Note: Descriptions are shown in the official language in which they were submitted.
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H MII~TI~pgASB DBTSRf~SNT TAHLCT
The present invention relates to mufti-phase dctecgent tablets. In particular,
it relates to
mufti-phase detergent tablets having improvtd pH control, cleaning and enzyme
performance together with excellent product sh~ength, integrity and
dissolutiaa
characteristics.
Detergent compositions in tablet form are known in the art. It is u~derscood
that
detergent compositions in tablet form hold several advarttagcs over detergeti<
compositions in particulate form, such as case of dosing. handling,
truosportatia~n and
stotagC.
Detergetrt tabkta are most commonhr prepared by pre-mixing compote of a dent
composition and forming the pne-mixed detergent components into a tablet using
any
suitable equipaneut, ptefeisbly a tablet press. 'tablets are typlcaliy formed
by
compression of the cod of the desargest composition sa fleet the tablets
produced
are scWciently robust to be abler to withstand handl;rg and traa~porigtioa
without
sustaining damage. In addition to being robust, tablets must also dissolve
sufytcieatly
fast so that the detetgcm compote are ieka,sed into the wash water as soon as
possible
at the beginning of the wash cydc.
How~cvcr, a dichotomy exists is that as compression force is increased, the
rate of
dissolution of the tablets is slower_ The precast imrentian thetsfore sales to
fud a
balance between tablet robustness and tablet dissolution.
Solutions to thin problem, as seen in the prior atrt, have inchxled
compretsiag the tablets
with low compression pressure. However tablets made ip this way, although
having a
fast relative dissolution rate, tend to crumble, becoming damaged and
unacceptable to the
consu~r. Other solutions have included preparing tablets using a high relative
compression pres~ur, in order to achieve the required level of rodusmcss, and
comprising a dissolution aid, such as an effervescent agent.
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Mufti-phase detergent tablets described in the prior art are prepared by
compressing a
first composition in a tablet press to form a substantially planar first
Layer. A further
detergent composition is then delivered to the tablet press on top of the
first layer. This
second composition is then compressed to form another substantially planar
second
layer. Thus the first layer is generally subjected to more than one
compression as it is
also compressed during the compression of the second composition. Typically
the first
and second compression forces are in the same order of magnitude. The
Applicant has
found that where this is the case, because the compression. force must be
sufficient to
bind the first and second compositions together, the force used in both the
first and
second compression steps must be in the range of from about 4,000 to about
20,000 kg
(assuming a tablet cross-section of about 10 cmz). - A consequence of this is
a slower rate
of tablet dissolution. Other mufti-phase tablets exhibiting differential
dissolution are
prepared such that the second layer is compressed at a lower force than the
first layer.
However, although the dissolution rate of the second layer is improved, the
second layer
is soft in comparison to the first Layer and is therefore vulnerable to damage
caused by
handling and transportation.
There is a further aspect of the hardness/dissolution dichotomy that
particularly applies
to tablet compositions containing acid-based effervescent or disrupting
agents.
Thus, improved dissolution can be achieved by incorporating an effervescent
(bi)carbonate/acid couple in amounts sufficient to lead to rapid disruption of
the
detergent tablet, but the higher the level of effervescent agent and the
faster the
dissolution of the tablet, the worse the pH control, cleaning and enzyme
performance
during the vital first four or five minutes of the wash. In a fixed cycle
washing machine,
it is important to achieve the optimum pH for cleaning and enzyme performance
as
rapidly as possible, especially when the detergent contains enzymes of high
specificity.
Applicant has now discovered that this can be achieved by the use of a mufti-
phase
detergent tablet incorporating certain alkalising and acidifying agents and
formulated to
provide rapid dissolution in automatic dishwashing or laundry washing machine.
The present invention thus provides a mufti-phase detergent tablet having
improved pH
control, cleaning and enzyme performance together with excellent product
strength,
integrity and dissolution characteristics.
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3
Summary of the Invention
According to a first aspect of the invention, there is provided a mufti-phase
detergent
tablet for use in a washing machine, the tablet comprising a first phase
comprising
alkalising agent, and a second phase comprising acidifying agent, and wherein
the multi-
phase tablet has an initial pH of at least 9, preferably at least 9.3, more
preferably at least
9.5 and a pH rate change index (~pH) of no more than about 0.17, preferably no
more
than about 0.16, more preferably no more than about 0.15 and especially no
more than
about 0.14 units/min.
Preferred herein are mufti-phase detergent tablets wherein the alkalising
agent is a
silicate or mixture of silicates, preferably including at least a sodium
silicate of the
crystalline layered variety; while the acidifying agent (sometimes herein
referred to
simply as 'acid') is part of a (bi)carbonate/acid effervescent couple which
acts as
disrupting agent for the tablet.
Thus, according to a 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 comprising silicate alkalising agent includiing at least a
crystalline
layered sodium silicate of general formula I
NaMSix02x+I ~YH2~
wherein M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from
1.9 to 4
and y is a number from 0 to 30, preferably from 0 to 20, and
b) a second phase comprising a (bi)carbonate/acid disrupting agent,
and wherein the mufti-phase tablet has an initial pH of at least 9, preferably
at least 9.5
and a pH rate change index (apH) of no more than about 0.1? units/min,
preferably no
more than about O. I S units/min.
In preferred embodiments, the mufti-phase detergent tablets of the invention
contain
silicate alkalising agent and acid in a weight ratio of at least about 1:1,
preferably at least
about 5:1, and more preferably in the range from about 8:1 to about 25:1, this
being
preferred from the viewpoint of optimum pH control and clleaning performance.
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Thus, according at a further aspect of the invention, there is provided a
mufti-phase
detcrgent tablet for use in a washing machine, the tablet .comprising
a) a first phase comprising silicate alkalising agent including at least a
crystalline
layered sodium silicate of general formula I
NaMSix02x+1 ~YH2~ I
wherein M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from
1.9 to 4
and y is a number from 0 to 30, preferably from 0 to 20, and
b) a second phase comprising a (bi)carbonate/acid disrupting agent,
and wherein the tablet contains silicate alkalising agent and acid in a weight
ratio of at
Least about 1:1, preferably at least about 5:1.
Unless otherwise specified, all proportions and ratios herf;in are on an 'as-
used' weight
basis, i.e., including any water of hydration if added in hydrate form.
In preferred mufti-phase detergent tablets, the silicate alkalising agent
comprises at least
about 25%, preferably at least about 50% and more preferably at least about
75% by
weight thereof of the crystalline layered sodium silicate oif general formula
I and is
present in an amount of from about 1% to about 25%, preferably from about 5%
to about
20%, more preferably from about 8% to about 18% by weight of the tablet. The
acid, on
the other hand, generally comprises from about 0.1 % to about 10%, preferably
from
about 0.5% to about 5%, more preferably from about 0.8°ro to about 3%
of acid by weight
of the tablet. The tablets are preferably essentially free of silicate of the
metasilicate
variety.
The mufti~phase detergent tablets comprise two or more phases (additional
phases
sometimes being referred to herein as 'optional subsequent phases'), a first
phase
comprising an alkalising agent and a second phase comprising an acidifying
agent, the
compositions, relative proportions and dissolution kinetics of the phases
being
preferably such as to provide an initial pH of at least about: 9, more
preferably at least
about 9.3, and especially at least about 9.5, and a pH rate change index (OpH)
of no
more than about 0.17, preferably no more than about 0.16, more preferably no
moe than
about 0.15, and especially no more than about 0.14 units/rnin. The pH profile
of the
detergent tablets herein is generally measured in an automatic washing machine
in the
presence of a conventional soil load, the initial pH herein being taken to be
the pH of the
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S
wash medium at 1 minute after the start of dissolution and. the pH rate change
index
being taken to be the average pH change/minute between 1 and S minutes. The
multi-
phase tablets have generally rapid dissolution kinetics and are preferably
formulated such
that the second phase dissolves in a washing machine within S minutes.
In preferred embodiments, the first phase of the mufti-phase tablet is
composed of a built
active detergent composition comprising by weight thereof
( 1 ) from about I % to about 12%, preferably from about S'% to about 10% of
the
crystalline layered sodium silicate of general formula I,
(2) from 0% to about 70%, preferably from about 10% to about 60% of
polyphosphate,
zeolite, andlor polycarboxylate builders,
(3) from 0% to about 30%, preferably from about S% to at>out 20% of carbonate
andlor
bicarbonate, and
(4) from 0% to about 10%, preferably from 0% to about S°,~o of
amorphous silicate.
The second phase of the tablet, on the other hand, is preferably a detergent
active
composition comprising by weight thereof
(1) from about 1% to about 90%, preferably from about 10% to about 60%, more
preferably from about 2S% to about SO% of one or more enzyme compositions, and
(2) from about 10% to about 99%, preferably from about 30% to about 80% and
more
preferably from about 40% to about 60% by weight of a (bi)carbonate/acid
effervescent
couple comprising (bi)carbonate and acid in a weight ratio of from about 10:1
to about
1:10, preferably from about 6:1 to about 1:3, more preferalbly from about 4:1
to about
1:1.
Crystalline layered silicates suitable for use herein as alkalising agents
and/or builders
are disclosed for example, in EP-A-0164514, EP-A-0293640, DE-A-3417649 and DE-
A-
3742043. Preferred are the crystalline layered sodium silicates of general
formula I
wherein M is sodium or hydrogen, x is a number from 1.9 t:o 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. 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-
Na2Si20S, known as NaSKS-6 (trade name), available from Hoechst AG.
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Amorphous alkali metal silicates can also be present as alkalising agents
herein. A
preferred alkali metal silicate is sodium silicate having an Si02:Na20 ratio
of from 1.8
to 3.0, preferably from I .8 to 2.4, most preferably 2Ø Th.e alkali metal
silicate may be in
the form of either the anhydrous salt or a hydrated salt.
In preferred embodiments, the first phase is a compressed shaped body prepared
at an
applied compression pressure of at least about 250 kg/cm'', preferably at
least about 350
kg/cm2 (3.43 kN/cmz or 34.3 MPa), more preferably from about 400 to about 2000
kg/cm2, 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). The second phase, on the other hand, is preferably formed
at a
compression pressure of less than about 350 kg/cm2, preferably in the range
from about
40 kg/cmz to about 300 kg/cm2 and more preferably from about 70 to about 270
kg/cm2.
In preferred embodiments, moreover, the first phase is formed by compression
at a
pressure greater than that applied to the second phase. In tlhese embodiments,
the
compression pressures applied to the first and second phases will generally be
in a ratio
of at least about 1.2:1, preferably at least about 2:1, more preferably at
least about 4:1.
Although simple multi-layer tablets are envisaged for use herein, preferred
from the
viewpoint of optimum product integrity, strength (measure:d fox example by the
Child
Bite Strength [CBS] test) and dissolution characteristics are tablets wherein
the first
phase is in the form of a shaped body having at least one mould therein; and
the second
phase is in the form of a particulate solid compressed withiin said mould.
Such
embodiments are sometimes referred to herein as 'mould' embodiments. The
tablets of
the invention, both mould embodiments and otherwise, wil.i preferably have a
CBS of at
least about 8kg, preferably greater than about l0kg, more preferably greater
than about
l2kg, and especially greater than about l4kg, CBS being measured per the US
Consumer
Product Safety Commission Test Specification.
It is also preferred that the first and second phases herein are in a
relatively high weight
ratio to one another, for example at least about 6:1, preferably at least
about 10:1; also
that the tablet composition contain one or more detergent a~;,tives (for
example enzymes,
bleaches, bleach activators, bleach catalysts, surfactants, chelating agents
etc) which is
predominantly concentrated in the second phase, for examp~ie, at least about
SO%,
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
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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 SO%, preferably at least 60%, and more
preferably at
least 80% by weight of the detergent active to the wash liquor within 10, 5, 4
or even 3
minutes of the start of the wash process.
Detailed Description of the Invention
It is an object of the present invention to provide a detergf;nt 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 t:he 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 4490 using a dishwashing
machine available from Bosch on the normal 65°C washing program with
water hardness
at 18°H using a minimum of six replicates or a sufficient number to
ensure
reproducibility.
The mufti-phase detergent tablet of the present invention comprises a first
phase, a
second and optional subsequent phases. The first phase is preferably in the
form of a
shaped body of detergent composition comprising one or more detergent
components
(including one or more alkalising agents) as described below. Preferred
detergent
components include, builder, bleach, enzymes and surfactant. The components of
the
detergent composition are mixed together by; for example admixing dry
components or
spraying-on liquid components. The components are then :formed into a first
phase using
any suitable equipment, but preferably by compression, for example in a tablet
press.
Alternatively, the first phase can be prepared by extrusion, casting, etc.
In mould embodiments, the f rst phase is prepared such that it comprises at
least one
mould in the surface of the shaped body. In a preferred embodiment the mould
is created
using a specially designed tablet press wherein the surface of the punch that
contacts the
detergent composition is shaped such that when it contacts .and presses the
detergent
composition it presses a mould, or multiple moulds into the f rst phase of the
mufti-phase
CA 02337408 2003-12-09
dettxge~nt tablet. Preferably, the mould will have an inwardly concave or
generally
concave surface to provide improved adhesion to the second phase.
She tablets of the invention also include one or more~additional phases
prepared from a
composition or compositions which comprise one or more detergent components
{including at least one acidifying agent) as described below. At least one
phase (herein
reftired to as a second phase) preferably takes the form of a particulate
solid (which tenor
encompasses powders, granules. agglomerates, ana other pardcularta solids
including
mixtures thereof with liquid binders, meltable solids, spray-ones, etc)
compressed either
as a layer or intolwithin the one or more moulds of the first phase ofthe
detergent tablet
such that the second phase itself takes the form of a shaped body. Preforned
detergem
eomponcats include builders, colourants, binders. surfactants, disinlegtsting
agents and
enzymes, in particular amylase and protease enzymes. Suitable disintegrating
agmts
include agents that swell on contact with water or facilitate water influx
andlor efflux by
forming Channels itt the detergent tablet. Any known disintegrating or
egerveacing agent
suitable for use ie laundry or dishwashing applications is envisaged for use
herein.
Suitable disinttgrating agent include starch, starch derivatives such as
Atboea~
(tradename), Yivaptu~tradenama) bath available from Restenmaier.
Nyraoe~tradaoarnt)
available from Metsa-series , alginates, acetate trihydrate, burkeite,
monohydrated
carbonate formula NalCO,.H,O, hydrated STPP with a phase I content of at least
about
40% , cerboxymethylcellulose (CMC), CMC-based polynxrs, sodium serrate,
aluminium oxide. In addition, the second phase preferably also cotuaias a
combination
of (bi)carbonate and a ware solubk acid which together form an affervetetat
couple and
act as a disrupting agent far the tablet. Preferred acids include inorganic
acids such as
sulphamic acid and carboxylic acids such as citric, malic and makic acid and
mi7ctuces
thereof.
The components of the detergent composition are mixed together by for
exatfxplt
admixing dry components and adttiixing or spraying-on liquid componalts. The
components of the second and optionally subsequent phases are then phases are
then
compressed to form one or more layers or are fed into and retained within the
mould
provided by the first phase.
'Ii~e preferred mould embodiments of the present invtntion 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
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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
optional 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
having an average molecular weight of from about I 000 to about 12000,
especially those
of molecular weight 4000, 6000 and 9000, 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
polyethyleneglycol binders are highly preferred herein.
In a preferred aspect of the present invention the first phase weighs greater
than Sg.
More preferably the first phase weighs from I Og to 30g, even more preferably
from 15g
to 25g and most preferably form 18g to 24g. The second and optionally
subsequent
phases weigh less than 4g. More preferably the second and/or optionally
subsequent
phases weigh between lg and 3.Sg, most preferably from 1.3g to 2.Sg.
In another embodiment of the present invention, a barrier layer comprising a
barrier layer
composition is located between the first and second phase and/or optionally
subsequent
phases or indeed between the second and optionally subseduent 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 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 lbecause a low
compression
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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.
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 optional
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 15 minutes and the second and/or optional
subsequent phases dissolve in less than 5 minutes, more preferably less than
4.5 minutes,
most preferably less than 4 minutes. The time in which the first, second
and/or optional
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 optional
subsequent
phase(s).
The mufti-phase detergent tablets are prepared using any :>uitable tabletting
equipment.
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 desi fined tablet
press. 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 frst detergent composition is delivered into the die of ttie tablet press
and the punch is
lowered to contact and then compress the detergent composition to form a f rst
phase.
The first detergent composition is compressed using an applied pressure of at
least 250
kg/cm2, preferably between 350 and 2000 kg/cm2, more preferably 500 to 1500
kglcmz,
most preferably 600 to 1200 kg/cm2. The punch is then elc;vated, exposing the
first phase
containing a mould. A second and optional subsequent detergent compositions)
is then
delivered into the mould. The specially designed tablet prcas punch is then
lowered a
second time to lightly compress the second and optional subsequent detergent
compositions) to form the second and optional subsequent: phase(s). In another
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PCTIUS99/15491
embodiment of the present invention where an optional subsequent phase is
present the
optional subsequent phase is prepared in an optional subsequent compression
step
substantially similar to the second compression step described above. The
second and
optional subsequent detergent composition{s) is compressed at a pressure of
preferably
less than 350 kg/cm2, more preferably from 40 to 300 kg~cmz, most preferably
from 70 to
270 kg/cmz. After compression of the second detergent composition, the punch
is
elevated a second time and the mufti-phase detergent tablet is ejected from
the tablet
press. Mufti-layer tablets without moulds can be prepared in a similar manner
except
using a tablet punch having a planar surface.
The mufti-phase detergent tablets comprise two or more phases, a first phase
comprising
an alkalising agent and a second phase comprising an acidifying agent.
Preferred
alkalising agents herein have a pH in 1 % aqueous solution or dispersion
(25°C) of at
least about 9, preferably at least about 10; preferred acidifying agents, on
the other hand
have a pH under similar conditions of less than about 6.5. Preferred
alkalising and
acidifying agents are mufti-fimctional, for example they c,an also having
building or
sequestering functionality.
Each phase of the tablet is in general composed of one or amore compositions
comprising
detergent active components. Suitably, the compositions used in any of 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. In the following, the proportions
of these
active components are given by weight of the corresponding composition of
active
detergent components, unless specified otherwise.
Highly preferred detergent components of the first phase include a builder
compound, a
surfactant, an enzyme and a bleaching agent. Highly preferred detergent
components of
the second phase include builder, enzymes and disrupting agent.
Builders suitable for use herein include water-solu>rle builders such as
citrates,
carbonates and polyphosphates and partially water-soluble or insoluble
builders such as
crystalline layered silicates (EP-A-0164514 and EP-A-0293640) and
aluminosiiicates
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PCTIUS99/1549I
inclusive of Zeolites A, B, P, X, HS and MAP. The builder is typically present
at a level
of from about 1 % to about 80% by weight, preferably from about 10% to about
70% by
weight, most preferably from about 20% to about 60% by weight of composition.
Surfactants suitable herein include anionic surfactants such as alkyl
sulfates, alkyl ether
sulfates, alkyl benzene sulfonates, alkyl glyceryl sulfonates, alkyl and
alkenyl
sulphonates, alkyl ethoxy carboxylates, N-aryl sarcosinates, N-acyl taurates
and alkyl
succinates and sulfosuccinates, wherein the alkyl, alkenyl or acyl moiety is
CS-C20 ,
preferably C 10-C 1 g linear or branched; cationic surfactants such as choline
esters (US-
A-4228042, US-A-4239660 and US-A-4260529) and mono C6-C16 N-alkyl or alkenyl
ammonium surfactants wherein the remaining N positions are substituted by
methyl,
hydroxyethyl or hydroxypropyl groups; low and high cloud point nonionic
surfactants
and mixtures thereof including nonionic alkoxylated surfactants (especially
ethoxylates
derived from C6-Clg primary alcohols), ethoxylated-propoxylated alcohols
(e.g., Olin
Corporation's Poly-Tergent~ SLF18), epoxy-capped poly(oxyalkylated) alcohols
(e.g.,
Olin Corporation's Poly-Tergent~ SLF18B - see WO-A-94/22800}, ether-capped
poly(oxyalkylated) alcohol surfactants, and block polyoxyethylene-
polyoxypropylene
polymeric compounds such as PLURONIC~, REVERSEI) PLURONIC~, and
TETRONIC~ by the BASF-Wyandotte Corp., Wyandotte,, Michigan; amphoteric
surfactants such as the amine oxides and alkyl amphocarba~xylicc surfactants
such as
MiranoITM C2M; and zwitterionic surfactants such as the tretaines and
sultaines; and
mixtures thereof. Surfactants suitable herein are disclosed, far example, in
US-A-
3,929,678 , US-A- 4,259,217, EP-A-0414 549, WO-A-93/08876 and WO-A-931088?4.
Surfactants are typically present at a level of from about 0.:?% to about 30%
by weight,
more preferably from about 0.5% to about 10% by weight, most preferably from
about
1% to about 5% by weight of composition.
Enzymes suitable herein include bacterial and fungal cellulases such as
Carezyme and
Celluzyme (Novo Nordisk A/S); peroxidases; lipases such as Amano-P (Amano
Pharmaceutical Co.), M1 LipaseR and LipomaxR (Gist-Brocades) and Lipolase'~
and
Lipolase UltraR {Novo); cutinases; proteases such as EsperaseR, AlcalaseR,
DurazymR and
SavinaseR (Novo) and MaxataseR, MaxacalR, ProperaseR and MaxapemR (Gist-
Brocades);
and a and ~i amylases such as Purafect Ox AmR (Genencor) and Termamyl~, Bang,
FungamylR, DuramylR, and NatalaseR (Novo); and mixtures thereof. Enzymes are
preferably added herein as prills, granulates, or cogranulates at levels
typically in the
range from about 0.0001 % to about 2% pure enzyme by weiight of composition.
CA 02337408 2003-12-09
13
Bleaching agents suitable herein include chloriae and oxygen bleaches,
especially
inorganic ptrhydrate salts such as sodium perborate mono~and tetrahydrates and
sodium
percarbonate optionally coated to provide controlled rate of reiease (see, for
example,
GB~A-1466799 on sulfatelcarbonate coatings}, preformed organic peroxyacids ~d
mixtures thertof with organic peroxyacid bkach prxue~sars and/or ttatssition
metal-
containiag bleach catalysts (especially mangarxse or cobalt). Inorganic
perhydrate salts
are typically incorporated at levels in the range fionn a6otrt 1 % to about
40% by weight,
preferably from about 2% to about 30% by weight and more preferably from abut
5% to
about 23% by weight of composition. Peroxyacid bleach precursors preFerrtd for
use
herein include precursors of perbenzoic acid and substituted perbenzaie acid;
cationic
peroxyacid precursors; peracetic acid precursors such as TAED, sodium
acetoxyben~ene
sulfonate and pentaacetylglucoae; pernonanoic acid precursors such as sodium
3,5,5-
trimethythexanoyloxybenzene sulfonate (iso-NOHS) and sodium
nonanayloxybestxs'ne
sulfonait (NUBS); amidt substituted alkyl peroxyacid precursors (EP-A-
0170386): and .
be~oxazia peroxyacid pzscursors (EP-A-U332294 and Ei'-A-4482$07 Bkach
p~ursors are typically incorporated si levels in the range from about
0.5°/. to about
ZS%, preferably from about 1 % to about 10°/a by weight of composition
while the
preformed organic pcroxyacids themselves are typically incorporated at. ltvels
in the
range from 0.5% to 25% by weight, more preferably from I% to
10°l° by weight of
composition. Bleach catalysts preferred for use hereat include the manganese
tria~cyclononane and related complexes (US-A-4246612, US-A-522084); Co, Cu, Mn
and Fe bispyridylamine and related complexes (U$-A-5114511 ); and penmmine
a~ste
cobalt(III) and related complexes(U5-A-4810410),
Other Suitable components herein include organic polymers having dispersant,
anti-
redeposition, soil release or other detergency properties invention in levels
of from about
0.1% to about 30%, prefctably from about O.Sdrb~to about 1S%, most preferably
from
about 1 % to about 10'/a by weight of composition. Preferred anti-redeposition
polymers
herein include acrylic acid containing polymers such as Sokalaa~'A30, PA20,
PA15,
PA10 and Sokalan CP10 (BASF Gmbl~; AcusoI~SN, 480N, 450N (Rohm and Haas),
acrylic acidlmaleie acid copolymers such as Sokalan CPS and
acrylichnethacrylic
copolymers. Preferred soil release polymers herein include alkyl and
hydroxyaikyl
celluloses (US-A-4,000,093), polyoxyethylenes, polyoxypropylenes and
copolymers
thereof, and nonionic and anionic polymers based on terephthalate esters of
ethylene
glycol, propylene glycol and mixtures thet~caof,
CA 02337408 2003-12-09
14
Heavy metal sequestranis and crystal growth inhibitors are suitable for use
herein f to
levels getteratly from about 0.005'y6 to about 20%, preferably ftnm about 0.1
% to shunt
14%, mOrt preferably from about 0.25'/. to abotrt 7.5% and roost prefbrably
from about
O.S% to about 5% by weight of composition, for exampk diethyla~etriamine
perrta
(methylene phosphcmat~e), ethyknediamine tetra(mtthylme pbosp~tounate)
h~rlenediamin~e te<ra(medtylax Phote~ athyleae diphoaphonare. hydrr>xy
etliylerre-1,1~dighosphonate, nitrilotriatetata, ethyletaediaminotetracettte,
ethylenadiamine~N,N-disuccinate in their salt and free said farms.
?he cotnposiiians heroin. espedally for use in dishwashing, can contain a ion
inhibitor such ss organic silver coating agents in levels of from about O.OS%
to about
10%, praf~ably from about o.i% to about s% by weiglrt of composition
(espeeisily
paraflins such as winof ~0 sold by Wimeraltafl, Salabagr~, Gernmy~
cv>itainiag corrosion inhibitor cosllpounds (for example betsxotriazole and
benama~damole~
- see GB-A-1137741) and Mn(~ compounds, particularly Mn(II) salts of argt~nnte
li~ands
in levels of from about 0.005'/e to about 5%, preferably from about 0.01'J~i
to shook !%,
moos preferably from about 0.029 to about 0.4% by weight of the co~positloa
Other suitable corrrportems herein include oolourants, waiter-soluble
bistxttrth contpouads
such as bi~nuth acetate and bismuth citrate at levels of from shoat 0.01'!6 to
about 5%,
eazymo seabtlizars such as calcium ion, boric acid, propylene glycol and
chlorirja bleach
scavengers at levels of from about 0.01 % to about boo, lime soap disper~utts
(see w0-A~
93/08$77), suds suppcrsaors (see w0-93/08876 and EP-A-0705324 polymeric dye
tier idubiting agents, opt;cal brigittenas, pefiunes, sliers and day ~d
cationic
fabric soileners.
Detergent components suitable for ux heroin are described in revere detail in
the
Appendix to the Description (Ret~ ADwlL)
A prefetrzd machine dishwashing method comprises treating soiled articles
selected fiam
crockery, giaRSwart, silverware, metallic items, cutlery and tnixtnKS tlu~eo~
with an
aqueous liquid having ~fissolved or dispensed therein an effective amrnmt ofa
the hdtein
described compositions. By an effectivt amount is meant from 8g m 60g
ofptoduct
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 convernional
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WO 00/04117 PCT/US99/1549I
machine dishwashing methods. Preferably the detergent tablets are from 15g to
40g in
weight, more preferably from 20g to 35g in weight.
Machine laundry methods herein typically comprise treating soiled laundry with
an
aqueous wash solution in a washing machine having dissolved or dispensed
therein an
effective amount of the herein described compositions. 13y an effective amount
is meant
from 40g to 3008 of product dissolved or dispersed in a v~rash solution of
volume from S
to 65 litres, as are typical product dosages and wash solution volumes
commonly
employed in conventional machine laundry methods.
In a preferred use aspect .a dispensing device is employed in the washing
method. The
dispensing device is charged with the detergent product, and is used to
introduce the
product directly into the drum of the washing machine before the commencement
of the
wash cycle. Its volume capacity should be such as to be ;~.ble to contain
sufficient
detergent product as would normally be used in the washing method.
To allow for release of the detergent product during the wash the device may
possess a
number of openings through which the product may pass. Alternatively, the
device may
be made of a material which is permeable to liquid but impermeable to the
solid product,
which will allow release of dissolved product. Preferably, the detergent
product will be
rapidly released at the start of the wash cycle thereby providing transient
localised high
concentrations of product in the drum of the washing machine at this stage of
the wash
cycle.
Preferred dispensing devices are reusable and are designedl in such a way that
container
integrity is maintained in both the dry state and during the wash cycle.
Alternatively, the dispensing device may be a flexible container, such as a
bag or pouch.
The bag may be of fibrous construction coated with a water impermeable
protective
material so as to retain the contents, such as is disclosed in EP-A-0018678.
Alternatively it may be formed of a water-insoluble synthetic polymeric
material
provided with an edge seal or closure designed to rupture in aqueous media as
disclosed
in EP-A-0011500, EP-A-0011501, EP-A-0011502, and EP-A-0011968. A convenient
form of water frangible closure comprises a water soluble adhesive disposed
along and
sealing one edge of a pouch formed of a water impermeable polymeric film such
as
polyethylene or polypropylene.
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16
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 carlbonate
Silicate , Amorphous Sodium Silicate (Si02:Na20 ratio
= 2.0)
SKS-6 , Crystalline layered silicate of formula
8-Na~Si205
PB 1 . Anhydrous sodium perborate monohydrate
Nonionic . C1~-C15 mixed ethoxylated/propoxylated
fatty
alcohol with an averagf; degree of ethoxylation
of 3.8
and an average degree of propoxyIation of
4.5, sold
under the tradename Plurafac by BASF
TAED : Tetraacetyl ethylene di<~mine
HEDP . Ethane 1-hydroxy-1,1-diphosphonic acid
PAAC . Pentaamine acetate cobalt (III) salt
Paraffin . Paraffin oil sold under the tradename
Winog 70 by
Wintershall.
Protease . Proteolytic enzyme
Amylase . AmyloIytic enzyme.
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
The pH profile of the compositions was measured in a Hotpoint Delux, using the
Economy 50°C cycle and Newcastle City water {average hardness 8-9
grains per gallon)
as follows:
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WO OOJ04117 PCT/US99/15491
17
1. Preheat the dishwasher using Economy 50°C cycle. After main wash,
cool machine
using prewash cycles until internal temperature is approximately 25°C.
2. Weigh 70g of food soil . Food soil consists of oat flakes (960g), tea
(160g), spinach
(640g), full fat milk (200m1}, butter (320g}, mince and onions (440g}, eggs
(720g) and
Newcastle City water (41).
3. Start machine on cycle Economy 50°C. When arm roti~tion starts, open
door and add
tablet to bottom of machine and DIN soil to upper basket i.n upturned cup.
Close door
and start stop watch.
4. After 1 minute, take sample of water from side of machine and measure pH
{initial
pH)
5. After reading pH, pour test solution back into machine.
6. Continue taking test solutions at time intervals: 2, 3, 4, :5, 7, 10, 12
and 15 minutes,
replacing solution in machine after pH reading has been taken.
7. Compute OpH: (pHs m,~s -pHt m;"}~4
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 1.5 2.30 2.25 2.3
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
ii:
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WO 00/04117 PCT/US99115491
18
Paraffin 0.10 0.10 0.10 0.15 0.15 0.15
Perfume 0.02 0.02 0.02 0.013 0.013 0.013
Sulphate 0.502 0.05 2.843
Total 17.75g18.55g 21.07g 23.08 23.0g 25.38
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 follovvs. The detergent
active
composition of phase I is prepared by admixing the granular and liquid
components and
is then passed into the die of a conventional rotary press. '.Che 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
kglcm2
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/cm2, 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 initial pH of the compositions is in excess of 9.5 while ~pH is
less than
0.14 unitslmin. The tablets provide improved pH control, cleaning and enzyme
performance together with excellent product strength, integrity and
dissolution
characteristics.
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WO Op/04117
19
Appendix to the Descrintiion
Builders
Water-soluble builder compound
PCT/US99/15491
Ref ADW1L
Suitable water-soluble builder compounds include the water soluble monomeric
polycarboxylates, or their acid forms, homo or copolyme;ric 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 ai:oms, 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 containiing one carboxy group include the water soluble
salts of
lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates
containing two
carboxy groups include the water-soluble salts of succinic: acid, malonic
acid,
(ethylenedioxy) diacetic acid, ma.leic acid, diglycolic acid, tartaric acid,
tartronic acid and
fumaric acid, as well as the ether carboxylates and the sul:finyl
carboxylates.
Polycarboxylates containing three carboxy groups include;, in particular,
water-soluble
citrates, aconitrates and citraconates as well as succinate dlerivatives such
as the
carboxymethyloxysuccinates described in GB-A-1,379,241, lactoxysuccinates
described
in GB-A-1,389,732, and aminosuccinates described in NL~-A-7205873, and the
oxypolycarboxylate materials such as 2-oxa-1,1,3-propane; tricarboxylates
described in
GB-A-1,387,447.
Polycarboxylate containing four carboxy groups include o:xydisuccinates
disclosed in
GB-A-1,261,829, I,I,2,2-ethane tetracarboxylates, 1,1,3,3-propane
tetracarboxyIates and
1.,1,2,3-propane tetracarboxylates. Polycarboxylates cont~~ining sulfo
substituents
include the sulfosuccinate derivatives disclosed in GB-A-1,398,421, GB-A-
1,398,422
and US-A-3,936,448, and the sulfonated pyrolysed citrates. described in GB-A-
1,439,000.
Alicyclic and heterocyclic polycarboXylates include cyclopentane-cis,cis,cis-
tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-
tetrahydrofuran - cis, cis,
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WO 00/04117 PCTIUS99/15491
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 Fund the phthalic
acid
derivatives disclosed in GB-A-1,425,343.
Of the above, the preferred polycarboxylates are hydroxycarboxylates
containing up to
three carboxy groups per molecule, more particularly citrates.
The parent acids of the monomeric or oligomeric polycarboxylate chelating
agents or
mixtures thereof with their salts, e.g. citric acid or citrate/citric acid
mixtures are also
contemplated as useful builder components.
Borate builders, as well as builders containing borate-fornning materials that
can produce
borate under detergent storage or wash conditions can also be used but are not
preferred
at wash conditions less that SO°C, especially less than 4CI°C.
Examples of carbonate builders are the alkaline earth and alkali metal
carbonates,
including sodium carbonate and sesqui-carbonate and mixtures thereof with
ultra-fine
calcium carbonate as disclosed in DE-A-2,321,001.
Highly preferred builder compounds for use in the present compositions are
water-
soluble phosphate builders. Specific examples of water-soluble phosphate
builders are
the alkali metal tripolyphosphates, sodium, potassium and ammonium
pyrophosphate,
sodium and potassium and ammonium pyrophosphate, sodium and potassium
orthophosphate, sodium polymeta/phosphate in which the degree of
polymerisation
ranges from 6 to 21, and salts of phytic acid.
Specific examples of water-soluble phosphate builders are; the alkali metal
tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and
potassium and ammonium pyrophosphate, sodium and potassium orthophosphate,
sodium polymeta/phosphate in which the degree of polymerization ranges from 6
to 21,
and salts of phytic acid.
Partially soluble or insoluble builder compound
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WO 00104117 PCTIUS99/15491
21
The compositions herein can contain a partially water-soluble or water-
insoluble builder
compound. Partially soluble and insoluble builder compounds are particularly
suitable
for use in tablets prepared for use in laundry cleaning methods. Examples of
partially
water soluble builders include the crystalline layered silicz~tes as disclosed
for example,
in EP-A-OI64514 and EP-A-0293640. Preferred are the crystalline layered sodium
silicates of general formula
NaMSix02+1 ~yH20
wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number
from 0
to 20. Crystalline layered sodium silicates of this type preferably have a two
dimensional
'sheet' structure, such as the so called $-layered structure, as described in
EP-A-0164514
and EP-A-0293640. Methods for preparation of crystalline layered silicates of
this type
are disclosed in DE-A-3417649 and DE-A-3742043. For the purpose of the present
invention, x in the general formula above has a value of 2,3 or 4 and is
preferably 2.
The most preferred crystalline layered sodium silicate compound has the
formula b-
Na2Si205 , known as NaSKS-6 (trade name), available from Hoechst AG.
The crystalline layered sodium silicate material can be added, especially in
granular
detergent compositions, as a particulate in intimate admixture with a solid,
water-soluble
ionisable material as described in WO-A-92/18594. The solid, water-soluble
ionisable
material is selected from organic acids, organic and inorganic acid salts and
mixtures
thereof, with citric acid being preferred.
Examples of largely water insoluble builders include the sodium
alurninosilicates.
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 aluminasilicate zeolites can be naturally occurring materials, but are
preferably
synthetically derived. Synthetic crystalline aluminosilicate ion exchange
materials are
available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X,
Zeolite HS
and mixtures thereof.
CA 02337408 2001-O1-12
WO 00!04117 PCTNS99115491
22
A preferred method of synthesizing aluminosilicate zeolitE;s is that described
by
Schoeman et ai (published in Zeolite (1994) 14(2), 110-116), in which the
author
describes a method of preparing colloidal aluminosilicate .zeolites. The
colloidal
aluminosilicate zeolite particles should preferably be such that no more than
5% of the
particles are of size greater than 1 ~,m in diameter and not more than 5% of
particles are
of size less then 0.05 pm in diameter. Preferably the alum~inosiIicate zeolite
particles
have an average particle size diameter of between 0.01 ~m and 1 p,m, more
preferably
between 0.05 pm and 0.9 Vim, most preferably between 0.1 pm and 0.6 p,m.
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 disclo,~ed in EP-B-384,070 is a
suitable zeolite builder herein.
Preferred aluminosilicate zeolites are the colloidal aluminosilicate zeolites.
When
employed as a component of a detergent composition colloidal aluminosilicate
zeolites,
especially colloidal zeolite A, provide enhanced builder pe>rformance,
especially in terms
of improved stain removal, reduced fabric encrustation and improved fabric
whiteness
maintenance. Mixtures of colloidal zeolite A and colloidal zeolite Y are also
suitable
herein providing excellent calcium ion and magnesium ion sequestration
performance.
Surfactant
Suitable surfactants are selected from anionic, cationic, nonionic ampholytic
and
zwitterionic surfactants and mixtures thereof Automatic .dishwashing machine
products
should be low foaming in character and thus the foaming o~f the surfactant
system for use
in dishwashing should be suppressed or more preferably bc; low foaming,
typically
nonionic in character. Sudsing caused by surfactant syste~:ns used in laundry
cleaning
methods need not be suppressed to the same extent as is necessary for
dishwashing.
A typical listing of anionic, nonionic, ampholytic and zwitterionic classes,
and species of
these surfactants, is given in US-A-3,929,678. A list of suitable cationic
surfactants is
CA 02337408 2001-O1-12
WO 00104117 ' PCT/US99/15491
23
given in US-A-4,259,217. A listing of surfactants typically included in
automatic
dishwashing detergent compositions is given in EP-A-0414549 and WO-A-93/08876
and
WO-A-93/08874.
Nonionic surfactants
Nonionic ethoxylated alcohol surfactants
The alkyl ethoxylate condensation products of aliphatic alc,ohols with from 1
to 25
moles of ethylene oxide are suitable for use herein. The alll~yl 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 <;ondensation
products of
alcohols having an alkyl group containing from 8 to 20 carbon atoms with from
2 to 10
moles of ethylene oxide per mole of alcohol.
End-capped alkyl alkoxylate surfactants
A suitable endcapped alkyl alkoxylate surfactant is the epoxy-capped
poly(oxyalkylated)
alcohols represented by the formula:
R10[CH2CH(CH3)O]x[CH2CH20]y[CH2CH(OH)R2] (I)
wherein Rl 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 o:f from 0.5 to 1.5,
more
preferably i; 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~ SLI?-18B nonionic surfactants,
as
described; for example, in WO-A-94/22800.
Ether-capyed poly(oxyalkylated~ alcohols
Other suitable surfactants for use herein include ether-capped
poly(oxyalkylated)
alcohols having the formula:
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WO 00/04117 PCT/US99/I5491
24
R1 O[CH2CH(R3)O]x[CH2IkCH(OH)[CH21jOR2
wherein RI and R2 are linear or branched, saturated or unsaturated, aliphatic
or aromatic
hydrocarbon radicals having from 1 to 30 carbon atoms; R3 is H, or a linear
aliphatic
hydrocarbon radical having from 1 to 4 carbon atoms; x is an integer having an
average
value from 1 to 30, wherein when x is 2 or greater R3 ma;y be the same or
different and k
and j are integers having an average value of from 1 to I2, and more
preferably 1 to 5.
RI 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 alkyleneoxy
units as
described above. For instance, if x is 3, R3rnay be be selected to form
ethyleneoxy(EO)
or propyleneoxy(PO) and may vary in order of {EO)(PO)(EO), (EO){EO)(PO);
(EO)(EO)(EO); (PO}(EO)(PO); (PO)(PO)(EO) and (PO)(lP0)(PO). Of course, the
integer three is chosen for example only and the variation may be much larger
with a
higher integer value for x and include, for example, mulitple (EO) units and a
much
small number of (PO) units.
Particularly preferred surfactants as described above include those that have
a low cloud
point of less than 20°C. These low cloud point surfactants may then be
employed in
conjunction with a high cloud point surfactant as described in detail below
for superior
grease cleaning benefits.
Most preferred ether-capped poly(oxyalkylated) alcohol swfactants are those
wherein k
is I and j is I so that the surfactants have the formula:
Rl O[CH2CH{R3)OJXCH2CH(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
CA 02337408 2001-O1-12
WO 00/04I17 PCTIUS99/I5491
preferred are surfactants wherein R1 and R2 range from 9 to 14, R3 is H
forming
ethyleneoxy and x ranges from 6 to 15.
The ether-capped poly(oxyalkylated) alcohol surfactants comprise three general
components, namely a linear or branched alcohol, an alkylene oxide and an
alkyl ether
end cap. The alkyl ether end cap and the alcohol serve as a hydrophobic; oil-
soluble
portion of the molecule while the alkylene oxide group forms the hydrophilic,
water-
soluble portion of the molecule. .
These surfactants exhibit significant improvements in spotting and filming
characteristics
and removal of greasy soils, when used in conjunction with high cloud point
surfactants,
relative to conventional surfactants.
Generally speaking, the ether-capped poly(oxyalkylene) alcohol surfactants may
be
produced by reacting an aliphatic alcohol with an epoxide to form an ether
which is then
reacted with a base to form a second epoxide. The second epoxide is then
reacted with
an alkoxylated alcohol to form the novel compounds of the: present invention.
Nonionic ethox la~propoxylated fatty alcohol surfactants
The ethoxylated C6-C 1 g fatty alcohols and C6-C 1 g mixed
ethoxylated/propoxylated
fatty alcohols are suitable surfactants for use herein, particularly where
water soluble.
Preferably the ethoxylated fatty alcohols are the C 10-C 1 g E:thoxylated
fatty alcohols with
a degree of ethoxylation of from 3 to 50, most preferably these are the C 12-C
18
ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40.
Preferably the
mixed ethoxylated/propoxylated fatty alcohols have an alkyl chain length of
from 10 to
18 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of
propoxylation
of from 1 to 10.
Nonionic EO/PO condensates with propyl_, ene elycol
The condensation products of ethylene oxide with a hydrol>hobic 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
CA 02337408 2001-O1-12
WO ~0/04117
26
PCT/US99/15491
include certain of the commercially-available PIuronic3~'M surfactants,
marketed by
BASF.
Nonionic EO condensation roducts with ro lene oxide/ethylene diamine adducts
The condensation products of ethylene oxide with the po~oduct 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 o~f from 2500 to 3000.
Examples of this type of nonionic surfactant include cerl:ain of the
commercially
available TetronicTM compounds, marketed by BASF:
Mixed Nonionic Surfactant S stems
The compositions herein can also include a mixed nonionic surfactant system
comprising
at least one low cloud point nonionic surfactant and at least one high cloud
point
nonionic surfactant.
"Cloud point", as used herein, is a well known property of nonionic
surfactants which is
the result of the surfactant becoming less soluble with increasing
temperature, the
temperature at which the appearance of a second phase is observable is
referred to as the
"cloud point" (See Kirk Othmer's Encyclopedia of Chemical Technology, 3rd Ed.
Vol.
22, pp. 360-379).
As used herein, a "low cloud point" nonionic surfactant is def ned as a
nonionic
surfactant system ingredient having a cloud point of less tliian 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 ethox;ylates derived from
primary
alcohol, and polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO)
reverse
block polymers. Also, such low cloud point nonionic surfactants include, for
example,
ethoxylated-propoxylated alcohol (e.g., Olin Corporation's Poly-Tergent~
SLF18),
epoxy-capped poly(oxyalkylated) alcohols (e.g., Olin Corporation's Poly-
Tergent~
SLF18B series of nonionics, as described, for example, in 'WO-A-94/22800) and
the
ether-capped poly(oxyalkylated) alcohol surfactants.
CA 02337408 2004-10-06
27
Nonionic surfactants can optionally contain propylene oxide in an amount up to
15% by
weight. Other suitable nonionic surfactams can be prepared by the processes
described
in US-A-4,223,163.
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
PLURON1C~, REVERSED PLURONIC~, and TETRON1C~ by the BASF-Wyandotte
Corp., Wyandotte, Michigan, are also suitable herein. Preferred examples
include
REVERSED PLURON1C~ ?SR2 and TETRONIC~ 702, Such swfactants 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 alkyiphenol containing from 8 to 20 carbon atoms, with from 6 to 15
moles of
ethylene oxide per mole of alcohol or alkyl phenol on an average basis. Such
high cloud
point nonionic surfactants include, for example. TergitolTM 1 SS9 (supplied by
Union Carbide), RhodasurfrM TMD 8.5 (supplied by Rhone Poulenc). and NeodolTM
91-8 (supplied by Shell).
It is also preferred 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 1 1 io 15. Sch materials include, for
example. TergitolTM
1559 (supplied by Union Carbide). RhodasurfrM TMD 8.5 (supplied by Rhone
Poulenc). and
NeodolTM 91-8 (supplied by Shell).
Another suitable high cloud point nonionic surfactant is derived from a
straight or
preferably branched chain or secondary fatty alcohol containing from 6 to 20
carbon
atoms (C6-C2p alcohol), including secondary alcohols and branched chain
primary
alcohols. Preferably, high cloud point nonionic surfactants are branched or
secondary
alcohol ethoxylates, more preferably mixed C9/11 or Cl 1/IS branched alcohol
ethoxylates, condensed with an average of from 6 to 15 moles, preferably from
6 to 12
CA 02337408 2001-O1-12
WO 00/04117 PCTIUS99/15491
2$
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.
Anionic surfactants
Essentially any anionic surfactants useful for detersive purposes are
suitable. These can
include salts (including, for example, sodium, potassium, ammonium, and
substituted
ammonium salts such as mono-, di- and triethanolamine salts) of the anionic
sulfate,
sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate
surfactants are
preferred.
Other anionic surfactants include the isethionates such as the acyl
isethionates, N-acyl
taurates, fatty acid amides of methyl tauride, alkyl succinates and
sulfosuccinates,
monoesters of sulfosuccinate (especially saturated and unsaturated C 12-C 1$
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 resiin acids present in
or derived
from tallow oil.
Anionic sulfate surfactants
Anionic sulfate surfactants suitable for use herein include the linear and
branched
primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl
glycerol sulfates,
alkyl phenol ethylene oxide ether sulfates, the CS-C 1 ~ ac;yl-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 l 0-C 1 g alkyl sulfates, more preferably the C 11-C 15 branched chain alkyl
sulfates and
the C 12-C 14 linear chain alkyl sulfates.
Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting of the
C 1 p-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 e:thoxysulfate
surfactant is a
CA 02337408 2001-O1-12
WO 00/04117 PCT/US99/1549I
29
C 1 I -C l g, most preferably C I I -C 15 ~kYl sulfate which has been
ethoxylated with from
0.5 to 7, preferably from I to 5, males of ethylene oxide per molecule.
Mixtures of alkyl
sulfate and alkyl ethoxysulfate surfactants are also suitable herein (WO-A-
93/18124).
Anionic sulfanate surfactants
Anionic sulfonate surfactants suitable for use herein include the salts of C5-
C20 linear
alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary
alkane
sulfonates, C6-C24 olefin sulfonates, sulfonated polycarbaxylic 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 {'all~yl carboxyls'),
especially
certain secondary soaps as described herein.
Suitable alkyl ethoxy carboxylates include those with the :formula
RO(CH~CH20)x
CHZC00-M+ wherein R is a C6 to C I g alkyl group, x ranges from 0 to 10, and
the
ethoxylate distribution is such that, on a weight basis, the amount of
material where x is
0 is less than 20 % and M is a catian. Suitable alkyl polye;thoxy
polycarbaxylate
surfactants include those having the formula RO-(CHRI-CHR2-O)-R3 wherein R is
a Cg
to C I g alkyl group, x is from I to 25, Rl and R2 are selected from the group
consisting
of hydrogen, methyl acid radical, succinic acid radical, hydraxysuccinic acid
radical, and
mixtures thereof, and R3 is selected from the group consisting of hydrogen,
substituted
or unsubstituted hydrocarbon having between 1 and 8 cart>on 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 fox
use herein are water-soluble members selected from the group consisting of the
water-
soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-I-decanoic acid, 2-propyl-
1-
nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-I-heptanoic acid: Certain
soaps
may also be included as suds suppressors.
CA 02337408 2001-O1-12
- . WO 00/04117
Alkali metal sarcosinate surfactants
PCT/US99/15491
Other suitable anionic surfactants are the alkali metal sarcosinates of
formula R-CON
(Rl ) CH2 COOM, wherein R is a CS-C 1 ~ linear or branched alkyl or alkenyl
group, R 1
is a Cl-Cq, alkyl group and M is an alkali metal ion. Preferred examples are
the myristyl
and oleoyl methyl sarcosinates in the form of their sodiwm salts.
Amphoteric surfactants
Suitable amphoteric surfactants for use herein include the; amine oxide
surfactants and
the alkyl amphocarboxylic acids.
Suitable amine oxides include those compounds having the formula
R3(OR4)xN0(RS)2
wherein R3 is selected from an alkyl, hydroxyalkyl, acyl2unidopropoyl and
alkyl phenyl
group, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an
alkylene or
hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures
thereof; x is
from 0 to S, preferably from 0 to 3; and each RS is an alkwl or hydroxyalkyl
group
containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3
ethylene
oxide groups. Preferred are C I p-C 1 g alkyl dimethylamine oxide, and C 10_ 1
g acylamido
alkyl dimethylamine oxide.
A suitable example of an alkyl amphodicarboxylic acid is Miranol(TM) C2M Conc.
manufactured by Miranol, Inc., Dayton, NJ.
Zwitterionic surfactants
Zwitterionic surfactants can be broadly described as deriv2~tives of secondary
and tertiary
amines, derivatives of heterocyclic secondary and tertiary ;mines, or
derivatives of
quaternary ammonium, quaternary phosphonium or tertiar,~ sulfonium compounds.
Betaine and sultaine surfactants are exemplary zwitterionic: surfactants for
use herein.
Suitable betaines are those compounds having the formula R(R')2N+R2COO-
wherein R
is a C6-C I g hydrocarbyl group, each R I is typically C 1-C?; alkyl, and R2
is a C L-CS
hydrocarbyi group. Preferred betaines are C12-18 dimethyl-ammonio hexanoate
and the
CA 02337408 2001-O1-12
WO 00104117 PCT1US99115491
31
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 canonically charged group. Other suitable cationic ester
surfactants,
including choline ester surfactants, have for example been disclosed in US-A-
4228042,
US-A-4239660 and US-A-4260529.
Suitable cationic surfactants include the quaternary ammonium surfactants
selected from
mono C6-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 suitable for use herein included cellulases, hemi.cellulases,
peroxidases,
proteases, gluco-amylases, amylases, xylanases, lipases, phospholipases,
esterases,
cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases,
lipoxygenases,
ligninases, pullulanases, tannases, pentosanases, malanasca, f3-glucanases,
arabinosidases, hyaluronidase, chondroitinase, laccase and mixtures thereof.
Preferred enzymes include protease, amylase, lipase, pero~xidases, cutinase
andlor
cellulase in conjunction with one or more plant cell wall degrading enzymes.
The cellulases usable in the present invention include both bacterial or
fungal cellulase.
Preferably, they will have a pH optimum of between 5 and 12 and an activity
above 50
CEVU (Cellulose Viscosity Unit). Suitable cellulases are disclosed in US-A-
4,435,307,
J61078384 and WO-A-96/02653 which disclose fungal cellulases produced
respectively
from Humicola insolens, Trichoderma, Thielavia and Sporotrichum. EP-A-0739982
describes cellulases isolated from novel Bacillus species. Suitable cellulases
are also
disclosed in GB-A-2075028; GB-A-2095275, DE-A-2.247.832 and WO-A-95/26398.
Examples of such cellulases are cellulases produced by a strain of Humicola
insolens
(Humicola grisea var. thermoidea), particularly the Hunnicola strain DSM 1800.
Other
CA 02337408 2005-02-07
32
suitable cellulases are cellulases originated from Humicola insolens having a
molecular
weight of SOKDa, an isoelectric point of 5.5 and containing 4I S amino acids;
and a
"43kD endoglucanase derived from Humicola insolens, DSM 1800, exhibiting
cellulase
activity; a preferred endoglucanase component has the amino acid sequence
disclosed in
WO-A-91/17243. Also suitable cellulases are the EGIII cellulases from
Trichoderma
longibrachiatum described in WO-A-94/21801. Especially suitable cellulases are
the
celltilases having color care benefits. Examples of such cellulases are
cdllulases
(Novo). CarezymeTM and CelluzymeTM (Novo Nordisk A/S) are especially useful.
See also
WO-A-91/17244 and WO-A-91/21801. Other suitable cellulases for fabric care
and/or
cleaning properties are described in WO-A-96/34092, WO=A-96/17994 and WO-A-
95/24471:
Said cellulases are normally incorporated in detergent compositions at levels
from
O.OOOI % to 2% of active enzyme by weight of composition.
Peroxidase enzymes are used in combination with oxygen sources, e.g.
percarbonate,
perborate, persulfate; hydrogen peroxide, etc. They are used for "solution
bleaching", i.e.
to prevent transfer of dyes or pigments removed from substrates during wash
operations
to other substrates in the wash solution. Peroxidase enzymes are known in the
art, and
include, for example, horseradish peroxidase, ligninase and haloperoxidase
such as
chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are
disclosed, for example, in WO-A-89/099813, WO-A-89/09813 and in European
Patent
application EP No. 9Y202882.6, filed on November 6, 1991.
. Also suitable is the laccase enzyme.
Preferred enhancers are substitued phenthiazine and phenoxasine 10-
Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4-carboxylic acid
(EPC), 10-
phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO.-A-
94/12621) and substitued syringates (C3-CS substitued alkyl syringates) and
phenols.
Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.
Said cellulases and/or peroxidases are normally incorporated in detergent
composition at
levels from 0.0001% to 2% of active enzyme by weight of composition.
CA 02337408 2004-10-06
33
Other suitable enzymes that can be included in the detergent compositions of
the present
invention include lipases. Suitable lipase enzymes for detergent usage include
those
produced by microorganisms of the Pseudomonas group, such as Pseudomonas
stutzeri
ATCC 19.154, as disclosed in GB-A-1,372,034. Suitable lipases include those
which
show a positive immunological cross-reaction with the antibody of the lipase,
produced
by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is
available from
Amano Pharmaceutical Co. Ltd., I~'agoya, 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. Chromabacter
viscosum
var. lipolyricum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobac~er
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 M 1 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 suiiables are the lipolytic
enzymes described
in EP-A-0258068, WO-A-92/05249, WO-A-95/22615, WO-A-94/03578, WO-A-
95/35381 and WO-A-96/00292.
Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special
kind of
lipase, namely lipases which do not require interfacial activation. Addition
of cutinases
to detergent compositions have been described in e.g. WO-A-88/09367, WO-A-
90/09446, WO-A-94/14963 and WO-A-94/14964.
The lipases and/or cutinases are normally incorporated in detergent
composition at levels
from 0.0001 % to 2% of active enzyme by weight of composition.
Suitable proteases are the subtilisins which are obtained from particular
strains of B.
subtilis and B. licheniformis (subtilisin BPN and BPN'). One suitable protease
is
obtained from a strain of Bacillus, having maximum activity throughout the pH
range of
8-12, developed and sold as ESPERASE~ by Novo Industries A/S of Denmark,
hereinafter "Novo". The preparation of this enzyme and analogous enzymes is
described
in GB 1,243,784 to Novo. Other suitable proteases include ALCALASE~,
DURAZYM~ and SAVINASE~ from Novo and MAXATASE~~ MAXACAL~,
PROPERASE~ and MAXAPEM~ (protein engineered Maxacal) from Gist-Brocades.
Proteolytic enzymes also encompass modified bacterial serine proteases.;
CA 02337408 2001-O1-12
- WO 00/04117 PCTIUS99/15491
34
198? {particularly pages 17, 24 and 98), and which is called herein "Protease
B", and in
EP-A-0199404 which refers to a modified bacterial serine protealytic enzyme
which is
called "Protease A" herein. Suitable is what is called herein "Protease C",
which is a
variant of an alkaline serine protease from Bacillus in which lysine replaced
arginine at
position 27, tyrosine replaced valine at position 104, serine replaced
asparagine at
position I23, and alanime replaced threonine at position 274. Protease C is
described in
WO-A-91/06637. Genetically modified variants, particularly of Protease C, are
also
included herein.
A suitable protease referred to as "Protease D" is a carbonyl hydrolase
variant having an
amino acid sequence not found in nature, which is detxved 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, +12g, +135, +I56, +166, +195, +197, +204, +206,. +210, +2I6, +217, +218,
+222,
+260, +265, and/or +274 according to the numbering; of Bacillus
amyloliquefaciens
subtilisin, as described in WO-A-95/10591 and in the patent application of C.
Ghosh, et
al, "Bleaching Compositions Comprising Protease Enzymes" having US Serial No.
08/322,677, filed October 13, 1994.
Also suitable are proteases described in EP-A-0251 446 and WO-A-9I/06637,
protease
BLAP~ described in WO-A-91/02792 and their variants described in WO-A-
95/23221.
See also a high pH protease from Bacillus sp. NCIM:B 40338 described in WO-A-
93/18140. Enzymatic detergents comprising protease; one or more other enzymes,
and a
reversible protease inhibitor are described in WO-A-92103529. When desired, a
protease
having decreased adsorption and increased hydrolysis is available as described
in WO-A-
95/07791. A recombinant trypsin-like protease for detergents suitable herein
is described
in WO-A- 94/25583. Other suitable proteases are described in EP-A-0516 200.
Other suitable protease enzymes include protease enzymes which are a carbonyl
hydrolase variant having an amino acid sequence not fo~,znd 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 +2 2 0 in combination with one or more
of the
CA 02337408 2001-O1-12
WO U~JU4117
PCT/US99J15491
following residues: +33, +62, +67, +76, +100, +101, +103, +104, +107, +128,
+129,
+130, +132, +I35, +156, +158, +I64, +166, +167, +170, +209, +215, +217, +218
and
+222, where the numbered positions correspond to naturally-occurring
subtilisin from
Bacillus amvloliauefaciens or to equivalent amino acid residues in other
carbonyl
hydrolases or subtilisins (such as Bacillus lentus subtilisin). Preferred
enzymes of this
type include those having position changes +210, +76, +103, +I04, +156, and
+166.
The proteolytic enzymes are incorporated in detergent compositions at a level
of from
0.0001 % to 2%, preferably from 0.001 % to 0.2%, more preferably from 0.005%
to 0.1
pure enzyme by weight of composition.
Amylases (a and/or 13) can be included for removal of c~~rbohydrate-based
stains. WO-A-
94/02597 describes cleaning compositions which incorporate mutant amylases.
See also
WO-A-95/10603. Other amylases known for use in cleaning compositions include
both a
- and ~3-amylases. a-Amylases are known in the art and include those disclosed
in US-
A-5,003,257; EP-A-0252,666; WO-A-91/00353; FR-A-2,676,456; EP-A-0285,123; EP-
A-525,610; EP-A-0368,341; and GB-A-1,296,839. Other suitable amylases are
stability-
enhanced amylases described in WO-A-94/18314 and WO-A-96/05295 and amylase
variants having additional modification in the immediate parent available from
Novo
Nordisk A/S, disclosed in WO-A-95/10603. Also suitable are amylases described
in EP-
A-0277216, WO-A-95/26397 and WO-A-96/23873.
Examples of commercial a-amylases products are Purafect Ox Am~ from Genencor
and
Terrnamyl~, Ban~ ,Fungamyl~ and Duramyl~; Natalase ~ all available from Novo
Nordisk A/S Denmark, W0-A-95/26397 describes other suitable amylases : a-
amylases
characterised by having a specific activity at least 25% higher than the
specific activity of
Termamyl~ at a temperature range of 25°C to 55°C and at a pH
value in the range of 8
to 10, measured by ttze Phadebas~ a-amylase activity assay. Suitable are
variants of the
above enzymes, described in WO-A-96/23873. Other amylolytic enzymes with
improved
properties with respect to the activity level and the combination of
thermostability and a
higher activity level are described in WO-A-95135382.
Preferred amylase enzymes include those described in WO-A-95/26397 and in co-
pending application by Novo Nordisk PCT/DK96/00056.
CA 02337408 2001-O1-12
WO 00104117 PCT/US99/15491
36
The amylolytic enzymes are incorporated in detergent compositions at a level
of from
O.OOOI% to 2%, preferably from 0.00018% to 0.06%, more preferably from
0.00024% to
0.048% pure enzyme by weight of composition
In a particularly preferred embodiment, compositions herein comprise amylase
enzymes,
particularly those described in WO-A-95/26397 and co-pending application by
Novo
Nordisk PCT/DK96/00056 in combination with a complementary amylase.
By "complementary" it is meant the addition of one or more amylase suitable
for
detergency purposes. Examples of complementary amylases (a and/or 1~) are
described
below. WO-A-94/02597 and WO-A-95/10603 describe cleaning compositions which
incorporate mutant amylases. Other amylases known for use in cleaning
compositions
include both a- and (3-amylases. a-Amylases are known in the art and include
those
disclosed in US-A-5,003,257; EP-A-0252,666; WO-A-91/00353; FR-A-2,676,456; EP-
A-0 285123; EP-A-0525610; EP-A-0368341; and GB-A-11,296,839. Other suitable
amylases are stability-enhanced amylases described in WO-A-94118314 and WO-A-
96/05295 and amylase variants having additional modification in the immediate
parent
available from Novo Nordisk A/S, disclosed in WO-A-95/10603. Also suitable are
amylases described in EP-A-0277 216. Examples of commercial a-amylases
products
are Purafect Ox Am~ from Genencor and Termamyl~, Ban~ ,Fungamyl~ and
Duramyl~, all available from Novo Nordisk A/S Denmarlk. W095/26397 describes
other
suitable amylases : a-amylases characterised by having a specific activity at
least 25%
higher than the specific activity of Termamyl~ at a temperature range of
25°C to 55°C
and at a pH value in the range of 8 to 10, measured by the Phadebas~ a-amylase
activity
assay. Suitable are variants of the above enzymes, described in WO-A-96/23873.
Other
amylolytic enzymes with improved properties with respect to the activity level
and the
combination of thermostability and a higher activity level are described in WO-
A-
95/35382. Preferred complementary amylases for the pre:>ent invention are the
amylases
sold under the tradename Purafect Ox AmR described in WO-A- 94/18314, WO-A-
96/05295 sold by Genencor; Termamyl~, Fungamyl~, Ban~ Natalase~ and Duramyl~,
all available from Novo Nordisk A/S and Maxamyl~ by (list-Brocades.
The complementary amylase is generally incorporated in detergent compositions
at a
level of from 0.0001 % to 2%, preferably from 0.00018% 1:0 0.06%, more
preferably from
0.00024% to 0.048% pure enzyme by weight of compositiion. Preferably a weight
of pure
CA 02337408 2001-O1-12
WO 00/04117 PCT/US99/15491
37
enzyme ratio of specific amylase to the complementary amylase is comprised
between
9:1 to 1:9, more preferably between 4:1 to 1:4, and most preferably between 2:
I 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 m~esophilic or
extremophilic
(psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic,
acidophilic,
halophilic, etc.). Purified or non-purif ed 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 andlor physical modifications of
native
enzymes. Common practice as well is the expression of the enzyme via host
organisms in
which the genetic material responsible for the production of the enzyme has
been cloned.
Enzymes are normally incorporated in detergent composition at levels from
0.0001% to
2% of active enzyme by weight of composition. The enzymes can be added as
separate
single ingredients (prills, granulates, stabilized liquids, etc... containing
one enzyme ) or
as mixtures of two or more enzymes ( e.g. cogranulates ).
Other suitable detergent ingredients that can be added are enzyme oxidation
scavengers
which are described in copending European Patent application 92870018.6 filed
on
January 31, 1992. Examples of such enzyme oxidation scavengers are ethoxylated
tetraethylene polyamines.
A range of enzyme materials and means for their incorporation into synthetic
detergent
compositions is also disclosed in WO-A-9307263, WO-A-9307260, WO-A-8908694 and
US-A-3,553,139. Enzymes are further disclosed in US-A.~-4,101,457 and US-A-
4,507,219. Enzyme materials useful for liquid detergent formulations, and
their
incorporation into such formulations, are disclosed in US-A- 4,261,868.
Enzymes for
use in detergents can be stabilised by various techniques. Enzyme
stabilisation
techniques are disclosed and exemplified in US-A-3,600,319, EP-A-0199405 and
EP-A-
0200586. Enzyme stabilisation systems are also described, for example, in US-A-
3,519,570. A useful Bacillus, sp. AC13 giving proteases, xylanases and
cellulases, is
described in WO-A-9401532.
Bleaching-agent
CA 02337408 2001-O1-12
- wo 00/041 ~ ~
38
PCTNS99/15491
Suitable bleaching agents herein include chlorine and oxygen-releasing
bleaching agents.
In one preferred aspect the oxygen-releasing bleaching agent contains a
hydrogen
peroxide source and an organic peroxyacid bleach precursor compound. The
production
of the organic peroxyacid occurs by an in situ reaction c>f the precursor with
a source of
hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic
perhydrate bleaches. In an alternative aspect a preformed organic peroxyacid
is
incorporated directly into the composition. Compositions containing mixtures
of a
hydrogen peroxide source and organic peroxyacid precursor in combination with
a
preformed organic peroxyacid are also envisaged.
Inorganic uerhydrate bleaches
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 can be included as the crystalline
solid
without additional protection. For certain perhydrate salts however, a coated
form of the
material is used in order to provide better storage stability.
Sodium perborate can be in the form of the monohydrate of nominal formula
NaB02H202 or the tetrahydrate NaBO2H202.3H20. Alkali metal percarbonates,
particularly sodium percarbonate are preferred perhydrate;s for inclusion
herein. Sodium
percarbonate is an addition compound having a formula corresponding to
2Na2C03.3H2O2, 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
far localised
high bleach concentrations to arise. The percarbonate is most preferably
incorporated
into such compositions in a coated form which provides ire-product stability.
A suitable coating material providing in product stability comprises mixed
salt of a water
soluble alkali metal sulphate and carbonate. Such coating's together with
coating
processes have previously been described in GB-A-1,466,',799. The weight ratio
of the
mixed salt coating material to percarbonate lies in the range from 1 : 200 to
I : 4, more
preferably from 1 : 99 to I : 9, and most preferably from 1 : 49 to 1 : 19.
Preferably, the
mixed salt is of sodium sulphate and sodium carbonate whiich has the general
formula
Na2S04.n.Na2C03 wherein n is from 0.3 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
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WO 00/04117 PCT/US99115491
39
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 herein.
Potassium peroxymonopersulfate is another inorganic perlhydrate salt of
utility in the
compositions herein.
Peroxyacid bleach precursor
Peroxyacid bleach precursors are compounds which react with hydrogen peroxide
in a
perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach
precursors
may be represented as
O
X-C-L
where L is a leaving group and X is essentially any functi~anality, such that
on
perhydrolysis the structure of the peroxyacid produced is
O
X-C-OOH
Suitable peroxyacid bleach precursor compounds typically contain one or more N-
or O-
acyl groups, which precursors can be selected from a wid<~ range of classes.
Suitable
classes include anhydrides, esters, imides, lactams and ac;ylated derivatives
of imidazoles
and oximes. Examples of useful materials within these classes are disclosed in
GB-A-
1586789. Suitable esters are disclosed in GB-A-836988, GB-A-864798, GB-A-
1147871,
GB-A-2143231 and EP-A-0170386.
Leaving- rg_oups
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).
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WO 00/041 I7 PCTIUS99/15491
However, if L is too reactive, this activator will be di~cult to stabilise for
use in a
bleaching composition.
Preferred L groups are selected from the group consisting of
Y R3 R sY
-p , -O Y , and
O ~ O 4
-N-C-R - ~ -IN-C-CH-R
IR3 Y ,
Y
R3 Y
I I
-O-C H=C-C H=C H2 -O-C H=C-C H=(: H2
O C H -O 1r
II ~ 2 ~ ~ ~NR4
-p-C-R~ -NwC/NRa , _NwC/
' II II
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, R'1
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, R~ and R'1 may be substituted by essentially
any
functional group including, for example alkyl, hydroxy, alkoxy, halogen,
amine, nitrosyl,
amide and ammonium or alkyl ammonium groups.
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4i
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 I 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 h~~lide, 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 jfor example benzoyl
oxybenzene
sulfonate:
0
~O ~S03
Also suitable are the benzoylation products of sorbitol, glucose, and all
saccharides with
benzoylating agents, including for example:
OAc
Ac0 \~--p
\, OAc
/ OAc
OBz
Ac = COChI3; Bz = Benzoyl
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42
Perbenzoic acid precursor compounds of the imide typo; 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 b~enzoyl pyroglutamic
acid.
Other perbenzoic acid precursors include the benzoyl diiacyl peroxides, the
benzoyl
tetraacyl peroxides, and the compound having the formula:
0 0
o~
~~COOH
Phthalic anhydride is another suitable perbenzoic acid precursor compound
herein:
O
O
Suitable N-acylated lactam perbenzoic acid precursors have the formula:
O
11
O C-CH2-CHz
Rs-C-NwC H
2-ECH2 ]n
wherein n is from 0 to 8, preferably from 0 to 2, and R~ :is a benzoyl group.
Perbenzoic acid derivative precursors
Perbenzoic acid derivative precursors provide substituted perbenzoic acids on
perhydrolysis.
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WO 00104117 PCT/US99I15491
43
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 arr~ide groups.
A preferred class of substituted perbenzoic acid precursor compounds are the
ari~ide
substituted compounds of the following general formulae:
R1C_._NR2C~ R1~N.-C-R2-C~
' I
O R5 O or . R;i O OI
wherein Rl 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 ato7ms. R2 preferably
contains from
4 to 8 carbon atoms. Rl may be aryl, substituted aryl or alkylaryl containing
branching,
substitution, or both and may be sourced from either synthetic sources or
natural sources
including for example, tallow fat. Analogous structural variations are
permissible for
R2. The substitution can include alkyl, aryl, halogen, nitrogen, sulphur and
other typical
substituent groups or organic compounds. RS is preferably H or methyl. Rl and
RS
should not contain more than 18 carbon atoms in total. Amide substituted
bleach
activator compounds of this type are described in EP-A-0170386.
Cationic peroxyacid 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.
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WO 00/04117 PCT/US99115491
44
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 peraxyacid
precursor as described hereinafter
Cationic peroxyacid precursors are described in US-A-4,904,406; US-A-
4,751,015; US-
A-4,988,451; US-A-4,397,757; US-A-5,269,962; US-A-5,127,852; US-A-5,093,022;
US-A-5,106,528; GB-A-1,382,594; EP-A-0475512, EP-A-0458396 and EP-A-0284292;
and in JP87-318,332.
Suitable cationic peroxyacid precursors include any of the ammonium or alkyl
ammonium substituted alkyl or benzoyl oxybenzene suifonates, N-acylated
caproiactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.
A preferred cationically substituted benzoyl oxybenzene sulfonate is the 4-
(trimethyl
ammonium) methyl derivative of benzoyl oxybenzene sulfonate:
O
~/ 503
~+
A preferred cationically substituted alkyl oxybenzene sulfonate has the
formula:
SO
N
/ ~O~% 3
Preferred cationic peroxyacid precursors of the N-acylatE:d caprolactam. class
include the
trialkyl ammonium methylene benzoyl caprolactams, particularly trimethyl
ammonium
methylene benzoyl caprolactam:
CA 02337408 2001-O1-12
WO 00/04117 PCT/US99/15491
N~
0
Other preferred cationic peroxyacid precursors of the N-acylated caprolactam
class
include the trialkyl ammonium methylene alkyl caprolactams:
'--~ {CH2) ~ N
~+ ~/
where n is from 0 to 12, particularly from 1 to 5.
Another preferred cationic peroxyacid precursor is 2-(l~f,N,N-trimethyl
ammonium) ethyl
sodium 4-sulphophenyl carbonate chloride.
Allc~ perk carboxylic 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 l,
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
{NOBS), 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:
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WO 00/04117 PCT/US99/15491
46
R1-C-N.-RZ,C-~ RliNi-C~R2,C~~
II I i~ I II !!
O R5 O or R,~ O O
wherein RI 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 au~ alkyl group
containing 1 to 10
carbon atoms and L can be essentially any leaving group. RI preferably
contains from 6
to I2 carbon atoms. R2 preferably contains fram 4 to 8 carbon atoms. RI may be
straight chain or branched alkyl containing branching, substitution, or both
and may be
sourced from either synthetic sources or natural sources including for
example, tallow
fat. Analogous structural variations are permissible fo:r R2. The substitution
can
include alkyl, halogen, nitrogen, sulphur and other typical substituent groups
or organic
compounds. RS is preferably H or methyl. RI and R~> should not contain more
than 18
carbon atoms in total. Amide substituted bleach activator compounds of this
type are
described in EP-A-OI70386.
Benzoxazin orga~c peroxyacidprecursors
Also suitable are precursor compounds of the benzoxazin-type, as disclosed.for
exaruple
in EP-A-0332294 and EP-A-0482807, particularly those having the formula:
O
II
I
N C-R~
including the substituted benzoxazins of the type
..,o
o ,,c_R,
Ra N
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WO 00/04117 PCT/US99I15491
47
wherein R1 is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R~, 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
p
CEO
0
..~ o
N
Preformed or anic peroxyacid
A suitable class of organic peroxyacid compounds are the amide substituted
compounds
of the following general formulae:
R~ -C-N-R2-C-OOH R~ -N-C-RZ-C--OOH
~i ~ ~~ ~ - II
O R~ O or R'~ O O
wherein Rl is an alkyl, aryl or alkaryi group with from 1 to 14 carbon atoms,
R2 is an
alkylene, arylene, and alkarylene group containing fronry 1 to 14 carbon
atoms, and RS is
H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. R1
preferably
contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon
atoms.
Rl 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 far R2. The substitution can include alkyl, aryl, halogen,
nitrogen, sulphur
and other typical substituent groups or organic compomds. R5 is preferably H
or
methyl. Rl and RS should not contain more than i 8 carbon atoms in total.
Amide
substituted organic peroxyacid compounds of this type ~~re described in EP-A-
0170386.
Other organic peroxyacids include diacyl and tetraacylperoxides, especially
diperoxydodecanedioc acid, diperoxytetradecanedioc acid, and
diperoxyhexadecanedioc
CA 02337408 2001-O1-12
WO 00104117 PCT/US99/15491
48
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
controlling the release of any inorganic perhydrate salt, acting as a hydrogen
peroxide
source, to the wash solution.
Suitable controlled release means can include confining, the bleach to one
portion of the
composition. Another mechanism for controlling the rate of release of bleach
may be by
coating the bleach with a coating designed to provide the controlled release.
The coating
may therefore, for example, comprise a poorly water soluble material, or be a
coating of
sufficient thickness that the kinetics of dissolution of the thick coating
provide the
controlled rate of release.
The coating material may be applied using various methods. Any coating
material is
typically present at a weight ratio of coating material to bleach of from 1:99
to 1:2,
preferably from I :49 to I :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 inorgaiuc perhydrate salt
bleach source,
comprises sodium silicate of Si02 : Na20 ratio from 1 ~8 : 1 to 3.0 : 1,
preferably 1.8:1 to
2.4:1, and/or sodium metasilicate, preferably applied at: a level of from 2%
to 10%,
(normally from 3% to 5%) of Si02 by weight of the inorganic perhydrate salt.
Magnesium silicate can also be included in the coating.
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49
Any inorganic salt coating materials may be combined with organic binder
materials to
provide composite inorganic saltlorganic binder coatings. Suitable binders
include the
C 10-020 alcohol ethoxylates containing from 5 - 100 males of ethylene oxide
per mole
of alcohol and more preferably the C 15-020 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 010-020 alcohol ethoxylates containing from 5 - 100 moles of
ethylene oxide
per mole. Further examples of binders include the C 1 p-~C20 mono- and
diglycerol ethers
and also the C 10-020 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 al;glomeration.
Preferred
agglomeration processes include the use of any of the organic binder materials
described
hereinabove. Any conventional agglomerator/mixer ma;y be used including, but
not
limited to pan, rotary drum and vertical blender types. n~Iolten coating
compositions
may also be applied either by being poured onto, or spray atomized onto a
moving bed of
bleaching agent.
Other means of providing the required controlled release include mechanical
means for
altering the physical characteristics of the bleach to control its solubility
and rate of
release. Suitable protocols could include compression, .mechanical injection,
manual
injection, and adjustment of the solubility of the bleach compound by
selection of
particle size of any particulate component.
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WO 00/04117 PCTIUS9911S491
Whilst the choice of particle size will depend both on the composition of the
particulate
component, and the desire to meet the desired controlled release kinetics, it
is desirable
that the particle size should be more than 500 micrometers, preferably having
an average
particle diameter of from 800 to 1200 micrometers.
Additional protocols for providing the means of controlled release include the
suitable
choice of any other components of the composition such that when the
composition is
introduced to the wash solution the ionic strength enviromnent therein
provided enables
the required controlled release kinetics to be achieved.
Metal-containin~~ bleach catalyst
Bleach-cintaining compositions herein can additionally contain a metal
containing bleach
catalyst. Preferably the metal containing bleach catalyst is a transition
metal containing
bleach catalyst, more preferably a manganese or cobalt-containing bleach
catalyst.
A suitable type of bleach catalyst is a catalyst comprising; a heavy metal
cation of defined
bleach catalytic activity, such as copper, iron rations, an .auxiliary metal
ration having
little or no bleach catalytic activity, such as zinc or aluminium rations, and
a sequestrant
having defined stability constants for the catalytic and auxiliary metal
rations,
particularly ethylenediaminetetraacetic acid,
ethylenediarninetetra(methylenephosphonic
acid) and water-soluble salts thereof. Such catalysts are disclosed in US-A-
4,430,243.
Preferred types of bleach catalysts include the manganese-based complexes
disclosed in
US-A- 5,246,621 and US-A-5,244,594. Preferred examples of these catalysts
include
MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(PF6)2, MnIII2(u_O)1(u_
OAcn(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. Otluers are described in EP-
A-
0549,272. Other ligands suitable for use herein include 1,5,9-trimethyl-1,5,9-
triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, :?-methyl-1,4,7-
triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures
thereof.
For other examples of suitable bleach catalysts see US-A-4,246,612 and US-A-
5,22?,084. See also US-A-5,194,416 which teaches mononuclear manganese (IV)
complexes such as Mn(1,4,7-trimethyl-1,4,7-triazacyclononane)(OCH3)3-(PF6).
CA 02337408 2001-O1-12
WO 00/04117 PCTIUS99115491
51
Still another type of bleach catalyst, as disclosed in US-~A-5,114,606, is a
water-soluble
complex of manganese (III), and/or (IV) with a ligand which is a non-
carboxylate
polyhydroxy compound having at least three consecutive C-OH groups. Preferred
ligands include sorbitoi, iditol, dulsitol, mannitol, xylithol, arabitol,
adonitol, meso-
erythritol, meso-inositol, lactose, and mixtures thereof.
US-A-5,114,611 teaches a bleach catalyst comprising a complex of transition
metals,
including Mn, Co, Fe, or Gu, with an non-(macro)-cyclic iigand. Said ligands
are of the
formula:
R2 R3
R~-N=C-B-C=N-R4~
wherein Rl, R2, R3, and R4 can each be selected from H, substituted alkyl and
aryl
groups such that each Rl-N=C-R2 and R3-C=N-R4 fo~7n 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)2O2C1O4, Bis-(2,2'-bispyridylamine) copper(II)
perchlorate,
tris{di-2-pyridylamine) iron(II) perchlorate, and mixtwres thereof.
Preferred examples include binuclear Mn complexes r~rith tetra-N-dentate and
bi-N-
dentate ligands, including N4MnIII{u-O)2MnIVN4)+aund [Bipy2MnIII(u-
O)2~IVbipY2l-(C104)3-
While the structures of the bleach-catalyzing manganese complexes have not
generally
been elucidated, it may be speculated that they comprise chelates or other
hydrated
coordination complexes which result from the interaction of the carboxyl and
nitrogen
atoms of the ligand with the manganese cation. Likewise, the oxidation state
of the
CA 02337408 2001-O1-12
WO 00/04117 FCT/US99i15491
52
manganese cation during the catalytic process is not known with certainty, and
may be
the (+II}, (+III), (+IV) or (+V} valence state. Due to the ligands' possible
six points of
attachment to the manganese cation, it may be reasonab:Iy speculated that
multi-nuclear
species and/or "cage" structures rnay exist in the aqueous bleaching media.
Whatever
the form of the active Mn-ligand species which actually exists, it functions
in an
apparently catalytic manner to provide improved bleaching performances on
stubborn
stains such as tea, ketchup, coffee, wine, juice, and the like.
Other bleach catalysts are described, for example, in EP-A-0408131 (cobalt
complex
catalysts), EP-A-0384503, and EP-A-0306089 (metallo-~porphyrin catalysts), US-
A-
4,728,455 (manganeseJmultidentate ligand catalyst), US-A-4,711,748 and EP-A-
0224952, (absorbed manganese on alurninosilicate catalyst), US-A-4,601,845
(aluminosilicate support with manganese and zinc or magnesium salt), US-A-
4,626,373
{manganese/ligand catalyst), US-A- 4,119,557 (ferric complex catalyst), DE-A-
2,054,019 (cobalt chelant catalyst), CA-A-866,191 (transition metal-containing
salts),
US-A-4,430,243 (chelants with manganese cations and non-catalytic metal
cations), and
US-A-4,728,455 {manganese gluconate catalysts).
Other preferred examples include cobalt (III) catalysts having the formula:
Co[(NH3)nM'mB'bT'tQqPpj YY
wherein cobalt is in the +3 oxidation state; n is an integer from 0 to S
(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 bi~dentate 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 l; P is a pentadentate ligand; p is 0 or l; and n + m + 2b + 3t + 4q + Sp =
6; Y is one
or more appropriately selected counteranions present in a number y, where y is
an integer
from 1 to 3 (preferably 2 to 3; most preferably 2 when ~C' 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 t:he 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.
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WO 00/04117 PCT/US99/15491
53
Preferred cobalt catalysts of this type have the formula:
[Co~3)n(M~)mJ YY
wherein n is an integer from 3 to 5 (preferably 4 or 5; rr.~ost preferably 5);
M' is a labile
coordinating moiety, preferably selected from the groul> 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 acre cobalt
pentaamine chloride
salts having the formula [Co(NH3)SCIJ Yy, and especially [Co{NH3)SCIJCl2.
More preferred are the present invention compositions which utilize cobalt
(III) bleach
catalysts having the formula:
[Co(I'1H3)n(M)m(B)bJ TY
wherein cobalt is in the +3 oxidation state; n is 4 or 5 (preferably 5); M is
one or more
ligamds coordinated to the cobalt by one site; m is 0, 1 or 2 (preferably I );
B is a ligand
co-ordinated to the cobalt by two sites; b is 0 or 1 (preferably 0), and when
b=0, then
m+n = 6, and when b=1, then m=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).
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)~ ,
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), alkylethoxysulfo:nates (AES), etc.)
andlor anionic
polymers (e.g., polyacrylates, polymethacrylates, etc.).
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WO 00/04117 PCTNS99/15491
54
The M moieties include, but are not limited to, for example, F-, S04-2, NCS-,
SCN-,
5203-2, NH3, P043-, and carboxylates (which preferably are mono-carboxylates,
but
more than one carboxylate may be present in the moiety as long as the binding
to the
cobalt is by only one carboxylate per moiety, in which case the other
carboxylate in the
M moiety may be protonated or in its salt form). Optionally, M can be
protonated if
more than one anionic group exists in M (e.g., HPO42-,1HC03-, H2POq.',
HOC(O)CH2C(O)O-, etc.) Preferred M moieties are substituted and unsubstituted
C1-
C3p carboxylic acids having the formulas:
RC(O)O-
wherein R is preferably selected from the group consisting of hydrogen and C I-
C30
(preferably C1-Clg) unsubstituted and substituted alkyl, C6-C3d (preferably Cg-
Clg)
unsubstituted and substituted aryl, and C3-C3p (preferably CS-Clg)
unsubstituted and
substituted heteroaryl, wherein substituents are selected from the group
consisting of -
NR'3, -NR'4+, -C(O)OR', -OR', -C(O)NR'z, wherein R' is selected from the group
consisting of hydrogen and C1-C6 moieties. Such substituted R therefore
include the
moieties -(CH2)nOH and -(CH2)nNR'4+, wherein n is an integer from 1 to 1 b,
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,
rnaleic, succinic, adipic, phthalic, 2-ethylhexanoic, naphi:henoic, oleic,
pahnitic, triflate,
tartrate, stearic, butyric, citric, acrylic, aspartic, fumaric, Iauric,
linoleic, lactic, malic, and
especially acetic acid.
The B moieties include carbonate, di- and higher carboxylates (e.g., oxalate,
rnalonate,
malic, succinate, maleate), picolinic acid, and alpha and lbeta amino acids
(e.g., glycine,
alanine, beta-alanine, phenylalanine).
Cobalt bleach catalysts useful herein are known, being described for example
along with
their base hydrolysis rates, in M. L. Tobe, "Base Hydrolysis of Transition-
Metal
Complexes", Adv. Inorg. Bioinor~. Mech., (1983), 2, pages 1-94. For example,
Table
CA 02337408 2001-O1-12
WO 00!04117 PCTIUS99/15491
1 at page 17, provides the base hydrolysis rates (designated therein as kpH)
for cobalt
pentaamine catalysts complexed with oxalate (kOH= 2.5 x 10-4 M-1 s-1
{25°C)), NCS-
(kOH- 5.0 x 10'4 M-1 s-I (25°C)), formate (kOH= 5.8 x 10-4 M-1 s-1
(25°C)), and
acetate (kpH= 9.6 x 10-4 M-1 s-I (25°C)). The most preferred cobalt
catalyst useful
herein are cobalt pentaamine acetate salts having the fornlula [Co(NH3)50Ac]
Ty,
wherein OAc represents an acetate moiety, and especially cobalt pentaamine
acetate
chloride, [Co{NH3)50Ac]C12; as well as [Co(NH3)50Ac](OAc)2;
[Co(NH3)SOAc](PF6)2; [Co(NH3)SOAc](S04); [Co{NH3)50Ac](BF4)2; and
[Co(NH3)SOAc](N03)2 (herein "PAC").
These cobalt catalysts are readily prepared by known procedures, such as
taught for
example in the Tobe article hereinbefore and the references cited therein, in
US-A-
4,810,410, to Diakun et al, issued March 7,1989, J. Chem. Ed. (1989}; 66 (12),
1043-
45; The Synthesis and Characterization of Inorganic Compounds, W.L. Jolly
(Prentice-
Hall; 1970), pp. 461-3; Inor~. Chem., 18,1497-1502 (1!979); Inor;~. Chem., 21,
2881-
2885 (1982); Inor;g. Chem., 18, 2023-2025 {1979); Inorg;. Synthesis, 173-176
(1960);
and Journal of Physical Chemistry, 56, 22-25 (1952); as ~weli as the synthesis
examples
provided hereinafter.
Cobalt catalysts suitable for incorporation into the detergent tablets of the
present
invention may be produced according to the synthetic routes disclosed in US-A-
5,559,261, US-A-5,581,005, and US-A-5,597,936.
These catalysts may be co-processed with adjunct materials so as to reduce the
colour
impact if.desired for the aesthetics of the product, or to be included in
enzyme-containing
particles as exemplified hereinafter, or the compositions :may be manufactured
to contain
catalyst "speckles".
Or~polymeric compound
Organic polymeric compounds may be added as preferred components of the
detergent
tablets in accord with the invention. By organic polymeric compound it is
meant
essentially any polymeric organic compound commonly found in detergent
compositions
having dispersant, anti-redeposition, soil release agents o~r other detergency
properties.
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WO 00104117 PCTIUS99/15491
s6
Examples of organic polymeric compounds include the water soluble organic homo-
or
co-polymeric polycarboxylic acids, modified polycarbox:ylates 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 ~moiecuiar weight 2000-
10000
and their copolymers with any suitable other monomer units including modified
acrylic,
furnaric, malefic, itaconic, aconitic, mesaconic, citraconic; and
methylenemalonic acid or
their salts, malefic anhydride, acrylamide, alkylene, vinylmethyl ether,
styrene and any
mixtures thereof Preferred are the copolymers of acrylic acid and malefic
anhydride
having a molecular weight of from 20,000 to 100,000.
Preferred commercially available acrylic acid containing polymers having a
molecular
weight below 15,000 include those sold under the tradename Sokalan PA30, PA20,
PA15, PA10 and Sokalan CP10 by BASF GmbH, and those sold under the tradename
Acusol 45N, 480N, 460N by Rohm and Haas.
Preferred acrylic acid containing copolymers include those which contain as
monomer
units: a) from 90% to 10%, preferably from 80% to 20% by weight acrylic acid
or its
salts and b) from 10% to 90%, preferably from 20% to 80% by weight of a
substituted
acrylic monomer or its salts having the general formula -[CR2-CRl(CO-O-R3)]-
wherein
at least one of the substituents Rl, R2 or R3, preferably 1~1 or R2 is a 1 to
4 carbon alkyl
or hydroxyalkyl group, Rl or R2 can be a hydrogen and R3 can be a hydrogen or
alkali
metal salt. Most preferred is a substituted acrylic monomer wherein R1 is
methyl, R2 is
hydrogen (i.e. a methacrylic acid monomer). The most preferred copolymer of
this type
has a molecular weight of 3s00 and contains 60% to 80°ro 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-030s282, EP-A-
0305283 and
EP-A-0351629:
Other optional polymers may polyvinyl alcohols and acetates both modified and
non-
modified, cellulosics and modified cellulosics, polyoxyethylenes,
polyoxypropylenes,
and copolymers thereof, both modified and non-modified, terephthalate esters
of ethylene
or propylene glycol or mixtures thereof with polyoxyalkylene units. Suitable
examples
are disclosed in US-A-s,591,703, US-A-5,597,789 and L:fS-A-4,490,271.
CA 02337408 2001-O1-12
WO 00104117 PCT/US99115491
57
Soil Release Agents
Suitable polymeric soil release agents include those soil release agents
having: {a) one or
more nonionic hydrophile components consisting essentiallly 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) ~~ 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 lleast 50% oxyethylene
units;
or {b) one or more hydrophobe components comprising (i;l C3 oxyalkylene
terephthalate
segments, wherein, if said hydrophobe components also comprise oxyethylene
terephthalate, the ratio of oxyethylene terephthalate:C3 ox:yalkylene
terephthalate units is
2:1 or lower, (ii) C4-C6 alkylene or oxy C4-C6 alkylene segments, or mixtures
therein,
(iii) poly (vinyl ester) segments, preferably polyvinyl acetate, having a
degree of
polymerization of at least 2, or {iv) C1-C4 alkyl ether or C4 hydroxyalkyl
ether
substituents, or mixtures therein, wherein said substituents are present in
the form of C1-
C4 alkyl ether or C4 hydroxyalkyl ether cellulose derivatives, or mixtures
therein, or a
combination of (a) and (b).
Typically, the polyoxyethylene segments of (a)(i) will have a degree of
polymerization of
from 200, although higher levels can be used, preferably from 3 to 150, more
preferably
from 6 to 100. Suitable oxy C4-C6 alkylene hydrophobe segments include, but
are not
limited to, end-caps of polymeric soil release agents such as
M03S(CH2)nOCH2CH20-,
where M is sodium and n is an integer from 4-6, as disclosed in US-A-
4,721,580.
Polymeric soil release agents useful herein also include cellulosic
derivatives such as
hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate
or
propylene terephthalate with polyethylene oxide or polypropylene oxide
terephthalate,
and the like. Such agents are commercially available and include hydroxyethers
of
cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use
herein also
include those selected from the group consisting of C1-C4 alkyl and C4
hydroxyalkyl
cellulose; see US-A-4,000,093.
CA 02337408 2001-O1-12
WO 00/04117 PCTIUS99/15491
S$
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
EP-A-0219048.
Another suitable soil release agent is a copolymer having random blocks of
ethylene
terephthalate and polyethylene oxide (PEO} terephthalate. The molecular weight
of this
polymeric soil release agent is in the range of from 25,000 to 55,000: See US-
A-
3,959,230 and US-A-3,893,929.
Another suitable polymeric soil release agent is a polyester with repeat units
of ethylene
terephthalate units contains 10-15% by weight of ethylene terephthalate units
together
with 90-80% by weight of polyoxyethylene terephthalate nits, derived from a
polyoxyethylene glycol of average molecular weight 300-:1,000.
Another suitable polymeric soil release agent is a sulfonatE;d product of a
substantially
linear ester oligomer comprised of an oligomeric ester backbone of
terephthaloyl and
oxyalkyleneoxy repeat units and terminal moieties covalently attached to the
backbone.
These soil release agents are described fully in US-A-4,968,451. Other
suitable
polymeric soil release agents include the terephthalate polyesters of US-A-
4,711,730, the
anionic end-capped oligomeric esters of US-A-4,721,580 and the block polyester
oligomeric compounds of US-A-4,702,857. Other polymeric soil release agents
also
include the soil release agents of US-A-4,877,896 which discloses anionic,
especially
sulfoarolyl, end-capped terephthalate esters.
Another soil release agent is an oiigomer 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 I .8, and two end-cap units of
sodium 2-(2-
hydroxyethoxy)-ethanesulfonate.
Heaw metal ion sequestrant
CA 02337408 2001-O1-12
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59
The tablets of the invention preferably contain as an optional component a
heavy metal
ion sequestrant. By heavy metal ion sequestrant it is meant herein components
which act
to sequester (chelate) heavy metal ions. These components may also have
calcium and
magnesium chelation capacity, but preferentially they show selectivity to
binding heavy
metal ions such as iron, manganese and copper.
Heavy metal ion sequestrants, which are acidic in nature, having for example
phosphonic
acid or carboxylic acid functionalities, may be present either in their acid
form or as a
complex/salt with a suitable counter cation such as an alkali or alkaline
metal ion,
ammonium, or substituted ammonium ion, or any mixtures thereof. Preferably any
saltslcomplexes are water soluble. The molar ratio of said counter cation to
the heavy
metal ion sequestrant is preferably at least 1:1.
Suitable heavy metal ion sequestrants for use herein include organic
phosphonates, such
as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-
hydroxy
disphosphonates and nitrilo trimethylene phosphonates. Preferred among the
above
species are diethylenetriamine penta (methylene phosphonate), ethylenediamine
tetra(methylene phosphonate) hexamethylenediamine tetra {methylene
phosphonate) and
hydroxy-ethylene-1,1-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, ethylene:diamine 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~l_;~rowth inhibitor component
The detergent tablets preferably contain a crystal growth inhibitor component,
preferably
an organodiphosphonic acid component, incorporated preferably at a Ievel of
from 0.01%
to 5%, more preferably from 0.1% to 2% by weight of the compositions.
CA 02337408 2001-O1-12
WO OOJ04117 PCT/US99J15491
By organo diphosphonic acid it is meant herein an organ.o diphosphonic acid
which does
not contain nitrogen as part of its chemical structure. This def nition
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 <~.cid, 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 compositions herein optionally contains a water-soluble sulfate salt.
Where present
the water-soluble sulfate salt is at the level of from 0.1 °/. to 40%,
more preferably from
1% to 30%, most preferably from 5% to 25% by weight of composition.
The water-soluble sulfate salt may be essentially any salt of sulfate with any
counter
cation. Preferred salts are selected from the sulfates of the alkali and
alkaline earth
metals, particularly sodium sulfate.
Alkali Metal Silicate
A suitable alkali metal silicate is sodium silicate having an Si02:Na20 ratio
of from 1.8
to 3.0, preferably from 1.8 to 2.4, most preferably 2Ø ;indium silicate is
preferably
present at a level of less than 20%, preferably from 1% to 15%, most
preferably from 3%
to 12% by weight of Si02. The alkali metal silicate may be in the form of
either the
anhydrous salt or a hydrated salt.
The compositions herein can also contain sodium metasilicate, present at a
level of at
least 0.4% Si02 by weight. Sodium metasilicate has a nominal Si02 : Na20 ratio
of 1Ø
The weight ratio of said sodium silicate to said sodium metasilicate, measured
as Si02, is
preferably from 50:1 to 5:4, more preferably from 15:1 to 2:1, most preferably
from 10:1
to 5:2.
Colourant
CA 02337408 2004-10-06
61
The term 'colourant', as used herein, means any substance that absorbs
specific
wavelengths of light from the visible light spectrum. Such colourants when
added to a
detergent composition have the effect of changing the visible colour and thus
the
appearance of the detergent composition. Colourants may be for example either
dyes or
pigments. Preferably the colourants are stable in composition in which they
are to be
incorporated. Thus in a composition of high pH the colourant is preferably
alkali stable
and in a composition of low pH the colourant is preferably acid stable.
Examples of suitable dyes include reactive dyes, direct dyes, azo dyes.
Preferred dyes
include phthalocyanine dyes, anthraquinone dye, quinoline dyes, monoazo,
disazo and
polyazo. More preferred dyes include anthraquinone, quinoline and monoazo
dyes.
Preferred dyes include SANDOLANTM E-HRL l 80%, (tradename), SANDOI,ANTM
MILLING BLUE, TURQUOISE ACID BLUE (tradename) and SANDOLAN TM
BRILLIANT GREEN (tradename) all available from Clariant UK., HEXACOLTM
QUINOLINE YELLOW (trademane) and HEXACOLT"' BRILLIANT BLUE (tradename)
both available from Pointings, UK, ULTRA MARINE BLUE (tradPname) available
from
Nolliday or LEVAFIXTM TURQUISE BLUE EBA (tradename) available from Bayer, USA.
The colourant may be incorporated by any suitable method. Suitable methods
include
mixing all or selected detergent components with a colourant in a drum or
spraying all or
selected detergent components with the colourant in a rotating drum.
Colourant is typically added at a level of from 0.001 % to 1.5%, preferably
from 0.01
to 1.0%, most preferably from 0.1% to 0.3% by weight of composition.
Corrosion inhibitor compound
The compositions herein, especially for use in dishwashing, can contain a
corrosion
inhibitor preferably selected from organic silver coating agents, particularly
paraffin,
nitrogen-containing corrosion inhibitor compounds and Mn(Il) compounds,
particularly
Mn(1I) salts of organic ligands.
Organic silver coating agents are described in WO-A-94/16047 and EP-A-690122.
Nitrogen-containing corrosion inhibitor compounds are disclosed in EP-A-
0634478.
Mn(II) compounds for use in corrosion inhibition are described in EP-A-0672
749.
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WO 00/04117 PCTIUS99115491
62
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 ax!
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, valeric
acid, lactic acid, glycolic acid and (3, j3'- dihydroxyisobutyric acid.
Examples of suitable
polycarboxyIic acids include: n-butyl-malonic acid, isocitz~ic 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 hydrocwbon chain. Examples of
suitable fatty alcohois include; behenyl, arachidyl, cocoyl, oleyl and lauryl
alcohol,
ethylene glycol, glycerol, ethanol, isopropanol, vinyl alcohol, diglycerol,
xylitoi, sucrose,
erythritol, pentaerythritol, sorbitol or sorbitan.
Preferably, the fatty acid and/or fatty alcohol group of the fatty ester
adjunct material
have from I 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.
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63
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 monostearat~e, ethylene glycol
monostearate, sorbitan esters. Suitable sorbitan esters include sorbitan
monostearate,
sorbitan palmitate, sorbitan monolaurate, sorbitan monom;yristate, 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 rnc~nopalmitate,
glycerol
monobehenate, and glycerol distearate are preferred glycerol esters herein.
Suitable organic silver coating agents include triglyceride:>, 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
I IO°C and
comprise generally from 12 to 70 carbon atoms. Preferred are petroleum waxes
of the
paraff n 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 C 12-C20 methylamine oxide, and dialkyl
quaternary
ammonium compounds and salts, such as the CI2-C20 m~ethylammonium 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-vinylpynrolidone and N-
vinylimidazole,
and cellulose derivatives such as methylcellulose, carbox:ymethylcellulose and
hydroxyethy1ce11ulose are examples of such polymeric materials.
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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
sP~ies with a
ratio of cyclic to noncyclic hydrocarbons of from 1:I0 to 2:1, preferably from
1:5 to 1:I.
A paraffin oil meeting these characteristics, having a ratio of cyclic to
noncyclic
hydrocarbons of 32:68, is sold by Wintershall, Salzbergen, Germany, under the
trade
name WINOG ?0.
Nitrosen containing corrosion inhibitor compounds
Suitable nitrogen-containing corrosion inhibitor compounds include imidazole
and
derivatives thereof such as benzimidazole, 2-heptadecyl imidazole and those
imidazole
derivatives described in Czech Patent No. 139, 279 and GB-A-1,137,741, which
also
discloses a method for making imidazole compounds.
Also suitable as nitrogen-containing corrosion inhibitor compounds are
pyrazole
compounds and their derivatives, particularly those where the pyrazole is
substituted in
any of the 1, 3, 4 or 5 positions by substituents RI, R3, R4 and R$ where RI
is any of H,
CH20H, CONH3, or COCH3, R3 and RS are any of Cl.-C20 alkyl or hydroxyl, and R4
is any of H, NH2 or N02.
Other suitable nitrogen-containing corrosion inhibitor compounds include
benzotriazole,
2-mercaptobenzothiazole, I-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 suit~~ble.
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Mri(II) corrosion inhibitor compounds
The Mn(Ii) compound is preferably incorporated at a level to provide from 0.1
ppm to
250 ppm, more preferably from 0.5 ppm to 50 ppm, mostpreferably from 1 ppm to
20
ppm by weight of Mn(II) ions in bleaching solution.
The Mn (II) compound may be an inorganic salt in anhydrous, or any hydrated
forms.
Suitable salts include manganese sulphate, manganese caribonate, 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 nnanganese 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; Iauryl mercaptan,
thiophenol,
thionapthol, thionalide and thioanthranol. Also suitable are saturated or
unsaturated C 10-
C20 fatty acids, or their salts, especially aluminium tristearate. T'he C12-
C20 hYdroxy
fatty acids, or their salts, are also suitable. Phosphonated c>cta-decane and
other anti-
oxidants such as betahydroxytoluene (BHT) are also suitable.
Copolymers of butadiene and malefic acid, particularly those supplied under
the trade
reference no. 07787 by Polysciences Inc have been found to be of particular
utility as
corrosion inhibitor compounds.
Water-soluble bismuth com~oun_d
The compositions herein, especially for use in dishwashing;, can contain a
water-soluble
bismuth compound, preferably present at a level of from 0.005% to 20%, more
preferably from 0.01 % to 5%, most preferably from 0.1 % to 1 % by weight of
composition.
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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.
Enzy-me Stabilizing System
Preferred enzyme-containing compositions herein can comprise from 0.001 % to
10%,
preferably from 0.005% to 8%, most preferably from 0.01.% to 6%, by weight of
an
enzyme stabilizing system. The enzyme stabilizing system can be any
stabilizing
system which is compatible with the detersive enzyme. Such stabilizing systems
'can
comprise calcium ion, boric acid, propylene glycol, short chain carboxylic
acid, boronic
acid, chlorine bleach scavengers and mixtures thereof. Such stabilizing
systems can also
comprise reversible enzyme inhibitors, such as reversible protease inhibitors.
Lime soap dispersant compound
The compositions herein can contain a lime soap dispersant compound,
preferably
present at a level of from 0.1 % to 40% by weight, more preferably 1 % to 20%
by weight,
most preferably from 2% to 10% by weight of composition.
A lime soap dispersant is a material that prevents the precipitation of alkali
metal,
ammonium or amine salts of fatty acids by calcium or magnesium ions. Preferred
lime
soap disperant compounds are disclosed in WO-A-93/08877.
Suds suppressingrsystem
The compositions herein preferably comprise a suds suppressing system present
at a
level of from 0.0I% to IS%, preferably from 0.05% to 10%, most preferably from
0.1%
to 5% by weight of composition.
Suitable suds suppressing systems for use herein may comprise essentially any
known
antifoam compound, including, for example silicone antifbam compounds, 2-alkyl
and
alcanol antifoam compounds. Preferred suds suppressing systems and antifoam
compounds are disclosed in WO-A-93/08876 and EP-A-0705324.
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Polymeric dye transfer inhibiting agents
PCTIUS99115491
The compositions herein can also comprise from 0.01% to 10 %, preferably from
0.05%
to 0.5% by weight of polymeric dye transfer inhibiting agents.
The polymeric dye transfer inhibiting agents are preferably selected from
polyamine N-
oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,
polyvinylpyrrolidonepolyrners or combinations thereof.
Optical brightener
The compositions can also contain from 0.005% to 5% by weight of certain types
of
hydrophilic optical brighteners.
Hydrophilic optical brighteners useful herein include those having the
structural formula:
R2
Ri
H H N--C
N- N
N ~-.- N C ~ ~ CO
N H H "r"~
O~ l ~ N
SO M S03M ~Ri
RZ 3
wherein Rl is selected from anilino, N-2-bis-hydroxyeth~yl and NH-2-
hydroxyethyl; R2
is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino,
morphilino,
chloro and amino;.and M is a salt-forming cation such ass sodium or potassium.
When in the above formula, Rl is anilino; R2 is N-2-bis,-hydroxyethyl and M is
a cation
such as sodium, the brightener is 4,4',-bis[(4-anilino-b-(N-2-bis-
hydroxyethyl)-s-triazine-
2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular
brightener
species is commercially marketed under the tradename 'Tinopal-UNPA-GX by Ciba-
Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical
brightener
useful in the detergent compositions herein.
When in the above formula, Rl is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and
M is a canon such as sodium, the brightener is 4,4'-bis[:(4-anilino-6-(N-2-
hydroxyethyl-
N-methylamino)-s-triazine-2-y!)amino]2,2'-stilbenedisulfonic acid disodium
salt. This
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particular brightener species is commercially marketed under the tradename
Tinopal
SBM-GX by Ciba-Geigy Corporation.
When in the above formula, Rl is anilino, R2 is morphilino and M is a ration
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 compositions herein can contain a clay softening system comprising a clay
mineral
compound and optionally a clay flocculating agent.
'The clay mineral compound is preferably a smectite clay compound. Smectite
clays are
disclosed in the US-A-3,862,058, US-A-3,948,790, US-A-3,954,632 and US-A-
4,062,647. EP-A-0299575 and EP-A-0313146 describe suitable organic polymeric
clay
flocculating agents.
Cationic fabric softening-agents
Suitable cationic fabric softening agents include the water insoluble tertiary
amines or
dilong chain amide materials as disclosed in GB-A-1514:276 and EP-A-0011340.
Cationic fabric softening agents are typically incorporated at total levels of
from 0.5% to
15% by weight, normally from 1% to 5% by weight.
