Note: Descriptions are shown in the official language in which they were submitted.
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GEL FORM AUTOMATIC DISHWASHING COMPOSITIONS, METHODS OF
PREPARATION AND USE THEREOF
Technical field
The present invention is in the field of automatic dishwashing compositions,
in particular
it relates to dishwashing compositions in the form of anhydrous gels,
especially gels
comprising ,particulate material in the form of a suspension. The compositions
have
improved rheological and stability characteristics and are particularly useful
for cleaning
heavily soiled dishwashing loads and for the removal of cooked-, baked- and
burnt-on
soils. The invention also relates to multi-phase products comprising the
anhydrous
dishwashing compositions. The invention further relates to dishwashing
products in
unitised form, for example capsules, pouches, sachets, etc.
Background of the invention
Dishwashing loads are usually characterised by including articles made of
different
materials (i.e. stainless steel, glass, plastic, wood, ceramic, china,
porcelain, etc) and
soiled with different food residues (i.e. proteinaceous, carbohydrates,
grease, starch,
carotenoids, etc). The removal of all the soils from the dishwashing load
usually requires
a combination of several detergent ingredients. However, in many cases not all
the
ingredients are compatible with one another and it can be a difficult or
impossible task to
combine and stabilise them into a single composition.
Cooked-, baked- and burnt-on soils are amongst the most severe types of soils
to remove
from surfaces. The use of cleaning compositions containing solvent for helping
in the
removal of cooked-, baked- and burnt-on solids is known in the art. For
example, US-A-
5,102,573 provides a method for treating hard surfaces soiled with cooked-on,
baked-on
or dried-on food residues comprising applying a pre-spotting composition to
the soiled
article. The composition applied comprises surfactant, builder, amine and
solvent. US-
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A-5,929,007 provides an aqueous hard surface cleaning composition for removing
hardened dried or baked-an grease soil deposits. The composition comprises
nonionic
surfactant, chelating agent, caustic, a glycol ether solvent system, organic
amine and anti-
redeposition agents. WO-A-94/28108 discloses an aqueous cleaner concentrate
composition, that can be diluted to form a more viscous use solution
comprising an
effective thickening amount of a rod micelle thickener composition, lower
alkyl glycol
ether solvent and hardness sequestering agent. The application also describes
a method
of cleaning a food preparation unit having at least one substantially vertical
surface
having a baked food soil coating. In practice, however, none of the art has
been found to
be very effective in removing baked-on, polymerized soil from metal and other
substrates.
The use of solvents in the automatic dishwashing context is also known. JP-A-
10,017,900 discloses an automatic dishwashing auxiliary composition comprising
non-
ionic low foaming surfactant, organic solvent and water. The composition
delivers
detergency and drying benefits. JP-A-11,117,000 discloses a cleaning assistant
composition for automatic dishwashing machines comprising surfactant, organic
high-
molecular polyelectrolyte, water-soluble solvent and water. The claimed
assistant
composition helps in the cleaning of stubborn dirt such as that due to oil or
lipstick.
It is also known to use chlorine and peroxygen bleaches in automatic
dishwashing to
remove coloured stains such as tea and coffee and carotenoids stains. Chlorine
bleaches
are invariably the bleaches of choice in aqueous liquid products because they
have much
better stability than peroxygen bleaches. Peroxygen bleaches have the
advantage over
chlorine bleaches of greater compatibility with enzymes and of being suitable
for use
under lower alkalinity wash conditions. The incorporation of particulate
peroxygen
bleaches in stable liquid compositions raises considerable difficulties
however.
In these and other cases, it would be advantageous to include both solid and
liquid
ingredients in detergent compositions; for example, it would be very useful to
have a
liquid detergent comprising cleaning solvent and particulate peroxygen bleach.
A liquid
composition comprising solid ingredients must be chemically and physically
stable.
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Ideally, the liquid should be capable of homogeneously suspending the
particles without
reacting with them. A liquid composition comprising peroxygen bleach should be
anhydrous in order to prevent bleach decomposition due to bleach/water
interaction.
Another factor that should be taken into account, when formulating liquid
compositions
comprising solid ingredients, is that the compositions should have the right
rheology in
order to provide a product easy to pour and at the same time should be thick
enough so it
will not leak from the dishwasher dispenser.
The use of anhydrous compositions containing suspended particulate solids is
known in
the art. EP-A-266,199 discloses non-aqueous liquid cleaning products
formulated by
dispersing particulate solids in an organic solvent by using a structurant or
deflocculant
which causes a viscosity reduction at low shear rates in the solids/solvent
system or an
equivalent system in which the solids volume fraction is sufficiently high to
raise the
viscosity of the solvent. The organic solvent is preferably a liquid
surfactant. The solids
are any usable in liquid cleaning products, including detergency builders and
bleaches.
The structurants are Bronsted or Lewis acids. US-A-5,872,092 discloses
nonaqueous,
peroxygen bleach-containing liquid laundry detergent compositions in the form
of a
suspension of particulate material. The liquid phase contains an alcohol
ethoxylate
nonionic surfactant and a nonaqueous low polarity organic solvent while the
compositions may additionally contain a thickening, viscosity control and/or
dispersing
agent selected from acrylic acid-based polymers. US-A-5,164,106 discloses
nonaqueous
liquid automatic dishwasher detergent composition containing a dual bleach
system, the
dual bleach system being a chlorine bleach source and a bromide compound.
Thus, there is a need for a dishwashing detergent composition which is
effective against
all kinds of soils including cooked-, baked- and burnt-on soils as well as
coloured stains
and other bleachable and enzyme sensitive soils without the need to pretreat
heavily
soiled items or to use dishwashing additives. There is also a need for a
detergent in the
form of a particulate suspension in which segregation or separation of solid
particles does
not occur and which is easy to pour and does not leak from the dishwasher
dispenser.
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Sometimes it is desirable to have a dual or mufti-phase detergent system
comprising an
anhydrous and an aqueous composition which are simultaneously or sequentially
delivered into the dishwasher. Such mufti-phase systems allow further
refinement in
dishwashing performance and can provide superior overall end result. Problems
in the
delivery of mufti system compositions may arise when the different
compositions have
different viscosity characteristics. Therefore, it is another objective of the
present
invention to provide mufti composition systems with matched rheology in order
to allow
for an easy simultaneous and controlled delivery of the system compositions.
Unitised doses of dishwashing detergents are found to be more attractive and
convenient
to some consumers because they avoid the need of the 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 unitised form such as pouches,
capsules and sachets are also known in the art and are preferred by some users
from the
viewpoint of minimizing handling and contact of the detergent product with the
user's
skin and for avoiding inhalation of product vapors. Such products are prone to
a number
of additional problems, however. For example, in the case of pouches, sachets
and
capsules containing a peroxygen bleach-based detergent and having an outer
wall
material made of a moisture permeable material, bleach decomposition can give
rise to
bloating or even destruction of the outer wall of the product due to the
generation of
gaseous oxygen. Thus there is a need for unitised forms which deliver both.
improved
cleaning performance together with good chemical and physical product
stability.
Summary of the invention
According to a first aspect of the present invention, there is provided an
automatic
dishwashing composition in the form of an anhydrous, shear-thinning organo
solvent
based gel and which comprises a thickening system consisting essentially of
non-ionic
cellulosic material.
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The compositions herein take the form of an essentially anhydrous gel. By
"essentially
anhydrous" is meant that they contain less than about 5%, preferably less than
about 1%
free moisture. Highly preferred, however, are compositions which contain less
than
about 0.5%, more preferably less than about 0.1% and ever more preferably less
than
5 about 0.05% free moisture.
Anhydrous compositions with free moisture levels below 0.1 % are particularly
suitable
for the inclusion of moisture sensitive components. It will be understood that
additional
water can be present in the anhydrous composition forming part of hydrated
compounds,
i.e. bound water. It should also be understood that although the composition
should
contain less than about 0.5, preferably less than 0.1 and even more preferably
less than
0.05% by weight of the composition of free water at the time of manufacture,
the water
content could increase if the composition is exposed to the environment. For
example if
the composition is placed in a bottle and the bottle is left open for a period
of time, the
composition could pick up moisture from the surrounding environment.
Preferably,
however, the compositions for use herein are not hygroscopic and will be
stored under
moisture-tight conditions so that they will not tend to pick up water from the
surroundings. Free moisture can be measured by extracting 2 g of the product
into 50 ml
of dry methanol at room temperature for 20 minutes and then analysis a 1 ml
aliquot of
the methanol by Karl Fischer titration.
The matrix of the gel comprises an organic solvent system (which term is
understood to
include both single and mixed organo solvent compounds). Solvents preferred
herein
from the viewpoint of forming an anhydrous shear-thinning gel and of providing
homogeneous stable suspensions are organic solvents having: a fractional polar
Hansen
solubility parameter from about 10% to about 40% and a fractional dispersion
Hansen
solubility parameter from about 20% to about 60%. Fractional polar Hansen
solubility
parameter of a solvent is defined as the ratio (multiplied by 100) of the
polar Hansen
solubility parameter to the sum of the dispersion, polar and hydrogen bonding
Hansen
solubility parameters. Fractional dispersion Hansen solubility parameter of a
solvent is
defined as the ratio (multiplied by 100) of the dispersion Hansen solubility
parameter to
the sum of the dispersion, polar and hydrogen bonding Hansen solubility
parameters.
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Fractional hydrogen bonding Hansen solubility parameter of a solvent is
defined as the
ratio (multiplied by 100) of the hydrogen bonding Hansen solubility parameter
to the sum
of the dispersion, polar and hydrogen bonding Hansen solubility parameters.
Preferably
organic solvents for use herein additionally provide a cleaning function.
Especially
suitable for use herein are organic solvents whose fractional polar,
dispersion and
hydrogen bonding Hansen solubility parameters fall within the area defined by
a
quadrilateral having four vertices given by the following co-ordinates: (18,
50, 33), (10,
51, 38), (20, 25, 57) and (38, 20, 43) as plotted on a triangular diagram of
Hansen
solubility parameter with axes scaled between 0 and 100% (the first, second
and third co-
ordinates correspond to fractional polar, dispersion and hydrogen bonding
Hansen
solubility parameters, respectively). Examples of suitable solvents for use
herein include:
2-amino 2-methyl 1-propanol, dipropylene glycol, dipropylene glycol methyl
ether,
propanediol, monoethanolamine, di-ethyl glycol, glycerol, benzyl alcohol,
polyethylene
glycol solvents and mixtures thereof.
The compositions herein display excellent stability characteristics and
absence of
syneresis. Without, wishing to be bound by theory, it is believed that for
optimum
stability performance, the thickening system should be soluble in the solvent
system and
the anhydrous gel matrix. Most of the traditional thickener materials used in
liquid
detergents are insoluble or at least only swellable in typical organo solvent
systems, for
example polymeric thickener materials and clays. It has now been found however
that
cellulosic type thickeners, especially non-ionic cellulosic materials are
highly suitable in
conjunction with organo solvents as defined for providing stable anhydrous
gels and
suspensions with little or no syneresis. Suitable thickener materials for use
herein include
hydroxyethyl and hydroxymethyl cellulose (ETHOCEL and METHOCEL~ available
from Dow Chemical), hydroxpropyl cellulose (Klucel H and Klucel M) and
mixtures
thereof. Preferably, the thickener system used herein is in levels of from
about 0.05% to
about 2%, preferably from about 0.1 % to about 1 % and more preferably from
about 0.2%
to about 0.6% by weight of the composition. Suitable thickening systems for
use herein
comprise at least about 50%, preferably at least about 80%, more preferably at
least about
95% and especially at least about 99% of said non-ionic cellulosic material
and are
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essentially free of clay-type thickener materials or other thickener materials
which are
insoluble in the gel matrix.
Thus, according to another aspect of the invention, there is provided an
automatic
dishwashing composition in the form of an anhydrous, shear-thinning organo
solvent-
based gel comprising a soluble thickening system and wherein the organo
solvent has a
fractional polar Hansen solubility parameter from about 10% to about 40% and a
fractional dispersion Hansen solubility parameter from about 20% to about 60%.
The
compositions herein are highly suited to the preparation of stable
suspensions.
Although Stokes' law is strictly applicable to a single particle in an
infinite fluid, this law
can help to qualitatively understand and predict the stability of a
suspension. From
Stokes' law the terminal velocity of a particle in an infinite fluid, ut
(n~/s) can be
calculated as follows:
dpg~Pp -Pf)
ut =
18 ,u
where dp (m) is the particle diameter, g (m/sz) is the gravity constant, pp
(kg/m3) is the
particle density, pf (kg/m3) is the fluid density and p, (kg/m s) is the fluid
viscosity. A
perfectly stable suspension is that in which the terminal velocity of the
particle in the
given fluid is zero. Terminal velocity is determined by three variables, dp,
(pp - pf) and p..
The stability of a suspension increases as the viscosity increases, as the
particle diameter
decreases and as the difference between the liquid and the particle density
decreases. The
density difference between the particle and the liquid is fixed by the raw
materials used.
An increase in viscosity is achieved by the use of thickener agents. In shear-
thinning
systems, however, viscosity reduces under shear and leads to an increase in
terminal
velocity. The efficacy of the thickening systems utilized herein at levels of
less than 1%
with substantial absence of syneresis would suggest that they are uniquely
effective in the
way they behave under the application and removal of shear forces. Such
efficacy is
particularly important for producing compositions which are easy to pour and
capable of
being retained in a closed dishwasher dispenser as well as easy to flow once
the dispenser
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is opened. These requirements are herein fulfilled by the use of the shear-
thinning gel
compositions of the invention.
Thus according to another embodiment of the present invention there is
provided an
automatic dishwashing composition in the form of an anhydrous shear-thinning
solvent-
based gel and which comprises a detergent active or auxiliary in the form of a
particulate
suspension. Suitable organic solvents for use herein should be capable of
suspending
particulate material without reacting with it. The suspension should be stable
in order to
avoid a substantial separation of phases with time. Herein a suspension is
considered to
be stable when no visual phase separation can be observed after 30 days at
4~°C.
In a preferred embodiment the cleaning composition comprises particulate
material
having an average particle size from about 10 to about 100 pm, preferably from
about 25
to about 75 pm and preferably having less than 10% of particles below about 1
Vim, more
preferably below about 5 ~m and less than 10% of particles above about 150
Vim, more
preferably above about 100 Vim. Particle size is measured using a particle
size analyser
based on laser diffraction. This particle size distribution has been found
.especially
suitable for the particles to form a stable suspension in the organo solvent-
based gels used
herein.
Preferably the particulate material comprises a detergent active or auxiliary
selected from
bleaches, bleach activators, enzymes, alkalinity sources, builders,
surfactants and
mixtures thereof. Preferred compositions are those wherein the particulate
material
comprises a peroxygen bleaching agent and optionally an activator therefor.
The
bleaching agent can be selected from inorganic peroxides inclusive of
perborates and
percarbonates, organic peracids inclusive of preformed monoperoxy carboxylic
acids,
such as phthaloyl amido peroxy hexanoic acid, and di-acyl peroxides.
It is believed that bleach decomposition (probably due to bleaching agents
reacting with
traces of water) is mainly a self catalytic process catalysed by the free
radicals generated
from the decomposition process. Preferably, the composition of the invention
comprises
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a free radical scavenger, for reducing or stopping the bleach decomposition,
selected from
benzoic acids, sulfobenzenes and mixtures thereof.
Preferably the enzymes for use herein are enzyme prills having an average
particle size
smaller than about 100 ~,m, preferably smaller than about 75 ~,m and even more
preferably smaller than about 50 Vim. Alternatively, the enzymes could be in
the form of
a liquid anhydrous slurry stock.
In a preferred embodiment the composition of the invention is in the form of a
shear
thinning fluid having a shear index (n) (Herschel-Bulkey model) of from about
0 to about
0.8, preferably from about 0.3 to about 0.7, more preferably from about 0.4 to
about 0.6.
The fluid consistency index (K), on the other hand, can vary from about 0.1 to
about 50
Pa.s°. The shear index and consistency index are calculated (in S.I.
units) using Herschel-
Bulkey equation:
i = 'Cy -~ K'yn
The shear stress (i) is experimentally measured at different shear rate (y)
values (in the
range from about 1 s-1 and 150 s'), -the yield stress (iy) is calculated from
experimental
measurements, as described herein below, and shear stress, shear rate and
yield stress are
substituted into the equation and the shear index and consistency index are
calculated.
Rheology data is recorded at 25°C.
Especially useful for use herein are compositions having a viscosity greater
than about
8,000 cP (mPa s), preferably greater than 10,000 cP (mPa s), more preferably
greater than
15,000 cP (mPa s) as measured at a shear rate of 1 s' and a viscosity less
than about
5,000 cP (mPa s), preferably less than 2,000 cP (mPa s), more preferably less
than 1,000
cP (mPa s) as measured at a shear rate of 150 s' using the Rheometer described
below. In
addition, the compositions of the invention preferably have a yield stress of
from about 5
to about 50 Pa, preferably from about 10 to about 40 Pa and more preferably
from about
15 to about 25 Pa. Rheological data is obtained using a Rheometrics Dynamic
Stress
Rheometer with 40 mm parallel plate configuration, the plate gap being 0.9 mm
and the
shear stress ramp being from 0 to 60 Pa.. To measure yield stress, shear
stress is
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measured as a function of shear rate in the region up to about 1 s'. Shear
rate/shear stress
(Y-axis) versus shear stress (X-axis) is plotted. On the plot, a line tangent
to the X-axis is
drawn through the portion of the curve that is also parallel to the X-axis.
The yield stress
is the point where the plotted curve breaks from the tangent line.
5
Preferably, the composition used herein comprises from about 10% to about 90%,
more
preferably from about 20% to about 70% and more preferably from about 25% to
about
55% and especially from about 30% to about 35% of solvent by weight of
composition,
although solvent levels outside these ranges are also envisaged.
It is a feature of the invention that the anhydrous gel compositions provide
good stability
and compatibility of both bleaches and enzymes. Thus according to another
aspect of the
invention there is provided an organic solvent composition suitable for use in
automatic
dishwashing comprising from about 1% to about 99%, preferably from about 5% to
about
90%, especially from about 25% to about 80% and more especially from about 40%
to
about 55% of an organic solvent system for removing cooked-, baked-, or burnt-
on food
soil from cookware and tableware, from about 0.5% to about 50%, preferably
from about
5% to about 25% of bleach, from about 0.0001% to about 10% of detergency
enzyme,
and wherein the composition is in the form of an anhydrous gel comprising
bleach in the
form of a particulate suspension.
Some of the organic solvents suitable for use herein have an odor which is
perceived by
some consumers as unpleasant. In order to improve the odor perceived for the
user in
preferred embodiments an odor masking perfume can be introduced into the
composition.
The effect of the solvent system can be further improved by the addition of
certain
wetting agents. Preferably, the organic solvent system is used in conjunction
with a
wetting agent effective in lowering the surface tension of the solvent system,
preferably
to at least 1 mN/m less than that of the wetting agent. The wetting agent
itself is
preferably selected from organic surfactants having a surface tension less
than about 30
mN/m, more preferably less than about 28 mN/m and specially less than about 26
mN/m.
Preferred wetting agents for use herein are silicone polyether copolymers,
especially
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silicone poly(alkyleneoxide) copolymers wherein alkylene is selected from
ethylene,
propylene and mixtures thereof.
The compositions preferably have a pH (1% aqueous solution) in excess of about
9.0,
preferably in excess of about 10.5 and more preferably greater than about 11.
Even more
preferred are compositions having a pH greater than about 11.5, preferably
greater than
about 12 and more preferably greater than about 12.5 measured at 25°C.
A suitable way to deliver the compositions of the invention is by means of a
unit dose
product such as a water soluble capsule, pouch or sachet. Thus, in a preferred
embodiment of the invention there is provided an automatic dishwashing product
in the
form of a capsule, pouch or sachet comprising an amount and preferably a unit
dose
amount of the dishwashing compositions of the invention.
According to another aspect of the invention there is provided a mufti- phase
automatic
dishwashing product comprising separated but associated portions of an
anhydrous
composition as described hereinabove and an aqueous composition comprising one
or
more detergency actives or detergency auxiliaries. Preferably, the aqueous
composition
comprises form about 25 to about 50%, preferably form about 30 to about 40% of
solids
by weight of the composition. The composition can also comprise one or more
detergency enzymes, non-ionic surfactants, perfumes and thickeners. The pH of
the
aqueous composition is preferably from about 8 to about 12, more preferably
from about ,
9 to 11 and even more preferably from about 9 to 9.8 measured at 25°C.
In a preferred embodiment the mufti-phase cleaning product is contained and
delivered
from separate zones of a mufti-zone storage means such as a mufti-compartment
bottle or
pouch. The anhydrous and the aqueous phases are stored in different
compartments but
they can be simultaneously delivered at the same or different flowrate.
Alternatively they
can be delivered in phased or sequential fashion. In the case of mufti-phase
compositions
delivered at the same flowrate it is desirable to match the rheology of the
various
compositions. Compositions are considered to be rheology matched if they have
similar
yield stress (differing by less than about 50%, preferably by less than about
20%) and/or
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similar viscosities (differing by less than about 50%, preferably by less than
about 20%)
under the same shear conditions (especially at 1 s ' and 150 s l). Preferably
also, the
various compositions will have similar shear indices (differing by less than
about 50%,
preferably by less than about 20%).
Finally, there is also provided a method for making the anhydrous dishwashing
compositions described herein and which comprise a detergent active or
auxiliary in the
form of a particulate suspension. The method comprises the steps of
a) mixing the organo solvent with the thickener system to form a shear-
thinning
anhydrous carrier matrix;
b) milling the particulate material in a size reduction equipment to an
average particle
size from about 10 to about 100 ~.m, preferably from about 25 to about 75 ~,m
and
wherein less than 10% of particles are below about 1 pm, preferably below
about 5 ~,m
and less than 10% of particles are above about 150 pm, preferably above about
100
Vim; and
c) thereafter mixing the products of steps a) and b) to obtain a physically
stable
suspension.
There is also provided a method of washing cookware/tableware in an automatic
dishwashing machine using the compositions described herein.
Detailed description of the invention
The present invention envisages an automatic dishwashing composition in the
form of an
anhydrous, shear-thining organo solvent-based gel. It also envisages anhydrous
dishwashing compositions in the form of a particulate suspension. Especially
useful are
automatic dishwashing suspensions comprising an organic solvent, having a
cleaning
functionality, and a particulate peroxygen bleach. This will fulfil the
consumer desire of
being able to clean in an automatic dishwashing machine all kind of soils from
all kind of
cookware and tableware with a single detergent composition without the need of
pretreatment of the soiled articles.
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The present invention also envisages a multi-phase product comprising
anhydrous and
aqueous compositions and storage means comprising separate but associated
portions of
the compositions. Finally, the invention also envisages a method for making
the
anhydrous composition in the form of a suspension. The method provides a
chemically
and physically stable suspension.
The cleaning compositions herein comprise an organo solvent and a thickener
system and
can additionally comprise bleach, enzyme, alkalinity source, builder,
surfactant, free
radical scavenger, etc.
Organic solvent
The organic solvent system can simply act as a liquid carrier, but in
preferred
compositions, the solvent is capable of removing cooked-, baked- or baked-on
soils from
substrates and thus has detergent functionality in its own right. Organoamine
solvents are
particularly beneficial in this respect. In general terms, organic solvents
for use herein
should be selected so as to be compatible with the tableware/cookware as well
as with the
different parts of an automatic dishwashing machine. Furthermore, the solvent
system
(comprising a single solvent compound or a mixture of solvent compounds)
should be
effective and safe to use having a volatile organic content above 1 mm Hg (and
preferably above 0.1 mm Hg) of less than about 50%, preferably less than about
20%,
more preferably less than about 10% and even more preferably less than about
4% by
weight of the solvent system. Herein volatile organic content of the solvent
system is
defined as the content of organic components in the solvent system having a
vapor
pressure higher than the prescribed limit at 25°C and atmospheric
pressure. The
individual organic solvents used herein generally have a boiling point above
about 150°C,
flash point above about 50°C, preferably above 100°C and vapor
pressure below about 1
mm Hg, preferably below 0.1 mm Hg at 25°C and atmospheric pressure. In
addition, the
individual organic solvents preferably have a molar volume of less than about
500,
preferably less than about 250, more preferably less than about 200 cm3/mol,
these molar
volumes being preferred from the viewpoint of providing optimum soil
penetration and
swelling. In highly preferred embodiments, the solvent is essentially free
(contains less
than about 5% by weight) of solvent components having a boiling point below
about
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150°C, flash point below about 100°C or a vapor pressure above
about 1 mm Hg at 25°C
and atmospheric pressure.
A broad range of organic solvents are suitable for use herein but preferably
the organic
solvent is selected from alcohols, amines, esters, glycol ethers, glycols,
terpenes and
mixtures thereof. The organic solvent system is preferably selected from
organoamine
solvents, inclusive of alkanolamines, alkylamines, alkyleneamines and mixtures
thereof;
alcoholic solvents inclusive of aromatic, aliphatic (preferably C4 C,o) and
cycloaliphatic
alcohols and mixtures thereof; glycols and glycol derivatives inclusive of CZ
C3
(poly)alkylene glycols, glycol ethers, glycol esters and mixtures thereof; and
mixtures
selected from organoamine solvents, alcoholic solvents, and glycols and glycol
derivatives. In one preferred embodiment the organic solvent comprises
organoamine
(especially alkanolamine, more especially 2-aminalkanol) solvent and glycol
ether
solvent, preferably in a weight ratio of from about 3:1 to about 1:3, and
wherein the
glycol ether solvent is selected from 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
monobutyl ether, dipropylene glycol, dipropylene glycol methyl ether, and
mixtures
thereof. Preferably, the glycol ether is a mixture of diethylene glycol
monobutyl ether
and propylene glycol butyl ether, especially in a weight ratio of from about
1:2 to about
2:1. In other preferred embodiments, the organic solvent or solvent system is
selected
from Ci C3 alkylene, dialkylene, trialkylene and polyalkylene glycols, glycol
ethers and
esters and mixtures thereof. Of these, the polyalkylene glycols inclusive of
polyethylene
glycols having an average molecular weight in the range from about 200 to
about 700,
preferably from about 250 to about 600 are preferred in the context of capsule
and pouch
products and especially water-soluble partially hydrolysed PVA-based peroxygen
bleach-
containing capsule and pouch products from the viewpoint of providing
excellent product
stability, both chemical and physical, together with good cleaning performance
on baked-
on soils.
The optimum concentration of the solvent in the wash liquor from the viewpoint
of
achieving good cleaning performance on cooked-, baked- and burnt-on soils is
from
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about 100 ppm to about 10000 ppm, preferably from about 200 to about 8000 and
more
preferably from about 500 to about 5000 ppm.
Surfactant
5 In the composition of the present invention for use in automatic dishwashing
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
10 sarcosinates, N-acyl taurates and alkyl succinates and,sulfosuccinates,
wherein the alkyl,
alkenyl or aryl 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
15 cloud point nonionic surfactants and mixtures thereof including nonionic
alkoxylated
surfactants (especially ethoxylates derived from C6-C 1 g primary alcohols),
ethoxylated-
propoxylated alcohols (e.g., BASF's Poly-Tergent~ SLF18), epoxy-capped
poly(oxyalkylated) alcohols (e.g., BASF's 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 Ci2-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 composition. Preferred surfactants for use herein are low foaming
and include
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16
low cloud point nonionic surfactants and mixtures of higher foaming
surfactants with low
cloud point nonionic surfactants which act as suds suppresser therefor.
Builder
Builders suitable for use in detergent and cleaning compositions 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 fungal cellulases such as
Carezyme and
Celluzyme (Novo Nordisk A/S); peroxidases; lipases such as Amano-P (Amano
Pharmaceutical Co.), Ml 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 grills, granulates, or cogranulates at levels
typically in the
range from about 0.0001% to about 2% pure enzyme by weight of composition.
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Bleaching agent
Bleaching agents suitable herein include 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). 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 composition. 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 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 cobalt(III) and
related
complexes(US-A-4810410).
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
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18
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:
R10-(CH2 - i H -O)X - (CHZ -CH2 -O~ - (CH2 - i H-O)Z-H
R2 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.
Other low cloud point nonionic surfactants are the ether-capped
poly(oxyalkylated)
having the formula:
RIO(RIIO)"CH(CH3)ORIII
wherein, RI 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; RII may be the same or
different, and is
independently selected from the group consisting of branched or linear Cz to
C~ alkylene
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19
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 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.
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-1,1-diphosphonate, nitrilotriacetate, ethylenediaminotetracetate,
ethylenediamine-N,N'-disuccinate in their salt and free acid forms.
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The compositions 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 composition (especially paraffins such as Winog 70 sold by
Wintershall,
5 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 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 and fillers.
Unitised dose forms especially useful for use herein are water-soluble,
dispersible or
frangible pouches, sachets, and capsules which can be made in known manner,
for
example from extruded films or by blow-, injection- or rotary moulding..
Highly
preferred herein are water-soluble pouches. The pouch herein is typically a
closed
structure which comprises one or more compartments, made of materials
described
herein. Subject to the constraints of dispenser fit, the pouch can be of any
form, shape
and material which is suitable to hold the composition, e.g. without allowing
the release
of the composition from the pouch prior to contact of the pouch to water. The
exact
execution will depend on, for example, the type and amount of the composition
in the
pouch, the number of compartments in the pouch, the characteristics required
from the
pouch to hold, protect and deliver or release the composition and/or
components thereof.
The pouch or capsule is preferably made of a material which is soluble or
dispersible in
water, and has a water-solubility of at least 50%, preferably at least 75% or
even at least
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21
95%, as measured by the method set out here after .using a glass-filter with a
maximum
pore size of 20 microns. Preferred herein are polymeric materials.
50 grams ~ 0.1 gram of pouch material is added in a pre-weighed 400 ml beaker
and
245m1 ~ lml of distilled water is added. This is stirred vigorously on a
magnetic stirrer
set at 600 rpm, for 30 minutes. Then, the mixture is filtered through a folded
qualitative
sintered-glass filter with a pore size as defined above (max. 20 micron). 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 dispersability can be calculated.
Preferred polymers, copolymers or derivatives thereof suitable for use as
pouch or
capsule wall material are selected from polyvinyl alcohols, polyvinyl
pyrrolidone,
polyalkylene oxides, acrylamide, acrylic acid, cellulose, cellulose ethers,
cellulose esters,
cellulose amides, polyvinyl acetates, polycarboxylic acids and salts,
polyaminoacids or
peptides, polyamides, polyacrylamide, copolymers of maleic/acrylic acids,
polysaccharides including starch and natural gums such as xanthum and
carragum, and
gelatines. More preferred polymers are selected from polyacrylates and water-
soluble
acrylate copolymers, methylcellulose, carboxymethylcellulose sodium, dextrin,
ethylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose,
maltodextrin,
polymethacrylates, and most preferably selected from polyvinyl alcohols,
polyvinyl
alcohol copolymers and hydroxypropyl methyl cellulose (HPMC), and combinations
thereof. Preferably, the level of polymer in the pouch or capsule material,
for example a
PVA polymer, is at least 60%. Soft gelatin capsules are also preferred for use
herein.
The polymer can have any weight average molecular weight, preferably from
about 1000
to 1,000,000, more preferably from about 10,000 to 300,000 yet more preferably
from
about 20,000 to 150,000.
Mixtures of polymers can also be used. This can be beneficial for controlling
mechanical
and/or dissolution properties. Suitable mixtures include for example mixtures
wherein
one polymer has a higher water-solubility than another polymer, and/or one
polymer has
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22
a higher mechanical strength than another polymer. Also suitable are mixtures
of
polymers having different weight average molecular weights, for example a
mixture of
PVA or a copolymer thereof of a weight average molecular weight of about
10,000-
40,000, preferably around 20,000, and of PVA or copolymer thereof, with a
weight
average molecular weight of about 100,000 to 300,000, preferably around
150,000.
Also suitable herein are polymer blend compositions, for example comprising
hydrolytically degradable and water-soluble polymer blends such as polylactide
and
polyvinyl alcohol, obtained by mixing polylactide and polyvinyl alcohol,
typically
comprising about 1-35% by weight polylactide and about 65% to 99% by weight
polyvinyl alcohol.
Preferred for use herein are polymers which are from about 60% to about 98%
hydrolysed, preferably about 80% to about 90% hydrolysed, to improve the
dissolution
characteristics of the material.
Most preferred materials are PVA films known under the trade reference Monosol
M8630, as sold by Chris-Craft Industrial Products of Gary, Indiana, US, and
PVA films
of corresponding solubility and deformability characteristics. Other films
suitable for use
herein include films known under the trade reference PT film or the K-series
of films
supplied by Aicello, or VF-HP film supplied by Kuraray.
The pouch or capsule material herein can also comprise one or more additive
ingredients.
For example, it can be beneficial to add plasticisers, for example glycerol,
ethylene
glycol, diethyleneglycol, propylene glycol, sorbitol and mixtures thereof.
Other additives
include functional detergent additives to be delivered to the wash water, for
example
organic polymeric dispersants, etc.
Examples
Abbreviations used in Examples
In the examples, the abbreviated component identifications have the following
meanings:
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Carbonate . Anhydrous sodium carbonate
STPP (anhydrous): Sodium tripolyphosphate anhydrous
SKTP . Sodium potassium tripolyphosphate anhydrous
STPP (hydrated): Sodium tripolyphosphate hydrated to
approximately 8%
KOH : Potassium hydroxide
Silicate : Amorphous Sodium Silicate (SiO2:Na20
= from 2:1 to
4:1) .
Perborate : Sodium perborate monohydrate
PAAN : Pentaamine cobalt (III) acetate dichloride
salt
FN3 : Protease available from Genencor
Natalase : a-amylase available from Novo Nordisk
A/S
SLF 18 : Low foaming surfactant available from
BASF
ACNI : Alkyl capped non-ionic surfactant of
formula C9,1, H19/23
EO$-cyclohexyl acetal
C,4A0 : Tetradecyl dimethyl amine oxide
DPM : Dipropylene glycol methyl ether
DPG : Dipropylene glycol
2A2MP : 2-amino-2-methyl propanol
Methocel . Cellolosic thickener available from
Dow Chemical
BHT : Butyl hydroxy toluene
CaCl2 : Calcium chlorine
Proxel GXL : Preservative(1,2-benzisothiazolin-3-one)
available from
Zeneca, Inc
Polygel DI~I' . Thickener agent available from 3 V
Inc.
In the following examples all levels are quoted as parts by weight:
5-
Examples 1 to 6
The compositions of examples 1 to 6 are prepared in the following manner:
solvent and
thermally stable particulate material (i.e., sodium tripolyphosphate, sodium
potassium
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24
tripolyphosphate, silicate and carbonate) are added to a beaker. The mixture
is stirred for
3 minutes using a Cowles mixer blade. The resulting mixture is transferred to
a lab-scale
Ross emulsifier and ground for 10 minutes. After the 10 minutes the ground
mixture is
transferred back to the Cowles mixer blade and the mixture is heated, using a
hot plate,
until it reaches 30°C, at this point the thickener agent is added using
the Cowles blade
with high stirring speed. Once all the thickener is added, the beaker is
removed from the
hot plate. The mixture is stirred using the Cowles under high shear for 30
minutes. The
mixture is left without stirring for approximately 12 hours. Afterwards, the
particulate
bleach (whose particle size has been reduced to an average size of about 40 ~m
using an
attritor) and the enzymes are added to the mixture and the new mixture is
stirred using the
Cowles blade under high stirring speed to fully disperse the particulate
bleach and the
enzymes. After dispersion the new mixture is stirred for 10 minutes under
moderate to
high agitation.
Example 1 2 3 4 5 6
C,4 AO 1.50 1.54 1.55 1.54 1.0
ACNI 1.93
SLF 18 1.93 1.90 1.93 ' 1.5
STPP (anhydrous) 21.56 21.48 21.52 22.0 25.0
SKTP (anhydrous) 21.52
DPM 41.61 40.5 62.0
DPG 41.61 41.61
2A2MP 41.61
Perborate 4.34 4.34 4.34 4.34 3.5 12.395
PAAN 0.004 0.004 0.004 0.004 0.005 0.005
Natalase 0.44 0.44 0.44 0.44 0.44
FN3 0.51 0.51 0.51 0.51 0.60
Carbonate 23.44 23.44 23.44 23.44 25.0
Silicate 4.27 4.27 4.27 4.27 5.0
BHT 0.1 0.1 0.1 0.1
Methocel 0.3 0.3 0.3 0.3 0.35 0.6
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Perfume 1 1 1 1 0.105
The compositions display outstanding phase stability (no visual phase
separation after 30
days at 48°C), bleach stability (about 93% of available oxygen retained
after 6 weeks at
32°C), enzyme stability (about 93% of available oxygen retained after 6
weeks at 32°C)
5 as well as good transport stability.
Compositions of Examples 1 to 6 are used to wash a load of tableware and
cookware
having cooked-on, baked-on and burnt-on food soils. The load comprises
different soils
and different substrates: lasagne baked for 2 hours at 140°C on Pyrex,
lasagne cooked for
10 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. The load
is washed in a 5 litre
liquor capacity Bosch 6032 dishwashing machine, at 55°C without
prewash, placing 20
ml, in the main wash compartment, of the compositions given in Examples 1 to
6. The
15 compositions provide excellent removal of cooked-on, baked-on and burnt-on
food soils.
Examples 7 to 10
Examples 7 to 10 are dual systems compositions comprising an aqueous
composition and
an anhydrous composition. The anhydrous compositions are prepared in similar
manner
20 to the compositions of Examples 1 to 6. The compositions are stored in a
dual
compartment bottle and delivered simultaneously into the dishwasher dispenser.
Example 7 8 9 10
Aqueous composition
SI~TP 30 30
STPP (hydrated) 22 22
KOH 10.11 16.67 5.33 5.33
Polygel DKP 1.16 1.0 0.9 0.9
SLF18 1.0 2.5 3.0 3.0
C,4 AO . 1.33 1.60 1.60
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26
ACNI 3.0
Liquid FN3 0.6 0.6 0.9 0.9
Natalase 0.17 0.17 0.27 0.27
Propylene Glycol 0.5 2.0 6.0 6.0
Boric acid 3.0 3.0 4.0 4.0
CaCl2 0.37 0.37 0.37 0.37
Sodium benzoate 0.61 0.61 0.61 0.61
Proxel GXL 0.05 0.05 0.05 0.05
Perfume 0.1 0.1 0.1 0.1
Water up
to
100
Anhydrous composition
Cia AO 1.50 1.54 1.55 1.54
ACNI 1.93
SLF 18 1.93 1.90 1.93
STPP (anhydrous) 21.56 21.48 21.52
SKTP (anhydrous) 21.52
DPM 41.61
DPG 41.61 41.61
2A2MP 41.61
Perborate 4.34 4.34 4.34 4.34
PAAN 0.004 0.004 0.004 0.004
Natalase 0.44 0.44 0.44 0.44
FN3 0.51 0.51 0.51 0.51
Carbonate 23.44 23.44 23.44 23.44
Silicate 4.27 4.27 4.27 4.27
BHT 0.1 0.1 0.1 0.1
Methocel 0.3 0.3 0.3 0.3
Perfume 1 1 1 1
The anhydrous compositions display outstanding phase stability (no visual
phase
separation after 30 days at 48°C), bleach stability (about 93% of
available oxygen
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27
retained after 6 weeks at 32°C), enzyme stability (about 93% of
available oxygen retained
after 6 weeks at 32°C) as well as good transport stability.
The compositions of Examples 7 to 10 are used to wash a load of
tableware/cookware as
described in Examples 1 to 6. The compositions provide excellent removal of
cooked-on;
baked-on and burnt-on food soils.
Examples 11 to 14
Examples 11 to 14 are anhydrous compositions prepared in similar manner to the
compositions of Examples 1 to 6. The compositions are packaged in a single
compartment water-soluble PVA pouch (made from Monosol M8630 film as supplied
by
Chris-Craft Industrial Products) and the resulting product delivered into the
dishwasher
dispenser.
Example 11 12 13 14 15
C,4 AO 0.5 5.6 3.5
C,6AO 3.6 0.5
ACNI 4.6 4.6 2.5
SLF 18 5.6 4.6
STPP (anhydrous) 34 33 36 34 33.50
DPM 45.2 45.6 46.1
DPG 45.5 42.35
Savinase 1.7 1.6 1.6
Termamyl 1.6 1.6
Natalase 0.85
FN3 2.0 1.6 1.0 0.85
Silicate 16.0
Carbonate 10 10 10 10
Methocel 0.5 0.5 0.5 0.4 0.25
Perfume 0.5 0.5 0.5 0.5 0.2
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28
The anhydrous compositions display outstanding phase stability (no visual
phase
separation after 30 days at 48°C), bleach stability (about 93% of
available oxygen
retained after 6 weeks at 32°C), enzyme stability (about 93% of
available oxygen retained
after 6 weeks at 32°C) as well as good transport stability.
The compositions of Examples 11 to 14 are used to wash a load of
tableware/cookware as
described in Examples 1 to 6. The compositions provide excellent removal of
cooked-on,
baked-on and burnt-on food soils.
Examples 15 to 18
Examples 15 to 18 are anhydrous compositions prepared in similar manner to the
compositions of Examples 1 to 6. The compositions are packaged in a single
compartment water-soluble PVA pouch (made from Monosol M8630 film as supplied
by
Chris-Craft Industrial Products) and the resulting product delivered into the
dishwasher
dispenser.
Example 15 16 17 18
C,4 AO 1.2
C,6 AO 1.2 1.1
ACNI 1.1 1.1
SLF18 1.1
LF404 2.3
STPP (anhydrous) 34 34 34 34
Silicate 8 8 8 8
HEDP 0.7 0.7 0.7 0.7
Percarbonate 10 10 10 10
DPM 30 30
DPG 30 30
Savinase 0.5 0.5 0.5 0.5
Termamyl 0.5 0.5
FN3 0.5 0.5
CA 02415304 2003-O1-07
WO 02/06438 PCT/USO1/22707
29
Carbonate 13 13 13 13
Methocel 0.5 0.5 0.5 0.4
Perfume 0.5 0.5 0.5 0.5
The anhydrous . compositions display outstanding phase .stability (no visual
phase
separation after 30 days at 48°C), bleach stability (about 93% of
available oxygen
retained after 6 weeks at 32°C), enzyme stability (about 93% of
available oxygen retained
after 6 weeks at 32°C) as well as good transport stability.
The compositions of Examples 15 to 18 are used to wash a load of
tableware/cookware as
described in Examples 1 to 6. The compositions provide excellent removal of
cooked-on,
baked-on and burnt-on food soils.
In Examples 1 to 18, the DPM and DPG components are replaced with an equal
weight of
polyethylene glycol having a molecular weight of about 300. The resulting
compositions
display excellent phase, bleach, enzyme and transport stability. They are
also, effective in
the removal of cooked-on, baked-on and burnt-on food soils.
