Note: Descriptions are shown in the official language in which they were submitted.
CA 02333388 2003-12-23
MULTI-PHASE DETERGENT TABLET
Technical Field
The present invention relates to multi-phase detergent tablets.
Back rg_ound
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 dosing, 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
any
suitable equipment, preferably a tablet press. Tablets are typically formed by
compression of the components of the detergent composition so that the tablets
produced
are sufficiently robust to be able to withstand handling and transportation
without
sustaining damage. In addition to being robust, tablets must also dissolve
sufficiently
fast so that the detergent components are released into the wash water as soon
as possible
at the beginning of the wash cycle.
However, a dichotomy exists in that as compression force is increased, the
rate of
dissolution of the tablets is slower. The present invention therefore seeks to
find a
balance between tablet robustness and tablet dissolution.
Solutions to this problem, as seen in the prior art, have included compressing
the tablets
with low compression pressure. However tablets made in this way, although
having a
CA 02333388 2000-11-24
' .,
WO 00/04123 PCT/US99/14861
2
fast relative dissolution rate, tend to crumble, becoming damaged and
unacceptable to the
consumer. Other solutions have included preparing tablets using a high
relative
compression pressure, in order to achieve the required level of robustness,
and
comprising a dissolution aid, such as an effervescent agent.
Mufti-phase detergent tablets described in the prior art are prepared by
compressing a
first composition in a tablet press to form a substantially planar first
Layer. A further
detergent composition is then delivered to the tablet press on top of the
first layer. This
second composition is then compressed to form another substantially planar
second
layer. Thus the first layer is generally subjected to more than one
compression as it is
also compressed during the compression of the second composition. Typically
the first
and second compression forces are in the same order of magnitude. The
Applicant has
found that where this is the case, because the compression force must be
sufficient to
bind the first and second compositions together, the force used in both the
first and
second compression steps must be in the range of from about 4,000 to about
20,000 kg
(assuming a tablet cross-section of about 10 cm'). A consequence of this is a
slower rate
of tablet dissolution. Other mufti-phase tablets exhibiting differential
dissolution are
prepared such that the second layer is compressed at a lower force than the
first layer.
However, although the dissolution rate of the second layer is improved, the
second layer
is soft in comparison to the first layer and is therefore vulnerable to damage
caused by
handling and transportation.
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
slowing
the rate of dissolution of the lavatory block, the document teaches admixing
one or more
solubility control agents. Examples of such solubility control agents are
paradichlorobenzene, waxes, long chain fatty acids and alcohols and esters
thereof and
fatty alkylamides. Detergent tablets for use in laundry or automatic
dishwashing must
CA 02333388 2000-11-24
WO 00/04123 PCT1US99/14861
substantially dissolve within one cycle of the washing or dishwashing machine,
i.e.
within 15 to 120 minutes.
Summary of the Invention
According to a first aspect of the invention, there is provided a mufti-phase
detergent
tablet for use in a washing machine, the tablet comprising:
a) a first phase in the form of a shaped body having at least one mould
therein; and
b) a second phase in the form of a particulate solid compressed within said
mould.
In preferred embodiments, the first phase is a compressed shaped body prepared
at an
applied compression pressure of at least about 40 kg/ cmz , preferably at
least about 250
kg/ cm2, more preferably at least about 350 kg/cm2 (3.43 kN/cm2), even more
preferably
from about 400 to about 2000, and especially from about 600 to about 1200
kg/cm2
(compression pressure herein is the applied force divided by the cross-
sectional area of
the tablet in a plane transverse to the applied force - in effect, the
transverse cross-
sectional area of the die of the rotary press). It is also preferred that the
particulate solid
of the second phase (which terminology is intended to include the possibility
of multiple
'second' phases, sometimes referred to herein as 'optional subsequent phases')
be
compressed into said mould at an applied compression pressure less than that
applied to
the first phase and preferably at a compression pressure of less than about
350 kg/cm2,
preferably in the range from about 40 kg/cm' to about 300 kg/cmz and more
preferably
from about 70 to about 270 kg/cmz, such tablets being preferred herein from
the
viewpoint of providing optimum tablet integrity and strength (measured for
example by
the Child Bite Strength [CBS] test) and product dissolution characteristics.
The tablets
of the invention preferably have a CBS of at least about 6kg, preferably
greater than
about 8kg, more preferably greater than about l Okg, especially greater than
about 12kg,
and more especially greater than about l4kg, CBS being measured per the US
Consumer
Product Safety Commission Test Specification. Also, the compression pressures
applied
CA 02333388 2000-11-24
WO 00/04123 PCTNS99/14861
4
to the first and second phases will generally be in a ratio of at least about
1.2:1,
preferably at least about 2:1, more preferably at least about 4:1.
Thus, according to a further aspect of the invention, there is provided a
mufti-phase
detergent tablet for use in a washing machine, the tablet comprising:
a) a first phase in the form of a compressed shaped body having at least one
mould therein, the shaped body being prepared at a compression pressure of at
least
about 350 kg/cm2; and
b) a second phase in the form of a particulate solid compressed within said
mould, the
second phase being compressed at a pressure of less than about 350 kg/cmz.
In other preferred embodiments, the second phase is in the form of a
compressed or
shaped body adhesively contained, for example by physical or chemical
adhesion,
within the at least one mould of the first body. It is also preferred that the
first and
second phases are in a relatively high weight ratio to one another, for
example at least
about 6:1, preferably at least about 10:1; also that the tablet composition
contain one or
more detergent actives (for example enzymes, bleaches, bleach activators,
bleach
catalysts, surfactants, chelating agents etc) which is predominantly
concentrated in the
second phase, for example, at least about 50%, preferably at least about 60%,
especially
about 80% by weight of the active (based on the total weight of the active in
tablet) is in
the second phase of the tablet. Again, such compositions are optimum for
tablet strength,
dissolution, cleaning, and pH regulation characteristics providing, for
example, tablet
compositions capable of dissolving in the wash liquor so as to deliver at
least 50%,
preferably at least 60%, and more preferably at least 80% by weight of the
detergent
active to the wash liquor within 10, 5, 4 or even 3 minutes of the start of
the wash
process.
Thus, according to another aspect of the invention, there is provided a mufti-
phase
detergent tablet for use in a washing machine, the tablet comprising:
a) a first phase in the form of a shaped body having at least one mould
therein, and
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/14861
b) a second phase in the form of a particulate solid compressed within said
mould ,
and wherein the tablet comprises at least one detergent active and is
formulated such that
at least 50%, preferably at least 60%, more preferably at least 80% by weight
of the
detergent active is delivered to the wash within the first 10 minutes,
preferably within the
first S minutes, and more preferably within the first 3 minutes of the wash
process.
An additional benefit of the invention is the ability to achieve differential
dissolution of
the phases, such that one phase of the tablet will dissolve significantly
before another
phase, and may even dissolve essentially completely before the other phase has
dissolved. This is particularly valuable for the differential delivery of
detergent actives.
Thus, according to another aspect of the invention, there is provided a mufti-
phase
detergent tablet comprising:
a) a first phase in the form of a shaped body having at least one mould
therein; and
b) a second phase in the form of a compressed body adhesively contained within
said
mould, and wherein the tablet composition comprises one or more detergent
actives
which is predominantly concentrated in the second phase, and wherein the
second
phase additionally comprises a disrupting agent.
According to a further aspect of the invention there is provided a mufti-phase
detergent
tablet comprising:
a) a first phase in the form of a shaped body having at least one mould
therein; and
b) a second phase in the form of a compressed body adhesively contained within
said
mould, wherein the tablet composition comprises one or more detergent actives
which is
predominantly concentrated in the second phase, and wherein the second phase
additionally comprises a binder.
CA 02333388 2003-12-23
Suitably, the one or more detergent actives are selected from enzymes,
bleaches, bleach
activators, bleach catalysts. surfactants, chelating agents, crystal growth
inhibitors and
mixtures thereof, the enzyme actives being particularly preferred for boosting
cleaning
performance during the very initial cool-water stage of the washing or
cleaning
operation. Highly preferred for use herein, therefore, are enzyme detergent
actives and
especially enzymes and enzyme mixtures comprising one or more enzymes having
enhanced or optimum activity in the temperature range from 25°C to
55°C and at a pH
value in the range of 8 to 10 (e.g. Natalase).
Thus, according to a yet another aspect of the invention, there is provided a
multi-phase
detergent tablet comprising:
a) a first phase in the form of a shaped body having at least one mould
therein; and
b) a second phase in the form of a compressed body adhesively contained within
said
mould, and wherein the second phase additionally comprises an enzyme.
Detailed Description of the Invention
It is an object of the present invention to provide a detergent tablet that is
not only
sufficiently robust to withstand handling and transportation, but also at
least a significant
portion of which dissolves rapidly in the wash water providing rapid delivery
of
detergent active. It is preferred that at least one phase of the tablet
dissolves in the wash
water within the first ten minutes, preferably five minutes, more preferably
four minutes
of the wash cycle of an automatic dishwashing or laundry washing machine.
Preferably
the washing machine is either an automatic dishwashing or laundry washing
machine.
The time within which the mufti-phase tablet or a phase thereof or a detergent
active
component dissolves is determined according to DIN 44990 using a dishwashing
machine available from Bosc~h on the normal 65°C washing program with
water hardness
at I8°H using a minimum of six replicates or a sufficient number to
ensure
reproducibility.
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/14861
7
The mufti-phase detergent tablet of the present invention comprises a first
phase, a
second and optionally subsequent phases. The first phase is in the form of a
shaped body
of detergent composition comprising one or more detergent components as
described
below. Preferred detergent components include, builder, bleach, enzymes and
surfactant.
The components of the detergent composition are mixed together by, for example
admixing dry components or spraying-on liquid components. The components are
then
formed into a first phase using any suitable equipment, but preferably by
compression,
for example in a tablet press. Alternatively, the first phase can be prepared
by extrusion,
casting, etc. The first phase can take a variety of geometric shapes such as
spheres,
cubes, etc but preferred embodiments have a generally axially-symmetric form
with a
generally round, square or rectangular cross-section.
The first phase is prepared such that it comprises at least one mould in the
surface of the
shaped body. The mould or moulds can also vary in size and shape and in their
location,
orientation and topology relative to the first phase. For example, the mould
or moulds
can be generally circular, square or oval in cross-section; they can form an
internally-
closed cavity or recess in the surface of the shaped body, or they can extend
between
unconnected regions of the body surface (for example axially-opposed facing
surfaces) to
form one or more topological 'holes' in the shaped body; and they can be
axially or
otherwise symmetrically-disposed relative to the first phase or they can be
asymmetrically disposed. In a preferred embodiment the mould is created using
a
specially designed tablet press wherein the surface of the punch that contacts
the
detergent composition is shaped such that when it contacts and presses the
detergent
composition it presses a mould, or multiple moulds into the first phase of the
mufti-phase
detergent tablet. Preferably, the mould will have an inwardly concave or
generally
concave surface to provide improved adhesion to the second phase.
Alternatively, the
mould can be created by compressing a preformed body of detergent composition
disposed annularly around a central dye, thereby forming a shaped body having
a mould
in the form of a cavity extending axially between opposing surfaces of the
body.
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/14861
8
The tablets of the invention also include one or more additional phases
prepared from a
composition or compositions which comprise one or more detergent components as
described below. At least one phase (herein referred to as a second phase)
preferably
takes the form of a particulate solid (which term encompasses powders,
granules,
agglomerates, and other particulate solids including mixtures thereof with
liquid binders,
meltable solids, spray-ons, etc) compressed into/within the one or more moulds
of the
first phase of the detergent tablet such that the second phase itself takes
the form of a
shaped body. Optional further phases include one or more compositions in the
form a
separate layer or layers. Preferred detergent components include builders,
colourants,
binders, surfactants, disrupting agents and enzymes, in particular amylase and
protease
enzymes. In another preferred aspect of the present invention the second and
optionally
subsequent phases comprise a disrupting agent that may be selected from either
a
disintegrating agent or an effervescent agent. Suitable disintegrating agents
include
agents that swell on contact with water or facilitate water influx and/or
efflux by forming
channels in the detergent tablet. Any known disintegrating or effervescing
agent suitable
for use in laundry or dishwashing applications is envisaged for use herein.
Suitable
disintegrating agent include starches (such as natural, modified, and
pregelatinized
starches, eg those derived from corn, rice and potato starch), starch
derivatives such as U-
Sperse (tradename), Primojel (tradename) and Explotab (tradename), celluloses,
microcrystalline celluloses and cellulose derivatives such as Arbocel
(tradename) and
Vivapur (tradename) both available from Rettenmaier, Nymcel (tradename)
available
from Metsa-serla , Avicel (tradename), Lattice NT (tradename) and Hanfloc
(tradename),
alginates, acetate trihydrate, burkeite, monohydrated carbonate formula
Na2C03.H20,
hydrated STPP with a phase I content of at least about 40% ,
carboxymethylcellulose
(CMC}, CMC-based polymers, sodium acetate, aluminium oxide. Suitable
effervescing
agents are those that produce a gas on contact with water. Suitable
effervesing agents
may be oxygen, nitrogen dioxide or carbon dioxide evolving species. Examples
of
preferred effervescent agents may be selected from the group consisting of
perborate,
CA 02333388 2000-11-24
,w , ,
WO 00/04123 PCT/US99/14861
9
percarbonate, carbonate, bicarbonate in combination with carboxylic or other
acids such
as citric, sulphamic, malic or malefic acid.
The components of the detergent composition are mixed together by for example
admixing dry components and admixing or spraying-on liquid components. The
components of the second and optionally subsequent phases are then fed into
and
retained within the mould provided by the first phase.
The preferred embodiment of the present invention comprises two phases; a
first and a
second phase. The first phase will normally comprise one mould and the second
phase
will normally consist of a single detergent active composition. However, it is
envisaged
that the first phase may comprise more than one mould and the second phase may
be
prepared from more than one detergent active composition. Furthermore, it is
also
envisaged that the second phase may comprise more than one detergent active
composition contained within one mould. It is also envisaged that several
detergent
active compositions are contained in separate moulds. In this way potentially
chemically
sensitive detergent components can be separated in order to avoid any loss in
performance caused by components reacting together and potentially becoming
inactive
or exhausted.
In a preferred aspect of the present invention the first, second and/or
optionally
subsequent phases may comprise a binder. Where present the binder is selected
from the
group consisting of organic polymers, for example polyethylene and/or
polypropylene
glycols, especially those of molecular weight 4000, 6000 and 9000, paraffins,
polyvinyl
pyrolindone (PVP), especially PVP of molecular weight 90 000, polyacrylates,
sugars
and sugar derivatives, starch and starch derivatives, for example hydroxy
propyl methyl
cellulose (HPMC) and carboxy methyl cellulose (CMC); and inorganic polymers,
such as
hexametaphosphate. The binder is valuable both for tablet integrity and to
help achieve
differential dissolution of the first and second phases as described below.
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/14861
In a preferred aspect of the present invention the first phase weighs greater
than about 3g,
preferably greater than about 4g, more preferably greater than about Sg. More
preferably
the first phase weighs from about lOg to about 30g, even more preferably from
about lSg
to about 25g and most preferably from about 18g to about 24g. The second and
optionally subsequent phases weigh less than 4g. More preferably the second
and/or
optionally subsequent phases weigh between about O.lg and about 3.Sg,
preferably
between about lg and about 3.Sg, most preferably from about 1.3g to about
2.Sg.
In another embodiment of the present invention, a barrier layer comprising a
barner layer
composition is located between the first and second phase and/or optionally
subsequent
phases or indeed between the second and optionally subsequent phases. The
barrier layer
composition comprises at least one binder selected from the group as described
above.
The advantage of the presence of a barrier layer is to prevent or reduce
migration of
components from one phase to another phase, for example from the first phase
into the
second and/or optionally subsequent phases and vice versa.
The components of the second and optionally subsequent phases are preferably
compressed at a very low compression force relative to compression force
normally used
to prepare tablets. Thus an advantage of the present invention is that because
a low
compression force is used heat, force or chemically sensitive detergent
components can
be incorporated into the detergent tablet without sustaining the consequential
loss in
performance usually encountered when incorporating such components into
tablets.
Alternatively, the second phase or phases can be compressed at the same or
higher
compression force than the first phase in order to achieve differential
dissolution of the
phases as described below.
A further advantage of the present invention is the improved protection of the
second
phase against damage caused by for example handling and transportation. As
described
above mufti-phase detergent tablets have been prepared where the second layer
is
compressed at a lower compression force than the first layer. However although
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/14861
11
improving dissolution rate, the second layer of these tablets becomes
vulnerable to
damage, tending to crumble or chip on contact. The lightly compressed phases)
of the
detergent tablets of the present invention however are protected within the
mould
provided by the first phase of the detergent tablet.
Yet another advantage of the present invention is the ability to prepare a
mufti-phase
detergent tablet wherein one phase can be designed to dissolve, preferably
significantly
before another phase. In the present invention it is preferred that the second
and
optionally subsequent phases) dissolves before the first phase. According to
the
preferred weight ranges described above, it preferable that the first phase
dissolves in
from 5 to 20 minutes, more preferably from 10 to 1 S minutes and the second
and/or
optionally subsequent phases dissolve in less than 5 minutes, more preferably
less than
4.5 minutes, most preferably less than 4 minutes. Alternatively, the second
phase can
dissolve after the first or other phases, for example, where it is desired to
deliver cleaning
or rinsing benefits towards the end of the washing operation. The time in
which the first,
second and/or optionally subsequent phase dissolve are independent from each
other.
Thus in a particularly preferred aspect of the present invention differential
dissolution of
the phases is achieved. A particular benefit of being able to achieve
differential
dissolution of the mufti-phase detergent tablet is that a component that is
chemically
inactivated by the presence of another component can be separated into a
different phase.
In this case the component that is inactivated is preferably located in the
second and
optionally subsequent phase(s).
Yet another advantage of the present invention is the improved adherence
between the
phases of the mufti-phase tablet. It is believed that the improved adherence
is achieved
by reducing exposure of the second phase in comparison to mufti-phase tablets
known in
the art, resulting in the tablets of the present invention being less
susceptible to fracture
along the line of contact between the phases.
Process
CA 02333388 2003-12-23
12
The multi-phase detergent tablets are prepared using any suitable tabletting
equipment,
e.g., a Courto~ 8253. Preferably the tablets are prepared by compression in a
tablet. press
capable of preparing a tablet comprising a mould. In a particularly preferred
embodiment of the present invention the first phase is prepared using a
specially
designed tablet press following the procedure described below. The punches) of
this
tablet press are modified so that the surface of the punch that contacts the
detergent
composition has a convex surface,
A first detergent composition is delivered into the die of the tablet press
and the punch is
lowered to contact and then compress the detergent composition to form a first
phase.
The first detergent composition is compressed using an applied pressure
generally of at
least about 250 kg/cmz, preferably between about 350 and about 2000 kg/cmZ,
more
preferably about 500 to about 1500 kg/cm2, most preferably about 600 to about
1200
kg/cmz. The punch is then elevated, exposing the first phase containing a
mould. A
second and optionally subsequent detergent compositions) is then delivered
into the
mould. The specially designed tablet press punch is then lowered a second time
to
lightly compress the second and optionally subsequent detergent compositions)
to form
the second and optionally subsequent phase(s). In another embodiment of the
present
invention where an optionally subsequent phase is present the optionally
subsequent
phase is prepared in an optionally subsequent compression step substantially
similar to
the second compression step described above. The second and optionally
subsequent
detergent compositions) is compressed at a pressure of preferably less than
about 350
kg/cmz, more preferably from about 40 to about 300 kg/cmZ, most preferably
from about
70 to about 270 kg/cm2. After compression of the second detergent composition,
the
punch is elevated a second time and the multi-phase detergent tablet is
ejected from the
tablet press.
Detergent Components
The first and second and or optionally subsequent phases of the mufti-phase
detergent
tablet described herein are prepared by compression of one or more
compositions
comprising detergent active components. Suitably, the compositions used in any
of
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/14861
13
these phases may include a variety of different detergent components including
builder
compounds, surfactants, enzymes, bleaching agents, alkalinity sources,
colourants,
perfume, lime soap dispersants, organic polymeric compounds including
polymeric dye
transfer inhibiting agents, crystal growth inhibitors, heavy metal ion
sequestrants, metal
ion salts, enzyme stabilisers, corrosion inhibitors, suds suppressers,
solvents, fabric
softening agents, optical brighteners and hydrotropes.
Highly preferred detergent components of the first phase include a builder
compound, a
surfactant, an enzyme and a bleaching agent. Highly preferred detergent
components of
the second phase include builder, enzymes, crystal growth inhibitors and
disrupting
agents and/or binders
Builder compound
The 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
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,
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/14861
14
(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 polycarboxylates include cyclopentane-cis,cis,cis-
tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-
tetrahydrofuran - cis, cis,
cis-tetracarboxylates, 2,5-tetrahydrofuran - cis - dicarboxylates, 2,2,5,5-
tetrahydrofuran -
tetracarboxylates, 1,2,3,4,5,6-hexane - 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 hydroxycarboxylates
containing up to
three carboxy groups per molecule, more particularly citrates.
The parent acids of the monomeric or oligomeric polycarboxylate chelating
agents or
mixtures thereof with their salts, e.g. citric acid or citrate/citric acid
mixtures are also
contemplated as useful builder components.
CA 02333388 2000-11-24
.,
WO 00/04123 PCT/US99/14861
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 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,
CA 02333388 2000-11-24 ,
WO 00/04123 PCT/US99/14861 _
16
in EP-A-0164514, DE-A-3417649 and DE-A-3742043. Preferred are the crystalline
layered sodium silicates of general formula
NaMSix02+1 ~YH20
wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number
from 0
to 20. Crystalline layered sodium silicates of this type preferably have a two
dimensional
'sheet' structure, such as the so called 8-layered structure, as described in
EP 0 164514
and EP 0 293640. Methods for preparation of crystalline layered silicates of
this type are
disclosed in DE-A-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
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/1~4861
17
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 p.m in diameter and not more than 5% of
particles are
of size less then 0.05 pm in diameter. Preferably the aluminosilicate zeolite
particles
have an average particle size diameter of between 0.01 ~m and 1 Vim, more
preferably
between 0.05 p.m and 0.9 p.m, most preferably between 0.1 p.m and 0.6 pm.
Zeolite A has the formula
Na 12 [A102) 12 (Si02) 12~- xH20
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6
[(A102)g6(Si02)106~- 276 H20. Zeolite MAP, as disclosed in EP-B-384,070 is a
preferred zeolite builder herein.
Preferred aluminosilicate zeolites are the colloidal aluminosilicate zeolites.
When
employed as a component of a detergent composition colloidal aluminosilicate
zeolites,
especially colloidal zeolite A, provide enhanced builder performance in terms
of
providing improved stain removal. Enhanced builder performance is also seen in
terms
of reduced fabric encrustation and improved fabric whiteness maintenance;
problems
believed to be associated with poorly built detergent compositions.
A surprising finding is that mixed aluminosilicate zeolite detergent
compositions
comprising colloidal zeolite A and colloidal zeolite Y provide equal calcium
ion
sequestration performance versus an equal weight of commercially available
zeolite A.
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/14861
18
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 1% to
5%
by weight of the composition of active detergent components.
A typical listing of anionic, nonionic, ampholytic and zwitterionic classes,
and species of
these surfactants, is given in U.S.P. 3,929,678 issued to Laughlin and Heuring
on
December, 30, 1975. A list of suitable cationic surfactants is given in U.S.P.
4,259,217
issued to Murphy on March 31,1981. A listing of surfactants typically included
in
automatic dishwashing detergent compositions is given for example, in EP-A-
0414 549
and PCT Applications No.s WO 93/08876 and WO 93/08874.
Nonionic surfactant
Essentially any nonionic surfactants useful for detersive purposes can be
included in the
detergent tablet. Preferred, non-limiting classes of useful nonionic
surfactants are listed
below.
CA 02333388 2000-11-24
,.
WO 00/04123 PCT/US99/14861
19
Nonionic ethoxylated 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 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)O]x[CH2CH20]y[CH2CH(OH)R2] (I)
wherein R1 is a linear or branched, aliphatic hydrocarbon radical having from
4 to 18
carbon atoms; R2 is a linear or branched aliphatic hydrocarbon radical having
from 2 to
26 carbon atoms; x is an integer having an average value of from 0.5 to 1.5,
more
preferably 1; and y is an integer having a value of at least 15, more
preferably at least
20.
Preferably, the surfactant of formula I, at least 10 carbon atoms in the
terminal epoxide
unit [CH2CH(OH)R2]. Suitable surfactants of formula I, according to the
present
invention, are Olin Corporation's POLY-TERGENT~ SLF-18B nonionic surfactants,
as
described, for example, in WO 94/22800, published October 13, 1994 by Olin
Corporation.
Ether-capped poly(oxyalkylatedl alcohols
CA 02333388 2000-11-24
..
WO 00/04123 PCTNS99/14861
Preferred surfactants for use herein include ether-capped poly(oxyalkylated)
alcohols
having the formula:
R 1 O[CH2CH(R3)O]x[CH2]kCH(OH) [CH2]j OR2
wherein R1 and R2 are linear or branched, saturated or unsaturated, aliphatic
or aromatic
hydrocarbon radicals having from 1 to 30 carbon atoms; R3 is H, or a linear
aliphatic
hydrocarbon radical having from 1 to 4 carbon atoms; x is an integer having an
average
value from 1 to 30, wherein when x is 2 or greater R3 may be the same or
different and k
and j are integers having an average value of from 1 to 12, and more
preferably 1 to 5.
R1 and R2 are preferably linear or branched, saturated or unsaturated,
aliphatic or
aromatic hydrocarbon radicals having from 6 to 22 carbon atoms with 8 to 18
carbon
atoms being most preferred. H or a linear aliphatic hydrocarbon radical having
from I to
2 carbon atoms is most preferred for R3. Preferably, x is an integer having an
average
value of from 1 to 20, more preferably from 6 to 15.
As described above, when, in the preferred embodiments, and x is greater than
2, R3 may
be the same or different. That is, R3 may vary between any of the alklyeneoxy
units as
described above. For instance, if x is 3, R3may be be selected to form
ethlyeneoxy(EO)
or propyleneoxy(PO) and may vary in order of (EO)(PO)(EO), (EO)(EO)(PO);
(EO)(EO)(EO); (PO)(EO)(PO); (PO)(PO)(EO) and (PO)(PO)(PO). Of course, the
integer three is chosen for example only and the variation may be much larger
with a
higher integer value for x and include, for example, mulitple (EO) units and a
much
small number of (PO) units.
Particularly preferred surfactants as described above include those that have
a low cloud
point of less than 20°C. These low cloud point surfactants may then be
employed in
CA 02333388 2000-11-24
.. ,
WO 00/04123 PCT/US99/14861
21
conjunction with a high cloud point surfactant as described in detail below
for superior
grease cleaning benefits.
Most preferred ether-capped poly(oxyalkylated) alcohol surfactants are those
wherein k
is 1 and j is 1 so that the surfactants have the formula:
R1 O[CH2CH(R3)O]xCH2CH(OH)CH20R2
where 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 R1 and R2 range from 9 to 14, R3 is H
forming
ethyleneoxy and x ranges from 6 to 15.
The ether-capped poly(oxyalkylated) alcohol surfactants comprise three general
components, namely a linear or branched alcohol, an alkylene oxide and an
alkyl ether
end cap. The alkyl ether end cap and the alcohol serve as a hydrophobic, oil-
soluble
portion of the molecule while the alkylene oxide group forms the hydrophilic,
water-
soluble portion of the molecule.
These surfactants exhibit significant improvements in spotting and filming
characteristics
and removal of greasy soils, when used in conjunction with high cloud point
surfactants,
relative to conventional surfactants.
Generally speaking, the ether-capped poly(oxyalkylene) alcohol surfactants 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:
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/14861
22
Preparation of C12/14 alkyl glycidyl ether
A C12/14 fatty alcohol (100.00 g, 0.515 mol.) and tin (IV) chloride (0.58 g,
2.23 mmol,
available from Aldrich) are combined in a 500 mL three-necked round-bottomed
flask
fitted with a condenser, argon inlet, addition funnel, magnetic stirrer and
internal
temperature probe. The mixture is heated to 60 °C. Epichlorhydrin
(47.70 g, 0.515 mol,
available from Aldrich) is added dropwise so as to keep the temperature
between 60-65 °
C. After stirring an additional hour at 60 °C, the mixture is cooled to
room temperature.
The mixture is treated with a 50% solution of sodium hydroxide (61.80 g, 0.773
mol,
50%) while being stirred mechanically. After addition is completed, the
mixture is
heated to 90 °C for 1.5 h, cooled, and filtered with the aid of
ethanol. The filtrate is
separated and the organic phase is washed with water ( 100 mL), dried over
MgS04,
filtered, and concentrated. Distillation of the oil at 100-120 °C (0.1
mm Hg) providing
the glycidyl ether as an oil.
Preparation of C12/14 a1~9/11 ether capped alcohol surfactant
Neodol~ 91-8 (20.60 g, 0.0393 mol ethoxylated alcohol available from the Shell
chemical Co.) and tin (IV) 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 alkyl glycidyl ether (11.00 g, 0.0393 mol) is added dropwise over
15 min.
After stirring for 18 h at 60 °C, the mixture is cooled to room
temperature and dissolved
in an equal portion of dichloromethane. The solution is passed through a 1
inch pad of
silica gel while eluting with dichloromethane. The filtrate is concentrated by
rotary
evaporation and then stripped in a kugelrohr oven ( 100 °C, 0.5 mm Hg)
to yield the
surfactant as an oil.
Nonionic ethox Iy ated/~ropoxylated fatty alcohol surfactant
The ethoxylated C6-C 1 g fatty alcohols and C6-C 1 g mixed
ethoxylated/propoxylated
fatty alcohols are suitable surfactants for use herein, particularly where
water soluble.
CA 02333388 2003-12-23
23
Preferably the ethoxylated fatty alcohols are the C10-Cl g ethoxylated fatty
alcohols with
a degree of ethoxylation of from 3 to 50, most preferably these are the C12-
C18
ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40.
Preferably the
mixed ethoxylated/propoxylated fatty alcohols have an alkyl chain length of
from 10 to
18 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of
propoxylation
of from 1 to 10.
Nonionic EO/PO condensates with Qropylene glycol
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
BASFTM
Nonionic EO condensation products with propylene oxide/ethylene diamine
adducts
The condensation products of ethylene oxide with the product resulting from
the reaction
of propylene oxide and ethylenediamine are suitable for use herein. The
hydrophobic
moiety of these products consists of the reaction product of ethylenediamine
and excess
propylene oxide, and generally has a molecular weight of from 2500 to 3000.
Examples of this type of nonionic surfactant include certain of the
commercially
available TetronicTM 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
surfactant and at least one high cloud point nonionic surfactant.
CA 02333388 2003-12-23
24
"Cloud point", as used herein, is a well known property of nonionic
surfactants which is
the result of the surfactant becoming less soluble with increasing
temperature, the
temperature at which the appearance of a second phase is observable is
referred to as the
"cloud point" (See Kirk Othmer's Encyclopedia of Chemical Technology, 3'd Ed.
Vol.
22, pp. 360-379).
As used herein, a "low cloud point" nonionic surfactant is defined as a
nonionic
surfactant system ingredient having a cloud point of less than 30°C,
preferably less than
20°C, and most preferably less than 10°C. Typical low cloud
point nonionic surfactants
include nonionic alkoxylated surfactants, especially ethoxylates derived from
primary
alcohol, and polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO)
reverse
block polymers. Also, such low cloud point nonionic surfactants include, for
example,
ethoxylated-propoxylated alcohol (e.g., Olin Corporation's Poly-Tergent~
SLF18),
epoxy-capped poly(oxyalkylated) alcohols (e.g., Olin Corporation's Poly-
Tergent~
SLF18B series of nonionics, as described, for example, in WO 94/22800,
published
October 13, 1994 by Olin Corporation)and the ether-capped poly(oxyalkylated)
alcohol
surfactants.
Nonionic surfactants can optionally contain propylene oxide in an amount up to
I S% by
weight. Other preferred nonionic surfactants can be prepared by the processes
described
in U.S. Patent 4,223,163, issued September 16, 1980, Builloty.
Low cloud point nonionic surfactants additionally comprise a polyoxyethylene,
polyoxypropylene block polymeric compound. Block polyoxyethylene-
polyoxypropylene polymeric compounds include those based on ethylene glycol,
propylene glycol, glycerol, trimethylolpropane and ethylenediamine as
initiator reactive
hydrogen compound. Certain of the block polymer surfactant compounds
designated
PLURONIC~, REVERSED PLURONIC~, and TETRONIC~ by the BASF-Wyandotte
CA 02333388 2003-12-23
Corp., Wyandotte, Michigan, are suitable in ADD compositions of the invention.
Preferred examples include REVERSED PLURONIC~ 2582 and TETRONIC~ 702,
Such surfactants are typically useful herein as low cloud point nonionic
surfactants.
As used herein, a "high cloud point" nonionic surfactant is defined as a
nonionic
surfactant system ingredient having a cloud point of greater than 40°C,
preferably greater
than 50°C, and more preferably greater than 60°C. Preferably the
nonionic surfactant
system comprises an ethoxylated surfactant derived from the reaction of a
monohydroxy
alcohol or alkylphenol containing from 8 to 20 carbon atoms, with from 6 to 15
moles
of ethylene oxide per mole of alcohol or alkyl phenol on an average basis.
Such high
Tr~
cloud point nonionic surfactants include, for example, Tergitol 1559 (supplied
by Union
TM
Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc~, and Neodol 91-8
(supplied
by Shell)TM
It is also preferred for purposes of the present invention that the high cloud
point
nonionic surfactant further have a hydrophile-lipophile balance ("HLB"; see
Kirk Othmer
hereinbefore) value within the range of from 9 to 15, preferably 11 to 15.
Such
materials include, for example, Tergitol 1559 (supplied by Union Carbide),
Rhodasurf
TMD 8.5 (supplied by Rhone Poulenc), and Neodol 91-8 (supplied by Shell).
Another preferred high cloud point nonionic surfactant is derived from a
straight or
preferably branched chain or secondary fatty alcohol containing from 6 to 20
carbon
atoms (C6-C20 alcohol), including secondary alcohols and branched chain
primary
alcohols. Preferably, high cloud point nonionic surfactants are branched or
secondary
alcohol ethoxylates, more preferably mixed C9/1 l or C11/15 branched alcohol
ethoxylates, condensed with an average of from 6 to 15 moles, preferably from
6 to 12
moles, and most preferably from 6 to 9 moles of ethylene oxide per mole of
alcohol.
Preferably the ethoxylated nonionic surfactant so derived has a narrow
ethoxylate
distribution relative to the average.
CA 02333388 2000-11-24
-..
WO 00/04123 PCT/US99/14861
26
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
preferred.
Other anionic surfactants include the isethionates such as the acyl
isethionates, N-acyl
taurates, fatty acid amides of methyl tauride, alkyl succinates and
sulfosuccinates,
monoesters of sulfosuccinate (especially saturated and unsaturated C 12-C 1 g
monoesters)
diesters of sulfosuccinate (especially saturated and unsaturated C6-C 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 1 ~ acyl-N-(C 1-C4 alkyl)
and -N-(C 1-
C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such
as the
sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being
described
herein).
Alkyl sulfate surfactants are preferably selected from the linear and branched
primary
C 1 p-C 1 g alkyl sulfates, more preferably the C 11-C 15 branched chain alkyl
sulfates and
the C 12-C 14 linear chain alkyl sulfates.
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/14861
27
Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting of the
C l 0-C 1 g alkyl sulfates which have been ethoxylated with from 0.5 to 20
moles of
ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate
surfactant is a
C 11-C 1 g, most preferably C 11-C 15 alkyl sulfate which has been ethoxylated
with from
0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
A particularly preferred aspect of the invention employs mixtures of the
preferred alkyl
sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed
in PCT
Patent Application No. WO 93/18124.
Anionic sulfonate surfactant
Anionic sulfonate surfactants suitable for use herein include the salts of CS-
C20 linear
alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary
alkane
sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl
glycerol
sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates,
and any
mixtures thereof.
Anionic carboxylate surfactant
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 alkyl group, x ranges from O to 10, and
the
ethoxylate distribution is such that, on a weight basis, the amount of
material where x is
0 is less than 20 % and M is a cation. Suitable alkyl polyethoxy
polycarboxylate
surfactants include those having the formula RO-(CHR 1-CHR2-O)-R3 wherein R is
a C6
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/14861
28
to C I g alkyl group, x is from 1 to 25, R I and R2 are selected from the
group consisting
of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid
radical, and
mixtures thereof, and R3 is selected from the group consisting of hydrogen,
substituted
or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures
thereof.
Suitable soap surfactants include the secondary soap surfactants which contain
a
carboxyl unit connected to a secondary carbon. Preferred secondary soap
surfactants for
use herein are water-soluble members selected from the group consisting of the
water-
soluble salts of 2-methyl-I-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-
1-
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
(Rl } CH2 COOM, wherein R is a CS-C I ~ linear or branched alkyl or alkenyl
group, R1
is a CI-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)xN~(RS)2
wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl
phenyl
group, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an
alkylene or
hydroxyalkyiene group containing from 2 to 3 carbon atoms, or mixtures
thereof; x is
CA 02333388 2000-11-24
WO 00/04123 PCT1US99J14861
29
from 0 to 5, preferably from 0 to 3; and each RS is an alkyl or hydroxyalkyl
group
containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3
ethylene
oxide groups. Preferred are C 10-C 1 g alkyl dimethylamine oxide, and C 10-18
acylamido
alkyl dimethylamine oxide.
A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Conc.
manufactured by Miranol, Inc., Dayton, NJ.
Zwitterionic surfactant
Zwitterionic surfactants can also be incorporated into the detergent
compositions hereof.
These surfactants can be broadly described as derivatives of secondary and
tertiary
amines, derivatives of heterocyclic secondary and tertiary amines, or
derivatives of
quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds.
Betaine and sultaine surfactants are exemplary zwitterionic surfactants for
use herein.
Suitable betaines are those compounds having the formula R(R')2N+R2C00-
wherein R
is a C6-C 1 g hydrocarbyl group, each R1 is typically C 1-C3 alkyl, and R2 is
a C 1-CS
hydrocarbyl group. Preferred betaines are C12-18 dimethyl-ammonio hexanoate
and the
C10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex
betaine
surfactants are also suitable for use herein.
Cationic surfactants
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.
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/14861
Suitable cationic surfactants include the quaternary ammonium surfactants
selected from
mono C6-C 16, preferably C6-C l 0 N-alkyl or alkenyl ammonium surfactants
wherein the
remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl
groups
Enzymes
Enzymes are preferred detergent components of the first phase and more
particularly the
second and/or optionally further phases. Where present said enzymes are
selected from
the group consisting of cellulases, hemicellulases, peroxidases, proteases,
gluco-
amylases, amylases, xylanases, Iipases, phospholipases, esterases, cutinases,
pectinases,
keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, Iigninases,
pullulanases, tannases, pentosanases, maIanases,13-glucanases, arabinosidases,
hyaluronidase, chondroitinase, laccase or mixtures thereof.
Preferred enzymes include protease, amylase, lipase, peroxidases, cutinase
and/or
cellulase in conjunction with one or more plant cell wall degrading enzymes
The cellulases usable in the present invention include both bacterial or
fungal cellulase.
Preferably, they will have a pH optimum of between 5 and 12 and an activity
above 50
CEVU (Cellulose Viscosity Unit). Suitable cellulases are disclosed in U.S.
Patent
4,435,307, Barbesgoard et al, J61078384 and W096/02653 which disclose fungal
cellulases produced respectively from Humicola insolens, Trichoderma,
Thielavia and
Sporotrichum. EP 739 982 describes cellulases isolated from novel Bacillus
species.
Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275; DE-
OS-
2.247.832 and W095/26398.
Examples of such cellulases are cellulases produced by a strain of Humicola
insolens
(Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800.
Other
suitable cellulases are cellulases originated from Humicola insolens having a
molecular
CA 02333388 2003-12-23
3l
weight of SOKDa, an isoelectric point of 5.5 and containing 41 S amino acids;
and a
"43kD endoglucanase derived from Hucnicola insolens, DSM 1800, exhibiting
cellulase
activity; a preferred endoglucanase component has the amino acid sequence
disclosed in
PCT Patent Application No. WO 91/17243. Also suitable cellulases are the EGIII
cellulases from Trichoderma longibrachiatum described in W094/21801, Genencor,
published September 29, 1994. Especially suitable cellulases are the
cellulases having
color care benefits.
Carezyme and
Celluzyme (Novo Nordisk A/S) are especially useful. See also W091/17244 and
W091/21801. Other suitable cellulases for fabric care and/or cleaning
properties are
described in W096/34092, W096/17994 and W095/24471.
Said cellulases are normally incorporated in the detergent composition at
levels from
0.0001 % to 2% of active enzyme by weight of the detergent composition.
Peroxidase enzymes are used in combination with oxygen sources, e.g.
percarbonate,
perborate, persulfate, hydrogen peroxide, etc. They are used far "solution
bleaching", i.e.
to prevent transfer of dyes or pigments removed from substrates during wash
operations
to other substrates in the wash solution. Peroxidase enzymes are known in the
art, and
include, for example, horseradish peroxidase, ligninase and haloperoxidase
such as
chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are
disclosed, for example, in PCT International Application WO 891099813,
W089/09813
Also suitable is the laccase enzyme.
Preferred enhancers are substitued phenthiazine and phenoxasine 10-
Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4-carboxylic acid
(EPC), 10-
phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO
94/12621) and substitued syringates (C3-C5 substitued alkyl syringates) and
phenols.
Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.
CA 02333388 2000-11-24
..
WO 00/04123 PCT/US99/14861
32
Said cellulases and/or peroxidases are normally incorporated in the detergent
composition at levels from 0.0001 % to 2% of active enzyme by weight of the
detergent
composition.
Other preferred enzymes that can be included in the detergent compositions of
the
present invention include lipases. Suitable lipase enzymes for detergent usage
include
those produced by microorganisms of the Pseudomonas group, such as Pseudomonas
stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. Suitable
lipases include
those which show a positive immunological cross-reaction with the antibody of
the
lipase, produced by the microorganism Pseudomonas fluorescent IAM 1057. This
lipase
is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the
trade name
Lipase P "Amano," hereinafter referred to as "Amano-P". Other suitable
commercial
lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter
viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan;
Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth
Co.,
The Netherlands, and lipases ex Pseudomonas gladioli. Especially suitable
lipases are
lipases such as M1 LipaseR ~d LipomaxR (Gist-Brocades) and LipolaseR and
Lipolase
UltraR(Novo) which have found to be very effective when used in combination
with the
compositions of the present invention. Also suitables are the lipolytic
enzymes described
in EP 258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/03578,
WO 95/35381 and WO 96/00292 by Unilever.
Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special
kind of
lipase, namely lipases which do not require interfacial activation. Addition
of cutinases
to detergent compositions have been described in e.g. WO-A-88/09367
(Genencor); WO
90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilever).
The lipases and/or cutinases are normally incorporated in the detergent
composition at
levels from 0.0001 % to 2% of active enzyme by weight of the detergent
composition.
CA 02333388 2003-12-23
33
Suitable proteases are the subtilisins which are obtained from particular
strains of B.
subtilis and B. licheniformis (subtilisin BPN and BPN'). One suitable protease
is
obtained from a strain of Bacillus, having maximum activity throughout the pH
range of
8-12, developed and sold as ESPERASE~ by Novo Industries A/S of Denmark,
TM
hereinafter "Novo". The preparation of this enzyme and analogous enrymes is
described
in GB 1,243,784 to Novo. Other suitable proteases include KANNASE~~
ALCALASE~, DURAZYM~ and SAVINASE~ from Novo and MAXATASE~~
MAXACAL~, PROPERASE~ and MAXAPEMO (protein engineered Maxacal) from
Gist-Brocades. Proteolytic enzymes also encompass modified bacterial serine
proteases,
such as those described in European Patent Application Serial Number 87
303761.8,
filed April 28, 1987 (particularly pages 17, 24 and 98), and which is called
herein
"Protease B", and in European Patent Application 199,404, Venegas, published
October
29, 1986, which refers to a modified bacterial serine protealytic enzyme which
is called
"Protease A" herein. Suitable is what is called herein "Protease C", which is
a variant of
an alkaline serine protease from Baci lus in which lysine replaced arginine at
position 27,
tyrosine replaced valine at position 104, serine replaced asparagine at
position 123, and
alanine replaced threonine at position 274. Protease C is described in
WO 91/06637, Published May 16, 1991. Genetically modified
variants, particularly of Protease C, are also included herein.
A preferred protease referred to as "Protease D" is a carbonyl hydrolase
variant having an
amino acid sequence not found in nature, which is derived from a precursor
carbonyl
hydrolase by substituting a different amino acid for a plurality of amino acid
residues at a
position in said carbonyl hydrolase equivalent to position +76, preferably
also in
combination with one or more amino acid residue positions equivalent to those
selected
from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105,
+109,
+126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218,
+222,
+260, +265, and/or +274 according to the numbering of Bacillus
amyloliguefaciens
subtilisin, as described in W095110591.
CA 02333388 2003-12-23
34
Also suitable for the present invention are proteases described in patent
applications EP
251 446 and WO 91/06637, protease BLAP~ described in W091/02792 and their
variants described in WO 95/23221.
See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO
93/18140
A to Novo. Enzymatic detergents comprising protease, one or more other
enzymes, and
a reversible protease inhibitor are described in WO 92/03529 A to Novo. When
desired,
a protease having decreased adsorption and increased hydrolysis is available
as described
in WO 95/07791 to Procter & Gamble. A recombinant trypsin-like protease for
detergents suitable herein is described in WO 94/25583 to Novo. Other suitable
proteases
are described in EP 5I6 200 by Unilever.
Other preferred protease enzymes include protease enzymes which are a carbonyl
hydrolase variant having an amino acid sequence not found in nature, which is
derived
by replacement of a plurality of amino acid residues of a precursor carbonyl
hydrolase
with different amino acids, wherein said plurality of amino acid residues
replaced in the
precursor enzyme correspond to position +210 in combination with one or more
of the
following residues: +33, +62, +67, +76, +100, +101, +103, +104, +107, +128,
+129,
+130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218
and
+222, where the numbered positions correspond to naturally-occurring
subtilisin from
Bacillus amyloliquefaciens or_ to equivalent amino acid residues in other
carbonyl
hydrolases or subti(isins (such as Bacillus lentus subtilisin). Preferred
enzymes of this
type include those having position changes +210, +76, +103, +104, +156, and
+166.
The proteolytic enzymes are incorporated in the detergent compositions of the
present
invention a level of from 0.0001% to 2%, preferably from 0.001% to 0.2%, more
preferably from 0.005% to 0.1 % pure enzyme by weight of the composition.
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/14861
Amylases (a and/or 13) can be included for removal of carbohydrate-based
stains.
W094/02597, Novo Nordisk A/S published February 03, 1994, describes cleaning
compositions which incorporate mutant amylases. See also W095/10603, Novo
Nordisk A/S, published April 20, 1995. Other amylases known for use in
cleaning
compositions include both a- and ~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
W094/18314, published August 18, 1994 and W096/05295, Genencor, published
February 22, 1996 and amylase variants having additional modification in the
immediate
parent available from Novo Nordisk A/S, disclosed in WO 95/10603, published
April 95.
Also suitable are amylases described in EP 277 216, W095/26397 and W096/23873
(all
by Novo Nordisk).
Examples of commercial a-amylases products are Purafect Ox Am~ from Genencor
and
R
Termamyl~, Ban~ ,Fungamyl~ and Duramyl~, Natalase ~ 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 amylase enzymes include those described in W095/26397 and in co-
pending
application by Novo Nordisk PCT/DK96/00056.
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/14561
36
The amylolytic enzymes are incorporated in the detergent compositions of the
present
invention a level of from 0.0001 % to 2%, preferably from 0.00018% to 0.06%,
more
preferably from 0.00024% to 0.048% pure enzyme by weight of the composition
In a particularly preferred embodiment, detergent tablets of the present
invention
comprise amylase enzymes, particularly those described in W095/26397 and co-
pending
application by Novo Nordisk PCT/DK96/00056 in combination with a complementary
amylase.
By "complementary" it is meant the addition of one or more amylase suitable
for
detergency purposes. Examples of complementary amylases (a and/or 13) are
described
below. W094/02597 and W095/10603, Novo Nordisk A/S describe cleaning
compositions which incorporate mutant amylases. Other amylases known for use
in
cleaning compositions include both a- and (3-amylases. a-Amylases are known in
the art
and include those disclosed in US Pat. no. 5,003,257; EP 252,666; WO/91/00353;
FR
2,676,456; EP 285,123; EP 525,610; EP 368,341; and British Patent
specification no.
1,296,839 (Novo). Other suitable amylases are stability-enhanced amylases
described in
W094/18314, 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
CA 02333388 2003-12-23
37
described in WO 94/18314, W096/05295 sold by Genencor; Termamyl~, Fungamyl~,
R
Ban~ Natalase~ and Duramyl~, all available from Novo Nordisk A/S and Maxamyl~
TM
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 D.OUU
18% 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:I to 1:9, more preferably between
4:1 to
1:4, and most preferably between 2:1 and 1:2.
The above-mentioned enzymes may be of any suitable origin, such as vegetable,
animal,
bacterial, fungal and yeast origin. Origin can further be mesophilic or
extremophilic
(psychrophilic, psychrotrophic, thermophilic, barophilic, aikalophilic,
acidophilic,
halophilic, etc.). Purified or non-purified forms of these enzymes may be
used. Also
included by definition, are mutants of native enzymes. Mutants can be obtained
e.g. by
protein and/or genetic engineering, chemical and/or physical modifications of
native
enzymes. Common practice as well is the expression of the enzyme via host
organisms in
which the genetic material responsible for the production of the enzyme has
been cloned.
Said enzymes are normally incorporated in the detergent composition at levels
from
0.0001 % to 2% of active enzyme by weight of the detergent composition. The
enzymes
can be added as separate single ingredients (prills, granulates, stabilized
liquids, etc...
containing one enzyme ) or as mixtures of two or more enzymes ( e.g.
cogranulates ).
Other suitable detergent ingredients that can he added are enzyme oxidation
scavengers,
Examples of such enzyme oxidation scavengers are ethoxylated
tetraethylene polyamines.
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/14861
38
A range of enzyme materials and means for their incorporation into synthetic
detergent
compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genencor
International, WO 8908694 A to Novo, and U.S. 3,553,139, January S, 1971 to
McCarty
et al. Enzymes are further disclosed in U.S. 4,101,457, Place et al, July 18,
1978, and in
U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid
detergent
formulations, and their incorporation into such formulations, are disclosed in
U.S.
4,261,868, Hora et al, April 14, 1981. Enzymes for use in detergents can be
stabilised by
various techniques. Enzyme stabilisation techniques are disclosed and
exemplified in
U.S. 3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586,
October 29,
1986, Venegas. Enzyme stabilisation systems are also described, for example,
in U.S.
3,519,570. A useful Bacillus, sp. AC 13 giving proteases, xylanases and
cellulases, is
described in WO 9401532 A to Novo.
Bleaching went
A highly preferred component of the composition of detergent components is a
bleaching
agent. Suitable bleaching agents include chlorine and oxygen-releasing
bleaching
agents.
In one preferred aspect the oxygen-releasing bleaching agent contains a
hydrogen
peroxide source and an organic peroxyacid bleach precursor compound. The
production
of the organic peroxyacid occurs by an in situ reaction of the precursor with
a source of
hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic
perhydrate bleaches. In an alternative preferred aspect a preformed organic
peroxyacid is
incorporated directly into the composition. Compositions containing mixtures
of a
hydrogen peroxide source and organic peroxyacid precursor in combination with
a
preformed organic peroxyacid are also envisaged.
Inorganic nerhydrate bleaches
CA 02333388 2000-11-24
..
WO 00/04123 PCT/US99/14861
39
The compositions of detergent components preferably include a hydrogen
peroxide
source, as an oxygen-releasing bleach. Suitable hydrogen peroxide sources
include the
inorganic perhydrate salts.
The inorganic perhydrate salts are normally incorporated in the form of the
sodium salt at
a level of from 1 % to 40% by weight, more preferably from 2% to 30% by weight
and
most preferably from 5% to 25% by weight of the compositions.
Examples of inorganic perhydrate salts include perborate, percarbonate,
perphosphate,
persulfate and persilicate salts. The inorganic perhydrate salts are normally
the alkali
metal salts. The inorganic perhydrate salt may be included as the crystalline
solid
without additional protection. For certain perhydrate salts however, the
preferred
executions of such granular compositions utilize a coated form of the material
which
provides better storage stability for the perhydrate salt in the granular
product.
Sodium perborate can be in the form of the monohydrate of nominal formula
NaB02H202 or the tetrahydrate NaB02H202.3H20.
Alkali metal percarbonates, particularly sodium percarbonate are preferred
perhydrates
for inclusion 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 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
CA 02333388 2000-11-24
..
WO 00/04123 PCT/US99/14861
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.
Peroxyacid bleachprecursor
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
CA 02333388 2000-11-24
.,
WO 00/04123 PCT/US99/14861
41
O
X-C-OOH
Peroxyacid bleach precursor compounds are preferably incorporated at a level
of from
0.5% to 20% by weight, more preferably from 1 % to 10% by weight, most
preferably
from 1.5% to 5% by weight of the compositions.
Suitable peroxyacid bleach precursor compounds typically contain one or more N-
or O-
acyl groups, which precursors can be selected from a wide range of classes.
Suitable
classes include anhydrides, esters, imides, lactams and acylated derivatives
of imidazoles
and oximes. Examples of useful materials within these classes are disclosed in
GB-A-
1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871,
2143231 and
EP-A-0170386.
Leaving ~rouns
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:
CA 02333388 2000-11-24
,.
WO 00/04123 PCTNS99/14861
42
Y R3 R 5Y
-O ~ , -O ~ Y , and -O
O O
I I
-N-C-R -N N -N-C-CH-R4
' ~ ~ R3 Y ,
Y
R3 Y
I I
-O-C H=C-C H=C HZ -O-C H=C-C H=C H2
O C H -O Y O
_~C-R~ -N\CiNR4 ' -N\C/ 4
~NR
II il
O O
R3 O Y
-O-C=CHR4 , and -N-S-CH-R4
R3 O
and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group
containing from 1 to
14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R4
is H or
R3, RS is an alkenyl chain containing from 1 to 8 carbon atoms and Y is H or a
solubilizing group. Any of R1, R3 and R4 may be substituted by essentially any
functional group including, for example alkyl, hydroxy, alkoxy, halogen,
amine, nitrosyl,
amide and ammonium or alkyl ammonium groups.
CA 02333388 2000-11-24
WO 00/04123 PCTNS99/14861
43
The preferred solubilizing groups are -S03-M+, -C02-M+, -S04 M+, -N+(R3)4X-
and
O<--N(R3)3 and most preferably -S03 M+ and -C02 M+ wherein R3 is an alkyl
chain
containing from 1 to 4 carbon atoms, M is a ration which provides solubility
to the
bleach activator and X is an anion which provides solubility to the bleach
activator.
Preferably, M is an alkali metal, ammonium or substituted ammonium 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:
0
~~~S03
Also suitable are the benzoylation products of sorbitol, glucose, and all
saccharides with
benzoylating agents, including for example:
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/14861
44
OAc
Ac0 \~n
~ OAc
/ OAc
OBz
Ac = COCH3; Bz = Benzoyl
Perbenzoic acid precursor compounds of the imide type include N-benzoyl
succinimide,
tetrabenzoyl ethylene diamine and the N-benzoyl substituted 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
o~1
~~COOH
Phthalic anhydride is another suitable perbenzoic acid precursor compound
herein:
O
,O
O
Suitable N-acylated lactam perbenzoic acid precursors have the formula:
CA 02333388 2000-11-24
..
WO 00/04123 PCTNS99/14861
O
II
Rs-O N-C H2- ~ H2
~C H2-EC H2 ]~
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-R2CL R~ -N-C-R2-C-L
O Rb 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 1 to 14 carbon atoms, and RS is H or an
alkyl, aryl,
or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any
leaving
group. R1 preferably contains from 6 to 12 carbon atoms. R2 preferably
contains from
4 to 8 carbon atoms. R1 may be aryl, substituted aryl or alkylaryl containing
branching,
CA 02333388 2000-11-24
,
WO 00/04123 PCT/US99/14861
46
substitution, or both and may be sourced from either synthetic sources or
natural sources
including for example, tallow fat. Analogous structural variations are
permissible for
R2. The substitution can include alkyl, aryl, halogen, nitrogen, sulphur and
other typical
substituent groups or organic compounds. RS is preferably H or methyl. R1 and
RS
should not contain more than 18 carbon atoms in total. Amide substituted
bleach
activator compounds of this type are described in EP-A-OI 70386.
Cationic~eroxyacid 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 peroxyacid precursors are described in U.S. Patents 4,904,406;
4,751,015;
4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K.
1,382,594; EP
475,512, 458,396 and 284,292; and in JP 87-318,332.
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/14861
47
Suitable cationic peroxyacid precursors include any of the ammonium or alkyl
ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated
caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.
A preferred cationically substituted benzoyl oxybenzene sulfonate is the 4-
(trimethyl
ammonium) methyl derivative of benzoyl oxybenzene sulfonate:
0
~O ~S03
~+
A preferred cationically substituted alkyl oxybenzene sulfonate has the
formula:
SO
~+
/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:
0
0
C.
~~~~ ~J
Other preferred cationic peroxyacid precursors of the N-acylated caprolactam
class
include the trialkyl ammonium methylene alkyl caprolactams:
CA 02333388 2000-11-24
,.
WO 00/04123 PCT/US99/14861
48
(CH2)n~ N
~+ ~/
where n is from 0 to 12, particularly from 1 to 5.
Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl
ammonium) ethyl
sodium 4-sulphophenyl carbonate chloride.
Alkyl percarboxylic acid bleach precursors
Alkyl percarboxylic acid bleach precursors form percarboxylic acids on
perhydrolysis.
Preferred precursors of this type provide peracetic acid on perhydrolysis.
Preferred alkyl percarboxylic precursor compounds of the imide type include
the N-
,N,N1N1 tetra acetylated alkylene diamines wherein the alkylene group contains
from 1
to 6 carbon atoms, particularly those compounds in which the alkylene group
contains 1,
2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly
preferred.
Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-tri-
methyl
hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate
(HOBS), sodium acetoxybenzene sulfonate (ABS) and penta acetyl glucose.
Amide substituted alkyl peroxyacid precursors
Amide substituted alkyl peroxyacid precursor compounds are also suitable,
including
those of the following general formulae:
CA 02333388 2000-11-24
WO 00/04123 PCT/US99114861
49
R~-C-N-R2-C-~ R~-N-C-R2-C-~
~ ~ R5 Ip IO
O R O or
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. R1 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.
Benzoxazin organic 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
C-R~
'N
including the substituted benzoxazins of the type
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/14861
R2 O
Ra ~O
0
R4 N C R~
R5
wherein R1 is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R4, and
RS may be
the same or different substituents selected from H, halogen, alkyl, alkenyl,
aryl,
hydroxyl, alkoxyl, amino, alkyl amino, COOR6 (wherein R6 is H or an alkyl
group) and
carbonyl functions.
An especially preferred precursor of the benzoxazin-type is:
O
II
O
of
..~ o
N
Preformed or anic peroxyacid
The organic peroxyacid bleaching system may contain, in addition to, or as an
alternative to, an organic peroxyacid bleach precursor compound, a preformed
organic
peroxyacid , typically at a level of from 0.5% to 25% by weight, more
preferably from
1 % to 10% by weight of the composition.
A preferred class of organic peroxyacid compounds are the amide substituted
compounds
of the following general formulae:
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/1~1861
51
R~-C-N-R2-C-OOH R~-N-C-R2-C-OOH
R5 IO O
O R O or
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. Rl
preferably
contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon
atoms.
R1 may be straight chain or branched alkyl, substituted aryl or alkylaryl
containing
branching, substitution, or both and may be sourced from either synthetic
sources or
natural sources including for example, tallow fat. Analogous structural
variations are
permissible for R2. The substitution can include alkyl, aryl, halogen,
nitrogen, sulphur
and other typical substituent groups or organic compounds. RS is preferably H
or
methyl. R1 and RS should not contain more than 18 carbon atoms in total. Amide
substituted organic peroxyacid compounds of this type are described in EP-A-
0170386.
Other organic peroxyacids include diacyl and tetraacylperoxides, especially
diperoxydodecanedioc acid, diperoxytetradecanedioc acid, and
diperoxyhexadecanedioc
acid. Dibenzoyl peroxide is a preferred organic peroxyacid herein. Mono- and
diperazelaic acid, mono- and diperbrassylic acid, and N-
phthaloylaminoperoxicaproic
acid are also suitable herein.
Controlled rate of release - means
A means may be provided for controlling the rate of release of bleaching
agent,
particularly oxygen bleach to the wash solution.
Means for controlling the rate of release of the bleach may provide for
controlled release
of peroxide species to the wash solution. Such means could, for example,
include
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/14861
52
controlling the release of any inorganic perhydrate salt, acting as a hydrogen
peroxide
source, to the wash solution.
Another mechanism for controlling the rate of release of bleach may be by
coating the
bleach with a coating designed to provide the controlled release. The coating
may
therefore, for example, comprise a poorly water soluble material, or be a
coating of
sufficient thickness that the kinetics of dissolution of the thick coating
provide the
controlled rate of release.
The coating material may be applied using various methods. Any coating
material is
typically present at a weight ratio of coating material to bleach of from 1:99
to 1:2,
preferably from 1:49 to 1:9.
Suitable coating materials include triglycerides (e.g. partially) hydrogenated
vegetable
oil, soy bean oil, cotton seed oil) mono or diglycerides, microcrystalline
waxes, gelatin,
cellulose, fatty acids and any mixtures thereof.
Other suitable coating materials can comprise the alkali and alkaline earth
metal
sulphates, silicates and carbonates, including calcium carbonate and silicas.
A preferred coating material, particularly for an inorganic perhydrate salt
bleach source,
comprises sodium silicate of Si02 : Na20 ratio from 1.8 : 1 to 3.0 : l,
preferably 1.8:1 to
2.4:1, and/or sodium metasilicate, preferably applied at a level of from 2% to
10%,
(normally from 3% to 5%) of Si02 by weight of the inorganic perhydrate salt.
Magnesium silicate can also be included in the coating.
Any inorganic salt coating materials may be combined with organic binder
materials to
provide composite inorganic salt/organic binder coatings. Suitable binders
include the
C l0-C2p alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide
per mole
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/14861
53
of alcohol and more preferably the C 15-C20 Primary alcohol ethoxylates
containing from
20 - 100 moles of ethylene oxide per mole of alcohol.
Other preferred binders include certain polymeric materials.
Polyvinylpyrrolidones with
an average molecular weight of from 12,000 to 700,000 and polyethylene glycols
(PEG)
with an average molecular weight of from 600 to 5 x 106 preferably 1000 to
400,000
most preferably 1000 to 10,000 are examples of such polymeric materials.
Copolymers
of malefic anhydride with ethylene, methylvinyl ether or methacrylic acid, the
malefic
anhydride constituting at least 20 mole percent of the polymer are further
examples of
polymeric materials useful as binder agents. These polymeric materials may be
used as
such or in combination with solvents such as water, propylene glycol and the
above
mentioned C 10-C20 alcohol ethoxylates containing from 5 - 100 moles of
ethylene oxide
per mole. Further examples of binders include the C 10-C2p mono- and
diglycerol ethers
and also the C10-C20 fatty acids.
Cellulose derivatives such as methylcellulose, carboxymethylcellulose and
hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their
salts are
other examples of binders suitable for use herein.
One method for applying the coating material involves agglomeration. Preferred
agglomeration processes include the use of any of the organic binder materials
described
hereinabove. Any conventional agglomerator/mixer may be used including, but
not
limited to pan, rotary drum and vertical blender types. Molten coating
compositions
may also be applied either by being poured onto, or spray atomized onto a
moving bed of
bleaching agent.
Other means of providing the required controlled release include mechanical
means for
altering the physical characteristics of the bleach to control its solubility
and rate of
release. Suitable protocols could include compression, mechanical injection,
manual
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/14861
54
injection, and adjustment of the solubility of the bleach compound by
selection of
particle size of any particulate component.
Whilst the choice of particle size will depend both on the composition of the
particulate
component, and the desire to meet the desired controlled release kinetics, it
is desirable
that the particle size should be more than S00 micrometers, preferably having
an average
particle diameter of from 800 to 1200 micrometers.
Additional protocols for providing the means of controlled release include the
suitable
choice of any other components of the detergent composition matrix such that
when the
composition is introduced to the wash solution the ionic strength environment
therein
provided enables the required controlled release kinetics to be achieved.
Metal-containing bleach catalyst
The compositions described herein which contain bleach as an detergent
component may
additionally contain as a preferred component, a metal containing bleach
catalyst.
Preferably the metal containing bleach catalyst is a transition metal
containing bleach
catalyst, more preferably a manganese or cobalt-containing bleach catalyst
A suitable type of bleach catalyst is a catalyst comprising a heavy metal
cation of defined
bleach catalytic activity, such as copper, iron cations, an auxiliary metal
cation having
little or no bleach catalytic activity, such as zinc or aluminium cations, and
a sequestrant
having defined stability constants for the catalytic and auxiliary metal
cations,
particularly ethylenediaminetetraacetic acid,
ethylenediaminetetra(methylenephosphonic
acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S.
Pat.
4,430,243.
Preferred types of bleach catalysts include the manganese-based complexes
disclosed in
U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples ofthese
catalysts
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/14861
include MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(PF6)2, MnIII2{u-
O)1(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(C104)2, MnIV4(u-
O)6(1,4,7-
triazacyclononane)4-(C104)2, MnIIIMnIV4(u-O)1(u-OAc)2-(1,4,7-trimethyl-1,4,7-
triazacyclononane)2-{C104)3, and mixtures thereof. Others are described in
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-
triazacyclononane, and mixtures thereof.
The bleach catalysts useful in the compositions herein may also be selected as
appropriate for the present invention. For examples of suitable bleach
catalysts see U.S.
Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat. 5,194,416 which
teaches
mononuclear manganese (IV) complexes such as Mn(1,4,7-trimethyl-1,4,7-
triazacyclononane)(OCH3)3-(PF6).
Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is
a water-
soluble complex of manganese (III), and/or (IV) with a ligand which is a non-
carboxylate
polyhydroxy compound having at least three consecutive C-OH groups. Preferred
ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol,
adonitol, meso-
erythritol, meso-inositol, lactose, and mixtures thereof.
U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of
transition metals,
including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand. Said ligands
are of the
formula:
R2 R3
1
R~-N=C-B-C=N-R4
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/14861
56
wherein Rl, 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-cobalt(II)
perchlorate,
Co(2,2-bispyridylamine)202C104, Bis-(2,2'-bispyridylamine) copper(II)
perchlorate,
tris(di-2-pyridylamine) iron(II) perchlorate, and mixtures thereof.
Preferred examples include binuclear Mn complexes with tetra-N-dentate and bi-
N-
dentate ligands, including N4MnIII(u-O)2MnIVN4)+and [Bipy2MnIII(u-
O)2MnIVbIPY2~-(C104)3
While the structures of the bleach-catalyzing manganese complexes of the
present
invention have not been elucidated, it may be speculated that they comprise
chelates or
other hydrated coordination complexes which result from the interaction of the
carboxyl
and nitrogen atoms of the ligand with the manganese cation. Likewise, the
oxidation
state of the manganese 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 cation, it may be reasonably speculated
that multi-
nuclear species and/or "cage" structures may exist in the aqueous bleaching
media.
Whatever the form of the active Mmligand 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 02333388 2000-11-24
..
WO 00/04123 PCTNS99/14861
57
Other bleach catalysts are described, for example, in European patent
application,
publication no. 408,131 (cobalt complex catalysts), European patent
applications,
publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S.
4,728,455
(manganese/multidentate ligand catalyst), U.S. 4,711,748 and European patent
application, publication no. 224,952, (absorbed manganese on aluminosilicate
catalyst),
U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium
salt),
U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,119,557 (fernc complex
catalyst),
German Pat. specification 2,054,019 (cobalt chelant catalyst) Canadian 866,191
(transition metal-containing salts), U.S. 4,430,243 (chelants with manganese
cations and
non-catalytic metal cations), and U.S. 4,728,455 (manganese gluconate
catalysts).
Other preferred examples include cobalt (III) catalysts having the formula:
Co[(NH3)nM~mB~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 + 5p =
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.
CA 02333388 2000-11-24
. , ,
WO 00/04123 PCT/US99/14861
58
Preferred cobalt catalysts of this type have the formula:
[Co(NH3)n(M')m] YY
wherein n is an integer from 3 to 5 (preferably 4 or 5; most preferably 5); M'
is a labile
coordinating moiety, preferably selected from the group consisting of
chlorine, bromine,
hydroxide, water, and (when m is greater than 1 ) combinations thereof; m is
an integer
from 1 to 3 (preferably 1 or 2; most preferably 1 ); m+n = 6; and Y is an
appropriately
selected counteranion present in a number y, which is an integer from 1 to 3
(preferably 2
to 3; most preferably 2 when Y is a -1 charged anion), to obtain a charge-
balanced salt.
The preferred cobalt catalyst of this type useful herein are cobalt pentaamine
chloride
salts having the formula [Co(NH3)SCIj Yy, and especially [Co(NH3)5Cl]C12.
More preferred are the present invention compositions which utilize cobalt
(III) bleach
catalysts having the formula:
[Co~H3)n(M)m(B)b] TY
wherein cobalt is in the +3 oxidation state; n is 4 or 5 (preferably 5); M is
one or more
ligands coordinated to the cobalt by one site; m is 0, 1 or 2 (preferably 1 );
B is a ligand
co-ordinated to the cobalt by two sites; b is 0 or 1 (preferably 0), and when
b=0, then
m+n = 6, and when b=l, then m=0 and n=4; and T is one or more appropriately
selected
counteranions present in a number y, where y is an integer to obtain a charge-
balanced
salt (preferably y is 1 to 3; most preferably 2 when T is a -1 charged anion);
and wherein
further said catalyst has a base hydrolysis rate constant of less than 0.23 M-
1 s-1 (25°C).
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/14861 _
59
Preferred T are selected from the group consisting of chloride, iodide, I3-,
formate,
nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PF6
, BF4-, B(Ph)4 ,
phosphate, phosphite, silicate, tosylate, methanesulfonate, and combinations
thereof.
Optionally, T can be protonated if more than one anionic group exists in T,
e.g., HP042-,
HC03-, H2P04-, etc. Further, T may be selected from the group consisting of
non-
traditional inorganic anions such as anionic surfactants (e.g., linear
alkylbenzene
sulfonates (LAS), alkyl sulfates (AS), 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-,
5203-2, NH3, POq.3-, and carboxylates (which preferably are mono-carboxylates,
but
more than one carboxylate may be present in the moiety as long as the binding
to the
cobalt is by only one carboxylate per moiety, in which case the other
carboxylate in the
M moiety may be protonated or in its salt form). Optionally, M can be
protonated if
more than one anionic group exists in M (e.g., HP042-, HC03-, H2P04 ,
HOC(O)CH2C(O)O-, etc.) Preferred M moieties are substituted and unsubstituted
Cl-
C30 carboxylic acids having the formulas:
RC(O)O-
wherein R is preferably selected from the group consisting of hydrogen and C1-
C30
(preferably C 1-C 1 g) unsubstituted and substituted alkyl, C6-C30 {preferably
C6-C 1 g)
unsubstituted and substituted aryl, and C3-C30 (preferably CS-C 1 g)
unsubstituted and
substituted heteroaryl, wherein substituents are selected from the group
consisting of -
NR'3, -NR'4+, -C(O)OR', -OR', -C(O)NR'2, wherein R' is selected from the group
consisting of hydrogen and C1-C6 moieties. Such substituted R therefore
include the
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/14861
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 alpha and beta amino acids
(e.g., glycine,
alanine, beta-alanine, phenylalanine).
Cobalt bleach catalysts useful herein are known, being described for example
along with
their base hydrolysis rates, in M. L. Tobe, "Base Hydrolysis of Transition-
Metal
Complexes", Adv. more. Bioinor~ Mech., (1983), 2, pages 1-94. For example,
Table
1 at page 17, provides the base hydrolysis rates (designated therein as kOH)
for cobalt
pentaamine catalysts complexed with oxalate (kOH= 2.5 x 10-4 M-1 s-1
(25°C)), NCS-
(kOH= S.0 x 10-4 M-1 s-1 (25°C)), formate (kOH= 5.8 x 10~ M-1 s-1
(25°C)), and
acetate (kOH= 9.6 x 10-4 M-1 s-1 (25°C)). The most preferred cobalt
catalyst useful
herein are cobalt pentaamine acetate salts having the formula [Co(NH3)SOAc]
Ty,
wherein OAc represents an acetate moiety, and especially cobalt pentaamine
acetate
chloride, (Co(NH3)SOAc]C12; as well as [Co(NH3)SOAc](OAc)2;
[Co(NH3)SOAc](PF6)2; [Co(NH3)SOAc](S04); [Co(NH3)SOAc](BF4)2; and
[Co(NH3)SOAc](N03)2 (herein "PAC").
CA 02333388 2003-12-23
61
These cobalt catalysts are readily prepared by known procedures, such as
taught for
example in the 'lobe article hereinbefore and the references cited therein, in
U.S. Patent
4,810,410, to Diakun et al, issued March 7,1989, J. Chem. Ed. (1989), 66 (12),
1043-
45; The Synthesis and Characterization of Inorganic Compounds, W.L. Jolly
(Prentice-
Hall; 1970), pp. 461-3; Inor~,_Chem., 18, 1497-1502 (1979); Inor~. Chem., 21,
2881-
2885 (1982); Inorg. Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-176
(1960);
and Journal of Physical Chemistry, 56, 22-25 (1952); as well as the synthesis
examples
provided hereinafter.
Cobalt catalysts suitable for incorporation into the detergent tablets of the
present
invention may be produced according to the synthetic routes disclosed in U.S.
Patent
Nos. 5,559,261, 5,581,005, and 5,597,936.
These catalysts may be co-processed with adjunct materials so as to reduce the
colour
impact if desired for the aesthetics of the product, or to be included in
enzyme-containing
particles as exemplified hereinafter, or the compositions may be manufactured
to contain
catalyst "speckles".
Organic nolvmeric compound
Organic polymeric compounds may be added as preferred components of the
detergent
tablets in accord with the invention. By organic polymeric compound it is
meant
essentially any polymeric organic compound commonly found in detergent
compositions
having dispersant, anti-redeposition, soil release agents or other detergency
properties.
Organic polymeric compound is typically incorporated in the detergent
compositions of
the invention at a level of from 0.1 % to 30%, preferably from 0.5% to 15%,
most
preferably from 1 % to 10% by weight of the compositions.
CA 02333388 2003-12-23
62
Examples of organic polymeric compounds include the water soluble organic homo-
or
co-polymeric polycarboxylic acids, modified polycarboxylates or their salts in
which the
polycarboxylic acid comprises at least two carboxyl radicals separated from
each other
by not more than two carbon atoms. Polymers of the latter type are disclosed
in GB-A-
1,596,756. Examples of such salts are polyacrylates of molecular weight 2000-
10000
and their copolymers with any suitable other monomer units including modified
acrylic,
fumaric, malefic, itaconic, aconitic, mesaconic, citraconic and
methylenemalonic acid or
their salts, malefic anhydride, acrylamide, alkylene, vinylmethyl ether,
styrene and any
mixtures thereof. Preferred are the copolymers of acrylic acid and malefic
anhydride
having a molecular weight of from 20,000 to I 00,000.
Preferred commercially available acrylic acid containing polymers having a
molecular
weight below 15,000 include those sold under the tradename Sokalan PA30, PA20,
PA15, PA10 and Sokalan CP10 by BASF GmbH, and those sold under the tradename
Acusol 45N, 480N. 460N by Rohm and via ~
Preferred acrylic acid containing copolymers include those which contain as
monomer
units: a) from 90% to 10%, preferably from 80% to 20% by weight acrylic acid
or its
salts and b) from 10% to 90%, preferably from 20% to 80% by weight of a
substituted
acrylic monomer or its salts having the general formula -[CR2-CR1 (CO-O-R3)]-
wherein
at least one of the substituents Rl, R2 or R3, preferably Rl or R2 is a 1 to 4
carbon alkyl
or hydroxyalkyl group, R1 or R2 can be a hydrogen and R3 can be a hydrogen or
alkali
metal salt. Most preferred is a substituted acrylic monomer wherein Rl is
methyl, R2 is
hydrogen (i.e. a methacrylic acid monomer). The most preferred copolymer of
this type
has a molecular weight of 3500 and contains 60% to 80% by weight of acrylic
acid and
40% to 20% by weight of methacrylic acid.
The polyamine and modified polyamine compounds are useful herein including
those
derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283
and
EP-A-351629.
CA 02333388 2000-11-24
WO 00/04123 PCTNS99/14861
63
Other optional polymers may polyvinyl alcohols and acetates both modified and
non-
modified, cellulosics and modified cellulosics, polyoxyethylenes,
polyoxypropylenes,
and copolymers thereof, both modified and non-modified, terephthalate esters
of ethylene
or propylene glycol or mixtures thereof with polyoxyalkylene units.
Suitable examples are disclosed in US patent Nos. 5,591,703 , 5,597,789 and
4,490,271.
Soil Release Agents
Suitable polymeric soil release agents include those soil release agents
having: (a) one or
more nonionic hydrophile components consisting essentially of (i)
polyoxyethylene
segments with a degree of polymerization of at least 2, or (ii) oxypropylene
or
polyoxypropylene segments with a degree of polymerization of from 2 to 10,
wherein
said hydrophile segment does not encompass any oxypropylene unit unless it is
bonded
to adjacent moieties at each end by ether linkages, or (iii) a mixture of
oxyalkylene units
comprising oxyethylene and from 1 to 30 oxypropylene units, said hydrophile
segments
preferably comprising at least 25% oxyethylene units and more preferably,
especially for
such components having 20 to 30 oxypropylene units, at least 50% oxyethylene
units;
or (b) one or more hydrophobe components comprising (i) C3 oxyalkylene
terephthalate
segments, wherein, if said hydrophobe components also comprise oxyethylene
terephthalate, the ratio of oxyethylene terephthalate:C3 oxyalkylene
terephthalate units is
2:1 or lower, (ii) C4-C6 alkylene or oxy C4-C6 alkylene segments, or mixtures
therein,
(iii) poly (vinyl ester) segments, preferably polyvinyl acetate, having a
degree of
polymerization of at least 2, or (iv) C1-C4 alkyl ether or C4 hydroxyalkyl
ether
substituents, or mixtures therein, wherein said substituents are present in
the form of Cl-
C4 alkyl ether or C4 hydroxyalkyl ether cellulose derivatives, or mixtures
therein, or a
combination of (a) and (b).
CA 02333388 2003-12-23
64
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 I50, more
preferably
from 6 to 100. Suitable oxy C4-C6 alkylene hydrophobe segments include, but
are not
limited to, end-caps of polymeric soil release agents such as
M03S(CH2)nOCH2CH20-,
where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent
4,721,580,
issued January 26, 1988 to Gosselink.
Polymeric soil release agents useful herein also include cellulosic
derivatives such as
hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate
or
propylene terephthalate with polyethylene oxide or polypropylene oxide
terephthalate,
and the like. Such agents are commercially available and include hydroxyethers
of
cellulose such as METHOCEL (Dow Cellulosic soil release agents for use herein
also
include those selected from the group consisting of C 1-C4 alkyl and C4
hydroxyalkyl
cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et
al.
Soil release agents characterized by polyvinyl ester) hydrophobe segments
include graft
copolymers of polyvinyl ester), e.g., C1-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-I S% 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.
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/14861
Another suitable polymeric soil release agent is a sulfonated product of a
substantially
linear ester oligomer comprised of an oligomeric ester backbone of
terephthaloyl and
oxyalkyleneoxy repeat units and terminal moieties covalently attached to the
backbone.
These soil release agents are described fully in U.S. Patent 4,968,451, issued
November
6, 1990 to J.J. Scheibel and E.P. Gosselink. Other suitable polymeric soil
release
agents include the terephthalate polyesters of U.S. Patent 4,711,730, issued
December 8,
1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S.
Patent
4,721,580, issued January 26, 1988 to Gosselink, and the block polyester
oligomeric
compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
Other
polymeric soil release agents also include the soil release agents of U.S.
Patent
4,877,896, issued October 31, 1989 to Maldonado et al, which discloses
anionic,
especially sulfoarolyl, end-capped terephthalate esters.
Another soil release agent is an oligomer with repeat units of terephthaloyl
units,
sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2-propylene units. The
repeat
units form the backbone of the oligomer and are preferably terminated with
modified
isethionate end-caps. A particularly preferred soil release agent of this type
comprises
one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-
propyleneoxy units in a ratio of from 1.7 to 1.8, and two end-cap units of
sodium 2-(2-
hydroxyethoxy)-ethanesulfonate.
Heavy metal ion sequestrant
The tablets of the invention preferably contain as an optional component a
heavy metal
ion sequestrant. By heavy metal ion sequestrant it is meant herein components
which act
to sequester (chelate) heavy metal ions. These components may also have
calcium and
magnesium chelation capacity, but preferentially they show selectivity to
binding heavy
metal ions such as iron, manganese and copper.
CA 02333388 2000-11-24
..
WO 00/04123 PCT/US99/14861
66
Heavy metal ion sequestrants are generally present at a level of from 0.005%
to 20%,
preferably from 0.1% to 10%, more preferably from 0.25% to 7.5% and most
preferably
from 0.5% to 5% by weight of the compositions.
Heavy metal ion sequestrants, which are acidic in nature, having for example
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 heavy
metal ion sequestrant is preferably at least 1:1.
Suitable heavy metal ion sequestrants for use herein include organic
phosphonates, such
as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-
hydroxy
disphosphonates and nitrilo trimethylene phosphonates. Preferred among the
above
species are diethylene triamine penta (methylene phosphonate), ethylene
diamine tri
(methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate)
and
hydroxy-ethylene 1,1 diphosphonate.
Other suitable heavy metal ion sequestrant for use herein include
nitrilotriacetic acid and
polyaminocarboxylic acids such as ethylenediaminotetracetic acid,
ethylenetriamine
pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric
acid, 2-
hydroxypropylenediamine disuccinic acid or any salts thereof.
Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or the
alkali metal,
alkaline earth metal, ammonium, or substituted ammonium salts thereof, or
mixtures
thereof. Preferred EDDS compounds are the free acid form and the sodium or
magnesium salt or complex thereof.
Cr sy tal ;growth inhibitor component
CA 02333388 2000-11-24
~ i
WO 00/04123 PCT/US99/14861
67
The detergent tablets preferably contain a crystal growth inhibitor component,
preferably
an organodiphosphonic acid component, incorporated preferably at a level of
from 0.01
to 5%, more preferably from 0.1 % to 2% by weight of the compositions.
By organo diphosphonic acid it is meant herein an organo diphosphonic acid
which does
not contain nitrogen as part of its chemical structure. This definition
therefore excludes
the organo aminophosphonates, which however may be included in compositions of
the
invention as heavy metal ion sequestrant components.
The organo diphosphonic acid is preferably a C1-C4 diphosphonic acid, more
preferably
a C2 diphosphonic acid, such as ethylene diphosphonic acid, or most preferably
ethane 1-
hydroxy-1,1-diphosphonic acid (HEDP) and may be present in partially or fully
ionized
form, particularly as a salt or complex.
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.
Alkali Metal Silicate
An alkali metal silicate is a preferred component of the tablet of the present
invention. 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%
CA 02333388 2000-11-24
i i~ . . .
WO 00/04123 PCTNS99/I4861
68
to I2% 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 first and/or second and/or optionally further phases may contain a
colourant, a
mixture of colourants, coloured particles or mixture of coloured particles
such that the
various phases have different visual appearances. Preferably one of either the
first or
the second phases comprises a colourant. Where both the first and second
and/or
subsequent phases comprise a colourant it is preferred that the colourants
have a different
visual appearance.
Examples of suitable dyes include reactive dyes, direct dyes, azo dyes.
Preferred dyes
include phthalocyanine dyes, anthraquinone dye, quinoline dyes, monoazo,
disazo and
CA 02333388 2003-12-23
69
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 BLilE
TM
(tradename) both available from Pointings, UK, ULTRA MARINE BLUE (tradename)
available from Holliday or LEVAFIX TURQUISE BLUE EBA (tradename) available
from Baye~USA.
The colourant may be incorporated into the phases by any suitable method.
Suitable
methods include mixing all or selected detergent components with a colourant
in a drum
or spraying all or selected detergent components with the colourant in a
rotating drum
Colourant when present as a component of the first phase is present at a level
of from
0.001% to 1.5%, preferably from 0.01% to 1.0%, most preferably from 0.1% to
0.3%.
When present as a component of the second and/or optionally further phases,
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%.
Corrosion inhibitor compound
The 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-
CA 02333388 2000-11-24
. .
WO 00/04123 PCT/US99/14861
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
polyhydric
alcohols having from 1 to 40 carbon atoms in the hydrocarbon chain. Examples
of
suitable fatty alcohols include; behenyl, arachidyl, cocoyl, oleyl and lauryl
alcohol,
ethylene glycol, glycerol, ethanol, isopropanol, vinyl alcohol, diglycerol,
xylitol, sucrose,
erythritol, pentaerythritol, sorbitol or sorbitan.
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/14861
71
Preferably, the fatty acid and/or fatty alcohol group of the fatty ester
adjunct material
have from 1 to 24 carbon atoms in the alkyl chain.
Preferred fatty esters herein are ethylene glycol, glycerol and sorbitan
esters wherein the
fatty acid portion of the ester normally comprises a species selected from
behenic acid,
stearic acid, oleic acid, palmitic acid or myristic acid.
The glycerol esters are also highly preferred. These are the mono-, di- or tri-
esters of
glycerol and the fatty acids as defined above.
Specific examples of fatty alcohol esters for use herein include: stearyl
acetate, palmityl
di-lactate, cocoyl isobutyrate, oleyl maleate, oleyl dimaleate , and tallowyl
proprionate.
Fatty acid esters useful herein include: xylitol monopalmitate,
pentaerythritol
monostearate, sucrose monostearate, glycerol monostearate, ethylene glycol
monostearate, sorbitan esters. Suitable sorbitan esters include sorbitan
monostearate,
sorbitan palmitate, sorbitan monolaurate, sorbitan monomyristate, sorbitan
monobehenate, sorbitan mono-oleate, sorbitan dilaurate, sorbitan distearate,
sorbitan
dibehenate, sorbitan dioleate, and also mixed tallowalkyl sorbitan mono- and
di-esters.
Glycerol monostearate, glycerol mono-oleate, glycerol monopalmitate, glycerol
monobehenate, and glycerol distearate are preferred glycerol esters herein.
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
CA 02333388 2003-12-23
72
comprise generally from 12 to 70 carbon atoms. Preferred are petroleum waxes
of the
paraffin and microcrystalline type which are composed of long-chain saturated
hydrocarbon compounds.
Alginates and gelatin are suitable organic silver coating agents herein.
Dialkyl amine oxides such as C12-C20 methylamine oxide, and dialkyl quaternary
ammonium compounds and salts, such as the C 12-C20 methylammonium halides are
also suitable.
Other suitable organic silver coating agents include certain polymeric
materials.
Polyvinylpyrrolidones with an average molecular weight of from 12,000 to
700,000,
polyethylene glycols (PEG) with an average molecular weight of from 600 to
10,000,
polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-
vinylimidazole,
and cellulose derivatives such as methylcellulose, carboxymethylcellulose and
hydroxyethylcellulose are examples of such polymeric materials.
Certain perfume materials, particularly those demonstrating a high
substantivity for
metallic surfaces, are also 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
TM
hydrocarbons of 32:68, is sold by Wintershall, Salzbergen, Germany, under the
trade
name WINOG 70.
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/14861
73
Nitrogen-containing corrosion inhibitor compounds
Suitable nitrogen-containing corrosion inhibitor compounds include imidazole
and
derivatives thereof such as benzimidazole, 2-heptadecyl imidazole and those
imidazole
derivatives described in Czech Patent No. 139, 279 and British Patent GB-A-
1,137,741,
which also discloses a method for making imidazole compounds.
Also suitable as nitrogen-containing corrosion inhibitor compounds are
pyrazole
compounds and their derivatives, particularly those where the pyrazole is
substituted in
any of the 1, 3, 4 or 5 positions by substituents R1, R3, R4 and RS where R1
is any of H,
CH20H, CONH3, or COCH3, R3 and R5 are any of C1-C20 alkyl or hydroxyl, and R4
is any of H, NH2 or N02.
Other suitable nitrogen-containing corrosion inhibitor compounds include
benzotriazole,
2-mercaptobenzothiazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole, thionalide,
morpholine,
melamine, distearylamine, stearoyl stearamide, cyanuric acid, aminotriazole,
aminotetrazole and indazole.
Nitrogen-containing compounds such as amines, especially distearylamine and
ammonium compounds such as ammonium chloride, ammonium bromide, ammonium
sulphate or diammonium hydrogen citrate are also suitable.
Mn(II) corrosion inhibitor compounds
The detergent tablets may contain an Mn(II) corrosion inhibitor compound. The
Mn(II)
compound is preferably incorporated at a level of from 0.005% to 5% by weight,
more
preferably from 0.01 % to 1 %, most preferably from 0.02% to 0.4% by weight of
the
compositions. Preferably, the Mn(II) compound is incorporated at a level to
provide
from 0.1 ppm to 250 ppm, more preferably from 0.5 ppm to 50 ppm, most
preferably
from 1 ppm to 20 ppm by weight of Mn(II) ions in any bleaching solution.
CA 02333388 2000-11-24
v ,
~ .
WO 00/04123 PCT/US99/14861
74
The Mn (II) compound may be an inorganic salt in anhydrous, or any hydrated
forms.
Suitable salts include manganese sulphate, manganese carbonate, manganese
phosphate,
manganese nitrate, manganese acetate and manganese chloride. The Mn(II)
compound
may be a salt or complex of an organic fatty acid such as manganese acetate or
manganese stearate.
The Mn(II) compound may be a salt or complex of an organic ligand. In one
preferred
aspect the organic ligand is a heavy metal ion sequestrant. In another
preferred aspect
the organic ligand is a crystal growth inhibitor.
Other corrosion inhibitor compounds
Other suitable additional corrosion inhibitor compounds include, mercaptans
and diols,
especially mercaptans with 4 to 20 carbon atoms including lauryl mercaptan,
thiophenol,
thionapthol, thionalide and thioanthranol. Also suitable are saturated or
unsaturated C 10-
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 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
CA 02333388 2000-11-24
. " . ," .
WO 00/04123 PCT/US99/Id861
species 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.
Enzvme Stabilizing System
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 soak dis~ersant compound
CA 02333388 2000-11-24
i ~ . ., , ,
WO 00/04123 PCT/US99/14861
76
The tablets of the present invention 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 sunnressin~ system
The detergent tablets 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 1 S%, preferably from 0.05% to 10%, most preferably from 0.1
% to 5%
by weight of the composition.
Suitable suds suppressing systems for use herein may comprise essentially any
known
antifoam compound, including, for example silicone antifoam compounds, 2-alkyl
and
alcanol antifoam compounds. Preferred suds suppressing systems and antifoam
compounds are disclosed in PCT Application No. W093/08876 and EP-A-705 324.
Polymeric dye transfer inhibitin~agents
The detergent tablets herein may also comprise from 0.01% to 10 %, preferably
from
0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.
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
CA 02333388 2003-12-23
77
'fhe detergent tablets suitable for use in laundry washing methods as
described herein,
also optionally contain from 0.005% to 5% by weight of certain types of
hydrophilic
optical brighteners.
Hydrophilic optical brighteners useful herein include those having the
structural formula:
Rl R2
H H NO
N\OON O C C O NOO N
rN H H N
M SO M
RZ SO3 3
wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2
is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino,
morphilino,
chloro and amino; and M is a salt-forming ration such as sodium or potassium.
When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is
a ration
such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-
hydroxyethyl)-s-triazine-
2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular
brightener
species is commercially marketed under the tradename Tinopal-LJNPA-GX by Ciba-
TM
Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical
brightener
useful in the detergent compositions herein.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and
M is a ration such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-
hydroxyethyl-
N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium
salt. This
particular brightener species is commercially marketed under the tradename
Tinopal
SBM-GX by Ciba-Geigy Corporation.
CA 02333388 2003-12-23
78
When in the above formula. R1 is anilino, R2 is morphilino and M is a canon
such as
sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-
yl)amino]2,2'-
stilbenedisulfonic acid, sodium salt. This particular brightener species is
commercially
marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
Clay softening-system
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
TM
Gamble Company describe suitable organic polymeric clay flocculating agents.
Cationic fabric softenine agents
Cationic fabric softening agents can also be incorporated into compositions in
accordance with the present invention which are suitable for use in methods of
laundry
washing. Suitable cationic fabric softening agents include the water insoluble
tertiary
amines or dilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B-
0 011
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.
Other optional ingredients
CA 02333388 2000-11-24
y ,
WO 00/04123 PCT/US99/14861 _
79
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.
~H of the compositions
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.
Machine dishwashingLmethod
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 washin» 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.
CA 02333388 2000-11-24
..
.,
WO 00/04123 PCT/IjS99/14861
In a preferred use aspect a dispensing device is employed in the washing
method. The
dispensing device is charged with the detergent product, and is used to
introduce the
product directly into the drum of the washing machine before the commencement
of the
wash cycle. Its volume capacity should be such as to be able to contain
sufficient
detergent product as would normally be used in the washing method.
Once the washing machine has been loaded with laundry the dispensing device
containing the detergent product is placed inside the drum. At the
commencement of the
wash cycle of the washing machine water is introduced into the drum and the
drum
periodically rotates. The design of the dispensing device should be such that
it permits
containment of the dry detergent product but then allows release of this
product during
the wash cycle in response to its agitation as the drum rotates and also as a
result of its
contact with the wash water.
To allow for release of the detergent product during the wash the device may
possess a
number of openings through which the product may pass. Alternatively, the
device may
be made of a material which is permeable to liquid but impermeable to the
solid product,
which will allow release of dissolved product. Preferably, the detergent
product will be
rapidly released at the start of the wash cycle thereby providing transient
localised high
concentrations of product in the drum of the washing machine at this stage of
the wash
cycle.
Preferred dispensing devices are reusable and are designed in such a way that
container
integrity is maintained in both the dry state and during the wash cycle.
Alternatively, the dispensing device may be a flexible container, such as a
bag or pouch.
The bag may be of fibrous construction coated with a water impermeable
protective
material so as to retain the contents, such as is disclosed in European
published Patent
Application No. 0018678. Alternatively it may be formed of a water-insoluble
CA 02333388 2000-11-24
WO 00/04123 PCT/US99/14861
81
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.
Examples
Abbreviations used in Examples
In the detergent compositions, the abbreviated component identifications have
the
following meanings:
STPP : Sodium tripolyphosphate
Bicarbonate : Sodium hydrogen carbonate
Citric Acid : Anhydrous Citric acid
Carbonate : Anhydrous sodium carbonate
Silicate : Amorphous Sodium Silicate (Si02:Na20 ratio
= 2.0)
SKS-6 : Crystalline layered silicate of formula 8-Na2Si205
pg 1 : Anhydrous sodium perborate monohydrate
Nonionic ~ C 13-C 15 mixed ethoxylatedlpropoxylated 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
pApC : Pentaamine acetate cobalt (III) salt
Paraffin : Paraffin oil sold under the tradename Winog 70 by
Wintershall.
Protease : Proteolytic enzyme
Amylase . Amylolytic enzyme.
CA 02333388 2000-11-24
., i ~ ~ .
WO 00/04123 PCT/US99/1d861 _
82
BTA : Benzotriazole
Sulphate : Anhydrous sodium sulphate.
PEG 3000 : Polyethylene Glycol molecular weight approximately
3000 available from Hoechst
PEG 6000 : Polyethylene Glycol molecular weight approximately
6000 available from Hoechst
pH : Measured as a 1 % solution in distilled water at 20°C
In the following examples all levels are quoted as parts by weight:
Examples I-IV
The following illustrates examples detergent tablets of the present invention
suitable for
use in a dishwashing machine.
I II III IV V VI
Phase 1
STPP 9.62 9.62 10.45 9.57 9.57 11.47
Silicate 0.50 0.67 1.60 1.00 1.00 2.40
SKS-6 1.5 1.50 2.30 2.25
Carbonate 2.33 2.74 3.5 3.59 4.10 5.25
HEDP 0.18 0.18 0.18 0.28 0.28 0.28
PB 1 2.45 2.45 2.45 3.68 3.68 3.68
PAAC 0.002 0.002 0.002 0.003 0.004 0.004
Amylase 0.148 0.110 0.110 0.252 0.163 0.163
Protease 0.06 0.06 0.06 0.09 0.09 0.09
Nonionic 0.40 0.80 0.80 1.20 1.20 1.20
PEG 6000 0.4 0.26 0.26 0.38 0.39 0.39
BTA 0.04 0.04 0.04 0.06 0.06
Paraffin 0.10 0.10 0.10 0.15 0.15 0.15
CA 02333388 2000-11-24
'., ., , ..
WO 00/04123 PCT/US99/14861 _
83
Perfume 0.02 0.02 0.02 0.013 0.013 0.013
Sulphate 0.502 0.05 2.843
Total 17.75g 18.55g 19.57g 23.Og 23.Og 23.Og
Phase 2
Amylase 0.30 0.35 0.25 0.30 0.35 0.25
Protease 0.25 0.22 0.30 0.25 0.22 0.30
Citric acid 0.3 0.30 0.3 0.30
Sulphamic acid 0.3 0.3
Bicarbonate 1.09 0.45 0.45 1.09 0.45 0.45
Carbonate 0.55 0.55
Silicate 0.64 0.64
CaCl2 0.07 0.07
PEG 3000 0.06 0.06 0.06 0.06 0.06 0.06
Total 2.Og 2.Og 2.Og 2.Og 2.Og 2.Og
The mufti-phase tablet compositions are prepared as follows. The detergent
active
composition of phase 1 is prepared by admixing the granular and liquid
components and
is then passed into the die of a conventional rotary press. The press includes
a punch
suitably shaped for forming the mould. The cross-section of the die is
approximately
30x38 mm. The composition is then subjected to to a compression force of 940
kg/cm2
and the punch is then elevated exposing the first phase of the tablet
containing the mould
in its upper surface. The detergent active composition of phase 2 is prepared
in similar
manner and is passed into the die. The particulate active composition is then
subjected to
a compression force of 170 kg/cmz, the punch is elevated, and the mufti-phase
tablet
ejected from the tablet press. The resulting
tablets dissolve or disintegrate in a washing machine as described above
within 12
' minutes, phase 2 of the tablets dissolving within 5 minutes. The tablets
provide excellent
dissolution and cleaning characteristics together with good tablet integrity
and strength.
F
