Note: Descriptions are shown in the official language in which they were submitted.
CA 02311517 2000-OS-25
WO 99/27067 PCT/tiS98/25074
Detergent Tablet
Technical Field
The present invention relates to a detergent tablet comprising a compressed
portion and a
non-compressed portion wherein the compressed portion dissolves at a faster
rate than
the non-compressed portion and the non-compressed portion comprises a
finishing
additive.
Background
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 detergent components
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 loss 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 detergent components that may potentially
react with each
other, especially when the components are compressed 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
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/2507.t
7
compression step are subjected to a cumulative and potentially greater overall
compression pressure. An increase in compression pressure is known to decrease
the rate
of dissolution of the tablet with the effect that the multiple layers 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.
The Applicant has found that by providing a detergent tablet comprising a
compressed
portion and a 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.
A further advantage of using a detergent tablet as described herein, is the
performance
benefits which may be achieved in being able to pn:pue a detergent tablet
where the
compressed portion has a faster rate of dissolution than the non-compressed
portion
Summar~of the Invention
According to the present invention there is provided a detergent tablet
comprising a
compressed portion and a non-compressed portion wherein:
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/2.5074
3
a) the compressed portion comprises a mould and dissolves at a faster rate
than the non-
compressed portion on a weight by weight basis, measured using the SOTAX
dissolution
test method described herein; and
b) the non-compressed portion is at least partially retained with the mould.
In another aspect of the present invention there is provided a detergent
tablet comprising
a compressed portion and a non-compressed portion wherein the compressed
portion
dissolves at a faster rate than the non-compressed portion on a weight by
weight basis,
measured using the SOTAX dissolution test method described herein and wherein
the
density of the non-compressed portion is at least 0.2 g/cm3 less than the
density of the
compressed portion.
In yet another aspect of the present invention there is provided a detergent
tablet
comprising a compressed portion and a non-compressed portion wherein:
a) the compressed portion dissolves at a faster rate than the non-compressed
portion on a
weight by weight basis, measured using the SOTAX dissolution test method
described
herein; and
b) the non-compressed portion is metasilicate-free.
In yet another aspect of the present invention there is provided a detergent
tablet
comprising a compressed portion and a non-compressed portion wherein:
a) the compressed portion dissolves at a faster rate than the non-compressed
portion on a
weight by weight basis, measured using the SOTAX dissolution test method
described
herein; and
b) the non-compressed portion comprises a finishing additive which is selected
from the
group consisting of organic polymeric compound, co-builder, enryme, oxygen
releasing
bleach, bleach precursor or catalyst, surfactant, crystal growth inhibitor,
bleach-
destroying agent.
In yet another aspect of the present invention there is provided a detergent
tablet
comprising a compressed portion and a non-compressed portion wherein:
a) the compressed portion dissolves at a faster rate than the non-compressed
portion on a
weight by weight basis measured using the SOTAX dissolution test method
described
herein; and
b) the non-compressed portion comprises a finishing additive which is a fabric
softener
or a rinse aid.
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98I2507y
Detailed Description of the Invention
The compressed portion of the present invention dissolves at a faster rate
than the non-
compressed portion on a weight by weight basis as measured by the Sotax
dissolution
test method outlined below. This difference in rate of dissolution means that
components
of the compressed and non-compressed portions can be delivered to the wash
water at
different points in the washing or rinsing cycle of the washing machine.
For the purposes of the present invention the compressed portion has a faster
dissolution
rate than the non-compressed portion meaning that the components of the
compressed
portion will be delivered to the was water before the components of the non-
compressed
portion. In another aspect of the present invention, the non-compressed
portion dissolves
at a temperature of less than 30°C. The compressed portion of the
detergent tablet will
begin to dissolve immediately on contact with water. Preferably at least 60%,
more
preferably at least 80%, most preferably at least 95% of the compressed
portion dissolves
in deionised water at 50°C within 12 minutes.
The non-compressed portion comprises at least one finishing additive as
described later.
Finishing additives are components that provide either a cleaning benefit e.g.
enzyme, a
soil anti-redeposition benefit e.g. organic polymeric compound or drainage
benefit e.g.
nonionic surfactant. The non-compressed portion also begins to dissolve on
contact with
water, although the slower dissolution rate of the non-compressed portion is
such that
less than 40%, preferably less than 20%, most preferably less than 10% or even
5% of
the non-compressed portion dissolves in deionised water at 50°C within
12 minutes.
In an alternative embodiment of the present invention the non-compressed
portion
dissolves in the rinsing cycle of the washing machine. In this embodiment the
finishing
additive can be either a fabric softener or a rinse aid. The fabric softener
is delivered into
the rinsing cycle of a laundry washing machine after the clothes have been
washed and
softens the fabric. The rinse aid is delivered into the rinsing cycle of the
dishwashing
and improves water drainage from the dishware and provides reduced spotting
and
filming benefits. In this embodiment of the present invention it is envisaged
that the
non-compressed portion does not begin to dissolve during the first 12 minutes
of the
washing cycle or that it begins to dissolve in the rinsing cycle.
Delayed dissolution of the non-compressed portion is described in more detail
later.
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/25074
J
Compressed portion
The compressed portion of the detergent tablet comprises at least one
detergent
component but preferably comprise a mixture of more than one detergent
component, which are then compressed to form a tablet. 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, enzyme
and an alkalinity source.
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 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 detergent components) are compressed using any
equipment suitable for forming compressed tablets, blocks, bricks or
briquettes;
described in more detail hereafter.
In a preferred embodiment the compressed portions 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 ef~ervesing 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.
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/2507J
6
The density of the compressed portion is generally in the range of from
1.3g/cm3 to
1.9g/cm3, more preferably from 1.4g/cm3 to 1.8g/cm3, most preferably from
1.4g/cm3 to
1.7g/cm3.
Density is calculated by dividing the weight (mass) of the compressed portion
by the
volume of the compressed portion. The volume is calculated by multiplying the
length
by the width by the breadth of the compressed portion.
Non-Compressed Portion
The non-compressed comprises a finishing additive but may also comprise one or
more
detergent components. 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. Where further detergent
components are
present in the non-compressed portion, preferred components include those that
that are
adversely affected by compression pressure of, for example a compression
tablet press.
Examples of such detergent components include, but are not limited to, enzyme,
corrosion inhibitor and perfume. These components are described in more detail
below.
The finishing additives and optional detergent components) may be in any form
for
example particulate (i.e. powder or granular), gel or liquid form. The non-
compressed
portion may also optionally comprise a carrier component. The 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 axed
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.
Preferably
CA 02311517 2000-OS-25
w0 99/27067 PCT/US98/25074
7
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.
Where the non-compressed portion comprises a solidified melt, the melt is
prepared by
heating a composition comprising the finishing additive and any optional
detergent
and/or 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
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/?.507.i
8
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 the finishing
additive and
optional detergent components. A preferred carrier component is an organic
polymer
that is solid at ambient temperature. Preferably the carrier component 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 finishing additive and optional detergent component. The flowable
non-
compressed portion may harden over time to form a solid, semi solid or highly
viscous
liquid 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 or gelling agent is
soluble.
Preferred solvents may be polar, non-polar, non-aqueous or anhydrous and may
include
for example water, glycerine, 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 or
gelling
agents. Any binding or gelling 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 or gelling 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.
In a preferred aspect of the present invention the non-compressed portion
comprises a
gel. In this aspect the gel is delivered to the compressed portion of the
detergent tablet,
but is preferably delivered into a mould provided by the compressed portion.
CA 02311517 2000-OS-25
WO 99127067 PCT/US98/25074
9
The gel comprises a thickening system in addition to the finishing additive
and other
optional detergent components. In addition the gel may also comprise solid
ingredients
to aid in the control of the viscosity of the gel in conjunction with the
thickening system.
Solid ingredients may also act to optionally disrupt the gel thereby aiding
dissolution of
the gel. When included, the gel portion typically comprises at least 1 S%
solid
ingredients, more preferably at least 30% solid ingredients and most
preferably at least
40% solid ingredients. However, due to the need to be able to pump and
otherwise
process the gel, the gel typically does not include more than 90% solid
ingredients.
As noted earlier, the gel comprises a thickening system to provide the
required viscosity
or thickness of the gel. The thickening system typically comprises a non-
aqueous liquid
diluent and an organic or polymeric gelling additive:
a) Liquid Diluent: the term "solvent" or "diluent" is used herein to connote
the liquid
portion of the thickening system. While some of the components of the non-
compressed
portion may actually dissolve in the "solvent"-containing phase, other
components may
be present as particulate material dispersed within the "solvent"-containing
phase. Thus
the term "solvent" is not meant to require that the components of the non-
compressed
portion be capable of actually dissolving in the solvent. Suitable types of
solvents useful
in the non-aqueous thickening systems herein include alkylene glycol mono
lower alkyl
ethers, propylene glycols, ethoxylated or propoxylated ethylene or propylene,
glycerol
esters, glycerol triacetate, lower molecular weight polyethylene glycols,
lower molecular
weight methyl esters and amides.
A preferred type of non-aqueous solvent for use herein comprises the mono-, di-
, tri-, or
tetra- C2-C3 alkylene glycol mono C2-C6 alkyl ethers. The specific examples of
such
compounds include diethylene glycol monobutyl ether, tetraethylene glycol
monobutyl
ether, dipropylene glycol monoethyl ether, and dipmpylene glycol monobutyl
ether.
Diethylene glycol monobutyl ether and dipropylene glycol monobutyl ether are
especially
preferred. Compounds of the type have been commercially marketed under the
tradenames Dowanol, Carbitol, and Cellosolve.
Another preferred type of non-aqueous solvent useful herein comprises the
lower
molecular weight polyethylene glycols (PEGs). Such materials are those having
molecular weights of at least 150. PEGS of molecular weight ranging from 200
to 600
are most preferred.
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/25074
Yet another preferred type of non-aqueous solvent comprises lower molecular
weight
methyl esters. Such materials are those of the general formula: R1-C(O)-OCH3
wherein
R1 ranges from 1 to 18. Examples of suitable lower molecular weight methyl
esters
include methyl acetate, methyl propionate, methyl octanoate, and methyl
dodecanoate.
The non-aqueous organic solvents) employed should, of course, be compatible
and non-
reactive with the finishing additive and other optional detergent components,
e.g.
enzymes. Such a solvent component will generally be utilized in an amount of
from 10%
to 60% by weight of the gel portion. More preferably, the non-aqueous, low-
polarity
organic solvent will comprise from 20% to 50% by weight of the gel portion,
most
preferably from 30% to 50% by weight of the gel portion.
b) Gelling Additive: a gelling agent or additive is added to the non aqueous
solvent of the
present invention to complete the thickening system. To form the gel required
for
suitable phase stability and acceptable rheology of the gel, the organic
gelling agent is
generally present to the extent of a ratio of solvent to gelling agent in
thickening system
typically ranging from 99:1 to 1:1. More preferably, the ratios range from
19:1 to 4:1.
The preferred gelling agents of the present invention are selected from castor
oil
derivatives, polyethylene glycol, sorbitols and related organic thixatropes,
organoclays,
cellulose and cellulose derivatives, pluronics, stearates and stearate
derivatives,
sugarlgelatin combination, starches, glycerol and derivatives thereof, organic
acid amides
such as N-lauryl-L-glutamic acid di-n-butyl amide, polyvinyl pyrrolidone and
mixtures
thereof.
The preferred gelling agents include castor oil derivatives. Castor oil is a
naturally
occurring trigIyceride obtained from the seeds of Ricinus Communis, a plant
which
grows in most tropical or subtropical areas. The primary fatty acid moiety in
the castor
oil triglyceride is ricinoleic acid (12-hydroxy oleic acid). It accounts for
90% of the fatty
acid moieties. The balance consists of dihydroxystearic, palmitic, stearic,
oleic, linoleic,
Iinolenic and eicosanoic moieties. Hydrogenation of the oil (e.g., by hydrogen
under
pressure) converts the double bonds in the fatty acid moieties to single
bonds, thus
"hardening" the oil. The hydroxyl groups are unaffected by this reaction.
CA 02311517 2000-OS-25
WO 99/27067 PCTNS98/25074
The resulting hydrogenated castor oil, therefore, has an average of about
three hydroxyl
groups per molecule. It is believed that the presence of these hydroxyl groups
accounts
in large part for the outstanding structuring properties which are imparted to
the gel
portion compared to similar liquid detergent compositions which do not contain
castor
oil with hydroxyl groups in their fatty acid chains. For use in the
compositions of the
present invention the castor oil should be hydrogenated to an iodine value of
less than ?0.
and preferably less than 10. Iodine value is a measure of the degree of
unsaturation of the
oil and is measured by the "Wijis Method," which is well-known in the art.
Unhydrogenated castor oil has an iodine value of from 80 to 90.
Hydrogenated castor oil is a commercially available commodity being sold, for
example,
in various grades under the trademark CASTORWAX® by NL Industries, Inc.,
Highstown, New 3ersey. Other Suitable hydrogenated castor oil derivatives are
Thixcin
R, Thixcin E, Thixatrol ST, Perchem R and Perchem ST, made by Rheox, Laporte.
Especially preferred is Thixatrol ST.
Polyethylene glycols when employed as gelling agents, rather than solvents,
are low
molecular weight materials, having a molecular weight range of from 1000 to
10,000,
with 3,000 to 8,000 being the most preferred.
Cellulose and cellulose derivatives when employed in the present invention
preferably
include: i) Cellulose acetate and Cellulose acetate phthalate (CAP); ii)
Hydroxypropyl
Methyl Cellulose (HPMC); iii~arboxymethylcellulose (CMC); and mixtures
thereof.
The hydroxypropyl methylcellulose polymer preferably has a number average
molecular
weight of 50,000 to 125,000 and a viscosity of a 2 wt.% aqueous solution at
25°C
(ADTMD2363) of 50,000 to 100,000 cps. An especially preferred hydroxypropyl
cellulose polymer is Methocel~ J75MS-N wherein a 2.0 wt.% aqueous solution at
25°C.
has a viscosity of about 75,000 cps.
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 gelatin may be used,
available from
for example Sigma. Type A gelatin is preferred since it has greater stability
in alkaline
conditions in comparison to type B. Preferred gelatin also has a bloom
strength of
between 65 and 300, most preferably between 75 and 100.
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/25074
1?
The gel may include a variety of other ingredients in addition to the
thickening agent as
herein before described and the finishing additive described in more detail
below.
Ingredients such as dyes may be included as well as structure modifying
agents.
Structure modifying agents include various polymers and mixtures of polymers
included
polycarboxylates, carboxymethylcelluloses and starches to aid in adsorption of
excess
solvent and/or reduce or prevent "bleeding" or leaking of the solvent from the
gel
portion, reduce shrinkage or cracking of the gel portion or aid in the
dissolution or
breakup of the gel portion in the wash. In addition, hardness modifying agents
may
incorporated into the thickening system to adjust the hardness of the gel if
desired.
These hardness control agents are typically selected from various polymers,
such as
polyethylene glycol's, polyethylene oxide, polyvinylpyrrolidone, polyvinyl
alcohol,
hydroxystearic acid and polyacetic acid and when included are typically
employed in
levels of less than 20% and more preferably less than 10% by weight of the
solvent in the
thickening system.
The gel is formulated so that it is a pumpable, flowable gel at slightly
elevated
temperatures of around 30°C or greater to allow increased flexibility
in producing the
detergent tablet, but becomes highly viscous or hardens at ambient
temperatures so that
the gel is maintained in position on the compressed portion of the detergent
tablet
through shipping and handling of the detergent tablet. Such hardening of the
gel may
achieved, for example, by (i) cooling to below the flowable temperature of the
gel or the
removal of shear, (ii) by solvent transfer, for example either to the
atmosphere of the
compressed body portion; or by (iii) by polymerisation of the gelling agent.
Preferably,
the gel is formulated such that it hardens sufficiently so that the maximum
force needed
to push a probe into the non-compressed portion preferably ranges from O.SN to
40N.
This force may be characterised by measuring the maximum force needed to push
a
probe, fitted with a strain gauge, a set distance into the gel. T'he set
distance may be
between 40% and 80% of the total gel depth. This force can be measured on a
QTS 25
tester, using a probe of 5 mm diameter. Typical forces measured are in the
range of 1N to
25N.
Where the non-compressed portion is an extrudate, the extrudate is prepared by
premixing detergent components of the non-compressed portion with optional
carrier
components to form a viscous paste. T'he 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
CA 02311517 2000-OS-25
w0 99/27067 PCT/US98/2507.~
13
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 affx 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,
alcohois, diols, esters and ethers, adipic acid, carboxylic acid, dicarboxylic
acid,
polyvinyl acetate (PVA), polyvinyl pyrrolidone (PVP), poiyacetic 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 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
S% 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.
The density of the non-compressed portion is generally from 0.7g/cm3 to
1.2g/cm3, more
preferably from 0.8g/cm3 to 1.2g/cm3, most preferably from 0.9g1cm3 to 1.1
g/cm3. The
density of the non-compressed portion is preferably at least 0.2g/cm3, more
preferably at
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/2507~
14
least 0.3g/cm3, most preferably at least 0.4g/cm3 less than the density of the
compressed
portion.
Density Measurement of the non-compressed portion: Preferably the density of
the
non-compressed portion 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 of known volume disposed below the funnel. The funnel is 130
mm
high and has internal diameters of 130 mm and 40 mm at its respective upper
and lower
extremities. It is mounted 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 non-compressed 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 non-
compressed portion removed from the cup by passing a straight edged implement
e.g. a
knife, across its upper edge. The filled cup is then weighed. The weight of
the non-
compressed portion is calculated by subtracting the weight of the cup from the
weight of
the cup plus the non-compressed portion. Density is then calculated by
dividing the
weight (mass) of the non-compressed portion by the volume of the cup.
Replicate
measurements are made as required.
The detergent tablet of the present invention is manufactured in according to
a process
described herein.
Delayed dissolution of the non-compressed portion
Delayed dissolution of the non-compressed portion may be achieved by, for
example
selecting particulate detergent components for use as components of the non-
compressed
portion that are encapsulated with a component which is slow dissolving or
partially
soluble in water. Such encapsulating materials include cellulose and cellulose
derivativese.g. cellulose acetate, cellulose acetate phthalate (CAP),
hydroxypropyl
Methyl Cellulose (HPMC), carboxymethylcellulose (CMC) and mixtures thereof.
The
hydroxypropyl methylcellulose polymer preferably has a number average
molecular
weight of 50,000 to200,000 and a viscosity of a 2 wt.% aqueous solution at
25°C
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/2507-t
15
(ADTMD2363) of 50,000 to 120,000 cps. An especially preferred hydroxypropyl
cellulose polymer is Methocel~ J75MS-N wherein a 2.0 wt.% aqueous solution at
25°C
has a viscosity of about 75;000 cps. Other preferred encapsulating materials
include
gelatine of bloom strength in the range of from 30 to 200, preferably from 75
to 200.
The thickness of the encapsulating material will determine the dissolution
rate of the
encapsulated detergent component and thus the delivery rate of the detergent
component
to the wash water. The encapsulated detergent components are then delivered to
the
compressed portion or are preferably suspended in a matrix of liquid or
preferably gel
that is delivered to the compressed portion. The non-compressed portion is
adhered to
the compressed portion by the methods described above.
Another example of a means by which the dissolution of the non-compressed
portion
may be delayed is premixing detergent components in a matrix which is slow
dissolving
or partially soluble in water. A particularly preferred matrix is a gel or
viscous liquid as
described above. The gel matrix preferably comprises organic or inorganic
polymers.
Preferred polymers include polyethylene glycol of molecular weight from 1,000
to
20,000, more preferably from 4,000 to 10,000 or even 12,000.
Yet another example of a means by which the dissolution of the non-compressed
portion
may be delayed is preparing a non-compressed portion as described above, then
delivering the non-compressed portion to the compressed portion and coating
the non-
compressed portion with a coating layer as described above.
In yet another example the non-compressed portion is such that it comprises at
least one
component which react with an outside stimulus, such as temperature or pH, to
initiate
dissolution. An example of a component that would initiate dissolution on
reaction to a
change in temperature is a wax. In particular it is envisaged that a suitable
wax will have
a melting temperature above room temperature, preferably above 40°C,
most preferably
above SO°C.
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 02311517 2000-OS-25
WO 99/27067 PCT/US98/2507a
16
The SOTAX waterbath is filled with water and the temperature gauge set to
50°C. Each
pot is then filled with 1 litre of deionised water and the stirrer set to
revolve at ?SOrpm.
The lid of the waterbath is closed, allowing the temperature of the deionised
water in the
pots to equilibrate with the water in the waterbath for I hour.
Equal weight of the compressed and non-compressed portions are weighed out.
The
compressed portion is placed in a first pot and the non-compressed portion is
placed in a
second pot. The lid is then closed. The compressed and non-compressed portions
are
visually monitored until they completely dissolves. The time is noted when the
compressed portion and the non-compressed portions have completely dissolved.
The
dissolution rate of the compressed portion or non-compressed portion is
calculated as the
average weight (g) of each portion dissolved in deionised water per minute.
Finishing additive
The non-compressed portion of the present invention comprises a finishing
additive. By
the term finishing additive it is meant an additive which is released into the
latter stages
of the washing cycle or into the rinsing cycle of a laundry washing or
dishwashing
machine.
Finishing additives suitable for use herein are selected from the group
consisting of
organic polymeric compound, enzymes, perfume component, oxygen releasing
bleaching
agent, precursor or catalyst, bleach destroying agent, co-builder, crystal
growth inhibitor,
surfactant, cationic fabric softening agent and a rinse aid.
Bleaching agent
Suitable bleaching agents for incorporation into the compressed portion
include both
oxygen releasing and chlorine bleaching agents. Bleaching agents suitable for
use as
finishing additive are oxygen-releasing bleaching agents.
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
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/2507a
17
bleaches. In an alternative preferred aspect a prefonmed 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.
Inor anic perhvdrate bleaches
The oxygen-releasing bleach preferably is a hydrogen peroxide source. 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.
Sodium perborate can be in the form of the monohydrate of nominal formula
NaB02H202 or the tetrahydrate NaB02H202.3H20.
Alkali metal percarbonates, particularly sodium percarbonate are prefen~ed
perhydrates for inclusion in compositions in accordance with the invention.
Sodium
percarbonate is an addition compound having a formula corresponding to
2Na2C03.3H202, 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
CA 02311517 2000-05-25
WO 99/27067 PCT/US98/25074
18
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.
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.
Peroxvacid bleach precursor
Peroxyacid bleach precursors are compounds which react with hydrogen peroxide
in a
perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach
precursors may be represented as
O
;,
X-C-L
where L is a leaving group and X is essentially any functionality, such that
on
perhydrolysis the structure of the peroxyacid produced is
O
X-C-OOH
CA 02311517 2000-OS-25
w0 99/27067 PCT/US98/25074
19
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 I .5% to 5% by weight of the compositions.
Suitable peroxyacid bleach precursor compounds typically contain one or more N-
or
O-acyt 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.
Leaving groins
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
Y , and
O
O
-NS C-R~ -N N -N-C-CH-R4
' ~ ~ ,
R3 Y
Y
R3 Y
-O-C H=C-C H=C HZ -O-C H=C-C H=C H2
CA 02311517 2000-OS-25
WO 99127067 PCTiLlS98n507.s
O ~ C H -C Y O
-O-C-R -N 2 \NR4 CwNRa
~C~ , _N~C/
II il
O O
3
R O Y
-O-C=CHR4 , and -N-S-CH-R4
R3 O
and mixtures thereof, wherein R 1 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
solubiiizing 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 preferre 3solubilizing groups are -S03-M+, -C02-M+, -S04-M+, - ~ (R3)4X-
and O<--N(R )3 and most preferably -S03-M and -C02-M wherein R rs an alkyl
chain containing from 1 to 4 carbon atoms, M is a ration which provides
solubility to
the bleach activator and X is an anion which provides solubility to the bleach
activator. Preferably, M is an allcali metal, ammonium or substituted ammonium
ration, with sodium and potassium being most preferred, and X is a halide,
hydroxide,
methylsulfate or acetate anion.
Perbenzoic acid precursor
Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
Suitable O-acylated perbenzoic acid precursor compounds include the
substituted and
unsubstituted benzoyl oxybenzene sulfonates, including for example benzoyl
oxybenzene sulfonate:
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/2507.t
21
0
O ~/ S03
Also suitable are the benzoylation products of sorbitol, glucose, and all
saccharides
with benzoylating agents, including for example:
OAc
Ac0
OAc ~Ac
OBz
Ac = COCH3; Bz = Benzoy!
Perbenzoic acid precursor compounds of the imide type include N-benzoyi
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 benzoyl
pyroglutamic acid.
Other perbenzoic acid precursors include the benzoyl diacyl peroxides, the
benzoyl
tetraacyl peroxides, and the compound having the formula:
0 0
oil
d ~~COOH
Phthalic anhydride is another suitable perbenzoic acid precursor compound
herein:
CA 02311517 2000-OS-25
WO 99/27067 PCT/tJS98/~5074
22
O
O O
O
Suitable N-acylated lactam perbenzoic acid precursors have the formula:
O
II
Rs-C _N-C H2- ( H2
~C H2-f CH2 In
wherein n is from 0 to 8, preferably from 0 to 2, and R6 is a benzoyl group.
Perbenzoic acid derivative precursors
Perbenzoic acid derivative precursors provide substituted perbenzoic acids on
perhydrolysis.
Suitable substituted perbenzoic acid derivative precursors include any of the
herein
disclosed perbenzoic precursors in which the benzoyl group is substituted by
essentially any non-positively charged (i.e.; non-cationic) functional group
including,
for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl and amide groups.
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 R1 is an aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is
an
arylene, or alkarylene group containing from I 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. RI preferably contains from 6 to 12 carbon atoms. R2
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/25074
23
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. R 1 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.
Cationic peroxacid precursors
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 pemxyacid 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; S,I06,528; 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
CA 02311517 2000-OS-25
WO 99/27067 PCT/1iS98/25074
24
ammonium) methyl derivative of benzoyl oxybenzene sulfonate:
0
~O ~S03
~+
A preferred cationically substituted alkyl oxybenzene sulfonate has the
formula:
O ~ S03_
.~ ~ +
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
Other preferred cationic peroxyacid precursors of the N-acylated caprolactam
class
include the trialkyl ammonium methylene alkyl caprolactams:
O O
il
// ~CH2) ~ N
~+ ~,
where n is from 0 to 12, particularly from 1 to S.
Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl
ammonium)
ethyl sodium 4-sulphophenyl carbonate chloride.
CA 02311517 2000-OS-25
WO 99/27067 PCTNS98/25074
Alkyl percarboxvlic acid bleach precursors
Alkyl percarboxylic acid bleach precursors form percarboxylic acids on
perhydrolysis.
Preferred precursors of this type provide peracetic acid on perhydrolysis.
Preferred alkyl percarboxylic precursor compounds of the imide type include
the N-
,N,N 1 N 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,~erox a~ cid ,precursors
Amide substituted alkyl peroxyacid precursor compounds are also suitable,
including
those of the following general formulae:
R~-C-N-R2-C-L R~-N-C-R2--C-L
i ~ ; ~ ~ ,i
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. R1 preferably
contains
from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. R
1
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.
CA 02311517 2000-OS-25
W'O 99/27067 PCT/US98/25079
26
Benzoxazin oreanic peroxyacid precursors
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
CEO
of
N C-R~
including the substituted benzoxazins of the type
C
R3 ~O
C _R~
R4 N
Rs
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.
An especially preferred precursor of the benzoxazin-type is:
O
II
CEO
C
N
Preformed organic peroxvacid
The organic peroxyacid bleaching system may contain, in addition to, or as an
alternative to, an organic peroxyacid bleach precursor compound; a preformed
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/25074
27
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:
R1 -C-N-R2-C-OOH
O R5 O or
R~ -N-C-R2-C-OOH
i~
R~ O O
wherein R1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms,
R2 is an
alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms,
and RS
is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. R1
preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4
to 8
carbon atoms. R1 may be straight chain or branched alkyl, substituted aryl or
alkylaryl containing branching, substitution, or both and may be sourced from
either
synthetic sources or natural sources including for example, tallow fat.
Analogous
structural variations are permissible for R2. The substitution can include
alkyl, aryl,
halogen, nitrogen, sulphur and other typical substituent groups or organic
compounds. RS is preferably H or methyl. R1 and RS should not contain more
than
18 carbon atoms in total. Amide substituted organic peroxyacid compounds of
this
type are described in EP-A-0170386.
Other organic peroxyacids include diacyl and tetraacylperoxides, especially
diperoxydodecanedioc acid, diperoxytetradecanedioc acid, and
diperoxyhexadecanedioc acid. Dibenzoyl peroxide is a preferred organic
peroxyacid
herein. Mono- and diperazelaic acid, mono- and diperbrassylic acid, and N-
phthaloylaminoperoxicaproic acid are also suitable herein.
Metal-containing bleach catalyst
Wherc the compressed portion or the non-compressed portion of the present
invention
contain an oxygen-releasing bleaching agent, a preferred additional component
is a metal
containing bleach catalyst. Preferably the metal containing bleach catalyst is
a transition
CA 02311517 2000-OS-25
W'O 99/27067 PCTNS98/250~.1
28
metal containing bleach catalyst, more preferably a manganese or cobalt-
containing
bleach catalyst.
A suitable type of bleach catalyst is a catalyse 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
canons, 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,
~III2(u-O) 1 (u-OAc)2( 1,4,7-trimethyl-1,4,7-triazacyclononane)2-(C104~,
MnIV4(u-O)6(1,4,7-triazacyclononane)4-(C104)2, MnIIIMnIV4(u-O)1(u-OAc)2-
(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(C104)3, and mixtures thereof.
Others
are described in European patent application publication no. 549,272. Other
ligands
suitable for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-
methyl-
1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-
1,4,7-
triazacycIononane, 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-
triazacyclononanexOCH3)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 (I~ 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
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/2507.t
29
are of the formula:
R2 R3
R ~ -N=C-B-C=N-R4
wherein R l , R2, R3, and R4 can each be selected from H, substituted alkyl
and aryl
groups such that each R1-N=C-R2 and R3-C=N-R4 form a five or six-membered
ring. Said ring can further be substituted. B is a bridging group selected
from O, S.
CRSR6, NR~ and C=O, wherein R5, R6, and R~ can each be H, alkyl, or aryl
groups,
including substituted or unsubstituted groups. Preferred ligands include
pyridine,
pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings.
Optionally,
said rings may be substituted with substituents such as alkyl, aryl, alkoxy,
halide, and
nitro. Particularly preferred is the ligand 2,2'-bispyridylamine. Preferred
bleach
catalysts include Co, Cu, Mn, Fe,-bispyridylmethane and -bispyridylamine
complexes.
Highly preferred catalysts include Co(2,2'-bispyridylamine)C12,
Di(isothiocyanato)bispyridylamine-cobalt (II), trisdipyridylamine-GObalt(II)
perchlorate, Co(2,2-bispyridylatnine)202C104, Bis-{2,2'-bispyridylamine)
copper(II)
perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and mixtures
thereof.
Preferred examples include binuclear Mn complexes with tetra-N-dentate and bi-
N-
dentate ligands, including N4MnIII(u-O)2~IVN4)+~d [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 canon. Likewise,
the
oxidation state of the manganese canon 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 canon, 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 Mn~ligand species
which actually exists, it functions in an apparently catalytic manner to
provide
improved bleaching performances on stubborn stains such as tea, ketchup,
coffee,
wine, juice, and the like.
CA 02311517 2000-OS-25
WO 99/27067 PCT/(iS98/25074
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.
4,728,45
(manganese/multidentate ligand catalyst), U.S. 4,711,748 and European patent
application, publication no. 224,952, (absorbed manganese on aluminosilicate
catalyst), U.S. 4,601,845 (aluminosilicate support with manganese and zinc or
magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,119,57
(ferric
complex catalyst), Genman Pat. specification 2,054,019 (cobalt co-builder
catalyst)
Canadian 866,191 (transition metal-containing salts), U.S. 4,430,243 (co-
builders 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[~3)nM~mB~bT~tQqPp~ YY
wherein cobalt is in the +3 oxidation state; n is an integer from 0 to 5
(preferably 4 or
5; most preferably 5); M' represents a monodentate ligand; m is an integer
from 0 to 5
(preferably 1 or 2; most preferably 1 ); B' represents a bidentate ligand; b
is an integer
from 0 to 2; T represents a tridentate ligand; t is 0 or 1; Q is a
tetradentate ligand; q is
0 or 1; P is a pentadentate ligand; p is 0 or 1; and n + m + 2b + 3t + 4q + $p
= 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~3~(M'~n~ YY
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/25074
31
wherein n is an integer from 3 to 5 (preferably 4 or 5; most preferably 5); M'
is a labile
coordinating moiety, preferably selected from the group consisting of
chlorine,
bromine, hydroxide, water, and (when m is greater than 1 ) combinations
thereof; m is
an integer from 1 to 3 (preferably 1 or 2; most preferably 1 ); m+n = 6; and Y
is an
appropriately selected counteranion present in a number y, which is an integer
from 1
to 3 (preferably 2 to 3; most preferably 2 when Y is a -1 charged anion), to
obtain a
charge-balanced salt.
The preferred cobalt catalyst of this type useful herein are cobalt pentaamine
chloride
salts having the formula [Co(NH3)SC1] Yy, and especially [Co{NH3)SC1]C12.
More preferred are the present invention compositions which utilize cobalt
(III)
bleach catalysts having the formula:
[Co(NH3)n(M)m(B)b] TY
wherein cobalt is in the +3 oxidation state; n is 4 or S (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=1, then m~ and n=4; and T is one or more
appropriately selected counteranions present in a number y, where y is an
integer to
obtain a charge-balanced salt (preferably y is 1 to 3; most preferably 2 when
T is a -1
charged anion); and wherein further said catalyst has a base hydrolysis rate
constant of
less than 0.23 M-1 s-1 (25°C).
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, methanesuifonate, 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), 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-,
S2O3'2, NH3, P043-, and carboxylates (which preferably are mono-carboxylates,
but
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/2507.1
32
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-,
HZP04-, HOC(O)CH2C(O)O-, etc.) Preferred M moieties are substituted and
unsubstituted C 1-C30 carboxylic acids having the formulas:
RC(O)O-
wherein R is preferably selected from the group consisting of hydrogen and C 1-
C30
(preferably C 1-C 1 g) unsubstituted and substituted alkyl, C6-C30 (preferably
C6-C 1 g)
unsubstituted and substituted aryl, and C3-C3p (preferably CS-C 1 g)
unsubstituted and
substituted heteroaryl, wherein substituents are selected from the group
consisting of -
NR';, -NR'4+, -C(O~R', -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.
The B moieties include carbonate, di- and higher carboxylates (e.g., oxalate,
malonate, malic, succinate, maleate), picolinic acid, and aipha 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. Inorgr 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 (kpH= 2.5 x 10''~ M-1 s-1
(25°
C)), NCS- (kOH= 5.0 x 10-4 M-1 s-1 (25°C)), formate (kpH= 5.8 x 10-'4
M-1 s-1
CA 02311517 2003-O1-29
33
{2~°C)), and acetate {kpll= 9.6 x 10-~ M'1 s'1 (25°C)). The most
pmfertrd cpbaEt
catalyst useful herein are cobalt pentaamine acatatc salts having the forrnuta
[Co(T~H~)3UpoJ Ty, whasin DAc rapresents an acetate moiety. at~d Especially
cobalt
pantaacnine aoc~tate chloride, [Co(NH3)5~~1C12; as well as
[Co{NH3)SOAcJ(tJAcn; I~o(NH3)54Ac](PFb)2~ [C~3)54Ac](S~la); (Co
(~3)SCAc](BF.~~; and [Co(NH3)SOAc](N03}2 (herein "PAC").
Th~a cobalt catalysts are ncadily prepared by known procedures, such as taught
far
example in the Tube article hEreixihefora and the referatces cited therein, io
U.S.
Pa~at 4,810,410, to Dialcua et al, i$sued Mmh 7,1989, ,L, Cue{ 1989), 66
{12), 1043-45; The Synthesis and Cactarls~tion of Inorganic Compounds, W.L.
Jolly (Prenriee-Hall; 1970 pp. 451-3: ~~r' -~ ChGm.,18. 1497-1502 (19?g); ~p~,
~ 71.. 2881-2885 (1982); Inor - ChGm..l$. 2023-2025 (1979); Inorg~
Synthasia, l73-176 (1960); arid ~fot~~ta1 o~hva~Che~t i~r. 5_ø, 22-25 (1952);
as
well as tha syttthcsis examples provided herdnefter.
t~Qi~t artalysta :ttitable for ittcorporetiop into tha detcr8eent tablets of
tha t
invention ttuay ba praduCad accordi,a~ to iha synthetic routm ditcloaed in
U.S. Fat~ont
Nos. 5,559,261, 5,581,005, and 5.599,r33b.
There catalysts may i~x eo procd with ttdju~ct s:ials ao as to salute the
colour
itttp~ct if dasirad for the aeSthctic~ 4f the product, or to be ittchsdai itt
et>zyma-
cc~nt~tiug particles as Exetnplifiod ha~fber. or the compositions may be
manttred to contain catalyst "spacldes".
Suitable eaxymeS fQr incorparatiort into the comprasad pa~tion ~ tlsa non-
compt~essed
portion as a flttishiag additive, ara aaiectad $~oxn the group oooeisting of
adll~tlasss,
hemiasllulr~as, pasoxida~es. prote~os. gluco-BlxtYla~, atxtYlases, xYl.
lipases,
phospholipases, Gsta~aaes, cutinases, peCtins, keratattaaas, reductases,
oxidises,
phenoioxidases, lipoxyganasea, ligninases, pullul~asES, t, ptntosansses,
malanasas, li-8lucanasas, ar4binosidasas, byalumnidaao. rbai~roltizuu~,
laccpac ar
mixtures theraof.
CA 02311517 2003-O1-29
~a
Preferred enzyma$ include protease, amylase, lipase, pexoxidases, cutinase
andlor
cellulose in conjunction with one or more plant cell wall degrading enzymes.
The cellulasac usable in the present invention include both bacteria! or
fungal
cellulose. Prefbly, they will have a pal optimum of between S and 12 and an
activity above 54 C~VU (Cellulose ViscQSiry Unit). Suitable rellulases are
disclosed
in U.S. Patent 4,435,307, Harbasgoard ct aI,1b1078384 and W09b102653 which
disclose fungal cellulases produced respeGtivaly from Humicola incolsns,
Trichodsrma, 'fhielavia and Sporotrichum. BP 739 982 describes cellulasea
isolated
frou~ novel Bacillus species. Suitable collttlases are also disclosed in GB-A-
2.075.02$;
C~B-A-2.095.273; DB-'OS-2.247,832 and WU9512b398.
Examples of such ccllutaaes are celluloseR produced by a strain of Humicola
it~sol~a
(Humicola grisex vat. thera~oidca), particululy the I~tuuicola swain DSM 1$00.
Other
suitable cellulases arc ceilulases originated from Humicola insolens having a
molexulu
weight of 50KI3a, an isoelecttic paint of 5.5 and contaiui~tg 415 amino acids;
and a
"43k15 endoglucanase derived iiom Humicvla itisolens, DSM I$00, exhibiting
collul~c aasivity; a prefeaed rndoglucaasse component has the amino acid
aeduenee
disclosed in PCT Patent Application No. WO 91/17243. Also suitable cellulases
are
the E4IlI cehulascs from Trichoderma longibrachiatum described in W094121801,
C3enencor, published September 29,1994. Especially amble cellulases are the
cellulases havitt$ color care benefits. Bxampka of such cellulases are
cellulasts
dsearibsd is >~eiropesu Patent No. 0 540 784 (Nova).
Carexynzo and Celluxyma (Novo Nordiaic.4lS) are oapecially useful. Sec also
W091/1'7244 and W091121801. Other suitable cellulases for feibxic cue andlur
cleaning properties are des~Cribed in WO9~'34092, W498/17994 acrd W095124471.
Said cellulasas are normally incorporated iu the detergent composhion at
levels from
0.0001 °rG to 2% of active enzyme by weight of the detergent
composition.
Peroxidase enzymes art used in co~ubiuatior~ with oxYasn sores, s.g.
pexcarbanate.
perborate, pexsulfate, hydrogen peroxide, etc. 'they are used for "soiutio~
bleaching",
i.e. to gravest ttansf~t of dyes or pigments removed from substrates during
wash
operations to other substrates in the wash solution. Peroxidax enzymes are
laaown in
the ut, and include, for example, horseradish pemxidase, ligninase and
haloperoxidase such as chlcrc- and bromo-peroxidase. Pemxidase-containing
CA 02311517 2003-O1-29
detergent compositions are disclosed, for example, in PCT International
A.ppliaatian
WO 89~b99813, W089/49t313 and is European Pataait No. OS40 784.
Also suitable is the lactase en~y~.~
Preferred enhancers are substitued phenthiazine and phenoxasine l b-
Phenothiazittepropionic~cid (PP's, 14-ethylphenathiazine-4-carboxylic acid
(EPCy,
10-phenoxazittepropionie acid (P4P) end 10-methylphenax~ne (de3atbed in WO
9411262 1 ) attd substltued syriagatas (C3-CS aubstituod alkyl syringsues)
:crud phenols.
Sodium parcari~onate or pa~bo~e are prefd sources of hydrogen peroxide.
Said celluleses andlar peroxidasas are normally incarparatad in the detergont
cotnpositian at levels ftmon 0.0001% to Z% ofactive ecraymc by weiglst of the
detergent aompoaition.
Other preferred enzymes that caa be iacludod iu the dat~gmrt caa~sitioas of
the
present invention include lipesea. Suitable lipase ertzyme,R fQt detergent
usage iaelude
these produced by tAid~oargant~a of thv Psoudomatws 8rroup, such as
Pseudoxaonas
acutz.~i ATC~c 19,1~t, so diceloaad ~ British gaunt 1,372,034. Suitable
lipsaes
include those which show a positive immttnologieal crass-reaction with the
artdbody
of the lipase, produced by the micrao:gat~n Pseudonrarras,~luorescem IAM 1037.
This lipase is available (rata A~onasm Pht~tmaceut~l Cv_ Ltd., Nagoya, Japaa,
tmdGr
the trade uamo x.ipsas P "Ahoatia," herd rtf~crr~ to as "Arnana-P". Other
suitable coau~aarcial llpases iaclude Amana-CES, lipasoa ex Chromobact~er
viseosum,
e.g. CJrromobacter vfscos~ vat. lipolynctm NRRLB 3b73 $~om Toyo Joa~o Co.,
Tagata, Japan; Chramabacrsr vlscosr~m lipase: from U.S_ siachemical Carp.,
U_S.A.
and l7isaynth Co., The Netlretlsnds, and lipaats ex Pseudomorrax gladfai~.
Frspecially
suitable lipasee an lipaaes welt as M1 LipaseR ~ Lipomsx~ (Gist Bmcmd~) gird
LipolascR and LipolBSe Ulua~(Novo) which have fouad to be very effective whoa
used in catabination With the compositions of the present inv~tian. Also
auitablea era
the lipolytic enzymes described it! EP 2S$ 068, WO 9ZI03ZA9 and W0 93122615 by
Npvo l~Tordisk sad in WO 94/03578, WO 95/3381 and WO 96/00292 by Unilaver.
Also sui#able are cuainaaea (EC 3.1.1.30] which cau be oansiderod as a :pedal
kind of
ligasa, gamely lipase: which da not recline interfacial activation. Addition
of cutirmses
to detergent campositians hive been d~tlbed in o.g. W15-A-8BJ093fsy
(Qeasneor);
CA 02311517 2003-O1-29
36
WO 90/09446 (Plant Creaetia System) and W4 94114963 and W4 94/149b4
(Urulcvcr).
The lipases and/or cutin~rses aro norn~ally iacorQarated in the detergent
composition at
1~vols fr~am 0.0001% to 2% ofactiva enzyme by weight of the detergent
composition.
Suitable professes are the subtilisins which art obtained from particular
strains of B.
subr~lis and B. lichen~'orrrris (subtilisin BPN and HpN'~ Oru' euitable
t~rotea°e i~
obtained from a strain of &roitlrrs, having maxims activity throughout the pH
range
of 8-12, developed and sold as ~SPIrRASE~ by Novo Industries A/S of Denrnarlc,
hereinafter "Novo". 'Ihe preparation of this enzyme and analogous ccu;yreus is
described in Cr8 1,?43.784 to Novo. Otber suitable proteasas include
ALCALASE~,
DURAZYM~ si7d SAVINASE~ from Novo and MA3CATAS>r~, MAXACAL~.
pROPF,itA.sE~ and MA3CAPEtvI~ (protein eagitteered Iwtsxacal) from Gisc-
Brocades. Protcolycic enzymes also encompass modified bsstcrial serine
professes,
which is c~l~ed hetdn
"Protease B", arrd is Europasn Patent ~.gpli~dOn 199.444. VImblishcd
oat~ber 29, 1986. which refers to a modif red bactetaal sarirte pratealytic
c~yale
Which 18 CallCd ~PTOtBSSC A" herein. r~lltt~ll~b t~ What 1S G~ICd h6r'elrl
which is a variant afar al>calixte seriae pmtaase from ,in which iyainc
rapleced
ar$~ina at position 27, ryrosarto ra~rlscad valine at position 1d4, sreplaced
axpaxagir~ at poe~tioa 123, sad alani~ne replaced tlu~nirie at position 274.
Protease C
f s described in EP 90915958:4, corresponding to WO 91106b3T, Published May
16,
1991, Genetically madifled variants, pa~tieularly of Protease C, are also
included
herein.
A preferred pratca_se refereed to as "Protease D" is a carbonyl hydrolasc
variant
having an ataino acid sequence not found is nature, whicb is derived from a
precursor
carbonyl hydrolase by ~~bsdttttiag a dit~'trer~t amino acid far' a plurality
of amino acid
residues at a position in Bald carbonyl hy4rola9e equivalent to po~sion +76,
preferably
also in c4mbir~atiaa with one or more amino acid residue positions equivalent
to those
selected from the group consisting Df +99, +101, +103, +144, +107, +123, +27,
+105, +109, +12b, +12~, +I35, +156, +166, +19S, +197, +?.04, +206, +210, +21b,
+217. +218, +222, *2b0. +265, andlor +274 according to the numbering
of.8oeilltrs
amyloliguaJaciens subtilisin, as dcxxibed in WU95/1059I ind in US Patent No.
5,677,272.
CA 02311517 2003-O1-29
7
Alx, suirabls far the preset invention are proteases described in patent
applications
EP 25144b and WO 91106437, protease BLAI~ described irr W091l02792 and their
variants described is WO 95123221.
Sao also a high pH protease from EMcillus sp. NCII~ 40338 described in WO
93118140 A to Novo. Enzymatic det~ents comprising protease, ocut car morn
other
enzymes, and a reversible protaisa inhibitor arc described in W4 92183529 A to
Novo. When desired, s protease having ~cxaased adsorption and greased
hydrolysis is available as describaci in WO 9S10T~91 to Procter & Ciarnble. A
recombinant crypsin-like protease for detergents suitable hora~ is described
in W4
94123583 to Novo. Other suitable pmteases are described in EP 516 200 by
Unilevar.
Clthcr prefarmd protease enzymes include protease enzymes which one a carbonyl
hydrolase variant having an amino acid sequence not found in ~tura, which is
derived
by replncsmeat of a plurality of amine acid residues of $ l~cursor csrboayl
hydmlase
with di~arent amino acids, wherein said plurality of a~irto acid residues
replaced is
the precursor o~yrne correspond to position +210 in combina#ivn with ot~ra or
more
of the following residues: +33. +62, ~t-67, +7d, +140, +101, +103. +10,4,
+107, +i28,
+129, +130, +132, +135, +156, +15$, +164, +166, +167, +170, +Z09, +215, +217,
+31 S and +222. where tho uutriberad positions correspond to ~y-accuering
subtilisin from ~ .g vlol~,g~j~g or to e9uivaleut amino acid residues is other
cerbottyl hydrolases or subtilisitxs (such as ~ lmgi8 subtilisirt). Prcfesced
et~zytnas of this typo include those having paaition eharsgss +214, +'~b,
+103, +104.
+154, sand +166.
1'he protoolytic are iruorporated in the detergent comps of tho present
invention a level of from 0.0001 % to Z°h, prefarsbly ltota 0.001
°r6 to 0.2%, mote
preferably Pram 0.0059'o to o.l% pure saaym~e by w~aight of the composition.
Amylases (a andlor i3) can ba included for retnoval of carbohydrate-besod
stains-
W094102597, Novo Nordisk AIS published February 03, 1994, describes ol~ag
compositions which incorporate ttautant amylases. Sae also W495110b03, Novo
Nordfsk AIB, published April 20, 1995. Orb amYlases latown for use it1
aleaniag
CA 02311517 2003-O1-29
compositions include Goth a- and (i-amylases. a-Amylases are known in the art
and
include those disciosad in US Pat, ao. 5,043,257; EP 252,666; W4/91/00353; FR
2,67G,45b; iJF 283,123; EP -525,610; EP 388,341; and Heitish Patent
apacification no.
1,296,839 (Novo). Otber suitable amylasas are stability-enhanced amylases
dascsibed
in WG94/18314, published August 18, 194 and W096/05295, Ganeoeor, published
February 2'?,1996 and amylase variants having additional modification in tha
immediate parent available front Novo Nordislc AIS, disclosed in WfJ 95110603,
published April 45. Also suitable ore ornylesea de9ann~bed iu EP 2?? 216, .
W095I26397 and W096I23873 (all by Novo Nordisk).
F.xataples of commerdal a-auxtylases priodueta are Pucafect Ox Am~ from
C~lertons~r
acrd Termsmyl~. Band ,~ungamyl~ gad Duramyl~, a!1 available from Novo Nordi$k
A/s De~sudc. W095I26397 describes other suitably amylases : oc-amylases
ch~C;carlsed by having a apeci~lc aeedvity at least 25~o higher than the
spacitfc activity
of Termamyl~ at a anaperaaire range of 25°C to 55°G and at a pH
value in the range
of $ to 10, measured by tha Pl>sd~bas~ a-arnyleso activity y. Suitable are
waria~s
of the above enzymes, described is W496123873 (Novo Nordiak). Qther amylolydc
eaxyr~a with improved properties with oespeet to the activity level and the
combination of tharmosmbility and a higbar aodvity level ara daaeribed in
wo~s~3s3aa.
Prafe~rred amylase anzymos include those described in 'W095126397 good in
WtJ96123873.
The amylolytic enzysttoe are iocorporatard in the dent compositions of the
pras~t
invrudon a level Of tom 0,0001°A to 2°~, preferably from 0.0001
S% to 4.06%, mesa
preferably from 4.00034°Ye to 0.04$% pmt onzy~e by weight of the
composition
In a particularly preferred ornboditttent, detergent tablets of the present
invoutivar
comprise amylase off, particul~ly tbose.dascrlbed is WU95IZ6397 and
iti W096J23873 in Gomtilnation with a cotnpl~antary amylase.
8y "complementary" it is ri~nt the addition of one or more amylaa~e suitable
for
detargartcy piuposes. Examples of corapletoantary amylases (a and/or A) are
de~ibod below W494/4i~97 and W(?95110603, Novo Nardisk AI$ desarihe
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/25073
39
cleaning compositions which incorporate mutant amylases. Other amylases known
for
use in cleaning compositions include both a- and ~i-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 W094/183I4, and W096/05295, Genencor and
amylase variants having additional modification in the immediate parent
available from
Novo Nordisk A/S, disclosed in WO 95/10603. 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: l 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, psychmtrophic, thermophilic, barophilic,
allcalophilic,
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
CA 02311517 2003-O1-29
4t7
modifications of native e~ymes. Common practice as wall is tire expression of
the
enzyme via host orgatsistns is which t>x genetic material responsible for the
production of the enzyme has been cloned
Said aazysrtes era normally i~orporated in the deux~gant compo$itioa at hiss
fmm
0.0o01'~e to zoo of active riy weight of the detargeat compositi4a. The
enzymes can be added as separate single ingredients (grills, granulates,
stabilized
liqetids, etc... containing one enzyme ) or as tnixmres of two or more enzymes
( a.g.
cogranulates ).
Other suitable decergerrt ingrCdieats that can bo added are enzyme oxlda~don
scavengers which are described in Buropesn Pit No. 0,553,60'7.
Examplaa of suctr axidatiott
scavengers are ethaxylated tetraethylane polyaminaa.
A range of amaterials and moans for choir ina~p~eutiou into ayathetio
detergent campositians is also disclosed in WO ~307~63 A and'WO p3~'~260 A to
Cronetrcor Intetnatioual, WO 8905694 A to Novo, apd U.S. 3,553,139, January 5,
1971 to McCatry et al. EttzyQres ate i~tber discloeod itr U.S. 4,101,457,
Place a a1,
July 18, 1978, and is U.S. 4,507,319, Hugries, March Z6, 1983. Enzyme
naatatats
useful for liquid dstsrgont formulabottt, and thrir itlcorpot~tion into e'uoh
formulations, are did in U_S. 4,261,868, Hara et al, April 14, 1981. ~
for use in detergents cap be stabilised by various teehniquas. E~nzyma
stabilisation
techniques ate disclosed sad exemplified in U.S. 3,640,319, August 17, 1971.
sedge
at al, EP 199,403 sad EF 200,86, October 29,1986, Ycn~as. Enzyme stabilissdoa
systems are also described, for example, in U.S. 3.519,570. A tue~I Bacillus.
sp.
AC 13 giving pretenses, xylansaes and cellulasas, is de:ctib~d in WO 9401532 A
to
Novo.
A blr~ch destroying 8g~t ie ~ prefernd flnishittg additive of the
aot~ompressed portion
of detergent tablets suitable for use in autoaoatic dishwasE>ing. Bloaoh
destroying agents
are delivered to the later stages of the washf~g cycle of a dishvv~a~g machlno
and serve
to destiny any remaining bleach present at the end of tbc washing cycle. It is
believed
CA 02311517 2003-O1-29
41
that bleacbang agent carried aver from the washing cycle to the rinsing cycle
causes
corrosion of silverware as described io fiP-A.636 888_
The bleach destroying agent cansiats of one or mare encapsulated additives.
Suitable
encapsulated additives include encapsulated enzymes suitably for oxygen
destruction For
axgmple peraxidases, e.a. cataiase, encapsulatod reducing agents, a.g.
thiosulphate,
encapsulated heavy metals or compounds thereof e.g. copper, iron, manganese,
zinc ar
titanium.
Suitable m~athbds of encapsulation are those already known iu t3~e art. The
preforred
ertcapaulatian dissolve gradually a.g. ~
Perfume CQm~~.
PerRune cdmponettts can be incorparatod iota the compressed portion, but are
preferably
incorporated as i3nishing additivca of the non-oompressod portion. By porfiune
component it is meant perfume oil, encapsulated perfttmes, perfumes with haul
beam
applied to a porous carrier sad thon optiarrallY ~d. pro-pat~mes and mixtee~s
~eraf, suitable p~rFu~es it~cttida those carautuartly available irt the art
and especiahy
those described iu US Patart Na. 6,35$,9 i 1.
panic poly~ria cwnpowtds may be iacarporaoed into tlx aoaapressed portion, but
are
preferably finishing additivos of the noacompr~sad portion in accord v~rith
the
invaadoa. By organic polyntorio compound it is meant c~tially ~y polymeric
organic co~apound comt~ty fowrd in deepest aaotposltiona havi~ag dispersaut,
ar~_
redepositiou, soil release agatnts 4r other de#ergency properties.
Organic polymeric coatpound is typically i>seorpoisted in the detergent
compositions
of the invention at a level Qf from O.l~o to 3o9~b, ptefcrnbly firnn 0.59 to
15~1e, most
preferably From, l f6 to 1 Q"~ by weight of the compositions.
Examples Ql'orgaxtic polymatic compaunda include tho water soluble organic
hotna.
or ca-polymeric polycarboxylic acids, modified polycarboxylates ar their salts
in
which the polycarboxylic acid camprisea at least two casbQxyl rattica>s
8rparated from
CA 02311517 2003-O1-29
42
each other by not more than two carbon atoms. pol~rmars of the latter type are
disclosed in GB~A-1.59b.756. Examples of such salts src polyacrylates of
molecular
weight from 500 to ~00,AO0; mart prefcrdbly from 1,000 tolOQ,000 and their
copolymers
with nay suitable ether monomer units including modified acrylic, fumaric,
malefic,
itaconic. aconitic, masaconic, citraco~ic and methylenamaloxtic acid or their
salts, malefic
anhydride, acrylamide, alkylcne, vinylmethyl ether, $tyrana and any mixtures
thereof.
Preferred are the copolymers Qf acrylic acid and malefic anhydride having a
molecular
wtight of from 20,000 to 100,040.
Preferred copy available acrylic acid containing polyeaas having a molecular
weight below 15.000 include those gold under the tradename Sokalan PA3o, pA20,
PA13, PA10 and Sakalan CP10 by BASF GmbH, and thoxe sold under the ttradauama
Acusol 43N, 490M, 4dON by Rohm and Iiaas.
hrafcnnd acrylic acid contavirir~ Qopolyma~ include those which contain as
monomer
units: a) from 90°/a to 10°/a, preferably from 80% to 2Q% by
weight acrylic acid or it'
salts sud b) from 10'~ to 90°Ye, preferably tom 2U°/a to 80e/o
by weight of a
subscitutad acrylic mariamer or its salts having the genera! fortriula -[CRS-
CR1 (GO-
o.R~>]- wherein at lit ane of the substituents Rl, R2 or R3, preferably Rl or
R2 is
a 1 to 4 carbon alkyl or hydroxyalkyl group, Rl or R~ can be a hydrogen and R3
can
lee a hydro~ or alkali moat salt. Mast prete~ed is a substituted acrylic
m~omsr
wherein Rl is methyl, R2 is hydrogen (i.e. a methacrylic acid monomer). The
most
prefesed oopoly~r~er of this type has a molecular weight of 3500 and comains
50% w
80'/e by v~eight of acrylic acid sad 40°1. to 20'Io by weight of
raathaorylia acid.
The polyamina and tttodif ed palyamine compounds arc useful luarsirs iacluding
thoaa
derived $tarn asp~tic acid such as those discio~vd in EP-A 345281, EP A 305283
aaa ~.A-3s 162.
Other options! polymers may include polyethylene imtninas (described in
coponding
Candldi~.t1 74pplication No. 2,252,857. ~ _
, polyethylene oar polyptapylatte glycol, polyvinyl alcohols
and acetates both modified and nou~modlfiad, cellulaaics attd modified
callulosies.
PolYoxY~Yl~~ I~IY~YP~PYI, end copaiymars theroaf, both modified sod non-
modified, terephthalate esters of ethylene ar propylene glycol ar mixiure9
thereof with
poiyoxyalkylerta waits,
CA 02311517 2000-05-25
WO 99/27067 PCTNS98/25074
43
Suitable examples are disclosed in US patent Nos. 5,591,703 , x,597,789 and
4,490,271.
Examples of polymeric soil release agents include those soil release agents
having: (a)
one or more nonionic hydrophile components consisting essentially of (i)
polyoxyethylene segments with a degree of polymerization of at least 2, or
(ii)
oxypropylene or polyoxypropylene segments with a degree of polymerization of
from 2
to 10, wherein said hydrophile segment does not encompass any oxypropylene
unit
unless it is bonded to adjacent moieties at each end by ether linkages, or
(iii) a mixture of
oxyalkylene units comprising oxyethylene and from 1 to 30 oxypropylene units,
said
hydrophile segments preferably comprising at least 25% oxyethylene units and
more
preferably, especially for such components having 20 to 30 oxypropylene units,
at least
SO% oxyethylene units; or (b) one or more hydrophobe components comprising (i)
C3
oxyalkylene terephthalate segments, wherein, if said hydrophobe components
also
comprise oxyethylene terephthalate, the ratio of oxyethylene terephthalate:C3
oxyalkylene terephthalate units is 2:1 or lower, (ii) C4-C6 alkylene or oxy C4-
C6
alkylene segments, or mixtures therein, (iii) poly (vinyl ester) segments,
preferably
polyvinyl acetate, having a degree of polymerization of at least 2, or (iv) C
1-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 (a)(i) will have a degree of
polymerization
of from 200, although higher levels can be used, preferably from 3 to 150,
more
preferably from 6 to 100. Suitable oxy C4-C6 alkylene hydrophobe segments
include, but are not limited to, end-caps of polymeric soil release agents
such as
M03S(CH2~OCH2CH20-, 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
terephthalate,
and the like. Such agents are commercially available and include hydroxyethcrs
of
cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use
herein
also include those selected from the group consisting of C1-C4 alkyl and C4
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/25074
44
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
terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight
of
this polymeric soil release agent is in the range of from 25,000 to 55,000.
See 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
oxyalkyieneoxy 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 ageats 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
Gosselink,
and the block polyester oligorneric compounds of U.S. Pateat 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
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/25074
4~
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.
Other suitable soil release agents include water-soluble cationic ethoxylated
amine
compounds with particulate soil/clay-soil removal and/or anti-redeposition
properties.
These cationic compounds are described in more detail in EP-B-111965, US
4659802
and US 4664848. Particularly preferred of these cationic compounds are
ethoxylated
cationic monoamines, diamines or triamines. Especially preferred are the
ethoxylated
cationic monoamines, diamines and triamines of the formula:
CH3 CH3
X --(-- OCH2CH2)n N+- CH2 - CH2 -f- CH2)a IV+-. CH2CH20 ~ X
b
(CH2CH20 ~ X (CH2CH20 ?n X
wherein X is a nonionic group selected from the group consisting of H, C1-C4
alkyi or
hydroxyalkyl ester or ether groups, and mixtures thereof, a is from 0 to 20,
preferably
from 0 to 4 (e.g. ethylene, propylene, hexamethylene) b is 2, 1 or 0; for
cationic
monoamines (b=0), n is preferably at least 16, with a typical range of from 20
to 35; for
cationic diamines or triamines, n is preferably at least about 12 with a
typical range of
from about 12 to about 42. These compounds where present in the composition,
are
generally present in an amount of from 0.01 to 30% by weight, preferably 0.05
to 10% by
weight.
Co-builder
Co-builders can be incorporated into the compressed portion, but are
preferably
incorporated as finishing additive of the non-compressed portion. By co-
builder it is
meant a compound which acts in addition to a builder compound (as described
below) to
sequester (chelate) heavy metal ions. These components may also have calcium
and
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/2507.1
46
magnesium chelation capacity, but preferentially they show selectivity to
binding heavy
metal ions such as iron, manganese and copper.
Co-builders 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 ~%
by weight of the compositions.
Co-builders, which are acidic in nature, having for example phosphonic acid or
carboxylic acid functionalities, may be present either in their acid form or
as a
complex/salt with a suitable counter cation such as an alkali or alkaline
metal ion,
ammonium, or substituted ammonium ion, or any mixtures thereof. Preferably any
salts/complexes are water soluble. The molar ratio of said counter cation to
the co-
builder is preferably at Ieast 1:1.
Suitable co-builders 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 co-builders 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 aanmonium salts thereof, or mixtures thereof.
Preferred
EDDS compounds are the free acid form and the sodium or magnesium salt or
complex
thereof.
Cationic fabric softeniq~_agents
Cationic fabric softening agents are suitable finishing additives in detergent
tablets which
are suitable for use in methods of laundry washing. The cationic softening
agents can be
delivered to the wash in the later stages of the wash cycle but are preferably
delivered in
the rinse cycle of the washing. Suitable cationic fabric softening agents
include the water
CA 02311517 2000-OS-25
WO 99/Z7067 PCTNS98/2507~
47
insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-
1 514
276 and EP-B-0 011 340.
Cationic fabric softening agents are typically incorporated at total levels of
from 0.5%
to 15% by weight, normally from 1 % to 5% by weight.
Crystal growth inhibitor
The non-compressed portion preferably contains a crystal growth inhibitor,
preferably an
organodiphosphonic acid component, incorporated preferably at a level of from
0.01 % to
5%, more preferably from 0.1% to 2% by weight of the compositions.
By organo diphosphonic acid it is meant herein an organo diphosphonic acid
which
does not contain nitrogen as part of its chemical structure. This definition
therefore
excludes the organo aminophosphonates, which however may be included in
compositions of the invention as heavy metal ion sequestrant components.
The organo diphosphonic acid is preferably a CI-C4 diphosphonic acid, more
preferably a C2 diphosphonic acid, such as ethylene diphosphonic acid, or most
preferably ethane 1-hydroxy-1,1-diphosphonic acid (HEDP) and may be present in
partially or fully ionized form, particularly as a salt or complex.
Nonionic surfactant
Essentially any nonionic surfactants can be included in either the compresed
or non-
compressed portions of the detergent tablet. Preferred, non-limiting classes
of useful
nonionic surfactants are listed below. Preferred nonionic surfacatnt
incorpoarated into
the compressed portion provide a suds suppression benefit. In a preferred
aspect of the
present invention, the finishing additive is a rinse aid composition
(described later)
comprising nonionic surfactant and a source of acidity.
Nonionic ethoxvlated alcohol surfactant
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
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/25074
48
contains from 6 to 22 carbon atoms. Particularly preferred are the
condensation
products of alcohols having an alkyl group containing from 8 to 20 carbon
atoms with
from 2 to 10 moles of ethylene oxide per mole of alcohol.
End-capped alkyl alkoxylate surfactant
A suitable endcapped alkyl alkoxylate surfactant is the epoxy-capped
poly(oxyalkylated) alcohols represented by the formula:
R10[CH2CH(CH3)OJx[CH2CH20]y[CH2CH(OH)R2J (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)R2J. 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.
Ether-capped polv(oxyalkylated) alcohols
Preferred surfactants for use herein include ether-capped poly(oxyalkylated)
alcohols
having the formula:
R1 O[CH2CH(R3)O]x[CH2JkCH(OH)[CH2JjOR2
wherein Rl 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.
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/2507.t
49
R 1 and R2 are preferably linear or branched, saturated or unsaturated,
aliphatic or
aromatic hydrocarbon radicals having from 6 to 22 carbon atoms with 8 to 18
carbon
atoms being most preferred. H or a linear aliphatic hydrocarbon radical having
from 1
to 2 carbon atoms is most preferred for R3. Preferably, x is an integer having
an
average value of from 1 to 20, more preferably from 6 to 15.
As described above, when, in the preferred embodiments, and x is greater than
2, R3
may be the same or different. That is, R3 may vary between any of the
alldyeneoxy
units as described above. For instance, if x is 3, R3may be be selected to
form
ethlyeneoxy(EO) or propyleneoxy(PO) and may vary in order of (EO)(PO)(EO),
(EOKEO)(PO); (EO)(EO)(EO); (PO)(EO)(PO); (PO)(PO)(EO) and (PO)(PO)(PO).
Of course, the integer three is chosen for example only and the variation may
be much
larger with a higher integer value for x and include, for example, mulitple
(EO) units
and a much small number of (PO) units.
Particularly preferred surfactants as described above include those that have
a low
cloud point of less than 20°C. These low cloud point surfactants may
then be
employed in conjunction with a high cloud point surfactant as described in
detail
below for superior grease cleaning benefits.
Most preferred ether-capped poly(oxyallcylated) alcohol surfactants are those
wherein
k is 1 and j is 1 so that the surfactants have the formula:
R1 O(CH2CH(R3~]xCH2CH(OH)CH20R2
where R1, 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 R 1 and R2 range from 9 to 14, R3 is H
forming ethyleneoxy and x ranges from 6 to 15.
The ether-capped poly(oxyalkylated) alcohol surfactants comprise three general
components, namely a linear or branched alcohol, an alkylene oxide and an
alkyl ether
end cap. The alkyl ether end cap and the alcohol serve as a hydrophobic, oil-
soluble
portion of the molecule while the alkylene oxide group forms the hydrophilic,
water-
soluble portion of the molecule.
CA 02311517 2000-OS-25
WO 99/27067 PCT/LiS98/25074
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 12/14 alkyl '~vcidvl ether
A C 12/ 14 fatty alcohol ( 100.00 g, 0.51 S mol.) and tin (I~ chloride (0.58
g, 2.23
mmol, available from Aldrich) are combined in a S00 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, SO%) 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 C /149/11 ~~ caolxd alcohol surfactant
Neodol~ 91-8 (20.60 g, 0.0393 mol ethoxylated alcohol available from the Shell
chemical Co.) and tin (I~ chloride (0.58 g, 2.23 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 C12/14 ~kyl 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
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/2507.i
51
( I 00 °C, 0.5 mm Hg) to yield the surfactant as an oil.
Nonionic ethoxvlated/propoxvlated fatty alcohol surfactant
The ethoxylated C6-C I g fatty alcohols and C6-C I g mixed
ethoxyiatedlpropoxylated
fatty alcohols are suitable surfactants for use herein, particularly where
water soluble.
Preferably the ethoxylated fatty alcohols are the C I 0-C 1 g ethoxylated
fatty alcohols
with a degree of ethoxylation of from 3 to 50, most preferably these are the C
1 ~-C I g
ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40.
Preferably the
mixed ethoxyiated/propoxylated fatty alcohols have an alkyl chain length of
from 10
to I 8 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of
propoxylation of from I to 10.
Nonionic EO/PO condensates with propylene 1Q vcol
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.
Nonionic EO condensation~roducts with ~rowlene oxide/ethylene diamine adducts
The condensation products of ethylene oxide with the product resulting from
the
reaction of propylene oxide and ethylenediamine are suitable for ust herein.
The
hydrophobic moiety of these products consists of the reaction product of
ethylenediamine and excess propylene oxide, and generally has a molecular
weight of
from 2500 to 3000. Examples of this type of nonionic surfactant include
certain of
the commercially available Tetronic'~'' compounds, marketed by BASF.
Mixed Nonionic Surfactant System
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
CA 02311517 2003-O1-29
52
surfactant and at least olie hiQ,h cloud paint nonionic surfac~aat as
described in co-
pending C~~ian P3ltQnt No. 2 ,.265, 8,25.
in a preferred ambodimont the detergent tablet comprising such a mixed
surfactant
system also ~nmpriaes an amount of water-aoiuble salt to provide conductivity
in
deionised water mea9ured at 25°C greater titan 3' milli ~iemertskm,
preferably greater
than 4 milli Siamenslcm, most preferably ~tcr tbett 4.5 milk Siamenslcm as
described in eo-pendiag C~8 Puf~tication I~o. 2,23?,948.
in gr~othar preferred e~ctbadimeat the mixed sur~taat system disSClves in
water
having a hardness of t 246mmoUL in arty suitable cold-X11 automatic diahwashcr
to
provide a solution with a Surface tension of less than 4 Dyacs/ctrtz at less
than 45°C,
preferably Lass thgut 40'C, most prafert~bly less than 35p~C at dex~bed is ao-
pendit~
Cna.~di_,an 7Patarit Na. 2,265,85. ,
In another prtsfferr~ed embodinunt the bi~h cloud point and low clatxi point
serclactants
of the mixed surfactant ayat~ era separstod:ucb that one of either fist high
cloud
point or low cloud paint ~xfactants is is a Srst mat~c and the ether is p~seat
br a d rilattiX as d~libad 1n CO~pendtl~ Canadian 8at~t~t No. 2 , 265 , 825.
For the pefrposes of the present
invention, the first msQix may ba a first particulate and tde second matrix
may be a
Secot~ particulate A surfa~etaut gray be appliwad to a pmrticulate by any
suitable known
rrnthod, preferably the cue~ra~at is Spr~yCd onto the particulate. In a
preferred aspect
the first matrix is the comprreaSed portion and the Socottd matri~t is tire
non-conspresscd
portion of the detQrggtnt tablet of ttte prasettt invention. Fraferably the
low cloud point
stufactarit is present in the cotapressed portion and the high cloud point
eurfaotatit is
present in the non-comb portion of the data~gant tablet of the present
invtntian.
In a preferred aspect of tine t faveution, the non-~co;aprosred pordQa
~ompri~es a
rinse aid. By rinse aid it is meant a composition that is delivered in the
rinse cycle of the
automatic dishwasl~r and provide izxtproved drainage of water sad reduced Spot
and film
forutatian on dishes.
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/25074
53
The rinse aid composition for use herein may comprise any of the components
commonly found as components of rinse aid compositions, for example nonionic
surfactants (described above), hydrotropes, solvent and a source of acidity.
Suitable hydrotropes include sodium, potassium and ammonium xylene sulfonates,
toluene sulfonate, cumene sulfonates and mixtures thereof. Hydrotrope is
typically
present at a level of from 0.5% to 20% by weight, preferably 1 % to 10% by
weight of the
rinse aid composition.
The rinse aid composition may contain one or more solvent at levels of from 1
% to 30%
by weight, preferably from 3% to 25% by weight, more preferably from S% to 20%
by
weight of the rinse aid composition, particularly when in liquid or gel form.
Suitable
solvents for use herein include the organic solvent having the general formula
RO(CH2C(Me)HO)nH, wherein R is an alkyl, alkenyl, or alkyl aryl group having
from
1 to 8 carbon atoms, and n is an integer from 1 to 4. Preferably, R is an
alkyl group
containing 1 to 4 carbon atoms, and n is 1 or 2. Especially preferred R groups
are n-
butyl or isobutyl. Preferred solvents of this type are 1-n-butoxypropane-2-of
(n=1);
and 1(2-n-butoxy-1-methylethoxy)propane-2-of (n=2), and mixtures thereof.
Other solvents useful herein include the water soluble CARBITOL solvents or
water-
soluble CELLOSOLVE solvents. Water-soluble CARBITOL solvents are compounds
of the 2-(2 alkoxyethoxy~thanol class wherein the alkoxy group is derived from
ethyl,
propyl or butyl; a preferred water-soluble carbitol is 2-(2-
butoxyethoxy~thanol also
known as butyl carbitol. Water-soluble CELLOSOLVE solvents are compounds of
the
2-allcoxyethoxy ethanol class, with 2-butoxyethoxyethanol being preferred.
Other suitable solvents are benryl alcohol, and diols such as 2-ethyl-1,3-
hexanediol and
2,2,4-trimethl-1,3-pentan'ediol.
The low molecular weight, water-soluble, liquid polyethylene glycols are also
suitable
solvents for use herein.
The alkane mono and diols, especially the C1-C6 alkane mono and diols are
suitable
for use herein. C1-C4 monohydric alcohols (eg: ethanol, propanol, isopropanol,
butanol and mixtures thereof] are preferred, with ethanol particularly
preferred. The
C1-C4 dihydric alcohols, including propylene glycol, are also preferred.
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/2507J
54
The pH of the rinse aid composition is preferably less than 7. The pH is
adjusted by
incorporating a source of acidity for example inorganic or organic acids
including for
example carboxylate acids (e.g. citric acid or succinic acid), polycarboxylate
acids (e.g.
polyacrylic acid), acetic acid, boric acid, malonic acid, adipic acid, fumaric
acid, lactic
acid, glycolic aicd, tartaric acid, tartronic acid, malefic acid, derivatives
and mixtures
thereof. A preferred acidity source is citric acid.
The rinse aid composition may also comprise other components such as builders,
co-
builders and other polymeric compounds (described above), especially
polyethylene
glycol (PEG), polyvinyl pyrrolidone, polyacrylate (especially those described
in US 5
240 632), polymethacrylate and copolymers thereof, acrylonitrile.
Process
As described above, the detergent tablets described herein are prepared by
separately
preparing the composition of finishing additives and/or 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 comprises at least one, but preferably more than one
detergent
component. The compressed portion is prepared by pre-mixing at least one, but
preferably a mixture of detergent components and/or optional carrier
components to form
a composition. Any pre-mixing will be carried out in a suitable mixer; for
example a pan
mixer, mtary 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. In 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.
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/25074
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
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 a finishing additive, but may also
optionally
comprise one or more detergent components. The components of the non-
compressed
portion are pre-mixed using any known suitable mixing equipment. In addition
the non-
compressed portion may optionally comprise a carrier
with which the finishing additive and optional 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 ete. 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.
It is also envisaged that the compressed portion may be prepared .having a
plurality of
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/25074
~6
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.
Detergent Components
The compressed portion of the detergent tablets described herein are prepared
by
compression composition of at least one, but preferably a mixture of detergent
components. A suitable pre-mixed composition may include a variety of
different
detergent active components including builder compounds, surfactants, enzymes,
bleaching agents (both oxygen releasing and chlorine), alkalinity sources,
coIourants,
perfume, lime soap dispersants, organic polymeric compounds including
polymeric dye
transfer inhibiting agents, crystal growth inhibitors, co-builders, metal ion
salts, enzyme
stabilisers, corrosion inhibitors, suds suppressers, solvents, fabric
softening agents,
optical brighteners and hydrotropes.
Highly preferred detergent components of the compressed portion include a
builder
compound, a surfactant, enzyme and bleaching agent.
Builder compound
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.
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
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/25074
57
although monomeric polycarboxylates are generally preferred for reasons of
cost and
performance.
Suitable carboxylates containing one carboxy group include the water soluble
salts of
lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates
containing
two carboxy groups include the water-soluble salts of succinic acid, malonic
acid,
(ethylenedioxy) diacetic acid, malefic acid, diglycolic acid, tartaric acid,
tartronic acid
and fumaric acid, as well as the ether carboxylates and the 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.
Alicyclic and heterocyclic polyearboxylates 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 - hexacarboxylates and
carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol
and
xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid
and the
phthalic acid derivatives disclosed in British Patent No. 1,425,343.
Of the above, the preferred polycarboxylates are hydmxycarboxylates 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 citratelcitric acid
mixtures are also
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/2507.t
58
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.
Specific examples of water-soluble phosphate builders are the alkali metal
tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and
potassium and ammonium pyrophosphate, sodium and potassium orthophosphate,
sodium polymeta/phosphate in which the degree of polymerization ranges from 6
to
21, and salts of phytic acid.
Partially soluble or insoluble builder compound
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
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/25074
59
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-3417649 and DE-A-3742043. For the purpose of the present invention, x in
the general formula above has a value of 2,3 or 4 and is preferably 2.
The most preferred crystalline layered sodium silicate compound has the
formula 8-
Na2Si205 , known as NaSKS-6 (trade name), available from Hoechst AG.
The crystalline layered sodium silicate material is preferably present in
granular
detergent compositions as a particulate in intimate admixture with a solid,
water-
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 0.5 and x is at least 5, preferably from 7.5 to 276,
more
preferably from 10 to 264. The aluminosilicate material are in hydrated form
and are
preferably crystalline, containing from 10% to 28%, more preferably from 18%
to
22% water in bound form.
The aluminosilicate zeolites can be naturally occurring materials, but are
preferably
synthetically derived. Synthetic crystalline aluminosilicate ion exchange
materials are
available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X,
Zeolite HS
and mixtures thereof.
A preferred method of synthesizing aluminosilicate zeolites is that described
by
Schoeman et al (published in Zeolite (1994) 14(2), 110-116), in which the
author
describes a method of preparing colloidal aluminosilicate zeolites. The
colloidal
aluminosilicate zeolite particles should preferably be such that no more than
5% of the
particles are of size greater than 1 ~m in diameter and not more than 5% of
particles
are of size less then 0.05 ~cn in diameter. Preferably the aluminosilicate
zeolite
particles have an average particle size diameter of between 0.01 ~m and 1 Vim,
more
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/25074
preferably between 0.05 um and 0.9 p.m, most preferably between 0.1 p,m and
0.6 Vim.
Zeolite A has the formula
Na 12 [A102) I2 (Si02)I2J~ X20
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6
[(A102)g6(Si02)106J~ 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 fording 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 preferably from I
% to
5% by weight of the composition of active detergent components.
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/2507d
61
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.
Nonionic Surfactant
Suitable nonionic surfactants are described above.
Anionic surfactant
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 prefern~ed.
Other anionic surfactants include the isethionates such as the acyl
isethionates, N-acyl
taurates, fatty acid amides of methyl tauride, alkyl succinates and
sulfosuccinates,
monoesters of sulfosuccinate (especially saturated and unsaturated C 12-C 18
monoesters) diesters of sulfosuccinate (especially saturated and unsaturated
C6-C 14
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 surfactant
Anionic sulfate surfactants suitable for use herein include the linear and
branched
primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl
glycerol
sulfates, alkyl phenol ethylene oxide ether sulfates, the CS-C 17 acyl-N-(C 1-
C4 alkyl)
and -N-{C1-C2 hydroxyalkyl) glucamine sulfates, and sulfates of
alkylpolysaccharides
such as the sulfates of allcylpolyglucoside (the nonionic nonsulfated
compounds being
described herein).
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98~ZSO~s
62
Alkyl sulfate surfactants are preferably selected from the linear and branched
primary
C 1 p-C 1 g alkyl sulfates, mare preferably the C 11-C 15 branched chain alkyl
sulfates
and the C 12-C 14 linear chain alkyl sulfates.
AIkyl 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 ~kYl 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 surfactant
Anionic sulfonate surfactants suitable for use herein include the salts of CS-
C20 linear
aIkylbenzene 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 carboxvlate surfactant
Suitable anionic carboxylate surfactants include the alkyl ethoxy
carboxylates, the
alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl
carboxyls'),
especially certain secondary soaps as described herein.
Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH20)x
CH2C00-M+ wherein R is a C6 to C 1 g allryl 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 ration. 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, R 1 and R2 are selected from the
group
consisting of hydrogen, methyl acid radical, succinic acid radical,
hydroxysuccinic acid
CA 02311517 2000-OS-25
WO 99/27067 PCTIUS98/25074
63
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-I-decanoic acid, 2-
propyl-
I-nonanoic acid, 2-butyl-I-octanoic acid and 2-pentyl-I-heptanoic acid.
Certain
soaps may also be included as suds suppressors.
Alkali metal sarcosinate surfactant
Other suitable anionic surfactants are the alkali metal sarcosinates of
formula R-CON
(RI) CI~i2 COOM, wherein R is a CS-C17 linear or branched alkyl or alkenyl
group,
R 1 is a C I -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 surfactant
Suitable amphoteric surfactants for use herein include the amine oxide
surfactants and
the alkyl amphocarboxylic acids.
Suitable amine oxides include those compounds having the formula
R3(OR4~N0(R5~ wherein R3 is selected from an alkyl, hydroxyallryl,
acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from
8 to
26 carbon atoms; R4 is an alkylene or hydroxyallcylene 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 gmups. Preferred are C I p-C I g
alkyl
dimethylamine oxide, and C 10.18 ~Yl~do alkyl dimethylamine oxide.
A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Conc.
manufactured by Miranol, Inc., Dayton, NJ.
Zwitterionic surfactant
CA 02311517 2000-OS-25
WO 99127067 PCT/US98/250'.l
64
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-Clg hydrocarbyl group, each Rl is typically Cl-C3 alkyl, and R2 is a
Cl-
CS hydrocarbyl group. Preferred betaines are C 12_ 1 g dimethyl-ammonio
hexanoate
and the C10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
Complex betaine surfactants are also suitable for use herein.
Cationic surfactants
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 16, preferably C6-C 1 p N-alkyl or alkenyl ammonium surfactants
wherein the remaining N positions are substituted by methyl, hydroxyethyl or
hydroxypropyl groups.
Water-soluble sulfate salt
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.
CA 02311517 2000-05-25
WO 99/27067 PCT/US98/25074
Alkali Metal Silicate
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 Si02 : Na20
ratio of 1Ø The weight ratio of said sodium silicate to said sodium
metasilicate,
measured as Si02, is preferably from 50:1 to 5:4, more preferably from 15:1 to
2:1,
most preferably from 10:1 to 5:2.
Colourant
The term 'colourant', as used herein, means any substance that absorbs
specific
wavelengths of light from the visible light spectrum. Such colourants when
added to
a detergent composition have the effect of changing the visible colour and
thus the
appearance of the detergent composition. Colourants may be for example either
dyes
or pigments. Preferably the colourants are stable in composition in which they
are to
be 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.
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/250~4
66
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 BRILLIANT
BLUE (tradename) both available from Pointings, UK, ULTRA hZARINE BLUE
(tradename) available from Holliday or LEVAFIX TURQUISE BLUE EBA
(tradename) available from Bayer, USA.
The coIourant 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 dnim.
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 I .0%, most
preferably from
0. I % 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 0.005% 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%.
Corrosion inhibitor comb
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/25074
67
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.
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 ~i,(3'-
dihydroxyisobutyric acid. Examples of suitable polycarboxylic acids include: n-
butyl-
malonic acid, isocitric acid, citric acid, malefic acid, malic acid and
succinic acid.
The fatty alcohol radical in the fatty ester can be represented by mono- or
poiyhydric
alcohols having firom 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,
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/2507.t
68
sucrose, erythritol, pentaerythritol, sorbitol or sorbitan.
Preferably, the fatty acid and/or fatty alcohol group of the fatty ester
adjunct material
have from 1 to 24 carbon atoms in the alkyl chain.
Preferred fatty esters herein are ethylene glycol, glycerol and sorbitan
esters wherein
the fatty acid portion of the ester normally comprises a species selected from
behenic
acid, stearic acid, oleic acid, palmitic acid or myristic acid.
The glycerol esters are also highly preferred. These are the mono-, di- or tri-
esters of
glycerol and the fatty acids as defined above.
Specific examples of fatty alcohol esters for use herein include: stearyl
acetate,
palmityl di-lactate, cocoyl isobutyrate, oleyl maieate, 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.
Suitable vegetable oils include soy bean oil, cotton seed oil, castor oil,
olive oil,
peanut oil, safflower oil, sunflower oil, rapeseed oil, grapeseed oil, palm
oil and corn
oil.
Waxes, including microcrystalline waxes are suitable organic silver coating
agents
herein. Preferred waxes have a melting point in the range from 35°C to
110°C and
comprise generally from 12 to 70 carbon atoms. Preferred are petroleum waxes
of
the paraffin and microcrystalline type which are composed of long-chain
saturated
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/:507.1
69
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 50; preferred paraffin oil selected from predominantly branched C25_45
species
with a ratio of cyclic to noncyclic hydrocarbons of from 1:10 to 2:1,
preferably from
1:5 to 1:1. A paraffin oil meeting these characteristics, having a ratio of
cyclic to
noncyclic hydrocarbons of 32:68, is sold by Wintershall, Salzbergen, Germany,
under
the trade name WINOG 70.
Nitrogen-containinp~corrosion inhibitor compounds
Suitable nitrogen-containing corrosion inhibitor compounds include imidazole
and
derivatives thereof such as benzimidazole, 2-heptadecyl imidazole and those
imidazole
derivatives described in Czech Patent No. 139, 279 and British Patent GB-A-
1,137,741, which also discloses a method for making imidazole compounds.
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98125074
7~
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 R l , R3, R4 and RS where
R 1 is any
of H, CH20H, CONH3, or COCH3, R3 and R5 are any of CI-C20 alkyl or hydroxyl,
and R4 is any of H, NH2 or N02.
Other suitable nitrogen-containing corrosion inhibitor compounds include
benzotriazole, 2-mercaptobenzothiazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole,
thionalide, morpholine, melamine, distearylamine, stearoyl stearamide,
cyanuric acid,
aminotriazole, aminotetrazole and indazole.
Nitrogen-containing compounds such as amines, especially distearylamine and
ammonium compounds such as ammonium chloride, ammonium bromide, ammonium
sulphate or diammonium hydrogen citrate are also suitable.
Mn(II) corrosion inhibitor compounds
The detergent tablets may contain as 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.
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 ligaad. In one
preferred aspect the organic ligand is a heavy metal ion sequestrant. In
another
preferred aspect the organic ligand is a crystal growth inhibitor.
Other corrosion inhibitor compounds
CA 02311517 2000-OS-25
WO 99/27067 PCTNS98/25074
71
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 l 0-C20 fatty acids, or their salts, especially aluminium
tristearate. The
C 12-C20 hydroxy fatty acids, or their salts, are also suitable. Phosphonated
octa-
decane and other anti-oxidants such as betahydroxytoluene (BHT) are also
suitable.
Copolymers of butadiene and malefic acid, particularly those supplied under
the trade
reference no. 07787 by Polysciences Inc have been found to be of particular
utility as
corrosion inhibitor compounds.
Hydrocarbon oils
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 50; preferred hydrocarbons
are
saturated and/or branched; preferred hydrocarbon oil selected from
predominantly
branched C25-45 sP~ies with a ratio of cyclic to noncyclic hydrocarbons of
from
1:10 to 2:1, preferably from 1:5 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 5%, most preferably from 0.1 %
to
1 % 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.
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/250'-t
72
Enzyme Stabilizin;~Svstem
Preferred 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 an enzyme stabilizing system. The enzyme stabilizing system can be any
stabilizing
system which is compatible with the detersive enzyme. Such stabilizing systems
can
comprise calcium ion, boric acid, propylene glycol, short chain carboxylic
acid,
boronic acid, chlorine bleach scavengers and mixtures thereof. Such
stabilizing
systems can also comprise reversible enzyme inhibitors, such as reversible
protease
inhibitors.
Lime soap dispersant compound
The compositions 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.
Suds su~nressinQ 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 die transfer inhibiting agents
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98125074
73
The detergent tablets herein may also comprise from 0.01 % to 10 %, preferably
from
0.0~% to 0.5% by weight of polymeric dye transfer inhibiting agents.
The polymeric dye transfer inhibiting agents are preferably selected from
polyamine
N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,
polyvinylpyrrolidonepolymers or combinations thereof.
Optical bri htener
The detergent tablets suitable for use in laundry washing methods as described
herein,
also optionally contain from 0.005% to S% by weight of certain types of
hydrophilic
optical brighteners.
Hydrophilic optical brighteners useful herein include those having the
structural
formula:
R, R2
N H H N
N O>-N O C C N N
/ N H H N
R2 S03M SG3M R~
wherein R1 is selected from aniiino, 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
canon such as sodium, the brighteaer is 4,4'; bis[(4-anilino-6-(N-2-bis-
hydroxyethyl)-
s-triazine-2-yl)amino]-2,2'-stilbeaedisulfonic acid and disodium salt. This
particular
brightener species is commercially marketed under the tradename Tinopai-LTNPA-
GX
by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic
optical
brightener useful in the detergent compositions herein.
When in the above formula, R 1 is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino
CA 02311517 2000-OS-25
WO 99/17067 PCT/LjS98/25074
74
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)aminoJ2,2'-stilbenedisulfonic acid
disodium salt. This particular brightener species is commercially marketed
under the
tradename Tinopal SBM-GX by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a cation
such as
sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-
yl)aminoJ2,2'-
stilbenedisulfonic acid, sodium salt. This particular brightener species is
commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy
Corporation.
Clav softening, s s
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.
Other optional ingredients
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.
pH of the com so_o itions
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
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/25074
portions are formulated to deliver different pH. In the rinse aid application
described
abobe, the compressed portion is formulated to deliver an alkaline pH whereas
the non-
compressed portion is formulated to deliver an acidic pH of less than 7,
preferably
between 0.5 and 6.5, most preferably between 1.0 and 5Ø
Machine dishwashingmethod
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 drtun 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.
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
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/250 7 J
76
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
ofthis
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.
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/25074
77
Examples
Abbreviations used in Examples
In the detergent compositions, the abbreviated component identifications have
the
following meanings:
STPP : Sodium tripolyphosphate
Citrate . Tri-sodium citrate dihydrate
Bicarbonate . Sodium hydrogen carbonate
Citric Acid : Anhydrous Citric acid
Carbonate : Anhydrous sodium carbonate
Silicate . Amorphous Sodium Silicate (Si02:Na20 ratio
= 1.6-
3.2)
PB 1 : Anhydrous sodium perborate monohydrate
PB4 : Sodium perborate tetrahydrate of nominal
formula
NaB02.3H20.H202
Nonionic : nonionic surfactant 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
TAED : Tetraacetyl ethylene diamine
HEDP : Ethane 1-hydroxy-1,1-diphosphonic acid
DETPMP : Diethyltriamine penta (methylene) phosphonate,
marketed by monsanto under the tradename bequest
2060
PAAC . Pentaamine acetate cobalt (III) salt
Paraffin . Paraffin oil sold under the tradename Winog
70 by
Wintershall.
Protease . Proteolytic enzyme
Amylase . Amylolytic enzyme.
BTA : Benzotriazole
PA30 : Polyacrylic acid of average molecular weight
approximately 4,500
Sulphate . Anhydrous sodium sulphate.
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/2507~
78
PEG 4000 : Polyethylene Glycol molecular weight approximately
4000 available from Hoechst
PEG 8000 : Polyethylene Glycol molecular weight approximately
8000 available from Hoechst
Sugar : Household sucrose
Gelatine : Gelatine Type A, 65 bloom strength available from
Sigma
Starch : modified carboxy methyl cellulose sold under the
tradename Nimcel available from metcaserle
Dodecandioic acid : C 12 dicarboxylic acid
Triacetin : Glycerin triacetate sold under the tradename available
from
Thixatrol : Castor oil derivative sold under the tradename Thixatrol
sold by Rheox
PVP : Poly vinyl pyrrolidone having a molecular weight of
300,000
PEO : Polyethylene oxide having a molecular weight of 45,040
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:
Example 1
The compressed portion is prepared by delivering the composition of 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
a tablet
wherein the compressed portion has a mould. The non-compressed portion is
poured into
the mould of the compressed portion. For the purposes of Examples A to H the
non-
compressed portion comprises a gelling agent. Once the non-compressed portion
has
been delivered to the cavity the detergent tablet is subjected to a
conditioning step,
during which time the non-compressed portion hardens.
A B C D
Compressed portion
STPP 52.8 55.1 51.00 -
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/2507.1
79
Citrate - _- - 26.4
Carbonate 15.4 14.0 14.00 -
Silicate 12.6 14.8 15.00 26.4
Protease - 1.00 - -
Amylase 0.95 0.75 0.75 0.60
PB1 12.6 12.50 12.5 1.56
PB4 - - - 6.92
Nonionic 1.65 1.50 2.00 1.50
PAAC - 0.016 - O.OI2
TAED - - - 4.33
HEDP - - - 0.67
DETPMP - - - 0.65
Paraffin - 0.50 0.50 0.42
BTA - 0.30 0.30 0.24
PA30 - - - 3.20
Perfume 0.05 - - -
Sulphate - - - 24.0
Misc/water to balance
Weight (g) 20.0 20.0 20.5 20.0
Non-compressed portion
Protease 12.8 - 10.0 4.5
N76D/S 103A/V 104I - 8.0 - 4.5
1
Amylase2 - 13.0 - 5.0
Nonionic Surfactant 30.0 22.0 5.0 8.5
Cellulose Ether3 12.0 7.5 6.0 15.0
Dipropyleneglycol - - 50.0 40.0
butylether
Glycerol Triacetate 34.0 34.0 - -
Thixatrol ST~ - - S.0 7.0
Polyethylene glycol4 4.0 2.0 - -
Metasilicate - - - 7.0
Silicate - 10.0 - -
Bleach5 _ - _ _
Misc/water
CA 02311517 2000-OS-25
WO 99/27067 PCT/CiS98/25074
Weight (g) 3.5 3.0 3.5 3.0
E F G H
Compressed portion
STPP 50.0 38.2 54.1
Citrate - - - 26.4
C arbonate 18.4 15 .0 14.0
Silicate 10.0 10.1 14.8 26.4
Protease - 1.00 -
Amylase 2.0 0.85 0.75 0.60
PB1 15.7 11.0 12.60 15.7
PB4 _ - _ -
Nonionic 0.80 0.5 1.50 0.80
PAAC - 0.008 0.016 -
TAED 1.30 - 1.30
HEDP - 0.92 - -
DETPMP - - - -
Paraffin - - 0.50 -
BTA - - 0.3 -
PA30 - - - -
Perfume 0.2 0.2 - 0.2
Sulphate 10.6 22.0 - 10.6
Misc/water to balance
Weight (g) 25.0 30.0 20.0 25.0
Non-compressed uortion
Protease - 4.0 - -
N76D/S 103A/V 104I 8.0 4.0 - -
1
Amylase2 - 13.0 - -
Nonionic Surfactant 15.0 0.5 10.0 2.0
Cellulose Ether3 3.0 0.5 9.0 1.5
Dipropyleneglycol - 35.0 50.0 -
butylether
Glycerol Triacetate 44.0 - - 38.0
CA 02311517 2003-O1-29
81
Thixatrol sr~ a.a . - s.oo 4.0
Poi echylonc lyaol4- 3.0 - -
Merasiiicate ~ - 40.0 - _
Silicate 26.0 - . - 28.0
BieaGhs - 5.0 25.0
Miter
~Veaght (g 5.0 5.0 Z.3 4.0
1 As disclosed in U.S. 3,677,22.
2 w~y~ ~ a~io~:d » wo~rz~~~3 ana is
o>ytained firom an alkalophilic Baccfllus species having a N-tatni~aa sequmue
of Hie-His-
A~nn-(31y-Thr-Asn-CSly-Thr-Met-Mct-G!n-Tyr-Phe-(31v-Trp-Tyr-Lcu-fro Asn-Asp.
3 sClected from sodium carboxy methyl cailuiose, methyl aelialose, hydroxy
ethyl
~~tluios. sad hydmxy propyl cellulc~sa and mixed ethors e.g.
hydxoxypropylmethylcellulose..
4 MW 4,000-8.000.
5 NaDCC, Sodium pare ~ ~ ae or sodium per carbonate.
CA 02311517 2000-OS-25
WO 99/27067 PCT/US98/2507.t
82
Example 2
The compressed portion is prepared by delivering the composition of detergent
components to a punch cavity of a modif ed 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 Examples I to
K the
non-compressed portion is in particulate form. The non-compressed portion is
then
poured into the mould of the compressed and coated with a coating layer. For
the
purposes of Example L to N the non-compressed portion comprises a binding
agent. The
non-compressed portion is poured into the mould of the compressed portion and
then
subjected to a conditioning step, during which time the non-compressed portion
hardens.
I J K L M N
Compressed portion
STPP 55.10 52.0 50.00 55.10 52.0 52.80
Citrate - - _
Carbonate 14.0 16.0 18.40 14.0 16.0 15.40
Silicate 14.80 15.0 10.00 14.80 15.0 12.60
Protease - - - 1.0
Amylase 0.75 0.75 2.0 0.75 0.75 0.95
PB 1 12.50 12.20 15.70 12.50 12.20 12.60
PB4 - - - -
Nonionic 1.5 1.50 0.80 1.5 1.50 1.65
PAAC 0.016 0.016 - 0.016 0.016 0.012
TAED - 1.30 -
HEDP _ _ _ _ -
DETPMP - -
Paraff'ln 0.50 0.5 0.50 0.50 0.5 0.55
BTA 0.30 0.3 0.33 0.30 0.3 0.33
PA30 - - - - -
Perfume - - 0.20 - - 0.05
Sulphate - 2.00 10.68 2.00 -
Misc/water to balance
Weight (g) 20.Og 20.Og 20.Og 22.Og 20.Og
CA 02311517 2000-OS-25
WO 99/27067
83
PCT/LJS98/25074
Non-compressed portion
Protease 7.00 8.40 5.00 - 12.1 8.3
Amylase 6.80 5.00 9.30 15.00 12.4 10.00
Bicarbonate 16.00 18.00 - 12.1 - 15.00
Citric acid 12.30 15.00 10.00 12.50
PEG 4000 4.00 - _ _ - -
PEG 8000 - 5.50 - _ _ _
PVP - - - 8.00 - -
PEO - - - 2.00 - _
Sugar - - 55.00 - 53.00 -
Gelatine - - 5.00 - 7.00 -
Starch - - 10.00 - - _
Water - - 10.00 - 10.00 -
Triacetin 42.00 45.00 - 51.00 - 45.00
Thixatrol 5.00
Misc./balance
Weight (g) 2.Sg 4.Og 2.Sg 2.Sg 3g S.Og
--
Coating Layer
odecandioic acid 90.00 82.00 - - _
Starch 10.00 10.00 - _ -
PEG _ 1~ -
Weight (g) 1.00 1.00 0.5 - _ _
~ Total weight (g) 23.Sg 25g 23.Og 22.Sg 25g 25g
of tablet ~ ~ ~ ~ ~
