Note: Descriptions are shown in the official language in which they were submitted.
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DISHWASHING METHOD
Technical field
The present invention is in the field of dishwashing, in particular it relates
to methods for
the delivery of dishwashing products into the rinse cycle of an automatic
dishwashing
machine. The methods allow for an improved cleaning of tough food residues and
reduction of filming and spotting of the washed articles.
Backeround of the invention
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 concentration of canons, specially Caz+ and Mgz+)
and by the
use of rinse aid containing sequestrant, dispersant and surfactant 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
allowing uniform drying of the washed utensils, ameliorating filming 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.
Nowadays, dishwashers are designed in such a way as to deliver approximately
from
about 2 to about 6 ml of rinse aid at or towards the end of the final rinse
cycle.
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Sometimes, this amount of rinse aid is not enough to control filming and
spotting,
however dispenser sizes and delivery programs are fixed parameters determined
by
dishwashing machine manufacturers and the user has no control over them. A
further
restriction which needs to be considered when formulating a rinse aid
composition is the
fact that the rinse aid needs to be stored in the rinse reservoir inside the
dishwasher,
usually during many cycles and therefore is 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 its 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 in order to provide controlled delivery of rinse
aid. For
example WO-A-00/6684 and WO-A-00/6688 describe a multi-phase tablet comprising
a
particle which comprises a core and a coating. The substances present in the
core are
active during the rinse 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 also describes a multi-phase tablet delivering actives
during the
rinse cycle. However, WO '84, WO '88, WO '67 and EP '24 are capable of
delivering
only small amount of actives into the rinse cycle.
US-A-5,453,216 describes 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 main wash cycle.
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
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the pre-wash). The remainder of the program is taken up with one or more post-
main
wash rinsing cycles. The perfect dishwashing process able to clean even the
toughest
residues while eliminating rinse-related problems such as filming and spotting
within the
constraints of current dishwashing machine design, has still to be developed.
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 and/or rinse aid and in the case of dishwashing under
hard water
conditions.
SummarK of the invention
An automatic dishwashing operation typically comprises three or more cycles: a
pre-wash
cycle, a main-wash cycle and one or more rinse cycles. In Europe, the pre-wash
cycle,
when used, is typically 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 usually comprises two or more separate cycles following
the main
wash, the first being cold and lasting between about 2 and 5 min, the second
one starting
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.
It has now been found that dishwashing performance can be significantly
improved by
delivery of one or more detergent products or components thereof into the
rinse following
the main wash, and especially into a rinse cycle prior to the final rinse
and/or into the
final rinse, under conditions of concentration and time such that the rinse
cycle
concentration factors and cofactors as herein defined exceed certain minimum
values. As
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used herein, the term "rinse cycle concentration factor" refers to the
integral of wash
liquor concentration of detergent product, treated as a time-dependent
function, over the
period of the rinse, i.e. from the start of the first rinse after the main-
wash to the end of
the final rinse. The term "pre-final rinse concentration factor" refers to the
same integral
but taken over the period from the start of the first rinse to the start of
the final rinse. The
terms "rinse cycle concentration cofactor" and "pre-final rinse cycle
concentration
cofactor" are analogous quantities specified for individual components of the
detergent
product, for example, chlorine bleach, protease, etc. The concentration
factors and
cofactors are calculated herein by trapezoidal graphical integration of the
wash liquor
concentration function at time intervals of 1 minute over the appropriate time
period.
It has also been surprisingly found that the use of liquid or gel detergent
for the main-
wash cycle combined with the use of similar amounts of liquid or gel detergent
during the
rinse cycle provides excellent cleaning results with minimum film formation
resulting
from hardness/detergent interaction. Without being bounded by the theory, it
is believed
that detergents in solid form (such as powders or tablets) can give rise to
the formation of
a film onto the washed articles during the main wash, therefore a rinse cycle
and rinse aid
is needed to prevent this film. Apparently, this film does not occur in the
case of liquid
or gel detergent, suggesting that the rinse cycle can be used to achieve extra
cleaning
whilst maintaining good rinsing and finishing performance.
According to a first aspect of the present invention, there is provided a
method of
washing cookware/tableware in an automatic dishwashing machine having a main-
wash,
optional pre-wash and one or more post main-wash rinse cycles wherein one or
more
dishwashing products are dosed into the one or more rinse cycles and wherein
the dosing
regime is such as to provide a rinse cycle concentration factor (C~) of at
least about 1.3 x
104, preferably at least about 1.8 x 104 more preferably at least about 2.4 x
104 and
especially at least about 3.2 x 104 ppm min, wherein C~ is defined as:
~ec(t)dt
wherein c(t) is the wash liquor concentration of dishwashing product as a
function of
dishwashing time variable t, t~ is the time corresponding to the start of the
first rinse, and
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to is the time corresponding to the end of the final rinse, all times being
measured in min
from the start of the dishwashing operation.
For calculation purposes, it is assumed that where a dishwashing product takes
less than 1
minute to dissolve or to disperse substantially to a particle size of less
than 53 pm (270
mesh) after contact with the wash liquor, the product is considered to
dissolve
instantaneously and the wash liquor concentration of the product as function
of time
simply equates to the cumulative total of dishwashing product dosed into the
wash liquor
as a function of time. This assumption generally applies to most liquids, gels
and paste-
type products. Otherwise, the wash liquor concentration can be determined by
means
known by the skilled man in the art. For example, in the case of slowly
dissolving blocks
the weight of the block can be monitored at regular 1 minute time intervals.
In the case
of powders, samples of wash solution can be taken at regular 1 minute time
intervals and
filtered, the filtered solid being dried and weighed to quantify the amount of
product
which is not dissolved, i.e. which does not pass a 270 mesh filter.
Measurements are
repeated a sufficient number of times to obtain a statistical significance
(95%
confidence). For the purpose of the present invention it is suitable to
deliver powders
having fast dissolution times so they will have more time to act.
In a preferred embodiment herein, the dishwashing machine has two or more
rinse cycles
and the dosing regime is such as to provide a pre-final rinse concentration
factor (CPfr) of
at least about 1.0 x 103, preferably at least about 3.0 x 103, and more
preferably at least
about 4.0 x 103, especially at least about.5.0 x 103 ppm min, where CPS is
defined as:
~Jc(t)dt
wherein tf is the time corresponding to the start of the final rinse and t~ is
as defined
above. Achieving a pre-final rinse concentration factor within the specified
range is
important herein for securing an optimum combination of tough food cleaning
and
filming/spotting performance.
Thus, according to another aspect of the present invention, there is provided
a method of
washing cookware/tableware in an automatic dishwashing machine having a main-
wash,
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optional pre-wash and two or more rinse cycles, wherein one or more
dishwashing
products are dosed into the rinse after the main wash and prior to the final
rinse cycle and
wherein the dosing regime is such as to provide a pre-final rinse
concentration factor
(CP f~) of at least about 1.0 x 103, preferably at least about 3.0 x 103, and
more preferably at
least about 4.0 x 103, and especially at least about.5.0 x 103 ppm min, where
Cpfr is
defined as:
~rc(t)dt
wherein tr is the time corresponding to the start of the first rinse, and tf
is the time
corresponding to the start of the final rinse.
In preferred embodiments two or more dishwashing products are dosed into the
rinse and
the dosing regime is such as to provide a final rinse concentration factor
(Cfr) of at least
about 1.2 x 103, preferably at least about 5.0 x 103 more preferably at least
about 1.0 x
104 and especially at least about 3.0 x 104 ppm min, wherein Cfr is defined
as:
~e c(t)dt
r
wherein t f is the time corresponding to the start of the final rinse, and to
is the time
corresponding to the end of the final rinse.
In preferred embodiments the dosage concentration of the one or more
dishwashing
products delivered into the rinse liquor is greater than about 1500 ppm,
preferably greater
than about 2000 ppm and more preferably greater than about 3000 ppm.
Preferably also
the one or more dishwashing products are present in the rinse liquor for a
period of at
least about S min, preferably at least about 7 min, more preferably at least
about 10 min,
and especially at least about 15 min. It is also preferred that the one or
more dishwashing
products are present in the rinse liquor prior to the final rinse for at least
about 2 min,
preferably at least about S min, more preferably at least about 7.5 min.
In preferred embodiments the dosing regime is also such as to provide one or
more of the
following rinse cycle concentration cofactors:
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a) an alkali concentration cofactor (C~, alk) of at least about 1.0 x 103,
preferably at
least about 3.0 x 103, more preferably at least about 5.0 x 103 and especially
at
least about 1.0 x 104 ppm min;
b) an acid concentration cofactor (C~, a~) of at least about 3.0 x 103,
preferably at
least about 4.0 x 103, more preferably at least about 5.0 x 10' and specially
at
least about 1.0 x 104 ppm min;
c) an active chlorine concentration cofactor (C~, ~,,,) of at least about 1.0
x 103,
preferably at least about 2.0 x 103 and more preferably at least about 4.0 x
103
ppm min;
d) an active protease concentration cofactor (C~, prot) of at least about 30,
preferably
at least about 50 and more preferably at least about 100 ppm min;
e) an active amylase concentration cofactor (C~, amyl) of at least about 5,
preferably
at least about 8 and more preferably at least about 16 ppm min;
f) an active pectinase concentration cofactor (C~, pect) of at least about
400,
preferably at least about 600 and more preferably at least about 1200 ppm min;
g) a total active enzyme concentration cofactor (Cr, e,~) of at least about
35,
preferably at least about 60 and more preferably at least about 120 ppm min;
h) an active oxygen concentration cofactor (C~, ox) of at least about 400,
preferably
at least about 600 and more preferably at least about 1200 ppm min;
i) a diacyl peroxide concentration cofactor (C~, diacyl) of at least about
400,
preferably at least about 600 and more preferably at least about 1200 ppm min;
j) an A13+ concentration cofactor (C~, a~) of at least about 500, preferably
at least
about 750 and more preferably at least about 1500 ppm min;
k) a Znz+ concentration cofactor (C~, Zn) of at least about 500, preferably at
least
about 750 and more preferably at least about 1500 ppm min;
1) a surfactant concentration cofactor (C~,S"~.) of at least about ,
preferably at least
about 2.0 x 103, preferably at least about 3.0 x 103 and more preferably at
least
about 6.0 x 103 ppm min;
m) a sequestrant or builder concentration cofactor (C~, Seq) of at least about
2.0 x 103,
preferably at least about 4.0 x 103 and more preferably at least about 8.0 x
103
ppm mm;
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n) a polymeric dispersant concentration cofactor (C~, disp) of at least about
4.0 x 102,
preferably at least about 8.0 x 10z and more preferably at least about 1.6 x
103
ppm min;
o) a silicone concentration cofactor (C~, S;;) of at least about 3.0 x 102,
preferably at
least about 6.0 x 102 and more preferably at least about 1.2 x 103 ppm min;
wherein the rinse cycle concentration cofactor (C~, auX) for a given detergent
auxiliary
(aux) is defined as:
~eca,~ (t)dt
wherein cauX(t) is the wash liquor concentration of the detergent auxiliary as
a function of
the dishwashing time variable t. In order to calculate Cr, aux samples of the
wash liquor are
taken at 1 minute intervals throughout the rinse and the corresponding
concentration of
auxiliary is measured using an appropriate analytical technique. The
concentration
cofactors are then determined by trapezoidal graphical integration of wash
liquor
concentration of the specified auxiliary at time intervals of 1 minute. Wash
liquor
concentrations are determined in known manner, by taking suitably sized
aliquots of the
wash liquor and performing conventional analytical techniques on the aliquot.
In the case
of enzymes, active enzyme concentration is generally determined by
spectrophotometric
or other suitable methods using the substrate, pH, temperature, buffer and
incubation
conditions set out in the manufacturer's product data sheets and related test
methods for
the particular enzyme and calibrated against solutions of known specific and
total enzyme
activity.
For example, in the case of amylases, activity through the wash can be
measured by
taking 1 ml aliquot every minute. The aliquot is added to 5 ml of phosphate
buffered
solution (14.42 g NazHP04, 2.59 g KHZP04 in 1 litre of deionised water, to
give a pH of
8.3) and 0.5 ml of 20% w/v sodium sulphite solution, the mixture is placed in
a 37°C
water bath and a Phadebas tablet (Available from Pharmacia Ltd.) is added, the
mixture is
left to incubate for 15 minutes. After 15 minutes the reaction is stopped by
the addition
of lml of 1M sodium hydroxide. The mixture is filtered and the absorbance of
the liquor
is measured at 620 nm (using a Pharmacia Biotech Ultropec 2000
spectophotometer) and
from here the active enzyme concentration is read from graphs precalibrated
against
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amylases (such as Termamyl) of known specific activity in known active
concentration
levels.
In the case of proteases, activity through the wash can be measured by taking
1 ml aliquot
every minute. The aliquot is added to 0.7 ml of sodium sulphite solution (2.5
g/1), 2 ml of
0.4% N-N-dimethylcasein solution and 1 ml of 0.65% 2,4,6 trinitro benzene
sulphonic
acid solution. The test is carried out at 49 °C and pH 9Ø The
absorbance of the liquor is
measured (using a Pharmacia Biotech Ultropec 2000 spectophotometer) and from
here
the active enzyme concentration is read from graphs precalibrated against
proteases (such
as Savinase) of known specific activity in known active concentration levels.
Preferred herein from the viewpoint of achieving optimum tough food cleaning
and
rinsing/fmishing performance are wash processes wherein certain active
components are
delivered into the rinse prior to the final rinse. Thus, according to another
aspect of the
invention, there is provided a method of washing cookware/tableware in an
automatic
dishwashing machine having a main-wash, optional pre-wash and two or more
rinse
cycles, wherein one or more dishwashing products are dosed into the rinse
after the main
wash and prior to the final rinse cycle and wherein the dosing regime is such
as to
provide one or more of the following pre-final rinse concentration cofactors
(CPfr~ aux)~
a) an alkali concentration cofactor (Cpfr, alk) of at least about 2.0 x 102,
preferably at
least about 1.5 x 103 and more preferably at least about 2.5 x 103 ppm min;
b) an acid concentration cofactor (CPfr, a~) of at least about 6.0 x 10z,
preferably at least
about 2.0 x 103 and more preferably at least about 2.5 x 103 ppm min;
c) an active 'chlorine concentration cofactor (CPfr. ~n,) of at least about
200, preferably at
least about 1.0 x 103 ppm min;
d) an active protease concentration cofactor (CPfr Prot) of at least about 6,
preferably at
least about 25 ppm min;
e) an active amylase concentration cofactor (CPfr, amyl) of at least about 1,
preferably at
least about 4 ppm min
f) an active pectinase concentration cofactor (CPfr, Pect) of at least about
80, preferably at
least about 300 ppm min;
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g) a total active enzyme concentration cofactor (Cpfr, e,~) of at least about
7, preferably
at least about 30 ppm min;
h) an active oxygen concentration cofactor (CPfr, ox) of at least about 80,
preferably at
least about 300 ppm min;
i) a diacyl peroxide concentration cofactor (CPfr, diacyl) of at least about
80, preferably at
least about 300 ppm min;
j) an Af+ concentration cofactor (CPfr, a,) of at least about 100, preferably
at least about
275 ppm min;
k) a Zn2+ concentration cofactor (Cpfr, ~,) of at least about 100, preferably
at least about
275 ppm min;
1) a surfactant concentration cofactor (CPfr, S~~e) of at least about 4.0 x
102, preferably at
least about 1.5 x 103;
m) a sequestrant or builder concentration cofactor (CPfr, seq) of at least
about 4.0 x 102,
preferably at least about 2.0 x 103 ppm min;
n) a polymeric dispersant concentration cofactor (Cpfr, a;sP) of at least
about 80,
preferably at least about 4 x 102 ppm min;
o) a silicone concentration cofactor (Cps, S;,) of at least about 60,
preferably at least
about 300 ppm min;
wherein the pre-rinse cycle concentration cofactor (Cpfr, a~X) for a given
detergent auxiliary
(aux) is defined as:
~J c4,~ (t)dt
wherein ca~X(t) is the wash liquor concentration of the detergent auxiliary as
a function of
the dishwashing time variable t, tr is the time corresponding to the start of
the first rinse,
and tf is the time corresponding to the start of the final rinse.
In other preferred embodiments, two or more dishwashing products are dosed
into the
rinse and the dosing regime is such as to provide one or more of the following
final
rinse concentration cofactors:
a) an alkali concentration cofactor (C~, a,k) of at least about 2.4 x 102,
preferably at least
about 1.0 x 103, more preferably at least about 2.0 x 103 and especially about
4.0 x
103 ppm min;
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b) an acid concentration cofactor (Cfr, a~) of at least about 6.0 x 102,
preferably at least
about 2.5 x 103, more preferably at least about 4.0 x 103 and especially about
8.0 x
103 ppm min;
c) an active chlorine concentration cofactor (C fr, ~n~) of at least about
200, preferably at
least about 1.0 x 103 more preferably at least about 2.0 x 103 ppm min;
d) an active protease concentration cofactor (Cfr, prod of at least about 6,
preferably at
least about 25 more preferably at least about SO ppm min;
e) an active amylase concentration cofactor (Cfr, amyl) of at least about 1,
preferably at
least about 4 more preferably at least about 8 ppm min
f) an active pectinase concentration cofactor (Cfr, Pest) of at least about
80, preferably at
least about 300 more preferably at least about 600 ppm min;
g) a total active enzyme concentration cofactor (C fr> enZ) of at least about
7, preferably at
least about 30 more preferably at least about 60 ppm min;
h) an active oxygen concentration cofactor (Cfr, ox) of at least about 80,
preferably at
least about 300 more preferably at least about 600 ppm min;
i) a diacyl peroxide concentration cofactor (Cfr, diacyl) of at least about
80, preferably at
least about 300 more preferably at least about 600 ppm min;
j) an Al3+ concentration cofactor (Cfr, a,) of at least about 100, preferably
at least about
275 more preferably at least about 550 ppm min;
k) a Zn2+ concentration cofactor (Cf~, Z~) of at least about 100, preferably
at least about
275 more preferably at least about S50 ppm min;
1) a surfactant concentration cofactor (Cfr, surf) of at least about 4 x 102,
preferably at
least about 1.5 x 103 more preferably at least about 3.0 x 103 ppm min;
m) a sequestrant or builder concentration cofactor (Cfr> Seq) of at least
about 4 x 10z,
preferably at least about 2 x 103 more preferably at least about 4.0 x 103 ppm
min;
n) a polymeric dispersant concentration cofactor (Cfr, a;sp) of at least about
80,
preferably at least about 4.0 x 10z more preferably at least about 8.0 x 102
ppm min;
o) a silicone concentration cofactor (C fr> Sa) of at least about 60,
preferably at least about
300 more preferably at least about 600 ppm min;
wherein the final rinse cycle concentration cofactor (Cfr, aux) for a given
detergent auxiliary
(aux) is defined as:
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I f Ca,~ (t)Ci't
wherein ca~x(t) is the wash liquor concentration of the detergent auxiliary as
a function of
the dishwashing time variable t, tf is the time corresponding to the start of
the final rinse,
and to is the time corresponding to the end of the final rinse.
In an especially preferred embodiment, the dosing regime is such as to provide
a pre-
rinse alkali concentration factor (CP fr, alk) of at least about 200,
preferably at least about
1500 ppm min, a pre-rinse active chlorine concentration factor (Cpfr, ~,,~) of
at least
about 200, preferably at least about 1000 ppm min, and a final rinse acid
concentration cofactor (Cfr, a~) of at least about 600, preferably at least
about 2500,
more preferably at least about 4000 and especially at least about 8000 ppm
min.
Preferably also, the dosing regime is such that the rinse liquor at a point
prior to the
final rinse has a pH greater than about 10, preferably greater than about 11;
and at a
point during the final rinse has a pH lower than about 8, preferably lower
than about
7.
Preferably the one or more dishwashing compositions are delivered into the
rinse by
means of a trigger-activated mechanical dosing device designed to achieve the
requisite
concentration factors and cofactors. Suitable for use herein are dosing
devices which
contain sufficient dishwashing product for a single dishwashing rinse cycle or
for a
plurality of dishwashing rinse cycles, in the same or different dishwashing
operations.
Any device capable of storing and dosing one or more dishwashing products at
pre-
determined times in the rinse cycle is suitable for use herein. The device
keeps the
dishwashing products enclosed until a pre-determined time at which the
products is/are
released, usually by opening of one or more outlets of the device. The outlet
opening
time can be controlled by any mechanism known in the art, such as for example
a timer, a
shape memory alloy, a shape memory polymer, a sensor which detects stimulus
from the
wash liquor (pH, conductivity, pCa, pNa, temperature, motion, turbidity, etc)
or some
other means capable of providing a physical or chemical trigger.
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The device can contain only one compartment or a plurality of compartments for
the
storage of one or more products. Where there are products containing mutually
incompatible ingredients, such products are normally placed in different
compartments in
the device. For example, it is useful to have separate compartments when
bleach and
bleach activator are to be delivered into the rinse or when bleach and enzymes
are to be
delivered into the rinse. Different products can be dosed at the same time or
at different
times in order to optimise the cleaning and finishing benefits in the
dishwashing process.
Other ways to deliver the dishwashing products into the rinse cycle are for
example a
slow-release block, a single or multi-compartment sachet with sensitive seals
(pH,
temperature, ionic strength, etc), a single or multi-compartment porous sachet
with a
pore-occluding coating (sensitive to pH, temperature, ionic strength, etc) or
a single or
multi-compartment water permeable sachet comprising an encapsulated
dishwashing
product (sensitive to pH, temperature, ionic strength, etc).
In preferred embodiments, at least one and preferably all of the dishwashing
products
is/are in liquid or gel form. In the case of solid form products, preferably
at least 50% of
the solid delivered into the rinse cycle dissolves in less than about 4 min,
preferably less
than about 3 min, more preferably less than about 2 min and even more
preferably less
than about 1 min.
In a highly preferred embodiment one or more of the dishwashing products
comprises a
detergency builder, preferably an organic soluble builder in an amount
effective to reduce
the concentration of Ca2+ in the rinse liquor below about 70 ppm expressed as
calcium
carbonate, preferably below about 35 ppm and more preferably below about 18
ppm.
Such a low Caz+ concentration is beneficial not only for the washed
dishware/tableware
but also for the heating element of the dishwasher. The Caz+ in the rinse
liquor can be
measured using for example atomic absorption.
Without wishing to be bound by the theory, it is believed that a film can be
left on the
dishware/tableware after the main wash. It has also been found that this film
can be
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dissolved by very soft water, i.e., water containing less than about 70 ppm,
preferably less
than about 35 ppm and more preferably less than about 18 ppm of Caz+, a level
which
may not be attained even with the use of a salt softening system. Herein the
soft water is
obtained by the use of soluble builders in appropriate concentrations and
concentration
factors and cofactors. Among the suitable organic soluble builders for use
herein are
organo aminophosphonic acid, organo diphosphonic acid, carboxylic acid and
polycarboxylic acid and their salts and complexes. Preferred for use herein
are ethane 1-
hydroxy-1,1-diphosphonic acid (HEDP) and citric acid or their salts.
In another preferred embodiment one or more of the dishwashing products
comprises a
polymeric dispersant, highly preferred herein being a polymeric dispersant
which
comprises an olefinically unsaturated carboxylic acid monomer and at least one
monomer
unit selected from sulfonated monomers. The polymeric dispersant is effective
in
suspending the film that is formed on the dishware/tableware after the main
wash cycle.
Preferred for use herein are tetrapolymers of 4-sulfophenol methallyl ether,
sodium
methallyl sulfonate, acrylic acid and methyl methacrylate.
Preferably the concentration of polymeric dispersant in the rinse liquor is
less than about
300, preferably less than about 200, more preferably less than about 150 ppm
and even
more preferably less than about 100 ppm.
Spotting in plasticware after the dishwashing process is a common feature
produced as
consequence of uneven drying of the water from the surface of the ware after
the rinsing
step. To help minimize spotting one or more of the dishwashing products
preferably
comprises a wetting agent capable of providing the rinse liquor with a surface
tension of
less than about 24 mN/m, preferably less than about 23 mN/m and even more
preferably
less than about 21 mN/m. The low surface tension of the wash liquor allows for
sheeting
of the water, avoiding the spotting in plasticware. Preferred wetting agents
for use herein
are siloxane surfactants especially trisiloxanes.
Also preferred for use herein from the viewpoint of reducing spotting is a
chlorine
bleaching agent. Chlorine bleach greatly improves cleaning performance of the
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automatic dishwashing operation, in particular it 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.
In another embodiment one or more of the dishwashing products comprises a
surface
substantive modifying polymer. Surface substantive modifying polymers suitable
for use
herein are selected from polyvinyl pyrrolidone and copolymers thereof;
especially
copolymers of polyvinyl pyrrolidone with a comonomer selected from vinyl
imidazole,
acrylic acid, methacrylic acid, N-oxide and mixtures thereof.
Preferably, the one or more dishwashing products provides the final rinse
liquor with a
pH of less than about 10, preferably less than about 9 and even more
preferably less than
about 8 as measured at room temperature.
In another embodiment one or more of the dishwashing products comprises a
fibrous
food degrading enzyme. The addition of fibrous food degrading enzyme is
especially
valuable for the cleaning of the machine itself. Usually after the dishwashing
process
there can be a lot food residues left over in the filter and other parts of
the dishwashing
machine. The use of machine cleaner products is known in the art, however,
these
usually necessitate running the machine empty. The present method allows for
the
simultaneous cleaning of dishware/tableware and the dishwashing machine
interior.
Suitable fibrous food degrading enzymes for use herein include pectinases and
are
normally employed at a pH of less than about 7, preferably less than about 6
as measured
at room temperature.
Detailed description of the invention
The present invention envisages a dishwashing method based on the use of one
or more
rinse cycles to provide chemical cleaning after the main wash and/or to
improve finishing
of the dishware/tableware by delivering high amounts of actives into the
rinse. The
actives are preferably delivered early into the rinse and preferably prior to
the final rinse
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so as to provide both tough food cleaning benefits and finishing benefits at
one and the
same time. Embodiments in which one or more dishwashing products are delivered
prior
to the final rinse and one or more dishwashing products are thereafter
delivered into the
final rinse are also highly preferred. According to preferred embodiments of
the
invention, the dishwashing products are delivered by means of purpose-built
dosing
devices. Suitable dosing devices allow for the storage of the dishwashing
products in one
or more compartments and for simultaneous or sequential dosing of the products
in one or
more cycles, wherein the products are in solid, liquid, gel or paste form.
The method of the invention also envisages the use of products comprising
chlorine
bleach, organic soluble builders and polymeric dispersants to reduce filming
and spotting;
the use of products comprising wetting agents to facilitate uniform drying and
the use of
surface substantive modifying polymers to improve the finishing of
dishware/tableware.
Finally, the method of the invention also envisages the use of products
comprising fibrous
food degrading enzymes which contribute to the cleaning of the machine itself.
The dishwashing products can be delivered using any suitable device capable of
delivering a predetermined amount of product at a predetermined time. For
example, a
dosing device suitable for use herein comprises a housing with at least one
opening
wherein the opening is removably closed by a cover. Inside the housing, the
dosing
device comprises at least one product compartment for storing the product to
be dosed.
The compartment can have any suitable shape sufficient to ensure easy and
complete
release of its contents. The device can be electrically operated, in which
case the device
would also comprise at least one compartment for storing electromechanical
components.
While the dosing device can have any suitable shape, a preferred one is made
out of two
hemispheres, one comprising at least one product compartment for containing at
least one
product to be released, and the other hemisphere comprising an
electromechanical
compartment containing the power supply, at least one sensor, actuator systems
and a
microchip for driving a logic control program.
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By sensor is meant a chip or similar electronic device which detects a
stimulus in the
dosing device's environment, for example in the wash water (such as pH,
temperature,
ionic strength, etc). Preferably, the sensor is directly coupled to a
microchip which
transforms the stimulus into an electric impulse which is then sent to the
actuator. The
sensor is housed in the electromechanical compartment of the device and
secured for
example with brackets and screws. The microchip which is preferably integrated
to the
sensor itself is an electronic circuit which runs a basic program, so called
logic control
program. The logic control program integrates different parameters of the wash
which
are sensed in the medium (i.e. the wash water), and also integrates the type
of product
that needs to be released and the desired rinse cycle concentration factors,
in order to
calculate at what times) during the rinse, said products must be released. The
specific
construction of the electronic circuit of the microchip will be appropriately
chosen by a
person skilled in the art.
The sensor structure and construction is adapted to the stimulus to be
detected, and the
choice of the appropriate sensor construction will be easily determined by a
person
skilled in the art. One dosing device suitable for use herein comprises at
least one sensor,
such that it can react to at least one stimulus present in its environment. It
will be
appreciated that the more stimuli said device detects, the more accurate the
product
dosing and/or release will be.
The dosing device can alternatively be controlled by means of memory shape
alloys or
polymers, which properties are determined by temperature.
By dosing device is meant a device with which it is possible to measure the
right amount
of product to be released during the rinse cycle, for example depending on the
wash
conditions, including but not limited to the amount of items to be washed, the
composition of the washing environment (for instance the wash water), the
nature of the
product which is used for the wash, the required rinse cycle concentration
factors, etc.
The dosing can be done by the user her/himself with instructions as to the
requisite
dosing regime. For example, this can be done by using the size of the device's
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compartment to measure the right amount of product to be released at a
requisite part of
the rinse. In this case, the device comprises a means, for example dosing line-
up marks,
that will help the user chose the right amount of product. Alternatively, the
user can
introduce a cartridge of product into the dosing device, said cartridge
containing a
predetermined amount of product, e.g. for one or several wash(es).
Alternatively, the dosing is done by the device itself, which is constructed
so that at least
one compartment can be opened and closed again during the wash. In this case,
the
compartment does not comprise line-up marks, the user fills it completely
before the
wash. During the rinse cycle, the dosing device first opens to release
product, then senses
or calculates when the concentration of product is sufficient and finally
closes to prevent
over-dosing of the product. In this case, the concentration sensing can be
done by
checking one component which is a characteristic of the product to being
released, for
example, the level of bleach can be sensed, in case the product to be released
is bleach.
The skilled person will be able to determine which compound must be sensed,
depending
on which product is released. Of course, 'a corresponding and suitable sensor
must be
integrated to the dosing device in this case, and the control logic program
must be
adapted accordingly.
Preferably, the dosing device comprises a means to enable it to stand on a
flat surface, for
example on a table. This means can be for example a flat portion of the
housing, an
outside surface or a stand. Alternatively, in the case of power operated
device, the
electronic components which are the heaviest part of said device are located
in the bottom
portion of said device, so that when the device is put on a flat surface, it
always stays in
the upright position. Once activated, the dosing device most preferably stays
as a single
unite, so that the user does not have to remove more than one portion of the
device from
the dishwashing machine.
The materials used for the housing and the cover might be of any type, and
they may be
made out of one or several materials. Preferred materials for the housing and
the cover
are synthetic materials, for example plastic or rubber, so as to be resistant
to liquids
and/or temperature variations. It is highly preferred that once closed, the
dosing device
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be liquid-tight. Of course, all materials used in the dosing device should be
chosen such
that they resist the conditions of use. Preferably, they are heat resistant so
as to withstand
the dish-washing temperatures. Examples of hard materials include but are not
limited to
polypropylene (PP), polycarbonate (PC), copolymers of butadiene and styrene,
and the
like.
The housing and the cover are preferably made by injection molding. In case
they are
made out of more than one material, co-injection molding process will be
preferred,
where applicable, since it is less expensive than molding several insert
portions separately
and then assembling them. For instance, co-injection molding can be used for
the
housing, to make it out of hard plastic, with some portions made out of a non-
slipping
rubber material. It is preferred that at least some portions of the dosing
device's outer
surface (including housing and cover) are made out of a rubber-like material,
which will
help to prevent noise. Preferably, the dosing device is secured to the walls
of the
dishwashing machine, for example by means of a magnet or by adhesive means.
In the case of a power-operated device, the dosing device comprises at least
one means
for storing energy and releasing it, such that the contents of said dosing
device is released
at a given predetermined time during the rinse cycle. It is preferred that the
dosing device
also comprises at least one sensor which is linked to the means, to determine
when the
environment, for example the wash water, requires that the dosing device be
opened and
the product released. Also preferably, the dosing device comprises an actuator
which is
linked to the cover, so as to activate the opening of said cover during the
wash. Finally,
the dosing device further comprises a microchip that monitors the data
received from the
sensors, and gives a signal to the actuator to open said dosing device at the
right time
during the wash cycle, in order to meet the required concentration factors and
cofactors.
The dosing device is preferably portable, that is to say that it is not too
bulky and heavy
and can easily be handheld and manipulated by a user for in-house usage. Its
dimensions
must be such that it can be put into a dishwasher. Preferably, its greatest
outer dimension
does not exceed 20 cm. Also preferably, its overall weight does not exceed 5
kg when
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empty, more preferably, it does not exceed 2.5 kg when empty, even more
preferably its
weight is not more than 1 kg when empty.
The dosing device for use herein is preferably self contained. By self
contained is meant
that the dosing device, once filled with product and closed, can work
independently from
any other device. Particularly, it comprises its own power source, and all
means
necessary to determine properly the right time its contents needs to be
released, only by
sensing its external environment. Alternatively, the power can be transmitted
via a coil
transmitter, which receives electricity via a remote generator. The sensing
and/or
microchip means can also be provided as a separate unit with signals for
actuating the
dosing device being transmitted by Bluetooth or some other wireless
communication
device.
Alkali materials for use herein are any materials capable of providing the
dishwashing
liquor with a pH above 7, preferably above 8, more preferably above 10 and
even more
preferably above 11. Preferred for use herein are caustic agents such as
alkali
hydroxides, especially sodium hydroxide, potassium hydroxide and mixtures
therefore.
Acidic materials for use herein are any materials capable of providing the
dishwashing
liquor with a pH below 7, preferably below 6, more preferably below 5 and even
more
preferably below 4. Suitable for use herein are organic acids, for example
carboxylic
acids, such as citric and succinic acids, polycarboxylic acids, such as
polyacrylic acid and
also acetic acid boric acid, malonic acid, their derivatives and mixtures
thereof. Also
suitable for use herein are inorganic acids and their salts, especially useful
are salt of
inorganic acids containing a cation which plays a role in the dishwashing
process as for
example aluminium. Preferred for use herein is aluminium sulphate, which
provides the
dishwashing liquior with an adequate pH and provides glass care benefits.
Organic soluble builder
Organic soluble builders for use herein are capable of reducing the
concentration of Caz+
below about 4 ppm, preferably below about 2 ppm and more preferably below 1
ppm.
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The organic soluble builder is preferably present at a level of from about 1
to about 80%,
preferably from about 5 to about 70% and more preferably from about 10 to
about 60%
by weight of the composition.
Suitable for use herein are organo aminophosphonic acid or one of its salts or
complexes.
By organo aminophosphonic acid component it is meant herein an organic
compound
comprising at least one phosphonic acid group, and at least one amino group.
The organo
aminophosphonic acid component may be present in its acid form or in the form
of one of
its salts or complexes with a suitable counter cation, and reference herein to
the acid
component implicitly includes reference to the salts or complexes. Preferably
any
salts/complexes are water soluble, with the alkali metal and alkaline earth
metal
salts/complexes being especially preferred.
Suitable organo aminophosphonic acid components for use herein include the
amino
alkylene poly (alkylene phosphonic acids) and nitrilo trimethylene phosphonic
acids.
Preferred are diethylene triamine penta (methylene phosphonic acid) and
hexamethylene
diamine tetra (methylene phosphonic acid).
A preferred component of the dishwashing products used herein is an organo
diphosphonic acid or one of its salts or complexes. Said organo diphosphonic
acid may
act in combination with the organo aminophosphonic acid component to further
enhance
the prevention of calcium deposit formation. By organo diphosphonic acid it is
meant
herein an organo diphosphonic acid which does not contain nitrogen as part of
its
chemical structure. This definition therefore excludes the organo
aminophosphonates.
The organo diphosphonic acid component may be present in its acid form or in
the form
of one of its salts or complexes with a suitable counter cation. Preferably
any
salts/complexes are water soluble, with the alkali metal and alkaline earth
metal
salts/complexes being especially preferred. The organo diphosphonic acid is
preferably a
C1-C4 diphosphonic acid, more preferably a C2 diphosphonic acid, such as
ethylene
diphosphonic acid, or most preferably ethane 1-hydroxy-1,1-diphosphonic acid
(HEDP).
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Suitable water-soluble carboxylate or polycarboxylate builders include
carboxylic and
polycarboxylic acids their salts and complexes. The carboxylate or
polycarboxylate
builder can be momomeric or oligomeric in type although monomeric
polycarboxylates
are generally preferred for reasons of cost and performance. Monomeric and
oligomeric
builders can be selected from acyclic, alicyclic, heterocyclic and aromatic
carboxylates.
Suitable carboxylates containing one carboxy group include lactic acid,
glycolic acid and
ether derivatives thereof as disclosed in Belgian Patent Nos. 831,368, 821,369
and
821,370. Polycarboxylates containing two carboxy groups include succinic acid,
malonic
acid, (ethylenedioxy) diacetic acid, malefic acid, diglycolic acid, tartaric
acid, tartronic
acid and fumaric acid and their water-soluble salts, as well as the ether
carboxylates
described in German Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent
No.
3,935,257 and the sulfinyl carboxylates described in Belgian Patent No.
840,623.
Polycarboxylates containing three carboxy groups include, in particular, water-
soluble
citrates, aconitrates and citraconates as well as succinate derivatives such
as the
carboxymethyloxysuccinates described in British Patent No. 1,379,241,
lactoxysuccinates
described in British Patent No. 1,389,732, and aminosuccinates described in
Netherlands
Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-
propane
tricarboxylates described in British Patent No. 1,387,447. Citric acid and
citrates are
highly preferred for use herein.
Polycarboxylates containing four carboxy groups include oxydisuccinates
disclosed in
British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-
propane
tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
Polycarboxylates containing sulfo substituents include the sulfosuccinate
derivatives
disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent
No.
3,936,448, and the sulfonated pyrolysed citrates described in British Patent
No.
1,439,000.
Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-
tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-
tetrahydrofuran - cis, cis,
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cis-tetracarboxylates, 2,5-tetrahydrofuran - cis - dicarboxylates, 2,2,5,5-
tetrahydrofuran
tetracarboxylates, 1,2,3,4,5,6-hexane - hexacarboxylates and carboxymethyl
derivatives
of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic
polycarboxylates
include mellitic acid, pyromellitic acid and the phthalic acid derivatives
disclosed in
British Patent No. 1,425,343.
Of the above, the preferred polycarboxylates are hydroxycarboxylates
containing up to
three carboxy groups per molecule, more particularly citrates, especially
sodium citrate.
Polymeric dispersant
Preferably, polymeric dispersants are used in a level of from about 50 to
about 200 ppm,
preferably from about 70 to 120 ppm in the rinse liquor. Suitable polymers
comprise
from about 50 to about 99% by weight, preferably from about 70 to about 98%,
most
preferably from about 75 to about 95% by weight of an olefinically unsaturated
carboxylic acid monomer and from about 1% to about 50%, preferably from about
2 to
about 30%, most preferably from about 5 to about 25% by weight of at least one
monomer unit selected from the group consisting of
(a) copolymerizable sulfonated monomers,
(b) copolymerizable nonionic monomers or
(c) mixtures of (a) and (b).
The olefinically unsaturated carboxylic acid monomer for use herein is
intended to
include aliphatic, branched or cyclic, mono- or dicarboxylic acids, the alkali
or alkaline
earth metal or ammonium salts thereof, and the anhydrides thereof. Useful
olefmically
unsaturated acids of this class include acrylic acid comonomers typified by
acrylic acid
itself, methacrylic acid, ethacrylic acid, alpha-chloro-acrylic acid, alpha-
cyano acrylic
acid, beta methyl-acrylic acid (crotonic acid), alpha-phenylacrylic acid, beta-
acryloxy
propionic acid, sorbic acid, alpha-chloro sorbic acid, angelic acid, cinnamic
acid, p-chloro
cinnamic acid, beta-styryl acrylic acid (1-carboxy-4-phenyl butadiene-1,3),
itaconic acid,
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malefic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic
acid,fumaric acid,
and tricarboxyethylene.
For the polycarboxylic acid monomers, an anhydride group is formed by the
elimination
of one molecule of water from two carboxyl groups located on the same
polycarboxylic
acid molecule. Preferred carboxylic monomers for use in this invention are the
monoolefinic acrylic acids having a substituent selected from the class
consisting of
hydrogen, halogen and hydroxyl groups, monovalent alkyl radicals, monovalent
aryl
radicals, monovalent aralkyl radicals, monovalent alkaryl radicals and
monovalent
cycloaliphatic radicals. As used herein, (meth) acrylic acid is intended to
include acrylic
acid and methacrylic acid. Preferred unsaturated carboxylic acid monomers are
acrylic
and methacrylic acid, more preferably acrylic acid.
Examples of sulfonate monomers (a) include, but not limited to, allyl
hydroxypropanyl
sulfonate ether, allylsulfonic acid, methallylsulfonic acid, styrene sulfonic
acid, vinyl
toluene sulfonic acid, acrylamido alkane sulfonic acid, allyloxybenzene
sulfonic acid, 2-
alkylallyloxybenzene sulfonic acid such as 4-sulfophenol methallyl ether, and
the alkali
or alkaline earth metal or ammonium salts thereof.
The copolymerizable nonionic monomers (b) are vinyl or allyl compounds
selected from
the group consisting of C1-C6 alkyl esters of (meth)acrylic acid, acrylamide
and the C1
C6 alkyl-substituted acrylamides, the N-alkyl-substituted acrylamides and the
N-alkanol
substituted acrylamides, N-vinyl pyrrolidone or any other vinyl amide. Also
useful are the
C1-C6 alkyl esters and C1-C6 alkyl half esters of unsaturated vinylic acids,
such as
malefic acid and itaconic acid.
Preferred nonionic monomers are selected from the group consisting of methyl
(meth)acrylate, mono- and dimethyl maleate, mono- and di-ethyl itaconate, and
(meth)allyl acetates, propionates and valerates. Particularly preferred is
methyl
methacrylate. Minor amounts of crosslinking monomers such as diallyl maleate,
alkylene
bisacrylamide and triallyl cyanurate may also be employed herein.
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The average molecular weight of the polymers ranges from 1500 to 250,000,
preferably
from 5,000 to 100,000.
A suitable example of polymeric dispersant include, but are not limited to a
tetrapolymer
of 4-sulfophenol methallyl ether, sodium methallyl sulfonate, acrylic acid and
methyl
methacrylate. The monomer unit, sulfophenol methallyl ether, has a formula
(I):
CH2=C(CH3)CH20C6H4S03M (I)
where M represents hydrogen, alkali metal, alkaline earth metal or ammonium
ions.
Other suitable examples of polymeric dispersant include, but are not limited
to, a
copolymer of acrylic acid and 4-sulfophenol 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; and a copolymer of acrylic acid and acrylamide. Preferably,
the
polymer is the tetrapolymer of 4-sulfophenol methallyl ether, sodium methallyl
sulfonate,
acrylic acid and methyl methacrylate.
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.
Wetting agent
Wetting agents suitable for use herein are surfactants and include anionic,
amphoteric,
zwitterionic, nonionic and semi-polar surfactants. Preferred nonionic
surfactants include
silicone surfactants, such as Silwet copolymers, preferred Silwet copolymers
include
Silwet L-8610, Silwet L-8600, Silwet L-77, Silwet L-7657, Silwet L-7650,
Silwet L-
7607, Silwet L-7604, Silwet L-7600, Silwet L-7280 and mixtures thereof.
Preferred for
use herein is Silwet L-77.
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Surface substantive modifying polymer
Preferably the surface substantive polymer is selected 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,
preferred copolymers comprise at least about 5%, most preferably at least
about 15%,
especially at least about 40% by weight thereof of the comonomer. Highly
preferred
comonomers include aromatic monomers such as vinyl imidazole and carboxylic
monomors such as acrylic acid and methacrylic acid.
PVP preferred for use herein has an average molecular weight of from about
2,500 to
about 400,000, preferably from about 5,000 to about 200,000, more preferably
from
about 5,000 to about 50,000, and most preferably from about 5,000 to about
15,000.
Suitable polyvinylpyrrolidones are commercially available from ISP
Corporation, New
York, NY and Montreal, Canada under the product names PVP K-15 (viscosity
molecular
weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60
(average
molecular weight of 160,000), and ~ PVP K-90 (average molecular weight of
360,000).
PVP K-15 is also available from ISP Corporation. Other suitable
polyvinylpyrrolidones
which are commercially available from BASF Corporation include Sokalan HP 165
and
Sokalan HP 12. Other polyvinylpyrrolidones known 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. Preferred PVPVI polymers have an average molecular
weight of from about 1,000 to about 5,000,000, more preferably from 5,000 to
2,000,000,
even more preferably from about 5,000 to about 500,000 and most preferably
from about
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5,000 to about 15,000. Preferred PVPVI polymers comprise at least 45%,
preferably at
least 50% N-vinylimidazole monomers. 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.
Fibrous food degrading enzyme
Suitable enzymes for use herein include enzyme which acts to break down pectic
bondings. Preferably incorporated into the dishwashing product at a level of
from
0.0001% to 2%, preferably from 0.0005% to 0.5%, more preferably from 0.001% to
0.05% active enzyme by weight of dishwashing product and at about 10 to about
200,
preferably from about 40 to about 150 ppm in the wash liquor.
Preferred for use herein is polygalacturanase enzyme. By polygalacturanase
enzyme it is
meant herein any enzyme which acts to break down pectic substances by cleaving
the
glycosidic bonds between galacturonic acid molecules. Pectic substances may be
found in
plant tissues, and are common constituents of fruit juices such as orange,
tomato and
grape juices. Pectic substances contain galacturonic acids and/or their
derivatives.
Pectic substances include pectins and pectic acids. Pectins are, in general,
polymers made
up of chains of galacturonic acids joined by alpha-1-4 glycosidic linkages.
Typically, in
natural pectins approximately two-thirds of the carboxylic acid groups are
esterified with
methanol. Partial hydrolysis of these methyl esters gives low methoxyl
pectins, which
tend to form gels with calcium ions. Complete methyl ester hydrolysis gives
pectic acids.
are not polygalacturanase.
Other pectic enzymes for use herein include, for example, the pectin
methylesterases
which hydrolyse the pectin methyl ester linkages, and the pectin
transeliminases or lyases
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which act on the pectic acids to bring about non-hydrolytic cleavage of alpha-
4 glycosidic
linkages to form unsaturated derivatives of galacturonic acid.
Polygalacturanase enzymes herein include naturally derived polygalacturanase
enzymes
and any variants obtained by, for example, genetic engineering techniques. Any
such
variants may be specifically designed with regard to the optimization of
performance
efficiency in the detergent compositions of the invention. For example,
variants may be
designed such that the stability of the enzyme to commonly encountered
components of
such compositions is increased. Alternatively, the variant may be designed
such that the
optimal pH or temperature performance range of the enzyme variant is tailored
to suit the
particular detergent application.
Polygalacturanase enzymes may be derived from plants, especially fruits, and
from
fungal sources. A common fungal source is provided by certain strains of the
Aspergillus
Niger group. Commercially available pectic enzymes tend to be mixtures of
pectic
enzymes of the pectin methylesterase, polygalacturonase and pectin lyase
types; therefore
further purification to isolate polygalacturanase enzymes substantially free
of other pectic
enzyme using standard enzyme purification techniques is required.
Polygalacturanase can
be isolated from these commercial mixtures by standard protein separation
methods that
are well known in the art.
Preferably, the polygalacturanase is obtained through recombinant DNA
techniques
wherein the genetic material coding only for polygalacturanase is isolated
from a natural
host and transferred into a suitable production organism, like Aspergillus
Niger,
Aspergillus Orayze, or Bacillus Subtilus for subsequent fermentation,
recovery, and
purification of the polygalacturanase protein.
Commercially available pectic enzymes include those sold under the Pectinex AR
tradename by Novo Industries A/S, those sold under the Rapidase tradename by
International Bio-Synthetics (a division of Gist-Brocades BV), those sold
under the
Cytolase tradename by Genencor International, and those sold under the
tradename,
Clarex by Solvay Enzymes. Such enzymes may be used following purification
isolate
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polygalacturanase enzymes substantially free of other pectic enzyme. Preferred
are pectic
enzyme compositions consisting essentially of polygalacturanase enzymes
Surfactant
In the methods of the present invention surfactant can be used as part of a
dishwashing
product. For use herein the detergent surfactant is preferably low foaming by
itself or in
combination with other components (i.e. suds suppressers). 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-acyl 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 chlorine 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., BASF Poly-
Tergent~ SLF18), epoxy-capped poly(oxyalkylated) alcohols (e.g., BASF Poly-
Tergent~
SLF18B - see WO-A-94/22800), ether-capped poly(oxyalkylated) alcohol
surfactants,
and block polyoxyethylene-polyoxypropylene polymeric compounds such as
PLURONIC~, REVERSED PLURONIC~, and TETRONIC~ by the BASF-Wyandotte
Corp., Wyandotte, Michigan; amphoteric surfactants such as the C,2-Czo alkyl
amine
oxides (preferred amine oxides for use herein include lauryldimethyl amine
oxide and
hexadecyl dimethyl amine oxide), and alkyl amphocarboxylic surfactants such as
MiranolTM C2M; and zwitterionic surfactants such as the betaines and
sultaines; and
mixtures 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 dishwashing product and at about 10 to about 2000,
preferably from about 20 to about 1000 ppm of the wash liquor. Preferred
surfactant for
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use herein are low foaming and include low cloud point nonionic surfactants
and
mixtures of higher foaming surfactants with low cloud point nonionic
surfactants which
act as suds suppresser therefor.
Inorganic builder
In addiction to the organic soluble builder described hereinabove inorganic
builders can
also be comprised in the products used herein. Suitable inorganic builders
include
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 dishwashing
product
and at from about 10 to about 2000, preferably from about 100 to about 1000
ppm of the
wash liquor.
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
Additionally or in place of the fibrous food degrading enzymes described
hereinabove
other enzymes can also be comprised in the products used herein. 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 LipolaseR 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 (3
amylases
such as Purafect Ox AmR (Genencor) and TermamylR, 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 0.1 to
about 2000,
preferably from about 1 to about 1000, more preferably from about 3 to about
300 mg of
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active enzyme per 100 g of dishwashing product, determined according to the
supplier's
specific activity data for the particular enzyme. The total enzyme level is
typically at
least about 50, preferably at least about 100 and more preferably at about 150
mg/100 g
or product, or at least about 2, preferable at least about 4 and more
preferably at least
about 6ppm of wash liquor.
Bleaching agent
Bleaching agents suitable herein include chlorine and oxygen bleaches,
especially
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) and organic
peroxides.
Inorganic perhydrate salts are typically incorporated at levels in the range
from about 1%
to about 40% by weight, preferably from about 2% to about 30% by weight and
more
preferably from abut 5% to about 25% by weight of dishwashing product.
Peroxyacid
bleach precursors preferred for use herein include precursors of perbenzoic
acid and
substituted perbenzoic acid; cationic peroxyacid precursors; peracetic acid
precursors
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 (HOBS); 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 product 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 product. 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 cobalt(III) and related complexes(US-A-4810410). Organic
peroxides
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suitable for use herein include diacyl and tetraacylperoxides, especially
dibenzoyl
peroxide.
Low cloud point non-ionic surfactants and suds suppressers
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
temperature, the temperature at which the appearance of a second phase is
observable is
referred 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 30° 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/EO/PO) reverse block
polymers. Also, such low cloud point nonionic surfactants include, for
example,
ethoxylated-propoxylated alcohol (e.g., BASF's Poly-Tergent~ SLF18) and epoxy-
capped poly(oxyalkylated) alcohols (e.g., BASF's Poly-Tergent~ SLF18B series
of
nonionics, as described, for example, in US-A-5,576,281).
Preferred low cloud point surfactants are the ether-capped poly(oxyalkylated)
suds
suppresser having the formula:
Rl O-( CHz - CH -O)X - (CHz -CH2 -O~ - (CHz - CH -O)Z-H
Rz R3
wherein R' is a linear, alkyl hydrocarbon having an average of from about 7 to
about 12
carbon atoms, Rz 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.
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Other low cloud point nonionic surfactants are the ether-capped
poly(oxyalkylated)
having the formula:
R,O(R"O)nCH(CH3)OR",
wherein, R, is selected from the group consisting of linear or branched,
saturated or
unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon
radicals
having from about 7 to about 12 carbon atoms; R" may be the same or different,
and is
independently selected from the group consisting of branched or linear CZ to
C, alkylene
in any given molecule; n is a number from 1 to about 30; and R", is selected
from the
group consisting of
(i) a 4 to 8 membered substituted, or unsubstituted heterocyclic ring
containing
from 1 to 3 hetero atoms; and
(ii) linear or branched, saturated or unsaturated, substituted or
unsubstituted,
cyclic or acyclic, aliphatic or aromatic hydrocarbon radicals having from
about 1 to about 30 carbon atoms;
(b) provided that when RZ is (ii) then either: (A) at least one of R' is other
than Cz
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 C, to CS
alkyl.
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%, preferably from about 0.5% to about 15%, most preferably
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 CPS 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 mixtures thereof.
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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 product, for example diethylenetriamine penta
(methylene
phosphonate), ethylenediamine tetra(methylene phosphonate)
hexamethylenediamine
tetra(methylene phosphonate), ethylene diphosphonate, hydroxy-ethylene-1,1-
diphosphonate, nitrilotriacetate, ethylenediaminotetracetate, ethylenediamine-
N,N'-
disuccinate in their salt and free acid forms.
The products used herein 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 about
5% by weight of product (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 product.
Other suitable components herein include 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 EP-A-0705324), polymeric dye
transfer inhibiting agents, optical brighteners, perfumes, fillers and clay.
Solvents
Solvents that can be used herein include: i) alcohols, such as benzyl alcohol,
1,4-
cyclohexanedimethanol, 2-ethyl-1-hexanol, furfuryl alcohol, 1,2-hexanediol and
other
similar materials; ii) amines, such as alkanolamines (e.g. primary
alkanolamines:
monoethanolamine, monoisopropanolamine, diethylethanolamine, ethyl
diethanolamine;
secondary alkanolamines: diethanolamine, diisopropanolamine, 2-
(methylamino)ethanol;
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ternary alkanolamines: triethanolamine, triisopropanolamine); alkylamines
(e.g. primary
alkylamines: monomethylamine, monoethylamine, monopropylamine, monobutylamine,
monopentylamine, cyclohexylamine), secondary alkylamines: (dimethylamine),
alkylene
amines (primary alkylene amines: ethylenediamine, propylenediamine) and other
similar
materials; iii) esters, such as ethyl lactate, methyl ester, ethyl
acetoacetate, ethylene
glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate,
diethylene
glycol monobutyl ether acetate and other similar materials; iv) glycol ethers,
such as
ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene
glycol
monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol
monomethyl ether,
diethylene glycol monoethyl ether, propylene glycol butyl ether and other
similar
materials; v) glycols, such as propylene glycol, diethylene glycol, hexylene
glycol (2-
methyl-2, 4 pentanediol), triethylene glycol, composition and dipropylene
glycol and
other similar materials; and mixtures thereof.
Liquid dishwashing products containing low quantities of low molecular weight
primary
or secondary alcohols such as methanol, ethanol, propanol and isopropanol can
be
usedherein. Other suitable carrier solvents used in low quantities includes
glycerol,
propylene glycol, ethylene glycol, 1,2-propanediol, sorbitol and mixtures
thereof.
Examples:
Abbreviations used in Examples
In the examples, the abbreviated component identifications have the following
meanings:
FN3 : Protease available from Genencor
Natalase : Amylase from Novo Nordisk A/S
Pectinase Ultra: Pectinase available from Novo Nordisk A/S
SP
Plurafac 400 : C 13-C 15 mixed ethoxylated/propoxylated fatty
alcohol
with an average degree of ethoxylation of 3.8
and an average
degree of propoxylation of 4.5, available from
BASF
C,4A0 : Tetradecyl dimethyl amine oxide
ACNI : Alkyl capped non-ionic surfactant of formula
C9", H,9~23 EO8-
cyclohexyl acetal
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Alcosperse : PAA/MMA/SPEM/SME polymer available from Alco
240 Chemical
Citric acid : Citric acid
HEDP : Ethane 1-hydroxy-1,1-diphosphonic acid
Silwet 77 . Siloxane surfactant available from Ckwitko
PVNO : Poly-4-vinylpyridine N-oxide available from
BASF
STPP : Sodium tripolyphosphate
KOH : Potassium hydroxide
NaOH : Sodium hydroxide
DCICA . Dichloroisocyanuric acid (Sodium Salt)
Percarbonate : Sodium percarbonate of the nominal formula
2Na2C03.3H202
Silicate 3:2 : Amorphous Sodium Silicate (Si02:Na20 ratio
= 3:2)
SLF 18 : Low foaming surfactant available from BASF
Polygel DKP : Dipotassium phosphate gel available from 3V
Inc.
Water : De-ionised water
In the following examples all levels are quoted as parts by weight.
Examples 1 to 8
A load of dishware/tableware is placed into a Bosch Siemens 6032 dishwashing
machine
having a 5 litres wash water capacity. The load comprises different soils and
different
substrates: lasagne baked for 2 hours at 140°C on Pyrex, lasagne cooked
for 2 hours at
150°C on stainless steel, potato and cheese cooked for 2 hours at
150°C on stainless steel,
egg yolk cooked for 2 hours at 150°C on stainless steel and sausage
cooked for 1 hour at
120°C followed by 1 hour at 180°C. A Fairy tablet (available
from Procter & Gamble) is
placed in the dispenser for delivery in the main wash. 20 ml of the
compositions of
examples 1 to 8 are introduced into a dosing device as previously described
which is
secured to one of the dishwasher internal walls. The dosing device is
programmed in
such a way as to open and deliver the product at the start of the first rinse
cycle. The
dishwashing machine is operated in its normal 55°C program. The rinse
cycle
concentration factor is 3 x 104 ppm min for each example. The washing method
provided
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excellent removal of cooked-on, baked-on and burnt-on food soils as well as
excellent
shine, filming and spotting performance.
Example 1 2 3 4 5 6 7 8
FN3 1.9 1.9 1.9 2 1.5 2 1
Natalase 5.75 5.75 5.75 4 5 6 4
Pectinase 2 2 S
Plurafac 400 1.8 1 2 1.5 2
C,4 AO 2 2 1 1.5
ACNI 0.5 1 1 0.5
Alcosperse 5 4
240
Citric acid 25 25 30
HEDP 20 18 22
Silwet 77 1 0.1 0.1 0.5 0.5 0.2
PVNO 0.1 0.1 0.1 0.1 0.2
Perfume 1 0.5 0.5 1 0.3 0.4 0.2 0.8
Dye 0.3 0.4 0.2 0.4 0.2 0.4 0.05 0.1
Water up
to
100
Examples 9 to 12
A load of dishware/tableware is placed into a Bosch Siemens 6032 dishwashing
machine
having a 5 litres wash water capacity. The load comprises different soils and
different
substrates: lasagne baked for 2 hours at 140°C on Pyrex, lasagne cooked
for 2 hours at
150°C on stainless steel, potato and cheese cooked for 2 hours at
150°C on stainless steel,
egg yolk cooked for 2 hours at 150°C on stainless steel and sausage
cooked for 1 hour at
120°C followed by 1 hour at 180°C. 20 ml of the compositions of
examples 9 to 12 are
placed in the dispenser for delivery in the main wash. 20 ml of the
compositions of
examples 9 to 12 are introduced into a dosing device as previously described
which is
secured to one of the dishwasher internal walls. The dosing device is
programmed in
such a way as to open and deliver the product at the start of the first rinse
cycle. The
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dishwashing machine is operated in its normal 55°C program. The rinse
cycle
concentration factor is 3 x 104 ppm min for each example. The washing method
provided
excellent removal of cooked-on, baked-on and burnt-on food soils as well as
excellent
shine, filming and spotting performance.
Example 9 10 11 12
STPP 28.00 28.00 28.00 28.00
KOH 5.30 5.30 5.30 5.30
Silicate 3:2 1.0 1.0 1.0 1.0
Polygel DKP 0.55 0.55 0.55 0.55
SLF18 1.25 1.25
C,6 AO 0.40 0.40
ACNI 3.00 3.00
Water up
to
100
Examples 13 to 16
A load of dishware/tableware is placed into a Bosch Siemens 6032 dishwashing
machine
having a 5 litres wash water capacity. The load comprises different soils and
different
substrates: lasagne baked for 2 hours at 140°C on Pyrex, lasagne cooked
for 2 hours at
150°C on stainless steel, potato and cheese cooked for 2 hours at
150°C on stainless steel,
egg yolk cooked for 2 hours at 150°C on stainless steel and sausage
cooked for 1 hour at
120°C followed by 1 hour at 180°C. A Fairy tablet (available
from Procter & Gamble) is
placed in the dispenser for delivery in the main wash. Dual compartment
pouches
comprising 5 g of composition A (examples 13 to 16) in a cold water soluble
compartment and 10 g of composition B (examples 13 to 16) in a hot water
soluble
compartment are introduced into a dosing device as previously described which
is
secured to one of the dishwasher internal walls. The dosing device is
programmed in
such a way as to open and deliver the pouches at the start of the first rinse
cycle. The
pouches are designed to deliver composition A into the pre-final rinse cycle
and
composition B into the final rinse cycle. The dishwashing machine is operated
in its
normal 55°C program. The pre-final rinse cycle concentration factor is
5 x 103 ppm min
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and the final rinse cycle concentration factor is 2 x 104 ppm min for each
example. The
washing method provided excellent removal of cooked-on, baked-on and burnt-on
food
soils as well as excellent shine. Examples 13 to 16 were repeated but
delivering
compositions A and B into the pre-final rinse and final rinse cycles
respectively by means
of the dosing device herein described. Excellent results were obtained.
Example 13 14 15 16
Composition A
NaOH 50 30 50 30
DCICA 50 70
Percarbonate 50 70
Composition B
Citric acid 88 87 92 97
SLF18 10 11 7
Perfume 2 2 1 3
39
