Note: Descriptions are shown in the official language in which they were submitted.
CA 02578875 2007-03-09
CLEAMNO PRODUCT
Tec 'cal field
The present invention is in the field of automatic washing, in particular it
relates to washing
products in unit dose form comprising a plurality of zones adapted to release
different
compositions in different cycles of the washing process. The products provide
excellent
cleaning and finishing benefits.
Bckg,round of the igvention
Two of the unsolved problems in the field of automatic dishwashing are those
of cleaning
tough food residues and, of preventing filming and spotting of washed
articles, especially
glass and plastic articles. Filming and spotting are believed to occur, among
other reasons,
due to the formation of insoluble salts resulting from the combination between
the ions
generated from the dishwashing detergent and the ions present in the
dishwasher water. Food
soils also play a significant role in causing filming and spotting.
Traditionally, this problem
has been ameliorated by the use of salt in order to soften the water (that is
to reduce the
concentratiQn of cations, specially Ce and Mg24) and by the use of rinse aid
containing
sequestrant, dispersant and smfactant which to some extent help to control the
hardness of the
ions present in the water and to reduce the surface tension of the dishwashing
liquor, thus
avoiding the formation of liquid droplets and atlowing uniform drying of the
washed utensils,
ameliorating filmmg and spotting issues.
However, some consumers do not use salt or rinse aid or the water is so hard
that salt and
rinse aid are not enough to overcome filming and spotting problems. Moreover,
the problem
of food soils and removal of tough food residues still remains a significant
issue.
Typically, the machine dishwashing process involves the steps of dosing
detergent into the
dispenser at the beginning of each wash and filling the salt and rinse aid
reservoirs at
intervals as required. Some users may find it iuaconvenient to carry out all
these steps and
prefer a simpler process involving the use of a single product performing alI
the functions
required for the dishwashing process. Unitised doses of dishwashing detergents
are found to
be more attractive and convenient to some consumers, additionally they avoid
the need of the
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CA 02578875 2007-03-09
consumer to measure the product thereby giving rise to a more precise dosing
and avoiding
wasteful overdosing or underdosing. For this reason automatic dishwashing
detergent
products in tablet form have become very popular. Detergent products in pouch
form are also
known in the art.
Rinse aid compositions need to be stored in the rinse reservoir inside the
dishwasher, usaally
during many cycles and therefore subject to the temperature changes associated
with the
dishwashing process. Thus rinse aid compositions need to be very stable in
order to
withstand these temperature changes without affecting their physical form
and/or chemical
structure. This usually requires the use of very dilute compositions, which
limits even further
the amount of actives that can be delivered into the rinse cycle.
Some attempts have been made to provide controlled deliveryof =inse aid. For
example WO-
A-00/6684 and WO-A-00/6688 describe a miilti-phase tablet comprising
a'particle which
comprises a core and a coating. The substances present in the core are active
during the rinae
cycle and the coating comprises at least one compound whose solubility
increases with a
declining concentration of a specific ion in the surrounding medium. WO-A
99/27067
describe a multi-phase tablet with a compressed and non-compressed portion
where the non-
compressed portion does not dissolve until the rinse cycle. EP-A 851,024
descnbes a multi-
layer tablet, having a first layer for dalivery into the main wash and a
second layer
comprising a substance which has a melting point between 55 C and 70 C and
which is
substantially delivery into the rinse cycle. However, the tablets described in
WO '84, WO
'88, WO '67 and EP '24 only deliver actives into one of the rinses cycles and
are not capable
of selectively delivering different compositioiis into differenfirinse cycles.
US-A-5,453,216 descri'bes the delivery of actives in the rinse cycle by means -
of coated
particles. The particles, which are introduced into the pre-wash and into main-
wash cycles,
comprise a core comprising an inorganic builder salt and a waxy coating having
a melting
point above 65 C. Particles are said to have a diameter from about 1 to about
2.5 mm. As
such, it seems likely that a large proportion of the particles will be flushed
away with the
main wash liquor at the end of the 4uin wash cycle.
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CA 02578875 2007-03-09
WO 01/96514 relates to a mechanical dishwashing composition comprising an anti-
scaling
polymer and a vehicle releasing at least an effective amount of the polymer
into a penultimate
and/or final rinse of a dishwashing cycle.
Some detergent ingredients used in dishwashing detergent compositions are
liquids. These
liquid ingredients can be difficult or costly to include in a solid detergent
composition. Also,
certain ingcedients are preferably transported and supplied to detergent
manufacturers in a
liquid form and require additional, and sometimes costly, process steps to
enable them to be
included in a solid detergent composition. An example. of these detergent
ingredients are
1 o surfactants, especiaUy nonionic surfactants which are typica[ly liquid at
room temperature or
are typically transported and supplied to detergent manufacturers m liquid
form. Another
example are organic solvents. It would be advantageous to have a detergent
composition
which allows the different ingredients to be in their natural state i.e.,
liquid or solid.
The majority of automatic dishwashers have wash programs which last at least
one hour but
only a relatively small proportion of the total wash program is devoted to
active detersive
cleaning (i:e. the main-wash cycle, which lasts for about 20 min, and possibly
the pre-wash)
and only a relative small portion of the final rinse cycle (determined by the
dishwasher
design) is devoted to chemical finishing. These times do not seem to be
sufficient for
achieving a satisfactory removal of tough food residues and preventing filming
and spotting,
however delivery programs are fixed parameters determined by dishwashing
machine
manufactureis and the user has no control over them.
In view of the above there is still a need for improving tough food cleaning
whilst reducing
filming and spotting, especially in those instances where users wish to avoid
or limit the use
of salt andlor rinse aid and in the case of dishwashing under hard water
conditions.
Summarv of the invention
An automatic dishwashing operation typically comprises three or morecycles: a
pre-wash
cycle, a main-wash cycle and one or.more rinse cycles. In Europe, the pre-wash
cycle, when
used, is typica2ly a cold water cycle lasting about 6 or 7 min. In the main-
wash cycle the
water comes in cold and is heated up to about 55 or 65 C, the cycle lasting
about 20 min.
Rinsing tisually comprises two or more separate cycles following the main
wash, the first
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CA 02578875 2007-03-09
being cold and lasting between about 2 and 5 min, the fmal one starking cold
with heat-up to
about 65 C or 70 C and lasting about 20 min. The dishwashing machine is filled
with cold
water at the start of each cycle and emptied at the end of each cycle through
a filter. A
typical dishwashing machine is designed for the delivery of from about 20 to
about 40 grams
of detergent from the dispenser into the main-wash and from about 2 to about 6
ml of rinse
aid at or towards the end of the final rinse cycle. In the U.S. the pre-wash
may itself be
followed by a separate rinse cycle prior to the main-wash. For purposes of the
invention the
term rinse is restricted to rinse cycles following the main-wash.
According to a first aspect of the invention there is provided an automatic
laundry or
dishwashing product in unit dose form eomprising at least three distinct zones
including a
prlmary cleaning zone, a secondary cleaning zone and a finishing zone and
wherein in use in
an automatic laundry or dishwashing machine having a main-wash cycle and a
phngtity of
post main-wash rinse cycles, the primary cleaning zone releases a primary
cleaning
composition into the main wash, the secondary cleaning zone releases a
secondary cleaning
composition into a pre-Snal rinse, preferably the first rinse, and the
fli.nishing zone releases a
fuiishing composition into the final rinse.
The product of the invention allows for flexible formulation, permitting, for
exaYnple, the
separation of mutually-incompati'ble ingredients either on storage or in the
wash liquor and
the separation of ingredients in different physical forms; it also allows for
sequential
controlled release, i.e, allows for the releasing of different products into
different cycles
providing an optimisation of the washing process. The addition of a secondary
cleaning
composition permits the delivery of ingredients having a different cleaning
mechanism to the
primary cleaning composition, providing extra-cleaning by removing any
remaining residues
left after the main-wash. The product of the invention also allows for an
optimisation of the
finishing process, even without the use of salt or rinse aid, firstly because
the cleaned articles
present less spotting than when washed with a single detergent during the main-
wash and
secondly because the product of the invention can deliver more chemistry for a
longer period
of time during the main wash and rinse cycles. Furthermore, the product of the
invention
provides care and protection of the dishwareJtableware.
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By primary and secondary cleaning compositions are herein meaut compositions
comprising
automatic cleaning ingcedients and/or auxiliaries. The primary and secondery
cleaning
compositions can be similar but preferably they are compositions having a
complementary
cleaning effect (e.g., first cleaning composition comprises detergency enzymes
and second
cleaning composition comprises chlorine bleach).
In a preferred embodiment, the prunary cleaning zone is. a high alkaluuty
cleaning zone, the
secondary cleaning zone is a low alkalinity cleaning zone and the finishing
zone is a neutral
or acidic finishing zone, preferably the primary cleaning composition provides
a wash liquor
pH.of about 10 or above, the secondary cleaning composition provides a wash
liquor pH of
from about 8 to about 9.5 and the finishing composition provides a wash liquor
of about 5 or
below. This combination of cleaning under different alkalinity conditions
followed by acidic
rinse provides excellent cleaning and finishing results.
In a preferred embodiment, the primary cleaning composition has a reserve
allcalinity in the
range from about 10 to about 20 g NaOH/100 g of product: "Reserve alkalinity",
as used
herein refers to, the ability of a composition to maintain an alkali pH in the
presence of acid.
This is relative to the ability of a composition to have sufficient alkali in
reserve to deal with
any added acid while maintaining pH. More specifically, it is defined as the
grams of NaOH
per 100 g of product, exceeding pH 9.5, in product. The reserve alkalinity for
a solution.is
detemiined in the following manner.
A Mettler DL77 automatic titrator with a Mettler DG115-SC glass pH electrode
is calibrated
using pH 4, 7 and 10 buffers (or buffers spanning the expected pH range). A 1%
solution of
the composition to be tested is prepared in distilled water. The weight of the
sample is noted.
The pH of the 1% solution is measured and the solution is titrated down to pH
9.5 using a
solution of 0.25N HCL. The reserve allcalinity (RA) is calculated in the
following way:
RA- %NaOHxSpecific gravity
%NaOH=nril HClxNormality of HClx4Ox 100/Weight of sample aliquot titrated(g)x
1000
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Preferably the primary cleaning composition comprises carbonate and phosphate
detergency
builders in a ratio of from about 1:4 to about 5:1, preferably from about 1:2
to about 3:1, such
compositions being optimum for cost and performance. The carbonate builder for
use haein
can be selected from alkali metal carbonates, sesquicarbonates, percarbonates
and mixtures
thereof, especially sodium carbonate. Preferably the primary cleaning
composition also
comprises alkali metal silicates in order to provide protection against
corrosion of inetals and
against attack on dishware, including china and glassware or for machine
protection. The
compositions are preferably free of inetasilioates.
The product of the invention pennits the separation of mutually-incompatible
ingredients
either on storage and/or in use, such as for example enzymes and chlorine
bleach. Thus, in a
preferred embodiment the primary cleaning composition comprises a detergency
enzyme. In
another prefened embodiment the secondary cleaning composition comprises a
bleaching
agent, preferably a chlorine bleach and optionally a detergency builder,
preferably a
phosphate detergency builder. In a-dishvt+ashing application, the builder
promotes the
degradation of tough food soils such as for exainple lasagne and egg. Without
wishing to be
bound by theory, it is believed that these soils contain significant amount of
calcium and
therefore they can be degraded by builders. Chlorine bleach removes residual
stains such a as
tea and coffee, removes protein spots and promotes shine.
In still another preferred embodiment the primary cleaning composition
comprises a
detergenoy enzyme and at the same time, the secondary cleaniag composition
comprises a
bleaching agent. This not only brings unique cleaning benefits but also
permits the reduction
of the levels of enzymes as compared with those used in traditional detergent
without loss of
performance. It is preferred that fhe prunary cleaning composition comprises
an oxygen
bleach. Oxygen bleach forming part of the primary cleaning composition and
therefore
delivered into the main-wash and chlorine bleach forming part of the secondary
cleaning
composition and therefore delivered into a pre-final rinse, preferably the
first rinse,
synergistically complement each other boosting the overall bleaehi.ng
performance of the
product, even without using a bleach catalyst. Benefits can be seen, for
example in the.
removal of black tea stains. Oxygen bleach in the main wash removes the bulk
of the stain
and chlorine bleach in the first rinse attacks the residual stain. This stain
removal can be
more efficient than when using higher amount of only one bleaching agent.
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CA 02578875 2007-03-09
The main role of the finishing composition is to provide the cleaned articles
with a good final
feel, aesthetics and appearance, for example in the case of
dishwareJtableware, substantially
free of fihning and spotting and having a good gloss and shine. This can be
achieved, for
instance, by removing aiksline salt deposits fonned during the main-wash and.
by promoting
5. sheeting and uniform drying of the articles. In a prefen-ed embodiment the
finishing
composition includes an acidity source selected from organo aminophosphonic
acids and
amfnopolyphosphonic acids, organo phosphonic acids and polyphosphonic acids,
carboxylic
acids, polycarboxylic acids, sulfonic acids, polysulfonic acids and mixturas
thereof.
Preferably, the acidity source is a polycarboxylic acid especially citric
acid. Preferably, the
finishing composition also comprises a chlorine scavenger in order to provide
care and
protection to the dishwareJtableware, especially to metallic and in particular
silver articles.
In a preferred embodiment the fmishing zone is enclosed within the secondary
cleaning zone
(which protects the finishuig composition during the main wash) and the
secondary cleaning
zone is enclosed within the primary cleaning zone, alternatively, the
finishing and the
secondary cleaning zone can be enclosed within the primaiy cleaning zone. This
second
alternative can be favourable from the manufacturing viewpoint. The delivery
of different
compositions in different cycles can be achieved - by including physical,
chemical or
mechanical trigger-means for releasing the. primary cleaning, secondary
cleaning and
fmishing compositions into the wash or rinse liquors. Trigger-means for the
primary
cleaning, secondary- cleaning and finishing compositions serve to protect the
different
compositions of the product from dissolution before the desired moment and
deliver each
composition at a defined point in time. Preferably, the delivery of the
different compositions
is performed at optimum times in each cycle and in a discontinuous way (as
opposed to slow
delivery such as that provided by a detergent block or tablet) in order to
provide the
ingredients with an optimum working time. The trigger means are each
responsive to one or
more of temperature, pli, redox potential, ionic concentration, enzymatic
reaction or time.
In a preferred embodiment cach zone of the product has associated trigger
means as follow:
i) the primary cleaning zone is associated with a temperature-dependent
primary trigger, said
primary cleaning trigger being responsive to a rise in temperatnre above a
trigger temperature
(Tp;m,). Preferably the trigger temperature, Tp;,, is at least about 20 C,
more preferably at
least about 259C and especially at least about 28 C with an optional trigger
delay (t,,õ) of less
than about 4 min, preferably less than about 2;
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CA 02578875 2007-03-09
ii) the secondary cleaning. zone is associated with a primed inverse
temperattna-dependent
secondary cleaning trigger, said secondary trigger being responsive to a fall
in tennpwature
below a trigger temperature (T.) and being primed to trigger by a rise in
temperature above
a trigger priming temperatare (T'no) which is greater than T... Preferably the
secondary
cleaning trigger has trigger temperature T,. of less than about 40 C, more
preferably less
than about 35 C, especially less than about 30 C and a trigger priming
temperature (T'.) of
at least 40 C, preferably at least 45 C, more preferably at least 48 C; and
iii) the finishing zone is associated with a temperature-dependent finishing
trigger, said
finishing trigger being responsive to a rise in temperature above a tnigger
temperature (T&).
Preferably the finishing trigger has a trigger temperature Tf, of at least
about 45 C, more
preferably at least about 48 C, especially at least about 50 C with an
optional trigger delay
(tf.) of less thaii about 1 min, preferably less than about 30 sec.
The product of the invention pennits a controlled release of the difFerent
compositions into
the wash or rinse liquor at very well deSned points of the washing or rinsing,
maximizing the
efficacy of each composition. In a prefwed embodiment T'. is greater than T.
In other
preferred embodiments, Tfiõ is greater or equal than T'M.
Temperature-dependent trlggers preclude the delivery of the associated
composition before
the trigger temperature is reached. By "primed trigger" is meant a trigger
which needs to be
triggered by an additional trigger (priming trigger) before it can be
activated itself. By
"inverse- temperature-dependent trigger" is meant a trigger which is activated
by a fall in
temperatare below a given trigger temperature. By "trigger-delay" is meant a
period of delay
after the trlgger-temperature is reached and before the trigger is activated.
The trigger means
can be selected from temperature solubility-dependent filtns (i.e, films
having solubility
characteristics dependent upon temperature), coatings, sprays-on,
agglomerating materials,
binding materials and mixtures thereof. The primary cleaning trigger serves to
protect the
prlmary composition during the pre-wash and to deliver it into the main-wash.
The
secondary cleaning trigger serves to protect the secondary composition during
the main-wash
and to deliver it during a pre-final rinse cycle, preferably during the first
rinse. The f nishing
cleaning trigger serves to protect the primary composition during pre-final
rinse cycles and to
deliver it into the final rsnse.
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CA 02578875 2007-03-09
In a preferred embodiment the primary cleaning tcigger is in the form of a
film and the
primary cleaning zone is in the form of a pouch or capsule. In use, the
product can be placed
within the washing machine dispenser and released during the main cycle of the
washing
process. The dispensers of some washing machines are not completely water
tight, mainly
for two reasons, either the dispenser has some aperhares allowing water
ingross or the
dispenser is sealed with a reibber band that can deform with time due to the
high wash
temperature. Water ingress into the dispenser can cause premature leaking of
some of the
pouch content which is thus prematurely lost, for example in the case of
dishwashing, at the
end of the pre-wash. This problem is especially acute in the case of pouches
comprising
liquid compositions having a low viscosity wherein a considerable amount of
the product can
be lost before the main-wash cycle. Sometimes, it is usefal to place the
product outside the
dispenser, for example, in order to avoid volume constraints. The problem of
ingredient
release before the main-wash can be overcome by using a primary trigger means
which is not
activated during the pre-wash (in Buropean maehines, the pre-wash is usually a
cold water
cycle (about 20 C or less) without. detergent and lasting for about 10 to 15
min) and is
triggered at or after the start of the main-wash cycle.
The pnmary and secondary cleaning zones and the finishing zone can be in the
form of a
pouch, capsule, tablet or compact, the triggers can be in the form of a film
or capsule. wall
and the compositions can be in the form of powder, compressed powder, liquid,
liquid-solid
svspension, gel or paste.
The primary cleaning composition can be in the form of powder, compressed
powder,
transparent or translucent liquid, liquid-solid suspension, gel or paste.
Alternatively, the
primary cleaning zone can be in the form of a coated tablet.
Preferably, the prirnary finishing zone is in the form of a pouch or capsule.
It is also
preferred that the secondary and the finishing zones are in the form of a
pouch or capsule.
Alternatively, the secondary and/or the finishing zones can be in the form of
a compressed
powder, wherein the trigger means are either coated on the surface of the
compressed powder
(for example by spraying or encapsulation techniques) or. agglomerated into
the compressed
powder.
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According to another aspect of the invention, there is provided an automatic
laundry or
dishwashing product in unit dose form comprising one or more zones, each
comprising a
detergent active or auxiliary, at least one zone having a primed, inverse-
temperature tcigger
means associated with said zone for releasing the detergent active or
auxiliary into the wash
or rinse liquor. Preferably the zone having a primed, inverse-temperature
tcigger means
associated comprises a bleaching agent, especially chlorine bleach.
The secondary zone can alternatively have a primed, physico-chemical trigger
means. These
means can make use of the different conditions found towards the end of the
main-wash and
at the beginning of a penultimate cycle. Useful physico-ehemical trigger means
are for
example: i) electrolyte sensitive materials which are insoluble in the
presence of high
concentrations of ions (towards the end of the main-wash) but possess good
solubility at low
ionic concentration; and ii) pH sensitive materials which are insoluble at
high pH (above 10)
and soluble at pH below 9.
There is also provided a process for making the product of the invention
comprising the steps
of
a) making a first pouch or capsule of a temperature-dependent trigger
material,
said pouch or capsule containing the finishing coinposition;
.20 b) making a second pouch or capsule of a primed inverse temperature-
dependent
material, said pouch containing the secondary cleaning composition and the
first pouch formed in step a; and
c) making a third pouch or capsule of a temperature-dependent trigger material
including the primary cleaning composition and the second pouch or capsule
formed in step b.
In another process embodiment, there is provided a process for making the
product of the
invention comprising the steps of:
a) maicing a coated' compressed powder compact containing the finishing
composition wherein the coating comprises temperature-dependent trigger
material;
b) malcing a first pouch or capsule of a primed inverse temperature-dependent
material, said pouch or eapsule containing the secondary cleaning composition
and the coated compressed powder compact formed in step a; and
CA 02578875 2007-03-09
c) making a second pouch or capsule of a temperature-dependent trigger
material
said pouch containing the prunary cleaning composition and the firat pouch
formed in step b.
These processes are very versatile and item'ble, they permit to modify the
manufacture of
each zone independently without affecting other parts of the process.
According to another aspect of the present invention, there is provided a
polymeric material
for use as primed inverse temperatare-dependent means which is water insoluble
at
temperatures above about 40 C and water soluble at temperatures below about 40
C. This
enables dissolution of the polymeric material during the first rinse. It has
been found that a
polymeric material comprising an inverse solubility polymer and polyvinyl
alcohol in a ratio
of at least 1:1, preferably at least 2:1 and more preferably. at least about
3:1 can fulfil the
requirement of being insoluble above about 40 C and water soluble at
ftmpeatures below
about40 C.
Preferred inverse solubility polymer for use herein are hydroxybutyl
methylcellulose
(HBMC), hydroxypropyl methylcellulose (HPMC) and mixtures thereof. Preferably,
the
polymeric material also comprises a cross-linking agent such as for example
boric acid and a
plasticider such as for example glycerol, in order to avoid brittleness in the
film.
According to anothex aspect of the invention there is provided a method of
washing
cookware/tableware in an automatic dishwashing machine using the product of
the invention.
The product can be placed either in the dispenser or outside the dispenser,
for example,
cutlery basket, a net or on the floor of the machine, providing maximum
convenience for the
user and avoiding volume constriction from the formulation viewpoint. Also
provided is a
method of washing laundry in a laundry washing machine using the product of
the invention.
The product of the invention is excellent for the removal of hot beverages
stains such as for
example tea and coffee stains, thus there is also provided a method of
removing tea, and
coffee stains from cookware and tableware or from laundry articles comprising
washing the
cookwareltableware or laundry articles in an automatic dishwashing or laundry
machine in
the presence of the product of the invention. The product of the invention
also provides
11
CA 02578875 2007-03-09
excellent shine and care benefits on crockery, glass and/or plasticware and
finishing benefits
on laundry.
DetaiW descriution of the inyention
5The present invention envisages a washing product comprising different
compositions for
delivery at different times of the washing process. The products allows for a
controlled
delivery in various cycles of the washing and this is translated into
excellent cleaning and
finishing performances. The washed articles present excellent shine.
The ingredients described herein can be used in any of the three compositions
of the product
of the invention.
Surfactant
Preferably, the surFactant for use in the product of the present invention,
especially when the
product is used in automatic dishwashing, is a low foaming sur~actant by
itself or in
combination with- other components (i.e. suds suppressers). Surfactants
preferably comprise
part of the primary or secondary cleaning composition. Surfactants suitable
herein include
anionic surfactants such as alkyl sulfates, alkyl ether sulfates, alkyl
benzene sulfonates, alkyl
glyceryl sulfonates, alkyl and alkenyl * sulphonates, allryl ethoxy
carboxylates, N-acyl
sarcosinates, N-acyl taurates and alkyl succinates and stilfosuccinates,
wherain the alkyl,
alkenyl or acyl moiety is C5-C20, preferably C10-CI8 linear or 'branched;
cationic
surfactants such as chlorine esters (tIS-A4228042, US-A-4239660 and US-A-
4260529) and
mono C6-C16 N-alkyl or alkenyl ammonium surfactants wherein the remaining N
positions
are substitutad by methyl, hydroxyethyl or hydroxypropyl groups; low and high
cloud point
nonionic surfactants and mixtures thereof including nonionic a]koxylated
surfactants'
(especially. ethoxylates derived from C6-C18 Pritnary alcohols), ethoxylated-
propoxylated
alcohols (e.g., BASF Poly-Tergent SLF18), epoxy-capped poly(oxyalkylated)
alcohols
(e.g., BASF Poly-Tergent SLP18B - see WO-A-94/22800), ether-capped
poly(oxyalkylated) alcohol surfactants, and block polyoxyethylene-
polyoxypropylene
polymeric compounds such as PLURONIC , REVERSED PLURONIC , and
TBTRONIC by the BASF-Wyandotte Corp., Wyandotte, Michigan; amphoterie
surfactants
such as the C12-Cao alkyl amine oxides (preferred arnine oxides for use herein
include C12
lauryldimethyl amine oxide, C14 and C16 hexadecyl dimethyl amine oxide), and
alkyl
12
CA 02578875 2007-03-09
amphocarboxylic surfactants such as MiranolTm C2M; and zwitterionic
surfactants such as
the betaines and sultaines; and mixiures thereof. Surfactants suitable herein
are disclosed, for
example, in US-A-3,929,678, US-A 4,259,217, EP A 0414 549, WO-A-93/08876 and
WO-
A-93/.08874. Surfactants are typically present at a level of from about 0.2%
to about 30% by
weight, more preferably from about 0.5% to about 10% by weight, most
preferably from
about 1% to about 5% by weight of the total composition. Preferred surfactant
for use herein
are low foaming and inalude low cloud point nonion.ic _ surfactants and
mixtures of higher
foaming surfactants with low cloud point nonionic surfactants which act as
suds suppresser
therefor. Other preferred smfa.ctaazits, especially for use in the finishing
composition are
silicone surfactants, such as Silwet copolymers, preferred Silwet copolymers
include Silwet
L-8610, Silwet I.=8600, Silwet L-77, Silwet L-7657, Silwet L-7650, Silwet L-
7607, Silwet L-
7604, Silwet L-7600, Silwet 1,7280 and mixtnres thereof. Preferred for use
herein is Silwet
L-77.
Builder
Builders suitable for use herein include water-soluble builders such as
citrates, carbonates
and polyphosphates e.g. sodium tripolyphosphate and sodium tripolyphosphate
hexahydrate,
potassium tripolyphosphate and. mixed sodium and potassium tripolyphosphate
salts; and
partially water-soluble or insoluble builders such as crystalline layered
silicates (EP-A-
0164514 and EP-A-0293640) and aluminosilicates inclusive of Zeolites A, B, P,
X, HS and
MAP. The builder is typically present at a level of from about 1% to about 80%
by weight,
preferably from about 10% to about 70% by weight, most preferably from about
20% to
about 60% by weight of composition.
Amorphous sodium silicates having an Si02:Na20 ratio of from 1.8 to 3.0,
preferably from
1.8 to 2.4, most preferably 2.0 can also be used herein although highly
preferred from the
viewpoint of long term storage stability are compositions containing less than
about 22%,
preferably less than about 15% total (amorphous and crystalline) silicate.
Enzyme
Enzymes suitable herein include bacterial and flmgal cellulases such as
Carezyme and
Celluzyme (Novo Nordisk A/S); peroxidases; lipases such as Amano-P (Amano
Phnrmaceutical Co.), MI LipaseR and LipomaxR (Gist-Brocades) and LipolaseR and
Lipolase
U1iraR (Novo); cutinases; proteases such as EsperaseR, AlcalaseR, DurazyinR
and SavinaseR
13
CA 02578875 2007-03-09
(Novo) and MaxataseR, MaxacalR, ProperaseR and MaxapemR (Gist-Brocades); a and
P
amylases such as Purafect Ox AmR (Genencor) and Termamyli; BanR Fimgamy1R
DuramylR, and NatalaseR (Novo); pectinases; and mixtures thereof. Enzymes are
preferably
added herein as prills, granulates, or cogranulates at levels typically in the
range from about
0.0001% to about 2% pure enzyme by weight of composition.
Bleaching agent
Bleaching agents suitable herein include oxygen (especially in the primary
composition) and
chlorine (especially in the secondary composition) bleaches. Preferred. oxygen
bleaches are
inorganic perhydrate salts such as sodium perborate mono-and tetrahydrates and
sodium
percarbonate optionally coated to provide controlled rate of release (see, for
example, GB-A-
1466799=on sulfate/carbonate coatings), preformed organic peroxyacids and
mixtures thereof
with organic peroxyacid bleach precursors and/or transition metal-containing
bleach catalysts
(especially manganese or cobalt). Inorganic perhydrate salts are typically
incorporated at
levels in the range from about 1% to about 40'/o by weight, prefierably from
about 2% to
about 30% by weight and more preferably fiom abut 5% to about 25% by weight of
composition. Peroxyacid bleach precursors preferred for use herein include
precursors of
perbenzoic acid and substituted perbenzoic acid; cationic peroxyacid
precursors; peracetic
acid precarsors such as TAED, sodium acetoxybenzene sulfonate and
pentaacetylglucose;
pernonanoic acid precursors such as sodium 3,5,5-trimethylhexanoyloxybenzene
sulfonate
(iso-NOBS) and sodium nonanoyloxybenzene sulfonate (NOBS); amide substituted
alkyl
peroxyacid precursors (EP-A-0170386); and benzoxazin peroxyacid 'precursors
(EP-A-
0332294 and EP-A-0482807). Bleach precursors are typically incorporated at
levels in the
range from about 0.5% to about 25%, preferably from about 1% to about 10% by
weight of
composition while the preformed organic peroxyacids themselves are typically
incorporated
at levels in the range from 0.5% to 25% by weight, more preferably from 1% to
10% by
weight of composition. Bleach catalysts preferred for use herein include the
manganese
triazacyclononane and related complexes (US-A-4246612, US-A-5227084); Co, Cu,
Mn and
Fe bispyridylamine and related complexes (US-A-5114611); and pentamine acetate
3o cobalt(III) and related complexes(US-A-4810410).
Chlorine bleach is preferred for use in the secondary composition, especially
as agent for
reducing spotting. Chlorine bleach greatly improves cleaning performance; in
particular it
14
CA 02578875 2007-03-09
remove stains left by tea, coffee or fruit juices. Chlorine bleach is also
very good in the
removal of protein films from dishware/tableware caused by soil food or by
enzymes
deposition. Additionally chlorine bleach is an excellent sanitizer and
germicide. Chlorine
bleaching agents preferred for use herein are. those which yield a
hypochlorite species in
aqueous solutions including alkali metal and atkaline earth metal
hypochlorites, hypochlorite
addition products, chloramines, chlorimines, ohloramides, and chlorimides.
Specific
examples of compounds of this type include sodium hypochlorite, potassium
hypochlorite,
monobasic ealcium hypochlorite, dibasic magnesium hypochlorite, chlorinated
trisodium
phosphate dodecahydrate, potassium dichloroisocyanurate, sodium
dichloroisocyanurate,
1o sodium dichloroisocyanurate dihydrate, trichlorocyanuric acid, 1,3-dichloro-
5,5-
dimethylhydantoin, N-chlorosulfhmide, Chloramine T, Dicbloramine T, Chloramine
B and
Dichloramine B. A prefermd bleaching agent for use in the compositions of the
instant
invention is sodium dichloroisocyanurate.
Bleach seavenger
A scavenger is useful to substantially reduce the presence of a free chlorine
source, HOCI and
other oxidizing chlorine containing sources to Cl' ions or to substantially
reduce hydrogen
peroxide or paroxy acid bleaches to non-oxidizing .Vecies in order to protect
dishware/tableware from corrosion, especially metallic arEicles and in
particular silver
artieles, such as crockery.
Useful scavengers include amines, preferably primary and secondary amines,
including
primary and secondary fatty amines, and alkanolamines; ammonium salts; amine
functional
polymers; amino acid homopolymers with amino groups and their salts, such as
polyarginine,
polylysine, polyhistidine; amino acids and their salts,.preferably those
having more tlum one
amino group per molecule. Other suitable scavengers include sulfur-oxyacids
and salts
thereof such as the alkali metal and ammonium salts of sulfur-oxyacids
including sodium
bisulfite (NaHSO3), ammonium sulfite ((NH4)2 SOs), sodium sulfite (Na2 S03)
sodium
thiosulfite (Naz S2 03), sodium metabisulfite (Na2 S2 03), potassium
metabisulfite (K2 S2 0s),
lithium hydrosulphite (Li2 S2 04), or other reducing agents potassium iodide
(KI), ferrous
ammoniurn sulfate [Fe(1VIi4 S04)2 ]. A preferred scavenger for chlorine is
sodium bisulfite.
Other useful chlorine scavengers which can be used are tris (hydroxymethyl)
aminomethane,
2-amino-2-methyl-1, 3-propanediol, 2-amino-2-ethyl-1, 3-propanediol, 2-amino-l-
butanol, 1-
amino-2 propanol, 2-amino-l-propanol, and 2-amino-2-methyl-l-propanol.
Preferred for use
CA 02578875 2007-03-09
herein are antioxidants such as ascorbic acid; carbamate, phenols and
mixtenres thereof,
especially preferred for use in the fi~nishing composition is ascorbic acid.
Suitable levels of
bleach scavenger for use here in are from 0.01% to 5% by weight pf the
composition,
preferably from 0.1% to 0.5%.
Low cloud point non-ionic surfactants and suds suppressors
The suds suppressers suitable for use herein include nonionic surfactants
having a low cloud
point. "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
temperatura, the
1o temperature at which the appearance of a second phase is observable is
refen-ed to as the
"cloud point" (See Kirk Othmer, pp. 360-362). As-used herein, a "low cloud
point" nonionic
surfactant is defined as a nonionic surfactant system ingredient having a
cloud point of less
than 300 C., preferably less than about 20 C.; and even more preferably less
than about 10
C., and most preferably less than about 7.5 C. Typical low cloud point
nonionic surfactants
include nonionic alkoxylated surfactants, especially ethoxylates derived from
primary
alcohol, and polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/8O/PO)
reverse
block polymers. Also, such low cloud. point nonionic surfactants include, for
example,
ethoxylated-propoxylated alcohol (e.g., BASF Poly-Tergent SLF18) and epoxy-
capped
poly(oxyalkylated) alcohols (e.g., BASF Poly-Tergent(V SLF18B series of
nonionics, as
2o descnbed, for example, in US-A-5,576,281).
Preferred low cloud point surfactants are the ether-capped poly(oxyalkylated)
suds suppresser
having the formula:
RlO-(CH2 -- CH -O)x - (CH2 CH2 -O}y - (CH2 CH-O)z-H
RZ R3
wherein Rt is a linear, alkyl hychooarbon having an average of from about 7 to
about 12
carbon atoms, R2 is a linear, alkyl hydrocarbon of about 1 to about 4 carbon
atoms, R3 is a
linear, alkyl hydrocarbon of about 1 to about 4 carbon atoms, x is an integer
of about 1 to
about 6, y is an integer of about 4 to about 15, and z is an integer of about
4 to about 25.
16
CA 02578875 2007-03-09
Other low cloud point nonionic surfactants are the ether-capped
poly(oxyalkylated) having
the formula:
Ri0(RIIO)nCH(CH3)ORnm
wherein, RI is selected from the group consisting of linear or branched,
saturated or
unsaturated, substituted or unsnbstituted, aliphatic or aromatic hydrocarbon
radicals having
from about 7 to about 12 carbon atoms; RII may be the same or different, and
is independently
selected from the group consisting of branched or linear C2 to C7 alkylene in
any given
molecule; n is a number from 1 to about 30; and Rm is selected from the group
consisting oF
(i) a 4 to 8 membered substituted, or unsabstituted heterocyclic ring
containing from
i to 3 hetero atoms; and
(ii) linear or branched, satarated or unsaturated, substituted or
unsubstituted, cyclic or
acyclic, aliphatic or aromatic hydrocarbon radicals having from about I to
about
30 carbon atoms;
(b) piovided that when R2 is (ii)= then either: (A) at least one of R! is
other than C2 to
C3 alkylene; or (B) RZ has from 6 to 30 carbon atoms, and with the further
proviso
that when RZ has from 8 to 18 carbon atoms, R is other than C1 to CS aIIcyl.
Sulfonated anti-scaling polymer
Sulfonated anti-scaling polymers are suitable for use herein in any of the
primary or
secondary cleaning compositions or the finishing composition. The product can
comprise
form about 0.5 to 6%, preferably from about 3.5 to about 5% by weight of the
composition of
the polymer. The polymer generally comprises from about 0.1% to about 90%,
preferably
from about 1% to about 30% by weight.of a sulfonic acid containing monomer.
Examples of
sulfonate monomers include, but are not limited to, allyl hydroxypropanyl
sulfonate ethers,
allyisulfonic acids, methallylsulfonic acids, styrene sulfonic acids, vinyl
toluene sulfonic
acids, acrylamido alkane sulfonic acids, allyloxybenzene sulfonic acids, 2-
alkylallyloxybenzene sulfonic acids such as 4-sulfophenol methallyl ether, and
the allm1i or
alkaline earth metal or ammonium salts thereof.
Suitable examples of scale-inhibiting copolymers include, but are not limited
to tetrapolymers
of 4-sulfophenol mthallyl ether, sodium methallyl sulfonate, acrylic acid and
methyl
methacrylate. The monomer unit, sulfophenol methallyl ether, has the formula:
CH2 = C(CH3) CH2OC6HaSO3M
17
CA 02578875 2007-03-09
where M represents hydrogen, aikali metal, aikalime earth metal or ammonium
ions.
Other suitable examples of scale-inhibiting copolytners include, but are not
limited to, a
copolymer of acrylic acid and 4sulfophenol methallyl ether; a copolymer of
acrylic acid and
2-acrylamido-2-methylpropane sulfonate; a terpolymer of acrylic acid, .2-
acrylamido-2-
methylpropane sulfonate and sodium styrene sulfonate; a copolymer of acrylic
acid and vinyl
pyrrolidone; a copolymer of acrylic acid and acrylamide; and a polymer of
sulfophenyl
methallyl ether, sodium methailyl sulfonate, acrylic acid, methyl methscrylate
and 2-
acrylamido-2-methyl propane sulfonic acid. Preferably, the polymer is the
tetrapolymer of 4-
sulfophenol methallyl ether, sodium methallyl sulfonate, acrylic acid and
methyl
methacrylate. Preferred for use herein are copolymers comprising polyacrylic
acid, methyl
methacrylate, sulfopbenol methallyl ether and sodium methallyl sulfonate.
Preferred commercial available copolymers include: Alcosperse 240, Aquatreat
AR 540 and
Aquatreat MPS supplied by Alco Chemical; Acumer 3100 and Acumer 2000 supplied
by
Rohm & Haas; Goodrich K-798, K-775 and K-797 supplied by BF Goodrich; ACP 1042
supplied by ISP technologies Inc.; and polyacrylic acid/acrylamide supplied by
Aldrich. A
particularly preferred copolymer is Alcosperse 240 supplied by Alco Chemical.
Surface substantive modifying polymer
Preferably the sarface substantive polymer is select,ed from the group
consisting of homo and
copolymers of polyvinyl pyrrolidone (PVP), suitable levels for use herein are
from about
0.001 to about 10%, preferably from about 0.01 to about 1% by weight of
the'dishwashing
product and at from about 1 to about 200, preferably from about 20 to about
100 ppm in the
rinse liquor. In general terms such homo and copolymers can have an average
molecular
weight (eg as measured by light scattering) in the range from about 1,000 to
about 5,000,000,
preferably from about 5,000 to about 500,000. In addition, prefeTed copolymers
comprise at
least about 5%, most preferably at least about 15%, especially at least about
40% by weight
thereof of the comonomer. Higlily preferred comonomers include aromatic
monomers such
as vinyl imidazole and carboxylic monomors such as acrytic acid and
methacrylic acid.
Suitable polyvinylpyrrolidones are c.ommercially available from ISP
Corporation, New York,
NY and Montreal, Canada under the product names PVP K-15, PVP K-30, PVP K-60
and
18
CA 02578875 2007-03-09
PVP K-90. Other suitable polyvinylpyn;nlidones which are commercially
available from
BASF Corporation include Sokalan HP 165 and Sokalan HP 12. Other
polyvinylpyrrolidones
lrnown to persons skilled in the detergent field, see for example EP-A-
262,897 and EP-A-
256,696, are also suitable.
A particularly preferred copolymer of polyvinyl pyrrolidone is N-
vinylimidazole N-
vinylpyrrolidone (PVPVI) polymers available from for example BASF under the
trade name
Luvitec VP155K18P. Another suitable PVP copolymer is a quaternized PVPVI, for
example,
the compound sold under the tradename Luvitec Quat 73W by BASF.
Other suitable copolymers of vinylpyrrolidone for use in the compositions of
the present
invention are copolymers of polyvinylpyrrolidone and acrylic acid or
methacrylic acid.
Other suitable components herein include organic polymers having dispecsant,
anti-
redeposition, soil release or other detergency properties invention in levels
of from about
0.1% to about 30%, preferably from about 0.5% to about 15%, most pmeferably
from about
1% to about 10% by weight of composition. Preferred anti-redeposition polymers
herein
include acrylic acid containing polymers such as Sokalan PA30, PA20, PA15,
PA10 and
Sokalan CP10 (BASF GmbH), Acusol 45N, 480N, 460N (Rohm and Haas), acrylic
acid/maleic acid copolymers such as Sokalan CP5 and acrylic/methacrylic
copolymers.
Preferred soil release polymers herein include alkyl and hydroxyalkyl .
celluloses (US-A-
4,000,093), polyoxyethylenes, polyoxypropylenes and copolymers thereof, and
nonionic and
anionic polymers based on terephthalate esters of ethylene glycol, propylene
glycol and
mixtares thereof.
Heavy metal sequestrants and crystal growth inhibitors are suitable for use
herein in levels
generally from about 0.005% to about 20%, preferably from about 0.1% to about
10%, more
preferably from about 0.25% to about 7.5% and most preferably from about 0.5%
to about
5% by weight of composition, for example diethylenetriamine penta (methylene
phosphonate), ethylenediamine tetra(methylene phosphonate)
hexamethylenediamine
tetra(methylene phosphonate), ethylene diphosphonate, hydroxy-ethylene-l,l-
diphosphonate,
nitdlotriacetate, ethylenediaminotetracetate, ethylenediamine-N,N'-disuccinate
in their salt
and free acid forms.
19
CA 02578875 2007-03-09
The compositions herevn can contain a corrosion inhibitor such as organic
silver coating
agents in levels of from about 0.05% to about 10%, preferably from about 0.1%
to aboux 5% .
by weight of composition (especially paraffins such as Winog 70 sold by
Wintershall,
Salzbergen, Germany), nitrogen-containing corrosion inhibitor compounds (for
example
benzotriazole and benzimadazole - see GB-A 1137741) and Mn(II) compounds,
particularly
Mn(II) salts of organic ligands in levels of from about 0.005% to about 5%,
preferably from
about 0.01% to about 1%, more preferably from about 0.02% to about 0.4% by
weight of the
composition.
Other suitable components herein inolude colorants, water-soluble bismuth
compounds such
as bismuth acetate -and bismuth citrate at levels of from about 0.01% to about
5%, enzyme
stabilizers such as calcium ion, boric acid, propylene glycol and chlorine
bleach scavengers at
levels of from about 0.01 % to about 6%, lime soap dispersants (see WO-A-
93/08877), suds
suppressors (see WO-93/08876 and =BR-A-0705324), polymeric dye transfer
inhibiting
agents, optical brighteners, perfimies, fillers and clay.
Liquid detergent compositions can contain low quantities of low molecular
weight primary or
secondary alcohols such as methanol, ethanol, propanol and isopropanol can be
used in the
liquid detergent of the= present invention. Other suitable carrier solvents
used in low
quantities includes glycerol, propylene glycol, ethylene glycol, 1,2-
propanediol, sorbitol and
mixtiures thereof.
Trigger-means
The trigger-means used herein are specific for each zone of the product.
Primary cleaning trigger means
The function of the primary trigger cleaning means is to protect the primary
cleaning zone
from premature dissolution especially during the pre-wash, either as the
results of water
leaking into the dispenser or from the wash water itself for the case in which
the product is
placed in the drum of the machine or outside the dispenser. According, the
primary trigger
enables delivery of the primary cleaning composition at the appropriate point
of the main-
wash. For optimum performance of the primary composition, sometimes is
desirable to
deliver the composition when the washing water has reached above a certain
temperature
(most of the ingredients of the composition present optimum performance above
40 C,
CA 02578875 2007-03-09
delivery of the ingredients before reaching this temperature can sometimes be
wastefal). A
suitable trigger means for the primary cleaning zone is a temperature-
dependeat trigger
means, such as for example materials which are substantially insoluble in cold
water and
soluble in warm water. The material can optionally have a trigger delay of
less than about 4
min, preferably less than about 2, trigger delay for example being set by the
thiclmess of a
film material. The combination of trigger-temperature and dissolution delay
can give a very
precise control of the point in which the primary composition is delivered.
Preferably the primary trigger material has a water solubility according to
the hereinbelow
.1o defined test of less than about 50%, more preferably less than about 20%
and especially less
than about 5% under cold water conditions (20 C or below) when exposed to the
water for at
least 10 minutes, preferably at least 15 minutes; and a water solubility of at
least about 50%,
more preferably at least about 75% and especially at least about 95% under
warm water
conditions (30 C or above, preferably 40 C or above) when exposed to the water
for about 5
minutes and preferably when exposed to the water for about 3 minutes. Such
trigger
materials are herein referred to as being substantially insoluble in cold
water but soluble in
warm water. Sometimes this is abbreviated simply to "warm water soluble".
Apart from
providing precise controlled release, this kind of material also solves the
problem of gelling
when handling the product with wet hands.
50 grams t 0.1 gram of pouch material is added in a pre-weighed 400 ml beaker
and 245m1 t
lml of distilled water is added. This is kept at the desired temperature, by
using a water bath,
and stirred vigorously on a magnetic stirrer set at 600 rpm, for the desired
time. Then, the
mixture is filtered through a folded qualitative sintered-glass filter with a
maximum pore size
of 20 m. The water is dried off from the collected filtrate by any
conventional method, and
the weight of the remaining material is determined (which is the dissolved or
dispersed
fraction). Then, =the % solubility or dispeisability can be calculated.
Preferred primary trigger materials for use herein are commercially avaflable
polyvinyl
alcohols (PVA) obtained by hydrolysis of polyvinyl acetates. The solubility of
these films
can be selectively adjusted by the degree of hydrolysis of the PVA or by using
a cross-linking
agent. Examples of commercially available PVA suitable for use herein are BP26
available
from Aicello, L10 and L15 available from Aquafilm, VF-M and VM-S available
from
21
CA 02578875 2007-03-09
Kuraray and E-2060 available from Monosol, especially preferred for use herein
is BP26
available from Aicello. The thickness of the $hn can influence the dissolution
kinetics, filnas
having a thiclmess between about 5 and about 100 pm being preferred for use
herein.
Secondary eleaning tdgger means
The fimction of the secondary trigger cleaning mans is to protect the
secondary cleaning
zone from dissolution during the main-wash and only permit the delivery of the
composition
during a pre-final rinse, preferably the first rinse cycle. The first rinse
cycle is generally a
cold cycle, so that if the main-wash is itself a cold-water fill, the
secondary cleaning zone is
exposed to the same temperatare conditions at the beginning of the main-wash
and during the
first rinse cycle. The delivery of the secondary composition in the first
rinse cycle is
therefore accomplished by means of a primed secondary trigger means. This
secondary
trigger means is primed by a so-called secondary priming trigger, preferably a
tenuperature-
dependent priming trigger means which is responsive to the temperature
conditions
encountered during the hot stage of the main-wash cycle. The priming
temperature (T'e.) is .
preferably. at least 40 C, more preferably at least 45 C, and especially at
least 48 C.
Preferably the priming trigger material has a water solubility according to
the hereinabove
defined test of less than about 500/o, more preferably less than about 20% and
especiaUy less
than about 5% under cold water conditions (20 C or below) when exposed to the
water for at
least 10 minutes, preferably at least 15 minutes; and a water solubility of at
least about 5001o,
more preferably at least about 75% and especially at least about 95% under hot
water
conditions (40 C or above, preferably 48 C or above) when exposed to the water
for about 5
minutes and preferably when exposed to the water for about 3 minutes. Such
trigger
materials are herein referred to as being substantially insoluble in cold
water but soluble in
hot water. Sometimes this is abbreviated simply to "hot water soluble".
Preferred priming trigger means for use herein are commercially available
polyvinyl alcohols
(PVA) obtained by hydrolysis of polyvinyl acetates. The solubility of these
films ea.n be
selectively adjusted by the degree of hydrolysis of the PVA or by using a
cross-linking agent.
Examples of commercially available PVA suitable for use herein are LA25, LA38
available
from Aicello, A127 and L15 available from Aquafihn, Hi-Selon and H-221
available from
Nippon Goshei and M1000, M1030 and M1040 available from Monosol, especially
preferred
for use herein is M1030 available from Monosol. The thiclcness of the film can
influence the
22
CA 02578875 2007-03-09
dissolution lcinetics, films having a thickness between about 5 and about 100
pm being
preferred for use herein. The priming trigger material should be chosen to
ensure that T',m is
greater than Tpft.
Other priming trigger means suitable, for use herein include substances having
a melting
range which lies between about 40 C and about 70 C. These substances include
natural and
synthetic waxes, paraffins (satarated aliphatic hydrocarbons) and mixtures
thereo~
After the prlming trigger means has been activated (generally when the main
wash water
l0 reaches a temperature above 40 C, preferably above 48 C) the secondary
trigger is in a
primed condition such that it can itself be triggered by exposure to the hot
temperature of the
wash liquor. However the secondary trigger means is. not activated until watm
or low
tempera.ture is reached (less than about 40 C, preferably less -than about 35
C, more
preferably less than about 30 C). Suitable materials for use as primed.trigger
means are
16 inverse solubility temperature-dependent materials, such as for example,
polymeric material
comprising an inverse solubility polymer and polyvinyl alcohol in a ratio of
at least 1:1,
preferably at least 2:1 and more preferably at least about 3:1 and which can
fulfil the
requirement of being substantially insoluble above,about 40 C and
substantially water soluble
at temperatures below about 40 C. An inverse solubility polymer is defined as
a polymer
20 which is substantially insoluble in hot water and soluble in cold.water.
These materials
usually have a low temperature gel point. This gel is very stable and once
frnmed will be
very difficult to break-up. Inverse solubility polymers can be selected from
alkylated andlor
hydroxyalkylated polysaccharides, cellulose ethers, polyisopropylacrylamide
and mixtures
thereof. Preferred for use herein is hydroxypropylmethylcellulose.
Finishing trigger means
The funation of the finishing trigger means is to protect the fmishing zone
from dissolution
during the first rinse cycle and only permit the delivery of the composition
during the final
rinse cycle. This finishing trigger means is preferably a temperature
dependent trigger means.
The tdgger temperature (Tfm) is at least 45 C, preferably at least 48 C; more
preferably at
least 50 C.
Preferably the fnishing trigger material has a water solubility according to
the hereinabove
defined test of less than about 50%, more preferably less than about 20% and
especially less
23
CA 02578875 2007-03-09
than about 5% unde,r cold water conditions (20 C or below) when exposed to the
water for at
least 10 minutes, preferably at least 15 minutes; and a water solubility of at
least about 50%,
more preferably at least about 75% and especially at least about 95% under hot
water
conditions (45 C or above, preferably 48 C or above, more preferably 50 C or
above) when
exposed to the water for about 5 minutes and preferably when exposed to the
water for about
3 minubes. Such trigger materials are herein referred to as being
substantially insoluble in
cold water but soluble in hot water. Somet3mes this is abbreviated simply tD
"hot water
soluble". Suitable mafierials for use as finishing trigger materials can be
similar to those used
for priming trigger means described herein above and also EF30 and EF35
supplied from
Aicello. The trigger material should be chosen herein to ensure that Taõ is
greater than T'BOC.
A preferred material for use herein is M1030 available from Monosol.
Other finishing trigger means suitable for use herein include substances
having a meltlstg
range which lies between about 50 C and about 75 C, preferably between about
'60 C and
about 70 C. These substances include natural and synthetic waxes, parafEns
(saturated
aliphatic hydrocarbons) and mixtinm thereof.
Pouches for use herein can be prepared according to methods known in the art,
such as for
example vacuum-forming, thermo-forming or a combination of both.
Examnles
Abbreviations used inExamples
In the examples, the abbreviated component identifications have the following
meanings:
Carbonate : Anhydrous sodium carbonate
STPP : Sodium tripolyphosphate anhydrous
HEDP : Hydroxyethanedimethylenephosphonic acid
Silicate : Amorphous Sodium Silicate (SiOZ:NaaO = from 2:1 to
4:1)
Percarbonate : Sodium percarbonate of the nominal formula
2Na2CO3.3H20Z
Amylase : a-amylase available from Novo Nordisk A/S
Protease : protease available from Genencor
NaDCC : Dicbloroisocyanuric acid (Sodium Salt)
24
CA 02578875 2007-03-09
Plurafac 400 = C13-C15 mixcd ethoxylated/propoxylated fatty alcohol
with an avera.ge degree of ethoxylation of 3.8 and an
average degree of propoxylation of 4.5, available from
BASF
Plurafac 404 = C13'C15 mixed ethoxylated/propoxylated fatty alcohol
with an average degree of ethoxylation of 4 and an
average degree of propoxylation of 5, available from
BASF
PVA : Polyvinyl alcohol of 13,000-23,000 molecular weight
and hydrolysis level of 98% available from Aldrich
HPMC : Methoce1311 having a geiation temperature of 40-50 C
available from Dow
&le 1
The composition of Table 1 is niade in the form of a three-compartment pouch,
the weight of
the pouch being 24 g. A first pouch is formed from Monoso11030 (finishing
trigger means)
containing the finishing composition. A second pouch is formed having two
layers of
different fihn materials, the inner layer is formed from a hand cast film
having the final
composition given in Table 2 (primed secondary trigger means) and the outer
layer is formed
from Monoso11030 (priming trigger means). This pouch contains the secondary
composition
and the first pouch. A third pouch is formed from Aicello BP26 (primary
cleaning trigger
means) contain'vag the primary composition and the second pouch.
A load of tableware and cutlery is washed in a Bosch Siemens 6032 dishwashing
machine,
operated in its normal 65 C program having a 5 I wash water capacity, with the
exemplified
pouch. The pouch is placed in the dispenser of the dishwashing machine. The
primary
cleaning composition is released into the main wash, the secondary cleaning
composition into
the first rinse cycle and the fmishing composition into the final rinse cycle.
The washed load
presents excellent cleaning, care and shine benefits.
Table I
CA 02578875 2007-03-09
% by
weight
Prtma com on
STPP 20
Silicate 4
Carbonate 22
Percarbonate 4
Am lase 2
Protease 1
Plurafac LF404 1
SecondmT com tion
NaDCC 4
STPP 23
Finishing composition
Citric Acid 17
Plucafac 400 1.7
Ascorbic acid 0.3
Table 2
In dients % by wei ht
HPMC 57
PVA 25
Boric acid 1
Glycerol 9
Water 8
The film was made by preparing an aqneous solution with the ingredients of
Table 2 in the
following mannei: 4000 g of deionised water were weighed into a 5 litre glass
beaker. The
beaker was placed on a hotplate and the water stirred with a magnetic stirrer
bar at 500 rpm.
32.4 g=of PVA were added to the water. The temperature of the hotplate was set
to 90 C.
The beaker was covered with cling film to minimise evaporation during heating.
When the
solution temperattwe reached 90 C (typicaIly 2 hours) all of the PVA had
dissolved and the
heating was switched off. The solution was allowed to cool to 70 C (stirring
continuously)
and then the cling film removed and 72 g of HPMC were added The HPMC was
allowed to
disperse (typically 5 minutes). 32g of Boric acid solution (4% by weight in
deionised water)
was then added foIIowed by12 g of glycerol. The beaker was then covered again
with cling
film and allowed to cool forther. As the tempera.turedropped below
approximately 45 C the
26
CA 02578875 2007-03-09
solution began to thicken significantly as the HPMC dissolved. The solution
was kept
stirring for approximately 3 hours while cooling. The beaker was removed from
the
hotplate/stirrer and placed in an oven at 40 C overnight.
The solution was cast in the following manner. The solution, glass plates and
a casting bar
were stored in an oven at 40 C. A glass plate at 40 C was taken and the
surface was coated
with a thin layer of paraifln oil (Winog 70) by applying with a tissue and
wiping off with a
clean tissue. The casting bar (2mm gap) at 40 C was then placed at one end of
the glass plate.
The solution was then poured along the length of the casting bar keeping the
pouring height to
1 o a minimum to prevent formation of air bubbles. The casting bar was then
pushed along the
length of the glass plate to leave a layer of solution 2mm thick. The glass
plate with solution
coating was then placed in an oven at 40 C to dry for 16-18 hours. After
drying the resulting
film was peeled away from the glass. The resulting film bad a thickness of
about 40 m and
contained about 7% moisture.
Ex e 2
The dishwashing operation is repeated as in Example. 1 but the pouch,
weighting 29g, is
placed on the floor of the dishwashing machine.
27
