Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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MACHINE DISHWASHING COMPOSITIONS AND RINSE AID COMPOSITIONS
This application is a continuation-in-part of U.S. Serial
No. 08/898,758, filed July 23, 1997.
This invention relates to a nonchlorine containing machine
dishwashing detergent or rinse aid formulation which
delivers excellent final glassware appearance.
Background of the Invention
Machine dishwashing detergents constitute a generally
recognized distinct class of detergent compositions,
particularly as compared to detergents designed for fabric
laundering., As an example, a spotless and film-free
appearance of glasses and silverware is the expected final
result of a machine dishwashing run while, in many
laundering operations, substances which may leave a greasy,
oily or soapy residue can be tolerated.
In general, machine dishwashing detergents are mixtures of
ingredients whose purpose, in combination, is to break down
and remove food soils; to inhibit foaming caused by certain
food soils; and to remove stains such as might be caused by
beverages such as coffee and tea or by vegetable soils such
as carotenoid soils. While necessary for these various
cleaning benefits, machine dishwashing detergents can also
create or exacerbate other problems. As an example,
carbonate and phosphate salts, often detergent ingredients,
are known to contribute to the formation of hard water films
on glasses. In European applications, the water used to
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prepare the solution for the washing process is often
treated (softened? to remove hardness ions such as calcium
and magnesium with the result that hard water residues on
washware are reduced. Nevertheless, spotting and filming
from soil residues and precipitates from the detergent
formulation can remain a problem, especially if the ion
exchange unit serving the dishwashing machine is operating
inefficiently.
Conventional machine dishwashing detergents employ strong
alkalis such as sodium hydroxide, bleaches such as
hypochlorite, and builders such as phosphates in order to
assist in the cleaning steps outlined above. However,
environmental factors, such as restrictions on phosphate
and chlorine levels, and safety considerations have lead to
the search for a new class of lower pH detergent
formulations. Further, conventional formulations can damage
items unique to machine dishwashing such as silverware,
glassware and dishware. Certain of these items can be
expensive to replace and force the consumer to separate them
out from the rest of the table ware for hand washing - an
obvious inconvenience. This new class of detergent
formulations employs various detersive enzymes, including
arnylolytic and proteolytic enzymes, to compensate for the
loss in cleaning effectiveness inherent at these lower pH
values. Unfortunately, the conventional hypochlorite bleach
system is incompatible with this enzymatic route and, as a
consequence, oxygen bleaching systems have been adopted.
While the soil removal properties of these enzymatic
formulations can match that of the conventional detergents,
they have one notable weakness in the area of spotting and
filming on glasses. The absence of chlorine bleach,
alkalinity and phosphate builders generally results in
higher spotting and filming scores under controlled
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laboratory testing and in a higher frequency of complaints
from consumers in these two areas.
Spotting and filming of glassware are the chief criteria by
which the performance of a dishwashing formulation is
judged. Spotting is an obvious reference to discrete
residues on glassware which have resulted when water
droplets have completely evaporated and left behind any
dissolved solids. Filming refers to a more uniform
deposition over a large, contiguous portion of the glass
surface. Without wishing to be bound by theory, it is
believed that this film can sometimes be of organic origin
(resulting from soil in the wash liquor) but is also often
inorganic in nature, due to the formation of some mineral
precipitate.
Accordingly, it is an object of the present invention to
provide a new and improved machine dishwashing composition.
Preferred compositions are free from chlorine bleach but
may, optionally, contain an oxygen bleach. It is another
object herein to provide dishwashing detergent compositions
which contain effective levels of a cationic or amphoteric
polymer which provides superior glassware appearance as
evidenced by reduced spotting and filming. Another object
herein is to provide a dishwashing rinse aid formulation
containing an effective level of the cationic or amphoteric
polymer.
Low molecular weight homopolymers of acrylic acid (such as
Acusol 445, ex Rohm and Haas) discussed in Witak, D. et al.
"Exploring Options for Dishwashing Detergents in the 1990s",
HAPPI, August 1990; p. 64 may be used in combination with a
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reduced or zero level of a phosphate builder, to give a
reduced film score on glasses.
A copolymer of malefic acid or malefic anhydride and a CZ_4
olefin comonomer is described as an additive for chlorine-
free machine dishwashing detergent formulations in lieu of
chlorine bleach in U.S. 5,232,622. This hydrophobically
modified polyacrylate is also described as reducing the
incidence of spot formation with a margarine/milk soil in a
20 zero phosphate formulation in Shulman, J.E. "Non Phosphate
ADDS", (July 1992) HAPPI, p. 130. Both spotting and
filming are controlled by a combination of Acusol 460ND and
either of Acusol 479N (a copolymer of acrylic acid and
malefic acid) or Acusol 445. Such a combination of
polyacrylates has also been described in U.S. 5,279,756.
Terpolymers of acrylic acid, acrylamide or butyl acrylate,
and an aminoacryloyl derivative are disclosed as being
useful at 0.5 to 7~ levels in a machine dishwashing
detergent formulation for reducing spotting and filming in
the presence of a margarine/milk soil in U.S. 5,308,532.
The performance of said terpolymers was found to surpass
that of a 4500 MW homopolymer of acrylic acid (i.e. Acusol
445N, ex. Rohm and Haas). Similar claims are made for a
copolymer of acrylic acid and the aminoacryloyl derivative
in EP 0 560 519 A2.
Low molecular weight homopolymers of malefic acid are
disclosed in US 5,545,348 as being superior to copolymers of
acrylic acid and malefic acid or to copolymers of malefic acid
and an olefin comonomer with respect to reducing filming.
U.S. Patent No. 5,597,789 discloses a dishwashing
composition comprising a mixture of disilicate and a low
molecular weight, modified polyacrylate copolymer. The
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copolymer was described to reduce filming on glassware
relative to acrylic acid/maleic acid copolymers of 70,000 MW
or acrylic acid homopolymers of 4500 MW.
In summary, the prior art teaches the use of anionic, vinyl
polymers consisting chiefly of acrylic acid or modified
polyacrylates for the improvement of spotting and filming in
chlorine-free machine dishwashing detergent formulations.
However, the prior art does not suggest that cationic
polymers reduce spotting and filming during machine
dishwashing. Nor does it suggest that cellulosic materials,
and especially cationically modified cellulose polymers,
should offer any benefit in glass appearance.
Summary of the Invention
It has now been discovered that a class of water soluble,
cationic or amphoteric polymers provide enhanced appearance
to glassware when incorporated in the dishwashing process as
evidenced, in part, by a reduction of formation of spots and
film on washed glass articles.
Accordingly the present invention describes a detergent
composition which reduces spotting and filming on glassware
cleaned in an automatic dishwashing machine, comprising:
a) a water soluble cationic or amphoteric polymer having a
cationic monomer unit which is an ethylenically
unsaturated compound as described by formula I
Hr R1
I
R2 Rs
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i
wherein R is hydrogen, hydroxyl, or a C1 to C3o straight
or branched alkyl radical; RZ is hydrogen, a C1 to C3o
straight or branched alkyl, a C1 to C3o straight or
branched alkyl substituted aryl, aryl substituted C1 to
C3o straight or branched alkyl radical or a poly
oxyalkene condensate of an aliphatic radical, and R3 is
a heteroatomic organic radical containing either one or
more quaternerized nitrogen atoms or one or more amine
groups having a pKa of about 6 or greater and a positive
charge over a portion of the pH interval pH 2 to 11.
b) 1 to 90~ by weight of a builder.
The invention also describes a rinse aid composition for use
in an automatic dishwashing maching comprising:
a) a water soluble cationic or amphoteric polymer having a
cationic monomer unit which is an ethylenically
unsaturated compound as described by formula I
I~ R1
I
R~ R~
wherein R1 is hydrogen, hydroxyl, or a C1 to C3o straight
or branched alkyl radical; RZ is hydrogen, a C1 to C3o
straight or branched alkyl, a C1 to C3o straight or
branched alkyl substituted aryl, aryl substituted C1 to
C3o straight or branched alkyl radical or a poly
oxyalkene condensate of an aliphatic radical, and R3 is
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a heteroatomic organic radical containing either one or
more quaternerized nitrogen atoms or one or more amine
groups having a pKa of about 6 or greater and a positive
charge over a portion of the pH interval pH 2 to 11.
The invention further describes use of a water soluble
cationic or amphoteric polymer in an automatic dishwashing
composition or a rinse aid to reduce spotting and/or filming
or cleaned glassware.
The present invention comprises incorporation of specific
water soluble cationic or amphoteric polymers in the
dishwashing process to improve the appearance of washed
glass articles. The essential polymers in this invention may
be incorporated at any point in the dishwashing process. The
polymers may be incorporated into typical detergent or rinse
aid formulations, or may be incorporated in any desired form
such as tablets, powders, granulates, pastes, liquids, and
gels.
Detailed Description of the Invention
The present invention comprises incorporation of water
soluble cationic or amphoteric polymers in the dishwashing
process to improve the appearance of washed glass articles.
The essential polymers in this invention may be incorporated
at any point in the dishwashing process. The polymers may
be incorporated into typical detergent or rinse aid
formulations, or may be incorporated in any desired form
such as tablets, powders, granulates, pastes, liquids, and
gels.
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watP-r Sol,abl_e Cationicor Amphoteric Polymer
A water soluble cationic or amphoteric polymer is here
defined to include polymers which, because of their
molecular weight or monomer composition, are soluble or
dispersible to at least the extent of 0.01 by weight in
distilled water at 25°C. Water soluble cationic or
amphoteric polymers include polymers in which one or more of
the constituent monomers are selected from the list of
copolymerizable cationic monomers. These monomer units
contain a positive charge over a portion of the pH range 2-
11. A partial listing of such monomers is presented in
"'Water-Soluble Synthetic Polymers: Properties and Behavior,
Volume II", by P. Molyneux, CRC Press, Boca Raton, 1983,
ISBN 0-8493-6136- incorporated herein by reference.
Additional monomers can be found in the "International
Cosmetic Ingredient Dictionary, 5th Edition", edited by J.A.
Wenninger and G.N. McEwen, The Cosmetic, Toiletry, and
Fragrance Association, Washington DC, 1993, ISBN 1-882621-
06-9, incorporated herein by reference. A third source of
such monomers can be found in "Encyclopedia of Polymers and
Thickeners for Cosmetics", by R.Y. Lochhead and W.R. Fron,
Cosmetics & Toiletries, vol. 108, May 1993, pages 95-135,
herein incorporated.
Specifically, monomers useful in this invention may be
represented structurally as ethylenically unsaturated
compounds as in formula I.
3 0 ~ ~I
I
~2 ~3
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wherein R1 is hydrogen, hydroxyl, or a C1 to C3o straight or
branched alkyl radical; RZis hydrogen, or a C1_3o straight or
branched alkyl, a C1_3o straight or branched alkyl substituted
aryl, aryl substituted C1_3o straight or branched alkyl
radical, or a polyoxyalkene condensate of an aliphatic
3
radical; and R is a heteroatomic organic radical containing
either one or more quaternized nitrogen atoms or one or more
amine groups which possess a positive charge over a portion
of the pH interval pH 2 to 11. For purposes of this
invention the term "organic radical" means straight or
branched saturated aliphatic, straight or branched
unsaturated aliphatic or aromatic radical. Such amine
groups can be further delineated as having a pKa of about 6
or greater, as defined by R. Laughlin in "Cationic
Surfactants, Physical Chemistry", edited by D.N. Rubingh and
P.M. Holland, Marcel Dekker, New York, 1991, ISBN 0-8247-
8357-3.
Examples of cationic monomers of formula I include, but are
not limited to, co-poly 2-vinyl pyridine and its co-poly 2-
vinyl N-alkyl quaternary pyridinium salt derivatives; co-
poly 4-vinyl pyridine and its co-poly 4-vinyl N-alkyl
quaternary pyridinium salt derivatives; co-poly 4-
vinylbenzyltrialkylammonium salts such as co-poly 4-
vinylbenzyltrimethylammonium salt; co-poly 2-vinyl
piperidine and co-poly 2-vinyl piperidinium salt; co-poly 4-
vinylpiperidine and co-poly 4-vinyl piperidinium salt; co-
poly 3-alkyl 1-vinyl imidazolinium salts such as co-poly 3-
methyl 1-vinyl imidazolinium salt; acrylamido and
methacrylamido derivatives such as co-poly dimethyl
aminopropylmethacrylamide, co-poly acrylamidopropyl
trimethylammonium salt and co-poly methacrylamidopropyl
trimethylammonium salt; acrylate and methacrylate
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derivatives such as co-poly dimethyl aminoethyl
(meth)acrylate, co-poly ethanaminium N,N,N trimethyl 2-[(1-
oxo-2 propenyl) oxy] -salt , co-poly ethanaminium N,N,N
trimethyl 2-[(2 methyl-1-oxo-2 propenyl) oxy] - salt , and
co-poly ethanaminium N,N,N ethyl dimethyl 2-[(2 methyl-1-
oxo-2 propenyl) oxy] - salt.
Also included among the cationic monomers suitable for this
invention are co-poly vinyl amine and co-polyvinylammonium
salt; co-poly diallylamine, co-poly methyldiallylamine, and
co-poly diallyldimethylammonium salt; and the ionene class
of internal cationic monomers as defined by D. R. Berger in
"Cationic Surfactants, Organic Chemistry", edited by J.M.
Richmond, Marcel Dekker, New York, 1990, ISBN 0-8247-8381-6,
herein incorporated by reference. This class includes co-
poly ethylene imine, co-poly ethoxylated ethylene imine and
co-poly quaternized ethoxylated ethylene imine; co-poly
[(dimethylimino) trimethylene (dimethylimino) hexamethylene
disalt], co-poly [(diethylimino) trimethylene
(dimethylimino) trimethylene disalt]; co-poly
[(dimethylimino) 2-hydroxypropyl salt]; co-polyquaternium-2,
co-polyquaternium-17, and co-polyquaternium 18, as defined
in the "International Cosmetic Ingredient Dictionary, 5th
Edition", edited by J.A. Wenninger and G.N. McEwen.
Additionally, useful monomers are derived from the cationic
co-poly amido-amine having the chemical structure of formula
II.
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NH-C2H4- i -C2H4NH-~CO(CH2)4-CO...
~2
I~OH
'CH2 +~ - CH2-CHOH-CH CH3 ~3 n
N-~H2
~HOH
~2
...CO'(CH2)4~'~-C~4 -'N-C2H4-NH ...
and from the quaternized polyimidazoline having the chemical
structure of formula III
N \ / N-CH2CH2-
\CH3 CH3
wherein n is 1 to 100,000 and x is chosen from the halides:
chloride, bromide, and iodide; or from hydroxide, phosphate,
sulfate, hydrosulfate, ethyl sulfate, methyl sulfate,
formate, and acetate.
An additional class of cationic monomers suitable for this
invention are those arising from natural sources and
include, but are not limited to, cocodimethylammonium
hydroxypropyl oxyethyl cellulose, lauryldimethylammonium
hydroxypropyl oxyethyl cellulose, stearyldimethylammonium
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hydroxypropyl oxyethyl cellulose, and
stearyldimethylammonium hydroxyethyl cellulose; guar 2-
hydroxy-3-(trimethylammonium) propyl ether salt; cellulose
2-hydroxyethyl 2-hydroxy 3-(trimethyl ammonio) propyl ether
salt.
It is likewise envisioned that monomers containing cationic
sulfonium salts such as co-poly 1-[3-methyl-4-(vinyl-
benzyloxy)phenyl] tetrahydrothiophenium chloride would also
be applicable to the present invention.
Preferred cationic monomers are diallyldimethylammonium
salts, having the chemical structure as unpolymerized or
polymerized monomer, respectively, of formula IVa or Ivb.
+~H3
H2C=CH-CH2-N-CH2-CH=CH2
~H3
unpolymerised monomer
Na
iv~
x-v-~ n
I Vb
polymerised monomer
wherein n is 1 to 100,000 and x is chosen from the halides:
chloride, bromide, and iodide; or from hydroxide, phosphate,
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sulfate, hydrosulfate, ethyl sulfate, methyl sulfate,
formate, and acetate.
Water soluble amphoteric polymers suitable for incorporation
into the present invention can also include polymers in
which one or more of the constituent monomers are selected
from the list of copolymerizable, internally amphoteric
monomers. These monomer units contain both one or more
positive charges and one or more negative charges over a
portion of the pH range 2-11. Such internally amphoteric
monomers include those species possessing formal anionic and
cationic charges such as N,N-dimethyl, N-acetyl
aminoethylmethacrylate. Also included are monomers which,
while not possessing formal charges, have one or more
resonance forms which result in the occurrence of fractional
cationic and anionic charges being separated within the
monomer. Monomers in this class are typified by vinyl
pyrrolidone, as described in "Water-Soluble Synthetic
Polymers: Properties and Behavior, Volume I", by P.
Molyneux, CRC Press, Boca Raton, 1983, ISBN 0-8493-6135-4,
incorporated herein by reference. Further examples include
vinyl oxazolidone; vinyl methoxazolidone; and vinyl
caprolactam.
The mole fraction of the cationic or amphoteric polymer
which~is composed of the above-described cationic or
amphoteric monomer units can range from 1 to 100,
preferably from 1 to 50~, and most preferably from 2 to 20~
of the entire polymer. The remaining monomer units
comprising the cationic or amphoteric polymer are chosen
from the class of anionic monomers and the class of nonionic
monomers or solely from the class of nonionic monomers. In
the former case, the polymer is an amphoteric polymer while
in the latter case it can be a cationic polymer, provided
that no amphoteric co-monomers are present.
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The anionic monomers comprise a class of monounsaturated
compounds which possess a negative charge over the portion
of the pH range from pH 2 to 11 in which the cationic
monomers possess a positive charge. The nonionic monomers
comprise a class of monounsaturated compounds which are
uncharged over the pH range from pH 2 to 11 in which the
cationic monomers possess a positive charge A suitable class
of both the anionic and the nonionic monomers are the vinyl
(ethylenically unsaturated) substituted compounds
corresponding to formula V.
H R4
V
~5 ~6
wherein R4, RS, and R6 are independently hydrogen, a C1 to C3
alkyl, a carboxylate group or a carboxylate group
substituted with a C1 to C3a linear or branched heteroatomic
alkyl or aromatic radical, a heteroatomic radical or a poly
oxyalkene condensate of an aliphatic radical.
The class of anionic monomers are represented by the
compound described by formula V in which at least one of the
R4, R5, or R6 comprises a carboxylate, substituted
carboxylate, phosphonate, substituted phosphonate, sulfate,
substituted sulfate, sulfonate, or substituted sulfonate
group. Preferred monomers in this class include but are not
limited to -ethacrylic acid, -cyano acrylic acid, -
dimethacrylic acid, methylenemalonic acid, vinylacetic acid,
allylacetic acid, acrylic acid, ethylidineacetic acid,
propylidineacetic acid, crotonic acid, methacrylic acid,
malefic acid, fumaric acid, itaconic acid, sorbic acid,
angelic acid, cinnamic acid, -styryl acrylic acid (1-
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carboxy-4-phenyl butadiene-1,3), citraconic acid, glutaconic
acid, aconitic acid, -phenylacrylic acid, -acryloxy
propionic acid, citraconic acid, vinyl benzoic acid, N-vinyl
succinamidic acid, and mesaconic acid. Also included in the
list of preferred monomers are co-poly styrene sulfonic
acid, 2-methacryloyloxymethane-1-sulfonic acid, 3-
methacryloyloxypropane-1-sulfonic acid, 3-(vinyloxy)propane-
1-sulfonic acid, ethylenesulfonic acid, vinyl sulfuric acid,
4-vinylphenyl sulfuric acid, ethylene phosphonic acid and
vinyl phosphoric acid. Most preferred anionic monomers
include acrylic acid, methacrylic acid and malefic acid. The
polymers useful in this invention may contain the above
monomers and the alkali metal, alkaline earth metal, and
ammonium salts thereof.
A suitable class of nonionic monomers are represented by the
compounds of formula V in which none of the R4, R5, or R6
contain the above mentioned negative charge containing
radicals. Suitable monomers in this class include, but are
not limited to, vinyl alcohol; vinyl acetate; vinyl methyl
ether; vinyl ethyl ether; acrylamide, methacrylamide and
other modified acrylamides; vinyl propionate; alkyl
acrylates (esters of acrylic or methacrylic acid); and
hydroxyalkyl acrylate esters. A second class of nonionic
monomers include co-poly ethylene oxide, co-poly propylene
oxide, and co-poly oxymethylene.
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Another class of suitable nonionic monomers includes
naturally derived materials such as celluloses and starches.
A most preferred nonionic monomer is hydroxyethylcellulose,
with the chemical structure illustrated in formula V1.
10
M
R= H, -(-CNzCHzO-~-H
wherein M is 1 to 100,000 and n is 1 to 15.
The average molecular weight of the polymers of this
invention range from about 1000 to about 10 , with the
preferred molecular weight range depending on the polymer
composition.
A particularly useful class of cationic polymers in this
invention are copolymers of diallyldimethylammonium salt and
hydroxyethylcellulose, designated by the Cosmetic, Toiletry,
and Fragrance Association as "Polyquaternium 4". Preferred
examples are materials supplied commercially by the
National Starch and Chemicals Company under the trade names
Celquat L-200 and Celquat H-100. A sample of L-200 had a
composition of 45/55 diallyldimethylammonium chloride/
hydroxyethylcellulose, while a sample of H-100 was composed
of 11/89 diallyldimethylammonium chloride/ hydroxyethyl
cellulose, when characterized by NMR (mole fractions). Both
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polymer samples have molecular weights greater than
1,000,000 as determined by gel permeation chromatography.
It is understood that the polymers in this invention may be
incorporated into the dishwasher at any point in the wash
process. An effective amount of said polymer is 0.025 to
5.00 grams, preferably 0.1 to 3.00 grams, most preferably
0.2 to 2.50 grams per wash cycle, all by weight. If the
polymer is incorporated into a typical concentrated
detergent formulation, this effective amount is equivalent
to a polymer concentration of 0.1 to 20.0, preferably 0.4
to 12.0, and most preferably 0.8 to 10.0 by weight of the
formulation. In a typical rinse aid composition, this
effective amount is equivalent to a polymer concentration of
0.5 to 90.0, preferably 2.0 to 60.0, and most preferably
4.0 to 50.0 by weight of the formulation.
Typical detergent compositions may comprise builders and
other optional components. Rinse aid compositions typically
comprise an aqueous liquid containing surfactants,
hydrotropes, an ingredient such as citric acid that can act
as a builder and pH control agent, and other optional
components. Thus, the essential polymeric ingredients
herein described above may be incorporated into the
dishwashing process in conjunction with conventional
ingredients, preferably selected from builders, enzymes,
buffering systems, oxygen bleaching systems, surfactants,
heavy metal ion sequestrants, antiscalants, corrosion
inhibitors, antifoams, lime soap dispersant compounds,
solvents, and hydrotropes.
A typical aqueous rinse aid composition would be
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Wt$
Nonionic surfactant 1 - 40
Builder/pH adjuster agent 1 - 60
Hydrotrope (optional) 1 - 20
Water Balance
The compositions of the present invention which utilize a
water-soluble phosphate builder typically contain this
builder at a level of from 1 to 90~ by weight, preferably
from 10 to 80~ by weight, most preferably from 20 to 70~ by
weight of the composition. Specific examples of water-
soluble phosphate builders are the alkali metal
tripolyphosphates, sodium, potassium and ammonium
pyrophosphate, sodium and potassium orthophosphate, sodium
polymeta/phosphate in which the degree of polymerization
ranges from about 6 to 21, and salts of phytic acid. Sodium
or potassium tripolyphosphate is most preferred.
The compositions of the present invention which utilize a
water-soluble nonphosphate builder typically contain this
builder at a level of from 1 to 90~ by weight, preferably
from 10 to 80~ by weight, most preferably from 20 to 70~ by
weight of the composition. Suitable examples of
non-phosphorus-containing inorganic builders include
water-soluble alkali metal carbonates, bicarbonates,
sesquicarbonates, borates, silicates, including layered
silicates such as SKS-6 ex. Hoechst, metasilicates, and
crystalline and amorphous aluminosilicates. Specific
examples include sodium carbonate (with or without calcite
seeds), potassium carbonate, sodium and potassium
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bicarbonates, silicates including layered silicates and
zeolites.
Organic detergent builders can also be used as nonphosphate
builders in the present invention. Examples of organic
builders include alkali metal citrates, succinates,
malonates, fatty acid sulfonates, fatty acid carboxylates,
nitrilotriacetates, oxydisuccinates, alkyl and alkenyl
disuccinates, oxydiacetates, carboxymethyloxy succinates,
ethylenediamine tetraacetates, tartrate monosuccinates,
tartrate disuccinates, tartrate monoacetates, tartrate
diacetates, oxidized starches, oxidized heteropolymeric
polysaccharides, polyhydroxysulfonates, polycarboxylates
such as polyacrylates, polymaleates, polyacetates,
polyhydraxyacrylates, polyacrylate/polymaleate and
polyacrylate/ polymethacrylate copolymers,
acrylate/maleate/vinyl alcohol terpolymers,
aminopolycarboxylates and polyacetal carboxylates, and
polyaspartates and mixtures thereof. Such carboxylates are
described in U.S. Patent Nos. 4,144,226, 4,146,495 and
4,686,062. Alkali metal citrates, nitrilotriacetates,
oxydisuccinates, acrylate/maleate copolymers and
acrylate/maleate/vinyl alcohol terpolymers are especially
preferred nonphosphate builders.
Enzymes capable of facilitating the removal of soils from a
substrate may also be present in a combined amount of up to
about 10~ by weight of active enzyme. Such enzymes include
proteases, amylases, lipases, esterases, cellulases,
pectinases, lactases and peroxidases as conventionally
incorporated into dishwashing compositions.
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Preferred commercially available protease enzymes include
those sold under the tradenames Alcalase, Savinase,
Durazyme, Esperase and Everlase from Novo Industries A/S
(Denmark); and those sold by Genencor International under
the tradenames Maxacal, Purafect OxP and Properase.
Preferred commercially available amylases include those -
amylases sold under the tradenames Termamyl, Duramyl and BAN
from Novo Industries and those sold by Genencor
International under the tradenames Maxamyl, Purafect OxAm
and Purafect HpAm. Preferred commercially available lipases
include Lipolase and Lipolase Ultra from Novo Industries and
Lipomax sold by Genencor International.
When the essential polymers of the invention are
incorporated in detergent or rinse aid compositions, the pH
of the compositions may optionally be adjusted by the use of
various pH adjusting agents.
For detergent compositions, a buffering system may be
present in order to deliver a pH of about 6 to about 11 in
the wash water. Materials which may be selected for the
buffering system include water-soluble alkali metal
carbonates, bicarbonates, sesquicarbonates, borates,
silicates, layered silicates such as SKS-6 ex Hoechst,
metasilicates, phytic acid, citric acid, borate and
crystalline and amorphous aluminosilicates and mixtures
thereof. Preferred examples include sodium and potassium
carbonate, sodium and potassium bicarbonates, borates and
silicates, including layered silicates.
Alternatively, if the essential polymers of the invention
are incorporated into rinse aid formulations the pH of
typical rinse aid compositions are in the range of 0.5 to
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6.5 when measured as 1~ solutions. Thus the pH of rinse aid
compositions may optionally be adjusted by the use of
various acidifying pH adjusting agents. Preferred
acidification agents include inorganic and organic acids
including, for example, carboxylic acids, such as citric and
succinic acids, polycarboxylic acids, such as polyacrylic
acid, and also acetic acid, boric acid, malonic acid, adipic
acid, fumaric acid, lactic acid, glycolic acid, tartaric
acid, tartronic acid, malic acid, their derivatives and any
mixtures of the foregoing.
The present invention may optionally contain an oxygen
bleach source chosen from the following:
PPrpxy 1Pa ;ng Agents - The oxygen bleaching agents of the
compositions include organic peroxy acids and
diacylperoxides. Typical monoperoxy acids useful herein
include alkyl peroxy acids and aryl peroxy acids such as:
i) peroxybenzoic acid and ring-substituted peroxybenzoic
acids, e.g., peroxy-alpha-naphthoic acid, and magnesium
monoperoxyphthalate
ii) aliphatic and substituted aliphatic monoperoxy acids,
e.g., peroxylauric acid, peroxystearic acid, epsilon-
phthalimido-peroxyhexanoic acid and o-carboxybenzamido
peroxyhexanoic acid, N-nonylamidoperadipic acid and N-
nonylamidopersuccinic acid.
iii) Cationic peroxyacids such as those described in U.S.
5,422,028, 5,294,362; and 5,292,447, Oakes et al., U.S.
S/N 08/738,504; and U.S. S/N 08/210,973, Oakes et al.,
herein incorporated by reference.
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iv) Sulfonyl peroxyacids such as compounds described in
U.S. 5,039,447 (Monsanto Co.), herein incorporated by
reference.
Typical diperoxy acids useful herein include alkyl diperoxy
acids and aryl diperoxy acids, such as:
v) 1,12-diperoxydodecanedioic acid
vi) 1,9-diperoxyazelaic acid
vii) diperoxybrassylic acid; diperoxysecacic acid and
diperoxy-isophthalic acid
viii) 2-decyldiperoxybutan-1,4-dioic acid
ix) N,N1-terephthaloyl-di(6-aminopercaproic acid).
A typical diacylperoxide useful herein includes
dibenzoylperoxide.
Inorganic peroxygen compounds are also suitable for the
present invention. Examples of these materials useful in
the invention are salts of monopersulfate, perborate
monohydrate, perborate tetrahydrate, and percarbonate.
Preferred peroxy bleaching agents include salts of perborate
monohydrate, perborate tetrahydrate, percarbonate and
monopersulfate, epsilon-phthalimido-peroxyhexanoic acid, o-
carboxybenzamidoperoxyhexanoic acid, and mixtures thereof.
The organic peroxy acid is present in the composition in an
amount such that the level of organic peroxy acid in the
wash solution is about 1 ppm to about 300 ppm AvOx,
preferably about 2 ppm to about 200 ppm AvOx.
The oxygen bleaching agent may be incorporated directly into
the formulation or may be encapsulated by any number of
encapsulation techniques.
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A preferred encapsulation method is described in U.S. Patent
No. 5,200,236 issued to Lang et al., herein incorporated by
reference. In the patented method, the bleaching agent is
encapsulated as a core in a paraffin wax material having a
melting point from about 40°C to 50°C. The wax coating has a
thickness of from 100 to 1500 microns.
~3lPach Precursors - Suitable peracid precursors for peroxy
bleach~compounds have been amply described in the
literature, including GB Nos. 836,988; 855,735; 907,356;
907;358; 907,950; 1,003,310 and 1,246,339; U.S. Patent Nos.
3,332,882 and 4,128,494.
Typical examples of precursors are polyacylated alkylene
diamines, such as N,N,N',N'-tetraacetylethylene diamine
(TAED) and N,N,N',N'-tetraacetylmethylene diamine (TAMD);
acylated glycolurils, such as tetraacetylglycoluril (TAGU);
triacetylcyanurate, sodium sulfophenyl ethyl carbonic acid
ester, sodium acetyloxybenene sulfonate (SABS), sodium
nonanoyloxy benzene sulfonate (SNOBS) and choline
sulfophenyl carbonate. Peroxybenzoic acid precursors are
known in the art, e.g., as described in GB-A-836,988.
Examples of suitable precursors are phenylbenzoate; phenyl
p-nitrobenzoate; o-nitrophenyl benzoate; o-carboxyphenyl
benzoate; p-bromophenylbenzoate; sodium or potassium
benzoyloxy benzene-sulfonate; and benzoic anhydride.
Preferred peroxygen bleach precursors are sodium p-
benzoyloxybenzene sulfonate, N,N,N',N'-tetraacetylethylene
diamine, sodium nonanoyloxybenzene sulfonate and choline
sulfophenyl carbonate.
The peroxygen bleach precursors are present in the
composition in an amount from about 1 to about 20 weight
percent, preferably from about 1 to about 15 wt.~, most
preferably from about 2 to about 15 wt.°s. To deliver a
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functional peroxygen bleach from a precursor, a source of
hydrogen peroxide is required. The hydrogen peroxide source
is preferably a compound that delivers hydrogen peroxide on
dissolution. Preferred sources of hydrogen peroxide are
sodium perborate, either as the mono- or tetrahydrate and
sodium percarbonate. The source of hydrogen peroxide, when
included in these compositions is present at a Level of
about 1~ to about 40~ by weight, preferably from about 2~ to
about 30~ by weight, most preferably from about 4$ to about
25g by weight.
Bleach Catalyst - An effective amount of a bleach catalyst
can also be present in the invention. A number of organic
catalysts are available such as the sulfonimines as
described in U.S. Patents 5,041,232; 5,047,163 and
5,463,115.
Transition metal bleach catalysts are also useful,
especially those based on manganese, iron, cobalt, titanium,
molybdenum, nickel, chromium, copper, ruthenium, tungsten
and mixtures thereof. These include simple water-soluble
salts such as those of iron, manganese and cobalt as well as
catalysts containing complex ligands.
Suitable examples of manganese catalysts containing organic
ligands are described in U.S. Pat. 4,728,455, U.S. Pat.
5,114,606, U.S. Pat 5,153,161, U.S. Pat. 5,194,416, U.S.
Pat. 5,227,084, U.S. Pat. 5,244,594, U.S. Pat.5,246,612,
U.S. Pat. 5,246,621, U.S. Pat. 5,256,779, U.S. Pat.
5,274,147, U.S. Pat. 5,280,117 and European Pat. App. Pub.
Nos. 544,440, 544,490, 549,271 and 549,272. Preferred
examples of these catalysts include MniV2(u-O)2(1,4,7-
trimethyl-1,4,7-triazacyclononane)z(PF6)2, MnIII2(u-0)1(u-
OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2(CI04)a,
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~IV4 (u-O) 6 (1, 4, 7-triazacyclononane) 4 (CI04) 4, MnIIIMnIV9 (u-
O)1(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2(C104)3.
Mniv(1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH3)3(PF6),
and mixtures thereof. Other metal-based bleach catalysts
include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat.
5,114,611.
Iron and manganese salts of aminocarboxylic acids in general
are useful herein including iron and manganese
aminocarboxylate salts disclosed for bleaching in the
photographic color processing arts. A particularly useful
transition metal salt is derived from ethylene-
diaminedisuccinate and any complex of this ligand with iron
or manganese.
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-
erythritol, meso-inositol, lactose and mixtures thereof.
Especially preferred is sorbitol.
U.S. Patent No. 5,114,611 teaches a bleach catalyst
comprising a complex of transition metals, including
manganese, cobalt, iron or copper with a non-(macro)-cyclic
ligand. Other examples include Mn gluconate, Mn(CF3S03)2,
and binuclear Mn complexed with tetra-N-dentate and bi-N-
dentate ligands, including ~~]j,py2~III (u-0) Z~IVbipy2] - (CIOQ) 3.
Other bleach catalysts are described, for example, in
European Pat. App. Pub. Nos. 408,131 (cobalt complexes),
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384,503 and 306,089 (metallo-porphyrins), U.S. Pat.
4,728,455 (manganese/multidenate ligand), U.S. Pat.
4,711,748 (absorbed manganese on aluminosilicate), U.S. Pat.
4,601,845 (aluminosilicate support with manganese, zinc or
magnesium salt), U.S. Pat. 4,626,373 (manganese/ligand),
U.S. Pat. 4,119,557 (ferric complex), U.S. Pat. 4,430.243
(Chelants with manganese cations and non-catalytic metal
canons), and U.S. Pat. 4,728,455 (manganese gluconates).
Useful catalysts based on cobalt are described in Pat. App.
Pub. Nos. WO 96/23859, WO 96/23860 and w0 96/23861 and U.S.
Pat. 5,559,261. w0 96/23860 describe cobalt catalysts of
the type [ConLmXp] ZY2, where L is an organic ligand molecule
containing more than one heteroatom selected from N, P, O
and S; X is a coordinating species; n is preferably 1 or 2;
m is preferably 1 to 5; p is preferably 0 to 4 and Y is a
counterion. One example of such a catalyst is N,N'-
Bis(salicylidene)ethylenediaminecobalt (II). Other cobalt
catalysts described in these applications are based on
Co(III) complexes with ammonia and mon.-, bi-, tri- and
tetradentate ligands such as [Co(NH3)SOAc]z+ with C1 , OAc ,
PF6 , S04 , and BF4 anions .
Certain transition-metal containing bleach catalysts can be
prepared in the situ by the reaction of a transition-metal
salt with a suitable chelating agent, for example, a mixture
of manganese sulfate and ethylenediaminedisuccinate. Highly
colored transition metal-containing bleach catalysts may be
co-processed with zeolites to reduce the color impact.
When present, the bleach catalyst is typically incorporated
at a level of about 0.0001 to about 10~ by wt., preferably
about 0.001 to about 5~ by weight.
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Optionally, a surfactant selected from the list including
anionic, nonionic, cationic, amphoteric, and zwitterionic
surfactants and mixtures of these surface active agents may
be included in a composition containing the essential
polymers. Such surfactants are well known in the detergent
arts and are described at length in "Surface Active Agents
and Detergents", Vol. 2 by Schwartz, Perry and Birch,
Interscience Publishers, Inc., 1959, herein incorporated by
reference. Low foaming surfactants are most suitable for
machine dishwashing applications.
Preferred surfactants are one or a mixture of:
An~~~» surfactants - Anionic synthetic detergents can be
broadly described as surface active compounds with one or
more negatively charged functional groups. An important
class of anionic compounds are the water-soluble salts,
particularly the alkali metal salts, of organic sulfur
reaction products having in their molecular structure an
alkyl radical containing from about 6 to 24 carbon atoms and
a radical selected from the group consisting of sulfonic and
sulfuric acid ester radicals.
Primary Alkyl Sulfates
i
R OS03 M
where R~ is a primary alkyl group of 8 to 18 carbon atoms and
M is a solubilizing cation. The alkyl group R~ may have a
mixture of chain lengths. It is preferred that at least
two-thirds of the R alkyl groups have a chain length of 8 to
14 carbon atoms. This will be the case if R is coconut
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alkyl, for example. The solubilizing cation may be a range
of cations which are in general monovalent and confer water
solubility. An alkali metal, notably sodium, is especially
envisaged. Other possibilities are ammonium and substituted
ammonium ions, such as trialkanolammonium or
trialkylammonium.
Alkyl Ether Sulfates
R O ( CHZ CHZ O ) n S03 M
where R~ is a primary alkyl group of 8 to 18 carbon atoms, n
has an average value in the range from 1 to 6 and M is a
solubilizing cation. The alkyl group R may have a mixture
of chain lengths. It is preferred that at least two-thirds
of the R~ alkyl groups have a chain length of 8 to 14 carbon
atoms. This will be the case if R~ is coconut alkyl, for
example. Preferably n has an average value of 2 to 5.
Fatty Acid Ester Sulfonates
8 9
R CH ( S03 M) COZ R
where Re is an alkyl group of 6 to 16 atoms, R9 is an alkyl
group of 1 to 4 carbon atoms and M is a solubilizing cation.
The group R8 may have a mixture of chain lengths. Preferably
at least two-thirds of these groups have 6 to 12 carbon
a
atoms. This will be the case when the moiety R CH(-)C02(-)
is derived from a coconut source, for instance. It is
preferred that R9 is a straight chain alkyl, notably methyl
or ethyl.
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Alkyl Benzene Sulfonates
io
R ArS03 M
where Rlo is an alkyl group of 8 to 18 carbon atoms, Ar is a
benzene ring (C6H4) and M is a solubilizing cation. The
group R1o may be a mixture of chain lengths. Straight chains
of 11 to 14 carbon atoms are preferred.
Paraffin sulfonates having 8 to 22 carbon atoms, preferably
12 to 16 carbon atoms, in the alkyl moiety. These
surfactants are commercially available as Hostapur SAS from
Hoechst Celanese.
Olefin sulfonates having 8 to 22 carbon atoms, preferably 12
to 16 carbon atoms. U.S. Patent No. 3,332,880 contains a
description of suitable olefin sulfonates.
Organic phosphate based anionic surfactants include organic
phosphate esters such as complex mono- or diester phosphates
of hydroxyl- terminated alkoxide condensates, or salts
thereof. Included in the organic phosphate esters are
phosphate ester derivatives of polyoxyalkylated alkylaryl
phosphate esters, of ethoxylated linear alcohols and
ethoxylates of phenol. Also included are nonionic
alkoxylates having a sodium alkylenecarboxylate moiety
linked to a terminal hydroxyl group of the nonionic through
an ether bond. Counterions to the salts of all the
foregoing may be those of alkali metal, alkaline earth
metal, ammonium, alkanolammonium and alkylammonium types.
Particularly preferred anionic surfactants are the fatty
acid ester sulfonates with formula:
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RgCH ( S03 M ) COz R9
where the moiety RBCH(-)COZ(-) is derived from a coconut
9
source and R is either methyl or ethyl; primary alkyl
sulfates with the formula:
R OS03 M
wherein R is a primary alkyl group of 10 to 18 carbon atoms
and M is a sodium cation; and paraffin sulfonates,
preferably with 12 to 16 carbon atoms to the alkyl moiety.
Nonionic surfactants - Nonionic surfactants can be broadly
defined as surface active compounds with one or more
uncharged hydrophilic substituents. A major class of
nonionic surfactants consists of those compounds produced by
the condensation of alkylene oxide groups with an organic
hydrophobic material which may be aliphatic or alkyl
aromatic in nature. The length of the hydrophilic or
polyoxyalkylene radical which is condensed with any
particular hydrophobic group can be readily adjusted to
yield a water-soluble compound having the desired degree of
balance between hydrophilic and hydrophobic elements.
Illustrative, but not limiting examples, of various suitable
nonionic surfactant types are:
Polyoxyalkene condensates of aliphatic carboxylic acids,
whether linear- or branched-chain and unsaturated or
saturated, especially ethoxylated and/or propoxylated
aliphatic acids containing from about 8 to about 18 carbon
atoms in the aliphatic chain and incorporating from about 2
to about 50 ethylene oxide and/or propylene oxide units.
Suitable carboxylic acids include "coconut" fatty acids
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(derived from coconut oil) which contain an average of about
12 carbon atoms, "tallow" fatty acids (derived from
tallow-class fats) which contain an average of about 18
carbon atoms, palmitic acid, myristic acid, stearic acid and
lauric acid,
Polyoxyalkene condensates of aliphatic alcohols, whether
linear- or branched-chain and unsaturated or saturated,
especially ethoxylated and/or propoxylated aliphatic
alcohols containing from about 6 to about 24 carbon atoms
and incorporating from about 2 to about 50 ethylene oxide
and/or propylene oxide units. Suitable alcohols include
"coconut" fatty alcohol, "tallow" fatty alcohol, lauryl
alcohol, myristyl alcohol and oleyl alcohol.
Ethoxylated fatty alcohols may be used alone or in admixture
with anionic surfactants, especially the preferred
surfactants above. The average chain lengths of the alkyl
group R11 in the general formula:
m
R 0(CHZ CHZ O)n H
is from 6 to 20 carbon atoms. Notably the group R11 may have
chain lengths in a range from 9 to 18 carbon atoms.
The average value of n should be at least 2. The numbers of
ethylene oxide residues may be a statistical distribution
around the average value. However, as is known, the
distribution can be affected by the manufacturing process or
altered by fractionation after ethoxylation. Particularly
preferred ethoxylated fatty alcohols have a group R11 which
has 9 to 18 carbon atoms while n is from 2 to 8.
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Also included within this category are nonionic surfactants
having a formula:
lz
R - ( CH12CH0 ) X ( CHzCH20 ) y ( CHZCHO ) ZH
~ 13 ~ 19
R R
wherein Rlz is a linear alkyl hydrocarbon radical having an
average of 6 to 18 carbon atoms, R13 and R19 are each linear
alkyl hydrocarbons of about 1 to about 4 carbon atoms, x is
an integer of from 1 to 6, y is an integer of from 4 to 20
and z is an integer from 4 to 25.
One preferred nonionic surfactant of the above formula is
Poly-Tergent SLF-18, a registered trademark of the Olin
Corporation, New Haven, Conn., having a composition of the
above formula where Rlz is a C6-Clo linear alkyl mixture, R13
and R14 are methyl, x averages 3, y averages 12 and z
averages 16. Another preferred nonionic surfactant is:
R15 O-(CH2 HO)~ (CH2CH20)k(CH2)OH)R6)1
~H3
wherein Rls is a linear, aliphatic hydrocarbon radical having
from about 4 to about 18 carbon atoms including mixtures
thereof; and R16 is a linear, aliphatic hydrocarbon radical
having from about 2 to about 26 carbon atoms including
mixtures thereof; j is an integer having a value of from 1
to about 3; k is an integer having a value from 5 to about
30; and 1 is an integer having a value of from 1 to about 3.
Most preferred are compositions in which j is 1, k is from
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about 10 to about 20 and 1 is 1. These surfactants are
described in WO 94/22800. Other preferred nonionic
surfactants are linear fatty alcohol alkoxylates with a
capped terminal group, as described in U.S. 4,340,766 to
BASF. Particularly preferred is Plurafac LF403 ex. BASF.
Another nonionic surfactant included within this category
are compounds of formula:
R~ ~- (CH2CH20)q H
wherein R1~ is a C6-C24 linear or branched alkyl hydrocarbon
radical and q is a number from 2 to 50; more preferably R1~
is a C8-C18 linear alkyl mixture and q is a number from 2 to
15.
Polyoxyethylene or polyoxypropylene condensates of alkyl
phenols, whether linear- or branched-chain and unsaturated
or saturated, containing from about 6 to 12 carbon atoms and
incorporating from about 2 to about 25 moles of ethylene
oxide and/or propylene oxide.
Polyoxyethylene derivatives of sorbitan mono-, di-, and
tri-fatty acid esters wherein the fatty acid component has
between 12 and 24 carbon atoms. The preferred
polyoxyethylene derivatives are of sorbitan monolaurate,
sorbitan trilaurate, sorbitan monopalmitate, sorbitan
tripalmitate, sorbitan monostearate, sorbitan
monoisostearate, sorbitan tristearate, sorbitan monooleate,
and sorbitan trioleate. The polyoxyethylene chains may
contain between about 4 and 30 ethylene oxide units,
preferably about 10 to 20. The sorbitan ester derivatives
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contain 1, 2 or 3 polyoxyethylene chains dependent upon
whether they are mono-, di- or tri-acid esters.
Polyoxyethylene-polyoxypropylene block copolymers having
formula:
HO ( CH2CH20 ) a ( CH ( CH3 ) CH20 ) b ( CH2CH20 ) ~H
or
HO ( CH ( CH3 ) CH20 ) d ( CH2CH20 ) a ( CH ( CH3 ) CH20 ) fH
wherein a, b, c, d, a and f are integers from 1 to 350
reflecting the respective polyethylene oxide and
polypropylene oxide blocks of said polymer. The
polyoxyethylene component of the block polymer constitutes
at least about 10~ of the block polymer. The material
preferably has a molecular weight of between about 1,000 and
15,000, more preferably from about 1,500 to about 6,000.
These materials are well-known in the art. They are
available under the trademark "Pluronic" and "Pluronic R", a
product of BASF Corporation.
Amine oxides having formula:
18 19 20
R R R N=O
wherein R18, R19 and R2~ are saturated aliphatic radicals or
substituted saturated aliphatic radicals. Preferable amine
oxides are those wherein R1$ is an alkyl chain of about 10 to
19 20
about 20 carbon atoms and R and R are methyl or ethyl
groups or both Rla and R19 are alkyl chains of about 6 to
about 14 carbon atoms and R2~ is a methyl or ethyl group.
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Amy rnte_r,'_c svnthetic detergents - can be broadly described
as derivatives of aliphatic tertiary amines, in which the
aliphatic radical may be straight chain or branched and
wherein one of the aliphatic substituents contain from about
8 to about 18 carbons and one contains an anionic
water-solubilizing group, i.e., carboxy, sulpho, sulphato,
phosphato or phosphono. Examples of compounds falling
within this definition are sodium 3-dodecylamino propionate
and sodium 2-dodecylamino propane sulfonate.
~w~tterionic synthetic deter~er nts - can be broadly described
as derivatives of aliphatic quaternary ammonium, phosphonium
and sulphonium compounds in which the aliphatic radical may
be straight chained or branched, and wherein one of the
aliphatic substituents contains from about 8 to about 18
carbon atoms and one contains an anionic water-solubilizing
group, e.g., carboxy, sulpho, sulphato, phosphato or
phosphono. These compounds are frequently referred to as
betaines. Besides alkyl betaines, alkyl amino and alkyl
amido betaines are encompassed within this invention.
Alkyl Glycosides
21 22 L
R O(R O)n (Z )p
wherein R21 is a monovalent organic radical (e.g., a
monovalent saturated aliphatic, unsaturated aliphatic or
aromatic radical such as alkyl, hydroxyalkyl, alkenyl,
hydroxyalkenyl, aryl, alkylaryl, hydroxyalkylaryl,
arylalkyl, alkenylaryl, arylalkenyl, etc.) containing from
about 6 to about 30 (preferably from about 8 to 18 and more
preferably from about 9 to about 13) carbon atoms; R22 is a
divalent hydrocarbon radical containing from 2 to about 4
carbon atoms such as ethylene, propylene or butylene (most
preferably the unit (R220)n represents repeating units of
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ethylene oxide, propylene oxide and/or random or block
combinations thereof); n is a number having an average value
of from 0 to about 12; Zj represents a moiety derived from a
reducing saccharide containing 5 or 6 carbon atoms (most
preferably a glucose unit); and p is a number having an
average value of from 0.5 to about 10 preferably from about
0.5 to about 5.
Examples of commercially available materials from Henkel
Kommanditgesellschaft Aktien of Dusseldorf, Germany include
APG 300, 325 and 350 with R21 being C9-C11, n is 0 and p is
1.3, 1.6 and 1.8-2.2 respectively; APG 500 and 550 with R2i
is C1z-C13, n is 0 and p is 1.3 and 1.8-2.2, respectively; and
APG 600 with R21 being C12-C14, n is 0 and p is 1.3.
While esters of glucose are contemplated especially, it is
envisaged that corresponding materials based on other
reducing sugars, such as galactose and mannose are also
suitable.
Particularly preferred nonionic surfactants are
polyoxyethylene and polyoxypropylene condensates of linear
aliphatic alcohols.
The preferred range of surfactant is from about 0.5 to 30~
by wt., more preferably from about 0.5 to 15~ by weight of
the composition.
The detergent compositions herein may also optionally
contain one or more transition metal chelating agents.
These components may also have calcium and magnesium
chelation capacity, but preferentially they show selectivity
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to binding heavy metal ions. Such chelating agents can be
selected from the group consisting of amino carboxylates,
amino phosphonates, polyfunctionally-substituted aromatic
chelating agents and mixtures therein. Vdithout intending to
be bound by theory, it is believed that the benefit of these
materials is due in part to their exceptional ability to
remove iron and manganese ions from washing solutions by
formation of soluble chelates.
Amino carboxylates useful as optional chelating agents
include ethylenediaminetetraacetates, N-
hydroxyethylethylenediaminetriacetates, nitrilotriacetates,
ethylenediamine tetraproprionates, triethylenetetraamine-
hexaacetates, diethylenetriaminepentaacetates,
ethylenediamine disuccinate, and ethanoldiglycines, alkali
metal, ammonium, and substituted ammonium salts therein and
mixtures therein.
Amino phosphonates are also suitable for use as chelating
agents in the compositions of the invention when at least
low levels of total phosphorus are permitted in detergent
compositions, and include ethylenediaminetetrakis
(methylenephosphonates) and diethylenetriaminepentakis
(methylenephosphonates). Preferably, these amino
phosphonates do not contain alkyl or alkenyl groups with
more than about 6 carbon atoms.
Polyfunctionally-substituted aromatic chelating agents are
also useful in the compositions herein. See U.S. Patent No.
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.
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- 38 -
If utilized, these chelating agents will generally comprise
from about 0.1~ to about 10~ by weight of the detergent
compositions herein. More preferably, if utilized, the
chelating agents will comprise from about 0.1~ to about 5.0~
by weight of such composition.
Scale formation on dishes and machine parts can be a
significant problem. It can arise from a number of sources
but, primarily it results from precipitation of either
alkaline earth metal carbonates, phosphates or silicates.
Calcium carbonate and phosphates are the most significant
problem. To reduce this problem, ingredients to minimize
scale formation can be incorporated into the composition.
These include polyacrylates of molecular weight from 1,000
to 400,000 examples of which are supplied by Rohm & Haas,
BASF and Alco Corp. and polymers based on acrylic acid
combined with other moieties. These include acrylic acid
combined with malefic acid, such as Sokalan CP5 and CP7
supplied by BASF or Acusol 479N supplied by Rohm & Haas;
with methacrylic acid such as Colloid 226/35 supplied by
Rhone-Poulenc; with phosphonate such as Casi 773 supplied by
Buckman Laboratories; with malefic acid and vinyl acetate
such as polymers supplied by Hl~ls; with acrylamide; with
sulfophenol methallyl ether such as Aquatreat AR 540
supplied by Alco; with 2-acrylamido-2-methylpropane sulfonic
acid such as Acumer 3100 supplied by Rohm & Haas or such as
K-775 supplied by Goodrich; with 2-acrylamido-2-
methylpropane sulfonic acid and sodium styrene sulfonate
such as K-798 supplied by Goodrich; with methyl
methacrylate, sodium methallyl sulfonate and sulfophenol
methallyl ether such as Alcoperse 240 supplied by Alco;
polymaleates such as Belclene 200 supplied by FMC;
polymethacrylates such as Tamol 850 from Rohm & Haas;
CA 02327308 2000-10-04
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polyaspartates; ethylenediamine disuccinate; organo
polyphosphonic acids and their salts such as the sodium
salts of aminotri(methylenephosphonic acid) and ethane 1-
hydroxy-1,1-diphosphonic acid. The anti-scalant, if
present, is included in the composition from about 0.05 to
about 10~ by weight, preferably from 0.1~ to about 5~ by
weight, most preferably from about 0.2~ to about 5~ by
weight.
It should be noted that some antiscalant polymers, notably
polyacrylates, are claimed as providing some glassware
appearance benefit. The essential polymers of this invention
are notable in that they provide a marked improvement in
glassware appearance for systems which contain antiscalant
polymers.
The composition my optionally contain corrosion inhibitors
to reduce the tarnishing of silver flatware. Such
inhibitors include benzotriazole and other members of the
azole family. Particularly preferred azoles, including
imidazoles, are described in Gary et al., U.S. Patent No.
5,480,576, incorporated herein by reference. Additional
antitarnish additives include water-soluble bismuth
compounds such as bismuth nitrate as taught in GB 2,297,096
A; heavy metal salts of copper, iron, manganese, zinc, or
titanium (EP 0 636 688 A1, GB 2,283,494 A); paraffin oil;
and non-paraffin oil organic agents such as fatty esters of
mono or polyhydric alcohols as claimed in EP 0 690 122 A2.
The compositions of the present invention, when formulated
for use in machine dishwashing compositions, preferably
CA 02327308 2000-10-04
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comprise an antifoam system. Suitable antifoam systems for
use herein may comprise essentially any known antifoam
compound, including, for example, silicone antifoams,
silicone oil, mono- and distearyl acid phosphates, mineral
oil, and 2-alkyl and alcanol antifoam compounds. Even if
the machine dishwashing composition contains only low
foaming surfactants, the antifoam assists to minimize foam
which food soils can generate. The compositions may include
0.02 to 2~ by weight of antifoam, preferably, 0.05 to 1.0~.
Preferred antifoam systems are described in Angevaare et
al.; U.S. Serial No. 08/539,923, incorporated herein by
reference.
The compositions of the invention may contain a lime soap
dispersant compound, which has a lime soap dispersing power
(LSDP), as defined hereinafter, of no more than 8,
preferably no more than 7, most preferably no more than 6.
The lime soap dispersant compound is preferably present at a
level of from 0.1~ to 40~ by weight, more preferably 1~ to
20~ by weight, most preferably from 2~ to 10~ by weight of
the compositions.
A lime soap dispersant is a material that prevents the
precipitation of alkali metal, ammonium or amine salts of
fatty acids by calcium or magnesium ions. A numerical
measure of the effectiveness of a lime soap dispersant is
given by the lime soap dispersing power (LSDP) which is
determined using the lime soap dispersion test as described
in an article by H.C. Borghetty and C.A. Bergman, J. Am.
Oil. Chem. Soc., volume 27, pages 88-90, (1950). This
lime soap dispersion test method is widely used by
practitioners in this art field being referred to , for
example, in the following review articles; W.N. Linfield,
CA 02327308 2000-10-04
WO 99158633 PCT/EP98/05003
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Surfactant Science Series, Volume 7, p 3; W.N. Linfield,
Tenside Surf. Det. , Volume 27, pages 159-161, (1990); and
M.K. Nagarajan, W.F. Maslar, Cosmetics and Toiletries,
Volume 104, pages 71-73, (1989). The LSDP is the ~ weight
ratio of dispersing agent to sodium oleate required to
disperse the lime soap deposits formed by 0.025g of sodium
oleate in 30 ml of water of 333 ppm CaC03 (Ca:Mg = 3:2)
equivalent hardness.
Surfactants having good lime soap dispersant capability will
include certain amine oxides, betaines, sulfobetaines, alkyl
ethoxysulfates and ethoxylated alcohols.
Exemplary surfactants having a LSDP of no more than 8 for
use in accord with the invention include C16-C18 dimethyl
amine oxide, C12-C18 alkyl ethoxysulfates with an average
degree of ethoxylation of from 1-5, particularly C12-Cis alkyl
ethoxysulfate surfactant with a degree of ethoxylation of
about 3 (LSDP=4) and the C13-Cls ethoxylated alcohols with an
average degree of ethoxylation of either 12 (LSDP = 6) or
30, sold under the trade names Lutensol A012 and Lutensol
A030 respectively, by BASF GmbH.
The compositions of the invention may contain organic
solvents, particularly when formulated as nonaqueous liquids
or gels. The compositions in accord with the invention
preferably contain a solvent system present at levels of
from about 1~ to about 30~ by weight, preferably from about
3~ to 25~ by weight, more preferably form about 5~ to about
20~ by weight of the composition. The solvent system may be
a mono or mixed solvent system. Preferably, at least the
major component of the solvent system is of low volatility.
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Suitable organic solvent for use herein has the general
formula RO(CH2C(Me)HO)nH, wherein R is an alkyl, alkenyl, or
alkyl aryl group having from 1 to 8 carbon atoms, and n is
an integer from 1 to 4. Preferably, R is an alkyl group
containing 1 to 4 carbon atoms, and n is 1 or 2. Especially
preferred R groups are n-butyl or isobutyl. Preferred
solvents of this type are 1 -n-butoxypropane-2-of (n = 1):
and 1(2-n-butoxy-1 -methylethoxy)propane-2-of (n = 2), and
mixtures thereof.
Other solvents useful herein include the water soluble
CARBITOL~ solvents or water-soluble CELLOSOLVE' solvents.
Water-soluble CARBITOL~ solvents are compounds of the 2-(2
alkoxyethoxy)ethanol class wherein the alkoxy group is
derived from ethyl, propyl or butyl; a preferred water-
soluble carbitol is 2(2-butoxyethoxy) ethanol also known as
butyl carbitol. Water-soluble CELLOSOLVE solvents are com-
pounds of the 2-alkoxyethoxy ethanol class, with 2-
butoxyethoxyethanol being preferred.
Other suitable solvents are benzyl alcohol, and diols such
as 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-
pentanediol.
The low molecular weight, water-soluble, liquid polyethylene
glycols are also suitable solvents for use herein.
The alkane mono and diols, especially the C1-C6 alkane mono
and diols are suitable for use herein. C1-CQ monohydric
alcohols (eg: ethanol, propanol, isopropanol, butanol and
mixtures thereof) are preferred, with ethanol particularly
preferred. The C1-C9 dihydric alcohols, including propylene
glycol, are also preferred.
CA 02327308 2000-10-04
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When the essential polymers of this invention are
incorporated into rinse aid compositions, these compositions
may also contain water. The compositions of the invention
may contain hydrotropes, particularly when formulated as
aqueous liquids or gels. The hydrotrope is typically
present at levels of from about 0.5~ to about 20~,
preferably from about 1~ to about 10~, by weight.
Useful hydrotropes include sodium, potassium, and ammonium
xylene sulfonates, sodium, potassium, and ammonium toluene
sulfonate, sodium, potassium and ammonium cumene sulfonate,
and mixtures thereof.
The following examples will help to distinguish this
invention from the prior art and illustrate its embodiment
more fully. Unless indicated otherwise, all parts,
percentages and portions referred to are by weight.
This example demonstrates the superior performance of the
essential polymers of this invention when compared to
commercially available polymers claimed to improve glassware
appearance during the automatic dishwashing process.
Machine dishwashing detergent formulations used for all
examples were prepared as described in Table 1. Product 1
is a granular automatic dishwashing detergent based on a non
- phosphate builder while Product 2 is a phosphate - built
tablet.
CA 02327308 2000-10-04
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- 44 -
:....::: :;,::::.:i:.;,a.i:~
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.................. ..;f.. .: t..
....r. ..:. :...>:....::. /f..::W............~. . :.....::::::i
. .:ff :... : f . .... t
~: ~ft. ....... ........... ............................
. .: ~::.~::~.if ~ r. r:...:::
~: ..,1 : : :.::...:::::. ........... tv;a:
..... rt:. .;;;::t.,i:i:OY: .;::'.:?::.
. I .... . lr/ n .... :;:: ::: J:
..:~ :: fi:::::..:.... . a.ia:'
./ r.,:..:. .: ff . L...:: v::. 4:~:tS:t4:4t:
f ~
r .y::4::i::4:i:4:4:::::.~ v....
!r
..... : . ...
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:
:
i
':4i:~::ii:i~t4:i:,
/ f j
/
ff/
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.... , .
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. ... ............:..
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r
i
::::....
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:T::.~ : ...:.....:........ .. ...,.......r'.
Sodium tripolyphosphate 50.60
Tri-sodium citrate dehydrate 36.45
Acrylate homopolymer 1 1.95 3.30
2 3.90
Acrylate/maleate copolymer
Sodium silicate 1.95
Amorphous sodium silicate 29.34
( SiO~ : Na~O = 2 )
Sodium bicarbonate 15.80
Sodium perborate monohydrate 15.75 9.00
Tetraacetyl ethylene diamine - 2.75 2.40
83~
Anionic
12.40
4
Nonionic 1.00
Enzymes 7.30 3.06
1, 2, 3 Benzotriazole 0.05
Solid ketone particles dispersed 1.35
in an organic carrier
Polybutadiene6 0.45
Sodium hydroxyethane diphosphonic 1.10
acid
1 Sokalan PA25 ex BASF
2 Sokalan CP5 ex BASF
3 Alpha Step ML 40 ex Henkel
9 LF 403 ex BASF
5 Dehypon 2429 ex Henkel
6 ex Elf Atochem
~ bequest 2016 ex Monsanto
10 clean glasses were placed on the upper rack of an
Electrolux ESF 675 automatic dishwasher. 40.Og ASTM Standard
Food Soil, described in section 5.2 of ASTM Method D 3556-
85, "Standard Test Method far Deposition on Glassware During
Mechanical Dishwashing", was spread on the dishwasher door.
The soil consists of 80.0 margarine and 20.0 low fat
powdered milk. Along with the ASTM soil, 10 egg yolk soiled
CA 02327308 2000-10-04
WO 99158633 PCT/EP98/05003
- 45 -
plates and 10 starch soiled plates were placed on the bottom
rack of the dishwasher. A Normal wash program consisted of
a cold prewash, 65°C main wash followed by two cold rinses,
and a heated (to 65°C) final rinse with a non-heated dry
cycle. Water was adjusted to 500 ppm hardness (expressed as
CaC03) with a Ca:Mg ratio of 4:1. Product 1 was used for
both tests described in this example. In Test 1, l9.Og of
Product 1 was dosed via the dispenser cup of the automatic
dishwasher together with 0.95 g of polymer. In Test 2,
detergent was dosed via the dispenser cup while 0.3g of the
polymer was dosed directly into the machine at the beginning
of the final rinse. After completion of the wash program,
the appearance of the washed glassware was assessed visually
using a light box as described in section 4.4 of ASTM Method
D 3556-85. The light box is essentially a darkened room
with the glasses being placed on racks and illuminated from
within to disclose spots or film. All interior surfaces of
the light box are black, so that the only light present is
that which passes up through the tumblers. Washed glasses
were scored using a 0 - 5 scale in which 0 is clean and 5 is
completely covered with spots or heavy chalky film,
respectively. The rating scale is described further in
section 6.6 of ASTM Method D-3556-85. Results are recorded
in Table 2.
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WO 99/58633 PCf/EP98/05003
- 46 -
. ......... ...........................:::: .-.....::.:::.:..-....-.-
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k.,.a;Sii:i:fi::::::.~::::.:::::..:::::i::::r.:...................
Control (no additive) 4.1 1.2 4.1 1.2
Co-polymer of 1.4 0.8 1.1 1.2
diallyldimethyl ammonium
chloride and
hydroxyethylcellulose
(Polyquaternium 4)
Co-polymer of acrylic 3.2 0.8 3.8 1.3
acid and
acrylamidopropyltrimethy
1 ammonium chloride
Modified polyaczylic 3.8 1.3 4.0 3.8
acid (MW 4500)
Polyacryl4c acid 2.0 2.3 2.7 4.1
(MW 4500)
Co-polymer of malefic 4.3 0.5 2.9 1.3
acid and olefin
s
(MW 15000)
Poly (acrylate / 4.0 1.0 4.4 1.8
6
methacrylate) (MW 3500)
1 Celquat H-100 ex National Starch and Specialty Chemicals
2 ex ROHM & HAAS
3 Norasol 470 ex ROHM & HAAS
4 Acusol 445ND ex ROHM & HAAS
s Acusol 450ND ex ROHM & HAAS
6 Acusol 480ND ex ROHM & HAAS
It is important to note that the high wash temperatures
(65°C) and water hardness (500ppm) conditions used in this
example are known to promote scale formation which results
in higher spotting or filming scores on glassware.
This example clearly demonstrates the ability of the
essential polymers of this invention to deliver glass
appearance benefits superior to those of the other polymers
CA 02327308 2000-10-04
WO 99/58633 PCT/EP98/05003
- 47 -
used in this example. These prior art materials are claimed
by their manufacturers to deliver improved glass appearance
(e. g. spotting and film deposition) under the stressful
conditions described above. Additionally, as indicated in
Table 1, antiscalant polymers are present in the detergent
formulation used for these tests. The essential polymers of
this invention clearly provide a glassware appearance
benefit superior to any that may be provided by the
antiscalant polymers.
This example illustrates the negligible effects of detergent
type, water hardness, dishwasher type and wash program, and
mode of incorporation on the level of benefits delivered by
the essential polymers of this invention added to the
dishwashing process.
The results for Product 1 shown in Table 3 were obtained
using the Normal program of an Electrolux ESF 675 automatic
dishwasher, as described in Example 1. 40.Og ASTM Standard
Food Soil was spread on the dishwasher door. Along with the
ASTM soil, 10 egg yolk soiled plates and 10 starch soiled
plates were placed on the bottom rack of the dishwasher.
Water hardness was adjusted to 500 ppm with a Ca:Mg ratio of
4:1. The essential polymer of the invention was dosed into
the main wash via the dispenser cup at a level of 0.95 g; or
at 0.308 into the final rinse. 10 washed glasses were
visually assessed and scored on the 0 to 5 scale with 0
being clean and 5 completely covered with spots or heavy
chalky film, respectively.
The results shown for Product 2 in Table 3 were obtained
using the Economy program of a Siemens SE 29290 EU automatic
dishwasher. This program comprises a cold prewash, main
CA 02327308 2000-10-04
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wash cycle heated to 55°C, intermediate cold rinse, a 70°C
final rinse, and a non - heated drying step. Water hardness
was adjusted to either 75 ppm or 300 ppm with a Ca: Mg ratio
of 4:1. The soil load and evaluation procedure was
identical to that used for Product 1. 1.2 g of polymer was
dosed into the main wash with Product 2; or into the final
rinse; or divided into 2 equal parts and dosed one part with
the detergent via the dispenser cup and the other part into
the final rinse.
Fffp~t of water hardness mode of incorporation, dishwasher
~voe and wash oroaram
The experimental data shown in Table 3 indicate that the
essential polymers of the invention are capable of
effectively reducing spot formation when used with both non-
phosphate and phosphate based automatic dishwashing
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- 49 -
formulations. The data further shows that the essential
polymers provide improved glassware appearance over a range
of water hardness, mode of incorporation, dishwasher type
and wash program.
The spotting and filming characteristics of a given
formulation are known to depend upon the machine dishwasher
type and even the wash program chosen. The superior
performance of the essential polymers of the invention
across machine types and wash programs demonstrates the
robust nature of its effectiveness. Additionally, as
indicated in Table 1, antiscalant polymers are present in
both of the detergent formulation used for these tests. The
essential polymers of this invention clearly provide a
glassware appearance benefit superior to any that may be
provided by the antiscalant polymers.
Example 3 demonstrates the effect of the essential polymers
of the invention on glass appearance with and without heavy
soil loads being present in the wash.
This set of experiments was carried out in an Electrolux ESF
675 automatic dishwasher using the Normal program. Water
hardness was adjusted to 500ppm with Ca: Mg = 4:1. The soil
load consisted of 10 egg yolk and 10 starch soiled plates as
well as 40.Og of the ASTM Standard Food Soil. When
introduced into the main wash, the essential polymer was
dosed together with Product 1 (composition see in Example 1)
via the dispenser cup at a level of 0.95 g; or at either
0.158 or 0.3g respectively into the final rinse.
CA 02327308 2000-10-04
WO 99/58633 PCT/EP98/05003
- 50 -
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No additive 4.0 1.8 4.0 0.8
Main wash (0.95g) 2.0 1.0 0.5 0.5
Final rinse (0.15g) 1.2 0.75 1.95 1.85
Final rinse (0.3g) ---- ---- 0.75 1.5
Even though these wash conditions were chosen so as to
increase and accelerate spot deposition on the glassware,
the data shown in Table 4 demonstrate that the essential
polymers of the invention are a very effective ingredients
for reducing spotting on the glassware during the wash,
regardless of the level of food residues present in the wash
liquor.
