Note: Descriptions are shown in the official language in which they were submitted.
CA 02362955 2004-09-02
MULTI-P~1ASE DETERGENT' J'ABLET
1~
Technical Field
The present invention relates to mufti-phase detergent tablets- In particular,
it relates to
mufti-phase detergent tablets having improved robustness and product integrity
togetlter
with excellent dissolution characteristita. the invention also relates to
methods of
manufacturing rnulti-phase detergent tablets and to detergt:nt auxiliary
compositions
usefultherein.
Hac ground
Detergent compositions in tablet form arc known in the art. Tt is understood
that
detergent compositions in tablet form hold several advantages over detergent
compositions in particulate form, such as case of dosing, handling,
transportation and
storagt.
Detergent tablets are most commonly prepared by pre-mixing components of a
detergent
composition and forming the pre-mixed detergent components into a tablet using
any
suitable equipment, preferably a tablet press. 'tablets are typically formed
by
compression of the components of the detergent composition so that the tablets
produced
34 are sufficiently robust to be able to withstand handling and transportation
without
sustaining damage. In addition to being robust, tablets must also dissolve
sufficiently fast
so that the detergent components are released into the wash water as soon as
possible at
the beginning of the wash cycle.
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However, a dichotomy exists in that as compression force is increased, the
rate of
dissolution of the tablets becomes slower. The present invention therefore
seeks to find a
balance between tablet robustness and tablet dissolution.
Solutions to this problem, as seen in the prior art, have included compressing
the tablets
with low compression pressure. However tablets made in this way, although
having a fast
relative dissolution rate, tend to crumble, becoming damaged and unacceptable
to the
consumer. Other solutions have included preparing tablets using a high
relative
compression pressure, in order to achieve the required level of robustness,
and comprising
a dissolution aid, such as an effervescent agent.
Mufti-phase detergent tablets described in the prior art are prepared by
compressing a first
composition in a tablet press to form a substantially planar first layer. A
further detergent
composition is then delivered to the tablet press on top of the first layer.
This second
composition is then compressed to form another substantially planar second
layer. Thus
the first layer is generally subjected to more than one compression as it is
also
compressed during the compression of the second composition. Typically the
first and
second compression forces are in the same order of magnitude. The Applicant
has found
that where this is the case, because the compression force must be sufficient
to bind the
first and second compositions together, the force used in both the first and
second
compression steps must be in the range of from about 4,000 to about 20,000 kg
(assuming
a tablet cross-section of about 10 cmz). A consequence of this is a slower
rate of tablet
dissolution. Other mufti-phase tablets exhibiting differential dissolution are
prepared
such that the second layer is compressed at a lower force than the first
layer. However,
although the dissolution rate of the second layer is improved, the second
layer is soft in
comparison to the first layer and is therefore vulnerable to damage caused by
handling
and transportation. Moreover, the two layers are found to have poor adhesion
characteristics and can break up under the relatively mild stress conditions
found in
storage or transportation.
The present invention therefore provides mufti-phase detergent tablets for use
in
automatic dishwashing, laundry, etc and which have improved integrity and
robustness
together with excellent dissolution characteristics. The invention also
provides methods
of manufacturing mufti-phase detergent tablets and detergent auxiliary
compositions
useful therein.
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Summary of the Invention
According to a first aspect of the invention, there is provided a mufti-phase
detergent
tablet for use in a washing machine, the tablet comprising a first phase in
adhesive contact
with one or more second phases, and wherein at least the first phase is in the
form of a
compressed particulate solid incorporating a cogranulated detergency additive
composition comprising polymeric polycarboxylate and inorganic Garner.
The compositions of the invention thus comprise multiple phases in adhesive
contact with
one another, at least a first phase of which is in the form of a compressed
particulate solid
incorporating cogranules of a detergency additive composition. In preferred
embodiments, at least one and preferably each second phase is also in the form
of a
compressed particulate solid and, if desired, can also incorporate cogranules
of the same
or different detergency additive composition. Surprisingly, inclusion of the
detergency
additive composition in the first phase improves inter-phase adhesion at a
given tablet
compaction force (even where the second phase is free of cogranulated additive
composition) and allows a significant reduction in compaction force on both
first and
second phases whilst delivering improved tablet solubility and bite strength.
A preferred cogranulated detergency additive composition for incorporation
herein
comprises i) from about 0.1 % to about 60%, preferably from about 1 % to about
25 %,
more preferably from about S% to about 20% by weight thereof of polymeric
polycarboxylate, ii) from about 40% to about 99.9%, preferably from about 70%
to about
99%, more preferably from 80% to about 95% by weight thereof of inorganic
carrier, and
optionally iii) from 0% to about 50%, preferably from about 0.5% to about 20%
by
weight thereof of one or more organic auxiliaries, preferably selected from
chelating
agents, surfactants, polymeric disintegrants, solubility aids and mixtures
thereof.
Polymeric polycarboxylates suitable for inclusion in the detergency additive
composition
include i) homo- and copolymers of one or more carboxylic monomers selected
from
acrylic acid, methacrylic acid, alpha-chloroacrylic acid, alpha-hydroxyacrylic
acid, malefic
acid, itaconic acid, and mixtures thereof, and ii) copolymers of one or more
of the above
carboxylic monomers with one or more nonionic monomers selected from
acrylamide,
acrylonitrile, vinyl esters such as vinyl acetate, methylvinyl ketone,
acrolein, styrene and
alpha-methyl styrene, alkyl vinyl ethers, esters and amides of carboxylic
monomers such
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as (C,-C4)-alkyl (meth)acrylates, and water-soluble salts and mixtures
thereof. Of the
above, preferred are homo- and copolymers of acrylic and methacrylic acid
The polymeric polycarboxylates herein can be in acid , neutralised or
partially neutralised
form with sodium, potassium, ammonium or other counterions. Molecular weights
of the
polymeric polycarboxylates can vary widely e.g. weight averages ranging from
about S00
to about 5,000,000, but normally weight average molecular weights will fall in
the range
from about 1000 to about 100,000. Preferably, the polymeric polycarboxylates
will be in
liquid or liquifiable form, for example as a solution, dispersion, slurry or
emulsion in a
liquid or liquifiable medium such as water or a water/organic solvent mixture.
Generally,
liquid or liquifiable polymeric polycarboxyate mixtures suitable for use
herein have a
polymer solids content of at least about 10%, preferably from about 20% to
about 70%,
more preferably from about 40% to about 60% by weight thereof.
The inorganic carrier herein generally comprises one or more inorganic salts
and in
preferred embodiments is selected from alkali metal silicate, alkali metal
carbonate, alkali
metal bicarbonate, alkali metal sesquicarbonate, alkali metal sulfate, alkali
metal
tripolyphosphate, and mixtures thereof. Of these, highly preferred is an
inorganic carrier
which comprises a mixture of alkali metal carbonate and alkali metal sulfate,
preferably in
a weight ratio of from about 3:1 to about 1:3, more preferably from about 2:1
to about
l:l, and especially from about 1.8:1 to about 1.5:1. The inorganic Garner
normally takes
the form of a powder or mixture of powders having a weight-average particle
size of less
than about 200~m, preferably less than about 150~m, such carriers being
preferred from
the viewpoint of providing optimum granulometry, tablet strength, inter-phase
adhesivity
and solubility characteristics.
Thus according to another aspect of the invention, there is provided a
cogranulated
detergency additive composition comprising i) from about 0.1 % to about 60%,
preferably
from about 1% to about 25%, more preferably from about 5% to about 20% by
weight of
polymeric polycarboxylate, ii) from about 40% to about 99.9%, preferably from
about
70% to about 99%, more preferably from 80% to about 95% by weight of inorganic
Garner in the form of a powder or mixture of powders having a weight-average
particle
size of less than about 200~m, preferably less than about 150~m, and
optionally iii) from
0% to about 50%, preferably from about 0.5% to about 20% by weight of one or
more
organic auxiliaries selected from chelating agents, surfactants, polymeric
disintegrants,
solubility aids and mixtures thereof.
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A preferred method for making the tablets herein comprises the siep of
admixing a liquid
feed comprising the polymeric polycarboxylate with a powder fetid comprising
the
inorganic carrier and subjecting the mixture to conditions of agitation and
heat to form
cogranules of the detergency additive composition In a highly preferred
embodiment, the
liquid feed and powder feed are admixed under essentially non-evaporative
conditions to
form a wet cagranular output stream and flee: wet cagranular output stream is
subsequently
subjected to boat-drying, for example in a fluidised bed. let subsequent
steps, the
coganules are compacted optionally with other detergent tablet ingredients to
faint the
I4 first phase of the tablet, the second phase is superposed in particulate or
tablet form on or
over the first phase and thereallGer the first phase and superposed second
phase axe ftuther
compacted to fo,xn the final mufti-phase detergent tablet.
lvrfanufacture of the cogranular deterge»cy additive composition is preferably
undertaken
in a vertical, short retention time, plow-type agglornerator such as a Sehugi
Flexomi~
followed by drying of the wet agglomerates in a fluidizcd bed dryer with fines
recycling
arid size reduction as necessary to achieve: the requisite granule size
distn'bution. The
liquid feed, ususally in the form of a solaition, dispersion, slurry or
emulsion of polymeric
polycarboxylate in a liquid or liquifiable medium such as water or a
waterlorganie solvent
mixture, is preferably appiied to the powder feed by spray-on at a slightly
elevated
temperature in order is provide an appropriate feed viscosity.
The powder food, on the ether hand, comprises inorganic carnet, preferably in
the fotTn of
a powder or mixture of powders having a weight-average particle size of less
than about
200pm, preferably less than about 150prn, together with any recycled fines.
The
iiquid:powder feed ratio is ge,rtcraily less than about 0.5 preferably less
than about 0.4,
more preferably from about 0.1 to about 0.35, and especially from about 0.2 to
about 0.3.
In preferred ctnbodiments, the powder feed comprises a mixture of alkali metal
carbwttate
and a~ati racial sulfate in a weight ratio of fzom about 3:1 to about I :3,
mare preferably
from at~out 2-I to about I-I, and t'specially from about 1.8:1 to about 1.5:1.
The process herein is highly preferred from the viewpoint of providing
cogranular
detergency additive compositions having the requisite granulometry far making
compacted mufti-phase detergent tablets of ~aptimum strength, adhesion, and
solubility
characteristics.
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Thus, according to further aspect of the invention there is provided a method
of making a
cogranular detergency additive composition comprising admixing a liquid feed
comprising a polymeric polycarboxylate with a powder feed comprising inorganic
carrier
and subjecting the mixture to conditions of agitation and heat, and wherein
the polymeric
polycarboxylate is in the form of a solution, dispersion, slurry or emulsion
in a liquid or
liquifiable medium, the inorganic Garner is in the form of a powder or mixture
of
powders having a weight-average particle size of less than about 200~m,
preferably less
than about 150~m, and wherein the liquid:powder feed ratio is less than about
0.5,
preferably less than about 0.4, more preferably from about 0.1 to about 0.35,
and
especially from about 0.2 to about 0.3.
From the granulometry viewpoint, preferred cogranuar detergent additive
compositions
have an apparent density in the range from about 400 to about 1100 g/l,
preferably from
about 600 to about 900 g/1, a median granule size of from about 400 to about
700,
preferably from about 450 to about 650 p,m, and a size distribution such that
no more
than about S% by weight is greater than 1500~m, preferably 1400~.m, and at
least about
95% by weight is greater than 200~m, preferably 250~m. In addition, the
cogranuar
detergent additive compositions preferably have a final moisture content of
less than
about 5%, preferably from about 1% to about 3% by weight thereof. The
cogranulated
detergency additive composition generally comprises at least about 5%,
preferably from
about 10% to about 80%, more preferably from about 20% to about 60% by weight
of the
final tablet.
In compositional terms, a preferred cogranulated detergency additive
composition for use
herein i) from about 1% to about 25%, preferably from about 5% to about 20% by
weight
thereof of polymeric polycarboxylate, ii) from about 30% to about 85%,
preferably from
about 45% to about 65% by weight thereof of alkali metal carbonate, alkali
metal
bicarbonate, alkali metal sesquicarbonate or mixture thereof, and iii) from
about 13% to
about 69%, preferably from about 15% to about 50% by weight thereof of alkali
metal
sulfate, and optionally iv) from 0% to about 5% by weight thereof of organic
chelating
agent. Such a composition is highly suited for incorporation in so-called nil-
P detergent
tablets, i.e., tablets containing no phosphate builder and a minimal amount,
if any, of
phosphorus-containing chelating agents. Generally such tablets will contain
phosphorus
in an amount less than about 0.5%, preferably less than about 0.1% by weight.
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Thus, according to a still further aspect of the invention, there is provided
a cogranulated
detergency additive composition comprising from about 5% to about 20% by
weight of
polymeric polycarboxylate and from about 80% to about 95% by weight of
inorganic
Garner, the inorganic carrier comprising i) from about 45% to about 65% by
weight of the
additive composition of alkali metal carbonate, alkali metal bicarbonate,
alkali metal
sesquicarbonate or mixture thereof, and ii) from about 15% to about 50% by
weight of
the additive composition of alkali metal sulfate.
Organic chelating agents suitable for inclusion in the cogranulated detergency
additive
composition or in the remainder of the tablet composition include
diethylenetriamine
penta (methylene phosphonate), ethylenediamine tetra(methylene phosphonate)
hexamethylenediamine tetra(methylene phosphonate), ethylene diphosphonate,
hydroxy-
ethylene-1,1-diphosphonate, nitrilotriacetate, ethylenediaminotetracetate,
ethylenediamine-N,N'-disuccinate, methylglycinediacetic acid in their salt and
free acid
forms.
Polymeric disintegrants suitable for inclusion in the cogranulated detergency
additive
composition or in the remainder of the tablet composition include starch,
cellulose and
derivatives thereof, alginates, sugars, polyvinylpyrrolidones, swellable clays
and mixtures
thereof.
Solubility aids suitable for inclusion in the cogranulated detergency additive
composition
or in the remainder of the tablet composition include water-soluble hydrated
salts having
a solubility in distilled water of at least about 25g/100g at 25°C,
preferably selected from
hydrates of sodium acetate, sodium potassium tartrate, sodium citrate and
mixtures
thereof.
The detergent tablets herein comprise at least one first phase in adhesive
contact with one
or more second phases (sometimes referred to herein as 'optional subsequent
phases'). In
preferred embodiments, the first phase is a compressed shaped body prepared at
an
applied compression pressure of at least about 40 kg/cmz, preferably at least
about 250
kg/cmz, more preferably at least about 350 kg/cm2 (3.43 kN/cm2 or 34.3 MPa),
even more
preferably from about 400 to about 2000 kg/cm2, and especially from about 600
to about
1600 kg/cmz (compression pressure herein is the applied force divided by the
cross-
sectional area of the tablet in a plane transverse to the applied force - in
effect, the
transverse cross-sectional area of the die of the rotary press). The second
phase, on the
other hand, is preferably formed at a compression pressure of less than about
350 kg/cm2,
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preferably in the range from about 40 kg/cmz to about 300 kg/cm2 and more
preferably
from about 70 to about 270 kg/cm2. In preferred embodiments, moreover, the
first phase
is formed by compression at a pressure greater than that applied to the second
phase. In
these embodiments, the compression pressures applied to the first and second
phases will
generally be in a ratio of at least about 1.2:1, preferably at least about
2:1, more preferably
at least about 4:1.
Although simple mufti-layer tablets are envisaged for use herein, preferred
from the
viewpoint of optimum product integrity, strength (measured for example by the
Child
Bite Strength [CBS] test) and dissolution characteristics are tablets wherein
the first phase
is in the form of a shaped body having at least one mould therein; and the
second phase is
in the form of a particulate solid compressed within said mould. Such
embodiments are
sometimes referred to herein as 'mould' embodiments. The tablets of the
invention, both
mould embodiments and otherwise, will preferably have a CBS of at least about
6kg,
preferably greater than about 8kg, more preferably greater than about lOkg,
especially
greater than about l2kg, and more especially greater than about l4kg, CBS
being
measured per the US Consumer Product Safety Commission Test Specification.
It is also preferred that the first and second phases herein are in a
relatively high weight
ratio to one another, for example at least about 6:1, preferably at least
about 10:1; also
that the tablet composition contain one or more detergent actives (for example
enzymes,
bleaches, bleach activators, bleach catalysts, surfactants, chelating agents
etc) which is
predominantly concentrated in the second phase, for example, at least about
50%,
preferably at least about 60%, especially about 80% by weight of the active
(based on the
total weight of the active in tablet) is in the second phase of the tablet.
Again, such
compositions are optimum for tablet strength, dissolution, cleaning, and pH
regulation
characteristics providing, for example, tablet compositions capable of
dissolving in the
wash liquor so as to deliver at least 50%, preferably at least 60%, and more
preferably at
least 80% by weight of the detergent active to the wash liquor within 10, 5, 4
or even 3
minutes of the start of the wash process.
Detailed Description of the Invention
It is an object of the present invention to provide a detergent tablet that is
not only
sufficiently robust to withstand handling and transportation, but also at
least a significant
portion of which dissolves rapidly in the wash water providing rapid delivery
of detergent
active. It is preferred that at least one phase of the tablet dissolves in the
wash water
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within the first ten minutes, preferably five minutes, more preferably four
minutes of the
wash cycle of an automatic dishwashing or laundry washing machine. Preferably
the
washing machine is either an automatic dishwashing or laundry washing machine.
The
time within which the mufti-phase tablet or a phase thereof or a detergent
active
component dissolves is determined according to DIN 44990 using a dishwashing
machine
available from Bosch on the normal 65°C washing program with water
hardness at 18°H
using a minimum of six replicates or a sufficient number to ensure
reproducibility.
The mufti-phase detergent tablet of the present invention comprises a first
phase, a second
and optional subsequent phases. The first phase is preferably in the form of a
shaped
body of detergent composition comprising the cogranular detergency additive
composition and one or more detergent components as described below. Preferred
detergent components include, builder, bleach, enzymes and surfactant. The
components
of the detergent composition are mixed together by, for example admixing dry
components or spraying-on liquid components. The components are then formed
into a
first phase using any suitable equipment, but preferably by compression, for
example in a
tablet press. Alternatively, the first phase can be prepared by extrusion,
casting, etc.
In mould embodiments, the first phase is prepared such that it comprises at
least one
mould in the surface of the shaped body. In a preferred embodiment the mould
is created
using a specially designed tablet press wherein the surface of the punch that
contacts the
detergent composition is shaped such that when it contacts and presses the
detergent
composition it presses a mould, or multiple moulds into the first phase of the
mufti-phase
detergent tablet. Preferably, the mould will have an inwardly concave or
generally
concave surface to provide improved adhesion to the second phase.
The tablets of the invention also include one or more additional phases
prepared from a
composition or compositions which comprise one or more detergent components as
described below. At least one phase (herein referred to as a second phase)
preferably
takes the form of a particulate solid (which term encompasses powders,
granules,
agglomerates, and other particulate solids including mixtures thereof with
liquid binders,
meltable solids, spray-ons, etc) compressed either as a layer or into/within
the one or
more moulds of the first phase of the detergent tablet such that the second
phase itself
takes the form of a shaped body. Preferred detergent components include
builders,
colourants, binders, surfactants, disrupting agents and enzymes, in particular
amylase and
protease enzymes. In another preferred aspect of the present invention the
second and
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optional subsequent phases comprise a disrupting agent that may be selected
from either a
disintegrating agent or an effervescent agent. Suitable disintegrating agents
include
agents that swell on contact with water or facilitate water influx and/or
efflux by forming
channels in the detergent tablet. Any known disintegrating or effervescing
agent suitable
S for use in laundry or dishwashing applications is envisaged for use herein.
Suitable
disintegrating agent include starch, starch derivatives such as Arbocel
(tradename),
Vivapur (tradename) both available from Rettenmaier, Nymcel (tradename)
available
from Metsa-serla , alginates, acetate trihydrate, burkeite, monohydrated
carbonate formula
NazC03.H20, hydrated STPP with a phase I content of at least about 40% ,
10 carboxymethylcellulose (CMC), CMC-based polymers, sodium acetate, aluminium
oxide.
Suitable effervescing agents are those that produce a gas on contact with
water. Suitable
effervesing agents may be oxygen, nitrogen dioxide or carbon dioxide evolving
species.
Examples of preferred effervescent agents may be selected from the group
consisting of
perborate, percarbonate, carbonate, bicarbonate in combination with inorganic
acids such
as sulphamic acid and/or carboxylic acids such as citric, malic and malefic
acid and
mixtures thereof
The components of the detergent composition are mixed together by for example
premixing dry components and admixing, preferably by spray-on, the liquid
components.
The components of the second and optional subsequent phases are then
compressed to
form one or more layers or are fed into and retained within the mould provided
by the
first phase.
The preferred mould embodiments of the present invention comprises two phases;
a first
and a second phase. The first phase will normally comprise one mould and the
second
phase will normally consist of a single detergent active composition. However,
it is
envisaged that the first phase may comprise more than one mould and the second
phase
may be prepared from more than one detergent active composition. Furthermore,
it is
also envisaged that the second phase may comprise more than one detergent
active
composition contained within one mould. It is also envisaged that several
detergent
active compositions are contained in separate moulds. In this way potentially
chemically
sensitive detergent components can be separated in order to avoid any loss in
performance
caused by components reacting together and potentially becoming inactive or
exhausted.
In a preferred aspect of the present invention the first phase weighs greater
than about 3g,
preferably greater than about 4g. More preferably the first phase weighs from
about l Og
CA 02362955 2004-09-02
11
to about 30g, even more preferably from about 1 Sg to about 25g and most
preferably form
about 1$g to about 24g. The second and optional subsequent phases weigh less
than
about 4g. More preferablytihe second and/or optional subsequent phases weigh
between
about 0.2g and about 3.Sg, most preferably from ahoutlg to about 2.Sg.
The components of the second and optional subsequent phases are compressed,
especially
in the mould embodiments, at a much lower compression force relative to the
compression force naturally used to prepare high strength tablets. Ai the same
time, the
tablets of the invention display excellent adherence between phases and
product integrity.
Thus an advantage of the present invea~tion is chat because a lower
compression farce is
used heat, force or chemically sensitive detergent cornponexats can be
.incorporate into
the detergent tablet without sustaining the consequential lass in performance
usually
encountered when incorporating such eompanertts into tablets.
. Yet another advantage of the present invention is the ability to prepare a
mufti-phase
detergent tablet wherein one phase can be designed to dissolve or disperse,
preferably
significantly before another phase. Fn the present invention it is preferred
that the second
and optional subsequent phases) dissolves or disperses before the first phase.
According
to the preferred weight ranges described above, it preferable that the fn-st
phase dissolves
or disperses in from 5 to 20 minutes, more preferably from 10 to 15 minutes
and the
second andlor optional subsequent phases dissolves or disperses in less than 5
minutes,
more preferably less than 4.5 minutes, most pr~cferably less Than 4 minutes.
The time in
which the first, second andlor optional subsequent phase dissolve or disperse
are
independent from each other. Thus in a particularly preferred aspect of the
present
invention differential dissolution of the phases is achieved. A particular
benefit of being
able to achieve differential dissolution ofihe mufti-phase detergent tabltt is
that a
eotxlponent that is chemically inactivated by the presence of another
camponrnt can be
separated into a different phase. In this case the coa,ponent that is
inactivated is
preferably located in the second and optioztal subsequent phase(s).
Tho mufti-phase deter ent tablets are prepared using any suitable tabletting
equipment,
e.g., a Courtoy 8253.. Preferably the tablets are prepared by compression in a
tablet press
capable of preparing a tablet comprising a mould. 1n a particularly preferred
embodiment
of the present invention the first phase is prepared using a specially
designed tablet press.
The punches) of this tablet press arc modified so that the surface of the
punch that
conx.~tcts the detergent composition has a convex surface.
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A first detergent composition is delivered into the die of the tablet press
and the punch is
lowered to contact and then compress the detergent composition to form a first
phase.
The first detergent composition is compressed using an applied pressure of at
least 250
kg/cmz, preferably between 350 and 2000 kg/cmz, more preferably 500 to 1800
kg/cmz,
most preferably 600 to 1500 kg/cmz. The punch is then elevated, exposing the
first phase
containing a mould. A second and optional subsequent detergent compositions)
is then
delivered into the mould. The specially designed tablet press punch is then
lowered a
second time to lightly compress the second and optional subsequent detergent
compositions) to form the second and optional subsequent phase(s). In another
embodiment of the present invention where an optional subsequent phase is
present the
optional subsequent phase is prepared in an optional subsequent compression
step
substantially similar to the second compression step described above. The
second and
optional subsequent detergent compositions) is compressed at a pressure of
preferably
less than 350 kg/cm2, more preferably from 40 to 300 kg/cm2, most preferably
from 70 to
270 kg/cm2. After compression of the second detergent composition, the punch
is
elevated a second time and the mufti-phase detergent tablet is ejected from
the tablet
press. Mufti-layer tablets without moulds can be prepared in a similar manner
except
using a tablet punch having a planar surface.
The first and second and or optional subsequent phases of the mufti-phase
detergent tablet
described herein are prepared by compression of one or more compositions
comprising
detergent active components. Suitably, the compositions used in any of these
phases
may, in addition to the cogranulated detergency additive composition, include
a variety of
different detergent components including builder compounds, surfactants,
enzymes,
bleaching agents, alkalinity sources, colourants, perfume, lime soap
dispersants, organic
polymeric compounds including polymeric dye transfer inhibiting agents,
crystal growth
inhibitors, heavy metal ion sequestrants, metal ion salts, enzyme stabilisers,
corrosion
inhibitors, suds suppressers, solvents, fabric softening agents, optical
brighteners and
hydrotropes. In the following, the proportions of these active components,
including any
amounts contained in the cogranulated detergency additive composition, are
given by
weight of the corresponding composition of active detergent components, unless
specified
otherwise.
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Highly preferred detergent components of the first phase include a builder
compound, a
surfactant; an enzyme and a bleaching agent. Highly preferred detergent
components of
the second phase include builder, enzymes and disrupting agent.
Builders suitable for use herein include water-soluble builders such as
citrates, carbonates
and polyphosphates and partially water-soluble or insoluble builders such as
crystalline
layered silicates (EP-A-0164514 and EP-A-0293640) and aluminosilicates
inclusive of
Zeolites A, B, P, X, HS and MAP. The builder is typically present at a level
of from
about 1 % to about 80% by weight, preferably from about 10% to about 70% by
weight,
most preferably from about 20% to about 60% by weight of composition.
Surfactants suitable herein include anionic surfactants such as alkyl
sulfates, alkyl ether
sulfates, alkyl benzene sulfonates, alkyl glyceryl sulfonates, alkyl and
alkenyl
sulphonates, alkyl ethoxy carboxylates, N-acyl sarcosinates, N-acyl taurates
and alkyl
succinates and sulfosuccinates, wherein the alkyl, alkenyl or acyl moiety is
CS-C20 ,
preferably C l 0-C 1 g linear or branched; cationic surfactants such as
choline esters (US-
A-4228042, US-A-4239660 and US-A-4260529) and mono C6-C16 N-alkyl or alkenyl
ammonium surfactants wherein the remaining N positions are substituted by
methyl,
hydroxyethyl or hydroxypropyl groups; low and high cloud point nonionic
surfactants and
mixtures thereof including nonionic alkoxylated surfactants (especially
ethoxylates
derived from C6-C 1 g primary alcohols), ethoxylated-propoxylated alcohols
(e.g., Olin
Corporation's Poly-Tergent~ SLF18), epoxy-capped poly(oxyalkylated) alcohols
(e.g.,
Olin Corporation's Poly-Tergent~ SLF18B - see WO-A-94/22800), ether-capped
poly(oxyalkylated) alcohol surfactants, and block polyoxyethylene-
polyoxypropylene
polymeric compounds such as PLURONIC~, REVERSED PLURONIC~, and
TETRONIC~ by the BASF-Wyandotte Corp., Wyandotte, Michigan; amphoteric
surfactants such as the amine oxides and alkyl amphocarboxylicc surfactants
such as
MiranolTM C2M; and zwitterionic surfactants such as the betaines and
sultaines; and
mixtures thereof. Surfactants suitable herein are disclosed, for example, in
US-A-
3,929,678 , US-A- 4,259,217, EP-A-0414 549, WO-A-93/08876 and WO-A-93/08874.
Surfactants are typically present at a level of from about 0.2% to about 30%
by weight,
more preferably from about 0.5% to about 10% by weight, most preferably from
about
1% to about 5% by weight of composition.
Enzymes suitable herein include bacterial and fungal cellulases such as
Carezyme and
Celluzyme (Novo Nordisk A/S); peroxidases; lipases such as Amano-P (Amano
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Pharmaceutical Co.), Ml LipaseR and LipomaxR (Gist-Brocades) and LipolaseR and
Lipolase UltraR (Novo); cutinases; proteases such as EsperaseR, AlcalaseR,
DurazymR and
SavinaseR (Novo) and MaxataseR, MaxacalR, ProperaseR and MaxapemR (Gist-
Brocades);
and a and (3 amylases such as Purafect Ox AmR (Genencor) and TermamylR, Bang,
FungamylR, DuramylR, and NatalaseR (Novo); and mixtures thereof. Enzymes are
preferably added herein as prills, granulates, or cogranulates at levels
typically in the
range from about 0.0001 % to about 2% pure enzyme by weight of composition.
Bleaching agents suitable herein include chlorine and oxygen bleaches,
especially
inorganic perhydrate salts such as sodium perborate mono-and tetrahydrates and
sodium
percarbonate optionally coated to provide controlled rate of release (see, for
example, GB-
A-1466799 on sulfate/carbonate coatings), preformed organic peroxyacids and
mixtures
thereof with organic peroxyacid bleach precursors and/or transition metal-
containing
bleach catalysts (especially manganese or cobalt). Inorganic perhydrate salts
are typically
incorporated at levels in the range from about 1 % to about 40% by weight,
preferably
from about 2% to about 30% by weight and more preferably from abut 5% to about
25%
by weight of composition. Peroxyacid bleach precursors preferred for use
herein include
precursors of perbenzoic acid and substituted perbenzoic acid; cationic
peroxyacid
precursors; peracetic acid precursors such as TAED, sodium acetoxybenzene
sulfonate
and pentaacetylglucose; pernonanoic acid precursors such as sodium 3,5,5-
trimethylhexanoyloxybenzene sulfonate (iso-NOBS) and sodium nonanoyloxybenzene
sulfonate (HOBS); amide substituted alkyl peroxyacid precursors (EP-A-
0170386); and
benzoxazin peroxyacid precursors (EP-A-0332294 and EP-A-0482807). Bleach
precursors are typically incorporated at levels in the range from about 0.5%
to about 25%,
preferably from about 1% to about 10% by weight of composition while the
preformed
organic peroxyacids themselves are typically incorporated at levels in the
range from
0.5% to 25% by weight, more preferably from 1% to 10% by weight of
composition.
Bleach catalysts preferred for use herein include the manganese
triazacyclononane and
related complexes (US-A-4246612, US-A-5227084); Co, Cu, Mn and Fe
bispyridylamine
and related complexes (US-A-5114611); and pentamine acetate cobalt(III) and
related
complexes(US-A-4810410).
Other suitable components herein include organic polymers having dispersant,
anti-
redeposition, soil release or other detergency properties invention in levels
of from about
0.1% to about 30%, preferably from about 0.5% to about 15%, most preferably
from
about 1 % to about 10% by weight of composition. Preferred anti-redeposition
polymers
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herein include acrylic acid containing polymers such as Sokalan PA30, PA20,
PA15,
PA10 and Sokalan CP10 (BASF GmbH), Acusol 45N, 480N, 460N (Rohm and Haas),
acrylic acid/maleic acid copolymers such as Sokalan CPS and
acrylic/methacrylic
copolymers. Preferred soil release polymers herein include alkyl and
hydroxyalkyl
celluloses (US-A-4,000,093), polyoxyethylenes, polyoxypropylenes and
copolymers
thereof, and nonionic and anionic polymers based on terephthalate esters of
ethylene
glycol, propylene glycol and mixtures thereof.
Heavy metal sequestrants and crystal growth inhibitors are suitable for use
herein in
10 levels generally from about 0.005% to about 20%, preferably from about 0.1%
to about
10%, more preferably from about 0.25% to about 7.5% and most preferably from
about
0.5% to about 5% by weight of composition, for example diethylenetriamine
penta
(methylene phosphonate), ethylenediamine tetra(methylene phosphonate)
hexamethylenediamine tetra(methylene phosphonate), ethylene diphosphonate,
hydroxy-
15 ethylene-1,1-diphosphonate, nitrilotriacetate, ethylenediaminotetracetate,
ethylenediamine-N,N'-disuccinate, methylglycinediacetic acid in their salt and
free acid
forms.
The compositions herein, especially for use in dishwashing, can contain a
corrosion
inhibitor such as organic silver coating agents in levels of from about 0.05%
to about
10%, preferably from about 0.1% to about S% by weight of composition
(especially
paraffins such as Winog 70 sold by Wintershall, Salzbergen, Germany), nitrogen-
containing corrosion inhibitor compounds (for example benzotriazole and
benzimadazole
- see GB-A-1137741) and Mn(II) compounds, particularly Mn(II) salts of organic
ligands
in levels of from about 0.005% to about 5%, preferably from about 0.01% to
about 1%,
more preferably from about 0.02% to about 0.4% by weight of the composition.
The first, second and/or optional subsequent phases of the tablet can also
comprise a
binder. Where present the binder is selected from the group consisting of
organic
polymers, for example polyethylene and/or polypropylene glycols having an
average
molecular weight of from about 1000 to about 12000, especially those of
molecular
weight 4000, 6000 and 9000, polyvinyl pyrrolidone (PVP), especially PVP of
molecular
weight 90 000, polyacrylates, sugars and sugar derivatives, starch and starch
derivatives,
for example hydroxy propyl methyl cellulose (HPMC) and carboxy methyl
cellulose
(CMC); and inorganic polymers, such as hexametaphosphate. The
polyethyleneglycol
binders are highly preferred herein.
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Other suitable components herein include colourants, water-soluble bismuth
compounds
such as bismuth acetate and bismuth citrate at levels of from about 0.01% to
about 5%,
enzyme stabilizers such as calcium ion, boric acid, propylene glycol and
chlorine bleach
scavengers at levels of from about 0.01 % to about 6%, lime soap dispersants
(see WO-A-
93/08877), suds suppressors (see WO-93/08876 and EP-A-0705324), polymeric dye
transfer inhibiting agents, optical brighteners, perfumes, fillers and clay
and cationic
fabric softeners.
Detergent components suitable for use herein are described in more detail in
the Appendix
to the Description (Ref: ADW1L)
The detergent tablets herein are preferably formulated to have a not unduly
high pH,
preferably a pH in 1 % solution in distilled water of from about 8.0 to about
12.5, more
preferably from about 9.0 to about 11.8, most preferably from about 9.5 to
about 11.5.
A preferred machine dishwashing method comprises treating soiled articles
selected from
crockery, glassware, silverware, metallic items, cutlery and mixtures thereof,
with an
aqueous liquid having dissolved or dispensed therein an effective amount of a
the herein
described compositions. By an effective amount is meant from 8g to 60g of
product
dissolved or dispersed in a wash solution of volume from 3 to 10 litres, as
are typical
product dosages and wash solution volumes commonly employed in conventional
machine dishwashing methods. Preferably the detergent tablets are from 15g to
40g in
weight, more preferably from 20g to 35g in weight, although tablets of a lower
weight
(e.g. as little as 2g) may be suitable in some circumstances.
Machine laundry methods herein typically comprise treating soiled laundry with
an
aqueous wash solution in a washing machine having dissolved or dispensed
therein an
effective amount of the herein described compositions. By an effective amount
is meant
from 40g to 300g of product dissolved or dispersed in a wash solution of
volume from 5
to 65 litres, as are typical product dosages and wash solution volumes
commonly
employed in conventional machine laundry methods.
In a preferred use aspect a dispensing device is employed in the washing
method. The
dispensing device is charged with the detergent product, and is used to
introduce the
product directly into the drum of the washing machine before the commencement
of the
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wash cycle. Its volume capacity should be such as to be able to contain
sufficient
detergent product as would normally be used in the washing method.
To allow for release of the detergent product during the wash the device may
possess a
number of openings through which the product may pass. Alternatively, the
device may
be made of a material which is permeable to liquid but impermeable to the
solid product,
which will allow release of dissolved product. Preferably, the detergent
product will be
rapidly released at the start of the wash cycle thereby providing transient
localised high
concentrations of product in the drum of the washing machine at this stage of
the wash
cycle.
Preferred dispensing devices are reusable and are designed in such a way that
container
integrity is maintained in both the dry state and during the wash cycle.
Alternatively, the dispensing device may be a flexible container, such as a
bag or pouch.
The bag may be of fibrous construction coated with a water impermeable
protective
material so as to retain the contents, such as is disclosed in EP-A-0018678.
Alternatively
it may be formed of a water-insoluble synthetic polymeric material provided
with an edge
seal or closure designed to rupture in aqueous media as disclosed in EP-A-
0011500, EP-
A-0011501, EP-A-0011502, and EP-A-0011968. A convenient form of water
frangible
closure comprises a water soluble adhesive disposed along and sealing one edge
of a
pouch formed of a water impermeable polymeric film such as polyethylene or
polypropylene.
Examples
Abbreviations used in Examples
In the detergent compositions, the abbreviated component identifications have
the
following meanings:
Citrate : Sodium citrate, anhydrous
Bicarbonate : Sodium hydrogen carbonate
Citric Acid : Anhydrous Citric acid
Carbonate : Powdered anhydrous sodium carbonate, 73%<150~m
Silicate : Amorphous Sodium Silicate (Si02:Na20 ratio = 2.0)
SKS-6 ; Crystalline layered silicate of formula 8-Na2Si205
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PB 1 : Anhydrous sodium perborate monohydrate
Polymer 480N : Sodium polyacrylate/methacrylate copolymer
solution
(~45% active) supplied by Norso Haas
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 Plurafac by BASF
TAED : Tetraacetyl ethylene diamine
HEDP : Ethane 1-hydroxy-1,1-diphosphonic acid
Chelant : Magnesium stabilised
diethylenetriaminepenta(methylene phosphonic
acid)
sodium salt solution
PAAC : Pentaamine acetate cobalt (III) salt
Paraffin : Paraffin oil sold under the tradename Winog
70 by
Wintershall.
Protease : Proteolytic enzyme
Amylase : Amylolytic enzyme.
BTA : Benzotriazole
Sulphate : Powdered anhydrous sodium sulphate, 59%<150~,m
PEG 400 : Polyethylene Glycol average molecular weight
approximately 400 available from Hoechst
PEG 4000 : Polyethylene Glycol average molecular weight
approximately 4000 available from Hoechst
In the following
examples all
levels are quoted
as parts by weight:
Examples I-VI
The following examples illustrate nil-P detergent tablets of the present
invention suitable
for use in a dishwashing machine. In the following, components are quoted as
parts by
weight on a 100% active basis.
I II III IV V VI
Phase 1
Cogranule
Carbonate 4.70 4.00 3.50 4.30 5.10 4.90
Polymer 480N 1.30 1.20 1.50 1.40 1.60 1.00
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Sulphate 3.00 2.50 2.00 2.20 3.10 2.50
Water 0.20 0.10 0.20 0.20 0.20 0.10
Other Components
Citrate 4.10 5.00 5.90 3.50 3.30 4.50
HEDP 0.06 0.04 0.07
Silicate 2.10 0.67 2.50 2.00 2.40
SKS-6 1.50 2.30
Chelant 0.11 0.14 0.09 0.11 0.12 0.15
PB1 3.00 2.45 2.70 3.50 2.50 3.10
TAED 0.50 1.00 1.10
PAAC 0.002 0.002 0.002 0.003 0.004 0.004
Amylase 0.12 0.11 0.11 0.13 0.16 0.15
Protease 0.12 0.06 0.06 0.09 0.10 0.09
Nonionic 0.50 0.80 0.60 0.80 0.40 0.90
PEG 4000 0.25 0.26 0.26 0.38 0.33 0.29
BTA 0.04 0.04 0.04 0.05 0.06 0.06
Paraffin 0.10 0.10 0.10 0.15 0.15 0.15
Perfume 0.02 0.02 0.02 0.013 0.013 0.013
Total 20.222g18.952g20.622g 19.126g 20.307g20.307g
Phase 2
Amylase 0.30 0.35 0.25 0.30 0.35 0.25
Protease 0.30 0.22 0.3 0.25 0.22 0.30
Citric acid 0.25 0.20 0.30 0.30
Sulphamic acid 0.30 0.30
Bicarbonate 0.70 0.45 0.56 1.09 0.45 0.45
Carbonate 0. 5 0. 5
5 5
Silicate 0.64
CaCl2 0.07 0.07
PEG 4000 0.08 0.042 0.075 0.07 0.04 0.045
PEG 400 0.08 0.018 0.015 0.02 0.015
Total 1.63g 2.Og 1.4g 2.Olg 2.Og 2.Og
The multi-phase tablet compositions are prepared as follows. The cogranular
detergency
additive compositions are initially prepared by spray-on of a liquid feed of
Polymer 480N
onto a powder feed containing carbonate, sulphate and recycled fines in a
Schugi
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WO 00/52130 PCT/US00/05302
Flexomix 160 followed by drying of the wet agglomerates in a fluidized bed
dryer with
fines recycling and size reduction as necessary to achieve the requisite
granule size
distribution. The Schugi is set at a rotation speed of about 3000 rpm and a
blade position
of 2°. The temperature of the liquid feed is in the region of
30°C to 40°C. The
liquid:powder feed ratio is in the range from about 0.2 to about 0.3. After
size reduction
in a hammer mill and screening, the dried granules have an apparent density in
the range
from about 700 to about 800 g/1, a median granule size of from about 520 to
about 570
Vim, and a size distribution such that no more than about 5% by weight is
greater than
1400~m and at least about 95% by weight is greater than 250~m. Any generated
fines
10 are recycled through the Schugi.
The detergent active composition of phase 1 is then prepared by admixing the
cogranular
detergency additive compositions and the remaining granular and liquid
components and
15 is then passed into the die of a conventional rotary press. The rotary
press includes a
punch suitably shaped for forming the mould. The cross-section of the die is
approximately 30x38 mm. The composition is then subjected to to a compression
force of
1220 kg/cmz and the punch is then elevated exposing the first phase of the
tablet
containing the mould in its upper surface. The detergent active composition of
phase 2 is
20 prepared in similar manner and the composition is then passed into the die.
The phase 2
particulate compositions have a mean particle size of from about 430-470~m.
The
particulate active composition is then subjected to a compression force of 150
kg/cmz, the
punch is elevated, and the multi-phase tablet ejected from the tablet press.
The tablets
provide improved tablet integrity, inter-phase adhesion and strength together
with
excellent dissolution and cleaning characteristics.
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Appendix to the Descri tp ion
Builders
Water-soluble builder compound
Suitable water-soluble builder compounds include the water soluble monomeric
polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic
acids or their
salts in which the polycarboxylic acid comprises at least two carboxylic
radicals separated
from each other by not more that two carbon atoms, carbonates, bicarbonates,
borates,
phosphates, and mixtures of any of the foregoing.
The carboxylate or polycarboxylate builder can be monomeric or oligomeric in
type
although monomeric polycarboxylates are generally preferred for reasons of
cost and
performance.
Suitable carboxylates containing one carboxy group include the water soluble
salts of
lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates
containing two
carboxy groups include the water-soluble salts of succinic acid, malonic acid,
(ethylenedioxy) diacetic acid, malefic acid, diglycolic acid, tartaric acid,
tartronic acid and
fumaric acid, as well as the ether carboxylates and the sulfmyl carboxylates.
Polycarboxylates containing three carboxy groups include, in particular, water-
soluble
citrates, aconitrates and citraconates as well as succinate derivatives such
as the
carboxymethyloxysuccinates described in GB-A-1,379,241, lactoxysuccinates
described
in GB-A-1,389,732, and aminosuccinates described in NL-A-7205873, and the
oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates
described in
GB-A-1,387,447.
Polycarboxylate containing four carboxy groups include oxydisuccinates
disclosed in GB-
A-1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane
tetracarboxylates and
1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo
substituents include
the sulfosuccinate derivatives disclosed in GB-A-1,398,421, GB-A-1,398,422 and
US-A-
3,936,448, and the sulfonated pyrolysed citrates described in GB-A-1,439,000.
Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-
tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-
tetrahydrofuran - cis, cis,
cis-tetracarboxylates, 2,5-tetrahydrofuran - cis - dicarboxylates, 2,2,5,5-
tetrahydrofuran -
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22
tetracarboxylates, 1,2,3,4,5,6-hexane - hexacarboxylates and carboxymethyl
derivatives of
polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic
polycarboxylates
include mellitic acid, pyromellitic acid and the phthalic acid derivatives
disclosed in GB-
A-1,425,343.
Of the above, the preferred polycarboxylates are hydroxycarboxylates
containing up to
three carboxy groups per molecule, more particularly citrates.
The parent acids of the monomeric or oligomeric polycarboxylate chelating
agents or
mixtures thereof with their salts, e.g. citric acid or citrate/citric acid
mixtures are also
contemplated as useful builder components.
Borate builders, as well as builders containing borate-forming materials that
can produce
borate under detergent storage or wash conditions can also be used but are not
preferred at
wash conditions less that 50°C, especially less than 40°C.
Examples of carbonate builders are the alkaline earth and alkali metal
carbonates,
including sodium carbonate and sesqui-carbonate and mixtures thereof with
ultra-fine
calcium carbonate as disclosed in DE-A-2,321,001.
Highly preferred builder compounds for use in the present compositions are
water-soluble
phosphate builders. Specific examples of water-soluble phosphate builders are
the alkali
metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium
and
potassium and ammonium pyrophosphate, sodium and potassium orthophosphate,
sodium
polymeta/phosphate in which the degree of polymerisation ranges from 6 to 21,
and salts
of phytic acid.
Specific examples of water-soluble phosphate builders are the alkali metal
tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and
potassium and ammonium pyrophosphate, sodium and potassium orthophosphate,
sodium
polymeta/phosphate in which the degree of polymerization ranges from 6 to 21,
and salts
of phytic acid.
Partially soluble or insoluble builder compound
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WO 00/52130 23 PCT/US00/05302
The compositions herein can contain a partially water-soluble or water-
insoluble builder
compound. Partially soluble and insoluble builder compounds are particularly
suitable
for use in tablets prepared for use in laundry cleaning methods. Examples of
partially
water soluble builders include the crystalline layered silicates as disclosed
for example, in
EP-A-0164514 and EP-A-0293640. Preferred are the crystalline layered sodium
silicates
of general formula
NaMSix02+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 preferably have a two
dimensional
'sheet' structure, such as the so called 8-layered structure, as described in
EP-A-0164514
and EP-A-0293640. Methods for preparation of crystalline layered silicates of
this type
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 and is
preferably 2.
The most preferred crystalline layered sodium silicate compound has the
formula 8-
Na2Si205 , known as NaSKS-6 (trade name), available from Hoechst AG.
The crystalline layered sodium silicate material can be added, especially in
granular
detergent compositions, as a particulate in intimate admixture with a solid,
water-soluble
ionisable material as described in WO-A-92/18594. The solid, water-soluble
ionisable
material is selected from organic acids, organic and inorganic acid salts and
mixtures
thereof, with citric acid being preferred.
Examples of largely water insoluble builders include the sodium
aluminosilicates.
Suitable aluminosilicates include the aluminosilicate zeolites having the unit
cell formula
Naz[(A102)z(Si02)y]. xH20 wherein z and y are at least 6; the molar ratio of z
to y is
from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more
preferably from 10 to
264. The aluminosilicate material are in hydrated form and are preferably
crystalline,
containing from 10% to 28%, more preferably from 18% to 22% water in bound
form.
The aluminosilicate zeolites can be naturally occurring materials, but are
preferably
synthetically derived. Synthetic crystalline aluminosilicate ion exchange
materials are
available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X,
Zeolite HS
and mixtures thereof.
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WO 00/52130 PCT/LTS00/05302
24
A preferred method of synthesizing aluminosilicate zeolites is that described
by
Schoeman et al (published in Zeolite (1994) 14(2), 110-116), in which the
author
describes a method of preparing colloidal aluminosilicate zeolites. The
colloidal
aluminosilicate zeolite particles should preferably be such that no more than
5% of the
particles are of size greater than 1 ~.m in diameter and not more than 5% of
particles are of
size less then 0.05 ~m in diameter. Preferably the aluminosilicate zeolite
particles have
an average particle size diameter of between 0.01 pm and 1 Vim, more
preferably between
0.05 ~m and 0.9 q.m, most preferably between 0.1 ~.m and 0.6 qm.
Zeolite A has the formula
Na 12 [A102) 12 (Si02)12~~ X20
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6
[(A102)g6(Si02)106~~ 276 H20. Zeolite MAP, as disclosed in EP-B-384,070 is a
suitable zeolite builder herein.
Preferred aluminosilicate zeolites are the colloidal aluminosilicate zeolites.
When
employed as a component of a detergent composition colloidal aluminosilicate
zeolites,
especially colloidal zeolite A, provide enhanced builder performance,
especially in terms
of improved stain removal, reduced fabric encrustation and improved fabric
whiteness
maintenance. Mixtures of colloidal zeolite A and colloidal zeolite Y are also
suitable
herein providing excellent calcium ion and magnesium ion sequestration
performance.
Surfactant
Suitable surfactants are selected from anionic, cationic, nonionic ampholytic
and
zwitterionic surfactants and mixtures thereof. Automatic dishwashing machine
products
should be low foaming in character and thus the foaming of the surfactant
system for use
in dishwashing should be suppressed or more preferably be low foaming,
typically
nonionic in character. Sudsing caused by surfactant systems used in laundry
cleaning
methods need not be suppressed to the same extent as is necessary for
dishwashing.
A typical listing of anionic, nonionic, ampholytic and zwitterionic classes,
and species of
these surfactants, is given in US-A-3,929,678. A list of suitable cationic
surfactants is
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WO 00/52130 25 PCT/US00/05302
given in US-A-4,259,217. A listing of surfactants typically included in
automatic
dishwashing detergent compositions is given in EP-A-0414549 and WO-A-93/08876
and
WO-A-93/08874.
Nonionic surfactants
Nonionic ethoxylated alcohol surfactants
The alkyl ethoxylate condensation products of aliphatic alcohols with from 1
to 25
moles of ethylene oxide are suitable for use herein. The alkyl chain of the
aliphatic
alcohol can either be straight or branched, primary or secondary, and
generally contains
from 6 to 22 carbon atoms. Particularly preferred are the condensation
products of
alcohols having an alkyl group containing from 8 to 20 carbon atoms with from
2 to 10
moles of ethylene oxide per mole of alcohol.
End-capped alkyl alkoxylate surfactants
A suitable endcapped alkyl alkoxylate surfactant is the epoxy-capped
poly(oxyalkylated)
alcohols represented by the formula:
R10[CH2CH(CH3)O]x[CH2CH20]y[CH2CH(OH)R2] (I)
wherein R1 is a linear or branched, aliphatic hydrocarbon radical having from
4 to 18
carbon atoms; R2 is a linear or branched aliphatic hydrocarbon radical having
from 2 to
26 carbon atoms; x is an integer having an average value of from 0.5 to 1.5,
more
preferably l; and y is an integer having a value of at least 15, more
preferably at least
20.
Preferably, the surfactant of formula I, at least 10 carbon atoms in the
terminal epoxide
unit [CH2CH(OH)R2]. Suitable surfactants of formula I, according to the
present
invention, are Olin Corporation's POLY-TERGENT~ SLF-18B nonionic surfactants,
as
described, for example, in WO-A-94/22800.
Ether-capped pol~(oxyalk 1~) alcohols
Other suitable surfactants for use herein include ether-capped
poly(oxyalkylated) alcohols
having the formula:
CA 02362955 2001-08-23
WO 00/52130 26 PCT/US00/05302
R1 O[CH2CH(R3)O]x[CH2]kCH(OH)[CH2]jOR2
wherein R1 and R2 are linear or branched, saturated or unsaturated, aliphatic
or aromatic
hydrocarbon radicals having from 1 to 30 carbon atoms; R3 is H, or a linear
aliphatic
hydrocarbon radical having from 1 to 4 carbon atoms; x is an integer having an
average
value from 1 to 30, wherein when x is 2 or greater R3 may be the same or
different and k
and j are integers having an average value of from 1 to 12, and more
preferably 1 to 5.
R1 and R2 are preferably linear or branched, saturated or unsaturated,
aliphatic or
aromatic hydrocarbon radicals having from 6 to 22 carbon atoms with 8 to 18
carbon
atoms being most preferred. H or a linear aliphatic hydrocarbon radical having
from 1 to
2 carbon atoms is most preferred for R3. Preferably, x is an integer having an
average
value of from 1 to 20, more preferably from 6 to 15.
As described above, when, in the preferred embodiments, and x is greater than
2, R3 may
be the same or different. That is, R3 may vary between any of the alkyleneoxy
units as
described above. For instance, if x is 3, R3may be be selected to form
ethyleneoxy(EO)
or propyleneoxy(PO) and may vary in order of (EO)(PO)(EO), (EO)(EO)(PO);
(EO)(EO)(EO); (PO)(EO)(PO); (PO)(PO)(EO) and (PO)(PO)(PO). Of course, the
integer
three is chosen for example only and the variation may be much larger with a
higher
integer value for x and include, for example, mulitple (EO) units and a much
small
number of (PO) units.
Particularly preferred surfactants as described above include those that have
a low cloud
point of less than 20°C. These low cloud point surfactants may then be
employed in
conjunction with a high cloud point surfactant as described in detail below
for superior
grease cleaning benefits.
Most preferred ether-capped poly(oxyalkylated) alcohol surfactants are those
wherein k is
1 and j is 1 so that the surfactants have the formula:
R1 O[CH2CH(R3)O]xCH2CH(OH)CH20R2
where Rl, R2 and R3 are defined as above and x is an integer with an average
value of
from 1 to 30, preferably from 1 to 20, and even more preferably from 6 to 18.
Most
CA 02362955 2001-08-23
WO 00/52130 2,~ PCT/US00/05302
preferred are surfactants wherein R1 and R2 range from 9 to 14, R3 is H
forming
ethyleneoxy and x ranges from 6 to 15.
The ether-capped poly(oxyalkylated) alcohol surfactants comprise three general
components, namely a linear or branched alcohol, an alkylene oxide and an
alkyl ether
end cap. The alkyl ether end cap and the alcohol serve as a hydrophobic, oil-
soluble
portion of the molecule while the alkylene oxide group forms the hydrophilic,
water-
soluble portion of the molecule.
These surfactants exhibit significant improvements in spotting and filming
characteristics
and removal of greasy soils, when used in conjunction with high cloud point
surfactants,
relative to conventional surfactants.
Generally speaking, the ether-capped poly(oxyalkylene) alcohol surfactants may
be
produced by reacting an aliphatic alcohol with an epoxide to form an ether
which is then
reacted with a base to form a second epoxide. The second epoxide is then
reacted with an
alkoxylated alcohol to form the novel compounds of the present invention.
Nonionic ethoxvlated/~ronoxylated fatty alcohol surfactants
The ethoxylated C6-C 1 g fatty alcohols and C6-C 1 g mixed
ethoxylated/propoxylated fatty
alcohols are suitable surfactants for use herein, particularly where water
soluble.
Preferably the ethoxylated fatty alcohols are the C 10-C 1 g ethoxylated fatty
alcohols with
a degree of ethoxylation of from 3 to 50, most preferably these are the C 12-C
18
ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40.
Preferably the
mixed ethoxylated/propoxylated fatty alcohols have an alkyl chain length of
from 10 to
18 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of
propoxylation
of from 1 to 10.
Nonionic EO/PO condensates with propylene~lycol
The condensation products of ethylene oxide with a hydrophobic base formed by
the
condensation of propylene oxide with propylene glycol are suitable for use
herein. The
hydrophobic portion of these compounds preferably has a molecular weight of
from 1500
to 1800 and exhibits water insolubility. Examples of compounds of this type
include
certain of the commercially-available PluronicTM surfactants, marketed by
BASF.
CA 02362955 2001-08-23
WO 00/52130 PCT/US00/05302
28
Nonionic EO condensation products with,propylene oxide/ethylene diamine
adducts
The condensation products of ethylene oxide with the product resulting from
the reaction
of propylene oxide and ethylenediamine are suitable for use herein. The
hydrophobic
moiety of these products consists of the reaction product of ethylenediamine
and excess
propylene oxide, and generally has a molecular weight of from 2500 to 3000.
Examples
of this type of nonionic surfactant include certain of the commercially
available Tetronic
TM compounds, marketed by BASF.
Mixed Nonionic Surfactant Systems
The compositions herein can also include a mixed nonionic surfactant system
comprising
at least one low cloud point nonionic surfactant and at least one high cloud
point nonionic
surfactant.
"Cloud point", as used herein, is a well known property of nonionic
surfactants which is
the result of the surfactant becoming less soluble with increasing
temperature, the
temperature at which the appearance of a second phase is observable is
referred to as the
"cloud point" (See Kirk Othmer's Encyclopedia of Chemical Technology, 3rd Ed.
Vol. 22,
pp. 360-379).
As used herein, a "low cloud point" nonionic surfactant is defined as a
nonionic surfactant
system ingredient having a cloud point of less than 30°C, preferably
less than 20°C, and
most preferably less than 10°C. Typical low cloud point nonionic
surfactants include
nonionic alkoxylated surfactants, especially ethoxylates derived from primary
alcohol,
and polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverse block
polymers. Also, such low cloud point nonionic surfactants include, for
example,
ethoxylated-propoxylated alcohol (e.g., Olin Corporation's Poly-Tergent~
SLF18),
epoxy-capped poly(oxyalkylated) alcohols (e.g., Olin Corporation's Poly-
Tergent~
SLF18B series of nonionics, as described, for example, in WO-A-94/22800) and
the
ether-capped poly(oxyalkylated) alcohol surfactants.
Nonionic surfactants can optionally contain propylene oxide in an amount up to
1 S% by
weight. Other suitable nonionic surfactants can be prepared by the processes
described in
US-A-4,223,163.
CA 02362955 2004-09-02
29
Low cloud point nonionic surfactants additionally comprise a polyoxycthylene,
palyoxypropylene block polymeric compound. Block polyoxyethyle~ne-
polyoxypropylenc polymeric compounds inchtde those based on ethylene glycol,
propylene glycol, glycerol, trimathylolpropane and ethylenediamine as
initiatarreactive
hydrogen compound. Certain of the block polymer surfactant compounds
designated
PLUROIJIC~, R)rV$RSED PLLIROl'TIC~, and TETROAT1C~ by the BASF-Wyandotte
Corp., Wyandotte, ll~chigan, are also suitable herein. Preferred examples
include
REVERSED pLURCN1C~ 2582 and TETROhTIC~ 702, Such surfactants are typically
l0 useful herein as low cloud point nonionic surfactants.
~1s used herein, a "high cloud paint" nonionic surfactant is defined as a
nonionic
surfactant system ingredient having a cloud point of greater than 40°C,
preferably greater
than 50°C, and more preferably greater than GO°C. Preferably the
nonionic surfactant
system comprises an etttoxylated surfactant derived from the reaction of a
monobydroxy
alcohol or alkylphenol cont<~ining from 8 to 2Q carbon atoms, with from 6 to
15 moles of
ethylene oxide per mole of alcohol or alkyl phenol an an average basis. Such
high cloud
point noaiotiac surfactants include, far example, Tergitol 15 S~(suppiied by
Union
Cart~ide), Rhadasurf TtvID 8 S (supplied by Rhone Poulenc), and IVeodol 91 8
(supplied
by 5he11).
It is also preferred that the high cloud point nonionic surfactant further
have a hydrophile-
lipophile balance ("1-ILB"; see Kirk Qthrnct hereiribefore) value within the
range of from
9 to 15, preferably 11 to 1 S_ Such materials include, for example, Tergitol
1559
(supplied by Union Carbide), RhadasurfTMD $.5 (supplied by Rhone Potlltttc),
and
Neodol 91-8 (supplied by Shell).
Another suitable high cloud point nonianio surfactant is derived from a
srraig~t or
preferably branched chain or secondary fatty alcohol containing from 6 to 20
carbon
atoms (C6-C2d alcohol), including secondary alcohols and branched chain
primary
alcohols. Preferably, high cloud point nonionic surfactants are branched or
secondary
alcohol ethuxylates, snore preferably mixed 09/11 or Cl l Il S branched
alcohol
ethoxylates, condensed with an average of from 6 to 15 moles, preferably from
6 #0 12
moles, and most preferably from 6 to 9 moles of ethylene oxide per mole of
alcohol.
Preferably the ethoxylated nonionic surfactant so derived h.as a narrow
ethoxylate
distribution relative to the average.
CA 02362955 2001-08-23
WO 00/52130 30 PCT/US00/05302
Anionic surfactants
Essentially any anionic surfactants useful for detersive purposes are
suitable. These can
include salts (including, for example, sodium, potassium, ammonium, and
substituted
ammonium salts such as mono-, di- and triethanolamine salts) of the anionic
sulfate,
sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate
surfactants are
preferred.
Other anionic surfactants include the isethionates such as the acyl
isethionates, N-acyl
taurates, fatty acid amides of methyl tauride, alkyl succinates and
sulfosuccinates,
monoesters of sulfosuccinate (especially saturated and unsaturated C 12-C 18
monoesters)
diesters of sulfosuccinate (especially saturated and unsaturated C6-C14
diesters), N-acyl
sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such
as rosin,
hydrogenated rosin, and resin acids and hydrogenated resin acids present in or
derived
from tallow oil.
Anionic sulfate surfactants
Anionic sulfate surfactants suitable for use herein include the linear and
branched primary
and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol
sulfates, alkyl
phenol ethylene oxide ether sulfates, the CS-C 1 ~ acyl-N-(C 1-C4 alkyl) and -
N-(C 1-C2
hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as
the
sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being
described
herein).
Alkyl sulfate surfactants are preferably selected from the linear and branched
primary
C 10-C 1 g alkyl sulfates, more preferably the C 11-C 15 branched chain alkyl
sulfates and
the C 12-C 14 linear chain alkyl sulfates.
Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting of the
C 10-C 1 g alkyl sulfates which have been ethoxylated with from 0.5 to 20
moles of
ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate
surfactant is a
C 11-C 1 g, most preferably C 11-C 15 alkyl sulfate which has been ethoxylated
with from
0.5 to 7, preferably from 1 to S, moles of ethylene oxide per molecule.
Mixtures of alkyl
sulfate and alkyl ethoxysulfate surfactants are also suitable herein (WO-A-
93/18124).
CA 02362955 2001-08-23
WO 00/52130 PCT/US00/05302
31
Anionic sulfonate surfactants
Anionic sulfonate surfactants suitable for use herein include the salts of CS-
C20 linear
alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary
alkane
sulfonates, C6-C2q. olefin sulfonates, sulfonated polycarboxylic acids, alkyl
glycerol
sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates,
and any mixtures
thereof.
Anionic carboxylate surfactant
Suitable anionic carboxylate surfactants include the alkyl ethoxy
carboxylates, the alkyl
polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'),
especially
certain secondary soaps as described herein.
Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH20)x
CH2C00-M+ wherein R is a C6 to Clg alkyl group, x ranges from 0 to 10, and the
ethoxylate distribution is such that, on a weight basis, the amount of
material where x is 0
is less than 20 % and M is a canon. Suitable alkyl polyethoxy polycarboxylate
surfactants include those having the formula RO-(CHR1-CHR2-O)-R3 wherein R is
a C6
to Clg alkyl group, x is from 1 to 25, R1 and R2 are selected from the group
consisting of
hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid
radical, and
mixtures thereof, and R3 is selected from the group consisting of hydrogen,
substituted or
unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures
thereof.
Suitable soap surfactants include the secondary soap surfactants which contain
a carboxyl
unit connected to a secondary carbon. Preferred secondary soap surfactants for
use herein
are water-soluble members selected from the group consisting of the water-
soluble salts
of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic
acid, 2-
butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps may also be
included
as suds suppressors.
Alkali metal sarcosinate surfactants
Other suitable anionic surfactants are the alkali metal sarcosinates of
formula R-CON
(Rl) CH2 COOM, wherein R is a CS-C1~ linear or branched alkyl or alkenyl
group, R1 is
CA 02362955 2001-08-23
WO 00/52130 PCT/US00/05302
32
a Cl-Cq, alkyl group and M is an alkali metal ion. Preferred examples are the
myristyl
and oleoyl methyl sarcosinates in the form of their sodium salts.
Amphoteric surfactants
Suitable amphoteric surfactants for use herein include the amine oxide
surfactants and the
alkyl amphocarboxylic acids.
Suitable amine oxides include those compounds having the formula
R3(OR4)xN0(RS)2
wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl
phenyl
group, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an
alkylene or
hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures
thereof; x is
from 0 to 5, preferably from 0 to 3; and each RS is an alkyl or hydroxyalkyl
group
20
containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3
ethylene
oxide groups. Preferred are C 10-C 1 g alkyl dimethylamine oxide, and C 10-18
acylamido
alkyl dimethylamine oxide.
A suitable example of an alkyl amphodicarboxylic acid is Miranol(TM) C2M Conc.
manufactured by Miranol, Inc., Dayton, NJ.
Zwitterionic surfactants
Zwitterionic surfactants can be broadly described as derivatives of secondary
and tertiary
amines, derivatives of heterocyclic secondary and tertiary amines, or
derivatives of
quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds.
Betaine and sultaine surfactants are exemplary zwitterionic surfactants for
use herein.
Suitable betaines are those compounds having the formula R(R')2N+R2C00-
wherein R
is a C6-Clg hydrocarbyl group, each R1 is typically Cl-C3 alkyl, and R2 is a
C1-CS
hydrocarbyl group. Preferred betaines are C12-18 dimethyl-ammonio hexanoate
and the
C10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex
betaine
surfactants are also suitable for use herein.
Cationic surfactants
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WO 00/52130 33 PCT/US00/05302
Cationic ester surfactants used in this invention are preferably water
dispersible
compound having surfactant properties comprising at least one ester (i.e. -COO-
) linkage
and at least one cationically charged group. Other suitable cationic ester
surfactants,
including choline ester surfactants, have for example been disclosed in US-A-
4228042,
US-A-4239660 and US-A-4260529.
Suitable cationic surfactants include the quaternary ammonium surfactants
selected from
mono C6-C16, preferably C6-C10 N-alkyl or alkenyl ammonium surfactants wherein
the
remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl
groups.
Enz~es
Enzymes suitable for use herein included cellulases, hemicellulases,
peroxidases,
proteases, gluco-amylases, amylases, xylanases, lipases, phospholipases,
esterases,
cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases,
lipoxygenases,
ligninases, pullulanases, tannases, pentosanases, malanases,13-glucanases,
arabinosidases,
hyaluronidase, chondroitinase, laccase and mixtures thereof.
Preferred enzymes include protease, amylase, lipase, peroxidases, cutinase
and/or
cellulase in conjunction with one or more plant cell wall degrading enzymes.
The cellulases usable in the present invention include both bacterial or
fungal cellulase.
Preferably, they will have a pH optimum of between 5 and 12 and an activity
above 50
CEVU (Cellulose Viscosity Unit). Suitable cellulases are disclosed in US-A-
4,435,307,
J61078384 and WO-A-96/02653 which disclose fungal cellulases produced
respectively
from Humicola insolens, Trichoderma, Thielavia and Sporotrichum. EP-A-0739982
describes cellulases isolated from novel Bacillus species. Suitable cellulases
are also
disclosed in GB-A-2075028; GB-A-2095275, DE-A-2.247.832 and WO-A-95/26398.
Examples of such cellulases are cellulases produced by a strain of Humicola
insolens
(Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800.
Other
suitable cellulases are cellulases originated from Humicola insolens having a
molecular
weight of SOKDa, an isoelectric point of 5.5 and containing 415 amino acids;
and a
"43kD endoglucanase derived from Humicola insolens, DSM 1800, exhibiting
cellulase
activity; a preferred endoglucanase component has the amino acid sequence
disclosed in
WO-A-91/17243. Also suitable cellulases are the EGIII cellulases from
Trichoderma
CA 02362955 2001-08-23
WO 00/52130 PCT/US00/05302
34
longibrachiatum described in WO-A-94/21801. Especially suitable cellulases are
the
cellulases having color care benefits. Examples of such cellulases are
cellulases described
in European patent application No. 91202879.2, filed November 6, 1991 (Novo).
Carezyme and Celluzyme (Novo Nordisk A/S) are especially useful. See also WO-A-
91/17244 and WO-A-91/21801. Other suitable cellulases for fabric care and/or
cleaning
properties are described in WO-A-96/34092, WO-A-96/17994 and WO-A-95/24471.
Said cellulases are normally incorporated in detergent compositions at levels
from
0.0001 % to 2% of active enzyme by weight of composition.
Peroxidase enzymes are used in combination with oxygen sources, e:g.
percarbonate,
perborate, persulfate, hydrogen peroxide, etc. They are used for "solution
bleaching", i.e.
to prevent transfer of dyes or pigments removed from substrates during wash
operations
to other substrates in the wash solution. Peroxidase enzymes are known in the
art, and
include, for example, horseradish peroxidase, ligninase and haloperoxidase
such as
chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are
disclosed, for example, in WO-A-89/099813, WO-A-89/09813 and in European
Patent
application EP No. 91202882.6, filed on November 6, 1991 and EP No.
96870013.8, filed
February 20, 1996. Also suitable is the laccase enzyme.
Preferred enhancers are substitued phenthiazine and phenoxasine 10-
Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4-carboxylic acid
(EPC), 10-
phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO-A-
94/12621) and substitued syringates (C3-CS substitued alkyl syringates) and
phenols.
Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.
Said cellulases and/or peroxidases are normally incorporated in detergent
composition at
levels from 0.0001 % to 2% of active enzyme by weight of composition.
Other suitable enzymes that can be included in the detergent compositions of
the present
invention include lipases. 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-A-1,372,034. Suitable lipases include those
which
show a positive immunological cross-reaction with the antibody of the lipase,
produced
by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is
available from
Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P
CA 02362955 2001-08-23
WO 00/52130 PCT/US00/05302
"Amano," hereinafter referred to as "Amano-P". Other suitable commercial
lipases
include Amano-CES, lipases ex Chromobacter viscosum, 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
5 Netherlands, and lipases ex Pseudomonas gladioli. Especially suitable
lipases are lipases
such as M1 LipaseR ~d LipomaxR (Gist-Brocades) and LipolaseR and Lipolase
UltraR(Novo) which have found to be very effective when used in combination
with the
compositions of the present invention. Also suitables are the lipolytic
enzymes described
in EP-A-0258068, WO-A-92/05249, WO-A-95/22615, WO-A-94/03578, WO-A
10 95/35381 and WO-A-96/00292.
Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special
kind of
lipase, namely lipases which do not require interfacial activation. Addition
of cutinases to
detergent compositions have been described in e.g. WO-A-88/09367, WO-A-
90/09446,
15 WO-A-94/14963 and WO-A-94/14964.
The lipases and/or cutinases are normally incorporated in detergent
composition at levels
from 0.0001% to 2% of active enzyme by weight of composition.
20 Suitable proteases are the subtilisins which are obtained from particular
strains of B.
subtilis and B. licheniformis (subtilisin BPN and BPN'). 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
25 in GB 1,243,784 to Novo. Other suitable proteases include ALCALASE~,
DURAZYM~ and SAV1NASE~ from Novo and MAXATASE~~ MAXACAL~,
PROPERASE~ and MAXAPEM~ (protein engineered Maxacal) from Gist-Brocades.
Proteolytic enzymes also encompass modified bacterial serine proteases, such
as those
described in European Patent Application Serial Number 87 303761.8, filed
April 28,
30 1987 (particularly pages 17, 24 and 98), and which is called herein
"Protease B", and in
EP-A-0199404 which refers to a modified bacterial serine protealytic enzyme
which is
called "Protease A" herein. Suitable is what is called herein "Protease C",
which is a
variant of an alkaline serine protease from Bacillus in which lysine replaced
arginine at
position 27, tyrosine replaced valine at position 104, serine replaced
asparagine at
35 position 123, and alanine replaced threonine at position 274. Protease C is
described in
CA 02362955 2004-09-02
36
WO-A-91/06637. Genetically modified variants, particularly of protease C, are
also
included herein,
A suitable protease referred to as "Protease D" is a carbonyl hydrolase
variant Staving an
amino acid sequence not found in nature, which is derived from a prectwsar
carbonyl
hydrolase by substituting a different amino acid for a plurality of amino acid
residues at a
position in said carbonyl hydrolase equivalent to position +7f, preferably
also in
combination with one or more amino acid residue positions equivalent to Chase
selected
from the group consisting of +99, +101, +103, +1 Od, a~ 107, +123, +27, +105,
+109, +126,
+12$, +135, +156, +166, +195, +197, +204, +206, +210, ~-216, +217,1218, +222,
+260,
+265, and/or +2'74 according to the numbering of Bacillus umyloliquefacieras
subtilisin, as
desaribtd in WQ A-95/10591
Also suitable are proteases described in 1JP-A-0251 44G and W~~A-91/06637,
protease
B1.A)'~ described in WO-A-91/02792 and their variants described in WO-A-
95123221.
See also a high pl-I protease from Bacillus sp. NCTMH 40338 described in WO-A-
93/l 8140. Enzymatic dettrgents comprising protease, one ar mare other
enzymes, and $
reversible protease inhibitor are described in WD-A-92103529. When desired, a
protease
having decreased adsorption and increased hydrolysis is available as described
in WO-A-
95107791. A recombinant trypsin-like protease for detergents suitable herein
is described
in WO-A- 94l2S5113, Outer suitable proteases are described in EF'-A-0516 200.
Other suitable protease enzymes include protease enTymcs which art a carbonyl
hydrolase variant having an a~xiino acid sequence not found in nature, which
is derived by
replacement of a plurality of amino acid residues of a precursor carbonyl
hydrolasc with
different amino acids, whertin said plurality of amino acid residues replaced
in the
pt~ecursor enzyme correspond to position +210 in combination with one dr more
of the
following residues: 133, +62, +67, +76, +100, +101, +103, +I04, +107, +128,
+129,
+130, +132, +135, +156, +15$, -H164, +166, +1~7, +170, *209, +215, *217, +218
and
+222, where the numbered positions correspond to naturally-occurring
subtilisin from
Hacillus amyloliauefaciens or to equivalent amino acid residues in other
carbonyl
hydrolases ar subtilisins (such as ~cillus 1~ subtilisin). Preferred enzymes
of this
type include those having position changes ~f-210, +76, +103, +104, +156, and
w166.
CA 02362955 2001-08-23
WO 00/52130 37 PCT/US00/05302
The proteolytic enzymes are incorporated in detergent compositions at a level
of from
0.0001 % to 2%, preferably from 0.001 % to 0.2%, more preferably from 0.005%
to 0.1
pure enzyme by weight of composition.
Amylases (a and/or 13) can be included for removal of carbohydrate-based
stains. WO-A-
94/02597 describes cleaning compositions which incorporate mutant amylases.
See also
WO-A-95/10603. Other amylases known for use in cleaning compositions include
both a
- and ~3-amylases. a-Amylases are known in the art and include those disclosed
in US-A-
5,003,257; EP-A-0252,666; WO-A-91/00353; FR-A-2,676,456; EP-A-0285,123; EP-A-
525,610; EP-A-0368,341; and GB-A-1,296,839. Other suitable amylases are
stability-
enhanced amylases described in WO-A-94/18314 and WO-A-96/05295 and amylase
variants having additional modification in the immediate parent available from
Novo
Nordisk A/S, disclosed in WO-A-95/10603. Also suitable are amylases described
in EP-
A-0277216, WO-A-95/26397 and WO-A-96/23873.
Examples of commercial a-amylases products are Purafect Ox Am~ from Genencor
and
Termam 1~ Ban~
y , ,Fungamyl and Duramyl , Natalase all available from Novo
Nordisk A/S Denmark. WO-A-95/26397 describes other suitable amylases : a-
amylases
characterised by having a specific activity at least 25% higher than the
specific activity of
Termamyl~ at a temperature range of 25°C to 55°C and at a pH
value in the range of 8 to
10, measured by the Phadebas~ a-amylase activity assay. Suitable are variants
of the
above enzymes, described in WO-A-96/23873. Other amylolytic enzymes with
improved
properties with respect to the activity level and the combination of
thermostability and a
higher activity level are described in WO-A-95/35382.
Preferred amylase enzymes include those described in WO-A-95/26397 and in co-
pending application by Novo Nordisk PCT/DK96/00056.
The amylolytic enzymes are incorporated in detergent compositions at a level
of from
0.0001% to 2%, preferably from 0.00018% to 0.06%, more preferably from
0.00024% to
0.048% pure enzyme by weight of composition
In a particularly preferred embodiment, compositions herein comprise amylase
enzymes,
particularly those described in WO-A-95/26397 and co-pending application by
Novo
Nordisk PCT/DK96/00056 in combination with a complementary amylase.
CA 02362955 2001-08-23
WO 00/52130 38 PCT/US00/05302
By "complementary" it is meant the addition of one or more amylase suitable
for
detergency purposes. Examples of complementary amylases (a and/or 13) are
described
below. WO-A-94/02597 and WO-A-95/10603 describe cleaning compositions which
incorporate mutant amylases. Other amylases known for use in cleaning
compositions
include both a- and (3-amylases. a-Amylases are known in the art and include
those
disclosed in US-A-5,003,257; EP-A-0252,666; WO-A-91/00353; FR-A-2,676,456; EP-
A-
0 285123; EP-A-0525610; EP-A-0368341; and GB-A-1,296,839. Other suitable
amylases
are stability-enhanced amylases described in WO-A-94/18314 and WO-A-96/05295
and
amylase variants having additional modification in the immediate parent
available from
Novo Nordisk A/S, disclosed in WO-A-95/10603. Also suitable are amylases
described in
EP-A-0277 216. Examples of commercial a-amylases products are Purafect Ox Am~
from Genencor and Termamyl~, Ban~ ,Fungamyl~ and Duramyl~, all available from
Novo Nordisk A/S Denmark. W095/26397 describes other suitable amylases : a-
amylases characterised by having a specific activity at least 25% higher than
the specific
activity of Termamyl~ at a temperature range of 25°C to 55°C and
at a pH value in the
range of 8 to 10, measured by the Phadebas~ a-amylase activity assay. Suitable
are
variants of the above enzymes, described in WO-A-96/23873. Other amylolytic
enzymes
with improved properties with respect to the activity level and the
combination of
thermostability and a higher activity level are described in WO-A-95/35382.
Preferred
complementary amylases for the present invention are the amylases sold under
the
tradename Purafect Ox AmR described in WO-A- 94/18314, WO-A-96/05295 sold by
Genencor; Termamyl~, Fungamyl~, Ban~ Natalase~ and Duramyl~, all available
from
Novo Nordisk A/S and Maxamyl~ by Gist-Brocades.
The complementary amylase is generally incorporated in detergent compositions
at a
level of from 0.0001% to 2%, preferably from 0.00018% to 0.06%, more
preferably from
0.00024% to 0.048% pure enzyme by weight of composition. Preferably a weight
of pure
enzyme ratio of specific amylase to the complementary amylase is comprised
between 9:1
to 1:9, more preferably between 4:1 to 1:4, and most preferably between 2:1
and 1:2.
The above-mentioned enzymes may be of any suitable origin, such as vegetable,
animal,
bacterial, fungal and yeast origin. Origin can further be mesophilic or
extremophilic
(psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic,
acidophilic,
halophilic, etc.). Purified or non-purified forms of these enzymes may be
used. Also
included by definition, are mutants of native enzymes. Mutants can be obtained
e.g. by
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WO 00/52130 39 PCT/US00/05302
protein and/or genetic engineering, chemical and/or physical modifications of
native
enzymes. Common practice as well is the expression of the enzyme via host
organisms in
which the genetic material responsible for the production of the enzyme has
been cloned.
Enzymes are normally incorporated in detergent composition at levels from
0.0001 % to
2% of active enzyme by weight of composition. The enzymes can be added as
separate
single ingredients (grills, granulates, stabilized liquids, etc... containing
one enzyme ) or
as mixtures of two or more enzymes ( e.g. cogranulates ).
Other suitable detergent ingredients that can be added are enzyme oxidation
scavengers
which are described in copending European Patent application 92870018.6 filed
on
January 31, 1992. Examples of such enzyme oxidation scavengers are ethoxylated
tetraethylene polyamines.
A range of enzyme materials and means for their incorporation into synthetic
detergent
compositions is also disclosed in WO-A-9307263, WO-A-9307260, WO-A-8908694 and
US-A-3,553,139. Enzymes are further disclosed in US-A-4,101,457 and US-A-
4,507,219. Enzyme materials useful for liquid detergent formulations, and
their
incorporation into such formulations, are disclosed in US-A- 4,261,868.
Enzymes for use
in detergents can be stabilised by various techniques. Enzyme stabilisation
techniques are
disclosed and exemplified in US-A-3,600,319, EP-A-0199405 and EP-A-0200586.
Enzyme stabilisation systems are also described, for example, in US-A-
3,519,570. A
useful Bacillus, sp. AC13 giving proteases, xylanases and cellulases, is
described in WO-
A-94015 32.
Bleaching agent
Suitable bleaching agents herein include chlorine and oxygen-releasing
bleaching agents.
In one preferred aspect the oxygen-releasing bleaching agent contains a
hydrogen
peroxide source and an organic peroxyacid bleach precursor compound. The
production
of the organic peroxyacid occurs by an in situ reaction of the precursor with
a source of
hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic
perhydrate
bleaches. In an alternative aspect a preformed organic peroxyacid is
incorporated directly
into the composition. Compositions containing mixtures of a hydrogen peroxide
source
and organic peroxyacid precursor in combination with a preformed organic
peroxyacid
are also envisaged.
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Inor anic perhydrate bleaches
Examples of inorganic perhydrate salts include perborate, percarbonate,
perphosphate,
5 persulfate and persilicate salts. The inorganic perhydrate salts are
normally the alkali
metal salts. The inorganic perhydrate salt can be included as the crystalline
solid without
additional protection. For certain perhydrate salts however, a coated form of
the material
is used in order to provide better storage stability.
10 Sodium perborate can be in the form of the monohydrate of nominal formula
NaB02H202 or the tetrahydrate NaB02H202.3H20. Alkali metal percarbonates,
particularly sodium percarbonate are preferred perhydrates for inclusion
herein. Sodium
percarbonate is an addition compound having a formula corresponding to
2Na2C03.3H202, and is available commercially as a crystalline solid. Sodium
15 percarbonate, being a hydrogen peroxide addition compound tends on
dissolution to
release the hydrogen peroxide quite rapidly which can increase the tendency
for localised
high bleach concentrations to arise. The percarbonate is most preferably
incorporated
into such compositions in a coated form which provides in-product stability.
20 A suitable coating material providing in product stability comprises mixed
salt of a water
soluble alkali metal sulphate and carbonate. Such coatings together with
coating
processes have previously been described in GB-A-1,466,799. The weight ratio
of the
mixed salt coating material to percarbonate lies in the range from 1 : 200 to
1 : 4, more
preferably from 1 : 99 to 1 : 9, and most preferably from 1 : 49 to 1 : 19.
Preferably, the
25 mixed salt is of sodium sulphate and sodium carbonate which has the general
formula
Na2S04.n.Na2C03 wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0
and most
preferably n is from 0.2 to 0.5. Another suitable coating material providing
in product
stability, comprises sodium silicate of Si02 : Na20 ratio from 1.8 : 1 to 3.0
: 1, preferably
1.8:1 to 2.4:1, and/or sodium metasilicate, preferably applied at a level of
from 2% to
30 10%, (normally from 3% to 5%) of Si02 by weight of the inorganic perhydrate
salt.
Magnesium silicate can also be included in the coating. Coatings that contain
silicate
and borate salts or boric acids or other inorganics are also suitable. Other
coatings which
contain waxes, oils, fatty soaps can also be used herein.
35 Potassium peroxymonopersulfate is another inorganic perhydrate salt of
utility in the
compositions herein.
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WO 00/52130 41 PCT/US00/05302
Peroxyacid bleach precursor
Peroxyacid bleach precursors are compounds which react with hydrogen peroxide
in a
perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach
precursors
may be represented as
O
X-C-L
where L is a leaving group and X is essentially any functionality, such that
on
perhydrolysis the structure of the peroxyacid produced is
O
X-C-OOH
Suitable peroxyacid bleach precursor compounds typically contain one or more N-
or O-
acyl groups, which precursors can be selected from a wide range of classes.
Suitable
classes include anhydrides, esters, imides, lactams and acylated derivatives
of imidazoles
and oximes. Examples of useful materials within these classes are disclosed in
GB-A-
1586789. Suitable esters are disclosed in GB-A-836988, GB-A-864798, GB-A-
1147871,
GB-A-2143231 and EP-A-0170386.
Leaving groups
The leaving group, hereinafter L group, must be sufficiently reactive for the
perhydrolysis
reaction to occur within the optimum time frame (e.g., a wash cycle). However,
if L is
too reactive, this activator will be difficult to stabilise for use in a
bleaching composition.
Preferred L groups are selected from the group consisting of:
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WO 00/52130 42 PCT/US00/05302
R3 R 5Y
-O ~ , -O ~ Y , and -O
4
-N-C-R -N N -N-C-CH-R
' ~ ~ Rs Y ,
Y
R3 Y
I I
-O-C H=C-C H=C H2 -O-C H=C-C H=C H2
> >
O C H -C Y O
4
-O-C-R~ -N\ jNR4 ' -N\ jNR
C C
O O
R3 O Y
-O-C=CHR4 , and -N-S-CH-R4
R3 O
and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group
containing from 1 to
14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R4
is H or
R3, RS is an alkenyl chain containing from 1 to 8 carbon atoms and Y is H or a
solubilizing group. Any of R1, R3 and R4 may be substituted by essentially any
functional group including, for example alkyl, hydroxy, alkoxy, halogen,
amine, nitrosyl,
amide and ammonium or alkyl ammonium groups.
The preferred solubilizing groups are -S03 M+, -C02 M+, -S04 M+, -N+(R3)4X and
O<--N(R3)3 and most preferably -S03 M+ and -COZ M+ wherein R3 is an alkyl
chain
containing from 1 to 4 carbon atoms, M is a cation which provides solubility
to the bleach
activator and X is an anion which provides solubility to the bleach activator.
Preferably,
M is an alkali metal, ammonium or substituted ammonium cation, with sodium and
CA 02362955 2001-08-23
WO 00/52130 43 PCT/US00/05302
potassium being most preferred, and X is a halide, hydroxide, methylsulfate or
acetate
anion.
Perbenzoic acid precursor
Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
Suitable O-acylated perbenzoic acid precursor compounds include the
substituted and
unsubstituted benzoyl oxybenzene sulfonates, including for example benzoyl
oxybenzene
sulfonate:
0
~/ S03
Also suitable are the benzoylation products of sorbitol, glucose, and all
saccharides with
benzoylating agents, including for example:
OAc
Ac0 \~~
~~ -OAc
OAc
OBz
Ac = COCH3; Bz = Benzoyl
Perbenzoic acid precursor compounds of the imide type include N-benzoyl
succinimide,
tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas. Suitable
imidazole
type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl
benzimidazole and other useful N-acyl group-containing perbenzoic acid
precursors
include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic
acid.
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WO 00/52130 44 PCT/US00/05302
Other perbenzoic acid precursors include the benzoyl diacyl peroxides, the
benzoyl
tetraacyl peroxides, and the compound having the formula:
0 0
o-~
~~COOH
Phthalic anhydride is another suitable perbenzoic acid precursor compound
herein:
0
~o
0
Suitable N-acylated lactam perbenzoic acid precursors have the formula:
O
I I
R6-O N-C H2- ~ H2
~CH2~CH2ln
wherein n is from 0 to 8, preferably from 0 to 2, and R6 is a benzoyl group.
Perbenzoic acid derivative precursors
Perbenzoic acid derivative precursors provide substituted perbenzoic acids on
perhydrolysis.
Suitable substituted perbenzoic acid derivative precursors include any of the
herein
disclosed perbenzoic precursors in which the benzoyl group is substituted by
essentially
any non-positively charged (i.e.; non-cationic) functional group including,
for example
alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl and amide groups.
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WO 00/52130 PCT/US00/05302
A preferred class of substituted perbenzoic acid precursor compounds are the
amide
substituted compounds of the following general formulae:
R~ CNR2CL R~ NCR2CL
O R5 O or R5 O O
5
wherein R1 is an aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is
an arylene,
or alkarylene group containing from 1 to 14 carbon atoms, and RS is H or an
alkyl, aryl,
or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any
leaving
group. R1 preferably contains from 6 to 12 carbon atoms. R2 preferably
contains from
10 4 to 8 carbon atoms. R1 may be aryl, substituted aryl or alkylaryl
containing branching,
substitution, or both and may be sourced from either synthetic sources or
natural sources
including for example, tallow fat. Analogous structural variations are
permissible for R2.
The substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other
typical
substituent groups or organic compounds. RS is preferably H or methyl. R1 and
RS
15 should not contain more than 18 carbon atoms in total. Amide substituted
bleach
activator compounds of this type are described in EP-A-0170386.
Cationic perox. a~precursors
20 Cationic peroxyacid precursor compounds produce cationic peroxyacids on
perhydrolysis.
Typically, cationic peroxyacid precursors are formed by substituting the
peroxyacid part
of a suitable peroxyacid precursor compound with a positively charged
functional group,
such as an ammonium or alkyl ammonium group, preferably an ethyl or methyl
25 ammonium group. Cationic peroxyacid precursors are typically present in the
compositions as a salt with a suitable anion, such as for example a halide ion
or a
methylsulfate ion.
The peroxyacid precursor compound to be so canonically substituted may be a
perbenzoic
30 acid, or substituted derivative thereof, precursor compound as described
hereinbefore.
Alternatively, the peroxyacid precursor compound may be an alkyl percarboxylic
acid
precursor compound or an amide substituted alkyl peroxyacid precursor as
described
hereinafter
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WO 00/52130 46 PCT/US00/05302
Cationic peroxyacid precursors are described in US-A-4,904,406; US-A-
4,751,015; US-
A-4,988;451; US-A-4,397,757; US-A-5,269,962; US-A-5,127,852; US-A-5,093,022;
US-
A-5,106,528; GB-A-1,382,594; EP-A-0475512, EP-A-0458396 and EP-A-0284292; and
in JP87-318,332.
S
Suitable cationic peroxyacid precursors include any of the ammonium or alkyl
ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated
caprolactams,
and monobenzoyltetraacetyl glucose benzoyl peroxides.
A preferred cationically substituted benzoyl oxybenzene sulfonate is the 4-
(trimethyl
ammonium) methyl derivative of benzoyl oxybenzene sulfonate:
O
~O ~S03
~+
A preferred canonically substituted alkyl oxybenzene sulfonate has the
formula:
SO
\ N+ I I O 3
/ O
Preferred cationic peroxyacid precursors of the N-acylated caprolactam class
include the
trialkyl ammonium methylene benzoyl caprolactams, particularly trimethyl
ammonium
methylene benzoyl caprolactam:
O O
O ,N
~N
/+
Other preferred cationic peroxyacid precursors of the N-acylated caprolactam
class
include the trialkyl ammonium methylene alkyl caprolactams:
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WO 00/52130 47 PCT/US00/05302
O Q
~N
y+ w/ (CH2)n
where n is from 0 to 12, particularly from 1 to 5.
Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl
ammonium) ethyl
sodium 4-sulphophenyl carbonate chloride.
Alk,~percarboxylic acid bleach precursors
Alkyl percarboxylic acid bleach precursors form percarboxylic acids on
perhydrolysis.
Preferred precursors of this type provide peracetic acid on perhydrolysis.
Preferred alkyl percarboxylic precursor compounds of the imide type include
the N-
,N,N1N1 tetra acetylated alkylene diamines wherein the alkylene group contains
from 1
to 6 carbon atoms, particularly those compounds in which the alkylene group
contains 1,
2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly
preferred.
Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-tri-
methyl
hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate
(HOBS), sodium acetoxybenzene sulfonate (ABS) and penta acetyl glucose.
Amide substituted alkyl neroxyacid precursors
Amide substituted alkyl peroxyacid precursor compounds are also suitable,
including
those of the following general formulae:
R~ CNR2CL R~ NCR2CL
O R5 O or R5 O O
wherein Rl is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene
group
containing from 1 to 14 carbon atoms, and RS is H or an alkyl group containing
1 to 10
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WO 00/52130 48 PCT/US00/05302
carbon atoms and L can be essentially any leaving group. Rl preferably
contains from 6
to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. Rl may be
straight chain or branched alkyl containing branching, substitution, or both
and may be
sourced from either synthetic sources or natural sources including for
example, tallow fat.
S Analogous structural variations are permissible for R2. The substitution can
include
alkyl, halogen, nitrogen, sulphur and other typical substituent groups or
organic
compounds. RS is preferably H or methyl. Rl and RS should not contain more
than 18
carbon atoms in total. Amide substituted bleach activator compounds of this
type are
described in EP-A-0170386.
Benzoxazin or ag nic perox a~precursors
Also suitable are precursor compounds of the benzoxazin-type, as disclosed for
example
in EP-A-0332294 and EP-A-0482807, particularly those having the formula:
O
I I
I
C-
including the substituted benzoxazins of the type
R2 O
~O
I
wherein Rl is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R4, and
RS may be
the same or different substituents selected from H, halogen, alkyl, alkenyl,
aryl, hydroxyl,
alkoxyl, amino, alkyl amino, COOR6 (wherein R6 is H or an alkyl group) and
carbonyl
functions.
An especially preferred precursor of the benzoxazin-type is:
CA 02362955 2001-08-23
WO 00/52130 49 PCT/US00/05302
O
~C
N
Preformed organic peroxyacid
A suitable class of organic peroxyacid compounds are the amide substituted
compounds
of the following general formulae:
R~ CNR2 COOH R~ NC-R2COOH
O R5 O or R5 O O
wherein R1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms,
R2 is an
alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms,
and RS is
H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. R1
preferably
contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon
atoms.
R1 may be straight chain or branched alkyl, substituted aryl or alkylaryl
containing
branching, substitution, or both and may be sourced from either synthetic
sources or
natural sources including for example, tallow fat. Analogous structural
variations are
permissible for R2. The substitution can include alkyl, aryl, halogen,
nitrogen, sulphur
and other typical substituent groups or organic compounds. RS is preferably H
or
methyl. R1 and RS should not contain more than 18 carbon atoms in total. Amide
substituted organic peroxyacid compounds of this type are described in EP-A-
0170386.
Other organic peroxyacids include diacyl and tetraacylperoxides, especially
diperoxydodecanedioc acid, diperoxytetradecanedioc acid, and
diperoxyhexadecanedioc
acid. Dibenzoyl peroxide is a preferred organic peroxyacid herein. Mono- and
diperazelaic acid, mono- and diperbrassylic acid, and N-
phthaloylaminoperoxicaproic
acid are also suitable herein.
Controlled rate of release - means
A means may be provided for controlling the rate of release of bleaching
agent,
particularly oxygen bleach to the wash solution.
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WO 00/52130 PCT/US00/05302
SO
Means for controlling the rate of release of the bleach may provide for
controlled release
of peroxide species to the wash solution. Such means could, for example,
include
controlling the release of any inorganic perhydrate salt, acting as a hydrogen
peroxide
source, to the wash solution.
Suitable controlled release means can include confining the bleach to one
portion of the
composition. Another mechanism for controlling the rate of release of bleach
may be by
coating the bleach with a coating designed to provide the controlled release.
The coating
may therefore, for example, comprise a poorly water soluble material, or be a
coating of
sufficient thickness that the kinetics of dissolution of the thick coating
provide the
controlled rate of release.
The coating material may be applied using various methods. Any coating
material is
typically present at a weight ratio of coating material to bleach of from 1:99
to 1:2,
preferably from 1:49 to 1:9. Suitable coating materials include triglycerides
(e.g.
partially) hydrogenated vegetable oil, soy bean oil, cotton seed oil) mono or
diglycerides,
microcrystalline waxes, gelatin, cellulose, fatty acids and any mixtures
thereof. Other
suitable coating materials can comprise the alkali and alkaline earth metal
sulphates,
silicates and carbonates, including calcium carbonate and silicas.
A preferred coating material, particularly for an inorganic perhydrate salt
bleach source,
comprises sodium silicate of Si02 : Na20 ratio from 1.8 : 1 to 3.0 : 1,
preferably 1.8:1 to
2.4:1, and/or sodium metasilicate, preferably applied at a level of from 2% to
10%,
(normally from 3% to 5%) of Si02 by weight of the inorganic perhydrate salt.
Magnesium silicate can also be included in the coating.
Any inorganic salt coating materials may be combined with organic binder
materials to
provide composite inorganic salt/organic binder coatings. Suitable binders
include the
Clp-C20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide
per mole of
alcohol and more preferably the C 15-C20 primary alcohol ethoxylates
containing from 20
- 100 moles of ethylene oxide per mole of alcohol.
Other preferred binders include certain polymeric materials.
Polyvinylpyrrolidones with
an average molecular weight of from 12,000 to 700,000 and polyethylene glycols
(PEG)
with an average molecular weight of from 600 to 5 x 106 preferably 1000 to
400,000
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WO 00/52130 PCT/US00/05302
51
most preferably 1000 to 10,000 are examples of such polymeric materials.
Copolymers
of malefic anhydride with ethylene, methylvinyl ether or methacrylic acid, the
malefic
anhydride constituting at least 20 mole percent of the polymer are further
examples of
polymeric materials useful as binder agents. These polymeric materials may be
used as
such or in combination with solvents such as water, propylene glycol and the
above
mentioned C10-C20 alcohol ethoxylates containing from 5 - 100 moles of
ethylene oxide
per mole. Further examples of binders include the C 10-C20 mono- and
diglycerol ethers
and also the C 10-C20 fatty acids.
Cellulose derivatives such as methylcellulose, carboxymethylcellulose and
hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their
salts are
other examples of binders suitable for use herein.
One method for applying the coating material involves agglomeration. Preferred
agglomeration processes include the use of any of the organic binder materials
described
hereinabove. Any conventional agglomerator/mixer may be used including, but
not
limited to pan, rotary drum and vertical blender types. Molten coating
compositions may
also be applied either by being poured onto, or spray atomized onto a moving
bed of
bleaching agent.
Other means of providing the required controlled release include mechanical
means for
altering the physical characteristics of the bleach to control its solubility
and rate of
release. Suitable protocols could include compression, mechanical injection,
manual
injection, and adjustment of the solubility of the bleach compound by
selection of particle
size of any particulate component.
Whilst the choice of particle size will depend both on the composition of the
particulate
component, and the desire to meet the desired controlled release kinetics, it
is desirable
that the particle size should be more than 500 micrometers, preferably having
an average
particle diameter of from 800 to 1200 micrometers.
Additional protocols for providing the means of controlled release include the
suitable
choice of any other components of the composition such that when the
composition is
introduced to the wash solution the ionic strength environment therein
provided enables
the required controlled release kinetics to be achieved.
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WO 00/52130 52 PCT/US00/05302
Metal-containing bleach catal rest
Bleach-cintaining compositions herein can additionally contain a metal
containing bleach
catalyst. Preferably the metal containing bleach catalyst is a transition
metal containing
bleach catalyst, more preferably a manganese or cobalt-containing bleach
catalyst.
A suitable type of bleach catalyst is a catalyst comprising a heavy metal
cation of defined
bleach catalytic activity, such as copper, iron cations, an auxiliary metal
cation having
little or no bleach catalytic activity, such as zinc or aluminium cations, and
a sequestrant
having defined stability constants for the catalytic and auxiliary metal
cations, particularly
ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic
acid) and
water-soluble salts thereof. Such catalysts are disclosed in US-A-4,430,243.
Preferred types of bleach catalysts include the manganese-based complexes
disclosed in
US-A- 5,246,621 and US-A-5,244,594. Preferred examples of these catalysts
include
MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(PF6)2, MnIII2(u-O)1(u-
OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(C104)2, MnIV4(u-O)6(1,4,7-
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. Others are described in EP-
A-
0549,272. Other ligands suitable for use herein include 1,5,9-trimethyl-1,5,9
triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7
triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures
thereof.
For other examples of suitable bleach catalysts see US-A-4,246,612 and US-A-
5,227,084.
See also US-A-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 US-A-5,114,606, is a
water-soluble
complex of manganese (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, xylithol, arabitol,
adonitol, meso-
erythritol, meso-inositol, lactose, and mixtures thereof.
US-A-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:
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53
R2 R3
R~ -N=C-B-C=N-R4
wherein Rl, R2, R3, and R4 can each be selected from H, substituted alkyl and
aryl
groups such that each Rl-N=C-R2 and R3-C=N-R4 form a five or six-membered
ring.
Said ring can further be substituted. B is a bridging group selected from O,
S. CRSR6,
NR~ and C=O, wherein R5, R6, and R~ can each be H, alkyl, or aryl groups,
including
substituted or unsubstituted groups. Preferred ligands include pyridine,
pyridazine,
pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings. Optionally,
said rings may
be substituted with substituents such as alkyl, aryl, alkoxy, halide, and
nitro. Particularly
preferred is the ligand 2,2'-bispyridylamine. Preferred bleach catalysts
include Co, Cu,
Mn, Fe,-bispyridylmethane and -bispyridylamine complexes. Highly preferred
catalysts
include Co(2,2'-bispyridylamine)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.
Preferred examples include binuclear Mn complexes with tetra-N-dentate and bi-
N-
dentate ligands, including N4MnIII(u-O)2MnIVN4)+and [Bipy2MnIII(u-
O)2MnIVbIPY2~-(C104)3
While the structures of the bleach-catalyzing manganese complexes have not
generally
been elucidated, it may be speculated that they comprise chelates or other
hydrated
coordination complexes which result from the interaction of the carboxyl and
nitrogen
atoms of the ligand with the manganese cation. Likewise, the oxidation state
of the
manganese cation during the catalytic process is not known with certainty, and
may be the
(+II), (+III), (+IV) or (+V) valence state. Due to the ligands' possible six
points of
attachment to the manganese cation, it may be reasonably speculated that mufti-
nuclear
species and/or "cage" structures may exist in the aqueous bleaching media.
Whatever the
form of the active Mwligand species which actually exists, it functions in an
apparently
catalytic manner to provide improved bleaching performances on stubborn stains
such as
tea, ketchup, coffee, wine, juice, and the like.
Other bleach catalysts are described, for example, in EP-A-0408131 (cobalt
complex
catalysts), EP-A-0384503, and EP-A-0306089 (metallo-porphyrin catalysts), US-A-
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54
4,728,455 (manganese/multidentate ligand catalyst), US-A-4,711,748 and EP-A-
0224952,
(absorbed manganese on aluminosilicate catalyst), US-A-4,601,845
(aluminosilicate
support with manganese and zinc or magnesium salt), US-A-4,626,373
(manganese/ligand catalyst), US-A- 4,119,557 (ferric complex catalyst), DE-A-
2,054,019
(cobalt chelant catalyst), CA-A-866,191 (transition metal-containing salts),
US-A-
4,430,243 (chelants with manganese cations and non-catalytic metal cations),
and US-A-
4,728,455 (manganese gluconate catalysts).
Other preferred examples include cobalt (III) catalysts having the formula:
Co[~3)nM~mB~bT~tQqPp~ Yy
wherein cobalt is in the +3 oxidation state; n is an integer from 0 to 5
(preferably 4 or 5;
most preferably 5); M' represents a monodentate ligand; m is an integer from 0
to 5
(preferably 1 or 2; most preferably 1); B' represents a bidentate ligand; b is
an integer
from 0 to 2; T' represents a tridentate ligand; t is 0 or 1; Q is a
tetradentate ligand; q is 0
or 1; P is a pentadentate ligand; p is 0 or l; and n + m + 2b + 3t + 4q + Sp =
6; Y is one or
more appropriately selected counteranions present in a number y, where y is an
integer
from 1 to 3 (preferably 2 to 3; most preferably 2 when Y is a -1 charged
anion), to obtain
a charge-balanced salt, preferred Y are selected from the group consisting of
chloride,
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 co-ordination sites
stabilise the
cobalt under automatic dishwashing conditions such that the reduction
potential for cobalt
(III) to cobalt (II) under alkaline conditions is less than 0.4 volts
(preferably less than 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
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WO 00/52130 PCT/US00/05302
selected counteranion present in a number y, which is an integer from 1 to 3
(preferably 2
to 3; most preferably 2 when Y is a -1 charged anion), to obtain a charge-
balanced salt.
The preferred cobalt catalyst of this type useful herein are cobalt pentaamine
chloride
salts having the formula [Co(NH3)SCl] Yy, and especially [Co(NH3)SCl]C12.
More preferred are the present invention compositions which utilize cobalt
(III) bleach
catalysts having the formula:
10 [Co(NH3)n(M)m(B)b] TY
wherein cobalt is in the +3 oxidation state; n is 4 or 5 (preferably 5); M is
one or more
ligands coordinated to the cobalt by one site; m is 0, 1 or 2 (preferably 1);
B is a ligand
co-ordinated to the cobalt by two sites; b is 0 or 1 (preferably 0), and when
b=0, then m+n
15 = 6, and when b=l, then m=0 and n=4; and T is one or more appropriately
selected
counteranions present in a number y, where y is an integer to obtain a charge-
balanced
salt (preferably y is 1 to 3; most preferably 2 when T is a -1 charged anion);
and wherein
further said catalyst has a base hydrolysis rate constant of less than 0.23 M-
1 s-1 (25°C).
20 Preferred T are selected from the group consisting of chloride, iodide, I3-
, formate,
nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PF6-
, BF4-, B(Ph)4-,
phosphate, phosphite, silicate, tosylate, methanesulfonate, and combinations
thereof.
Optionally, T can be protonated if more than one anionic group exists in T,
e.g., HP042-
HC03-, H2P04-, etc. Further, T may be selected from the group consisting of
non-
25 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-, S04-2, NCS-,
SCN-,
30 S203-2, NH3, POq.3-, and carboxylates (which preferably are mono-
carboxylates, but
more than one carboxylate may be present in the moiety as long as the binding
to the
cobalt is by only one carboxylate per moiety, in which case the other
carboxylate in the M
moiety may be protonated or in its salt form). Optionally, M can be protonated
if more
than one anionic group exists in M (e.g., HP042-, HC03-, H2P04-,
HOC(O)CH2C(O)O-
35 , etc.) Preferred M moieties are substituted and unsubstituted C1-C30
carboxylic acids
having the formulas:
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WO 00/52130 56 PCT/US00/05302
RC(O)O-
wherein R is preferably selected from the group consisting of hydrogen and C1-
C30
(preferably C1-Clg) unsubstituted and substituted alkyl, C6-C30 (preferably C6-
Clg)
unsubstituted and substituted aryl, and C3-C30 (preferably CS-Clg)
unsubstituted and
substituted heteroaryl, wherein substituents are selected from the group
consisting of -
~~3~ -~~4+~ -C(O)OR', -OR', -C(O)NR'2, wherein R' is selected from the group
consisting of hydrogen and C1-C6 moieties. Such substituted R therefore
include the
moieties -(CH2)nOH and -(CH2)nNR'4+, wherein n is an integer from 1 to 16,
preferably
from 2 to 10, and most preferably from 2 to S.
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, fiunaric, lauric,
linoleic, lactic, malic, and
especially acetic acid.
The B moieties include carbonate, di- and higher carboxylates (e.g., oxalate,
malonate,
malic, succinate, maleate), picolinic acid, and alpha and beta amino acids
(e.g., glycine,
alanine, beta-alanine, phenylalanine).
Cobalt bleach catalysts useful herein are known, being described for example
along with
their base hydrolysis rates, in M. L. Tobe, "Base Hydrolysis of Transition-
Metal
Complexes", Adv. Inorg. Bioinorg; Mech., (1983), 2, pages 1-94. For example,
Table
1 at page 17, provides the base hydrolysis rates (designated therein as kOH)
for cobalt
pentaamine catalysts complexed with oxalate (kOH= 2.5 x 10-4 M-1 s-1
(25°C)), NCS-
(kOH= 5.0 x 10-4 M-1 s-1 (25°C)), formate (kOH= 5.8 x 10-4 M-1 s-1
(25°C)), and
acetate (kOH= 9.6 x 10-4 M-1 s-1 (25°C)). The most preferred cobalt
catalyst useful
herein are cobalt pentaamine acetate salts having the formula [Co(NH3)SOAc]
Ty,
wherein OAc represents an acetate moiety, and especially cobalt pentaamine
acetate
chloride, [Co(NH3)SOAc]C12; as well as [Co(NH3)SOAc](OAc)2;
[Co(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
US-A-
4,810,410, to Diakun et al, issued March 7,1989, J. Chem. Ed. (1989), 66 (12),
1043-45;
The Synthesis and Characterization of Inorganic Compounds, W.L. Jolly
(Prentice-Hall;
1970), pp. 461-3; Inor~. Chem., 18, 1497-1502 (1979); 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.
Cobalt catalysts suitable for incorporation into the detergent tablets of the
present
invention may be produced according to the synthetic routes disclosed in US-A-
5,559,261, US-A-5,581,005, and US-A-5,597,936.
These catalysts may be co-processed with adjunct materials so as to reduce the
colour
impact if desired for the aesthetics of the product, or to be included in
enzyme-containing
particles as exemplified hereinafter, or the compositions may be manufactured
to contain
catalyst "speckles".
Or ag nic polymeric compound
Organic polymeric compounds may be added as preferred components of the
detergent
tablets in accord with the invention. By organic polymeric compound it is
meant
essentially any polymeric organic compound commonly found in detergent
compositions
having dispersant, anti-redeposition, soil release agents or other detergency
properties.
Examples of organic polymeric compounds include the water soluble organic homo-
or
co-polymeric polycarboxylic acids, modified polycarboxylates or their salts in
which the
polycarboxylic acid comprises at least two carboxyl radicals separated from
each other by
not more than two carbon atoms. Polymers of the latter type are disclosed in
GB-A-
1,596,756. Examples of such salts are polyacrylates of molecular weight 2000-
10000
and their copolymers with any suitable other monomer units including modified
acrylic,
fumaric, malefic, itaconic, aconitic, mesaconic, citraconic and
methylenemalonic acid or
their salts, malefic anhydride, acrylamide, alkylene, vinylmethyl ether,
styrene and any
mixtures thereof. Preferred are the copolymers of acrylic acid and malefic
anhydride
having a molecular weight of from 20,000 to 100,000.
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58
Preferred commercially available acrylic acid containing polymers having a
molecular
weight below 15,000 include those sold under the tradename Sokalan PA30, PA20,
PA15,
PA10 and Sokalan CP10 by BASF GmbH, and those sold under the tradename Acusol
45N, 480N, 460N by Rohm and Haas.
Preferred acrylic acid containing copolymers include those which contain as
monomer
units: a) from 90% to 10%, preferably from 80% to 20% by weight acrylic acid
or its salts
and b) from 10% to 90%, preferably from 20% to 80% by weight of a substituted
acrylic
monomer or its salts having the general formula -[CR2-CRl(CO-O-R3)]- wherein
at least
one of the substituents Rl, R2 or R3, preferably Rl or R2 is a 1 to 4 carbon
alkyl or
hydroxyalkyl group, Rl or R2 can be a hydrogen and R3 can be a hydrogen or
alkali
metal salt. Most preferred is a substituted acrylic monomer wherein Rl is
methyl, R2 is
hydrogen (i.e. a methacrylic acid monomer). The most preferred copolymer of
this type
has a molecular weight of 3500 and contains 60% to 80% by weight of acrylic
acid and
40% to 20% by weight of methacrylic acid.
The polyamine and modified polyamine compounds are useful herein including
those
derived from aspartic acid such as those disclosed in EP-A-0305282, EP-A-
0305283 and
EP-A-03 S 1629.
Other optional polymers may polyvinyl alcohols and acetates both modified and
non-
modified, cellulosics and modified cellulosics, polyoxyethylenes,
polyoxypropylenes, and
copolymers thereof, both modified and non-modified, terephthalate esters of
ethylene or
propylene glycol or mixtures thereof with polyoxyalkylene units. Suitable
examples are
disclosed in US-A-5,591,703, US-A-5,597,789 and US-A-4,490,271.
Soil Release Agents
Suitable polymeric soil release agents include those soil release agents
having: (a) one or
more nonionic hydrophile components consisting essentially of (i)
polyoxyethylene
segments with a degree of polymerization of at least 2, or (ii) oxypropylene
or
polyoxypropylene segments with a degree of polymerization of from 2 to 10,
wherein said
hydrophile segment does not encompass any oxypropylene unit unless it is
bonded to
adjacent moieties at each end by ether linkages, or (iii) a mixture of
oxyalkylene units
comprising oxyethylene and from 1 to 30 oxypropylene units, said hydrophile
segments
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preferably comprising at least 25% oxyethylene units and more preferably,
especially for
such components having 20 to 30 oxypropylene units, at least 50% oxyethylene
units; or
(b) one or more hydrophobe components comprising (i) C3 oxyalkylene
terephthalate
segments, wherein, if said hydrophobe components also comprise oxyethylene
terephthalate, the ratio of oxyethylene terephthalate:C3 oxyalkylene
terephthalate units is
2:1 or lower, (ii) C4-C6 alkylene or oxy C4-C6 alkylene segments, or mixtures
therein,
(iii) poly (vinyl ester) segments, preferably polyvinyl acetate, having a
degree of
polymerization of at least 2, or (iv) C1-C4 alkyl ether or C4 hydroxyalkyl
ether
substituents, or mixtures therein, wherein said substituents are present in
the form of C1-
C4 alkyl ether or C4 hydroxyalkyl ether cellulose derivatives, or mixtures
therein, or a
combination of (a) and (b).
Typically, the polyoxyethylene segments of (a)(i) will have a degree of
polymerization of
from 200, although higher levels can be used, preferably from 3 to 150, more
preferably
from 6 to 100. Suitable oxy C4-C6 alkylene hydrophobe segments include, but
are not
limited to, end-caps of polymeric soil release agents such as
M03S(CH2)nOCH2CH20-,
where M is sodium and n is an integer from 4-6, as disclosed in US-A-
4,721,580.
Polymeric soil release agents useful herein also include cellulosic
derivatives such as
hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate
or
propylene terephthalate with polyethylene oxide or polypropylene oxide
terephthalate,
and the like. Such agents are commercially available and include hydroxyethers
of
cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use
herein also
include those selected from the group consisting of C1-C4 alkyl and C4
hydroxyalkyl
cellulose; see US-A-4,000,093.
Soil release agents characterized by polyvinyl ester) hydrophobe segments
include graft
copolymers of polyvinyl ester), e.g., C 1-C6 vinyl esters, preferably
polyvinyl acetate)
grafted onto polyalkylene oxide backbones, such as polyethylene oxide
backbones. See
EP-A-0219048.
Another suitable soil release agent is a copolymer having random blocks of
ethylene
terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight
of this
polymeric soil release agent is in the range of from 25,000 to 55,000. See US-
A-
3,959,230 and US-A-3,893,929.
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Another suitable polymeric soil release agent is a polyester with repeat units
of ethylene
terephthalate units contains 10-15% by weight of ethylene terephthalate units
together
with 90-80% by weight of polyoxyethylene terephthalate units, derived from a
polyoxyethylene glycol of average molecular weight 300-5,000.
Another suitable polymeric soil release agent is a sulfonated product of a
substantially
linear ester oligomer comprised of an oligomeric ester backbone of
terephthaloyl and
oxyalkyleneoxy repeat units and terminal moieties covalently attached to the
backbone.
These soil release agents are described fully in US-A-4,968,451. Other
suitable
polymeric soil release agents include the terephthalate polyesters of US-A-
4,711,730, the
anionic end-capped oligomeric esters of US-A-4,721,580 and the block polyester
oligomeric compounds of US-A-4,702,857. Other polymeric soil release agents
also
include the soil release agents of US-A-4,877,896 which discloses anionic,
especially sul-
foarolyl, end-capped terephthalate esters.
Another soil release agent is an oligomer with repeat units of terephthaloyl
units,
sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2-propylene units. The
repeat
units form the backbone of the oligomer and are preferably terminated with
modified
isethionate end-caps. A particularly preferred soil release agent of this type
comprises
one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-
propyleneoxy units in a ratio of from 1.7 to 1.8, and two end-cap units of
sodium 2-(2-
hydroxyethoxy)-ethanesulfonate.
Heave metal ion sequestrant
The tablets of the invention preferably contain as an optional component a
heavy metal
ion sequestrant. By heavy metal ion sequestrant it is meant herein components
which act
to sequester (chelate) heavy metal ions. These components may also have
calcium and
magnesium chelation capacity, but preferentially they show selectivity to
binding heavy
metal ions such as iron, manganese and copper.
Heavy metal ion sequestrants, which are acidic in nature, having for example
phosphonic
acid or carboxylic acid functionalities, may be present either in their acid
form or as a
complex/salt with a suitable counter cation such as an alkali or alkaline
metal ion,
ammonium, or substituted ammonium ion, or any mixtures thereof. Preferably any
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salts/complexes are water soluble. The molar ratio of said counter cation to
the heavy
metal ion sequestrant is preferably at least 1:1.
Suitable heavy metal ion sequestrants for use herein include organic
phosphonates, such
as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-
hydroxy
disphosphonates and nitrilo trimethylene phosphonates. Preferred among the
above
species are diethylenetriamine penta (methylene phosphonate), ethylenediamine
tetra(methylene phosphonate) hexamethylenediamine tetra (methylene
phosphonate) and
hydroxy-ethylene-1,1-dipho sphonate.
Other suitable heavy metal ion sequestrant for use herein include
nitrilotriacetic acid and
polyaminocarboxylic acids such as ethylenediaminotetracetic acid,
ethylenetriamine
pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric
acid, 2-
hydroxypropylenediamine disuccinic acid or any salts thereof.
Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or the
alkali metal,
alkaline earth metal, ammonium, or substituted ammonium salts thereof, or
mixtures
thereof. Preferred EDDS compounds are the free acid form and the sodium or
magnesium salt or complex thereof.
Cr s~ tal growth inhibitor component
The detergent tablets preferably contain a crystal growth inhibitor component,
preferably
an organodiphosphonic acid component, incorporated preferably at a level of
from 0.01
to 5%, more preferably from 0.1% to 2% by weight of the compositions.
By organo diphosphonic acid it is meant herein an organo diphosphonic acid
which does
not contain nitrogen as part of its chemical structure. This definition
therefore excludes
the organo aminophosphonates, which however may be included in compositions of
the
invention as heavy metal ion sequestrant components.
The organo diphosphonic acid is preferably a C1-C4 diphosphonic acid, more
preferably a
C2 diphosphonic acid, such as ethylene diphosphonic acid, or most preferably
ethane 1-
hydroxy-1,1-diphosphonic acid (HEDP) and may be present in partially or fully
ionized
form, particularly as a salt or complex.
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Water-soluble sulfate salt
The compositions herein optionally contains a water-soluble sulfate salt.
Where present
the water-soluble sulfate salt is at the level of from 0.1% to 40%, more
preferably from
1% to 30%, most preferably from 5% to 25% by weight of composition.
The water-soluble sulfate salt may be essentially any salt of sulfate with any
counter
cation. Preferred salts are selected from the sulfates of the alkali and
alkaline earth
metals, particularly sodium sulfate.
Alkali Metal Silicate
A suitable alkali metal silicate is sodium silicate having an Si02:Na20 ratio
of from 1.8
to 3.0, preferably from 1.8 to 2.4, most preferably 2Ø Sodium silicate is
preferably
present at a level of less than 20%, preferably from 1% to 15%, most
preferably from 3%
to 12% by weight of Si02. The alkali metal silicate may be in the form of
either the
anhydrous salt or a hydrated salt.
The compositions herein can also contain sodium metasilicate, present at a
level of at
least 0.4% Si02 by weight. Sodium metasilicate has a nominal Si02 : Na20 ratio
of 1Ø
The weight ratio of said sodium silicate to said sodium metasilicate, measured
as Si02, is
preferably from 50:1 to 5:4, more preferably from 15:1 to 2:1, most preferably
from 10:1
to 5:2.
Colourant
The term 'colourant', as used herein, means any substance that absorbs
specific
wavelengths of light from the visible light spectrum. Such colourants when
added to a
detergent composition have the effect of changing the visible colour and thus
the
appearance of the detergent composition. Colourants may be for example either
dyes or
pigments. Preferably the colourants are stable in composition in which they
are to be
incorporated. Thus in a composition of high pH the colourant is preferably
alkali stable
and in a composition of low pH the colourant is preferably acid stable.
Examples of suitable dyes include reactive dyes, direct dyes, azo dyes.
Preferred dyes
include phthalocyanine dyes, anthraquinone dye, quinoline dyes, monoazo,
disazo and
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63
polyazo. More preferred dyes include anthraquinone, quinoline and monoazo
dyes.
Preferred dyes include SANDOLAN E-HRL 180% (tradename), SANDOLAN MILLING
BLUE (tradename), TURQUOISE ACID BLUE (tradename) and SANDOLAN
BRILLIANT GREEN (tradename) all available from Clariant UK, HEXACOL
QUINOLINE YELLOW (tradename) and HEXACOL BRILLIANT BLUE (tradename)
both available from Pointings, UK, ULTRA MARINE BLUE (tradename) available
from
Holliday or LEVAFIX TURQUISE BLUE EBA (tradename) available from Bayer, USA.
The colourant may be incorporated by any suitable method. Suitable methods
include
mixing all or selected detergent components with a colourant in a drum or
spraying all or
selected detergent components with the colourant in a rotating drum.
Colourant is typically added at a level of from 0.001 % to 1.5%, preferably
from 0.01
to 1.0%, most preferably from 0.1% to 0.3% by weight of composition.
Corrosion inhibitor compound
The compositions herein, especially for use in dishwashing, can contain a
corrosion
inhibitor preferably selected from organic silver coating agents, particularly
paraffin,
nitrogen-containing corrosion inhibitor compounds and Mn(II) compounds,
particularly
Mn(II) salts of organic ligands.
Organic silver coating agents are described in WO-A-94/16047 and EP-A-690122.
Nitrogen-containing corrosion inhibitor compounds are disclosed in EP-A-
0634478.
Mn(II) compounds for use in corrosion inhibition are described in EP-A-0672
749.
The functional role of the silver coating agent is to form 'in use' a
protective coating layer
on any silverware components of the washload to which the compositions of the
invention
are being applied. The silver coating agent should hence have a high affinity
for
attachment to solid silver surfaces, particularly when present in as a
component of an
aqueous washing and bleaching solution with which the solid silver surfaces
are being
treated.
Suitable organic silver coating agents herein include fatty esters of mono- or
polyhydric
alcohols having from 1 to 40 carbon atoms in the hydrocarbon chain.
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The fatty acid portion of the fatty ester can be obtained from mono- or poly-
carboxylic
acids having from 1 to 40 carbon atoms in the hydrocarbon chain. Suitable
examples of
monocarboxylic fatty acids include behenic acid, stearic acid, oleic acid,
palmitic acid,
myristic acid, lauric acid, acetic acid, propionic acid, butyric acid,
isobutyric acid, valeric
acid, lactic acid, glycolic acid and (3,(3'- dihydroxyisobutyric acid.
Examples of suitable
polycarboxylic acids include: n-butyl-malonic acid, isocitric acid, citric
acid, malefic acid,
malic acid and succinic acid.
The fatty alcohol radical in the fatty ester can be represented by mono- or
polyhydric
alcohols having from 1 to 40 carbon atoms in the hydrocarbon chain. Examples
of
suitable fatty alcohols include; behenyl, arachidyl, cocoyl, oleyl and lauryl
alcohol,
ethylene glycol, glycerol, ethanol, isopropanol, vinyl alcohol, diglycerol,
xylitol, sucrose,
erythritol, pentaerythritol, sorbitol or sorbitan.
Preferably, the fatty acid and/or fatty alcohol group of the fatty ester
adjunct material have
from 1 to 24 carbon atoms in the alkyl chain.
Preferred fatty esters herein are ethylene glycol, glycerol and sorbitan
esters wherein the
fatty acid portion of the ester normally comprises a species selected from
behenic acid,
stearic acid, oleic acid, palmitic acid or myristic acid.
The glycerol esters are also highly preferred. These are the mono-, di- or tri-
esters of
glycerol and the fatty acids as defined above.
Specific examples of fatty alcohol esters for use herein include: stearyl
acetate, palmityl
di-lactate, cocoyl isobutyrate, oleyl maleate, oleyl dimaleate , and tallowyl
proprionate.
Fatty acid esters useful herein include: xylitol monopalmitate,
pentaerythritol
monostearate, sucrose monostearate, glycerol monostearate, ethylene glycol
monostearate, sorbitan esters. Suitable sorbitan esters include sorbitan
monostearate,
sorbitan palmitate, sorbitan monolaurate, sorbitan monomyristate, sorbitan
monobehenate, sorbitan mono-oleate, sorbitan dilaurate, sorbitan distearate,
sorbitan
dibehenate, sorbitan dioleate, and also mixed tallowalkyl sorbitan mono- and
di-esters.
Glycerol monostearate, glycerol mono-oleate, glycerol monopalmitate, glycerol
monobehenate, and glycerol distearate are preferred glycerol esters herein.
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Suitable organic silver coating agents include triglycerides, mono or
diglycerides, and
wholly or partially hydrogenated derivatives thereof, and any mixtures
thereof. Suitable
sources of fatty acid esters include vegetable and fish oils and animal fats.
Suitable
vegetable oils include soy bean oil, cotton seed oil, castor oil, olive oil,
peanut oil,
safflower oil, sunflower oil, rapeseed oil, grapeseed oil, palm oil and corn
oil.
Waxes, including microcrystalline waxes are suitable organic silver coating
agents herein.
Preferred waxes have a melting point in the range from 35°C to
110°C and comprise
generally from 12 to 70 carbon atoms. Preferred are petroleum waxes of the
paraffin and
microcrystalline type which are composed of long-chain saturated hydrocarbon
compounds.
Alginates and gelatin are suitable organic silver coating agents herein.
Dialkyl amine oxides such as C12-C20 methylamine oxide, and dialkyl quaternary
ammonium compounds and salts, such as the C 12-C20 methylammonium halides are
also
suitable.
Other suitable organic silver coating agents include certain polymeric
materials.
Polyvinylpyrrolidones with an average molecular weight of from 12,000 to
700,000,
polyethylene glycols (PEG) with an average molecular weight of from 600 to
10,000,
polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-
vinylimidazole,
and cellulose derivatives such as methylcellulose, carboxymethylcellulose and
hydroxyethylcellulose are examples of such polymeric materials.
Certain perfume materials, particularly those demonstrating a high
substantivity for
metallic surfaces, are also usefizl as the organic silver coating agents
herein.
Polymeric soil release agents can also be used as an organic silver coating
agent.
A preferred organic silver coating agent is a paraffin oil, typically a
predominantly
branched aliphatic hydrocarbon having a number of carbon atoms in the range of
from 20
to 50; preferred paraffin oil selected from predominantly branched C25-45
species with a
ratio of cyclic to noncyclic hydrocarbons of from 1:10 to 2:1, preferably from
1:5 to 1:1.
A paraffin oil meeting these characteristics, having a ratio of cyclic to
noncyclic
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hydrocarbons of 32:68, is sold by Wintershall, Salzbergen, Germany, under the
trade
name WINOG 70.
Nitrogen-containing corrosion inhibitor compounds
Suitable nitrogen-containing corrosion inhibitor compounds include imidazole
and
derivatives thereof such as benzimidazole, 2-heptadecyl imidazole and those
imidazole
derivatives described in Czech Patent No. 139, 279 and GB-A-1,137,741, which
also
discloses a method for making imidazole compounds.
Also suitable as nitrogen-containing corrosion inhibitor compounds are
pyrazole
compounds and their derivatives, particularly those where the pyrazole is
substituted in
any of the 1, 3, 4 or 5 positions by substituents R1, R3, R4 and RS where R1
is any of H,
CH20H, CONH3, or COCH3, R3 and RS are any of C1-C20 alkyl or hydroxyl, and R4
is
any of H, NH2 or N02.
Other suitable nitrogen-containing corrosion inhibitor compounds include
benzotriazole,
2-mercaptobenzothiazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole, thionalide,
morpholine,
melamine, distearylamine, stearoyl stearamide, cyanuric acid, aminotriazole,
aminotetrazole and indazole.
Nitrogen-containing compounds such as amines, especially distearylamine and
ammonium compounds such as ammonium chloride, ammonium bromide, ammonium
sulphate or diammonium hydrogen citrate are also suitable.
Mn(II) corrosion inhibitor compounds
The Mn(II) compound is preferably incorporated at a level to provide from 0.1
ppm to
250 ppm, more preferably from 0.5 ppm to SO ppm, most preferably from 1 ppm to
20
ppm by weight of Mn(II) ions in bleaching solution.
The Mn (II) compound may be an inorganic salt in anhydrous, or any hydrated
forms.
Suitable salts include manganese sulphate, manganese carbonate, manganese
phosphate,
manganese nitrate, manganese acetate and manganese chloride. The Mn(II)
compound
may be a salt or complex of an organic fatty acid such as manganese acetate or
manganese
stearate.
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The Mn(II) compound may be a salt or complex of an organic ligand. In one
preferred
aspect the organic ligand is a heavy metal ion sequestrant. In another
preferred aspect the
organic ligand is a crystal growth inhibitor.
Other corrosion inhibitor compounds
Other suitable additional corrosion inhibitor compounds include, mercaptans
and diols,
especially mercaptans with 4 to 20 carbon atoms including lauryl mercaptan,
thiophenol,
thionapthol, thionalide and thioanthranol. Also suitable are saturated or
unsaturated C10-
C20 fatty acids, or their salts, especially aluminium tristearate. The C12-C20
hYdroxy
fatty acids, or their salts, are also suitable. Phosphonated octa-decane and
other anti-
oxidants such as betahydroxytoluene (BHT) are also suitable.
Copolymers of butadiene and malefic acid, particularly those supplied under
the trade
reference no. 07787 by Polysciences Inc have been found to be of particular
utility as
corrosion inhibitor compounds.
Water-soluble bismuth compound
The compositions herein, especially for use in dishwashing, can contain a
water-soluble
bismuth compound, preferably present at a level of from 0.005% to 20%, more
preferably
from 0.01 % to 5%, most preferably from 0.1 % to 1 % by weight of composition.
The water-soluble bismuth compound may be essentially any salt or complex of
bismuth
with essentially any inorganic or organic counter anion. Preferred inorganic
bismuth salts
are selected from the bismuth trihalides, bismuth nitrate and bismuth
phosphate.
Bismuth acetate and citrate are preferred salts with an organic counter anion.
Enzyme Stabilizing System
Preferred enzyme-containing compositions herein can comprise from 0.001 % to
10%,
preferably from 0.005% to 8%, most preferably from 0.01% to 6%, by weight of
an
enzyme stabilizing system. The enzyme stabilizing system can be any
stabilizing system
which is compatible with the detersive enzyme. Such stabilizing systems can
comprise
calcium ion, boric acid, propylene glycol, short chain carboxylic acid,
boronic acid,
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chlorine bleach scavengers and mixtures thereof. Such stabilizing systems can
also
comprise reversible enzyme inhibitors, such as reversible protease inhibitors.
Lime soap dispersant compound
The compositions herein can contain a lime soap dispersant compound,
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 composition.
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. Preferred
lime
soap disperant compounds are disclosed in WO-A-93/08877.
Suds sup,_pressing_system
The compositions herein preferably comprise a suds suppressing system present
at a level
of from 0.01% to 15%, preferably from 0.05% to 10%, most preferably from 0.1%
to 5%
by weight of composition.
Suitable suds suppressing systems for use herein may comprise essentially any
known
antifoam compound, including, for example silicone antifoam compounds, 2-alkyl
and
alcanol antifoam compounds. Preferred suds suppressing systems and antifoam
compounds are disclosed in WO-A-93/08876 and EP-A-0705324.
Polymeric dye transfer inhibiting agents
The compositions herein can also comprise from 0.01% to 10 %, preferably from
0.05%
to 0.5% by weight of polymeric dye transfer inhibiting agents.
The polymeric dye transfer inhibiting agents are preferably selected from
polyamine N-
oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,
polyvinylpyrrolidonepolymers or combinations thereof.
Optical brightener
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69
The compositions can also contain from 0.005% to 5% by weight of certain types
of
hydrophilic optical brighteners.
Hydrophilic optical brighteners useful herein include those having the
structural formula:
R1 R2
1V 1 1H H N O
N OON O C-C O NOO N
~N H H N
R2/ S03M S~3M Rt
wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2 is
selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino,
morphilino,
chloro and amino; and M is a salt-forming canon such as sodium or potassium.
When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is
a cation
such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-
hydroxyethyl)-s-triazine-
2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular
brightener
species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-
Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical
brightener
useful in the detergent compositions herein.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and
M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-
hydroxyethyl-N-
methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
This
particular brightener species is commercially marketed under the tradename
Tinopal
SBM-GX by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a cation
such as
sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-
yl)amino]2,2'-
stilbenedisulfonic acid, sodium salt. This particular brightener species is
commercially
marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
Clay softening s s
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The compositions herein can contain a clay softening system comprising a clay
mineral
compound and optionally a clay flocculating agent.
The clay mineral compound is preferably a smectite clay compound. Smectite
clays are
disclosed in the US-A-3,862,058, US-A-3,948,790, US-A-3,954,632 and US-A-
4,062,647. EP-A-0299575 and EP-A-0313146 describe suitable organic polymeric
clay
flocculating agents.
Cationic fabric softening_a_ge
Suitable cationic fabric softening agents include the water insoluble tertiary
amines or
dilong chain amide materials as disclosed in GB-A-1514276 and EP-A-0011340.
Cationic fabric softening agents are typically incorporated at total levels of
from 0.5% to
15% by weight, normally from 1% to 5% by weight.
