hardness", e.g.,
carbonate salts. Crystal growth inhibition, e.g., of Ca/Mg
carbonates, is another useful function of such materials. Prefer-
ably, such organic dispersants are polyacrylates or acrylate-
containing copolymers. "Polymeric Dispersing Agents, SOKALAN", a
printed publication of BASF Aktiengesellschaft, D-6700
Ludwigshaven, Germany, describes organic dispersants useful
herein. Sodium polyacrylate having a nominal molecular weight of
about 4500, obtainable from Rohm & Haas under the tradename as
ACUSOL 445N, or acrylate/maleate copolymers such as are available
under the tradename SOKALAN, from BASF Corp., are preferred
dispersants herein. These polyanionic materials are, as noted,
usually available as viscous aqueous solutions, often having
dispersant concentrations of about 30-50%. The organic dispersant
is most commonly fully neutralized; e.g., as the sodium salt form.
While the foregoing encompasses preferred organic dispersants
for use herein, it will be appreciated that other oligomers and
polymers of the general polycarboxylate type can be used,
according to the desires of the formulator. Suitable polymers are
generally at least partially neutralized in the form of their
alkali metal, ammonium or other conventional cation salts. The
alkali metal, especially sodium salts, are most preferred. While
the molecular weight of such dispersants can vary over a wide
2130465
- 13 -
range, it preferably is from about 1,000 to about 500,000, more
preferably is from about 2,000 to about 250,000, and most preferably
is from about 3,000 to about 100,000. Nonlimiting examples of such
materials are as followsO
For example, other suitable organic dispersants include those
disclosed in U.S. Patent 3,308,067 issued March 7, 1967, to Diehl.
Unsaturated monomeric acids that can be polymerized to form suitable
polymeric polycarboxylates include maleic acid (or maleic
anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic
acid, citraconic acid and methylenemalonic acid. The presence of
monomeric segments containing no carboxylate radicals such as
vinylmethyl ether, styrene, ethylene, etc. is suitable, preferably
when such segments do not constitute more than about 40% by weight
of the polymer.
Other suitable organic dispersants for use herein are
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 20X~ by weight of the polymer. Most
preferably, the polymer has a molecular weight of from about 4,000
to about 10,000 and an acrylamide content of from about 1% to about
15%, by weight of the polymer
Still other useful organic dispersants include acrylate/male-
ate or acrylate/fumarate copolymers with an average molecular weight
in acid form 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
2:1 Other such suitable copolymers based on a mixture of
unsaturated mono- and dicarboxylate monomers are disclosed in
European Patent Application No. 66.915, published December 15, 1982.
Yet other organic dispersants are useful herein, as illustrated by
water-soluble oxidized carbohydrates, e.g., oxidized starches
prepared by art-disclosed methodsO
With regard to the formulations herein, it is preferred that
the ratio of organic dispersant to Available Oxygen from monoper-
sulfate salts is in the range from about 0.5:1 to about 8:1,preferably from about 0.5:1 to about 5:1, by weight.
WO93/18129 2i3~ 46~ PCl'/US93/0189~
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DH-Ad.iusting Aqent - The compositions herein also contain at
least one source of alkalinity so as to achieve an in-use pH above
7. It will be appreciated by those familiar with compositions for
use in the home that accidental ingestion of high alkalinity
products can pose safety concerns. Moreover, such concerns would
be increased in the case of highly alkaline, low-dosage composi-
tions. While the invention is effective at a pH in the highly
alkaline range, it is an advantage herein not to be limited to
compositions with such alkalinity levels.
Wash pH's suitable for effective stain removal in the prac-
tice of this invention are generally in the range from about 8 to
about 11, more preferably from about to about 9.5 to about 10.5
when water-soluble silicates are present though the invention
encompasses other preferred embodiments in which the pH range is
from about 8 to about 9.5, from which water-soluble silicates are
absent and wherein the pH-adjusting function is performed only by
the carbonate ingredient which can take the form of sodium bicar-
bonate or a sodium carbonate/bicarbonate mixture. To be noted,
the perborate-type bleach systems are ineffective at the most
desirable low end of these ranges, especially in the low-dosed
product form provided herein. The water-soluble carbonate salts,
especially sodium carbonate and bicarbonate, are useful alkalinity
sources herein, and when present are typically used at levels from
about 5% to about 25X, preferably from about 8% to about 20% by
weight of the final granular product. It will be appreciated by
those familiar with ADD compositions that excessive amounts of
carbonate can result in undesirable filming on cleansed tableware.
However, the tendency to filming is offset by use of organic
dispersant materials disclosed hereinabove.
Importantly, material care benefits are best imparted to the
instant compositions either when they are formulated at the
moderate pH's (8-9.5) without soluble silicates (in which case
sodium bicarbonate, sodium carbonate or a mixture of the two will
be used for the pH-adjusting function), or when they are formu-
lated at the somewhat higher (9.5-10.5) pH range when a mixture of
water-soluble silicate and sodium carbonate is typically used as
pH-adjusting agent.
W o 93f18129 2 1 3 0 4 6 5 PCT/US93/0189~
When the compositions herein contain water-soluble silicate
as a component of the pH-adjusting agent, these silicates not only
provide alkalinity to the compositions, but also provide anti-
corrosion -benefits for aluminum utensils and appear to contribute
to glaze protection on chinaware.
Since the compositions herein are formulated to contain
limited amounts of free water for best storage stability, but
since on the other hand complete dehydration of silicates tends to
limit water-solubility of the compositions, it is important that
the water-soluble silicates processed into the formulations
ultimately have solid hydrous form. This can be achieved either by
admixing into the composition preformed solid hydrous silicates as
the water-soluble silicate component, or by relying on a more
inexpensive liquid silicate stock, which is dehydrated to a
limited extent during granule-making.
When water-soluble s1licates are used in the practice of the
invention, their level in the fully-formulated composition in
preferred embodiments is in the range from about 4% to about 25%,
more preferably from about 6% to about 15%, dry basis, based on
the weight of the automatic dishwashing detergent composition.
The mole ratio of SiO2 to the alkali metal oxide (M20, where M is
alkali metal) is typically from about 1 to about 3.2, preferably
from about 1.6 to about 3, more preferably from about 2 to about
2.4. Preferable H20 levels in commercial raw material forms of
the water-soluble silicate component itself are from about 15% to
about 25%, more preferably, from about 17% to about 20% of the
water-soluble silicate component.
The highly alkaline metasilicates can be employed, although
the less alkaline hydrous alkali metal silicates having a SiO2:M20
ratio of from about 2.0 to about 2.4 are preferred.
Sodium and potassium, and especially sodium silicates are
preferred. Particularly preferred alkali metal silicates are
granular hydrous sodium silicates having SiO2:Na20 ratios of from
2.0 to 2.4 available from PQ Corporation, named BRITESIL~ H20 and
BRITESIL H24. Most preferred is granular or powder-form hydrous
sodium silicate having a SiO2:Na20 ratio of about 2Ø Potassium
analogs could be employed, but are generally more expensive.
. ~.
2130~65
WO 93/18129 PCI/US93/01895
- 16 -
While typical forms, i.e., powder and granular, of hydrous
silicate particles are suitable, preferred silicate particles have
a mean particle size between about 300 and about 900 microns with
less than 40~O smaller than 150 microns and less than 5% larger
than 1700 microns. Particularly preferred is a silicate particle
with a mean particle size between about 400 and about 700 microns
with less than 20% smaller than 150 microns and less than 1%
larger than 1700 microns.
Chlorine Bleach Scavenqer - As noted hereinabove, the
preferred compositions herein contain detersive enzymes. It has
been determined that chlorine bleach species present in many water
supplies can attack and inactivate such 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
Available Chlorine, the total volume of water that comes in
contact with the enzyme during dishwashing is usually large;
accordingly, enzyme stability in-use can be problematic. Unlike
the more conventional Oxygen bleach perborate, the monopersulfate
bleach herein is not of its own accord a chlorine bleach scaven-
ger. However, it has now been determined that scavenger materials
such as sodium perborate can be used in the compositions as a
chlorine scavenger. Accordingly, preferred compositions herein
will contain up to about 1.5%, preferably from about 0.1% to about
0.5%, by weight of a chlorine bleach scavenger, such as a water-
soluble perborate salt. Either sodium perborate tetrahydrate or
sodium perborate monohydrate can be used for this chlorine scav-
enging purpose. Alternatively, boron-free scavengers may be used,
in which case somewhat larger quantities may be useful. Preferred
boron-free scavengers include percarbonate salts, malate salts,
tartrate, ammonium sulfate and lower alkanolamines.
Weak NonphosDhorus Builder - The compositions herein may also
contain a nonphosphorus detergency builder. It has been found
that weak builders, especially organic carboxylate builders having
a molecular weight below about 600, are especially useful to allow
an effective composition which does not etch glass or chinaware.
Normally, the formulators of detergent compositions attempt to
employ high levels of the strongest possible builder in their
formulations and indeed, when 0xygen bleaches such as perborate or
--'O 93/18129 2 1 3 0 ~ 6 ~ PCr/US93/01895
perborate with activator are used, stronger builders are needed
for the most satisfactory stain removal results. However, in
conjunction with monopersulfate salts, the balance of the composi-
tions herein provides adequate cleaning benefits even when zero to
relatively low amounts of weak builders are used and this permits
a substantial safety advantage with regard to the protection of
the glaze on fine china and the strength and clarity of glassware.
Citrate builders, particularly sodium citrate, are preferred for
use herein. lucoheptonate builders known in the art are likewise
useful. Sucn builders, especially sodium citrate or citric acid,
are preferably used at levels from about 2% to about 15% by
weight, more preferably about 3% to about 8% by weight of the
present compositions.
Bleach Stabilizer - The compositions herein will preferably
also contain a bleach stabilizer whose primary purpose is to
sequester transition metal ions that can decompose monopersulfate
bleach. Such bleach stabilizers generally are selected from
organic nitrogen-containing sequestrants and organic phosphorus-
containing sequestrants and are thus distinguished from the weak
builders herein which do not contain nitrogen or phosphorus.
Conveniently, bleach stabilizers can be blended with commercial
monopersulfate in granular form, e.g., in OXONE granules. It may
also be advantageous to have low levels of bleach stabilizer
dispersed throughout the composition. In this mode, it is believed
that the bleach stabilizer is principally active as a storage-
stabilizer for the bleach. Otherwise, bleach stabilizers such as
the common chelant diethylenetriaminepentaacetate can be added to
the compositions to provide the desired stabilizing function.
In more detail, the bleach stabilizer in the fully-formulated
granular automatic dishwashing detergent compositions herein can
be used at levels ranging from the minimum amount required for
bleach stabilizing purposes (e.g., as low as about 0.05% to 0.1%)
to much higher levels (e.g., about 0.5Z or higher) which are very
useful levels not only for best achieving the instant process, but
also for achieving enhanced functionality of the automatic dish-
washing detergent (e.g., food/beverage stain removal from dishes,
transition metal oxide film control or removal, and the like.)
When bleach stabilizer is present, more typical levels are thus
..
WO 93/18129 2 1 3 0 4 6 5 PCI /US93/0189'
- 18 -
from about 0.05% to about 2% or higher, preferably from about o.l%
to about 0.7%, all percentages on a weight basis of the final
automatic dishwashing composition.
Bleach stabilizers suitable for use herein of the organic
nitrogen-containing type are further illustrated by the sodium and
potassium salts of ethylenediaminetetraacetic acid (EDTA),
diethylenetriamine pentaacetic acid (DTPA), hydroxyethylenediamine
triacetic acid (HEDTA), triethylenetetramine hexaacetic acid
(TTHA), nitrilotriacetic acid (NTA), N,N'-(l-oxo-1,2,-ethanediyl)-
bis(aspartic acid) (OEDBA), and ethylenediamine disuccinic acid
(EDDS); see U.S. 4,704,233.
Bleach stabilizers of the organic phosphorus containing type
are further illustrated by ethylenediaminetetra-(methylenephos-
phonic acid), diethylenetriaminepenta(methylene phosphonic acid)
and hydroxy-ethylidine-diphosphonic acid (EHDP). Certain of these
materials have been found to behave somehat unpredictably, it is
believed due to variations in quality of raw material. Therefore,
such organic phosphorus-containing sequestrants are not as highly
preferred as the nitrogen types for use in the present invention.
Highly preferred bleach stabilizers are the nonphosphorus
chelants, such as EDDS and OEDBA. These are believed to have
attractive characteristics from the viewpoint of the environment;
for example, EDDS has two chiral centers and not only synthetic or
mixed isomers, but also the natural isomers such as the [S,S]
isomer can be used compatibly with this invention.
Of the foregoing bleach stabilizers, all but OEDBA deriva-
tives are well-known in the art. OED8A is disclosed by Glogowski
et al in U.S. Patent 4 983 315 issued January 8 1991.
A document generally useful in the context of this invention
for its disclosure of commercial chemicals including but not
limited to chelants their trademark names and commercial sources
of supply is Chem Cyclopedia 91 The Manual of Commercially
Available Chemicals", a publication of the American Chemical
Society 1990 ISBN 08412 - 1877-3.
~A
-'O 93/18129 21 3 0 4 6 5 PCl'/US93/0189~
- 19 -
Although, the sodium and potasslum, i.e., alkali metal salts
of the bleach stabilizers are preferred, they can, in general, be
in the acid form or can be partly or fully neutralized, e.g., as
the sodium salt.
Low-Sudsinq Surfactant - The compositions herein may contain
from 0% to about 10~., preferably from about 1% to about 7% by
weight of a surfactant, preferably a low sudsing surfactant of the
type typically used in conventional ADD compositions known in
commerce. Such surfactants not only provide some cleaning action
in the compositions, but also provide a "sheeting" action which
causes water to drain from china and glassware, thereby reducing
the tendency to form unsightly spots during drying in the auto-
matic dishwashing machine. Typically, such low sudsing surfact-
ants fall within the class known as nonionics, especially the
so-called "block" polyoxyethylene-polyoxypropylene nonionics, but
various other low-sudsing surfactants such as the long-chain
phosphates and phosphate esters can also be used. The following
is intended to further assist the formulator in the selection of
surfactants for use herein, but is not by way of limitation.
The surfactant can be, for example, an ethoxylated surfactant
derived from the reaction of a monohydroxy alcohol or alkylphenol
containing from about 8 to about 20 carbon atoms, excluding cyclic
carbon atoms if such are present, with from about 4 to about 15
moles of ethylene oxide per mole of alcohol or alkyl phenol on an
average basis. A particularly preferred ethoxylated nonionic
surfactant is derived from a straight chain fatty alcohol contain-
ing from about 16 to about 20 carbon atoms (C6-C20) alcohol),
preferably a C18 alcohol, condensed with an average of from about
6 to about 15 moles, preferably from about 7 to about 12 moles,
and most preferably from about 7 to about 9 moles of ethylene
oxide per mole of alcohol. Preferably the ethoxylated nonionic
surfactant so derived has a narrow ethoxylate distribution rela-
tive to the average. The ethoxylated nonionic surfactant can also
optionally contain propylene oxide in an amount up to about 15% by
weight of the surfactant.
Another type of nonionic surfactant contains the ethoxylated
monohydroxyalcohol or alkyl phenol and additionally comprises a
polyoxyethylene-polyoxypropylene block polymeric compound; the
W O 93/18129 ~30 46S PCT/US93/0189~
- 20 -
ethoxylated monohydroxy alcohol or alkyl phenol nonionic surfact-
ant comprising from about 20% to about 80%, preferably from about
30% to about 70%, of the total surfactant composition by weight.
Suitable block polyoxyethylene-polyoxypropylene polymeric
compounds include those based on ethylene glycol, propylene
glycol, glycerol, trimethylolpropane and ethylenediamine as an
initiator reactive hydrogen compound. Polymeric compounds made
from a sequential ethoxylation and propoxylation of initiator
compounds with a single reactive hydrogen atom, such as C12-C28
aliphatic alcohols, do not usually provide satisfactory suds
control. Certain of the block polymer surfactant compounds
designated PLURONIC, PLURAFAC and TETRONIC by the BASF-Wyandotte
Corp., Wyandotte, Michigan are suitable as the surfactant for use
herein. A particularly preferred embodiment contains from about
40% to about 70% of a polyoxypropylene, polyoxyethylene block
polymer blend comprising about 75%, by weight of the blend, of a
reverse block co-polymer of polyoxyethylene and polyoxypropylene
containing 17 moles of ethylene oxide and 44 moles of propylene
oxide; and about 25%, by weight of the blend, of a block
co-polymer of polyoxyethylene and polyoxypropylene, initiated with
tri-methylol propane, containing 99 moles of propylene oxide and
24 moles of ethylene oxide per mole of trimethylol propane.
Additional surfactants useful herein include relatively
low-molecular weight nonionic types having melting-points at or
above ambient temperatures, such as octyldimethylamine N-oxide
dihydrate, decyldimethylamine N-oxide dihydrate, C8-C12 N-methyl-
glucamides and the like. Such surfactants may advantageously be
blended in the instant compositions with short-chain anionic
surfactants, such as sodium octyl sulfate and similar alkyl
sulfates, though short-chain sulfonates such as sodium cumene
sulfonate could also be used. Short-chain nonionic types which
tend to be liquid or melt close to ambient temperatures may be
incorporated into the instant compositions by wicking them into an
inorganic support, such as preformed granule comprising porous
carbonate particles. Thus nonionics derived from monohydric
alkanols with ethylene oxide, such as ClOE3 through ClOE8, where
"E" refers to ethylene oxide, may be used in the instant
compositions.
' 'O 93/18129 213 0 ~ 6 5 PCI/US93/0189~
When suds rg tendencies of the compositions in-use are
adversely affe~ed by the use of surfactants with foaming
tendencies, limited amounts of conventional suds suppressors such
as silicone/silica mixtures, may be incorporated into the
surfactant system of the instant compositions as taught in the
literature.
Filler/ElectrolYte - The MPS-containing compositions herein
are formulated in "compact" form and are reliant on electrolyte
level for stain removal to a lesser degree than otherwise similar
compositions made using perborate or perborate/tetraacetylethyl-
enediamine. Thus, the instant compositions can be made substan-
tially free from, i.e., can be made with less than about 5%, and
preferably contain 0X, of so-called "inert" ingredients such as
sodium sulfate. Nonetheless, such filler ingredients may be used
if desired provided that the detergent remains compact, within the
spirit and scope of the invention.
Other OPtional Adiuncts - Optional adjuncts useful in the
practice of this invention include perfumes, borax and sodium or
potassium borates, pH 7-9 organic buffers and any compounds in the
published patent and journal literature known to accelerate or
enhance the bleaching action of monopersulfate salts. A non-
limiting example of such MPS-accelerator materials is the group
consisting of keto-compounds, including sodium acetate and
di-2-pyridyl ketone, the latter being more effective by virtue of
the electronic effect of the substituents. Activation of monoper-
sulfate is, of course, not limited to ketones in light of a
variety of compounds having C=N and C=S bonds. To be noted,
however, is that an advantage of the instant invention is its
simplicity and lack of reliance on any such MPS-activating com-
pound as an essential component. It has been found in the case of
activated perborate-containing ADD's that the activator, while
helping bleaching and stain removal under the controlled condi-
tions of technical test laboratories is capable of producing
erratic performance in the home on account of segregation as well
on account of the tendency of the highly reactive product of
activation (peracetic acid) to decompose wastefully on heating or
upon encountering dispersed food soils.
WO 93/18129 PCI'/US93/01895
S .,.
~3~46 - 22 -
Water Content - The water content of the compositions herein
should be kept to a level below about 9% by weight of free
moisture. This is due in part to the desirability of having
free-flowing granules, and is particularly important when using
OXONE as the monopersulfate salt. This monopersulfate salt is
acidic and, in the presence of water, may react with carbonate or
bicarbonate unless the limits on water content of the composition
are respected or an expensive protective coating is applied. It
is to be understood, however, that water can be used during the
formation of the compositions herein. Thus, other than the
monopersulfate, the balance of the compositions herein can be
prepared as mixtures in an aqueous slurry and dried in standard
fashion to provide substantially dry granules. Particles of dry
monopersulfate can then be dry-blended with the aforesaid, dried
balance of the composition.
The following examples illustrate compositions which come
within the scope of this invention, but are not intended to be
limiting thereof. In general, the compositions are prepared using
the following general processing methodology.
Process - Although the art includes processes which rely on
dry-mixing or spray-drying ingredients, such processes are not of
the general kind of interest herein as they generally produce
products with low density or high tendency to segregate in the
package. Thus for the present purposes, conventional automatic
dishwashing compositions can typically be made by a process
comprising two essential stages: mixing/drying wet-and-dry
ingredients, optionally including molten-form surfactants, to form
particles having granulometry generally appropriate for the
intended use; and mixing free-flowing, relatively dry components,
of compatible granulometry, with the product of the first stage.
The latter mixing stage is, of course, necessary since bleach-
active salts such as monopersulfate and enzyme prills are not
tolerant of the wet-stage processing.
As compared with the known processes for making granular
automatic dishwashing detergents with oxygen bleach, preferred
embodiments of this invention typically will comprise: (a) in the
presence of water, forming a fluid premix consisting essentially
of an organic dispersant and a bleach stabilizer; (b) one or more
~0 93/18129 2 1 3 0 4 6 5 P~/US93/0l89s
- 23 -
mixing/drying steps wherein the fluid premix is contacted with
solid-form water-soluble nonphosphorus salts, very preferably, by
means of conventional agglomeration and fluidized-bed drying
equipment, sequentially; and (c) addition of bleach-active salts.
Optionally, additional spray-ons or additions of other components
sucn as perfumes, and the like, can be performed. Particularly
f ~irable options which can be accommodated are illustrated by (i)
lnclusion of perfume in the step (a) premix; (ii) inclusion of
fluid-form surfactant in step (b) and (iii) inclusion of hydrous
silicates in step (c). Other optional adjuncts can also, in
general, be added in steps (a), (b) or (c). Minors, e.g., perfume
and colorants, typically comprise less than about 3% of the
finished formula.
EXAMPLE I
An ADD composition whose compactness is 60% that of conven-
tional ADD compositions (i.e., 40YO reduction in usage levels) is
as follows. The composition is designed for use at about 23.4 9
per wash cycle (3,600 ppm in wash water).
Inqredient % (wt.
Trisodium citrate1 13
Sodium carbonate (anhydrous basis) 17
Silicate (2.0 ratio)2 18
Nonionic surfactant 3 4.3
Sodium polyacrylate (m.w. 4,000)' 5.0
DTPAs 0.83
OXONE (% Av 0)6 15 (0.69)
TERMAMYL 60 T prill' 2.78
SAVINASE 6.0 T prillfi 1.67
Na2SO4/H20/minors9 Balance
1~risodium citrate dihydrate, expressed on anhydrous basis.
2BRITESIL H20, PQ Corp., expressed on anhydrous basis.
3C1~E7.9 blend with reverse PO-EO-PO block copolymer and
monostearyl acid phosphate at a weight ratio of about 39:60:1.
4ACCUSOL, Rohm & Haas.
5Diethylenetriamine pentaacetate, pentasodium salt, anhydrous
basis.
6The first number quoted being percentage of commercial-grade
OXONE in the composition.
WO 93~18129 PCI'/US93/01895
2l3~ 46S ~-
- 24 -
'Approximate prill content of active enzyme = 2.5%, dry
basis.
8Approximate prill content of active enzyme = 1.5%, dry
basis.
9Maximum 8% wt. H2O in composition.
~ EXAMPLE II
An ADD composition whose compactness is 50% that of conven-
tional ADD compositions (i.e., 50% reduction in usage levels) is
as follows. The composition is designed for use at about 19.5 9
per wash cycle (3,000 ppm in wash water).
Inqredient % (wt.)
Trisodium citrate1 15
Sodium carbonate (anhydrous basis) 20
Silicate (2.0 ratio)2 21.4
Nonionic surfactant3 3.5
Sodium polyacrylate (m.w. 4,000)4 5.3
DTPAs 2.44
OXONE (% Av 0) 20.7 (0.95)
TERMAMYL 60 T prill 1.1
SAVINASE 6.0 T prill 3.0
H20/minors6 Balance
lTrisodium citrate dihydrate, expressed on anhydrous basis.
2BRITESIL H20, PQ Corp., expressed on anhydrous basis.
3C18E~.g blend with block copolymer, as in Example I.
4ACCUSOL, Rohm & Haas.
sDiethylenetriamine pentaacetate, pentasodium salt, anhydrous
basis.
sMaximum 8.5% wt. H2O in composition.
EXAMPLE III
An ADD composition whose compactness is 50% that of
conventional ADD compositions (i.e., 50% reduction in usage
levels) is as follows. The composition is designed for use at
about 19.5 9 per wash cycle (3,000 ppm in wash water).
Inqredient % (wt.)
Trisodium citrate1 10
Sodium carbonate 20
Silicate (2.0 ratio)2 21
~"O 93/18129 213 0 4 6 5 P ~ /US93tO189~
Nonionic surfactant3 3.5
Sodium polyacrylate (m.w. 4,000)4 5.3
DTPAs 2.44
OXONE (~ Av 0) 15 (0.69)
SAVINASE 6.0 T prill 1.6
Na2SO4/H2O/minors6 Balance
1Trisodium citrate dihydrate, expressed on anhydrous basis.
2BRITESIL H20, PQ Corp., expressed on anhydrous basis.
3Cl 8 E7.9.
4ACCUS0L, Rohm & Haas.
5Diethylenetriamine pentaacetate, pentasodium salt.
6Maximum 7.5% wt. H20 in composition.
EXAMPLE IV
An ADD composition whose compactness is 50% that of conven-
tional ADD compositions (i.e., 50% reduction in usage levels) is
as follows. The composition is designed for use at about 19.5 9
per wash cycle (3,000 ppm in wash water). (This composition is
less preferred owing to the relatively high level of expensive
sodium citrate employed.)
Inqredient % (wt.)
Trisodium citrate1 39
Silicate (2.0 ratio SiO2:Na2O)2 28.6
Nonionic surfactant3 1.4
Organic dispersant4 5.7
OXONE (% Av 0) 20.7 (0.95)
TERMAMYL 60 T prill 2.4
SAVINASE 6.0 T prill 1.8
Na 2 SO4/H 2 O/minors 5 Balance
1Trisodium citrate dihydrate, expressed on anhydrous basis.
2BRITESIL H20, PQ Corp., expressed on anhydrous basis.
3Cl 8E7 . 9 .
4ACCUSOL, Rohm & Haas; sodium polyacrylate, m.w. 4,000.
5Maximum 6.57. wt. H20 in composition.
EXAMPLE V
An ADD composition whose compactness is 50% that of conven-
tional ADD compositions (i.e., 507O reduction in usage levels) is
as follows. The composition is designed for use at about 19.5 9
per wash cycle (3,000 ppm in wash water).
PCI /US93/0189
W093/18129 2~30~S6~
- 26 -
Inqredient % (wt.)
Trisodium citrate1 24.0
Sodium carbonate 12.5
Silicate (2.0 ratio)2 27.5
Nonionic surfactant3 1.5
Organic dispersant~ 6.0
OXONE (% Av 0) 15.5 (0.7)
TERMAMYL 60 T prill 0.8
SAVINASE 6 T prill 2.2
Na2SO4 10.0
H20/minorss Balance
1Trisodium citrate dihydrate, as supplied.
2BRITESIL H20, PQ Corp., as supplied.
3PLURAFAC LF 404, BASF Corp.
~Acrylate:maleate copolymer, sodium salt, m.w. 65,000, dry
basis.
sMaximum 9% wt. H20 in composition.
(This composition, in use, typically delivers 0.29 ppm active
enzyme TERMAMYL and 1.4 ppm active enzyme SAVINASE when 4,000 ppm
product is dissolved in water.)
EXAMPLE VI
An ADD composition whose compactness is 60% that of
conventional ADD compositions (i.e., 40% reduction in usage
levels) is as follows. The composition is designed for use at
about 23.4 9 per wash cycle (3,600 ppm in wash water).
Inqredient % (wt.)
Trisodium citrate1 20.0
Sodium bicarbonate 20.0
Nonionic surfactant 2 5.0
Organic dispersant3 4.0
DTPA~ 2.44
OXONE (% Av 0) 15.0 (0.69)
TERMAMYL 60 T prill 1.1
SAVINASE 6.0 T prill 2.0
Na2S0~/H20/minorss Balance
1Trisodium citrate dihydrate, expressed on anhydrous basis.
2 PLURAFAC LF 404, BASF Corp.
3Acrylate:maleate copolymer, sodium salt, m.w. 65,000.
)93/18129 2 1 3 0 ~ 6 5 PCT/US93/0189~
- 27 -
4Diethylenetriamine pentaacetate, pentasodium salt.
sMaximum 8X wt. H20 in composition.
EXAMPLE VII
The composition of Example VI is modified by removal of
sufficient Na2SO~ to allow for the inclusion of 1% by weight of
sodium perborate monohydrate. The resulting composition is useful
in water containing chlorine bleaches.
EXAMPLE VIII
The composition of Example I is modified by the inclusion of
3% (wt.) octyl dimethylamine N-oxide dihydrate surfactant (see
"High Active Alkyldimethylamine Oxidesn, K. R. Smith et al, J.
Amer. Oil Chemists' Soc., 1991, Vol. 68, pp 619-622) to provide
additional cleansing performance.
~ .
