Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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CLEANING COMPOSITION
Technical field
The present invention is in the field of hard surface cleaning compositions,
in particular it
relates to products and methods suitable for the removal of cooked-, baked-
and burnt-on
soils from cookware and tableware.
Background of the invention
Cooked-, baked- and burnt-on soils are amongst the most severe types of soils
to remove
from surfaces. Traditionally, the removal of cooked-, baked- and burnt-on
soils from
cookware and tableware requires soaking the soiled obj ect prior to a
mechanical action.
Apparently, the automatic dishwashing process alone does not provide a
satisfactory
removal of cooked-, baked- and burnt-on soils. Manual dishwashing process
requires a
tremendous rubbing effort to remove cooked-, baked- and burnt-on soils and
this can be
detrimental to the safety and condition of the cookware/tableware.
2o 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-A-
5,929,007
provides an aqueous hard surface cleaning composition for removing hardened
dried or
baked-on 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
haxdness
sequestering agent. The application also describes a method of cleaning a food
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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.
Thus, there is still need for cleaning compositions and methods used prior to
the washing
process of tableware and cookware soiled with cooked-on, baked-on or burnt-on
food in
order to facilitate the removal of these difficult food residues. There is
also a need for
cleaning compositions and methods having improved efficacy in baked-on soil
removal.
Summary of the invention
According to a first aspect of the present invention, there is provided a hard
surface
cleaning composition for removing cooked-, baked- or burnt-on soils (such as
grease,
meat, dairy, fruit, pasta and any other food especially difficult to remove
after the cooking
process) from cookware and tableware (including stainless steel, glass,
plastic, wood and
ceramic objects), wherein the composition comprises a soil swelling agent and
a
spreading auxiliary. In general terms, the composition has a liquid surface
tension of less
than about 26 mN/m, preferably less than about 25 mN/m, preferably less than
about 24.5
mN/m and more preferably less than about 24 mN/m and a pH, as measured in a
10%
solution in distilled water, of at least 10.5. The soil swelling agent and
spreading
auxiliary are present in the compositions herein in effective amounts, i.e.,
in amounts
effective to provide the necessary soil swelling and spreading
functionalities. The
efficacy of the soil swelling agent at low liquid surface tensions and high pH
appears to be
related to its ability to act as an agent for swelling, hydrating or otherwise
solvating the
cooked-, baked- or burnt-on soil. A soil swelling agent is understood herein
to be a
substance or composition capable of swelling cooked-, baked- or burnt-on soil
deposited
on a substrate after treating said substrate with the soil swelling agent
without the
application of external mechanical forces. Soil swelling effect can be
quantified by the
soil swelling index.
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The composition of the invention preferably has a pH, as measured in a 10%
solution in
distilled water, from at least about 10.5, preferably from about 11 to about
14 and more
preferably from about 11.5 to about 13.5. In the case of cleaning of cooked-,
baked- or
burnt-on soils cleaning performance is related in part to the high pH of the
cleaning
composition. However, due to the acidic nature of some of the soils, such as
for example
cooking oil, a reserve of alkalinity is desirable in order to maintain a high
pH. On the
other hand the reserve alkalinity should not be so high as to risk damaging
the skin of the
user. Therefore, the compositions of the invention preferably have a reserve
alkalinity of
less than about 5, more preferably less than about 4 and especially less than
about 3.
"Reserve alkalinity", as used herein refers to, the ability of a composition
to maintain an
alkali pH in the presence of acid. This is relative to the ability of a
composition to have
sufficient alkali in reserve to deal with any added acid while maintaining pH.
More
specifically, it is defined as the grams of NaOH per 100 cc's, exceeding pH
9.5, in
product. The reserve alkalinity for a solution is determined in the following
manner.
A Mettler DL77 automatic titrator with a Mettler DG115-SC glass pH electrode
is
calibrated using pH 4, 7 and 10 buffers (or buffers spanning the expected pH
range). A
1% solution of the composition to be tested is prepared in distilled water.
The weight of
the sample is noted. The pH of the 1 % solution is measured and the solution
is titrated
down to pH 9.5 using a solution of 0.25N HCL. The reserve alkalinity (RA) is
calculated
in the following way:
RA= %NaOHxSpecific gravity
%NaOH=ml HClxNormality of HC1x40x 100/Weight of sample aliquot titrated(g)x
1000
The addition of low level of surfactant selected from anionic, amphoteric,
zwitterionic,
nonionic and semi-polar surfactants and mixtures thereof, to the composition
of the
invention aids the cleaning process and also helps to care for the skin of the
user.
Preferably the level of surfactant is from about 0.05 to about 10%, more
preferably from
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about 0.09 to about 5% and more preferably from 0.1 to 2%. A preferred
surfactant for
use herein is an amine oxide surfactant.
The soil swelling index (SSI) is a measure of the increased thickness of soil
after
treatment with a substance or composition in comparison to the soil before
treatment with
the substance or composition. It is believed, while not being limited by
theory, that the
thickening is caused, at least in part, by hydration or solvation of the soil.
Swelling of the
soil makes the soil easier to remove with no or minimal application of force,
e.g. wiping,
rinsing or manual and automatic dishwashing. The measuring of this change of
soil
thickness gives the SSI.
The amount of substance or composition necessary to provide soil swelling
functionality
will depend upon the nature of the substance or composition and can be
determined by
routine experimentation. Other conditions effective for soil swelling such as
pH,
temperature and treatment time can also be determined by routine
experimentation.
Preferred herein, however are substances and compositions effective in
swelling cooked-,
baked- or burnt-on soils such as polymerised grease or carbohydrate soils on
glass or
metal substrates, whereby after the substance or composition has been in
contact with the
soil for 45 minutes or less, preferably 30 min or less and more preferably 20
min or less at
20°C, the substance or composition has an SSI at 5% aqueous solution
and pH of 12.8 of
at least about 15%, preferably at least about 20% more preferably at least
about 30% and
especially at least about 50%. Preferably also the choice of soil swelling
agent is such
that the final compositions have an SSI measured as neat liquids under the
same treatment
time and temperature conditions of at least about 100%, preferably at least
about 200%
and more preferably at least about 500%. Highly preferred soil swelling agents
and final
compositions herein meet the SSI requirements on polymerized grease soils
according to
the procedure set out below.
SSI is determined herein by optical profilometry, using, for example, a Zygo
NewView
5030 Scanning White Light Interferometer. A sample of polymerized grease on a
brushed, stainless steel coupon is prepared as described hereinbelow with
regard to the
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measurement of polymerized grease removal index. Optical profilometry is then
run on a
small droplet of approximately 10 pm thickness of the grease at the edge of
the grease
sample. The thickness of the soil droplet before (S;) and after (Sf) treatment
is measured
by image acquisition by means of scanning white light interferometry. The
interferometer
5 (Zygo NewView 5030 with 20X Mirau objective) splits incoming light into a
beam that
goes to an internal reference surface and a beam that goes to the sample.
After reflection,
the beams recombine inside the interferometer, undergo constructive and
destructive
interference, and produce a light and dark fringe pattern. The data are
recorded using a
CCD (charged coupled device) camera and processed by the software of the
interferometer using Frequency Domain Analysis. The dimensions of the image
obtained
(in pixels) is then converted in real dimension (gym or mm). After the
thickness of the soil
(S;) on the coupon has been measured the coupon is soaked in the invention
composition
at ambient temperature for a given length of time and the thickness of the
soil (Sf) is
measured repeating the procedure. set out above. If necessary, the procedure
is replicated
over a sufficient member of droplets and samples to provide statistical
significance.
The SSI is calculated in the following manner:
SSI = [(Sf - S;) / S;] x 100
The function of the spreading auxiliary is to reduce the interfacial tension
between the soil
swelling agent and soil, thereby increasing the wettability of soils by the
soil swelling
agents. The spreading auxiliary when added to the compositions herein
containing soil
swelling agents leads to a lowering in the surface tension of the
compositions, preferred
spreading auxiliaries being those which lower the surface tension below that
of the
auxiliary itself. Especially useful are spreading auxiliaries able to render a
surface tension
below about 26 mN/m, preferably below about 24.5 mN/m and more preferably
below
about 24 xnN/m, and especially below about 23.5 mN/m and a pH, as measured in
a 10%
solution in distilled water, of at least 10.5. Surface tensions are measured
herein at 25°C.
Without wishing to be bound by the theory, it is believed that the soil
swelling agent
penetrates and hydrates the soils. The spreading auxiliary facilitates the
interfacial
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process between the soil swelling agent and the soil and aids swelling of the
soil. The soil
penetration and swelling is believed to weaken the binding forces between soil
and
substrate. The resulting compositions are particularly effective in removing
soils of a
polymerized baked-on nature from metallic substrates.
0
Thus according to another aspect of the invention, there is provided a hard
surface
cleaning composition for the removal of cooked-, baked- or burnt-on
polymerised grease
from metallic, especially stainless steel cookware and tableware, the
composition
comprising a polymerised grease swelling agent and a spreading auxiliary and
wherein the
composition has a liquid surface tension of less than about 26 mN/m,
preferably less than
about 24.5 mN/m and more preferably less than about 24 mN/m and a pH, as
measured in
a 10% solution in distilled water, of at least 10.5.
The compositions of the invention are also particularly effective in removing
baked-on
carbohydrate based soils from cookware/tableware, apparently by a mechanism
including
swelling and rehydration of the soils. Thus, according to another aspect of
the invention a
hard surface cleaning composition is provided for the removal of cooked-,
baked- or
burnt-on carbohydrate soils from cookware and tableware, the composition
comprising a
carbohydrate soil swelling and agent and a spreading auxiliary and wherein the
composition has a liquid surface tension of less than about 26 mN/m,
preferably less than
about 24.5 mN/m and more preferably less than about 24 mN/m and a pH, as
measured in
a 10% solution in distilled water, of at least 10.5.
Preferred carbohydrate swelling agents herein act as rehydrating agents and
are able to
decrease the area under the curve of the absorbance of carbohydrate C-O infra-
red band
(spanning a wavelenth of from about 900 cm 1 to about 1200 cm 1 with major
peaks at
about 1016 cm 1 and about 1145 cm 1) by at least about 5% and preferably at
least about
10%, after said re-hydrating agent has been in contact with the soil for less
than about 30
P
min, preferably less than about 20 min. Again the rehydrating agent is applied
in the form
of an aqueous solution or dispersion and the level effective for rehydration
is determined
by routine experimentation.
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The compositions herein are characterized.by extremely low liquid surface
tensions and
contact angles on polymerized grease-coated substrates. In preferred
embodiments of the
invention the soil swelling agent and spreading auxiliary are selected such
that the hard
surface cleaning composition displays an advancing contact angle on a
polymerised
grease-coated glass substrate at 25°C of less than about 20°,
preferably less than about 10°
and more preferably less than about 5°.
The method for determining contact angle is as follows. A sample plate
(prepared as
described below) is dipped into and pulled out of a liquid and contact angles
calculated
after Wilhelmy Method. The force exerted on the sample according to the
immersion
depth is measured (using a Kruss K12 tensiometer and System K121 software) and
is
proportional to the contact angle of the liquid on the solid surface. The
sample plate is
prepared as follows: Spray 30-50 grams of Canola Oil into a beaker. Dip a
glass slide
(3x9x0.1 cm) into the Oil and thoroughly coat the surface. This results in an
evenly
dispersed layer of oil on the surface. Adjust the weight of product on the
slide's surface
until approximately 0.5 g of oil has been delivered and evenly distributed. At
this point,
bake the slides at 245°C for 20 minutes, and allow to cool to room
temperature.
According to another aspect of the invention there is provided a hard surface
cleaning
composition for the removal of cooked-, baked- or burnt-on soils from cookware
and
tableware, the composition comprising a soil swelling agent and a spreading
auxiliary and
wherein the composition displays an advancing contact angle (as measured by
the method
described herein above) on a polymerised grease-coated glass substrate at
25°C of less
than about 20°, preferably less than about 10° and more
preferably less than about 5°.
Spreading auxiliaries for use herein can be selected generally from organic
solvents,
wetting agents and mixtures thereof. In preferred embodiments the liquid
surface tension
of the spreading auxiliary is less than about 30 mN/m, preferably less than
about 28
mN/m, more preferably less than about 26 mN/m and more preferably less than
about
24.5 mN/m. Suitable organic solvents capable of acting as spreading
auxiliaries include
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alcoholic solvents, glycols and glycol derivatives and mixtures thereof.
Preferred for use
herein are mixtures of diethylene glycol monobutyl ether and propylene glycol
butyl ether.
Wetting agents suitable for use as spreading auxiliaries 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 fox use herein is Silwet L-77.
Other suitable wetting agents include organo amine surfactants, for example
amine oxide
surfactants. Preferably, the amine oxide contains an average of from 12 to 18
carbon
atoms in the alkyl moiety, highly preferred herein being dodecyl dimethyl
amine oxide,
tetradecyl dimethyl amine oxide, hexadecyl dimethyl amine oxide and mixtures
thereof.
Highly preferred herein are hard surface cleaning compositions comprising
mixed solvent
systems having soil swelling and spreading multi-functionality. Also highly
preferred
from the viewpoint of optimum removal of baked-on polymerised soils are
compositions
comprising a solvent having a limited miscibility in water (herein referred to
as a coupling
solvent) preferably in combination with a fully-miscible solvent, both
preferably at
specific levels in composition. Thus in another aspect of the invention, there
is provided
a hard surface cleaning composition for removing cooked-, baked- or burnt-on
soils from
cookware and tableware, the composition comprising from about 10% to about
40%,
preferably from about 12% to about 20% of organic solvent including from about
1 % to
about 15% of solvent acting as soil swelling agent and from about 7% to about
30% of
solvent acting as spreading auxiliary and which includes at least about 3.5%
of a water-
miscible solvent and at least about 3.5% of a coupling solvent having limited
miscibility
in water.
A water-miscible solvent herein is a solvent which is miscible with water in '
all
proportions at 25°C. A coupling solvent with limited miscibility is a
solvent with is
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miscible with water in some but not all proportions at 25°C. Preferably
the solvent has a
solubility in water at 25°C of less than about 30 wt%, more preferably
less than about 20
wt%. Preferably also the solubility of water in the solvent at 25°C is
less than about 30
wt%, more preferably less than about 20 wt%.
A preferred spreading auxiliary herein comprises a mixture of a fully water-
miscible
organic solvent and a coupling organic solvent having limited miscibility in
water and
wherein the ratio of water-miscible organic solvent to coupling organic
solvent is in the
range from about 4:1 to about 1:20, preferably from about 2:1 to about 1:6,
more
preferably from about 1.5:1 to about 1:3. Other suitable spreading auxiliaries
comprise a
wetting agent having a liquid surface tension of less than about 30 mN/m,
preferably less
than about 28 mN/m, more preferably less than about 26 mN/m and more
preferably less
than 24.5 mN/m. Preferably the wetting agent is an amine oxide. Highly
preferred
spreading auxiliaries comprise a mixture of the coupling solvent and the
wetting agent.
Thus, according to a further aspect of the invention, there is provided a hard
surface
cleaning composition for removing cooked-, baked- or burnt-on soils from
cookware and
tableware, the composition comprising a soil swelling agent, a coupling
solvent having
limited miscibility in water and a wetting agent and wherein the composition
has a liquid
surface tension of less than about 26 mN/m and preferably less than about 24.5
mN/m.
The compositions herein are further characterised by displaying surface
tension lowering
characteristics, which is believed is important for ensuring optimum soil
removal
performance on polymerised soils. Thus, according to another aspect of the
invention,
there is provided a hard surface cleaning composition for removing cooked-,
baked- or
burnt-on soils from cookware and tableware, the composition comprising an
organic
solvent system and a wetting agent, wherein the organic solvent system
includes at least
one solvent component acting as soil swelling agent and wherein the wetting
agent is
effective in lowering the surface tension of the solvent system to at least 1
mN/m less than
that of the wetting agent.
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Preferably the compositions of the present invention have a surface tension of
less than
about 24 mN/m and more preferably less than 23.5 mN/m.
Suitable soil swelling agents for use herein can be selected from organoamine
solvents
5 inclusive of alkanolamines, alkylamines, alkyleneamines and mixtures
thereof.
The compositions of the invention are characterized by excellent performance
on
polymerized grease and preferably the compositions of the present invention
have a
polymerised grease removal index of at least 25%, preferably at least 50%,
more
10 preferably at least 75%. Polymerized grease removal index is a measure of
how much
soil is removed from a surface after treatment with the composition of the
invention. The
soiled substrates are soaked in the invention composition at ambient
temperature for about
45 min or less, preferably for about 30 min or less and more preferably for
about 20 min
or less and then washed in a dishwasher without detergent or rinsing agent.
The substrates
are then dried and weighed and the soil removal is determined by gravimetric
analysis.
The soiled substrates are prepared as follows: Stainless steel coupons/slides
are
thoroughly cleaned with the product of the invention -and rinsed well with
water. The
slides are placed in a 50°C room to facilitate drying, if needed. The
coupons/slides are
allowed to cool to room temperature (about half an hour). The coupons/slides
are
weighed. Canola Oil, is sprayed into a small beaker or tri-pour (100 mL
beaker, 20-30
mL of Canola Oil). A one inch paint brush is dipped into the Canola Oil. The
soaked
brush is then rotated and pressed lightly against the side of the container 4-
6 times for
each side of the brush to remove excess Canola Oil. A thin layer of Canola Oil
is painted
onto the surface of the coupon/slide. Each slide is then stroked gently with a
dry brush in
order to ensure that only a thin coating of Canola Oil is applied (two even
strokes should
sufficiently remove excess). In this manner 0.1-0.2g of soil will be applied
to the
coupon/slide. The coupons/slides are arranged on a perfectly level cookie
sheet or oven
rack and placed in a preheated oven at 245°C. The slides/coupons axe
baked for 20
minutes. Coupons/slides are allowed to cool to room temperature (45 minutes).
The cool
coupons/slides are then weighed.
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It is a feature of the solvent-based compositions of the invention that they
display
excellent performance in direct application to soiled cookware and tableware.
The
organic solvent system includes at least one solvent component acting as soil
swelling
agent and desirably has a liquid surface tension of less than about 27 mN/m,
preferably
less than about 26 mN/m, more preferably less than about 25 mN/m. Furthermore,
the
organic solvent system preferably comprises a plurality of solvent components
in levels
such that the solvent system has an advancing contact angle on polymerised
grease-coated
glass substrate of less than that of corresponding compositions containing the
individual
components of the solvent system. Such solvent systems and compositions are
formed to
1 o be optimum for the removal of baked-on soils having a high carbon content
from
cookware and tableware. The compositions are preferably in the form of a
liquid or gel
having a pH of greater than about 9, preferably greater than 10.5 and
preferably greater
than about 11 as measured at 25°C.
Apart from the solvent parameters described above, the compositions of the
invention
should also meet certain Theological and other performance parameter including
both the
ability to be sprayed and the ability to cling to surfaces. For example, it is
desirable that
the product sprayed on a vertical stainless steel surface has a flow velocity
less than about
1 cm/s, preferably less than about 0.1 cm/s. For this purpose, the product 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. Highly preferred are shear thinning liquids having a shear index of 0.5
or lower. The
fluid consistency index, on the other hand, can vary from about 0.1 to about
50 Pa.s", but
is preferably less than about 1 Pa.s". More preferably, the fluid consistency
index is from
about 0.20 to about 0.15 Pa.s". The product preferably has a viscosity from
about 0.1 to
about 200 Pa s, preferably from about 0.3 to about 20 Pa s as measured with a
Brookfield
cylinder viscometer (model LVDII) using 10 ml sample, a spindle S-31 and a
speed of 3
rpm. Specially useful for use herein are compositions having a viscosity
greater than
about 1 Pa s, preferably from about 2 Pa s to about 4 Pa s at 6 rpm, lower
than about 2 Pa
~ s, preferably from about 0.8 Pa s to about 1.2 Pa s at 30 rpm and lower than
about 1 Pa s,
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preferably from about 0.3 Pa s to about 0.5 Pa s at 60 rpm. Rheology is
measured under
ambient temperature conditions (25° C).
Suitable thickening agents for use herein include viscoelastic, thixotropic
thickening
agents at levels of from about 0.1% to about 10%, preferably from about 0.25%
to about
5%, most preferably from about 0.5% to about 3% by weight. Suitable thickening
agents
include polymers with a molecular weight from about 500,000 to about
10,000,000, more
preferably from about 750,000 to about 4,000,000. The preferred cross-linked
polycarboxylate polymer is preferably a carboxyvinyl polymer. Such compounds ~
are
disclosed in U.S. Pat. No. 2,798,053, issued on Jul. 2, 1957, to Brown.
Methods for
making carboxyvinyl polymers are also disclosed in Brown. Carboxyvinyl
polymers are
substantially insoluble in liquid, volatile organic hydrocarbons and are
dimensionally
stable on exposure to air.
Other suitable thickening agents include inorganic clays (e.g. laponites,
aluminium
silicate, bentonite, fumed silica). The preferred clay thickening agent can be
either
naturally occurnng or synthetic. Preferred synthetic clays include the
synthetic smectite-
type clay sold under the trademark Laponite by Southern Clay Products, Inc.
Particularly
useful are gel forming grades such as Laponite RD and sol forming grades such
as
Laponite RDS. Natural occurnng clays include some smectite and attapulgite
clays.
Mixtures of clays and polymeric thickeners are also suitable for use herein.
Preferred for
use herein are synthetic smectite-type clays such as Laponite and other
synthetic clays
having an average platelet size maximum dimension of less than about 100 nm.
Laponite
has a layer structure which in dispersion in water, is in the form of disc-
shaped crystals of
about 1 nm thick and about 25 nm diameter. Small platelet size is valuable
herein for
providing a good sprayability, stability, rheology and cling properties as
well as desirable
aesthetic.
Other types of thickeners which can be used in this composition include
natural gums,
such as xanthan gum, locust bean gum, guar gum, and the like. The cellulosic
type
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thickeners: hydroxyethyl and hydroxymethyl cellulose (ETHOCEL and METHOCEL~
available from Dow Chemical) can also be used. Natural gums seem to influence
the size
of the droplets when the composition is being sprayed. It has been found that
droplets
having an average equivalent geometric diameter from about 3 pm to about 10
pm,
preferably from about 4 ~,m to about 7 ~,m, as measured using a TSI Aerosizer,
help in
odor reduction. Preferred natural gum for use herein is xanthan gum.
Highly preferred herein from the viewpoint of sprayability, cling, stability,
and soil
penetration performance is a mixture of Laponite and xanthan gum.
Additionally,
Laponite/ xanthan gum mixtures help the aesthetics of the product and at the
same time
reduce the solvent odor.
In preferred embodiments the hard surface cleaning compositions comprise an
organic
solvent system including at least one solvent component acting as soil
swelling agent and
wherein the organic solvent system is selected from alcohols, amines, esters,
glycol
ethers, glycols, terpenes and mixtures thereof. Suitable organic solvents can
be selected
from organoamine solvents, inclusive of alkanolamines, alkylamines,
alkyleneamines and
mixtures thereof; alcoholic solvents inclusive of aromatic, aliphatic
(preferably C4-Clo)
and cycloaliphatic alcohols and mixtures thereof; glycols and glycol
derivatives inclusive
Of C2-C3 (poly)alkylene glycols, glycol ethers, glycol esters and mixtures
thereof; and
mixtures selected from organoamine solvents, alcoholic solvents, glycols and
glycol
derivatives. Highly preferred organoamine solvents include 2-aminoalkanol
solvents as
disclosed in US-A-5,540,846.
In preferred compositions of the present invention the organic solvent
comprises
organoamine (especially alkanolamine) 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 monobutyl ether, ethylene glycol phenyl ether and mixtures
thereof.
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Preferred organoamine for use herein are alkanolamines, especially monoethanol
amine,
methyl amine ethanol and 2-amino-2methyl-propoanol. In a preferred composition
the
glycol ether is a mixture of diethylene glycol monobutyl ether and propylene
glycol butyl
ether, preferably in a weight ratio of from about 1:2 to about 2:1.
A preferred organic solvent system for use herein has a volatile organic
content above 1
mm Hg of less than about 50%, preferably less than about 20%, more preferably
less than
about 10%. Preferably, the organic solvent is essentially free of solvent
components
having a boiling point below about 150°C, flash point below about
50°C, preferably
below 100°C or vapor pressure above about 1 mm Hg. A highly preferred
organic solvent
system has a volatile organic content 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%.
In terms of solvent parameters, the organic solvent can be selected from:
a) polar, hydrogen-bonding solvents having a Hansen solubility parameter of at
least 20
(Mpa)l~a, a polarity parameter of at least 7 (Mpa)1~2, preferably at least 12
(Mpa)1~2 and
a hydrogen bonding parameter of at least 10 (Mpa)l~z
b) polar non-hydrogen bonding solvents having a Hansen solubility parameter of
at least
20 (Mpa)l~a, a polarity parameter of at least 7 (Mpa)1~2, preferably at least
12 (Mpa)l~z
and a hydrogen bonding parameter of less than 10 (Mpa)1~2
c) amphiphilic solvents having a Hansen solubility parameter below 20
(Mpa)1~~, a
polarity parameter of at least 7 (Mpa)1~2 and a hydrogen bonding parameter of
at least 10
(Mpa)1~2
d) non-polar solvents having a polarity parameter below 7 (Mpa)1~2 and a
hydrogen
bonding parameter below 10 (Mpa)1~2 and
e) mixtures thereof.
A problem generally associated with the use of organic solvents in cleaning
compositions
is that of solvent odor - an odor which many consumers do not like and which
they
perceive as "malodorous". Such compositions can be made more attractive to
consumers
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by using a high concentration of perfumes. The addition of such high
concentrations of
perfumes can alter or reduce the overall offensive character of the
compositions, but it
often results in an undesirably overbearing perfume odor. Even when the high
perfume
concentrations adequately modify, hide or otherwise mask the composition's
malodors,
5 these high concentrations do not necessarily result in improved perfume
substantivity or
longevity, thus resulting in the recurrence of malodor after the perfume has
volatilized.
It has now been found that a select combination of perfume materials as
defined herein
can be incorporated into the compositions of the invention to effectively
reduce the
10 intensity of or mask any malodors associated with the use of solvents in
the present
compositions. Thus according to another aspect, the present invention provides
a hard
surface cleaning composition comprising organic solvent as hwerein before
described and
a solvent odor masking perfume or perfume base. In general terms, the odor-
masking
perfume or perfume base comprises a mixture of volatile and non-volatile
perfume
15 materials wherein the level of non-volatile perfume materials (boiling
point above 250°C
at 1 atmosphere pressure) is preferably greater than about 20% by weight. In a
preferred
embodiment the perfume or perfume base comprises at least 0.001% by weight of
an
ionone or mixture of ionones inclusive of alpha, beta and gamma ionones.
Preferred
ionones are selected from gamma-Methyl Ionone, Alvanone extra, Irisia Base,
Cassis
Base 345-B and mixtures thereof. The perfume or perfume base may additionally
comprise a musk. The musk preferably has a boiling point of more than about
250°C.
Preferred musks are selected from Exaltolide Total, Habonolide and mixtures
thereof.
The masking perfume or perfume base can further comprise a high volatile
perfume
component or mixture of components having a boiling point of less than about
250°C.
Preferred high volatile perfume components are selected from decyl aldehyde,
benzaldehyde, cis-3-hexenyl acetate, allyl amyl glycolate, dihydromycenol and
mixtures
thereof.
The composition can additionally comprise a cyclodextrin, in order to help
control solvent
malodor. Cyclodextrins suitable for use herein are those capable of
selectively absorbing
solvent malodor causing molecules without detrimentally affecting the odor
masking or
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16
perfume molecules. Compositions for use herein comprise from about 0.1 to
about 3%,
preferably from about 0.5 to about 2% of cyclodextrin by weight of the
composition. As
used herein, the term "cyclodextrin" includes any of the known cyclodextrins
such as
unsubstituted cyclodextrins containing from six to twelve glucose units,
especially, alpha-
s cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin and/or their derivatives
and/or
mixtures thereof. The alpha-cyclodextrin consists of six glucose units, the
beta-
cyclodextrin consists of seven glucose units, and the gamma-cyclodextrin
consists of eight
glucose units arranged in a donut-shaped ring. The specific coupling and
conformation of
the glucose units give the cyclodextrins a rigid, conical molecular structure
with a hollow
interior of a specific volume. The "lining" of the internal cavity is formed
by hydrogen
atoms and glycosidic bridging oxygen atoms, therefore this surface is fairly
hydrophobic.
The unique shape and physical-chemical property of the cavity enable the
cyclodextrin
molecules to absorb (form inclusion complexes with) organic molecules or parts
of
organic molecules which can fit into the cavity. Malodor molecules can fit
into the
cavity.
Preferred cyclodextrins are highly water-soluble such as, alpha-cyclodextrin
and
derivatives thereof, gamma-cyclodextrin and derivatives thereof, derivatised
beta-
cyclodextrins, andlor mixtures thereof. The derivatives of cyclodextrin
consist mainly of
molecules wherein some of the OH groups axe converted to OR groups.
Cyclodextrin
derivatives include, e.g., those with short chain alkyl groups such as
methylated
cyclodextrins, and ethylated cyclodextrins, wherein R is a methyl or an ethyl
group; those
with hydroxyalkyl substituted groups, such as hydroxypropyl cyclodextrins
and/or
hydroxyethyl cyclodextrins, wherein R is a -CH2-CH(OH)-CH3 or a -CH~CHZ-OH
group; branched cyclodextrins such as maltose-bonded cyclodextrins; cationic
cyclodextrins such as those containing 2-hydroxy-3(dimethylamino)propyl ether,
wherein
R is CHI-CH(OH)-CH2-N(CH3)2 which is catiouc at low pH; quaternary ammonium,
e.g., 2-hydroxy-3-(trimethylammonio)propyl ether chloride groups, wherein R is
CH2-
CH(OH)-CHI-N+(CH3)3C1-; anionic cyclodextrins such as carboxymethyl
cyclodextrins, cyclodextrin sulfates, and cyclodextrin succinylates;
amphoteric
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17
cyclodextrins such as carboxymethyl/quaternary ammonium cyclodextrins;
cyclodextrins
wherein at least one glucopyranose unit has a 3-6-anhydro-cyclomalto
structure, e.g., the
mono-3-6-anhydrocyclodextrins, as disclosed in "Optimal Performances with
Minimal
Chemical Modification of Cyclodextrins", F. Diedaini-Pilard and B. Perly, The
7th
International Cyclodextrin Symposium Abstracts, April 1994, p. 49, and
mixtures thereof.
Other cyclodextrin derivatives are disclosed in US-A-3,426,011, US-A-
3,453,257, US-A-
3,453,258, US-A-3,453,259, US-A-3,453,260, US-A-3,459,731, US-A-3,553,191, US-
A-
3,565,887, US-A-4,535,152, US-A-4,616,008, US-A-4,678,598, US-A-4,638,058, and
US-A-4,746,734.
Highly water-soluble cyclodextrins are those having water solubility of at
least about 10 g
in 100 ml of water at room temperature, preferably at least about 20 g in 100
ml of water,
more preferably at least about 25 g in 100 ml of water at room temperature.
Examples of
preferred water-soluble cyclodextrin derivatives suitable for use herein are
hydroxypropyl
alpha-cyclodextrin, methylated alpha-cyclodextrin, methylated beta-
cyclodextrin,
hydroxyethyl beta-cyclodextrin, and hydroxypropyl beta-cyclodextrin.
Hydroxyalkyl
cyclodextrin derivatives preferably have a degree of substitution of from
about 1 to about
14, more preferably from about 1.5 to about 7, wherein the total number of OR
groups per
cyclodextrin is defined as the degree of substitution. Methylated cyclodextrin
derivatives
2o typically have a degree of substitution of from about 1 to about 18,
preferably from about
3 to about 16. A known methylated beta-cyclodextrin is heptakis-2,6-di-O-
methyl-(3-
cyclodextrin, commonly known as DIMEB, in which each glucose unit has about 2
methyl groups with a degree of substitution of about 14. A preferred, more
commercially
available methylated beta-cyclodextrin is a randomly methylated beta-
cyclodextrin having
a degree of substitution of about 12.6. The preferred cyclodextrins are
available, e.g.,
from American Maize-Products Company and blacker Chemicals (USA), Inc.
The compositions of the present invention are especially useful in direct
application for
pre-treatment of cookware or tableware soiled with cooked-, baked- or burnt-on
residues
(or any other highly dehydrated soils). The compositions are applied to the
soiled
substrates in the form for example of a spray or foam prior to automatic
dishwashing,
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18
manual dishwashing, rinsing or wiping. The pre-treated cookware or tableware
can feel
very slippery and as a consequence difficult to handle during and after the
rinsing process.
This can be overcome using divalent cations such as magnesium and calcium
salts,
especially suitable for use herein is magnesium chloride. The addition of from
about
0.01% to about 5%, preferably from about 0.1% to about 3% and more preferably
from
about 0.4% to about 2% (by weight) of magnesium salts eliminates the slippery
properties
of the cookware or tableware surface without negatively impacting the
stability of
physical properties of the pre-treatment composition. The compositions of the
invention
can also be used as automatic dishwashing detergent compositions or as a
component
thereof.
In a method aspect, the invention provides a method of removing cooked-, baked-
or
burnt-on soils from cookware and tableware comprising treating the
cookware/tableware
with the hard surface cleaning composition of the invention. There is also
provided a
method of removing cooked-, baked- or burnt-on polymerised grease soils or
carbohydrate
soils from metallic cookware and tableware comprising treating the
cookware/tableware
with the hard surface cleaning of the present invention. Preferred methods
comprise the
step of pre-treating the cookware/tableware with the composition of the
invention prior to
manual or automatic dishwashing. If desired the process of removing of cooked-
, burnt-
and baked-on soils can be facilitated if the soiled substrate is covered with
cling film after
the cleaning composition of the invention has been applied in order to allow
swelling of
the soil to take place. Preferably, the cling film is left in place for a
period of about 1 hour
or more, preferably for about 6 hours or more.
Detailed description of the invention
The present invention envisages hard surface cleaning compositions for the pre-
treatment
of cookware and tableware soiled with cooked-, baked- or burnt-on soils in
order to
facilitate the posterior cleaning process. This is mainly achieved by
compositions
3o containing a combination of a soil swelling agent and a spreading
auxiliary. The
invention also envisages methods for the removal of the soils mentioned above.
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19
Soil swelling agent is a substance or composition effective in swelling cooked-
, baked-
and burnt-on soils as disclosed above. Preferred soil swelling agents for use
herein
include organoamine solvents.
Spreading auxiliary is a substance or composition having surface tension
lowering
properties as described above. Suitable spreading auxiliaries for use herein
include
surfactants (especially those having a surface tension of less than about 25
mN/m) such as
silicone surfactants and amine oxide surfactants, organic solvents and
mixtures thereof.
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 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 30%, more preferably less
than about
10% by weight of the solvent system. Also they should have very mild pleasant
odors.
The individual organic solvents used herein generally have a boiling point
above about
150°C, flash point above about 50°C, preferably below
100°C and vapor pressure below
about 1 mm Hg, preferably below 0.1 mrn 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.
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,
beta-aminoalkanols; secondary alkanolamines: diethanolamine,
diisopropanolamine, 2-
(methylamino)ethanol; ternary alkanolamines: triethanolamine,
triisopropanolamine);
allcylamines (e.g. primary alkylamines: monomethylamine, monoethylamine,
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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,
5 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
10 glycol, diethylene glycol, hexylene glycol (2-methyl-2, 4 pentanediol),
triethylene glycol,
composition and dipropylene glycol and other similar materials; and mixtures
thereof.
Preferred solvents to be used herein as soil swelling agents comprise
alkanolamines,
especially monoethanolamine, beta-aminoalkanols, especially 2-amine-2methyl-
propanol
15 (since it has the lowest molecular weight of any beta-aminoalkanol which
has the amine
group attached to a tertiary carbon, therefore minimize the reactivity of the
amine group)
and mixtures thereof.
Preferred solvents for use herein as spreading auxiliaries comprise glycols
and glycol
20 ethers, especially diethylene glycol monobutyl ether, propylene glycol
butyl ether and
mixtures thereof.
Apart from the soil swelling and spreading auxiliary agent the hard surface
cleaning
compositions herein can comprise additional components inclusive of
surfactants other
that the wetting agents hereinbefore described, builders, enzymes, bleaching
agents,
allcalinity sources, thickeners, stabilising components, perfumes, abrasives,
etc. The
compositions can also comprise organic solvents having a Garner or diluent
function (as
opposed to soil swelling or spreading) or some other specialised function. The
compositions can be dispensed from any suitable device, such as bottles (pump
assisted
bottles, squeeze bottles), paste dispensers, capsules, pouches and multi-
compartment
pouches.
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21
Surfactants
In compositions and methods 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). In compositions and methods of the present
invention
for use in hard surface cleaning or pretreatment prior to dishwashing, the
detergent
surfactant is preferably foamable in direct application but low foaming in
automatic
dishwashing use. Surfactants suitable herein include anionic surfactants such
as alkyl
sulfates, alkyl ether sulfates, alkyl benzene sulfonates, alkyl glyceryl
sulfonates, alkyl and
1 o alkenyl sulphonates, alkyl ethoxy caxboxylates, 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., Olin
Corporation's Poly-Tergent~ SLF18), epoxy-capped poly(oxyalkylated) alcohols
(e.g.,
Olin Corporation's Poly-Tergent~ SLF18B - see WO-A-94/22800), ether-capped
poly(oxyalkylated) alcohol surfactants, and block polyoxyethylene-
polyoxypropylene
polymeric compounds such as PLURONIC~, REVERSED PLURONIC~, and
TETRONIC~ by the BASF-Wyandotte Corp., Wyandotte, Michigan; amphoteric
surfactants such as the Clz-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
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22
surfactant for 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.
Builder
Builders suitable for use in 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.
Preferably compositions for use herein comprise silicate in order to prevent
damage to
aluminium and some painted surfaces. 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.), 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 cc and ~i amylases such as Purafect Ox AmR (Genencor) and TermamylR, Bang,
FungamylR, DuramylR, and NatalaseR (Novo); and mixtures thereof. Enzymes are
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23
preferably added herein as prills, granulates, or cogranulates at levels
typically in the
range from about 0.0001 % to about 2% pure enzyme by weight of composition.
Bleaching agent
Bleaching agents suitable herein include 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). 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 fox 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 2S%,
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(l~ and
related
complexes(LTS-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
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24
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., Olin Corporation's Poly-Tergent~
SLF18) and
epoxy-capped poly(oxyalkylated) alcohols (e.g., Olin Corporation'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 - (CH2 -CH2 -O~ - (CH2 - i H-O)Z-H
Rz R3
wherein R1 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(Ru0)nCH(CH3)OR~
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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; Rn may be the same or different,
and is
independently selected from the group consisting of branched or linear CZ to
C7 alkylene
5 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,
10 cyclic or acyclic, aliphatic or aromatic hydrocarbon radicals having from
about
1 to about 30 carbon atoms;
(b) provided that when Ra is (ii) then either: (A) at least one of Rl is other
than C2
to C3 alkylene; or (B) RZ has from 6 to 30 carbon atoms, and with the further
proviso that when RZ has from 8 to 18 carbon atoms, R is other than Cl to CS
15 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
20 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
hydroxyallcyl
25 celluloses (LJS-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
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26
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.
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,
Salzbergen, Germany), nitrogen-containing corrosion inhibitor compounds (for
example
benzotriazole and benzimadazole - see GB-A-1137741) and Mn(In compounds,
particularly Mn(I~ 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, fillers and clay.
Liquid detergent compositions can contain water and other volatile solvents as
Garners.
Low quantities of low molecular weight primary or secondary alGOhols such as
methanol,
ethanol, propanol and isopropanol can be used in the liquid detergent of the
present
invention. Other suitable carrier solvents used in low quantities includes
glycerol,
propylene glycol, ethylene glycol, 1,2-propanediol, sorbitol and mixtures
thereof.
Odor-masking base
The odor masking base (which term includes fully-formulated odor-masking
perfumes or
a base composition for use therein) is preferably a mixture of ionones, musks
and highly
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volatile perfumes. Concentrations of the odor masking base preferably range
from about
0.001% to about 3%, more preferably from about 0.006% to about 2.5%, even more
preferably from about 0.0075% to about 1%, by weight of the composition.
The ionones, musks and highly volatile perfumes of the odor masking base are
characterized in part by their respective boiling point ranges. The ionones
and musks
preferably have a boiling point at 1 atmosphere of pressure of more than about
250° C,
whereas the highly volatile perfume components have a boiling point at 1
atmosphere of
pressure of less than about 250° C. The boiling point of many perfume
materials are
disclosed in, e.g., "Perfume and Flavor Chemicals (Aroma Chemicals)," S.
Arctander,
published by the author, 1969. Other boiling point values can be obtained from
different
chemistry handbooks and databases, such as the Beilstein Handbook, Lange's
Handbook
of Chemistry, and the CRC Handbook of Chemistry and Physics. When a boiling
point is
given only at a different pressure, usually lower pressure than the normal
pressure of one
atmosphere, the boiling point at normal or ambient pressure can be
approximately
estimated by using boiling point-pressure nomographs, such as those given in
"The
Chemist's Companion," A. J. Gordon and R. A. Ford, John Wiley & Sons
Publishers,
1972, pp. 30-36. When applicable, the boiling point values can also be
calculated by
computer programs, based on molecular structural data, such as those described
in
"Computer-Assisted Prediction of Normal Boiling Points of Pyrans and
Pyrroles," D. T.
Stanton et al, J. Chem. Inf. Comput. Sci., 32 (1992), pp. 306-316, "Computer-
Assisted
Prediction of Normal Boiling Points of Furans, Tetrahydrofurans, and
Thiophenes," D. T.
Stanton et al, J. Chem. Inf. Comput. Sci., 31 (1992), pp. 301-310, and
references cited
therein, and "Predicting Physical Properties from Molecular Structure," R.
Murugan et al,
Chemtech, June 1994, pp. 17-23.
Each of the ionone perfumes, highly volatile perfumes, and musk components of
the odor
masking base are described in detail hereinafter.
Highly Volatile Perfume
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The highly volatile perfume of the odor masking base comprises perfume
materials which
compete with the malodorous solvents to bind to the nasal receptor sites.
These highly
volatile perfumes are the frst odors recognized and identified by the brain,
and help
inhibit or mask the olfactory recognition of the solvents. Concentrations of
the highly
volatile perfume range from about 15% to about 85%, preferably from about 20%
to
about 80%, more preferably from about 35% to about 75%, even more preferably
from
about 45% to about 65%, by weight of the odor masking base.
The highly volatile perfumes are more volatile than the ionone and musk
components of
the odor masking base, and have a boiling point of less than about 250°
C, preferably less
than about 230°C, more preferably less than about 220° C. under
1 atmosphere of
pressure. These highly volatile perfumes are classified as either aldehydes
having from
about 2 to about 15 carbon atoms, esters having from about 3 to about 15
carbon atoms,'
alcohols having from about 4 to about 12 carbon atoms, ethers having from
about 4 to
about 13 carbon atoms, ketones having from about 3 to about 12 carbon atoms,
or
combinations thereof.
Nonlimiting examples of suitable aldehydes include n-decyl aldehyde, 10-
undecen-1-al,
dodecanal, 3,7-dimethyl-7-hydroxyoctan-1-al, 2,4-dimethyl-3-cyclohexene
carboxaldehyde, benzaldehyde, anisic aldehyde, and mixtures thereof.
Nonlimiting examples of suitable esters include ethyl acetate, cis-3-hexenyl
acetate, 2,6-
dimethyl-2,6-octadien-8-yl acetate, benzyl acetate, l,l-dimethyl-2-phenyl
acetate, 2-
pentyloxy allyl ester, allyl hexanoate, methyl-2-aminobenzoate, and mixtures
thereof.
Nonlimiting examples of suitable alcohols include n-octyl alcohol, beta-gamma-
hexenol,
2-trans-6-cis-nonadien-1-ol, 3,7-dimethyl-trans-2,6-octadien-1-ol, 3,7-
dimethyl-6-octen-1
ol, 3,7-dimethyl-1,6-octadien-3-ol, 2,6-dimethyl-7-octen-2-ol, 2-phenylethyl
alcohol, 2
cis-3,7-dimethyl-2,6-octadien-1-ol, 1-methyl-4-iso-propyl-1-cyclohexen-8-ol,
and
mixtures thereof.
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Nonlimiting examples of suitable ethers include amyl cresol oxide, 4-ethoxy-1-
methyl-
benzol, 4-methoxy- 1-methyl benzene, methyl phenylethyl ether, and mixtures
thereof.
Nonlimiting examples of suitable ketones include dimethyl acetophenone, ethyl-
n-amyl
ketone, 2-heptanone, 2-octanone, 3-methyl-2-(cis-2-penten- 1-yl)-2-cyclopenten-
1-one, 1-
1-methyl-4-iso-propenyl-6-cyclohexen-2-one, para-tertiary-amyl cyclohexanone,
and
mixtures thereof.
Preferred highly volatile perfumes include 2-pentyloxy allyl ester sold under
the
tradename Allyl Amyl Glycolate (available from International Flavors and
Fragrances,
Inc. located in New York, N.Y., U.S.A.); benzaldehyde sold under the tradename
Amandol (available from Rhone-Poulenc, Inc located in Princeton, N.J.,
U.S.A.); cis-3-
hexenyl acetate sold under the tradename Verdural extra (available from
International
Flavors and Fragrances, Inc. located in New York, N.Y., U.S.A.); 2,6-dimethyl-
7-octen-2-
0l sold under the tradename Dihydromyrcenol (available from International
Flavors and
Fragrances, Inc. located in New York, N.Y., U.S.A.); para-tertiary-amyl
cyclohexanone
sold under the tradename Orivone (available from International Flavors and
Fragrances,
Inc. located in New York, N.Y., U.S.A.); n-decyl aldehyde sold under the
tradename
Decyl Aldehyde (available from Aceto, Corp. located in Lake Success, N.Y.,
U.S.A.); and
mixtures thereof.
Nonlimiting examples of suitable highly volatile perfumes and their respective
boiling
point values under 1 atmosphere of pressure are given in US-A-5,919,440.
Ionone
The odor masking base preferably comprises an ionone perfume component (i.e.
an
ionone or mixture of ionones) at concentrations ranging from about 15% to
about 80%,
preferably from about 16% to about 60%, more preferably from about 16% to
about 40%,
by weight of the odor masking base. Ionones are a well known class of perfume
3o chemicals derived from natural oils or manufactured synthetically, which
are typically
colorless or pale yellow liquids exhibiting woody violet-like odors.
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The ionone perfume for use in the odor masking base has a boiling point under
1
atmosphere of pressure of more than about 250° C., preferably more than
about 255° C.,
even more preferably more than about 260° C., wherein the ionone
perfume is preferably
5 selected from methyl ionones, alpha ionones, beta ionones, gamma ionones, or
combinations thereof.
Nonlimiting examples of suitable ionones include 1-(2,6,6-Trimethyl-2-
cyclohexene-1-
yl)-1,6-heptadien-3-one, 2-Allyl-para-menthene-(4(8))-ono-3, Pseudo-allyl-
alpha-ionone,
alpha-Citrylidene cyclopentanone, 5-(2,6,6-Trimethyl-2-cyclohexen-1-yl)-4-
methyl-4-
10 penten-3-one, 6-(2,6,6-Trimethyl-2-cyclohexen-1-yl)-1-methyl-5-hexen-4-one,
2,6,6-
Trimethyl cyclohexyl-1-butenone-3, Dihydro-alpha-ionone, 4-(2,6,6-
Trimethylcyclohexen-1-yl)-butan-2-one, 4-(2-Methylene-6,6-dimethylcyclohexyl)-
butan-
2-one, 1-(2,5,6,6-Tetramethyl-2-cyclohexenyl)-butan-3-one, Dihydro-beta-hone,
Dihydro-
gamma-irone, 5-(2,6,6-Trimethyl-2-cyclohexenyl)-pentan-3-one, Dihydro-iso-
methyl-
15 beta-ionone, 6-(2,6,6-Trimethyl-2-cyclohexen- 1-yl)-5-hexen-4-one, alpha-
Ethyl-2,2,6-
trimethyl cyclohexane butyric aldehyde, 4-Methyl-6-(1,1,3-trimethyl-2'-
cyclohexen-2'-yl)-
3,5-hexadien-2-one, 6,10-Dimethyl undecan-2-one, 6-(2,6,6-Trimethyl-1-
cyclohexen- 1-
yl)-1-methyl-2,5-hexadien-4-one, 6-(2,6,6-Trimethyl-2-cyclohexen- 1-yl)-1-
methyl-2,5-
hexadien-4-one, 4-(2,2,6-Trimethyl-2-cyclohexen-1-yl)-3-buten-2-one, 4-(2,6,6-
20 Trimethyl-1-cyclohexen-1-yl)-3-buten-2-one, 4-(2-Methylene-6,6-
dimethylcyclohexyl)-3-
buten-2-one, Epoxy-2,3-beta-ionone, Ethyl-2,3-epoxy-3-methyl-5-(2,6,6-
trimethyl-2-
cyclohexenyl)-4-pentenoate, alpha-ionone methylanthranilate, Methyl-2,3-epoxy-
3-
methyl-5-(2,6,6-trimethyl-2-cyclohexenyl)-4-pentenoate, 4-(2,5,6,6-Tetramethyl-
2-
cyclohexen-1-yl)-3-buten-2-one, 6-Methyl-beta-ionone, 6-Methyl-gamma-ionone, 4-
25 (2,6,6-Trimethyl-2-cyclohexenyl)-2,3-dimethyl-2-buten-1-al, 4-(2,6,6-
Trimethyl-2-
cyclohexen-1-yl)-3-methyl-3-buten-2-one, 5-(2,6,6-Trimethyl-2-cyclohexen-1-yl)-
4-
penten-3-one, 5-(2,6,6-Trimethyl-1-cyclohexen-1-yl)-4-penten-3-one, 4-(2,6,6-
Trimethyl-
3-cyclohexen-1-yl)-3-methyl-3-buten-2-one, 5-(2-Methylene-6,6-
dimethylcyclohexyl)-4-
penten-3-one, 4-(2-Methylene-6,6-dimethylcyclohexyl)-3-methyl-3-buten-2-one, 4-
30 (2,3,6,6-Tetramethyl-2-cyclohexen-1-yl)-3-buten-2-one, 4-(2,4,6,6-
Tetramethyl-2-
cyclohexen-1-yl)-3-buten-2-one, 4-(2,4,6,6-Tetramethyl-1-cyclohexen-1-yl)-3-
buten-2-
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one, 5-Methyl-1-(3-methyl-3-cyclohexenyl)- 1 ,3-hexanedione, 2-Methyl-4-(2,6,6-
trimethyl-2-cyclohexenyl)-3-buten- 1-al, 3-Methyl-4-(2,4,6-trimethyl-3-
cyclohexenyl)-3-
buten-2-one, 4-(2-Methyl-5-iso-propenyl-1-cyclopenten-1-yl)-2-butanone, 4-
(2,6,6-
Trimethyl-7-cycloheptenyl)-3-buten-2-one, 4-(2,6,6-Trimethyl-4-cyclohexenyl)-3-
buten-
2-one, 2,6-Dimethylundeca-2,6,8-trim-10-one, 2,6,12-Trimethyl-trideca-2,6,8-
trien-10-
one, 2,6-Dimethyldodeca-2,6,8-trim-10-one, 2,6,9-Trirethylundeca-2,6,8-trim-10-
one, 4-
(2,6,6-Trimethyl-2-cyclohexen-1-yl)-3-methyl-3-buten-2-one, 4-(2,4,6-Trimethyl-
3-
cyclohexen-1-yl)-3-buten-2-one, 5-(2-Methylene-6,6-dimethylcyclohexyl)-4-
penten-3-
one, and mixtures thereof.
Preferred ionones include 4-(2,6,6-Trimethyl-3-cyclohexen-1-yl)-3-methyl-3-
buten-2-one
sold under the tradename Isoraldeine (available from Givaudan Roure, Corp.
located in
Teaneck, N.J., U.S.A.); 5-(2-Methylene-6,6-dimethylcyclohexyl)-4-penten-3-one
sold
under the tradename gamma-Methyl Ionone (available from Givaudan Roure, Corp.
located in Teaneck, N.J., U.S.A.); 4-(2,2,6-Trimethyl-2-cyclohexen-1-yl)-3-
buten-2-one
sold under the tradename alpha-lonone (available from International Flavors
and
Fragrances, Inc. located in New York, N.Y., U.S.A); 4-(2,6,6-Trimethyl-1-
cyclohexen-1-
y1)-3 -buten-2-one sold under the tradename beta-Ionone (available from
International
Flavors and Fragrances, Inc. located in New York, N.Y., U.S.A); 4-(2,6,6-
Trimethyl-2-
cyclohexen-1-yl)-3-methyl-3-buten-2-one sold under the tradename Methyl lonone
(available from Bush Boake Allen, Inc. located in Montvale, N.J., U.S.A.); and
mixtures
thereof.
Ionones may be incorporated into the odor masking base as one or more
individual
perfume
chemicals or as a specialty perfume containing a combination of perfume
chemicals
including
ionone perfume chemicals. Nonlimiting examples of ionone specialty perfumes
include
Alvanone Extra available from International Flavors and Fragrances, Inc.
located in New
York, N.Y., U.S.A., Irisia Base available from Firmenich, Inc located in
Princeton, N.J.,
U.S.A., Irival available from International Flavors and Fragrances, Inc.
located in New
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York, N.Y., U.S.A., Iritone available from International Flavors and
Fragrances, Inc.
located in New York, N.Y., U.S.A., and mixtures thereof.
The musk and highly volatile perfumes for use in the odor masking base can
also be
incorporated into the base as one or more individual perfume chemicals, or as
a specialty
perfume containing a combination of perfume chemicals. A nonlimiting example
of a
preferred highly volatile specialty perfume include Cassis Base 34S-B
available from
Firmenich, Inc, located in Princeton, N.J., U.S.A.. Nonlimiting examples of
suitable
ionone perfumes and their respective boiling point values under 1 atmosphere
of pressure
are given in US-A-5,919,440.
Musk
The odor masking base preferably comprises a musk component at concentrations
of from
about S% to about 70%, preferably from about 15% to about 50%, more preferably
from
about 20% to about 3S%, by weight of the odor masking base. Musk is a well
known
class of perfumes chemicals that is typically in the form of a colorless or
light yellow
material having a distinctive, musk-like odor.
The musk component for use in the odor masking base must have a boiling point
under 1
atmosphere of pressure of more than about 2S0° C., preferably more than
about 2SS° C.,
even more preferably more than about 260° C., wherein the musk
component is preferably
a polycyclic musk, macrocyclic musk, nitrocyclic musk, or combination thereof,
each
preferred musk component having more than about 12 carbon atoms, preferably
more
than about 13 carbon atoms, more preferably more than about 1 S carbon atoms.
Suitable polycyclic musks include S-Acetyl-1,1,2,3,3,6-hexamethylindan, 4-
Acetyl-1,1-
dimethyl-6-tertiary-butylindan, 7-Acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4
tetrahydronaphthalene, 1,1,4,4-Tetramethyl-6-ethyl-7-acetyl-1,2,3,4
tetrahydronaphthalene, 1,3,4,6,7,8-Hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta
gamma-2-benzopyran, and mixtures thereof.
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Suitable macrocyclic musks include cyclopentadecanolide, cyclopentadecanolone,
cyclopentadecanone, 3-Methyl-1-cyclopentadecanone, cycloheptadecen-9-one-1,
cycloheptadecanone, cyclohexadecen-7-olide, cyclohexadecen-9-olide,
cyclohexadecanolide,
ethylene tridecane dioate, 10-oxahexadecanolide, 11-oxahexadecanolide, 12-
oxahexadecanolide, and mixtures thereof.
Suitable nitrocyclic musks include 1,1,3,3,5-Pentamethyl-4,6-dinitroindan, 2,6-
Dinitro-3-
methoxy-1-methyl-4-tertiary-butylbenzene, 2,6-Dimethyl-3,5-dinitro-4-tertiary-
butyl-
acetophenone, 2,6-Dinitro-3,4,5-trimethyl-tertiary-butyl-benzene, 2,4,6-
Triinitro-1,3-
dimethyl-5-tertiary-butylbenzene, and mixtures thereof.
Preferred musks include 1,3,4,6,7,8-Hexahydro-4,6,6,7,8,8-hexamethyl-
cyclopenta-
gaxnma-2-benzopyran sold under the tradename Galaxolide (available from
International
Flavors and Fragrances, Inc. located in New York, N.Y., U.S.A.);
cyclopentadecanolide
sold under the tradename Exaltolide (available from Firmenich, Inc. located in
Princeton,
N.J., U.S.A.); ethylene tridecane dioate sold under the tradename Ethylene
Brassylate
(available from Fragrance Resource, Inc. located in Keyport, N.J., U.S.A.); 7-
Acetyl-
1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene sold under the tradename
Tonalid
(available from Givaudan Roure, Core. located in Teaneck, N.J., U.S.A.); and
mixtures
thereof. Nonlimiting examples of suitable musks and their respective boiling
point values
under 1 atmosphere of pressure are given in US-A-5,919,440.
Examples
Abbreviations used in Exam les
In the examples, the abbreviated component identifications have the following
meanings:
Carbonate : Anhydrous sodium carbonate
Silicate : Amorphous Sodium Silicate (Si02:Na20 ratio = 2.0)
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Laponite clay : Synthetic layered silicate available from Southern Clay
Products, Inc.
SLF18 . low foaming surfactant of formula C9(PO)3(EO)12(PO)is
available from Olin Corporation
AChII . alkyl capped non-ionic surfactant of formula C9m H19/23
EO8-cyclohexyl acetal
C16A0 . hexadecyl dimethyl amine oxide
C12A0 : dodecyl dimethyl amine oxide
Proxel GXL : preservative(1,2-benzisothiazolin-3-one) available from
Zeneca, Inc
Polygel premix . 5% active Polygel DIP in water available from 3V Inc.
MEA : Monoethanolamine
MAE : 2-(methylamino)ethanol
SF1488 : Polydimethylsiloxane copolymer
Butyl Carbitol : Diethylene glycol monobutyl ether
Dowanol PNB : Propylene glycol butyl ether
In the following examples all levels are quoted as parts by weight.
Examples 1 to 16
Examples 1 to 16 illustrate pre-treatment compositions used to facilitate the
removal of
cooked-on, baked-on and burnt-on food soils prior to the dishwashing process.
The
compositions of the examples are applied to a dishware load. 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. The dishware load
is allowed to soak for 10 minutes in the compositions of the examples, then
the dishwaxe
is rinsed under cold tap water. The dishware load is thereafter washed either
manually or
in an automatic dishwashing machine, for example in a Bosch 6032 dishwashing
machine, at 55°C without prewash, using a typical dishwashing detergent
compositions
containing, for example, alkalinity source, builders, enzymes, bleach, bleach
catalyst,
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non-ionic surfactant, suds- suppresser, silver corrosion inhibitor, soil
suspending
polymers, etc. The dishware load treated with compositions of the examples and
thereafter washed in the dishwashing machines present excellent removal of
cooked-on,
baked-on and burnt-on food soils.
5
Example 1 2 3 4
Pre-treatment
composition
Butyl Carbitol 5.00 5.00 5.00 5.00
.
Dowanol PNB 5.00 5.00 5.00 5.00
MEA 5.00 5.00 5.00 5.00
Carbonate 2.00 2.00 2.00 2.00
C16 AO 3.00 1.5 1.5
SLF18 3.00 1.5
ACM 1.5
Polygel DKP 1.00 1.00 1.00 1.00
Water 79.00 79.00 79.00 79.00
Example 5 6 7 8
Pre-treatment
composition
Laponite clay 1.0 0.5 0.8 0.3
Sodium silicate 0.3 0.3 0.3 0.3
Sodium cumene 1.0 1.0 1.0 1.0
sulfonate
Butyl Carbitol 5.00 5.00 5.00 5.00
Dowanol PNB 5.00 5.00 5.00 5.00
MEA 5.00 5.00 5.00 5.00
Carbonate 2.00 2.00 2.00 2.00
C16A0 1.00 1.5 1.5
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SLF 18 3.00 1.5
ACNI 1.5
Polygel DKP 0.5 0.2 0.7
Perfiune 0.2 0.2 0.2 0.2
Water to
100
Example 9 10 11 12
Pre-treatment
composition
Laponite clay 1.0 0:5 0.8 0.6
Xanthan gum 0.1 0.3 0.2 0.4
Sodium silicate 0.3 0.3 0.3 0.3
Sodium hydroxide 0.5 1.0 1.0 1.0
Butyl Carbitol 5.00 5.00 5.00 5.00
Dowanol PNB 5.00 5.00 5.00 5.00
MEA 5.00 5.00 5.00 5.00
Carbonate 2.00 2.00 2.00 2.00
MgCl2 1.00
C16 AO 1.00 3.00 1.5 1.5
SLF18 1.5
ACNI 1.5
Masking perfume 0.1 0.1 0.1 0.1
Perfume 0.1 0.1 0.1 0.1
Water to
100
Example 13 14 15 16
Pre-treatment
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composition
Laponite clay 1.0 1.25 0.8 0.3
Xanthan gum 0.1 0.15 0.2 0.4
Sodium silicate 0.3 0.75 0.3 0.3
Sodium hydroxide 0.5 0.4 1.0 1.0
Butyl Carbitol 5.00 5.00 5.00 5.00
Dowanol PNB 5.00 5.00 5.00 5.00
MEA . 5.00 5.00 5.00 5.00
Carbonate 2.00 2.00 2.00 2.00
MgCl2 1.00
C12A0 1.00 1.0 1.5 1.5
SLF18 1.5
ACNI 1.5
Masking perfume 0.05 0.2 0.1 0.2
Perfume 0.15 0.2 0.1
Water to
100
All the examples have a liquid surface tension at 25°C of below 24.5
mN/m, a pH of at
least 12 and a 45 min soil swelling index on polymerized grease soil/stainless
steel
substrate of at least 200%.
The masking perfume composition is given in the following table:
Ingredient
Allyl amyl glycolate0.5
Alvanone extra 2.0
Benzaldehyde 0.5
Cassis base 345 3.0
Cis-3-hexenyl 1.0
acetate
Decyl aldehyde 01.0
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Dihydro Myrcenol 63.0
Exaltolide 4.50
Habanolide 10.50
Ionone gamma methyl3.0
Irisia base 10.00
Orivone 1.0
