Note: Descriptions are shown in the official language in which they were submitted.
CA 02298510 2000-O1-28
WO 99/06522 ' ' PCT1US98/16144
The present invention provides a detergent tablet comprising a compressed
portion
and a non-compressed, non-encapsulating portion.
Detergent compositions in tablet form are known in the art. It is understood
that
detergent compositions in tablet form hold several advantages over detergent
compositions in particulate form, such as ease of handling, transportation and
storage.
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 a tablet press. Tablets are typically formed by compression of the
components
of the detergent composition into a tablet. However, the Applicant has found
that
some components of a detergent composition are adversely affected by the
compression pressure used to form the tablets. These components could not
previously be included in a detergent tablet composition without sustaining a
Ioss in
performance. In some cases the components may even have become unstable or
inactive as a result of the compression.
Furthermore as the components of the detergent composition are compressed, the
components are brought into close proximity with each other. A result of the
close
proximity of the components can be that certain of the components react with
each
other, becoming unstable, inactive or exhausted. A solution to this problem,
as seen
in the prior art, has been to separate components of the detergent composition
that
may potentially react with each other when the detergent composition is
compressed
CA 02298510 2000-O1-28
w
WO 99/06522 ' PCT/US98/16144
into tablet form. Separation of the components has been achieved by, for
example,
preparing multiple-layer tablets wherein the components that may potentially
react
with each other are contained in different layers of the tablet. Multiple-
layer tablets,
are traditionally prepared using multiple compression steps. Layers of the
tablet that
are subjected to more than one compression step are subjected to a cumulative
and
potentially greater overall compression pressure. An increase in compression
pressure of the tabletting press is known to decrease the rate of dissolution
of the
tablet with the effect that such multiple layer may not dissolve
satisfactorily in use.
Other methods of achieving separation of detergent components have been
described. For example EP-A 0,224,135 describes a dishwashing detergent in a
form which comprises a warm water-soluble melt, into which is pressed a cold
water-soluble tablet. The document teaches a detergent composition that
consists of
two parts, the first part dissolving in the pre-rinse and the second part
dissolving in
the main wash of the dishwasher.
EP-B-0,055,100 describes a lavatory block formed by combining a slow
dissolving
shaped body with a tablet. The lavatory block is designed to be placed in the
cistern
of a lavatory and dissolves over a period of days, preferably weeks. As a
means of
controlling the dissolution of the lavatory block, the document teaches
admixing one
or more solubility control agents. Examples of such solubility control agents
are
paradichlorobenzene, waxes, long chain fatty acids and alcohols and esters
thereof
and fatty alkylamides. Detergent tablets for use in laundry or automatic
dishwashing
must substantially dissolve within one cycle of the washing or dishwashing
machine,
i.e. within 30 to 120 minutes.
The Applicant has found that by providing a detergent tablet comprising a
compressed portion and a non-encapsulating, non-compressed portion detergent
components previously considered to be unacceptable for detergent tablets, can
be
incorporated into a detergent tablet. In addition, potentially reactive
components of
the detergent composition can be effectively separated.
i
1 I I
CA 02298510 2002-07-29
-3-
A further advantage of using a detergent tablet as described herein, is the
performance benefits which may be achieved in being able to prepare the
detergent tablet so that if required, the compressed portion and the non-
compressed portion have different rates of dissolution. Such performance
benefits are achieved by selectively delivering active detergent components
into the wash solution at different times.
SUMMARY OF THE INVENTION
According to the present invention there is provided a process for preparing a
detergent tablet comprising a compressed portion and a non-compressed, non-
encapsulating portion, the steps of said process comprising: (a) compressing a
composition comprising an active detergent component and a disrupting agent
which is a member selected from the group consisting of disintegrating agents,
effervescing agents and mixtures thereof to form at least one mould in said
compressed portion; and (b) delivering a composition comprising an active
detergent component in the form of a solid to said at least one mould of said
compressed portion to form at least one non-compressed non-encapsulating
portion; wherein said detergent tablet comprises more than one non-
compressed portion, the first and second and optional subsequent non-
compressed portions comprise particulates with substantially different average
particle size such that the difference in average particle size of the first
and
second and/or subsequent non- compressed portion is greater than 5%; and
wherein said first and second and/or subsequent non-compressed portions
have substantially different density such that the difference between the
density of the first and second and/or subsequent non- compressed portion is
greater than 5%.
In an alternative embodiment, there is also provided a process for preparing a
detergent tablet comprising a compressed portion and a non-compressed, non-
encapsulating portion, the steps of said process comprising: (a) compressing a
composition comprising an active detergent component and a disrupting agent
which is a member selected from the group consisting of disintegrating agents,
I . - I;
CA 02298510 2002-07-29
-4-
effervescing agents, and mixtures thereof to form at least one mould in said
compressed portion; (b) filling said at least one mould of said compressed
portion with a composition comprising an active detergent component in the
form of a liquid or a gel to form at least one non-compressed, non-
encapsulating portion.
DETAILED DESCRIPTION OF THE INVENTION
Thus, in accordance with the present invention it has been found that active
detergent components of a detergent tablet previously adversely affected by
the compression pressure used to form the tablets can now be included in a
detergent tablet. Examples of these components include bleaching agents and
enzymes. In addition, in accordance with the present invention, it has been
found that active detergent components of a detergent tablet may be separated
from one another by having one or more compatible components contained in
a compressed portion and one or more compatible components contained in a
non-compressed portion of the tablet. Examples of components that may
interact and may therefore require separation include bleaching agents, bleach
activators or catalysts and enzymes; bleaching agents and bleach catalysts or
activators; bleaching agents and surfactants; alkalinity sources and enzymes.
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
Furthermore, it may be advantageous to provide the compressed and the non-
compressed portions such that they dissolve in wash water with different
dissolution
rates. By controlling the rate of dissolution of each portion relative to one
another,
and by selection of the active detergent components in the respective
portions, their
order of release into the wash water can be controlled and the cleaning
performance
of the detergent tablet may be improved. For example it is often preferred
that
enrymes are delivered to the wash prior to bleaching agent and/or bleach
activator.
It may also be preferred that a source of alkalinity is released into the wash
water
more rapidly than other components of the detergent tablet. It is also
envisaged that
it may be advantageous to prepare a detergent tablet according to the present
invention wherein the release of certain components of the tablet is delayed
relative
to other components.
It is also envisaged that the tablet may comprise a plurality of compressed or
non-
compressed portions. For example, a plurality of compressed portions may be
arranged in layers and/or a plurality of non-compressed portions may be
present as
discrete sections of the tablet separated by a compressed portion. Thus, there
may
be a first and a second and optional subsequent compressed and/or non-
compressed
portions, each comprising an active detergent component and where at least the
first
and second portions may comprise different active detergent components or
mixtures of components. Such a plurality of compressed or non-compressed
portions may be advantageous, enabling a tablet to be produced which has for
example, a first and second and optional subsequent portions so that they have
different rates of dissolution. Such performance benefits are achieved by
selectively
delivering active detergent components into the wash water at different times.
The detergent tablets described herein are preferably between 1 Sg and 1 OOg
in
weight, more preferably between 18g and 80g in weight, even more preferably
between 20g and 60g in weight. The detergent tablet described herein that are
suitable for use in automatic dishwashing methods are most preferably between
20g
and 40g in weight Detergent tablets suitable for use in fabric laundering
methods are
CA 02298510 2000-O1-28
y
WO 99/06522 PC'T/US98/16144
most preferably between 40g and 100g, more preferably between 40g and 80g,
most
preferably between 40g and 6~g in weight. The weight ratio of compressed
portion
to non-compressed portion is generally greater than 0.x:1, preferably greater
than
1:l, more preferably greater than 2:1, even more preferably greater than 3:1
or even
4:1, most preferably at least 5:1.
The detergent tablets described herein have Child Bite Strength (CBS) which is
generally greater than l OKg, preferably greater than l2Kg, most preferably
greater
than l4Kg. CBS is measured as per the U.S. Consumer Product Safety Commission
Test Specification.
Child Bite Strength Test Method: According to this method the tablet is placed
horizontally between two strips/plates of metal. The upper and lower plates
are
hinged on one side, such that the plates resemble a human jaw. An increasing
downward force is applied to the upper plate, mimicking the closing action of
the
jaw, until the tablet breaks. The CBS of the tablet is a measure of the force
in
Kilograms, required to break the tablet.
The detergent tablets described herein generally have a dissolution rate of
faster than
0.33 g/min, preferably faster than 0.5 g/min, more preferably faster than 1.00
g/min,
even more preferably faster than 2.00 g/m, most preferably faster than 2.73
g/min.
Dissolution rate is measured using the SOTAX dissolution test method. For the
purposes of the present invention dissolution of detergent tablets is achieved
using a
SOTAX-(tradename) machine; model number AT7 available from SOTAX.
SOTAX Dissolution Test Method: The SOTAX machine consists of a temperature
controlled waterbath with lid. 7 pots are suspended in the water bath. 7
electric
stirring rods are suspended from the underside of the lid, in positions
corresponding
to the position of the pots in the waterbath. The lid of the waterbath also
serves as a
lid on the pots.
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
The SOTAX waterbath is filled with water and the temperature gauge set to
50°C.
Each pot is then filled with 1 titre of deionised water and the stirrer set to
revolve at
?SOrpm. The lid of the waterbath is closed, allowing the temperature of the
deioniscd water in the pots to equilibrate with the water in the waterbath for
1 hour.
The tablets are weighed and one tablet is placed in each pot, the lid is then
closed.
The tablet is visually monitored until it completely dissolves. The time is
noted
when the tablet has completely dissolved. The dissolution rate of the tablet
is
calculated as the average weight (g) of tablet dissolved in deionised water
per
minute.
Compressc OrtiOn
The compressed portion of the detergent tablet comprises at least one active
detergent component but may comprise a mixture of more than one active
detergent
components, which are compressed. Any detergent tablet component
conventionally
used in known detergent tablets is suitable for incorporation into the
compressed
portion of the detergent tablets of this invention. Suitable active detergent
components are described hereinafter. Preferred active detergent components
include builder compound, surfactant, bleaching agent, bleach activator,
bleach
catalyst, enryme and an alkalinity source.
Active detergent components) present in the compressed layer may optionally be
prepared-in combination with a carrier and/or a binder for example water,
polymer
(e.g. PEG), liquid silicate. The active detergent components are preferably
prepared
in particulate form (i.e. powder or granular form) and may be prepared by any
known method, for example conventional spray drying, granulation or
agglomeration. The particulate active detergent components) are then
compressed
using any suitable equipment suitable for forming compressed tablets, blocks,
bricks
or briquettes; described in more detail hereafter.
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98116144
The non-compressed, non-encapsulating portion (hereinafter non-compressed
portion) comprises at least one active detergent component, but may comprise a
mixture of more than one active detergent components. Active detergent
components suitable for incorporation in the non-compressed portion include
components that interact with one or more detergent components present in the
compressed portion. In particular, preferred components of the non-compressed
portion are those that are adversely affected by compression pressure of for
example
a compression tablet press. Examples of such active detergent components
include,
but are not limited to, surfactant, bleaching agent, bleach activator, bleach
catalyst,
enzyme, corrosion inhibitor, perfume and an alkalinity source. These
components
are described in more detail below. The active detergent components) may be in
any form for example particulate (i.e. powder or granular), gel or liquid
form. The
non-compressed portion in addition to comprising an active detergent
component,
may also optionally comprise a carrier component. The active detergent
component
may be present in the form of a solid, gel or liquid, prior to combination
with a
carrier component.
The non-compressed portion of the detergent tablet may be in solid, gel or
liquid
form.
The detergent tablet of the present invention requires that the non-compressed
portion-be delivered to the compressed portion such that the compressed
portion and
non-compressed portion contact each other. The non-compressed portion may be
delivered to the compressed portion in solid or flowable form. Where the non-
compressed portion is in solid form, it is pre-prepared, optionally shaped and
then
delivered to the compressed portion. The non-compressed portion is then
affixed to
a pre-formed compressed portion, for example by adhesion or by insertion of
the
non-compressed portion to a co-operating surface of the compressed portion.
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
Preferably the compressed portion comprises a pre-prepared depression or mould
into which the non-compressed portion is delivered.
The non-compressed portion is preferably delivered to the compressed portion
in
flowable form. The non-compressed portion is then affixed to the compressed
portion for example by adhesion, by forming a coating over the non-compressed
layer to secure it to the compressed portion, or by hardening, for example (i)
by
cooling to below the melting point where the flowable composition becomes a
solidified melt; (ii) by evaporation of a solvent; (iii) by crystallisation;
(iv) by
polymerisation of a polymeric component of the flowable non-compressed
portion;
(v) through pseudo-plastic properties where the flowable non-compressed
portion
comprises a polymer and shear forces are applied to the non-compressed
portion;
(vi) combining a binding agent with the flowable non-compressed portion. In an
alternative embodiment the flowable non-compressed portion may be an extrudate
that is affixed to the compressed portion by for example any of the mechanism
described above or by expansion of the extrudate to the parameters of a mould
provided by the compressed portion.
Preferably the compressed portion comprises a pre-prepared depression or mould
(hereafter referred to as 'mould') into which the non-compressed portion is
delivered. In an alternative embodiment the surface of the compressed portion
comprises more than one mould into which the non-compressed portion may be
delivered. The moulds) preferably at least partially accommodates one or more
non-compressed portions. The non-compressed portions) is then delivered into
the
mould and affixed to the compressed portion as described above.
The non-compressed portion may comprise particulates. The particulates may be
prepared by any known method, for example conventional spray drying,
granulation,
encapsulation or agglomeration. Particulates may be affixed to the compressed
portion by incorporating a binding agent or by forming a coating layer over
the non-
compressed portion.
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
Where the detergent tablet comprises more than one non-compressed portion, the
first and second and optional subsequent non-compressed portions may comprise
particulates having substantially different average particle size. By
substantially
different average particle size we mean that the difference between the
average
particle size of the first and second and/or subsequent compositions is
greater than
5%, preferably greater than 10%, more preferably greater than 15% or even 20%
of
the smaller average particle size.
The average particle size of the particulate detergent active components used
herein
is calculated using a series of Tyler sieves. The series consists of a number
of sieves
each having a different aperture size. Samples of a composition of active
detergent
components are sieved through the series of sieves (typically 5 sieves). The
weight
of a sample of composition retained in the sieve is plotted against the
aperture size
of the sieve. The aveiage particle size of the composition is defined as the
aperture
size through which 50% by weight of the sample of composition would pass.
In another embodiment the first and second and optional subsequent
compositions of
active detergent components have substantially different density such that the
difference between the density of the first and second and/or subsequent
compositions is greater than 5%, preferably greater than 10%, more preferably
greater than 15% or even 20% of the smaller density. Density of the
particulate
composition of active detergent components can be measured by any known method
suitable for measuring density of particulate material.
Preferably the density of the composition of active detergent components is
measured using a simple funnel and cup device consisting of a conical funnel
moulded rigidly on a base and provided with a flap valve at its lower
extremity to
allow the contents of the funnel to be emptied into an axially aligned
cylindrical cup
disposed below the funnel. The funnel is 130 mrn high and has internal
diameters
of 130 mm and 40 mm at its respective upper and lower extremities. It is
mounted
CA 02298510 2000-O1-28
WO 99106522 PCTNS98/16144
so that the lower extremity is 140 mm above the upper surface of the base. The
cup
has an overall height of 90 mm, an internal height of 87 mm and an internal
diameter
of 84 mm. Its nominal volume is 500 ml.
A density measurement iS taken by hand pouring the composition into the
funnel.
Once the funnel is filled, the flap valve is opened and powder allowed to run
through
the funnel, overfilling the cup. The filled cup is removed from the frame and
excess
powder removed from the cup by passing a straight edged implement e.g. a
knife,
across its upper edge. The filled cup is then weighed and the value obtained
for the
weight of powder doubled to provide a bulk density in grams/litre. Replicate
measurements are made as required.
Tablets in which one or more of the non-compressed portions comprise
particulates
and the average particle size and/or density of the first and second and
optionally
subsequent non-compressed portions are substantially different are preferred
where
the first and second and optionally subsequent non-compressed portions are
required
to have different rates of dissolution.
Where the non-compressed portion comprises a solidified melt, the melt is
prepared
by heating a composition comprising a detergent active component and optional
carrier components) to above its melting point to form a flowable melt. The
flowable melt is then poured into a mould and allowed to cool. As the melt
cools it
becomes solid, taking the shape of the mould at ambient temperature. Where the
composition comprises one or more carrier components, the carrier components)
may be heated to above their melting point, and then an active detergent
component
may be added. Carrier components suitable for preparing a solidified melt are
typically non-active components that can be heated to above melting point to
form a
liquid and cooled to form an intermolecular matrix that can effectively trap
active
detergent components. A preferred non-active carrier component is an organic
polymer that is solid at ambient temperature. Preferably the non-active
detergent
CA 02298510 2000-O1-28
WO 99/06522 PCTNS98/16144
12
components is polyethylene glycol (PEG). The compressed portion of the
detergent
tablet preferably provides a mould to accommodate the melt.
The flowable non-compressed portion may be in a form comprising a dissolved or
suspended active detergent component. The flowable non-compressed portion may
harden over time to form a solid, semi solid or highly viscous liquid non-
compressed
portion by any of the methods described above. In particular, the flowable non-
compressed portion may harden by evaporation of a solvent. Solvents suitable
for
use herein may include any known solvent in which a binding agent is soluble.
Preferred solvents may be polar or non-polar and may include water, alcohol,
(for
example ethanol, acetone) and alcohol derivatives. In an alternative
embodiment
more than one solvent may be used.
The flowable non-compressed portion may comprise one or more binding agents.
Any binding agent that has the effect of causing the composition to become
solid,
semi-solid or highly viscous over time is envisaged for use herein. Although
not
wishing to be bound by theory, it is believed that mechanisms by which the
binding
agent causes a non-solid composition to become solid, semi-solid or highly
viscous
include: chemical reaction (such as chemical cross linking), or effect
interaction
between two or more components of the flowable compositions either; chemical
or
physical interaction of the binding agent with a component of the composition.
Preferred binding agents include a sugar/gelatine combination, starch,
glycerol and
organic polymers. The sugar may be any monosaccharide ( e.g. glucose),
disaccharide (e.g. sucrose or maltose) or polysaccharide. The most preferred
sugar
is commonly available sucrose. For the purposes of the present invention type
A or
B gelatine may be used, available from for example Sigma. Type A gelatine is
preferred since it has greater stability in alkaline conditions in comparison
to type B.
Preferred gelatine also has a bloom strength of between 65 and 300, most
preferably
between 75 and 100. Preferred organic polymers include polyethylene glycol
(PEG)
of molecular weight from 500 to 10,000, preferably from 750 to 8000, most
preferably from 1000 to 6000 available from Hoechst.
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
13
Where the non-compressed portion is an extrudate, the extrudate is prepared by
premixing the active detergent components with optional carrier components to
form
a viscous paste. The viscous paste is then extruded using any suitable
commonly
available extrusion equipment such as for example a single or twin screw
extruder
available from for example APV Baker, Peterborough, U.K. The extrudate is then
cut to size either after delivery to the compressed portion, or prior to
delivery to the
compressed portion of the detergent tablet. The compressed portion of the
tablet
preferably comprises a mould into which the extruded non-compressed portion
may
be delivered.
In a preferred embodiment the non-compressed portion is coated with a coating
layer. The coating may be used to affix a non-compressed portion to the
compressed
portion. This may be particularly advantageous where the non-compressed
portion
comprises flowable particulates, gels or liquids.
The coating layer preferably comprises a material that becomes solid on
contacting
the compressed and/or the non-compressed portions within preferably less than
1 S
minutes, more preferably less than 10 minutes, even more preferably less than
5
minutes, most preferably less than 60 seconds. Preferably the coating layer is
water-soluble. Preferred coating layers comprise materials selected from the
group
consisting of fatty acids, alcohols, diols, esters and ethers, adipic acid,
carboxylic
acid, dicarboxylic acid, polyvinyl acetate (PVA), polyvinyl pyrrolidone (PVP),
polyacetic acid (PLA), polyethylene glycol (PEG) and mixtures thereof.
Preferred
carboxylic or dicarboxylic acids preferably comprise an even number of carbon
atoms. Preferably carboxylic or dicarboxylic acids comprise at least 4, more
preferably at least 6, even more preferably at least 8 carbon atoms, most
preferably
between 8 and 13 carbon atoms. Preferred dicarboxylic acids include adipic
acid,
suberic acid, azelaic acid, subacic acid, undecanedioic acid, dodecandioic
acid,
tridecanedioic and mixtures thereof. Preferred fatty acids are those having a
carbon
chain length of from C 12 to C22, most preferably from C 18 to C22. The
coating
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
14
layer may also preferably comprise a disrupting agent. Where present the
coating
layer generally present at a level of at least 0.05%, preferably at least 0.1
%, more
preferably at least 1%, most preferably at least 2% or even at least 5% of the
detergent tablet.
As an alternative embodiment the coating layer may encapsulate the detergent
tablet.
In this embodiment the coating layer is present at a level of at least 4%,
more
preferably at least 5%, most preferably at least 10% of the detergent tablet.
In a preferred embodiment the compressed and/or non-compressed portions and/or
coating layer additionally comprise a disrupting agent. The disrupting agent
may be
a disintegrating or effervescing agent. Suitable disintegrating agents include
agents
that swell on contact with water or facilitated water influx and/or efflux by
forming
channels in compressed and/or non-compressed portions . Any known
disintegrating or effervescing agent suitable for use in laundry or
dishwashing
applications is envisaged for use herein. Suitable disintegrating agent
include starch,
starch derivatives, alginates, 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
effervesing agents may be selected from the group consisting of perborate,
percarbonate, carbonate, bicarbonate and carboxylic acids such as citric or
malefic
acid.
An advantage of including a disrupting agent in the detergent tablet of the
present
invention is the transport, storage and handling benefits that can be achieved
by
increasing the hardness of the detergent tablet without adversely affecting
the
cleaning performance.
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
IS
According to the present invention there is also provided a process for
preparing a
detergent tablet comprising the steps of:
a) compressing an active detergent component to form a compressed portion; and
b) delivering a non-compressed, non-encapsulating portion comprising an active
detergent component to the compressed portion.
As described above, the detergent tablets described herein are prepared by
separately
preparing the composition of active detergent components forming the
respective
compressed portion and the non-compressed portion, then delivering or adhering
the
composition of the non-compressed portion to the compressed portion.
The compressed portion is prepared by obtaining at least one active detergent
component and optionally premixing with carrier components. Any pre-mixing
will
be carried out in a suitable mixer; for example a pan mixer, rotary drum,
vertical
blender or high shear mixer. Preferably dry particulate components are admixed
in a
mixer, as described above, and liquid components are applied to the dry
particulate
components, for example by spraying the liquid components directly onto the
dry
particulate components. The resulting composition is then formed into a
compressed
portion in a compression step using any known suitable equipment. Preferably
the
composition is formed into a compressed portion using a tablet press, wherein
the
tablet is prepared by compression of the composition between an upper and a
lower
punch. rn a preferred embodiment of the present invention the composition is
delivered into a punch cavity of a tablet press and compressed to form a
compressed
portion using a pressure of preferably greater than 6.3KN/cm2, more preferably
greater than 9KN/cm2, most preferably greater than 14.4KN/cm2.
In order to form a preferred tablet of the invention, wherein the compressed
portion
provides a mould to receive the non-compressed portion, the compressed portion
is
prepared using a modified tablet press comprising modified upper and/or lower
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
16
punches. The upper and lower punches of the modified tablet press are modified
such that the compressed portion provides one or more indentations which form
a
moulds) to which the non-compressed portion is delivered.
The non-compressed portion comprises at least one active detergent component.
Where the non-compressed portion comprises more than one active detergent
component the components are pre-mixed using any known suitable mixing
equipment. In addition the non-compressed portion may optionally comprise a
carrier with which the active detergent components are combined. The non-
compressed portion may be prepared in solid or flowable form. Once prepared
the
composition is delivered to the compressed portion. The non-compressed portion
may be delivered to the compressed portion by manual delivery or using a
nozzle
feeder or extruder. Where the compressed portion comprises a mould, the non-
compressed portion is preferably delivered to the mould using accurate
delivery
equipment, for example a nozzle feeder, such as a loss in weight screw feeder
available from Optima, Germany or an extruder.
Where the flowable non-compressed portion is in particulate form the process
comprises delivering a flowable non-compressed portion to the compressed
portion
in a delivery step and then coating at least a portion of the non-compressed
portion
with a coating layer such that the coating layer has the effect of
substantially
adhering the non-compressed portion to the compressed portion.
Where the flowable non-compressed portion is affixed to the compressed portion
by
hardening, the process comprises a delivery step in which the flowable non-
compressed portion is delivered to the compressed portion and a subsequent
conditioning step, wherein the non-compressed portion hardens. Such a
conditioning step may comprise drying, cooling, binding, polymerisation etc.
of the
non-compressed portion, during which the -non-compressed portion becomes
solid,
semi-solid or highly viscous. Heat may be used in a drying step. Heat, or
exposure
to radiation may be used to effect polymerisation in a polymerisation step.
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
17
It is also envisaged that the compressed portion may be prepared having a
plurality
of moulds. The plurality of moulds are then filled with a non-compressed
portion.
It is also envisaged that each mould can be filled with a different non-
compressed
portion or alternatively, each mould can be filled with a plurality of
different non-
compressed portions.
The compressed portion of the detergent tablets described herein are prepared
by
compression composition of active detergent components. A suitable composition
may include a variety of different detergent active 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.
Highly preferred active detergent components include a builder compound, a
surfactant, an enzyme and a bleaching agent.
The detergent tablets of the present invention preferably contain a builder
compound, typically present at a level of from 1 % to 80% by weight,
preferably
from 10% to 70% by weight, most preferably from 20% to 60% by weight of the
composition of active detergent components.
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
18
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 polycarboxyiates 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
sulfinyl 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 British Patent
No.
1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and
aminosuccinates described in Netherlands Application 7205873, and the
oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates
described
in British Patent No. 1,387,447.
Polycarboxylates containing four carboxy groups include oxydisuccinates
disclosed
in British Patent No. 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
British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448,
and
the sulfonated pyrolysed citrates described in British Patent No. 1,439,000.
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
19
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 - tetracarboxylates, 1,2,3,4,5,6-hexane - hexacarboxyiates and
carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol
and
xylitol. Aromatic polycarboxylates include mellitic acid, pyromeilitic acid
and the
phthalic acid derivatives disclosed in British Patent No. 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 German Patent Application No. 2,321,001
published on November 15, 1973.
Highly preferred builder compounds for use in the present invention 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.
CA 02298510 2000-O1-28
WO 99106522 PCT/US98/16144
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.
The detergent tablets of the present invention may contain a partially soluble
or
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, DE-A-3417649 and DE-A-3742043.
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 0 164514 and EP 0 293640.
Methods for preparation of crystalline layered silicates of this type are
disclosed in
DE-A-3_417649 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 is preferably present in
granular
detergent compositions as a particulate in intimate admixture with a solid,
water-
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
31
soluble ionisable material as described in PCT Patent Application No.
W092/18594. 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.~ 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.
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
S% 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 ~m
and I pm,
more preferably between 0.05 ~m and 0.9 Vim, most preferably between 0.1 pm
and
0.6 pm.
Zeolite A has the formula
Na 12 [A102) 12 (Si02)12J~ X20
CA 02298510 2000-O1-28
WO 99/06522 PCTNS98/16144
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
preferred 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
in
terms of providing improved stain removal. Enhanced builder performance is
also
seen in terms of reduced fabric encrustation and improved fabric whiteness
maintenance; problems believed to be associated with poorly built detergent
compositions.
A surprising finding is that mixed aluminosilicate zeolite detergent
compositions
comprising colloidal zeolite A and colloidal zeolite Y provide equal calcium-
ion
sequestration performance versus an equal weight of commercially available
zeolite
A. Another surprising finding is that mixed aluminosilicate zeolite detergent
compositions, described above, provide improved magnesium ion sequestration
performance versus an equal weight of commercially available zeolite A.
surfactant
Surfactants are preferred detergent active components of the compositions
described
herein. 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 methods must 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. The surfactant is typically present at a level of
from
0.2% to 30% by weight, more preferably from 0.5% to 10% by weight, most
CA 02298510 2000-O1-28
WO 99/06522 PCTIUS98/16144
?3
preferably from 1 % to 5% by weight of the composition of active detergent
components.
A typical listing of anionic, nonionic, ampholytic and zwitterionic classes,
and
species of these surfactants, is given in U.S.P. 3,929,678 issued to Laughlin
and
Heuring on December, 30, 1975. A list of suitable cationic surfactants is
given in
U.S.P. 4,259,217 issued to Murphy on March 31,1981. A listing of surfactants
typically included in automatic dishwashing detergent compositions is given
for
example, in EP-A-0414 549 and PCT Applications No.s WO 93/08876 and WO
93/08874.
Essentially any nonionic surfactants useful for detersive purposes can be
included in
the detergent tablet. Preferred, non-limiting classes of useful nonionic
surfactants
are listed below.
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.
A suitable endcapped alkyl alkoxylate surfactant is the epoxy-capped
poly(oxyalkylated) alcohols represented by the formula:
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
24
RIO[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 1; 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 94/22800, published October 13,
1994
by Olin Corporation.
Preferred surfactants for use herein include ether-capped poly(oxyalkylated)
alcohols
having the formula:
R1 O[CH2CH(R3)O]x[CH2]kCH(OH)[CH2]jOR2
wherein RI 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 R' 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
CA 02298510 2000-O1-28
WO 99/06522 ~ PCT/US98/16144
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
alklyeneoxy
units as described above. For instance, if x is 3, R3may be be selected to
form
ethlyeneoxy(EO) or propyieneoxy(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
(E0) 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 I and j is 1 so that the surfactants have the formula:
RI O[CH2CH(R3)O]xCH2CH(OH)CH20R2
where RI, 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 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
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
26
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 of
the
present invention 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. Examples of methods of preparing the ether-
capped poly(oxyalkylated) alcohol surfactants are described below:
Preparation of C~yyl glv~dyl et_h_er
A C12/14 fatty alcohol (100.00 g, 0.515 mol.) and tin (IV) chloride (0.58 g,
2.23
mmol, available from Aldrich) are combined in a 500 mL three-necked round-
bottomed flask fitted with a condenser, argon inlet, addition funnel, magnetic
stirrer
and internal temperature probe. The mixture is heated to 60 °C.
Epichlorhydrin
(47.70 g, 0.515 mol, available from Aldrich) is added dropwise so as to keep
the
temperature between 60-65 °C. After stirring an additional hour at 60
°C, the
mixture is cooled to room temperature. The mixture is treated with a 50%
solution
of sodium hydroxide (61.80 g, 0.773 mol, 50%) while being stirred
mechanically.
After addition is completed, the mixture is heated to 90 °C for 1.5 h,
cooled, and
filtered with the aid of ethanol. The filtrate is separated and the organic
phase is
washed with water ( 100 mL), dried over MgS04, filtered, and concentrated.
Distillation of the oil at 100-120 °C (0.1 mm Hg) providing the
glycidyl ether as an
oil.
Preparation of C12~14.~X1=~~/]l
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
27
Neodol~ 91-8 (20.60 g, 0.0393 mol ethoxylated alcohol available from the Shell
chemical Co.) and tin (IV) chloride (0.58 g, x.23 mmol) are combined in a 250
mL
three-necked round-bottomed flask fitted with a condenser, argon inlet,
addition
funnel, magnetic stirrer and internal temperature probe. The mixture is heated
to 60
°C at which point C 1 ~~14 alkyl glycidyl ether ( 11.00 g, 0.0393 mol)
is added
dropwise over 15 min. After stirring for 18 h at 60 °C, the mixture is
cooled to room
temperature and dissolved in an equal portion of dichloromethane. The solution
is
passed through a 1 inch pad of silica gel while eluting with dichloromethane.
The
filtrate is concentrated by rotary evaporation and then stripped in a
kugelrohr oven
( 100 °C, 0.5 mm Hg) to yield the surfactant as an oil.
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 1 g 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.
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 02298510 2000-O1-28
WO 99/06522 PCT/US98J16144
28
Nonionic EO condensation products with or~vlene oxide/ethvlene ~~aminP
arirt,~ctS
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 TetronicrM compounds, marketed by BASF.
In a preferred embodiment of the present invention the detergent tablet
comprises 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, aad most preferably less than I O°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~ SLF I 8), epoxy-capped poly(oxyalkylated) alcohols
(e.g., Olin Corporation's Poly-Tergent~ SLF 18B series of nonionics, as
described,
CA 02298510 2002-07-29
,9
for example, in WO 94/22800, published October 13, 1994 by Olin
Corporation)and
the ether-capped poly(oxyalkylated) alcohol surfactants.
Nonionic surfactants can optionally contain propylene oxide in an amount up to
15% by weight. Other preferred nonionic surfactants can be prepared by the
processes described in U.S. Patent 4,223,163, issued September 16, 1980,
Builloty.
Low cloud point nonionic surfactants additionally comprise a polyoxyethylene,
polyoxypropylene block polymeric compound. Block polyoxyethylene-
polyoxypropylene polymeric compounds include those based on ethylene glycol,
propylene glycol, glycerol, trimethylolpropane and ethylenediamine as
initiator
reactive hydrogen compound. Certain of the block polymer surfactant compounds
designated PLURONIC~, REVERSED PLURONIC~, and TETRONIC~ by the
BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable in ADD compositions
of the invention. Preferred examples include REVERSED PLURONIC~ 2582 and
TETRONIC~ 702, Such surfactants are typically useful herein as low cloud point
nonionic surfactants.
As used herein, a "high cloud point" nonionic surfactant is defined as a
nonionic
surfactant system ingredient having a cloud point of greater than 40°C,
preferably
greater than 50°C, and more preferably greater than 60°C.
Preferably the nonionic
surfactant system comprises an ethoxylated surfactant derived from the
reaction of a
monohydroxy alcohol or alkylphenol containing from 8 to 20 carbon atoms, with
from 6 to 15 moles of ethylene oxide per mole of alcohol or alkyl phenol on an
average basis. Such high cloud point nonionic surfactants include, for
example,
Tergitol 1559 (supplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by
Rhone
Poulenc), and Neodol 91-8 (supplied by Shell).
It is also preferred for purposes of the present invention that the high cloud
point
nonionic surfactant further have a hydrophile-lipophile balance ("HLB"; see
Kirk
CA 02298510 2002-07-29
WO 99/06522 PCT/US98/16144
Othmer hereinbefore) value within the range of from 9 to 15, preferably 1 I to
15.
Such materials include, for example, Tergitol l SS9 (supplied by Union
Carbide),
Rhodasurf TMD 8.5 (supplied by Rhone Poulenc), and Neodol 91-8 (supplied by
Shell).
Another preferred high cloud point nonionic surfactant is derived from a
straight or
preferably branched chain or secondary fatty alcohol containing from 6 to 20
carbon atoms (C6-C2p alcohol), including secondary alcohols and branched chain
primary alcohols. Preferably, high cloud point nonionic surfactants are
branched or
secondary alcohol ethoxylates, more preferably mixed C9/l l or C11/15 branched
alcohol ethoxylates, condensed with an average of from 6 to 15 moles,
preferably
from 6 to 12 moles, and most preferably from 6 to 9 moles of ethylene oxide
per
mole of alcohol. Preferably the ethoxylated nonionic surfactant so derived has
a
narrow ethoxylate distribution relative to the average.
In a preferred embodiment the detergent tablet comprising such a mixed
surfactant
system also comprises an amount of water-soluble salt to provide conductivity
in
deionised water measured at 25°C greater than 3 milli Siemens/cm,
preferably
greater than 4 milli Siemenslcm, most preferably greater than 4.5 milli
Siemens/cm .
In another preferred embodiment the mixed surfactant system dissolves in water
having a hardness of I .246mmo1~L in any suitable cold-fill automatic
dishwasher to
provide a solution with a surface tension of less than 4 Dynes/cm2 at less
than ~t5°C,
preferably less than 44°C, most preferably less than 35°C as
described in co-pending
U.S. Patent No. 6,013,613.
in another preferred embodiment the high cloud point and low cloud point
surfactants of the mixed surfactant system are separated such that one of
either the
high cloud point or low cloud point surfactants is present in a first matrix
and the
CA 02298510 2002-07-29
3l
other is present in a second matrix as described in U.S. Patent No. 6,013,613
For the purposes of the present
invention, the first matrix may be a first particulate and the second matrix
may be a
second particulate. A surfactant may be applied to a particulate by any
suitable
known method, preferably the surfactant is sprayed onto the particulate. In a
preferred aspect the first matrix is the compressed portion and the second
matrix is
the non-compressed portion of the detergent tablet of the present invention.
Preferably the low cloud point surfactant is present in the compressed portion
and
the high cloud point surfactant is present in the non-compressed portion of
the
detergent tablet of the present invention.
Atii~i~.~,t
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 1 g monoesters) diesters of sulfosuccinate (especially saturated and
unsaturated C6-C I4 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 suitable for use herein include the linear and
branched
primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl
glycerol
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
32
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 5, moles of ethylene oxide per
molecule.
A particularly preferred aspect of the invention employs mixtures of the
preferred
alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been
disclosed
in PCT Patent Application No. WO 93/18124.
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-C24 olefin sulfonates, sulfonated polycarboxylic acids,
alkyl
glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol
sulfonates, and
any mixtures thereof.
Anionic carboxylate surfactant
CA 02298510 2000-O1-28
WO 99/06522 PCTNS98/16144
33
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(CH~CH20)x
CH2C00-M+ wherein R is a C6 to C 1 g alkyl group, x ranges from O 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 cation. Suitable alkyl polyethoxy
polycarboxylate
surfactants include those having the formula RO-(CHR1-CHR2-O)-R3 wherein R is
a C6 to C 1 g 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.
Other suitable anionic surfactants are the alkali metal sarcosinates of
formula R-
CON (R1 ) CH2 COOM, wherein R is a CS-C 1 ~ linear or branched alkyl or
alkenyl
group, Rl is a C1-C4 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 ~~
CA 02298510 2000-O1-28
WO 99/06522 PCTNS98/16144
34
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
R~(OR4)xN0(RS)~ 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 containing from 1 to 3, or a polyethylene
oxide
group containing from 1 to 3 ethylene oxide groups. Preferred are C l0-C 1 g
alkyl
dimethylamine oxide, and C 10-18 acylamido alkyl dimethylamine oxide.
A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Conc.
manufactured by Miranol, Inc., Dayton, NJ.
Zwitterionic surfactant
Zwitterionic surfactants can also be incorporated into the detergent
compositions
hereof. These 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-C 1 g hydrocarbyl group, each Rl is typically C I-C3 alkyl,
and R~
is a C1-CS hydrocarbyl group. Preferred betaines are C12_18 dimethyl-ammonio
hexanoate and the C 10-18 acylamidopropane (or ethane) dimethyl (or diethyl)
betaines. Complex betaine surfactants are also suitable for use herein.
CA 02298510 2000-O1-28
WO 99106522 PCT/US98/16144
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 Patents No.s 4228042, 4239660 and 4260529.
Suitable cationic surfactants include the quaternary ammonium surfactants
selected
from mono C6-C I 6, preferably C6-C I 0 N-alkyl or alkenyl ammonium
surfactants
wherein the remaining N positions are substituted by methyl, hydroxyethyl or
hydroxypropyl groups.
In an embodiment of the present invention an enzyme is an essential feature of
the
detergent tablet. In other embodiments of the present invention an enzyme is
an
optional detergent active component. Where present said enzymes are selected
from
the group consisting of cellulases, hemicellulases, peroxidases, proteases,
gluco-
amylases, amylases, xylanases, lipases, phospholipases, esterases, cutinases,
pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases,
ligninases, pullulanases, tannases, pentosanases, malanases, !3-glucanases,
arabinosidases, hyaluronidase, chondroitinase, laccase or 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 U.S. Patent 4,435,307, Barbesgoard et al, J61078384 and W096/02653 which
disclose fungal cellulases produced respectively from Humicola insolens,
~i ~.,~~ ~.
CA 02298510 2002-07-29
WO 99/06522 PCTIUS98/16144
36
Trichoderma, Thielavia and Sporotrichum. EP 739 982 describes cellulases
isolated
from novel Bacillus species. Suitable cellulases are also disclosed in GB-A-
2.075.028; GB-A-2.095.275; DE-OS-2.247.832 and W095/26398.
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 ~veight of SOKDa, an isoelectric point of 5.5 and ccntaining 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 PCT Patent Application No. WO 91/17243. Also
suitable
cellulases are the EGIII cellulases from Trichoderma longibrachiatum described
in
W094/21801, Genencor, published September 29, 1994. Especially suitable
cellulases are the cellulases having color care benefits.
Carezyme and Celluzyme (Novo Nordisk A/S) are
especially useful. See also W091/17244 and W091/21801. Other suitable
cellulases
n
for fabric care andlor cleaning properties are described in W096/34092,
W096/17994 and W095124471.
Said ceUulases are normally incorporated in the detergent composition at
levels from
0.0001 % to 2% of active enzyme by weight of the detergent 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 PCT International
Application
WO 89/099813, W089I09813
i
CA 02298510 2002-07-29
37
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
94/12621) and substitued syringates (C3-CS substitued alkyl syringates) and
phenols. Sodium pPrcarbonate o~ perborate are preferred sources of hydrogen
peroxide.
Said cellulases and/or peroxidases are normally incorporated in the detergent
composition at levels from 0.0001 % to 2% of active enzyme by weight of the
detergent composition.
Other preferred 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 British Patent 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 "Amano," hereinafter
referred to
as "Amano-P". Other suitable commercial lipases include Amano-CES, lipases ex
Chromobacter viscosum, e.g. Chromobacter vfscosum var. lipolyticum NRRLB
3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from
U.S.
Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex
Pseudomonas gladioli. 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. Aiso suitables are the lipolytic enzymes described in
EP 258
i I ;
CA 02298510 2002-07-29
38
068, WO 92/05249 and WO 9/2261 ~ by Novo Nordisk and in WO 94/03578, WO
9/35381 and WO 96/00292 by Unilever.
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
(Genencor); WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO
94/14964 (Unilever).
The lipases and/or cutinases are normally incorporated in the detergent
composition
at levels from 0.0001 % to 2% of active enzyme by weight of the detergent
composition.
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 in GB 1,243,784 to Novo. Other suitable proteases include
ALCALASE~, DURAZYM~ and SAVINASE~ from Novo and MAXATASE~~
MA3~ACAL~, PROPERASE~ and MAXAPEM~ (protein engineered Maxacal)
from Gist-Brocades. Proteolytic enzymes also encompass modified bacterial
serine
protCaSGS, Such as those deSCtlbed in European Patent No. EP0233721A2 ,
published August 26, 1987 and Which is called herein
"Protease s° herein, -ana in European Patent Application 199,404,
Venegas,
published October 29, 1986, 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
l~crcillus in which
lysine replaced arginine at position 27, tyrosine replaced valine at position
104,
serine replaced asparagine at position 123, and alanine replaced threonine at
position
274. Protease C is described in EP 90915958:4, corresponding to WO 91/06637,
I ~ I
CA 02298510 2002-07-29
39
Published May 16, 1991. Genetically modified variants, particularly of
Protease C,
are also included herein.
A preferred protease referred to as "Protease D" is a carbonyl hydrolase
variant
having an amino acid sequence not found in nature, which is derived from a
precursor carbonyl hydrolase by substituting a different amino acid for a
plurality of
amino acid residues at a position in said carbonyl hydrolase equivalent to
position
+76, preferably also in combination with one or more amino acid residue
positions
equivalent to those selected from the group consisting of +99, +101, +103,
+104,
+107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204,
+206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the
numbering of Bacillus amyloliquejaciens subtilisin, as described in
W095/10591.
Also suitable for the present invention are proteases described in patent
applications ,
EP 251 446 and WO 91/06637, protease BLAP~ described in W091/02792 and
their variants described in WO 95/23221.
See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO
93118140 A to Novo. Enzymatic detergents comprising protease, one or more
other
enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to
Novo. When desired, a protease having decreased adsorption and increased
hydrolysis is available as described in WO 95107791 to Procter & Gamble. A
recombinant trypsin-like protease for detergents suitable herein is described
in WO
94/25583 to Novo. Other suitable proteases are described in EP 516 200 by
Unilever.
Other preferred protease enzymes include protease enzymes which are a carbonyl
hydrolase variant having an amino acid sequence not found in nature, which is
CA 02298510 2000-O1-28
WO 99/06522 PC'T/US98/16144
derived by replacement of a plurality of amino acid residues of a precursor
carbonyl
hydrolase with different amino acids, wherein said plurality of amino acid
residues
replaced in the precursor enzyme correspond to position +210 in combination
with
one or more of the following residues: +33, +62, +67, +76, +100, +101, +103,
+104,
+107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209,
+215; +2I7, +218 and +222, where the numbered positions correspond to
naturally-
occurring subtilisin from Bacillus ~3rloliauefaciens or to equivalent amino
acid
residues in other carbonyl hydrolases or subtilisins (such as Bacillus lentos
subtilisin). Preferred enzymes of this type include those having position
changes
+210, +76, +103, +104, +156, and +166.
The proteolytic enzymes are incorporated in the detergent compositions of the
present invention 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 the composition.
Amylases (a and/or 13) can be included for removal of carbohydrate-based
stains.
W094/02597, Novo Nordisk A/S published February 03, 1994, describes cleaning
compositions which incorporate mutant amylases. See also W095/10603, Novo
Nordisk A/S, published April 20, 1995. 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 Pat. no. 5,003,257; EP 252,666; WO/91/00353; FR
2,676,456; EP 285,123; EP 525,610; EP 368,341; and British Patent
specification
no. 1,296,839 (Novo). Other suitable amylases are stability-enhanced amylases
described in W094/18314, published August 18, 1994 and W096/05295, Genencor,
published February 22, 1996 and amylase variants having additional
modification in
the immediate parent available from Novo Nordisk A/S, disclosed in WO
95/10603,
published April 95. Also suitable are amylases described in EP 277 216,
W095/26397 and W096/23873 (all by Novo Nordisk).
Examples of commercial a-amylases products are Purafect Ox Am~ from Genencor
and Termamyl~, Ban~ ,Fungamyl~ and Duramyl~, all available from Novo
CA 02298510 2002-07-29
41
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 W096123873 (Novo Nordisk).
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
W095/35382.
Preferred amylase enzymes include those described in W095/26397.
The amylolytic enzymes are incorporated in the detergent compositions of the
present invention 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 the
composition
In a particularly preferred embodiment, detergent tablets of the present
invention
comprise amylase enzymes, particularly those described in W095126397 in
combination with a complementary amylase.
By "complementary" it is meant the addition of one or more amylase suitable
for
detergency purposes. Examples of complementary amylases (a and/or D) are
described below. W094/02597 and W095/ 10603, Novo Nordisk A/S 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 Pat, no. 5,003,257; EP
252,666;
WO/91/00353; Flt 2,676,456; EP 285,123; EP 525,610; EP 368,341; and British
Patent specification no. 1,296,839 (Novo). Other suitable amylases are
stability-
enhanced amylases described in W094/18314, and W096/05295, Genencor and
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
42
amylase variants having additional modification in the immediate parent
available
from Novo Nordisk A/S, disclosed in WO 95/1 Ob03. Also suitable are amylases
described in EP 277 216 (Novo Nordisk). 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 W096/23873 (Novo Nordisk). 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 W095/35382.
Preferred
complementary amylases for the present invention are the amylases sold under
the
tradename Purafect Ox AmR described in WO 94/18314, W096/05295 sold by
Genencor; Termamyl~, Fungamyl~, Ban~ and Duramyl~, all available from Novo
Nordisk A/S and Maxamyl~ by Gist-Brocades.
Said complementary amylase is generally incorporated in the detergent
compositions
of the present invention 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 the
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 protein and/or genetic engineering, chemical and/or physical
modifications of native enzymes. Common practice as well is the expression of
the
CA 02298510 2002-07-29
WO 99106522 PCT/US98/16144
43
enzyme via host organisms in which the genetic material responsible for the
production of the enzyme has been cloned.
Said enzymes are normally incorporated in the detergent composition at levels
from
0.0001 % to 2% of active enzyme by weight of the detergent composition. The
enzymes can be added as separate single ingredients (prills, 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.
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 9307263 A and WO 9307260 A to
Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5,
1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, Place
et al,
July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials
useful for liquid detergent formulations, and their incorporation into such
formulations, are disclosed in U.S. 4,261,868, Hora et al, April 14, 1981.
Enzymes
for use in detergents can be stabilised by various techniques. Enzyme
stabilisation
techniques are disclosed and exemplified is U.S. 3,600,319, August 17, 1971,
Gedge
et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme
stabilisation
systems are also described, for example, in U.S. 3,519,570. A useful Bacillus,
sp.
AC 13 giving pretenses, xylanases and cellulases, is described in WO 9401532 A
to
Novo.
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
44
A highly preferred component of the composition of active detergent components
is
a bleaching agent. Suitable bleaching agents 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 preferred 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.
The compositions of active detergent components preferably include a hydrogen
peroxide source, as an oxygen-releasing bleach. Suitable hydrogen peroxide
sources
include the inorganic perhydrate salts.
The inorganic perhydrate salts are normally incorporated in the form of the
sodium
salt at a level of from 1 % to 40% by weight, more preferably from 2% to 30%
by
weight and most preferably from 5% to 25% by weight of the compositions.
Examples of inorganic perhydrate salts include perborate, percarbonate,
perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts
are
normally the alkali metal salts. The inorganic perhydrate salt may be included
as
the crystalline solid without additional protection. For certain perhydrate
salts
however, the preferred executions of such granular compositions utilize a
coated
form of the material which provides better storage stability for the
perhydrate salt in
the granular product.
CA 02298510 2000-O1-28
WO 99/06522 PC'T/US98/16144
45
Sodium perborate can be in the form of the monohydrate of nominal formula
NaBO~H202 or the tetrahydrate NaB02H202.3H20.
Alkali metal percarbonates, particularly sodium percarbonate are preferred
perhydrates for inclusion in compositions in accordance with the invention.
Sodium
percarbonate is an addition compound having a formula corresponding to
2Na~C03.3H202, and is available commercially as a crystalline solid. Sodium
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.
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-1,466,799, granted to
Interox on 9th March 1977. 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 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 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.
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144 .
46
Other coatings which contain waxes, oils, fatty soaps can also be used
advantageously within the present invention.
Potassium peroxymonopersulfate is another inorganic perhydrate salt of utility
in the
compositions herein.
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
Peroxyacid bleach precursor compounds are preferably incorporated at a level
of
from 0.5% to 20% by weight, more preferably from 1% to 10% by weight, most
preferably from 1.5% to 5% by weight of the compositions.
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,
864798, 1147871, 2143231 and EP-A-0170386.
CA 02298510 2000-O1-28
WO 99106522 PCTNS98/16144
47
heaving ,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:
Y R3 R 5Y
-O ~ , -O ~ Y , and -O
O
-N-C-R -N N -N-C-CH-R4
' ~ . R3 Y ,
Y
R3 Y
I I
-O-CH=C-CH=CH2 -O-CH=C-CH=CH2
O Y O
4 C H2-C ~--C
-O-C._-R~ . -N~C/NR4 , -N.~C/NR4 ,
' II II
O O
R3 O Y
-O-C=CHR4 , and -N-S-CH-R4
R3 O
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
48
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 Rl, 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 -C02-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 potassium being most preferred, and X is a
halide, hydroxide, methylsulfate or acetate anion.
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:
~ 0u
(U
Also suitable are the benzoylation products of sorbitol, glucose, and all
saccharides
with benzoylating agents, including for example:
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
49
OAc
Ac0
OAc ~Ac
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
areas.
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 ben2oyl
pyroglutamic acid.
Other perbenzoic acid precursors include the benzoyl diacyl peroxides, the
benzoyl
tetraacyl peroxides, and the compound having the formula:
0 0
o-~
d ~~COOH
Phthalic anhydride is another suitable perbenzoic acid precursor compound
herein:
CA 02298510 2000-O1-28
WO 99!06522 PCT/US98/16144
0
~o
0
Suitable N-acylated lactam perbenzoic acid precursors have the formula:
O
I I
O C-CH2-CH2
6- II I
R C-NCH .-NCH
2 2 n
wherein n is from 0 to 8, preferably from 0 to 2, and R6 is a benzoyl group.
CA 02298510 2000-O1-28
WO 9910b522 PCT/US98/16144
51
Perbenzoic acid derivative ~ecursors
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.
A preferred class of substituted perbenzoic acid precursor compounds are the
amide
substituted compounds of the following general formulae:
R~ -C-N-R2-C-L R~ -N-C-R2----C --L
O R5 O or R5 O O
wherein R 1 is an aryl or alkaryi 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 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 should not contain more
than 18 carbon atoms in total. Amide substituted bleach activator compounds of
this type are described in EP-A-0170386.
CA 02298510 2000-O1-28
WO 99/06522 PCT/C1S98/16144
52
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 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 cationically substituted may be a
perbenzoic 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
Cationic peroxyacid precursors are described in U.S. Patents 4,904,406;
4,751,015;
4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K.
1,382,594;
EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
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:
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
53
O
i
O ~/ S03
~+
A preferred canonically substituted alkyl oxybenzene sulfonate has the
formula:
,SO
O ~ - ~ w' 3
,_, , +
.~' ~ ~ w.~=~ N\ /,\ , 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
/.,. ~ ~ N !w _,
.- ~-Wi v
s i
..~''~/ v !;
Qther preferred cationic peroxyacid precursors of the N-acylated caprolactam
class
include the trialkyl ammonium methylene alkyl caprolactams:
O O
~. N ~
'"~ N : (CH2)n i
+~.:- ,~ ,,
where n is from 0 to 12, particularly from 1 to 5.
i
CA 02298510 2000-O1-28
WO 99/06522 PCTNS98/16144
54
Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl
ammonium)
ethyl sodium 4-sulphophenyl carbonate chloride.
Alkvl percarboxvlic acid bleach nrecurcorc
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,N 1N 1 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 peroxyacid precursor compounds are also suitable,
inc,Iuding those of the following general formulae:
R~ -C-N-R2-C-L R~ --N-C--R2--C ---- L
O R5 O or R5 O O
wherein R1 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 carbon atoms and L can be essentially any leaving group. R
1
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4
to 8
carbon atoms. RI 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. 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. R1 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.
Also suitable are precursor compounds of the benzoxazin-type, as disclosed for
example in EP-A-332,294 and EP-A-482,807, particularly those having the
formula:
O
II
O
I
N C-R~
including the substituted benzoxazins of the type
~ O
~O
i
R4 N C -R~
R5
wherein R1 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.
i
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
56
An especially preferred precursor of the benzoxazin-type is:
O
II
CEO
C
.. o
N
The organic peroxyacid bleaching system may contain, in addition to, or as an
alternative to, an organic peroxyacid bleach precursor compound, a preformed
organic peroxyacid , typically at a level of from 0.5% to 25% by weight, more
preferably from 1 % to 10% by weight of the composition.
A preferred class of organic peroxyacid compounds are the amide substituted
compounds of the following general formulae:
R~ ---C--N-R2--C-OOH
O R5 O or
R~ -N-C-R2-C -OOH
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. R' 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
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
57
structural variations are permissible for R2. The substitution can include
alkyl, aryl,
halogen, nitrogen, sulphur and other typical substituent groups or organic
compounds. R~ 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.
A means may be provided for controlling the rate of release of bleaching
agent,
particularly oxygen bleach to the wash solution.
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 either
the
compressed-or non-compressed portions. Where more than one non-compressed
portions are present, the bleach may be confined to the first and/or second
and/or
optional subsequent non-compressed portions.
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
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
58
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 C 1 p-C20 alcohol ethoxylates containing from 5 - 100 moles of
ethylene
oxide per mole of alcohol and more preferably the C 15-C20 P~~'Y 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 most preferably 1000 to 10,000 are examples of such polymeric
materials. Copolymers of malefic anhydride with ethylene, methylvinyl ether or
CA 02298510 2000-O1-28
WO 99/06522 PCTNS98/16144
59
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 C l0-Cep 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 l0-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.
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
Additional protocols for providing the means of controlled release include the
suitable choice of any other components of the detergent composition matrix
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.
Metal-containing bleach cata~,v~,t
The compositions described herein which contain bleach as an active detergent
component may additionally contain as a preferred component, 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 U.S. Pat. 4,430,243.
Preferred types of bleach catalysts include the manganese-based complexes
disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples
of
these catalysts include MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2-
(PF6)2, MnIII2(u-O)1(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2-
{CI04)2,
~IV4(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-{CI04)3, and mixtures thereof.
Others
are described in European patent application publication no. 549,272. Other
tigands suitable for use herein include 1,5,9-trimethyl-1,5,9-
triazacyclododecane, 2-
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
61
methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-
tetramethyl-1,4,7-
triazacyclononane, and mixtures thereof.
The bleach catalysts useful in the compositions herein may also be selected as
appropriate for the present invention. For examples of suitable bleach
catalysts see
U.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat. 5,194.416
which
teaches mononuclear manganese (IV) complexes such as Mn(1,4,7-trimethyl-1,4,7-
triazacyclononane)(OCH3)3-(PF6).
Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is
a water-
soluble complex of manganese (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.
U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of
transition
metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand. Said
ligands are of the formula:
R2 R3
R ~ -N=C-B-C=N-R4
wherein R1, R2, R3, and R4 can each be selected from H, substituted alkyl and
aryl
groups such that each 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, NR7 and C=O, wherein R5, R6, and R7 can each be H, alkyl, or aryl
groups, including substituted or unsubstituted groups. Preferred ligands
include
pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole
rings.
Optionally, said rings may be substituted with substituents such as alkyl,
aryl,
alkoxy, halide, and vitro. Particularly preferred is the ligand 2,2'-
bispyridylamine.
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
62
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)20~Ci04, 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 of the
present
invention have not been elucidated, it may be speculated that they comprise
chelates
or other hydrated coordination complexes which result from the interaction of
the
carboxyl and nitrogen atoms of the ligand with the manganese 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 multi-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 tike.
Other bleach catalysts are described, for example, in European patent
application,
publication no. 408,131 (cobalt complex catalysts), European patent
applications,
publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S.
4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711,748 and
European
patent application, publicatiowno. 224,952, (absorbed manganese on
aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with
manganese
and zinc or magnesium salt), U.S. 4,626,373 (manganese/iigand catalyst), U.S.
CA 02298510 2000-O1-28
WO 99/06522 PCTNS98/16144
63
4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019
(cobalt
chelant catalyst) Canadian 866,191 (transition metal-containing salts), U.S.
4,430,243 (chelants with manganese cations and non-catalytic metal cations),
and
U.S. 4,728,455 (manganese gluconate catalysts).
Other preferred examples include cobalt (III) catalysts having the formula:
Co[(NH3)nM'mB'bTtQqPp] 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 Iigand;
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 l; P is a pentadentate ligand; p is 0 or 1; and n + m + Zb +
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 0; S; most preferably 5); M'
is a
labile coordinating moiety, preferably selected from the group consisting of
chlorine,
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
64
bromine, hydroxide, water, and (when m is greater than 1 ) combinations
thereof; m
is an integer from 1 to 3 (preferably 1 or 2; most preferably 1 ); m+n = 6;
and Y is an
appropriately selected counteranion present in a number y, which is an integer
from
1 to 3 (preferably 2 to 3; most preferably 2 when Y is a -1 charged anion), to
obtain
a charge-balanced salt.
The preferred cobalt catalyst of this type useful herein are cobalt pentaamine
chloride salts having the formula [Co(NH3)SCIJ Yy, and especially
[Co(NH3)~C1JC1~.
More preferred are the present invention compositions which utilize cobalt
(III)
bleach catalysts having the formula:
[Co~3)n(M)m(B)bJ 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 = 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-I s-1 (25°C).
Preferred T are selected from the group consisting of chloride, iodide, I3',
formate,
nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PF6-
, BF4-,
B(Ph)4-, phosphate, phosphite, silicate, tosylate, methanesulfonate, and
combinations thereof. Optionally, T can be protonated if more than one anionic
group exists in T, e.g., HP042-, HC03-, H2P04-, etc. Further, T may be
selected
from the group consisting of non-traditional inorganic anions such as anionic
surfactants (e.g., linear alkylbenzene sulfonates (LAS), alkyl sulfates (AS),
CA 02298510 2000-O1-28
WO 99/06522 PC'T/US98/16144
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-,
S203-~, NH3, P043-, and carboxylates (which preferably are mono-carboxylates,
but more than one carboxylate may be present in the moiety as long as the
binding to
the cobalt is by only one carboxylate per moiety, in which case the other
carboxylate
in the M moiety may be protonated or in its salt form). Optionally, M can be
protonated if more than one anionic group exists in M (e.g., HP042-, HC03-,
H2P04-, HOC(O)CH2C(O)O-, etc.) Preferred M moieties are substituted and
unsubstituted C1-C30 carboxylic acids having the formulas:
RC(O)O-
wherein R is preferably selected from the group consisting of hydrogen and C1-
C30
(preferably C 1-C 1 g) unsubstituted and substituted alkyl, C6-C30 (preferably
C6-
C 1 g) unsubstituted and substituted aryl, and C3-C30 (preferably CS-C 1 g)
unsubstituted and substituted heteroaryl, wherein substituents are selected
from the
group consisting of -NR'3, -NR'4+, -C(O)OR', -OR', -C(O)NR'2, wherein R' is
selected from the group consisting of hydrogen and C 1-C6 moieties. Such
substituted R therefore include the moieties -(CH2)nOH and -(CH2)nNR'4+,
wherein n is an integer from 1 to 16, preferably from 2 to 10, and most
preferably
from 2 to 5.
Most preferred M are carboxylic acids having the formula above wherein R is
selected from the group consisting of hydrogen, methyl, ethyl, propyl,
straight or
branched C4-C 12 alkyl, and benzyl. Most preferred R is methyl. Preferred
carboxylic acid M moieties include formic, benzoic, octanoic, nonanoic,
decanoic,
dodecanoic, malonic, malefic, succinic, adipic, phthalic, 2-ethylhexanoic,
naphthenoic, oleic, palmitic, triflate, tartrate, stearic, butyric, citric,
acrylic, aspartic,
fumaric, lauric, linoleic, lactic, malic, and especially acetic acid.
CA 02298510 2002-07-29
66
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
(kOl.r= 5.8 x 10-
4 M-1 s-1 (25°C)), and acetate (kOH= 9.6 x 10-'I M-1 s-1
(25°C)). The most
preferred cobalt catalyst useful herein are cobalt pentaamine acetate salts
having the
formula [Co(NH3)SOAcJ Ty, wherein OAc represents an acetate moiety, and
especially cobalt pentaamine acetate chloride, [Co(NH3)SOAcJCI2; as well as
[Co(NH3)SOAc](OAc)2; [Co(NH3)SOAcJ(PF6)2; [Co(NH3)SOAcJ(S04); [Co-
(NH3)SOAcJ(BF4)2; and [Co(NH3)SOAc](N03)2 (herein "PAC").
These cobalt catalysts are readily prepared by known procedures, such as
taught for
example in the Tobe article hereinbefore and the references cited therein, in
U.S.
Patent 4,810,410, to Diakun et al, issued March 7,1989, J. them. Ed. ( 1989),
~ø
(12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, W.L.
Jolly (Prentice-Hall; 1970), pp. 461-3; Iaa. ~. Chem.,1$, 1497-1502 (1979);
Ink
~" ~,, 2881-2885 (1982); Ino ,, Chem., l$, 2023-2025 (1979); Inorg.
Synthesis, 173-176 ( 1960); and o »aloof P.b,~i~al Chemistry, ~, 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 U.S.
Patent
Nos. 5,559,261, 5,581,005, and 5,597,936.
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
67
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".
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.
Organic polymeric compound is typically incorporated in the detergent
compositions
of the invention at a level of from 0.1 % to 30%, preferably from 0.5% to I
S%, most
preferably from 1 % to 10% by weight of the compositions.
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-1,59b,75b. 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.
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
68
Preferred commercially available acrylic acid containing polymers having a
molecular weight below 15,000 include those sold under the tradename Sokalan
PA30, PA20, PA 15, PA 10 and Sokalan CP 10 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, R1 or R2 can be a
hydrogen
and R3 can be a hydrogen or alkali metal salt. Most preferred is a substituted
acrylic monomer wherein R1 is methyl, R2 is hydrogen (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-305282, EP-A-
305283 and EP-A-351629.
Other optional polymers may polyvinyl alcohols and acetates both modified and
non-modified, cellulosics and modified cellulosics, polyoxyethylenes,
polyox_ypropylenes, 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 patent Nos. 5,591,703 , 5,597,789 and
4,490,271.
CA 02298510 2000-O1-28
WO 99/06522 PC'TNS98/16144
69
Suitable polymeric soil release agents include those soil release agents
having: (a)
one or more nonionic hydrophile components consisting essentially of (l)
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 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 (l) 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
C 1-C4 alkyl ether or C4 hydroxyalkyl ether cellulose derivatives, or mixtures
therein, or a combination of (a) and (b).
Typically, the polyoxyethylene segments of (aXi) will have a degree of
polymerization of from 200, although higher levels can be used, preferably
from 3
to ~ 5~, 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 U.S. Patent 4,721,580, issued January 26, 1988 to
Gosselink.
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
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
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
C I -C4
alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued
December
28, 1976 to Nicol, et al.
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 European Patent Application 0 219 048, published April 22, 1987
by Kud, et al.
Another suitable soil release agent is a copolymer having random blocks of
ethylene
terephthaiate 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 U.S.
Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to
Basadur issued July 8, 1975.
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
U.S.
Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
Other suitable polymeric soil release agents include the terephthalate
polyesters of
U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic
end-
capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
7i
Gosselink, and the block polyester oligomeric compounds of U.S. Patent
4,702,857,
issued October 27, 1987 to Gosselink. Other polymeric soil release agents also
include the soil release agents of U.S. Patent 4,877,896, issued October 31,
1989 to
Maldonado et al, which discloses anionic, especially sulfoarolyl, 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.
The detergent 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 are generally present at a level of from 0.005%
to
20%; preferably from 0.1% to 10%, more preferably from 0.25% to 7.5% and most
preferably from 0.5% to 5% by weight of the compositions.
Heavy metal ion sequestrants, which are acidic in nature, having for example
phosphoric 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.
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98I16144
72
Preferably any salts/complexes are water soluble. The molar ratio of said
counter
canon 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 diethylene triamine penta (methylene phosphonate),
ethylene
diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene
phosphonate) and hydroxy-ethylene 1,1 diphosphonate.
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.
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.
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
73
The organo diphosphonic acid is preferably a Cl-C4 diphosphonic acid, more
preferably a C~ diphosphonic acid, such as ethylene diphosphonic acid, or most
preferably ethane 1-hydroxy- l , l -diphosphonic acid (HEDP) and may be
present in
partially or fully ionized form, particularly as a salt or complex.
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
74
Water-soluble sulfate alt
The detergent tablet 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 the compositions.
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.
According to an embodiment of the present invention an alkali metal silicate
is an
essential component of the detergent tablet. In other embodiments of the
present
invention the presence of an alkali metal silicate is optional. A preferred
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.
Alkali metal silicate may also be present as a component of an alkalinity
system.
The alkalinity system also preferably contains sodium metasilicate, present at
a level
of at least 0.4% Si02 by weight. Sodium metasilicate has a nominal SiO~ : Na~O
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.
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
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 incorported. 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.
The compressed portion and/or non compressed may contain a colourant, a
mixture
of colourants, coloured particles or mixture of coloured particles such that
the
compressed portion and the non-compressed portion have different visual
appearances. Preferably one of either the compressed portion or the non-
compressed comprises a colourant.
Where the non-compressed portion comprises two or more compositions of active
detergent components, preferably at least one of either the first and second
and/or
subsequent compositions comprises a colourant. Where both the first and second
and/or subsequent compositions comprise a colourant it is preferred that the
colourants have a different visual appearance.
Where present the coating layer preferably comprises a colourant. Where the
compressed portion and the coating layer comprise a colourant, it is preferred
that
the, colourants provide a different visual effect.
Examples of suitable dyes include reactive dyes, direct dyes, azo dyes.
Preferred
dyes include phthalocyanine dyes, anthraquinone dye, quinoline dyes, monoazo,
disazo and 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
CA 02298510 2000-O1-28
WO 99/06SZZ PC'T/US98/16144
76
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 into the compressed and/or non-compressed
portion by any suitable method. Suitable methods include mixing all or
selected
active detergent components with a colourant in a drum or spraying all or
selected
active detergent components with the colourant in a rotating drum.
Colourant when present as a component of the compressed portion is present at
a
level of from 0.001 % to 1.5%, preferably from 0.01 % to 1.0%, most preferably
fmm 0.1% to 0.3%. When present as a component of the non-compressed portion,
colourant, is generally present at a level of from 0.001 % to 0.1 %, more
preferably
from O.n05% to 0.05%, most preferably from 0.007% to 0.02%. When present as a
component of the coating layer, colourant is present at a level of from 0.01 %
to
0.5%, more preferably from 0.02% to 0.1%, most preferably from 0.03% to 0.06%.
The detergent tablets of the present invention suitable for use in dishwashing
methods may contain corrosion inhibitors 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 PCT Publication No. W094/16047
and copending European application No. EP-A-690122. Nitrogen-containing
corrosion inhibitor compounds are disclosed in copending European Application
no.
EP-A-634,478. Mn(II) compounds for use in corrosion inhibition are described
in
copending European Application No. EP-A-672 749.
CA 02298510 2000-O1-28
-w 'v
_7
WO 99/06522 PCT/US98/16144
77
Organic silver coating agent may be incorporated at a level of from 0.05% to
10%,
preferably from 0.1% to 5% by weight of the total composition.
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.
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, Valerie acid, lactic acid, glycolic acid and
~,(3'-
dihydmxyisobutyric 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
alcottols 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.
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
78
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-, dl- 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.
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.
Suitabte 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
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
79
the paraffin and microcrystailine 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 C 12-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 useful 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 S0; preferred paraffin oil selected from predominantly branched C25-
4S
species with a ratio of cyclic to noncyclic hydrocarbons of from 1:10 to 2:1,
preferably from 1:S to 1:1. A paraffin oil meeting these characteristics,
having a
ratio of cyclic to noncyclic hydrocarbons of 32:68, is sold by Wintershall,
Salzbergen, Germany, under the trade name WINOG 70.
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
Nitrogen-con _n: corrosion inhibitor compo ~ndc
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 British
Patent
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.
The detergent tablets may contain an Mn(II) corrosion inhibitor compound. The
Mn(II) compound is preferably incorporated at a level of from 0.005% to 5% by
weight, more preferably from 0.01 % to 1 %, most preferably from 0.02% to 0.4%
by
weight of the compositions. Preferably, the Mn(II) compound is incorporated at
a
level to provide from 0.1 ppm to 250 ppm, more preferably from 0.5 ppm to 50
ppm,
most preferably from 1 ppm to 20 ppm by weight of Mn(II) ions in any bleaching
solution.
CA 02298510 2000-O1-28
WO 99/06522 PC'T/US98/16144
81
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.
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 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 C 10-C20 fatty acids, or their salts, especially aluminium
tristearate.
The C 1 ~-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 coaosion inhibitor compounds.
Another preferred active detergent component for use in the present invention
is a
hydrocarbon oil, typically a predominantly long chain, aliphatic hydrocarbons
having a number of carbon atoms in the range of from 20 to 50preferred
hydrocarbons are saturated and/or branched; preferred hydrocarbon oil selected
from
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
8?
predominantly branched C25_45 species with a ratio of cyclic to noncyclic
hydrocarbons of from 1:10 to 2:1, preferably from I :5 to 1:1. A preferred
hydrocarbon oil is paraffin. A paraffin oil meeting the characteristics as
outlined
above, having a ratio of cyclic to noncyclic hydrocarbons of 32:68, is sold by
Wintershall, Salzbergen, Germany, under the trade name WINOG 70.
Water-soluble bismuth compound
The detergent tablets of the present invention suitable for use in
dishwashing,
methods may contain a water-soluble bismuth compound, preferably present at a
level of from 0.005% to 20%, more preferably from 0.01% to S%, most preferably
from 0.1 % to I % by weight of the compositions.
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.
Prefeaed enzyme-containing compositions herein may comprise from 0.001 % to
10%, preferably from 0.005% to 8%, most preferably from 0.01 % to 6%, by
weight
of art etlzyme 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, chlorine bleach scavengers and mixtures
thereof.
Such stabilizing systems can also comprise reversible enzyme inhibitors, such
as
reversible protease inhibitors.
CA 02298510 2000-O1-28
WO 99106522 PCT/US98/16144
83
The compositions of active detergent components may 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 the compositions.
A lime soap dispersant is a material that prevents the precipitation of alkali
metal,
ammonium or amine salts of fatty acids by calcium or magnesium ions. Preferred
lime soap disperant compounds are disclosed in PCT Application No.
W093/08877.
ds sug~essina system
The detergent tblets of the present invention, when formulated for use in
machine
washing compositions, 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 the 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 PCT Application No. W093/08876 and EP-
A-705 324.
Polymeric dye transfer ink iting agents
The detergent tablets herein may also comprise from 0.01 % to 10 %, preferably
from
0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
84
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.
CA 02298510 2000-O1-28
WO 99106522 PCT/US98/16144
Qntic~ al brig tener
The detergent tablets suitable for use in laundry washing methods as described
herein, also optionally 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:
R~
N H H N
N N C C N N
~N H H N
R2 S03M S~3M Ri
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 cation 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)aminoJ-2,2'-stilbenedisulfonic acid and disodium
salt.
This particular brightener species is commercially marketed under the
tradename
Tinopal-LTNPA-GX by Ciba-Geigy Corporation. Tinopal-IJNPA-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
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
86
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, RI is aniIino, 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)aminoJ2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener
species is commercially marketed under the tradename Tinopal AMS-GX by Ciba
Geigy Corporation.
The detergent tablets suitable for use in laundry cleaning methods may 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 Patents No.s 3,862,058, 3,948,790, 3,954,632 and
4,062,647. European Patents No.s EP-A-299,575 and EP-A-313,146 in the name of
the Procter and Gamble Company describe suitable organic polymeric clay
flocculating agents.
Cationic fabric softening agents can also be incorporated into compositions in
accordance with the present invention which are suitable for use in methods of
laundry washing. Suitable cationic fabric softening agents include the water
insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-
1
514 276 and EP-B-0 Ol 1 340.
Cationic fabric softening agents are typically incorporated at total levels of
from
0.5% to IS% by weight, normally from 1% to 5% by weight.
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
87
Other optional ingredients suitable for inclusion in the compositions of the
invention
include perfumes and filler salts, with sodium sulfate being a preferred
filler salt.
The detergent tablets of the present invention are preferably not formulated
to have
an unduly high pH, in preference having a pH measured as a 1% solution in
distilled
water of from 8.0 to 12.5, more preferably from 9.0 to 11.8, most preferably
from
9.5 to 11.5.
In another aspect of the present invention the compressed and non-compressed
portions are formulated to deliver different pH.
CA 02298510 2000-O1-28
WO 99106522 PCT/US98/16144
88
Machine dishwashing method
Any suitable methods for machine washing or cleaning soiled tableware are
envisaged.
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 detergent tablet in accord with the invention. By an effective amount of the
detergent tablet it 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.
Laundry washing method
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 a machine laundry detergent tablet composition in
accord
with the invention. By an effective amount of the detergent tablet composition
it 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 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.
CA 02298510 2000-O1-28
WO 99/06522 PCTNS98/16144
89
Once the washing machine has been loaded with laundry the dispensing device
containing the detergent product is placed inside the drum. At the
commencement
of the wash cycle of the washing machine water is introduced into the drum and
the
drum periodically rotates. The design of the dispensing device should be such
that
it permits containment of the dry detergent product but then allows release of
this
product during the wash cycle in response to its agitation as the drum rotates
and
also as a result of its contact with the wash water.
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
European
published Patent Application No. 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 European published Patent
Application Nos. 0011500, 0011501, 0011502, and 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.
i
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
Abbreviations used in ramplg~
In the detergent compositions, the abbreviated component identifications have
the
following meanings:
STPP : Sodium tripolyphosphate
Citrate : Tri-sodium citrate dehydrate
Bicarbonate : Sodium hydrogen carbonate
Citric Acid : Anhydrous Citric acid
Carbonate : Anhydrous sodium carbonate
Silicate : Amorphous Sodium Silicate (Si02:Na20 ratio
= 1.6-3.2)
Metasilicate . Sodium metasilicate (Si02:Na20 ratio = 1.0)
PB 1 : Anhydrous sodium perborate monohydrate
PB4 : Sodium perborate tetrahydrate of nominal formula
NaB02.3H20.H202
Plurafac ~ C 13-C 1 S 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
Tergitol : Nonionic surfactant available under the tradename
Tergitol
15S9 from Union Carbide
SLF18 . Epoxy-capped poly(oxyalkylated) alcohol of
Example III of
WO 94/22800 wherein 1,2-epoxydodecane is substituted
for
1,2-epoxydecane available under the tradename
Polytergent
SLF 18D from OLIN.
TAED : Tetraacetyl ethylene diamine
HEDP : Ethane 1-hydroxy- l , l -diphosphonic acid
DETPMP : Diethyltriamine penta (methylen~j phosphonate,
marketed
by monsanto under the tradename bequest 2060
PAAC ~ : Pentaamine acetate cobalt (III) salt
CA 02298510 2000-O1-28
WO 99/06522 PCTNS98/16144
91
BzP : Benzoyl Peroxide
Paraffin : Paraffin oil sold under the tradename Winog 70 by
Wintershall.
Protease : Proteolytic enzyme
Amylase : Amylolytic enzyme.
BTA : Benzotriazole
PA30 : Polyacrylic acid of average molecular
weight approximately
4,500
480N : Random copolymer of 7:3 acrylate/methacrylate,
average
molecular weight 3,500
Sulphate . Anhydrous sodium sulphate.
PEG 3000 : Polyethylene Glycol molecular weight approximately
3000
available from Hoechst
PEG 6000 . Polyethylene Glycol molecular weight approximately
6000
available from Hoechst
Sugar . Household sucrose
Gelatine . Gelatine Type A, 65 bloom strength available
from Sigma
CMC : Carboxymethylcellulose
Dodecandioic Acid. C 12 dicarboxylic acid
Adipic Acid : C6 dicarboxylic acid
Lauric Acid : C 12 monocarboxylic acid
pH . Measured as a 1% solution in distilled water at 20°C
In the following examples all levels are quoted as % by weight of the
compressed
portion, the non-compressed portion or the coating layer:
The following illustrates examples detergent tablets of the present invention
suitable
for use in a dishwashing machine.
CA 02298510 2000-O1-28
WO 99!06522 PCT/US98/16144
92
The compressed portion is prepared by delivering the composition of active
detergent components to a punch cavity of a modified 12 head rotary tablet
press and
compressing the composition at a pressure of 13KN/cm2. The modified tablet
press
provides tablet wherein the compressed portion has a mould. For the purposes
of
Example A to F the non-compressed portion is in particulate form. The non-
compressed portion is accurately delivered to the mould of the compressed
portion
using a nozzle feeder. The non-compressed portion is adhered to the compressed
portion by coating the non-compressed portion with a coating layer which
contacts
the compressed portion.
A B C D E F
Compressed portion
STPP - 55.10 52.0 52.80 50.00 38.20
Citrate 26.40 - - _ _ _
Carbonate - 14.0 16.0 15.40 18.40 15.00
Silicate 26.40 14.80 15.0 12.60 10.00 10.10
Protease - - - 1.0 - -
Amylase 0.6 0.75 0.75 0.95 2.0 0.85
PB 1 1.56 12.50 12.20 12.60 15.70 11.00
PB4 6.92 _ _ _ _ _
hlonionic 1.50 1.5 1.50 1.65 0.80 1.65
PAC - 0.016 0.016 0.012 - 0.008
TAED 4.33 - - 1.30 -
HEDP 0.67 - - - 0.92
DETPMP 0.65 - - - - _
Paraffin 0.42 0.50 0.5 0.55 0.50 -
BTA 0.24 0.30 0.3 0.33 0.33
PA30 3,2 _ - - - _
Perfume - - - 0.05 0.20 0.2
Sulphate ' 24.05 - 2.00 - 10.68 22.07
CA 02298510 2000-O1-28
WO 99/06522 PCT/US98/16144
93
Misc/water to balance
Weight (g) 20.0 20.0 20.0 20.0 30.0
Non-compressed portion
Protease 12.80 8.12 9.92 8.00 8.00 8.00
Amylase 7.20 13.00 6.00 10.00 - 13.00
Metasilicate - 50.02 - 45.10 40.00 50.00
Bicarbonate - 13.00 20.02 13.00 6.00 13.00
Citric acid - 13.00 14.98 14.00 6.00 13.00
BzP - - - 9.00 - -
Citrate 35.00 - - - 40 -
Silicate 42.00 - 48.03 - - -
Weight (g) 5.0 3.0 3.0 3.0 5.0
Coating Layer
Dodecandioic acid - 90.00 82.00 - - 90.00
Adipic acid - - - 92.00 - -
Lauric acid - - 8.00 - -
Starch 15.00 10.00 10.00 8.0 - 10.00
PEG - - - - 100 -
height (g) 1.00 1.00 1.20 0.80 0.50 1.00
Total-weight (g) 25g 25g 20g 30g 18g 35g
of tablet
The compressed portion is prepared by delivering the composition of active
detergent components to a punch cavity of a modified 12 head rotary tablet
press and
compressing the composition at a pressure of 13KN/cm2. The modified tablet
press
provides tablet wherein the compressed portion has a mould. For the purposes
of
CA 02298510 2000-O1-28
y
WO 99106522 PCT/US98/16144
94
Examples G to K the non-compressed portion comprises active detergent
components and a binding agent. The non-compressed portion is then poured into
the mould of the compressed portion. The detergent tablet is then subjected to
a
conditioning step, during which time the non-compressed portion hardens.
G H I J K L
Compressed portion
STPP - 55.10 52.0 52.80 50.00 38.20
Citrate 26.40 - - _ _ _
Carbonate - 14.0 16.0 15.40 18.40 15.00
S i licate 26.40 14. 15.0 12.60 10.00 10.10
80
Protease - - - 1.0 -
~Yl~ 0.6 0.75 0.75 0.95 2.0 0.85
PB 1 1.56 12.50 12.20 12.60 15.70 11.00
PB4 6.92 - - - _ _
Nonionic 1.50 1.5 1.50 1.65 0.80 1.65
PAAC - 0.016 0.016 0.012 - 0.008
TAED 4.33 - - - 1.30 -
HEDP 0.67 - - - - 0.92
DETPMP 0.65 - - - _ _
Paraffin 0.42 0.50 0.5 0.55 0.50 -
BTA 0.24 0.30 0.3 0.33 0.33 -
PA30 3.2 _ _ _ _ _
Perfume - - - 0.05 0.20 0.2
Sulphate 24.05 - 2.00 - 10.68 22.07
Misc/water to balance
Weight (g) 20.0g 20.0g 20.0g 20.0g 22g 30.0g
CA 02298510 2000-O1-28
WO 99/06522 PCTJUS98/16144
Non-compressed portion
Tergitol - - 21.5 18.92 - -
PEG 3000 89.40 - - - - -
PEG 6000 86.9 - - - -
BzP 10.60 11.00 - - 20.00 20.00
Sugar - - 53.4 29.04 65.00 65.00
Gelatine - - 15.01 30.00 5.00 5.00
Starch - - - 10.00 - -
Water - - 10.00 10.00 10.00 10.00
Misc./balance
Weight (g) 2.5g S.Og 2.5g 2.5g 3g 3g
Total weight (g) 22.5g 25g 22.5g 22.5g 25g 33g
of tablet
