Note: Descriptions are shown in the official language in which they were submitted.
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DETERGENT PARTICLES COMPRISING METAL-CONTAINING BLEACH
CATALYSTS
Technical Field
The present invention relates to bleach catalyst-containing particles, and
to the preparation of these bleach catalyst-containing particles. These
particles are particularly useful components of detergent compositions,
such as laundry detergent compositions, hard surface cleaners, and
especially automatic dishwashing detergent compositions.
BACKGROUND OF THE INVENTION
The use of certain bleach catalysts, particularly those comprising
cobalt or manganese compounds, in detergent compositions has
been previously suggested. A preferred way of incorporating
such bleach catalyst components is in small particulate form.
However, the direct incorporation of small bleach catalyst
particles at typically very low levels into particulate detergent
compositions can present problems. Such compositions typically,
should be made up of particles having mean sizes which are all
similar to each other in order to avoid segregation of components
in the composition. Such compositions also often comprise
particles having mean particles size in a defined range of from
about 400 to about 2400 microns, more usually from about 500 to
about 2000 microns, to achieve good flow and absence of
dustiness properties. Any fine or oversize particles outside these
limits must generally be removed by sieving to avoid a particle
segregation problem. Fine bleach catalyst particles in a detergent
composition matrix may also cause chemical stability problems
caused by a tendency of the f ne particles to interact with other
components of the overall composition, such as other bleach
components.
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It has now been found that the above described problems may be
surprisingly ameliorated by incorporating the bleach catalyst as
composite particles in the form of micro-encapsulates which have
a size distribution smaller to that of the other components of the
particulate detergent composition, and which allow delivery of
the bleach catalyst particle into the wash solution.
Summary of the Invention
The present invention relates to bleach catalyst containing
composite particles suitable for incorporation into particulate
detergent compositions, said composite particles comprising by
weight of the particles
a) from 1 % to 50 % of the metal-containing bleach catalyst;
b) from 40 % to 99 % of the encapsulating material; and
c) from 0.5 % to 20 % water.
Detailed Description of the Invention
The compositions according to the present invention comprise
discrete particles of bleach catalyst and an encapsulating material.
These particles may optionally contain other components, such as
stabilizing additives and/or diluents. Each of these materials, the
steps in the composite particle preparation process, the particles
so prepared and particulate detergents containing these particles
are described in detail hereinafter.
Metal-containing Bleach Catalysts-
The present composite particles comprise metal-containing bleach
catalysts. Preferred are manganese and cobalt-containing bleach
catalysts .
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One type of metal-containing bleach catalyst is a catalyst system
comprising a transition metal canon of defined bleach catalytic
activity, such as copper, iron, titanium, ruthenium tungsten,
molybdenum, or manganese cations, an auxiliary metal cation
having little or no bleach catalytic activity, such as zinc or
aluminum cations, and a sequestrate having defined stability
constants for the catalytic and auxiliary metal canons, particu-
larly ethylenediaminetetraacetic acid, (methyienephosphonic
acid) and water-soluble salts thereof. Such catalysts are disclosed
in U.S. Pat. 4,430,243.
Other types of bleach catalysts include the manganese-based
complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat.
5,244,594. Preferred examples of these catalysts include
MnIV2(u-O)3( 1,4, 7-trimethyl-1,4, 7-triazacyciononane)2-(PF6)2
("MnTACN"), MnIII2(u-O)1(u-OAc)2(1,4,7-trimethyl-1,4,7-
triazacyclononane)2-(C104)2, MnIV4(u-O)6(i,4,7-
triazacyclononane)4-(C104)2,MnIIIMnIV4(u-O) 1 (u-OAc)2_
{1,4,7-trimethyl-1,4,7-triazacyclononane)2-(C104)3, and
mixtures thereof. See also European patent application
publication no. 549,272. Other ligands suitable for use herein
include I,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-
1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, and
mixtures thereof.
Bleach catalysts of particular use in automatic dishwashing
compositions and concentrated powder detergent compositions
may also be selected as appropriate for the present invention.
For examples of suitable bleach catalysts see U.S. Pat. 4,246,612
and U.S. Pat. 5,227,084.
See also U.S. Pat. 5,194,416 which teaches mononuclear
manganese (IV) complexes such as Mn{1,4,7-trimethyl-1,4,7-
triazacyclononane(OCH3)3_(PF6).
Still another type of bleach catalyst, as disclosed in U.S. Pat.
5,114,606, is a water-soluble complex of manganese (II), (III),
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andlor (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.
U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a
complex of transition metals, including Mn, Co, Fe, or Cu, with
an non-(macro)-cyclic ligand. Said Iigands are of the formula:
R' R3
R L-N =C-B-C=N-R''
wherein R1, R2, R3, and R4 can each be selected from H,
substituted alkyl and aryl groups such that each R1-N=C-R2 and
R3-C = N-R4 form a five or six-membered ring . Said ring can
further be substituted. B is a bridging group selected from O, S.
CRSR6, NR~ and C=O, wherein R5, R6, and R~ can each be H,
alkyl, or aryl groups, including substituted or unsubstituted
groups. Preferred ligands include pyridine, pyridazine,
pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings.
Optionally, said rings may be substituted with substituents such
as alkyl, aryl, alkoxy, halide, and vitro. Particularly preferred is
the ligand 2,2'-bispyridylamine. Preferred bleach catalysts
include Co, Cu, Mn, Fe,-bispyridylmethane and -
bispyridyiamine complexes. Highly preferred catalysts include
Co(_2,2'-bispyridylamine)C12, Di(isothiocyanato)bispyridylamine-
cobalt (II), trisdipyridylamine-cobalt(II) perchlorate, Co(2,2-
bispyridylamine)202C104, Bis-(2,2'-bispyridylamine) copper(II)
perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and
mixtures thereof.
Other examples include Mn gluconate, Mn(CF3S03)2,
Co(NH3)SCI, and the binuclear Mn complexed with tetra-N-
dentate and bi-N-dentate ligands, including N4MnIII(u_
O)2MnIVN4)+and [BipY2MnIII(u_p)2MnIVbipY2l-(C104)3.
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The bleach catalysts may also be prepared by combining a water-
soluble ligand with a water-soluble manganese salt in aqueous
media and concentrating the resulting mixture by evaporation.
' Any convenient water-soluble salt of manganese can be used
herein. Manganese (II), (III), (IV) and/or (V) is readily available
' on a commercial scale.
Other bleach catalysts are described, for example, in European
patent application, publication no. 408,131 (cobalt complex
catalysts), European patent applications, publication nos.
384,503, and 306,089 (metallo-porphyrin catalysts), U.S.
4,728,455 (manganese/multidentate ligand catalyst), U.S.
4,711,748 and European patent application, publication no.
224,952, (absorbed manganese on aluminosilicate catalyst), U.S.
4,601,845 {aluminosilicate support with manganese and zinc or
magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst),
U.S. 4,119,557 (ferric complex catalyst), German Pat.
specification 2,054,019 {cobalt chelant catalyst) Canadian
866,191 (transition metal-containing salts), U.S. 4,430,243
(chelants with manganese cations and non-catalytic metal
rations), and U.S. 4,728,455 (manganese gluconate catalysts).
Preferred are cobalt (III) catalysts having the formula:
Co[(NH3)nM'mB'bT'tQqPp~ Yy
wherein cobalt is in the +3 oxidation state; n is an integer from 0
to 5 (preferably 4 or 5; most preferably 5); M' represents a
monodentate ligand; m is an integer from 0 to 5 (preferably 1 or
2; most preferably 1); B' represents a bidentate ligand; b is an
integer from 0 to 2; T' represents a tridentate ligand; t is 0 or 1;
~ is a tetradentate ligand; q is 0 or 1; P is a pentadentate ligand;
pis0orl;andn+m+2b+3t+4q+Sp=6;Yisoneor
more appropriately selected counteranions present in a number y,
where y is an integer from 1 to 3 (preferably 2 to 3; most
preferably 2 when Y is a -1 charged anion), to obtain a charge-
balanced salt, preferred Y are selected from the group consisting
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of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate,
and combinations thereof; and wherein further at least one of the
coordination sites attached to the cobalt is labile under automatic
dishwashing use conditions and the remaining coordination sites '
stabilize the cobalt under automatic dishwashing conditions such
that the reduction potential for cobalt (III) to cobalt (II) under '
alkaline conditions is less than about 0.4 volts (preferably less
than about 0.2 volts) versus a normal hydrogen electrode.
Preferred cobalt catalysts of this type have the formula:
[Co(NH3)n(M')m) YY
wherein n is an integer from 3 to 5 (preferably 4 or 5; most
preferably 5); M' is a labile coordinating moiety, preferably
selected from the group consisting of chlorine, bromine,
hydroxide, water, and (when m is greater than 1) combinations
thereof; m is an integer from 1 to 3 (preferably 1 or 2; most
preferably 1); m+n = 6; and Y is an appropriately selected
counteranion present in a number y, which is an integer from 1 to
3 (preferably 2 to 3; most preferably 2 when Y is a -1 charged
anion), to obtain a charge-balanced salt.
The preferred cobalt catalyst of this type useful herein are cobalt
pentaamine chloride salts having the formula [Co(NH3)5C1] Yy,
and especially [Co(NH3)SCI]CI2.
More preferred are the present invention compositions which
utilize cobalt (III) bleach catalysts having the formula:
[Co(NH3)n(M)m(B)bl TY
wherein cobalt is in the +3 oxidation state; n is 4 or 5
{preferably 5); M is one or more ligands coordinated to the
cobalt by one site; m is 0, 1 or 2 (preferably 1); B is a ligand
coordinated to the cobalt by two sites; b is 0 or 1 (preferably 0),
and when b = 0, then m + n = 6, and when b = I , then m = 0 and
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n=4; and T is one or more appropriately selected counteranions
present in a number y, where y is an integer to obtain a charge-
balanced salt (preferably y is 1 to 3; most preferably 2 when T is
- a -1 charged anion); and wherein further said catalyst has a base
hydrolysis rate constant of less than 0.23 M-1 s-1 (25°C).
Preferred T are selected from the group consisting of chloride,
iodide, I3-, formate, nitrate, nitrite, sulfate, sulfite, citrate,
acetate, carbonate, bromide, PF6-, BFq.-, B(Ph)q.-, phosphate,
phosphate, silicate, tosylate, methanesulfonate, and combinations
thereof. Optionally, T can be protonated if more than one
anionic group exists in T, e.g., HPOq.2-, HC03-, H2P04-, etc.
Further, T may be selected from the group consisting of non-
traditional inorganic anions such as anionic surfactants (e.g.,
linear alkylbenzene sulfonates (LAS), alkyl sulfates (AS),
alkylethoxysulfonates (AES), etc.) and/or anionic polymers (e.g.,
polyacrylates, polymethacrylates, etc.).
The M moieties include, but are not limited to, for example, F-,
SOq.-2, NCS-, SCN-, S203-2, NH3, P043-, and carboxylates
(which preferably are mono-carboxylates, but more than one
carboxylate may be present in the moiety as long as the binding
to the cobalt is by only one carboxylate per moiety, in which case
the other carboxylate in the M moiety may be protonated or in its
salt form). Optionally, M can be protonated if more than one
anionic group exists in M (e.g., HPOq.2-, HC03-, H2P04-,
HOC(O)CH2C(O)O-, etc.) Preferred M moieties are substituted
and unsubstituted C I-C30 carboxylic acids having the formulas:
RC(O)O-
wherein R is preferably selected from the group consisting of
hydrogen and C 1-C30 (preferably C 1-C 1 g) unsubstituted and
substituted alkyl, C6-C30 (preferably C6-C 1 g) unsubstituted and
substituted aryl, and C3-C30 (preferably CS-Clg) unsubstituted
and substituted heteroaryl, wherein substituents are selected from
the group consisting of -NR' 3, -NR'q.'~' , -C(O)OR' , -OR' , -
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C(O)NR'2, wherein R' is selected from the group consisting of
hydrogen and C 1-C6 moieties. Such substituted R therefore
include the moieties -(CH2)nOH and -(CH2)nNR'4+, -wherein n
is an integer from 1 to about 16, preferably from about 2 to about
10, and most preferably from about 2 to about 5.
Most preferred M are carboxylic acids having the formula above
wherein R is selected from the group consisting of hydrogen,
methyl, ethyl, propyl, straight or branched C4-C 12 alkyl, and
benzyl. Most preferred R is methyl. Preferred carboxylic acid
M moieties include formic, benzoic, octanoic, nonanoic,
decanoic, dodecanoic, malonic, malefic, succinic, adipic,
phthalic, 2-ethylhexanoic, naphthenoic, oleic, palmitic, triflate,
tartrate, stearic, butyric, citric, acrylic, aspartic, fumaric, lauric,
linoleic, lactic, malic, and especially acetic acid.
The B moieties include carbonate, di- and higher carboxylates
(e.g., oxalate, malonate, malic, succinate, maleate), picolinic
acid, and alpha and beta amino acids (e.g., giycine, alanine,
beta-alanine, phenylalanine).
Cobalt bleach catalysts useful herein are known, being described
for example along with their base hydrolysis rates, in M. L.
Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv.
Inorg. Bioinorg. Mech., (1983), 2, pages 1-94. For example,
Table I at page 17, provides the base hydrolysis rates (designated
therein as kOH) for cobalt pentaamine catalysts comglexed with
oxalate (kOH= 2.5 x IO-4 M-1 s-1 (25°C)), NCS- {kpH= S.0 x
10-4 M-1 s-I (25°C)), formate (kpH= S.8 x 10-4 M-1 s-1 (25°
C)), and acetate {kOH= 9.6 x 10-4 M-I s-1 (25°C)). The most
preferred cobalt catalyst useful herein are cobalt pentaamine
acetate salts having the formula [Co(NH3)SOAc] Ty, wherein
OAc represents an acetate moiety, and especially cobalt
pentaamine acetate chloride, [Co(NH3)SOAc]C12; as well as
[Co(NH3}SOAc](OAc)2; [Co(NH3)SOAc]{PF6)2;
[Co(NH3)SOAc]{S04); [Co(NH3)SOAc](BF4)2; and
[Co(NH3)SOAc](N03)2 (herein "PAC").
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These cobalt catalysts are readily prepared by known procedures,
such as taught for example in the Tobe article hereinbefore and
the references cited therein, in U.S. Patent 4,810,410, to Diakun
et al, issued March 7,1989, J. Chem. Ed. (1989), f6 (12), 1043-
45; The Synthesis and Characterization of Inorganic Compounds,
W.L. Jolly (Prentice-Hall; 1970), pp. 461-3; Inorg_ Chem., 18,
1497-1502 (1979); Inorg. Chem., 21, 2881-2885 (1982); Inor~.
Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960);
and Journal of Physical Chemistry, 56, 22-25 ( 1952); as well as
the synthesis examples provided hereinafter.
The bleach catalyst-containing composite particles of the
invention comprise from 1 to 50 % , preferably from 2 % to 30 % ,
most preferably from 3 % to 25 % by weight of the metal-
containing bleach catalyst.
As a practical matter, and not by way of limitation, the cleaning
compositions and cleaning processes herein can be adjusted to
provide on the order of at least one part per hundred million of
the active bleach catalyst species in the aqueous washing
medium, and will preferably provide from about 0.01 ppm to
about 25 ppm, more preferably from about 0.05 ppm to about 10
ppm, and most preferably from about 0.1 ppm to about 5 ppm, of
the bleach catalyst species in the wash liquor. In order to obtain
such levels in the wash liquor of an automatic dishwashing
process, typical automatic dishwashing compositions herein will
comprise from about 0.0005 % to about 0.2 % , more preferably
from about 0.004 % to about 0.08 % , of bleach catalyst by weight
of the cleaning compositions.
Micro-encapsulates
The bleach catalyst-containing composite particles are comprised
of from 40 % to 99 % by weight, preferably 50 % to 98 % by
weight, most preferably 60 % to 97 % by weight encapsulating
material.
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The encapsulating material should be inert to reaction with the
bleach catalyst component of the particle under processing
conditions and after solidification. Furthermore the encapsulating
material is preferably water-soluble. Additionally, the
encapsulating material should be substantially free of moisture '
present as unbound water.
Examples of suitable encapsulating materials include gelatine,
hydrolyzed gelatine, film forming carbohydrates. Preferred
encapsulating materials are low-bloom gelatin, hydrolyzed
gelatine, and film-forming carbohydrates including dextrin and
gum Arabic.
The metal-containing bleach catalyst encapsulated composition
described above can be prepared by a method comprising
(1) dissolving the metal-containing bleach catalyst in an aqueous
medium,
(2) mixing the metal-containing bleach catalyst solution with an
aqueous solution of the encapsulating material,
(3) converting the mixture thus obtained into droplets of an
average particle size not exceeding 450 micrometer and
(4) reducing the moisture content of said particles to a value of
between 0.5 % and 20 % by weight to form a solid solution
of the metal-containing bleach catalyst in the encapsulating
material .
The encapsulating material should preferably have a molecular
weight which is substantially higher than that of the metal-
containing bleach catalyst. Thus, if the size of the molecules of
the metal-containing bleach catalyst is less than about 0.6 of that
of the encapsulating material, an extensive interstitial solid
solution i.e. a solid solution in which the solute molecules occupy
the interstitial space of the solvent lattice is obtained.
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The conversion of the mixture into droplets and the reduction of
the moisture content of the droplets are preferably effected by a
spray-drying technique.
In a preferred embodiment of the method of the invention the
mixture is spray-dried at an elevated temperature of below 100°C
while introducing a fine powder into the spray drying zone, as
explained in US patent specification no. 2,756,177. The fine
powder can be silicate or finely divided corn starch, preferably
finely divided corn starch.
In another preferred embodiment the mixture is spray-dried at a
temperature of above 100 ° C .
In a preferred embodiment, sugar (saccharose) or glucose syrup
can be added to the mixture to be spray-dried in order to lower
the viscosity of the mixture, the weight ratio of encapsulating
material to sugar being at least 35:65, preferably 50:50.
Preferably an oil such as coconut oil is incorporated in the
mixture to be spray-dried in the form of an emulsion. The
presence of the oil facilitates the formation of droplets when the
mixture is spray-dried, and amounts of from 2 % to 20 % by
weight, preferably 3 % to 10 % by weight are used. The most
preferred amount of oil is 5 % by weight.
The dry matter content of the mixture to be spray-dried may vary
within wide ranges but the viscosity is preferably maintained
within the range of from 70 cp to 200 cp at 60 ° C .
Preferably, the composite particles herein have a particle size of
from 10 to 450 micrometers.
Compositions, including detergent compositions herein,
preferably contain composite particles having a particle size
distribution such that at least 50 % by weight of the particles have
a particle size in the range of from 10 to 450 micrometers.
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Detergent Compositions
The micro-encapsulated particles herein are useful components of
detergent compositions, particularly those designed for use in
automatic dishwashing methods.
Detergent compositions according to the invention preferably
contains the bleach catalyst composition described above in an
amount of from 2 ppm to 1,000 ppm preferably from IO ppm to
100 ppm by weight of detergent composition of the pure bleach
catalyst by weight of the detergent composition.
The detergent composition may additionally contain detergent ingredients
e.g. builder components, other bleaches, bleach activators, silicates,
dispersant polymers, surfactants, enzyme stabilizers, suds suppressers,
corrosion inhibitors, fillers, hydrotropes and perfumes.
A preferred granular or powdered detergent composition comprises by
weight:
(a) from about O.I % to about 10% of the bleach catalyst composite
particles as hereinbefore described;
(b) a bleach component comprising from about 0.01 % to about 8 % (as
available oxygen "Av0") of a peroxygen bleach;
(c) from about 0.1 % to about 90 % of a pH adjusting component
consisting of water-soluble salt, builder or salt/builder mixture
selected from the group consisting of the alkali and alkaline earth
metal phosphates, carbonates, sesquicarbonates, citrates,
bicarbonates, and hydroxides, citric acid and mixtures thereof;
{d) from about 3 % to about 20 % silicate (as Si02);
(e) from 0 % to about 10 % of a low-foaming nonionic surfactant,
especially other than an amine oxide;
{f) from 0 % to about 10 % of a suds suppresser;
(g) from 0 % to about 25 % of a dispersant polymer.
Such compositions are typically formulated to provide an in-use wash
solution pH from about 9.5 to about 11.5.
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Bleaches
The fully-formulated detergent compositions herein preferably contain an
oxygen bleaching source. Oxygen bleach is employed in an amount
- sufficient to provide from 0.01 % to about 8 % , preferably from about
0.1 % to about 5.0 % , more preferably from about 0.3 % to about 4.0 % ,
most preferably from about 0.5 % to about 3 % of available oxygen (Av0)
by weight of the detergent composition.
Available oxygen of a detergent composition or a bleach component is the
equivalent bleaching oxygen content thereof expressed as % oxygen. For
example, commercially available sodium perborate monohydrate typically
has an available oxygen content for bleaching purposes of about 15
(theory predicts a maximum of about 16 % ). Methods for determining
available oxygen of a formula after manufacture share similar chemical
principles but depend on whether the oxygen bleach incorporated therein
is a simple hydrogen peroxide source such as sodium perborate or
percarbonate, is an activated type (e.g., perborate with tetra-acetyl
ethylenediamine) or comprises a performed peracid such as
monoperphthalic acid. Analysis of peroxygen compounds is well-known
in the art: see, for example, the publications of Swern, such as "Organic
Peroxides", Vol. I, D. H. Swern, Editor; Wiley, New York, 1970, L~C #
7Z-84965, incorporated by reference. See for example the calculation of
"percent active oxygen" at page 499. This term is equivalent to the terms
"available oxygen" or "percent available oxygen" as used herein.
The peroxygen bleaching systems useful herein are those capable of
yielding hydrogen peroxide in an aqueous liquor. These compounds
include but are not limited to the alkali metal peroxides, organic peroxide
bleaching compounds such as urea peroxide and inorganic persalt
bleaching compounds such as the alkali metal perborates, percarbonates,
perphosphates, and the like. Mixtures of two or more such bleaching
compounds can also be used.
Preferred peroxygen bleaching compounds include sodium perborate,
commercially available in the form of mono-, tri-, and tetra-hydrate,
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sodium pyrophosphate peroxvhydrate. urea peroxyhydrate, sodium
percarbonate, and sodium peroxide. Particularly preferred are sodium
perborate tetrahydrate, sodium perborate monohydrate and sodium
percarbonate. .
Suitable oxygen-type bleaches are further described in U.S. Patent No.
4,412,934 (Chung et al), issued November 1, 1983, and peroxyacid
bleaches described in European Patent Application 033,259. Sagel et al,
published September 13. 1989 .
Highly preferred percarbonate can be in uncoated or coated form. The
average particle size of uncoated percarbonate ranges from about 400 to
about 1200 microns, most preferably from about 400 to about 600
microns. If coated percarbonate is used, the preferred coating materials
include carbonate, sulfate, silicate, borosilicate, fatty carboxylic acids,
and mixtures thereof.
Preferably, the peroxygen bleach component in the composition is
formulated with an activator (peracid precursor). The activator is present
at levels of from about 0.01 % to about 15 % , preferably from about 1 % to
about 10 % , more preferably from about 1 % to about 8 % , by weight of
the composition. Preferred activators are selected from the group
consisting of tetraacetyi ethylene diamin (TAED), benzoylcaprolactam
(BzCL), 4-nitrobenzoylcaprolactam. 3-chiorobenzoylcaprolactam,
benzoyloxybenzenesulphonate IBOBS), nonanoyloxybenzenesulphonate
(NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulphonate (C 10-
OHSy, betuoylvalerolactam (BZVL), octanoyloxybenzenesulphonate (Cg-
OHS), perhydrolyzable esters and mixtures thereof, most preferably
benzoylcaprolactam and benzoylvalerolactam. Particularly preferred
bleach activators in the pH range from about 8 to about 9.5 are those
selected having an OBS or VL leaving group.
Preferred bleach activators are those described in U.S. Patent 5,130.045,
Mitchell et al, and 4.41?.934. Chung et al.
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The mole ratio of peroxygen bleaching compound (as Av0) to bleach
activator in the present invention generally ranges from at least 1:1,
preferably from about 20:1 to about 1:1, more preferably from about 10:1
to about 3:1.
Quaternary substituted bleach activators may also be included. The
present detergent compositions comprise a quaternary substituted bleach
activator (QSBA) or a quaternary substituted peracid (QSP); more
preferably, the former. -
The compositions in accordance with the present invention may also
comprise a diacylperoxide bleach. The diacyl peroxides are added
separately to the compositions at levels from about 0.01 % to about 15 % .
The individual diacyl peroxide particles used herein preferably have a
mean particle size of less than about 300 microns, preferably less than
about 200 microns, more preferably from about 1 to about 150 microns,
most preferably from about 10 to about 100 microns.
Tha~diacyt peroxide is preferably a diacyl peroxide of the general
formula:
RC(O)00(O)CR1
wherein R and R 1 can be the same or different, and each comprises a
hydrocarbyl group containing more than ten carbon atoms. Preferably, at
least one of these groups has an aromatic nucleus.
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Examples of suitable diacyl peroxides are those selected from the vroup
consisting of dibenzoyl peroxide ("benzoyl peroxide"), benzoyl elutaryl
peroxide, benioyl succinyl peroxide, di-(2-methybenzoyl) peroxide.
diphthaloyl peroxide and mixtures thereof, more preferably dibenzoyl
peroxide, diphthaloyl peroxides and mixtures thereof. The preferred
diacyl peroxide is dibenzoyl peroxide.
The diacyl peroxide thermally decomposes under wash conditions (i.e.
typically from about 38oC to about 7loC) to form free radicals. This
occurs even when the diacyl peroxide particles are water-insoluble.
Surprisingly, panicle size can play an important role in the performance
of the diacyl peroxide, not only in preventing residue deposit problems,
but also in enhancing the removal of stains, particularly from stained
plasticware. The mean particle size of the diacyl peroxide particles
produced in wash solution after dissolution of the particle composite
carrier material, as measured by a laser particle size analyzer (e.g.
Malvern) on an agitated mixture with water of the diacyI peroxide, is less
than about 300 microns, preferably less than about 200 microns.
Although water insolubility is an essential characteristic of the diacyl
peroxide used in the present invention, the size of the particles containing
it is also important for controlling residue formation in the wash and
maximizing stain removal performance.
Preferred diacyl peroxides used in the present compositions are also
formulated into a carrier material that melts within the range of from
about 38°C to about 77°C, preferably selected from the group
consisting
of polyethylene glycols, paraffin waxes, and mixtures thereof .
nH-Adiusting Control/Detere~y Builder Com vents
The detergent compositions herein will preferably provide wash solutions
having a pH of at least 7; therefore the compositions will typically
comprise a pH-adjusting detergency builder component selected from
water-soluble alkaline inorganic salts and water-soluble organic or
CA 02245560 1998-08-OS
V~'0 97!29174 PCT/US97/01462
17
inorganic builders. A wash solution pH of from 7 to about 13, preferably
from about 8 to about 12, more preferably from about 8 to about 11.0 is
desirable. The pH-adjusting components are selected so that when the
' detergent composition is dissolved in water at a concentration of 2000 -
6000 ppm, the pH remains in the ranges discussed above. The preferred
' non phosphate pH-adjusting component embodiments of the invention is
selected from the group consisting of:
{i) sodium/potassium carbonate or sesquicarbonate
{ii) sodium/potassium citrate
{iii) citric acid
{iv) sodium/potassium bicarbonate
(v) sodium/potassium borate, preferably borax
(vi) sodium/potassium hydroxide;
{vii) sodium/potassium silicate and
{viii) mixtures of (i)-(vii).
Illustrative of highly preferred pH-adjusting component systems are
binary mixtures of granular sodium citrate dihydrate with anhydrous
sodium carbonate, and three-component mixtures of granular sodium
citrate dihydrate, sodium carbonate and sodium disilicate.
The amount of the pH adjusting component included in the detergent
compositions is generally from about 0.9 % to about 99 % , preferably from
about 5 % to about 70 % , more preferably from about 20 % to about 50
by weight of the composition.
Any pH-adjusting system can be complemented (i.e. for improved
sequestration in hard water) by other optional detergency builder salts
selected from phosphate or nonphosphate detergency builders known in
the art, which include the various water-soluble, alkali metal, ammonium
or substituted ammonium borates, hydroxysulfonates, polyacetates, and
polycarboxylates. Preferred are the alkali metal, especially sodium, salts
of such materials. Alternate water-soluble, non-phosphorus organic
builders can be used for their sequestering properties. Examples of
polyacetate and polycarboxylate builders are the sodium, potassium,
lithium, ammonium and substituted ammonium salts of ethylenediamine
CA 02245560 2000-10-25
18
tetraacenc acid, ethylenediamine disuccinic acid (especially the S.S-form):
nitrilotriacetic acid, tartrate monosuccinic acid, tartrate disuccinic acid,
oxydiacetic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid,
melIitic acid. and sodium benzene polycarboxylate salts.
The detergency builders can be any of the detergency builders known in
the art, which include the various water-soluble, alkali metal, ammonium
or substituted ammonium phosphates, polyphosphates, phosphonates,
polyphosphonates, carbonates, borates, polyhydroxysulfonates,
polyacetates, carboxylates (e.g. citrates), aluminosilicates and
polycarboxylates. Preferred are the alkali metal, especially sodium, salts
of the above and mixtures thereof.
Specific examples of inorganic phosphate detergency builders which also
serve to adjust pH are sodium ("STPP") and potassium tripolyphosphates.
pyrophosphate, polymeric metaphosphate having a degree of
polymerization of from about 6 to 21, and orthophosphate. Examples of
poiyphosphonate builders are the sodium and potassium salts of ethylene
diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-1,
I-diphosphonic acid and the sodium and potassium salts of ethane, 1, I,2-
triphosphonic acid. Other phosphorus builder compounds are disclosed in
L;.S. Patent Nos. 3.159.581; 3.213.030: 3,422.021; 3,422.137,
3,400.176 and 3.400,148.
ion-phosphate detergency builders include but are not limited to the
various water-soluble, alkali metal, ammonium or substituted ammonium
borates, hydroxysulfonates, polyacetates, and polycarboxylates.
Preferred are the alkali metal, especially sodium, salts of such materials.
Alternate water-soluble, non-phosphorus organic builders can be used for
their sequestering properties. Examples of polyacetate and
poiycarboxylate builders are the sodium, potassium, lithium, ammonium
and substituted ammonium salts of ethylenediamine tetraacetic acid,
ethylenediamine disuccinic acid (especially the S,S- form); nitrilotriacetic
acid, tarcrate monosuccinic acid, tartrate disuccinic acid, oxydisuccinic
acid, carboxymethyioxysuccinic acid, mellitic acid, and sodium benzene
polycarboxylate salts.
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19
In general, the pH values of the detergent compositions can vary during
the course of the wash as a result of the water and soil present. The best
procedure for determining whether a given composition has the herein-
indicated pH values is as follows: prepare an aqueous solution or
dispersion of all the ingredients of the composition by mixing them in
finely divided form with the required amount of water to have a 3000 ppm
total concentration. Measure the pH using a conventional glass electrode
at ambient temperature, within about 2 minutes of forming the solution or
dispersion. To be clear, this procedure relates to pH measurement and is
not intended to be construed as limiting of the detergent compositions in
any way; for example, it is clearly envisaged that fully-formulated
embodiments of the instant detergent compositions may comprise a variety
of ingredients applied as coatings to other ingredients.
Silicates
The compositions of the type described herein optionally, but preferably
comprise alkali metal silicates and/or metasilicates. The alkali metal
silicates hereinafter described provide pH adjusting capability (as
described above), protection against corrosion of metals and against attack
on dishware, inhibition of corrosion to glasswares and chinawares. The
Si02 level is from about 0.5 % to about 20 % , preferably from about 1
to about 15 % , more preferably from about 2 % to about 12 % , most
preferably from about 3 % to about 10 % , based on the weight of the
detergent composition.
The ratio of Si02 to the alkali metal oxide (M20, where M=alkali metal)
is typically from about 1 to about 3.2, preferably from about 1 to about 3,
more preferably from about 1 to about 2.4. Preferably, the alkali metal
silicate is hydrous, having from about 15 % to about 25 % water, more
preferably, from about 17 % to about 20 % . Metasilicate having an
Si02:M20 ratio of about 1:1 is also useful.
Anhydrous forms of the alkali metal silicates with a Si02:M20 ratio of
2.0 or more are also less preferred because they tend to be significantly
less soluble than the hydrous alkali metal silicates having the same ratio.
CA 02245560 1998-08-OS
WO 97129174 PCT/US97/01462
Sodium and potassium, and especially sodium, silicates are preferred. A
particularly preferred alkali metal silicate is a granular hydrous sodium
silicate having a Si02:Na20 ratio of from 2.0 to 2.4 available from PQ
Corporation, named Britesil H20 and Britesil H24. Most preferred is a
granular hydrous sodium silicate having a Si02:Na20 ratio of 2Ø 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 % smaller than I 50
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.
Other suitable silicates include the crystalline layered sodium silicates
have the general formula:
NaMSix02x + 1. yH20
wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a
number from 0 to 20. Crystalline layered sodium silicates of this type are
disclosed in EP-A-0164514 and methods for their preparation are
disclosed in DE-A-3417649 and DE-A-3742043. For the purpose of the
present invention, x in the general formula above has a value of 2, 3 or 4.
The most preferred material is 8-Na2Si205, available from Hoechst AG
as NaSKS-6.
The crystalline layered sodium silicate material is preferably present in
granular detergent compositions as a particle in intimate admixture with a
solid, water-soluble ionisable material. The solid, water-soluble ionisable
material is selected from organic acids, organic and inorganic acid salts
and mixtures thereof.
Low-Foaming Nonionic Surfactant
Detergent compositions of the present invention can comprise low
foaming nonionic surfactants (LFNIs). LFNI can be present in amounts
from 0 to about 10 % by weight, preferably from about 1 % to about 8 % ,
more preferably from about 0.25 % to about 4 % . LFNIs are most
CA 02245560 2000-10-25
21
typically used in detergent compositions on account of the improved
water-sheeting action (especially from glass) which they confer to the
detergent composition product. They also encompass non-silicone,
nonphosphate polymeric materials further illustrated hereinafter which are
known to defoam food soils encountered in automatic dishwashing.
Preferred LFNIs include nonionic alkoxylated surfactants, especially
ethoxylates derived from primary alcohols, and blends thereof with more
sophisticated surfactants, such as the polyoxypropyiene/polyoxyethylene/
polyoxypropylene reverse block polymers. The PO/EO/PO polymer-type
surfactants are well-known to have foam suppressing or defoaming action,
especially in relation to common food soil ingredients such as egg.
The invention encorripasses preferred embodiments wherein LFNI is
present, and wherein this component is solid at temperatures below about
100oF, more preferably below about 120oF.
In a preferred embodiment, the LFNI is 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,
with from about 6 to about 15 moles of ethylene oxide per mole of alcohol
or alkyl phenol on an average basis.
A particularly preferred LFNI is derived from a straight chain fatty
alcohol containing from about 16 to about 20 carbon atoms (C 16-C20
alcohol), preferably a C 1 g 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 relative to the average.
The LFNI can optionally contain propylene oxide in an amount up to
about 15 7 by weight. Other preferred LFNI surfactants can be prepared
by the processes described in U.S. Patent 4,223,163, issued September
16, 1980, Buillory .
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22
Highly preferred detergent compositions herein wherein the LFNI is
present make use of ethoxylated monohydroxy alcohol or alkyl phenol and
additionally comprise a polyoxyethylene, polyoxypropylene block
polymeric compound; the ethoxylated monohydroxy alcohol or alkyl
phenol fraction of the LFNI comprising from about 20 % to about 80 % ,
preferably from about 30 % to about 70 % , of the total LFNI.
Suitable block polyoxyethylene-polyoxypropylene polymeric compounds
that meet the requirements described herein before include those based on
ethylene glycol, propylene glycol, glycerol, trimethylolpropane and
ethylenediamine as initiator reactive hydrogen compound. Polymeric
compounds made from a sequential ethoxylation and propoxylation of
initiator compounds with a single reactive hydrogen atom, such as C 12-18
aliphatic alcohols, do not generally provide satisfactory suds control in the
instant detergent compositions. Certain of the block polymer surfactant
compounds designated PLURONIC~ and TETRONIC~ by the BASF-
Wyandotte Corp., Wyandotte, Michigan, are suitable in detergent
composition compositions herein.
A particularly preferred LFNI contains from about 40 % to about 70 % of
a polyoxypropylene/polyoxyethylene/polyoxypropylene 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 polyoxyethyiene and
pol~xypropylene initiated with trimethylolpropane and containing 99
moles of propylene oxide and 24 moles of ethylene oxide per mole of
trimethylolpropane.
Suitable for use as LFNI in the detergent composition compositions are
those LFNI having relatively low cloud points and high hydrophilic-
lipophilic balance (HLB) . Cloud points of 1 % solutions in water are
typically below about 32oC and preferably lower, e.g., OoC, for optimum
control of sudsing throughout a full range of water temperatures.
LFNIs which may also be used include a C 1 g alcohol polyethoxylate,
having a degree of ethoxylation of about 8, commercially available SLF18
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w'O 97!29174 PCT/US97/OI462
23
from Olin Corp. and any biodegradable LFNI having the melting point
properties discussed herein above.
CA 02245560 2000-10-25
24
Anionic Co-surfactant
The automatic dishwashing detergent compositions herein can additionally
contain an anionic co-surfactant. When present, the anionic co-surfactant
is typically in an amount from 0~ to about 10%, preferably from about
0.1 ~o to about 8 % , more preferably from about 0.5 % to about 5 % , by
weight of the detergent composition.
Suitable anionic co-surfactants include branched or linear alkyl sulfates
and sulfonates. These may contain from about 8 to about 20 carbon
atoms. Other anionic cosurfactants include the alkyl benzene sulfonates
containing from about 6 to about 13 carbon atoms in the alkyl group, and
mono- and/or dialkyl phenyl oxide mono- and/or di-sulfonates wherein the
alkyl groups contain from about 6 to about 16 carbon atoms. All of these
anionic co-surfactants are used as stable salts, preferably sodium and/or
potassium.
Preferred anionic co-surfactants include sulfobetaines, becaines,
alkyl(polyethoxy)sulfates (AES) and alkyl (polyethoxy)carboxylates which
are usually high sudsing. Optional anionic co-surfactants are further
illustrated in published British Patent Application No. 2.116,199A; U.S.
Pat. No. 4,005.0?7, Hartman: U.S. Pat. No. 4,116.851, Rupe et al; and
U.S. Pat. No. 4.116.849, Leikhim .
Preferred alkyl(polyethoxy)sulfate surfactants comprise a primary alkyl
ethoxy sulfate derived from the condensation product of a C6-C 1 g alcohol
wit~t an average of from about 0.5 to about 20, preferably from about 0.5
to about 5, ethylene oxide groups. The C6-C I g alcohol itself is
preferable commercially available. C 1 ~-C 15 alkyl sulfate which has been
ethoxylated with from about 1 to about 5 moles of ethylene oxide per
molecule is preferred. Where the compositions of the invention are
formulated to have a pH of between 6.5 to 9.3, preferably between 8.0 to
9, wherein the pH is defined herein to be the pH of a 1 % solution of the
composition measured at 20oC, surprisingly robust soil removal,
particularly proteolytic soil removal, is obtained when C 10-C 1 g alkyl
ethoxysulfate surfactant, with an average degree of ethoxylation of from
CA 02245560 1998-08-OS
WO 97129174 PCTIU897/01462
0.5 to S is incorporated into the composition in combination with a
proteolytic enzyme, such as neutral or alkaline proteases at a level of
active enzyme of from 0.005 % to 2 % . Preferred alkyl(polyethoxy)sulfate
surfactants for inclusion in the present invention are the C 12-C 15 alkyl
ethoxysulfate surfactants with an average degree of ethoxylation of from I
to 5, preferably 2 to 4, most preferably 3.
Conventional base-catalyzed ethoxylation processes to produce an average
degree of ethoxylation of I2 result in a distribution of individual
ethoxylates ranging from 1 to 15 ethoxy groups per mole of alcohol, so
that the desired average can be obtained in a variety of ways. Blends can
be made of material having different degrees of ethoxylation and/or
different ethoxylate distributions arising from the specific ethoxylation
techniques employed and subsequent processing steps such as distillation.
Alkyl(polyethoxy)carboxylates suitable for use herein include those with
the formula RO(CH2CH20)x CH2C00-M+ wherein R is a C6 to C25
alkyl group, x ranges from O to 10, preferably chosen from alkali metal,
alkaline earth metal, ammonium, mono-, di-, and tri-ethanol-ammonium,
most preferably from sodium, potassium, ammonium and mixtures thereof
with magnesium ions. The preferred alkyl(polyethoxy)carboxylates are
those where R is a C 12 to C I g alkyl group .
Highly preferred anionic cosurfactants herein are sodium or potassium
salt-forms for which the corresponding calcium salt form has a low Kraft
temperature, e.g., 30oC or below, or, even better, 20oC or lower.
Examples of such highly preferred anionic cosurfactants are the
alkyl(poiyethoxy)sulfates.
Detersive Enzymes (includin~~iuncts)
Enzymes included in the present detergent compositions for a variety of
purposes, including removal of protein-based, carbohydrate-based, or
triglyceride-based stains from surfaces such as textiles or dishes, for the
prevention of refugee dye transfer, for example in laundering, and for
fabric restoration. Suitable enzymes include proteases, amylases, lipases,
cellulases, peroxidases, and mixtures thereof of any suitable origin, such
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WO 97/29174 PCT/US97/01462
26
as vegetable, animal, bacterial, fungal and yeast origin. Preferred
selections are influenced by factors such as pH-activity and/or stability
optima, thermostability, and stability to active detergents, builders and the
like. In this respect bacterial or fungal enzymes are preferred, such as
bacterial amylases and proteases, and fungal cellulases.
"Detersive enzyme", as used herein, means any enzyme having a
cleaning, stain removing or otherwise beneficial effect in an ADD,
laundry, hard surface cleaning or personal care detergent composition.
Preferred detersive enzymes are hydrolases such as proteases, amylases
and Iipases. Preferred enzymes for laundry purposes include, but are not
limited to, proteases, cellulases, lipases and peroxidases. Highly preferred
for automatic dishwashing are amylases and/or proteases, including both
current commercially available types and improved types which, though
more and more bleach compatible though successive improvements, have
a remaining degree of bleach deactivation susceptibility.
Enzymes are normally incorporated into detergent or detergent additive
compositions at levels sufficient to provide a "cleaning-effective amount" .
The term "cleaning effective amount" refers to any amount capable of
producing a cleaning, stain removal, soil removal, whitening,
deodorizing, or freshness improving effect on substrates such as fabrics,
dishware and the like. In practical terms for current commercial
preparations, typical amounts are up to about 5 mg by weight, more
typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent
composition. Stated otherwise, the finished detergent compositions herein
will typically comprise from 0.001 % to 5 % , preferably 0.01 % -1 % by
weight of a commercial enzyme preparation. Accordingly, the composite
particles herein will comprise from about 0.1 % to about 15 % , preferably
from about 1 % to about 10% , by weight of enzyme. Protease enzymes
are usually present in such commercial preparations at levels sufficient to
provide from 0.005 to 0.1 Anson units (AU) of activity per gram of
composition. For certain detergents, such as in automatic dishwashing, it
may be desirable to increase the active enzyme content of the commercial
preparation in order to minimize the total amount of non-catalytically
active materials and thereby improve spotting/filming or other end-results.
CA 02245560 2000-10-25
27
Higher active levels may also be desirable in highly concentrated
detergent formulations.
Suitable examples of proteases are the subtilisins which are obtained from
particular strains of B. subtilis and B. licheniformis. One suitable
protease is obtained from a strain of Bacillus, having maximum activity
throughout the pH range of 8-12, developed and sold as ESPERASE~ by
Novo Industries A/S of Denmark, hereinafter "Novo". The preparation
of this enzyme and analogous enzymes is described in GB 1,243,784 to
Novo. Other suitable proteases include ALCALASE~ and SAVINASE~
from Novo and MAXATASE~ from International Bio-Synthetics, Inc.,
The Netherlands; as well as Protease A as disclosed in EP 130,756 A,
January 9, 1985 and Protease B as disclosed in EP 303,761 A. April 28,
1987 and EP 130,756 A, January 9, 1985. See also a high pH protease
from Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo.
Enzymatic detergents comprising protease, one or more other enrymes,
and a reversible protease inhibitor are described in WO 9203529 A to
Novo. Other preferred proteases include those of WO 9510591 A to
Procter & Gamble . When desired, a protease having decreased
adsorption and increased hydrolysis is available as described in WO
9507791 to Procter & Gamble. A recombinant trypsin-like protease for
detergents suitable herein is described in WO 9425583 to Novo.
In more detail, an especially preferred protease, referred to as "Protease
D" is a carbonyl hydrolase variant having an amino acid sequence not
found in nature, which is derived from a precursor carbonyl hydrolase by
substituting a different amino acid for a plurality of amino acid residues at
a po4ition in said carbonyl hydrolase equivalent to position +76,
preferably also in combination with one or more amino acid residue
positions equivalent to those selected from the group consisting of +99,
+ 101, + 103, + 104, + 107, + 123, +27, + 105, + 109, + 126, + 128,
+ 135, + 156, + 166, + 195, + 197, +204, +206, +210, +216, +217,
+218, +?22, +260, +265, and/or +274 according to the numbering of
Bacillus amyloliquefaciens subtilisin.
CA 02245560 2000-10-25
28
Amylases suitable herein, especially for, but not limited to automatic
dishwashing purposes, include, for example, a-amylases described in GB
1.296,839 to Novo; RAPIDASE~, International Bio-Synthetics, Inc. and
TERMAMYL~. Novo. FUNGAMYL'~ from Novo is especially useful.
Engineering of enzymes for improved stability, e.g., oxidative stability, is
known. See, for example 1. Biological Chem., Vol. 260, No. 11, June
1985, pp 6518-6521. Certain preferred embodiments of the present
compositions can make use of amylases having improved stability in
detergents such as automatic dishwashing types, especially improved
oxidative stability as measured against a reference-point of TERMAMYL
~ in commercial use in 1993. These preferred amylases herein share the
characteristic of being "stability-enhanced" amylases, characterized, at a
minimum, by a measurable improvement in one or more of: oxidative
stability, e.g., to hydrogen peroxide/tetraacetylethylenediamine in
buffered solution at pH 9-10; thermal stability, e.g., at common wash
temperatures such as about 60oC; or alkaline stability, e.g., at a pH from
about 8 to about 11, measured versus the above-identified reference-point
amylase. Stability can be measured using any of the art-disclosed
technical tests. See, for example, references disclosed in WO 9402597.
Stability-enhanced amylases can be obtained from Novo or from
Genencor International. One class of highly preferred amylases herein
have the commonality of being derived using site-directed mutagenesis
from_one or more of the Baccillus amylases, especially the Bacillus a-
amylases, regardless of whether one, two or multiple amylase strains are
the immediate precursors. Oxidative stability-enhanced amylases vs. the
above-identified reference amylase are preferred for use, especially in
bleaching, more preferably oxygen bleaching, as distinct from chlorine
bleaching, detergent compositions herein. Such preferred amylases
include (a) an amylase according to the hereinbefore incorporated WO
9403597, Novo. Feb. 3, 1994, as further illustrated by a mutant in which
substitution is made, using alanine or threonine, preferably threonine, of
the methionine residue located in position 197 of the B. licheniformis
alpha-amylase, known as TERMAMYL~, or the homologous position
variation of a similar parent amylase, such as B. amyloliQuefaciens, B.
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WO 97/29174 PCTlUS97lOI462
29
subtilis, or B. stearothermophilus; (b) stability-enhanced amylases as
described by Genencor International in a paper entitled "Oxidatively
Resistant alpha-Amylases" presented at the 207th American Chemical
Society National Meeting, March I3-17 1994, by C. Mitchinson. Therein
it was noted that bleaches in automatic dishwashing detergents inactivate
alpha-amylases but that improved oxidative stability amylases have been
made by Genencor from B. licheniformis NCIB8061. Methionine (Met)
was identified as the most likely residue to be modified. Met was
substituted, one at a time, in positions 8, I5, 197, 256, 304, 366 and 438
leading to specific mutants, particularly important being M197L and
M 197T with the M 197T variant being the most stable expressed variant.
Stability was measured in CASCADE~ and SUNLIGHT~; (c)
particularly preferred amylases herein include amylase variants having
additional modification in the immediate parent as described in WO
9510603 A and are available from Novo as DURAMYL~. Other
particularly preferred oxidative stability enhanced amylase include those
described in WO 9418314 to Genencor International and WO 940259 7 to
Novo. Any other oxidative stability-enhanced amylase can be used, for
example as derived by site-directed mutagenesis from known chimeric,
hybrid or simple mutant parent forms of available amylases. Other
preferred enzyme modifications are accessible. See WO 9509909 A to
Novo.
Cellulases usable herein include both bacterial and fungal types,
preferably having a pH optimum between 5 and 9.5. U.S. 4,435,307,
Bar_besgoard et al, March 6, i 984, discloses suitable fungal cellulases
from Humicola insolens or Humicola strain DSM 1800 or a cellulase 2I2-
producing fungus belonging to the genus Aeromonas, and cellulase
extracted from the hepatopancreas of a marine mollusk, Dolabella
Auricula Solander. Suitable cellulases are also disclosed in GB-A-
2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME~
(Novo) is especially useful. See also WO 9117243 to Novo.
Suitable lipase enzymes for detergent usage include those produced by
microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri
ATCC 19.154, as disclosed in GB 1,372,034. See also lipases in
Japanese Patent Application 53,20487, laid open Feb. 24, 1978. This
CA 02245560 1998-08-OS
WO 97/29174 PCTlLTS97/01462
lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan,
under the trade name Lipase P "Amano, " or "Amano-P. " Other suitable
commercial Iipases include Amano-CES, iipases ex Chromobacter
viscosurn, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673
from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from
U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands,
and lipases ex Pseudomonas gladioli. LIPOLASE~ enzyme derived from
Hc~micola lanuginosa and commercially available from Novo, see also EP
341,947, is a preferred lipase for use herein. Lipase and amylase
variants stabilized against peroxidase enzymes are described in WO
9414951 A to Novo. See also WO 9205249 and RD 94359044.
Cutinase enzymes suitable for use herein are described in WO 8809367 A
to Genencor.
Peroxidase enzymes may be used in combination with oxygen sources,
e.g., percarbonate, perborate, hydrogen peroxide, etc., for "solution
bleaching" or prevention of transfer of dyes or pigments removed from
substrates during the wash to other substrates present in the wash solution.
Known peroxidases include horseradish peroxidase, ligninase, and
haloperoxidases such as chloro- or bromo-peroxidase. Peroxidase-
containing detergent compositions are disclosed in WO 89099813 A,
October 19, 1989 to Novo and WO 8909813 A to Novo.
A range of enzyme materials and means for their incorporation into
synthetic detergent compositions is also disclosed in WO 9307263 A and
WO 9307260 A to Genencor International, WO 8908694 A to Novo, and
U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further
disclosed in U.S. 4,101,457, Place et al, July 18, 1978, and in U.S.
4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid
detergent formulations, and their incorporation into such formulations, are
disclosed in U.S. 4,261,868, Hora et al, April 14, 1981. Enzymes for
use in detergents can be stabilised by various techniques. Enzyme
stabilisation techniques are disclosed and exemplified in U.S. 3,600,319,
August 17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29,
1986, Venegas. Enzyme stabilisation systems are also described, for
example, in U.S. 3,519,570. A useful Bacillus, sp. AC13 giving
CA 02245560 1998-08-OS
V1~0 97129174 PCT/1IS9711fI462
31
proteases, xylanases and cellulases, is described in VVO 9401532 A to
Novo.
Enzyme Stabilizing S. s
The enzyme-containing composite particles and/or overall detergent
compositions herein may comprise from about 0.001 % to about 20 % ,
preferably from about 0.005 % to about 8 % , most preferably from about
0.01 % to about 6 % , by weight of an enzyme stabilizing system. The
enzyme stabilizing system can be any stabilizing system which is
compatible with the detersive enzyme. Such a system may be inherently
provided by other formulation actives, or be added separately, e.g., by
the formulator or by a manufacturer of detergent-ready enzymes. Such
stabilizing systems can, for example, comprise calcium ion, boric acid.,
propylene glycol, short chain carboxylic acids, boronic acids, and
mixtures thereof, and are designed to address different stabilization
problems depending on the type of enzyme and type of detergent
composition.
One stabilizing approach is the use of water-soluble sources of calcium
and/or magnesium ions in the composite particles or in the finished
compositions which provide such ions to the enzymes. Calcium ions are
generally more effective than magnesium ions and are preferred herein if
only one type of cation is being used. Enzymatic detergent compositions
may comprise from about 1 to about 30, preferably from about 2 to about
20, . more preferably from about 8 to about 12 miilimoles of calcium ion
per kg of finished detergent composition, though variation is possible
depending on factors including the multiplicity, type and levels of
enzymes incorporated. Preferably water-soluble calcium or magnesium
salts are employed, including for example calcium chloride, calcium
hydroxide, calcium formate, calcium malate, calcium maleate, calcium
hydroxide and calcium acetate; more generally, calcium sulfate or
magnesium salts corresponding to the exemplified calcium salts may be
used. Further increased levels of calcium and/or magnesium may of
course be useful, for example for promoting the grease-cutting action of
certain types of surfactant.
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WO 97/29174 PCT/US97/01462
32
Another stabilizing approach is by use of borate species. See Severson,
U.S. 4,537,706. Borate stabilizers, when used, may be at levels of up to
% or more of the composite particles or the finished composition,
though more typically levels of up to about 3 % by weight of boric acid or
other borate compounds such as borax or orthoborate are used.
Substituted boric acids such as phenylboronic acid, butaneboronic acid, p-
bromophenylboronic acid or the like can be used in place of boric acid
and reduced levels of total boron in detergent compositions may be
possible though the use of such substituted boron derivatives.
Stabilizing systems of certain cleaning compositions, for example ADD's,
may further comprise from 0 to about 10 % , preferably from about 0.01
to about 6 % by weight, of chlorine bleach scavengers, added to prevent
chlorine bleach species present in many water supplies from attacking and
inactivating the enzymes, especially under alkaline conditions. While
chlorine levels in water may be small, typically in the range from about
0.5 ppm to about 1.75 ppm, the available chlorine in the total volume of
water that comes in contact with the enzyme, for example during dish- or
fabric-washing, can be relatively large; accordingly, enzyme stability to
chlorine in-use is sometimes problematic. Since perborate or
percarbonate, which have the ability to react with chlorine bleach, may be
present in certain of the instant compositions in amounts accounted for
separately from the stabilizing system, the use of additional stabilizers
against chlorine, may, most generally, not be essential, though improved
results may be obtainable from their use. Suitable chlorine scavenger
anions are widely known and readily available, and, if used, can be salts
containing ammonium cations with sulf te, bisulfite, thiosulflte,
thiosulfate, iodide, etc. Antioxidants such as carbamate, ascorbate, etc.,
organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali
metal salt thereof, monoethanolamine (MEA), and mixtures thereof can
likewise be used. Likewise, special enzyme inhibition systems can be
incorporated such that different enzymes have maximum compatibility.
Other conventional scavengers such as bisulfate, nitrate, chloride, sources
of hydrogen peroxide such as sodium perborate tetrahydrate, sodium
perborate monohydrate and sodium percarbonate, as well as phosphate,
condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate,
tartrate, salicylate, etc., and mixtures thereof can be used if desired. In
CA 02245560 2000-10-25
33
jeneral, since the chlorine scavenger function can be performed by
ingredients separately listed under better recognized functions, (e.g.,
hydrogen peroxide sources), there is no absolute requirement to add a
separate chlorine scavenger unless a compound performing that function
to the desired extent is absent from an enzyme-containing embodiment of
the invention; even then, the scavenger is added only for optimum results.
Moreover, the formulator will exercise a chemist's normal skill in
avoiding the use of any enzyme scavenger or stabilizer which is majorly
incompatible, as formulated, v~rith other reactive ingredients, if used. In
relation to the use of ammonium salts, such salts can be simply admixed
with the detergent composition but are prone to adsorb water and/or
liberate ammonia during storage. Accordingly, such materials, if present,
are desirably protected in a panicle such as that described in US
4,652,392, Baginski et al.
Silicone and Phosphate Ester Suds SCR r ors -
The detergent compositions optionally contain an alkyl phosphate ester
suds suppressor, a silicone suds suppressor, or combinations thereof.
Levels in general are from 0% to about 10%, preferably, from about
0.001 % to about 5%. Typical levels tend to be low, e.g., from about
0.01 % to about 3 % when a silicone suds suppressor is used. Preferred
non-phosphate compositions omit the phosphate ester component entirely.
Silicone suds suppressor technology and other defoaming agents useful
herein are extensively documented in "Defoaming, Theory and Industrial
Applications", Ed., P. R. Garrett, Marcel Dekker, N.Y., 1973, ISBN 0-
824~'8~~W _ . see especially the
chapters entitled "Foam control in Detergent Products" (Ferch et al) and
"Surfactant Antifoams" (Blease et al). See also U.S. Patents 3,933,672
and 4,136,045. Highly preferred silicone suds suppressors are the
compounded types known for use in laundry detergents such as heavy-
duty granules, although types hitherto used only in heavy-duty liquid
detergents may also be incorporated in the instant compositions. For
example, polydimethyisiloxanes having trimethylsilyl or alternate
endblocking units mad be used as the silicone. These may be
compounded with silica and/or with surface-active nonsilicon components,
CA 02245560 2000-10-25
34
as illustrated by a suds suppressor comprising 12 % silicone/ silica, 18 9
stearyi alcohol and 70 ~7o starch in granular form. A suitable commercial
source of the silicone active compounds is Dow Corning Corp.
Levels of the suds suppressor depend to some extent on the sudsing
tendency of the composition, for example, an detergent composition for
use at 2000 ppm comprising 2 % octadecyidimethylamine oxide may not
require the presence of a suds suppressor. Indeed, it is an advantage of
the present invention to select cleaning-effective amine oxides which are
inherently much lower in foam-forming tendencies than the typical coco
amine oxides. In contrast, formulations in which amine oxide is
combined with a high-foaming anionic cosurfactant, e.g., alkyl ethoxy
sulfate, benefit greatly from the presence of suds suppressors.
Phosphate esters have alto been asserted to provide some protection of
silver and silver-plated utensil surfaces, however, the instant compositions
can have excellent silvercare without a phosphate ester component.
Without being limited by theory, it is believed that lower pH
formulations, e.g., those having pH of 9.5 and below, plus the presence
of the essential amine oxide, both contribute to improved silver care.
If it is desired nonetheless to use a phosphate ester, suitable compounds
are disclosed in U.S. Patent 3.314,891, issued April 18. 1967, to
Schmolka et al . Preferred alkyl
phosphate esters contain from 16-20 carbon atoms. Highly preferred
alkylphosphate esters are monostearyl acid phosphate or monooleyl acid
phosphate, or salts thereof, particularly alkali metal salts, or mixtures
thereof.
It has been found preferable to avoid the use of simple calcium-
precipitating soaps as antifoams in the present compositions as they tend
to deposit on the dishware. Indeed, phosphate esters are not entirely free
of such problems and the formulator will generally choose to minimize the
content of potentially depositing antifoams in the instant compositions.
Corrosion Inhibitor
CA 02245560 2000-10-25
35
The detergent compositions may contain a corrosion inhibitor. Such
corrosion inhibitors are preferred components of automatic dishwashing
compositions in accord with the invention, and are preferably
incorporated at a level of from 0.05 % to 10 % , preferably from 0.1 % to
5 % by weight of the total composition.
Suitable corrosion inhibitors include paraffin oil typically a predominantly
branched aliphatic hydrocarbon having a number of carbon atoms in the
range of from 20 to 50: preferred paraff n oil selected from predominantly
branched C25-45 species with a ratio of cyclic to noncyclic hydrocarbons
of about 32:68; a paraffin oil meeting these characteristics is sold by
Wintershall, Salzbergen, Germany, under the trade name WINOG 70TM.
Other suitable corrosion inhibitor compounds include benzotriazole and
any derivatives thereof, mercaptans and ~diols, especially mercaptans with
4 to 20 carbon atoms including lauryl mercaptan, thiophenol, -
thionaphthol, thionalide and thioanthranol. Also suitable are the C 12-C20
fatty acids, or their salts, especially aluminum tristearate. The C 12-C20
hydroxy fatty acids, or their salts, are also suitable. Phosphonated octa-
decane and other anti-oxidants such as betahydroxytoluene (BHT) are also
suitable. Bismuth nitrate is also suitable.
A dispersant polymer may optionally be used in the instant detergent
compositions in the range from 0 °h to about 25 % , preferably from
about
0.5 9~ to about 20 % , more preferably from about 1 % to about 7 % by
weight of the overall composition. Dispersant polymers are also useful
for improved filming performance of the present ADD compositions,
especially in higher pH embodiments, such as those in which wash pH
exceeds about 9.5. Particularly preferred are polymers which inhibit the
deposition of calcium carbonate or magnesium silicate on dishware.
Dispersant polymers suitable for use herein are illustrated by the film-
forming polymers described in U.S. Pat. No. 4,379,080 (Murphy), issued
Apr. 5, 1983 .
CA 02245560 2000-10-25
36
Suitable polymers are preferably at least partially neutralized or alkali
metal, ammonium or substituted ammonium (e.g., mono-, di- or
triethanolammonium) salts of polycarboxylic acids. The alkali metal,
especially sodium salts are most preferred. While the molecular weight of
the polymer can vary over a wide range, it preferably is from about 1000
to about 500,000, more preferably is from about 1000 to about 250,000,
and most preferably, especially if the detergent composition is for use in
North American automatic dishwashing appliances, is from about 1000 to
about 10,000.
Other suitable dispersant polymers include those disclosed in U.S. Patent
No. 3,308,067 issued March 7, 1967, to Diehl.
Unsaturated monomeric acids that can be polymerized to form
suitable dispersant polymers include acrylic acid, malefic acid (or malefic
anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid,
citraconic acid and methyienemalonic acid. The presence of monomeric
segments containing no carboxylate radicals such as methyl vinyl ether,
styrene, ethylene, etc. is suitable provided that such segments do not
constitute more than about 50 % by weight of the dispersant polymer.
Copolymers of acrylamide and acrylate having a molecular weight of
from about 3,000 to about 100.000, preferably from about 4,000 to about
20.000, and an acrylamide content of less than about 50%, preferably less
than about 20% , by weight of the dispersant polymer can also be used.
Most preferably, such dispersant polymer has a molecular weight of from
about 4,000 to about 20.000 and an acrylamide content of from about 0 %
to about 15 °~, by weight of the polymer:
Particularly preferred dispersant polymers are low molecular weight
modified polyacrylate copolymers. Such copolymers contain as monomer
units: a) from about 90°x. to about 10%, preferably from about 80% to
about 20°~ by weight acrylic acid or its salts and b) from about 10% to
about 90 % , preferably from about 20 ~ to about 80 ~ by weight of a
substituted acrylic monomer or its salt and have the general formula: -
[(C(R2)C(R1)(C(O)OR3))- wherein the incomplete valences inside the
square braces are hydrogen and at least one of the substituents R1, R2 or
R3, preferably R 1 or~R'-, is a 1 to 4 carbon alkyl or hydroxyalkyl group,
CA 02245560 2000-10-25
37
R1 or R~ can be a hydrogen and R3 can be a hydrogen or alkali metal
salt. Most preferred is a substituted acrylic monomer wherein R 1 is
methyl, R2 is hydrogen and R3 is sodium.
The low molecular weight polyacrylate dispersant polymer preferably has
a molecular weight of less than about 15,000, preferably from about 500
to about 10,000, most preferably from about 1,000 to about 5,000, The
most preferred poiyacrylate copolymer for use herein has a molecular
weight of 3500 and is the fully neutralized form of the polymer
comprising about 70% by weight acrylic acid and about 30% by weight
methacrylic acid.
Other suitable modified polyacrylate copolymers include the low
molecular weight copolymers of unsaturated aliphatic carboxylic acids
disclosed in U.S. Patents 4,530,766, and 5,084,535 .
Other dispersant polymers useful herein include the polyethylene glycols
and polypropylene glycols having a molecular weight of from about 950
to about 30,000 which can be obtained from the Dow Chemical Company
of Midland, Michigan. Such compounds for example, having a melting
point within the range of from about 30° to about 100°C can be
obtained
at molecular weights of 1450, 3400, 4500, 6000, 7400, 9500, and
20,000. Such compounds are formed by the polymerization of ethylene
glycol or propylene glycol with the requisite number of moles of ethylene
or propylene oxide to provide the desired molecular weight and melting
poinE of the respective polyethylene glycol and polypropylene glycol. The
polyethylene, polypropylene and mixed glycols are referred to using the
formula HO(CH2CH20)m(CH~CH(CH3)O)n(CH(CH3)CH20)OH
wherein m, n, and o are integers satisfying the molecular weight and
temperature requirements given above.
Yet other dispersant polymers useful herein include the cellulose sulfate
esters such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl
cellulose sulfate, methylcellulose sulfate, and hydroxypropylcellulose
sulfate. Sodium cellulose sulfate is the most preferred polymer of this
group.
CA 02245560 2000-10-25
38
Other suitable dispersant polymers are the carboxylated polysaccharides,
particularly starches, celluloses and alginates, described in U.S. Pat. No.
3,7?3.3?'?, Diehl, issued Mar. 27, 1973; the dextrin esters of
polycarboxylic acids disclosed in U.S. Pat. No. 3,929,107, Thompson,
issued Nov. 11, 1975; the hydroxyalkyl starch ethers, starch esters,
oxidized starches, dextrins and starch hydrolysates described in U.S. Pat
No. 3,803,285, Jensen, issued Apr. 9, 1974; the carboxylated starches
described in U.S. Pat. No. 3,629,121, Eldib, issued Dec. 21, 1971; and
the dextrin starches described in U.S. Pat. No. 4,141,841, McDanald,
issued Feb. 27, 1979 . Preferred
cellulose-derived dispersant polymers are the carboxymethyl celluloses.
Yet another group of acceptable dispersants are the organic dispersanc
polymers, such as polyaspartate.
Depending on whether a greater or lesser degree of compactness is
required, filler materials can also be present in the detergent
compositions. These include sucrose, sucrose esters, sodium chloride,
sodium sulfate, potassium chloride, potassium sulfate, etc., in amounts up
to about 7096, preferably from 0°~ to about 40°X~ of the
detergent
composition. A preferred filler is sodium sulfate, especially in good
grades having low levels of trace impurities.
Sodiwn sulfate used herein preferably has a purity sufficient to ensure it is
notrrcactive with bleach: it may also be treated with low levels of
sequestrants, such as phosphonaces i~n magnesium-salt form. Note that
preferences, in terms of purity sufficient to avoid decomposing bleach,
applies also to builder ingredients.
Hydrotrope materials such as sodium benzene sulfonate, sodium toluene
sulfonate, sodium cumene sulfonate, etc., can be present in minor
amounts .
CA 02245560 1998-08-OS
W O 97!29174 PCT/gIS97/O 1462
39
Bleach-stable perfumes (stable as to odor); and bleach-stable dyes (such as
those disclosed in U.S. Patent 4,714,562, Roselle et al, issued December
22, 1987); can also be added to the present compositions in appropriate
amounts. Other common detergent ingredients are not excluded.
Since certain detergent compositions herein can contain water-sensitive
ingredients, e.g., in embodiments comprising anhydrous amine oxides or
anhydrous citric acid, it is desirable to keep the free moisture content of
the detergent compositions at a minimum, e.g., 7% or less, preferably 4%
or less of the detergent composition; and to provide packaging which is
substantially impermeable to water and carbon dioxide. Plastic bottles,
including refillable or recyclable types, as well as conventional barrier
cartons or boxes are generally suitable. When ingredients are not highly
compatible, e.g., mixtures of silicates and citric acid, it may further be
desirable to coat at least one such ingredient with a low-foaming nonionic
surfactant for protection. There are numerous waxy materials which can
readily be used to form suitable coated particles of any such otherwise
incompatible components.
Method for Gleaning
The detergent compositions herein may be utilized in methods for
cleaning soiled tableware and laundry.
A preferred method for cleaning soiled tableware comprises contacting
the tableware with a pH wash aqueous medium of at least 8. The aqueous
medium preferably comprises at least about 0. I ppm bleach catalyst and
available oxygen from a peroxygen bleach.
A preferred method for cleaning soiled tableware comprises using the
catalyst/enzyme-containing particles, low foaming surfactant and
detergency builder. The aqueous medium is formed by dissolving a solid-
form automatic dishwashing detergent in an automatic dishwashing
machine. A particularly preferred method also includes low levels of
silicate, preferably from about 3% to about i0% Si02.
CA 02245560 2000-10-25
40
Example 1
3.2:0 g gelatine (Bloom strength O) and 3,240 g sugar were
added to a 10 % by weight solution of metal-containing bleach
catalyst in 5,200 g water while stirring. Subsequently, 650 g
coconut oil was emulsified in the solution thus obtained.
The dry matter content of the mixture thus prepared was about
60 % , about 16 % being metal-containing bleach catalyst and the
viscosity was 96 cp at 55°C.
The mixture was spray-dried in a spray drying tower while
simultaneously introducing corn starch therein as a powdering
composition.
The mixture was introduced at a rate of 2 l/min. and the
temperature of the spray drying zone was about 70°C.
The final product (about 9.200 g) was sieved and the mesh 30 -
mesh 120 (ASTM) fraction was collected and analyzed. The
collected fraction contained 14.1 % metal-containing bleach
catalyst and the average particle diameter was about 350
micrometer.
~m~ile 2
2.388 g gelatine was dissolved in 2,135 g water by stirring and
heating to a temperature of about 60°C. A solution of 126 g
sodium hydroxide in 215 g water was added under stirring to the
gelatine solution at a temperature of 60°C. After stirring for 20
min. at 60°C 135 g concentrated sulfuric acid (9690 was added
and the pH-value was adjusted at about 5.5. 900 g of the
solution thus obtained ("hydrolyzed gelatine") was mixed with a
solution of 100 g metal-containing bleach catalyst in 1.150 g
water, 450 spray-dried glucose syrup ( "Monsweet R 1924 TM~ ana
50 g coconut oil while stirring at 55 °C. When the coconut had
CA 02245560 1998-08-OS
VVO 97129174 PCT1US97fOI462
49
been emulsified in the aqueous medium an additional amount of
700 g water was added. The dry matter content of the mixture
thus obtained was about 30 % , about 10 % being metal-containing
bleach catalyst. The viscosity of the mixture was about 50 cp at
60°C. The mixture was spray-dried in a conventional spray-
drying tower at an inlet temperature of 240°C and an outlet
temperature of 97 ° C .
The spray-dried product (about 900 g) was sieved and the sieve
fraction having a particle size of less than 100 mesh (ASTM) was
collected.
This fraction contained 9.7 % metal-containing bleach catalyst
and the average particle size was about 50 micrometer.
Example 3
1060 g gum arabic and 1010 g sugar (saccharose) were added to
a solution of 1375 g metal-containing bleach catalyst in 1850 g
water while stirring. 138 g coconut oil was emulsified in the
solution thus obtained.
The dry matter content of the mixture thus prepared was about
45 % , about 11.4 % being metal-containing bleach catalyst and the
viscosity was 108 cP at 57°C.
The mixture was spray-dried in a spray drying tower while
simultaneously introducing corn starch therein as a powdering
composition.
The mixture was introduced at a rate of 1.5 1/min. and the
temperature of the spray drying zone was about 65°C.
The final product (about 3500 g) was sieved and the mesh 30 -
mesh 170 (ASTM) fraction was collected and analysed.
CA 02245560 2000-10-25
42
The collected fraction contained 8.2 % metal-containing bleach
catalyst and the average particle diameter was about ~50
micrometers.
In the compositions, the abbreviated component identifications have the
following meanings:
Nonionic . C 13-C 15 mixed ethoxylated/propoxylated fatty
alcohol with an average degree of ethoxylation
of 3.8 and an average degree of propoxylation
of 4.5 sold under the tradename PlurafacTM
LF404 by BASF GmbH (low foaming)
Metasilicate . Sodium metasilicate (SiO2:Na20 ratio = 1.0)
Silicate : Amorphous Sodium Silicate (Si02:Na20 ratio
= 2.0)
Carbonate . Anhydrous sodium carbonate
Phosphate : Sodium tripolyphosphate
480h' . Random copolymer of 3:7 acrylic/methacrylic
acid, average molecular weight about 3,500
Citrate . Tri-sodium citrate dihydrate
PB l : Anhydrous sodium perborate monohydrate
TA)=D . Tetraacetyl ethylene diamine
Cationic precursor Cationic peroxyacid bleach precursor salt of
trialkyl ammonium methylene C5-alkyl
caprolactam with tosylate
CA 02245560 2000-10-25
43
BzP : Dibenzoyl peroxide
DETPMP : Diethylene triamine penta (methylene
phosphonic acid), marketed by Monsanto under
the tradename bequest 2060 TM
HEDP : Ethane 1-hydroxy-l,l-diphosphonic acid
Bismuth nitrate : Bismuth nitrate salt
Bismuth (HEDP) : Complex of bismuth and HEDP
Paraffin : Paraffin oil sold under the tradename Winog 70
by Wintershall.
BD/MA . Copolymer of butadiene/maleic acid as sold by
Polysciences inc under the tradename reference
no. 07787
Protease . Proteolytic enzyme sold under the tradename
S8V1n2Se~M by Novo Industries A/S (approx
0.9~ enzyme activity)
Amylase . Amylolytic enzyme sold under the tradename
TeTmaZny~M60T by Novo Industries A/S (approx
0.9 °r~ enzyme activity)
Amylolytic enzyme sold under the tradename
LE 17 by Novo. Industries A/S (approx 1 ~
enzyme activity)
Sulphate . Anhydrous sodium sulphate.
PH . Measured as a 1 % solution in distilled water at
20°C.
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WO 97/29174 PCT/US97/01462
44
In the following examples all levels of enzyme quoted are expressed as
active enzyme by weight of the composition.
CA 02245560 1998-08-OS
w0 97129174 PCT/US97/01462
EXamnle 1
The following bleach-containing machine dishwashing compositions were
prepared (parts by weight) . Compositions A is a comparative
' composition, compositions B to G are in accord with the invention.
A B C D E F G
Citrate 15.0 15.0 15.0 15.0 15.0 15.0 -
480N 6.0 6.0 6.0 6.0 6.0 6.0 -
Carbonate 17.5 17.5 17.5 17.5 17.5 17.5 -
- -
Phosphate - - _ _ _ - 38.0
Silicate (as 8.0 8.0 8.0 8.0 8.0 8.0 14.0
SiC?2)
Metasilicate 1.2 1.2 1.2 1.2 1.2 1.2 2.5
(as Si02)
PB 1 (Av0) 1.2 1.2 1.5 1.5 1.5 2.2 1.2
Bleach catalyst - 0.2 0.1 0.05 0.1 0.2 0.3
encapsulate
particle - formula
given below
TAED 2.2 2.2 2.2 - - 2.2 2.2
BzP - - - 0.8 - - -
Cationic - - - - 3.3 - -
' precursor
Paraffin 0.5 0.5 0.5 0.5 0.5 0.5 0.5
CA 02245560 1998-08-OS
WO 9?1291?4 PCT/US9?/01462
46
Bismuth - 0.2 0.2 0.2 0.3 0.4 0.2
nitrate
BD/MA - _ _
- - - 0.5
Protease 0.04 0.04 0.04 0.04 0.04 0.04 0.04
Amylase 0.03 0.03 0.03 0.03 0.03 0.03 -
BSA - - - - - - 0.03
DETPMP 0.13 0.13 0. 0.13 0.13 0.13 -
I3
I-iEDP 1.0 1.0 1.0 1.0 1.0 1.0 -
Nonionic 2.0 2.0 2.0 2.0 2.0 2.0 1.5
Sulphate 23.0 22.8 22.4 22.7 22.2 21.5 0.3
misc inc moisture
to balance
pH ( 1 % solution)10. 10.7 10.7 10. 10.7 10.7 11.0
7 7
Encapsulate particles containing zero-bloom gelatin at a level of
96.6 % and 3.4 % pentaamineacetocobalt (III) nitrate bleach
catalyst. Particle size of the encapsulates 10-4S0 micrometers.
