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Patent 2416327 Summary

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(12) Patent: (11) CA 2416327
(54) English Title: LOW SURFACE TENSION, ALKALINE HARD SURFACE CLEANER CONTAINING AN ORGANOAMINE
(54) French Title: NETTOYANT DE SURFACE, ALCALIN ET A FAIBLE TENSION SUPERFICIELLE, CONTENANT UN COMPOSE D'AMINE ORGANIQUE
Status: Expired and beyond the Period of Reversal
Bibliographic Data
(51) International Patent Classification (IPC):
  • C11D 3/43 (2006.01)
  • C11D 3/30 (2006.01)
(72) Inventors :
  • FOLEY, PETER ROBERT (United States of America)
  • HUTTON, HOWARD DAVID (United States of America)
  • KAISER, CARL-ERIC (United States of America)
  • ZHU, YONG (United States of America)
  • PIERONI, LUCIO (Japan)
  • SONG, BRIAN XIAOQING (United States of America)
(73) Owners :
  • THE PROCTER & GAMBLE COMPANY
(71) Applicants :
  • THE PROCTER & GAMBLE COMPANY (United States of America)
(74) Agent: WILSON LUE LLP
(74) Associate agent:
(45) Issued: 2008-07-22
(86) PCT Filing Date: 2000-12-21
(87) Open to Public Inspection: 2002-01-31
Examination requested: 2003-01-07
Availability of licence: N/A
Dedicated to the Public: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): Yes
(86) PCT Filing Number: PCT/US2000/034907
(87) International Publication Number: WO 2002008373
(85) National Entry: 2003-01-07

(30) Application Priority Data:
Application No. Country/Territory Date
PCT/US00/19619 (United States of America) 2000-07-19
PCT/US00/20255 (United States of America) 2000-07-25

Abstracts

English Abstract


A hard surface cleaning composition for removing cooked-, baked- or burnt-on
soils from cookware and tableware, the composition comprising an organoamine
solvent and wherein the composition has a liquid surface tension of less than
about 24.5 mN/m and a pH, as measured in a 10 % solution in distilled water,
or least than 10.5. The composition can be used as pre-treatment prior to the
dishwashing process. The composition provides excellent removal of polymerised
grease from metal and glass substrates.


French Abstract

Cette invention concerne une composition de nettoyage pour surfaces dures capables d'éliminer sur des ustensiles de cuisson et des pièces de vaisselle des salissures provoquées par des denrées alimentaires brûlées, calcinées, etc. La composition se caractérise par une tension superficielle inférieure à environ 24,5 mN/m et par un pH, mesuré dans une solution à 10 % dans de l'eau distillée, d'au moins 10,5. Cette composition peut être utilisée en pré-traitement avant nettoyage au lave-vaisselle. Elle convient particulièrement bien pour l'élimination de graisse polymérisée sur des substrats en métal et en verre.

Claims

Note: Claims are shown in the official language in which they were submitted.


-38-
WHAT IS CLAIMED IS:
1. A hard surface cleaning composition for removing cooked-, baked-, or burnt-
on soils from cookware and tableware, the composition comprising
a) a solvent system comprising:
i) an organoamine solvent;
ii) a water-miscible organic solvent; and
iii) a limited water-miscible organic solvent
wherein the water-miscible organic solvent and the limited water-miscible
organic solvent are selected from the group consisting of: alcohols, glycols,
esters,
glycol ethers, terpenes and mixtures thereof; and
b) water;
wherein the composition has a liquid surface tension of less than 24.5 mN/m at
25°C.
2. The composition according to claim 1 or claim 2 wherein the composition
further comprises a surfactant.
3. The composition according to claim 1 or claim 2 wherein the composition has
a pH as measured in a 10% solution of distilled water of at least 10.5.
4. The composition according to claim 1 or claim 2 wherein the composition has
a reserve alkalinity of less than about 5.
5. The composition according to claim 1 or claim 2 wherein the surfactant is
present in the composition at a level of from about 0.05% to about 10% by
weight of
the composition.
6. The composition according to claim 1 or claim 2 wherein the surfactant is
selected from the group consisting of anionic, amphoteric, zwitterionic, non-
ionic,
semi-polar surfactants and mixtures thereof.

-39-
7. The composition according to claim 6 wherein the surfactant comprises an
amine oxide.
8. The composition according to claim 1 or claim 2 wherein the organoamine
solvent is selected from the group consisting of alkanolamines, alkylamines,
alkyleneamines and mixtures thereof.
9. The composition according to claim 8 wherein the organoamine solvent
comprises an alkanolamine.
10. The composition according to claim 1 or claim 2 wherein the water-miscible
organic solvent is selected from the group consisting of: alcohols, glycols,
glycol
ethers and mixtures thereof.
11. The composition according to claim 10 wherein the water-miscible organic
solvent comprises a glycol ether.
12. The composition according to claim 11 wherein the water-miscible organic
solvent comprises diethylene glycol monobutyl ether.
13. The composition according to claim 1 or claim 2 wherein the limited water-
miscible organic solvent is selected from the group consisting of: alcohols,
glycols,
glycol ethers, esters, terpenes and mixtures thereof.
14. The composition according to claim 13 wherein the limited water-miscible
organic solvent comprises a glycol ether.
15. The composition according to claim 14 wherein the limited water-miscible
organic solvent comprises propylene glycol butyl ether.
16. The composition according to claim 1 or claim 2 wherein the composition is
capable of displaying an advancing contact angle on a soiled glass substrate
at 25° of
less than about 200°.
17. The composition according to claim 1 or claim 2 wherein the composition
exhibits a soil swelling index of at least about 100%.

-40-
18. The composition according to claim 1 or claim 2 wherein the solvent system
is
present in the composition at a level of from about 10% to about 40% by weight
of
the composition.
19. The composition according to claim 18 wherein the solvent system comprises
from about 1% to about 15% by weight of the composition of the organoamine
solvent.
20. The composition according to claim 18 wherein the solvent system comprises
from about 7% to about 30% by weight of the composition of a mixture of the
water-
miscible and limited water-miscible organic solvent.
21. The composition according to claim 20 wherein the solvent system comprises
at least about 3.5% by weight of the composition of the water-miscible organic
solvent.
22. The composition according to claim 20 wherein the solvent system comprises
at least about 3.5% by weight of the composition of the limited water-miscible
organic solvent.
23. The composition according to claim 1 or claim 2 wherein the weight ratio
of
water-miscible organic solvent to limited water-miscible organic solvent is
from about
2:1 to about 1:6.
24. The composition according to claim 1 or claim 2 wherein the surfactant
lowers
the liquid surface of the solvent system to at least 1 mN/m at 25°C
less than the liquid
surface tension of the surfactant.
25. The composition according to claim 1 or claim 2 wherein the composition
has
a soil removal index of at least 25%.
26. The composition according to claim 1 or claim 2 wherein the composition is
in
the form of a shear thinning fluid having a shear index (n) of from about 0.3
to about
0.7 and a consistency index of from about 0.20 to about 0.15 Pa.s n .

-41-
27. The composition according to claim 26 wherein the composition has a flow
velocity of less than about I cm/s when sprayed on a vertical stainless steel
surface.
28. The composition according to claim 1 or claim 2 wherein the composition
further comprises from about 0.1% to about 10% by weight of a thickening agent
selected from the group consisting of synthetic smectite clays, natural gums
and
mixtures thereof.
29. The composition according to claim 1 or claim 2 wherein the organoamine
and
the mixture of the water-miscible and limited water-miscible organic solvents
are
present in the solvent system at a weight ratio of from about 3:1 to about
1:3.
30. The composition according to claim 1 or claim 2 wherein the solvent system
has a volatile organic solvent content above 1 mm Hg of less than about 50%.
31. The composition according to claim 1 or claim 2 wherein the solvent system
is
free of solvent components that have a boiling point below about 150°C
and/or a flash
point below about 50°C and/or a vapor pressure of above about 1 mm Hg.
32. The composition according to claim 1 or claim 2 wherein the composition is
in
the form of a dishwashing pretreatment composition.
33. The composition according to claim 1 or claim 2 wherein the composition is
in
the form of an automatic dishwashing detergent composition.
34. The composition according to claim 1 or claim 2 wherein the composition
further comprises a salt having a divalent cation.
35. The composition according to claim 1 or claim 2 wherein the composition
further comprises a perfume component.
36. The composition according to claim 35 wherein the perfume component
comprises an ionone.

-42-
37. The composition according to claim 36 wherein the ionone is derived from a
natural containing ionone material selected from the group consisting of
mimosa,
violet, iris, orris and mixtures thereof.
38. The composition according to claim 35 wherein the perfume component
comprises a music having a boiling point of greater than about 250°C.
39. The composition according to claim 1 or claim 2 wherein the composition
further comprises from 0.1 % to 3% by weight of a cyclodextrin.
40. A hard surface cleaning composition for removing cooked-, baked-, or burnt-
on soils from cookware and tableware, the composition comprising:
a) ~a solvent system comprising less than or equal to about 20% by weight
of the composition, said solvent system comprising:
i) an organoamine;
ii) a water-miscible organic solvent; and
iii) a limited water-miscible organic solvent
wherein the water-miscible organic solvent and the limited water-miscible
organic solvent are selected from the group consisting of: alcohols, glycols,
esters,
glycol ethers, terpenes and mixtures thereof; and
b) a surfactant at a level of from about 0.05% to about 10% by weight of
the composition;
wherein the composition has a liquid surface tension of less than 24.5 mN/m at
25°C.
41. A hard surface cleaning composition for removing cooked-, baked-, or burnt-
on soils from cookware and tableware, the composition comprising:
a) a solvent system comprising:
i) a water-miscible organic solvent comprising a glycol ether; and

-43-
ii) ~a limited water-miscible organic solvent comprising a
dipropylene ether;
b) ~monoethanolamine; and
c) ~a surfactant at a level of from about 0.09% to about 5% by weight of
the composition;
wherein the composition has a liquid surface tension of less than 24.5 mN/m at
25°C.

Description

Note: Descriptions are shown in the official language in which they were submitted.


CA 02416327 2006-04-11
LOW SURFACE TENSION, ALKALINE HARD SURFACE CLEANER
CONTAINING AN ORGANOAMINE
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 object 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/tablewa.re.
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
hardness
sequestering agent. The application also describes a method of cleaning a food

CA 02416327 2003-01-07
WO 02/08373 PCT/US00/34907
2
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.
Stuiunary 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 an organoamine solvent. 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 organoamine solvent is present in the
compositions herein in
an effective amount, i.e., in an amount effective to provide cooked-, baked-
or burnt-on
soil removal functionality. The efficacy of the organoamine solvent 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.

CA 02416327 2003-01-07
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3
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 dainaging
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 HClx40x 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

CA 02416327 2006-04-11
4
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 coniposition 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 organoarnine solvents effective in swelling
cooked-, baked-
or baked-on soils such as polymerised grease or carbohydrate soils on glass or
metal
substrates, whereby after the organoamine 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
organoamine 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 organoamine 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.
TM
SSI is determi.ned 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

CA 02416327 2003-01-07
WO 02/08373 PCT/US00/34907
measurement of polymerized grease removal index. Optical profilometry is then
run on a
small droplet of approximately 10 m 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 ( m or mm). After the
thickness of the soil
(Si) 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 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 composition is selected such as to display 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

CA 02416327 2003-01-07
WO 02/08373 PCT/US00/34907
6
(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 250 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 removing cooked-, baked- or burnt-on soils from cookware and
tableware, the composition comprising an organoamine solvent and wherein the
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 compositions of the invention may additionally comprise a spreading
auxiliary. The
fiuiction of the spreading auxiliary is to reduce the interfacial tension
between the
organoamine and soil, thereby increasing the wettability of soils by the
organoamine. The
spreading auxiliary when added to the compositions herein 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 mN/m, and especially
below
about 23.5 mN/m. Surface tensions are measured herein at 25 C.
Without wishing to be bound by the theory, it is believed that the organoamine
penetrates
and hydrates the soils. The spreading auxiliary facilitates the interfacial
process between
the organoamine 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.
Spreading auxiliaries for use herein can be selected generally from organic
solvents,
wetting agents and mixtures thereof. In preferred embodiments the liquid
surface tension

CA 02416327 2006-04-11
7
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
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 SilwetTcopolymers, preferred
Silwet
copolymers include Silwet L-8610, Silwet L-8600, Silwet L-77, Silwet L-7657,
Silwet L-
7650, Silwet L-7607, Silwet L-7604, Silwet L-7600, Silwet L-7280 and mixtures
thereof.
Preferred for use herein is Silwet L-77.
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 based on organoamine solvents in combination with cosolvents acting as
spreading auxiliaries. 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 organo solvent including from about 1% to about 15% of
organoamine
solvent 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.

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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
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 burn.t-on soils from
cookware and
tableware, the composition comprising an organoamine solvent, 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 coinposition 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
an organoamine solvent component and wherein the wetting agent is effective in
lowering

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9
the surface tension of the solvent system to at least 1 mN/m less than that of
the wetting
agent.
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 organoamine solvents for use herein include alkanolainines,
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
polyinerised grease removal index of at least 25%, preferably at least 50%,
more
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 are baked for
20

CA 02416327 2003-01-07
WO 02/08373 PCT/US00/34907
minutes. Coupons/slides are allowed to cool to room temperature (45 minutes).
The cool
coupons/slides are then weighed.
It is a feature of the solvent-based compositions of the invention that they
display
5 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
10 such that the solvent system has an advancing contact angle on polymerised
grease-coated
glass substrate of less than that of corresponding coinpositions containing
the individual
components of the solvent system. Such solvent systems and compositions are
formed to
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 rheological 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

CA 02416327 2003-01-07
WO 02/08373 PCT/US00/34907
11
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,
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 weiglit 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 occurring 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 occurring 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 dimensioii 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.

CA 02416327 2007-05-02
12
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
thickeners: hydroxyethyl and hydroxymethyl cellvlose (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
m,
preferably from about 4 m to about 7 m, as measured using a TSI Aerosizei
help in
odor reduction. Preferred natural gum for use herein is xanthan gam.
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, including at least one
organoamine solvent
component. 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,

CA 02416327 2003-01-07
WO 02/08373 PCT/US00/34907
13
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.
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 inm 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)"2, 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)1i2
b) polar non-hydrogen bonding solvents having a Hansen solubility parameter of
at least
20 (Mpa)1/2, a polarity parameter of at least 7(Mpa)"2, preferably at least 12
(Mpa)l12
and a hydrogen bonding parameter of less than 10 (Mpa)"2
c) amphiphilic solvents having a Hansen solubility parameter below 20
(Mpa)1/2, a
polarity parameter of at least 7(Mpa)1/2 and a hydrogen bonding parameter of
at least 10
(mPa)v2
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.

CA 02416327 2003-01-07
WO 02/08373 PCT/US00/34907
14
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
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,
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
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 organoainine solvent as herein 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
perfiune
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 lonone, 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.

CA 02416327 2003-01-07
WO 02/08373 PCT/US00/34907
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
perfume molecules. Compositions for use herein comprise from about 0.1 to
about 3%,
5 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-
cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin and/or their derivatives
and/or
mixtures thereof. The alpha-cyclodextrin consists of six glucose units, the
beta-
10 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.
15 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, and/or mixtures thereof. The derivatives of cyclodextrin
consist mainly of
molecules wherein some of the OH groups are 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-2CH2-OH
group; branched cyclodextrins such as maltose-bonded cyclodextrins; cationic
cyclodextrins such as those containing 2-hydroxy-3(dimethylamino)propyl ether,
wherein
R is CH2-CH(OH)-CH2-N(CH3)2 which is cationic at low pH; quatemary ammonium,
e.g., 2-hydroxy-3-(trimethylammonio)propyl ether chloride groups, wherein R is
CH2-

CA 02416327 2003-01-07
WO 02/08373 PCT/US00/34907
16
CH(OH)-CH2-N+(CH3)3Cl-; anionic cyclodextrins such as carboxymethyl
cyclodextrins, cyclodextrin sulfates, and cyclodextrin succinylates;
amphoteric
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-3,426,01 1, 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, metliylated 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
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 DIlVIEB, 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 Wacker 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

CA 02416327 2003-01-07
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17
(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,
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. These methods
comprise the step
of pre-treating the coolcware/tableware with the composition of the invention
prior to
manual or automatic dishwashing. If desired, the process of removal 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

CA 02416327 2003-01-07
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18
facilitate the subsequent cleaning process. This is mainly achieved by
compositions
containing an organoamine solvent for swelling the soil. The invention also
envisages
methods for the removal of the soils mentioned above.
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% and even more preferably less than about 4% by weight of the solvent
system. Also
they should have very mild pleasant odours. 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
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.
Solvents that can be used herein include: i) alcohols, such as benzyl alcohol,
1,4-
cyclohexanedimethanol, 2-ethyl-l-hexanol, furfuryl alcohol, 1,2-hexa.nediol
and other
similar materials; ii) amines, such as alkanolamines (e.g. primary
alkanolamines:
monoethanolamine, monoisopropanolamine, diethylethanolamine, ethyl
diethanolamine,

CA 02416327 2003-01-07
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19
beta-aminoalkanols; secondary alkanolamines: diethanolamine,
diisopropanolamine, 2-
(methylamino)ethanol; ternary alkanolamines: triethanolamine,
triisopropanolamine);
alkylamines (e.g. primary alkylarnines: monomethylamine, monoethylamine,
monopropylamine, monobutylamine, monopentylamine, cyclohexylamine), secondary
alkylamines: (dimethylamine), alkylene amines (primary alkylene amines:
ethylenediamine, propylenediamine) and other similar materials; iii) esters,
such as ethyl
lactate, methyl ester, ethyl acetoacetate, ethylene glycol monobutyl ether
acetate,
diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether
acetate and
other similar materials; iv) glycol ethers, such as ethylene glycol monobutyl
ether,
diethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene
glycol
monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol
monoethyl ether,
propylene glycol butyl ether and other similar materials; v) glycols, such as
propylene
glycol, diethylene glycol, hexylene glycol (2-methyl-2, 4 pentanediol),
triethylene glycol,
composition and dipropylene glycol and other similar materials; and mixtures
thereof. '
Preferred solvents to be used herein as soil swelling agents comprise
alkanolamines,
especially monoethanolamine, beta-aminoalkanols, especially 2-amine-2methyl-
propanol
(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
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,
alkalinity sources, thickeners, stabilising components, perfumes, abrasives,
etc. The
compositions can also comprise organic solvents having a carrier or diluent
function (as
opposed to soil swelling or spreading) or some other specialised function. The

CA 02416327 2003-01-07
WO 02/08373 PCT/US00/34907
compositions can be dispensed from any suitable device, such as bottles (pump
assisted
bottles, squeeze bottles), paste dispensers, capsules, pouches and multi-
compartment
pouches.
5 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
10 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
alkenyl sulphonates, alkyl ethoxy carboxylates, N-acyl sarcosinates, N-acyl
taurates and
alkyl succinates and sulfosuccinates, wherein the alkyl, alkenyl or acyl
moiety is C5-C20,
15 preferably C 10-C 18 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
20 derived from C6-C18 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 C12-C20 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-

CA 02416327 2006-04-11
21
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
surfactant for use herein in automatic dishwashing' 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

CA 02416327 2003-01-07
WO 02/08373 PCT/USOO/34907
22
SavinaseR (Novo) and MaxataseR, MaxacalR, ProperaseR and MaxapemR (Gist-
Brocades);
and a and (3 amylases such as Purafect Ox AmR (Genencor) and TermamylR, BanR,
FungamylR, DuramylR, and NatalaseR (Novo); and mixtures thereof. Enzymes are
preferably added herein as prills, granulates, or cogranulates at levels
typically in the
range from about 0.0001 % to about 2% pure enzyme by 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 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 (NOBS); amide substituted alkyl peroxyacid precursors (EP-A-
0170386); and
benzoxazin peroxyacid precursors (EP-A-0332294 and EP-A-0482807). Bleach
precursors are typically incorporated at levels in the range from about 0.5%
to about 25%,
preferably from about 1% to about 10% by weight of composition while the
preformed
organic peroxyacids themselves are typically incorporated at levels in the
range from
0.5% to 25% by weight, more preferably from 1% to 10% by weight of
composition.
Bleach catalysts preferred for use herein include the manganese
triazacyclononane and
related complexes (US-A-4246612, US-A-5227084); Co, Cu, Mn and Fe
bispyridylamine
and related complexes (US-A-5114611); and pentamine acetate cobalt(III) and
related
complexes(US-A-4810410).

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WO 02/08373 PCT/US00/34907
23
Low cloud point non-ionic surfactants and suds suppressers
The suds suppressers suitable for use herein include nonionic surfactants
having a low
cloud point. "Cloud point", as used herein, is a well known property of
nonionic
surfactants which is the result of the surfactant becoming less soluble with
increasing
temperature, the temperature at which the appearance of a second phase is
observable is
referred to as the "cloud point" (See Kirk Othmer, pp. 360-362). As used
herein, a "low
cloud point" nonionic surfactant is defined as a nonionic surfactant system
ingredient
having a cloud point of less than 30 C., preferably less than about 20 C.,
and even more
preferably less than about 10 C., and most preferably less than about 7.5 C.
Typical low
cloud point nonionic surfactants include nonionic alkoxylated surfactants,
especially
ethoxylates derived from primary alcohol, and
polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverse block
polymers. Also, such low cloud point nonionic surfactants include, for
example,
ethoxylated-propoxylated alcohol (e.g., Olin Corporation's Poly-Tergent
SLF18) and
epoxy-capped poly(oxyalkylated) alcohols (e.g., Olin Corporation's Poly-
Tergent
SLF1 SB 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:
RlO'(CHZ -CH --O)X - (CHZ -CH2 -Oh, - (CH2 - CH-O)Z-H
R2 R3
wherein R' is a linear, alkyl hydrocarbon having an average of from about 7 to
about 12
carbon atoms, Ra 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.

CA 02416327 2006-04-11
24
Other low cloud point nonionic surfactants are the ether-capped-
poly(oxyalkylated)
having the fonnula:
RIO(RIIO)nCH(CH3)ORm
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 C2 to
C7 alkylene
in any given molecule; n is a number from 1 to about 30; and RIII 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 R2 is (ii) then either: (A) at least one of R' is other
than C2
to C3 alkylene; or (B) R2 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 C5
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 SokaTan PA30, PA20,
PA1S,
PA10 and Sokalan CP10 (BASF GmbH), AcusoP45N, 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.

CA 02416327 2006-04-11
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
5 about 5% by weight of composition, for example diethylenetriamine penta
(methylene
phosphonate), ethylenediamine tetra(methylene phosphonate)
hexamethylenediamine
tetra(methylene phosphonate), ethylene diphosphonate, hydroxy-ethylene-l,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
T-M
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) amd 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, fillers and clay.
Liquid detergent compositions can contain water and other volatile solvents as
carriers.
Low quantities of low molecular weight primary or secondary alcohols such as
methanol,
ethanol, propanol and isopropanol can be used in the liquid detergent of the
present
. invention. Other suitable carrier solvents used in low quantities includes
glycerol,
propylene glycol, ethylene glycol, 1,2-propanediol, sorbitol and mixtures
thereof.

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WO 02/08373 PCT/US00/34907
26
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
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
approxiniately
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.

CA 02416327 2003-01-07
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27
Each of the ionone perfumes, highly volatile perfumes, and musk components of
the odor
masking base are described in detail hereinafter.
Highly Volatile Perfume
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 first 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 Cõ
preferably less
than about 230 C., more preferably less than about 220 C at 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-l-al,
dodecanal, 3,7-dimethyl-7-hydroxyoctan-l-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, 1,1-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-l-ol, 3,7-dimethyl-trans-2,6-octadien-l-ol, 3,7-
dimethyl-6-octen-l-

CA 02416327 2003-01-07
WO 02/08373 PCT/US00/34907
28
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-l-o1, 1-methyl-4-iso-propyl-l-cyclohexen-8-ol,
and
mixtures thereof.
Nonlimiting examples of suitable ethers include amyl cresol oxide, 4-ethoxy-l-
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-
ol 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 perfiunes and their
respective boiling
point values at 1 atmosphere of pressure are given in US-A-5,919,440.
lonone
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%,

CA 02416327 2003-01-07
WO 02/08373 PCT/US00/34907
29
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
chemicals derived from natural oils or manufactured synthetically, which are
typically
colorless'or pale yellow liquids exhibiting woody violet-like odors.
The ionone perfume for use in the odor masking base has a boiling point at 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
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-l-
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-
penten-3-one, 6-(2,6,6-Trimethyl-2-cyclohexen-1-yl)-1-methyl-5-hexen-4-one,
2,6,6-
Trimethyl cyclohexyl-l-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-irone,
Dihydro-
gamma-irone, 5-(2,6,6-Trimethyl-2-cyclohexenyl)-pentan-3-one, Dihydro-iso-
methyl-
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-l-
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-
Trimethyl-l-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-
(2,6,6-Trimethyl-2-cyclohexenyl)-2,3-dimethyl-2-buten-l-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-

CA 02416327 2003-01-07
WO 02/08373 PCT/US00/34907
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-
(2,3,6,6-Tetramethyl-2-cyclohexen-1-yl)-3-buten-2-one, 4-(2,4,6,6-Tetramethyl-
2-
cyclohexen-l-yl)-3-buten-2-one, 4-(2,4,6,6-Tetramethyl-l-cyclohexen-1-yl)-3-
buten-2-
5 one, 5-Methyl-l-(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-l-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-trien-10-one, 2,6,12-Trimethyl-trideca-2,6,8-
trien-10-
10 one, 2,6-Dimethyldodeca-2,6,8-trien-10-one, 2,6,9-Trirethylundeca-2,6,8-
trien-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.
15 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
20 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-l-
cyclohexen-l-
yl)-3 -buten-2-one sold under the tradename beta-lonone (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
25 (available from Bush Boake Allen, Inc. located in Montvale, N.J., U.S.A.);
and mixtures
thereof.
lonones 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
30 chemicals including ionone perfume chemicals. Nonlimiting examples of
ionone specialty
perfumes include Alvanone Extra available from International Flavors and
Fragrances,

CA 02416327 2007-05-02
31
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.
z~
located in New 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 thereo~
Other suitable ionones containing materials for use herein are natiual
materials such as
mimosa, violet, iris, orris 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 345-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 at 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 5% to about 70%, preferably from about 15% to about 50%, more preferably
from
about 20% to about 35%, 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
at 1
atmosphere of pressure of more than about 250 C., preferably more than about
255 C.,
even more preferably more than about 2600 C., wherein the musk component is
preferably
a polycyclic musk, macrocyclic musk, nitrocyclic musk, or combination thereot
each
preferred musk component having more than about 12 carbon atoms, preferably
more
tlm about 13 carbon atoms, more preferably more than about 15 catbon atoms.

CA 02416327 2003-01-07
WO 02/08373 PCT/US00/34907
32
Suitable polycyclic musks include 5-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-
ganuna-2-benzopyran, and mixtures thereof.
Suitable macrocyclic musks include cyclopentadecanolide, cyclopentadecanolone,
cyclopentadecanone, 3-Methyl-l-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-l-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-
gamma-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, Corp. located in Teaneck, N.J., U.S.A.); and
mixtures
thereof. Nonlimiting examples of suitable musks and their respective boiling
point values
at 1 atmosphere of pressure are given in US-A-5,919,440.

CA 02416327 2006-04-11
33
Examples
Abbreviations used in Examples
In the examples, the abbreviated component identifications have the following
meanings:
Carbonate . Anhydrous sodium carbonate
Silicate Amorphous Sodium Silicate (Si02:Na20 ratio = 2.0)
Laponite clay . Synthetic layered silicate available from Southern Clay
Products, Inc.
SLF18 . low foaming surfactant available of formula
C9(PO)3(EO)12(PO)15 from Olin Corporation
ACNI . alkyl capped non-ionic surfactant of formula C9lj I H19r23
E08-cyclohexyl acetal
C16AO . hexadecyl dimethyl amine oxide
C12A0 . dodecyl dimethyl amine oxide
Proxel GXLTM . preservative(1,2-benzisothiazolin-3-one) available from
Zeneca, Inc
Polyge premix 5% active Polygel DKP in water available from 3V Inc.
MEA . Monoethanolamine
MAE . 2-(methylamino)ethanol
SF1488 . Polydimethylsiloxane copolymer
Butyl CarbitolTM . Diethylene glycol monobutyl ether
Dowanol PNBTM : Propylene glycol butyl ether
Cyclodextrin . Beta cyclodextrin available from Cerestar
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

CA 02416327 2003-01-07
WO 02/08373 PCT/US00/34907
34
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 dishware
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,
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.
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
C16A0 3.00 1.5 1.5
SLF18 3.00 1.5
ACTII 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

CA 02416327 2003-01-07
WO 02/08373 PCT/US00/34907
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
SLF18 3.00 1.5
AC1VI 1.5
Polygel DKP 0.5 0.2 0.7
Perfume 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 0.3 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
MgC12 1.00
C16 AO 1.00 3.00 1.5 1.5

CA 02416327 2003-01-07
WO 02/08373 PCT/US00/34907
36
SLF18 1.5
ACNI 1.5
Masking perfuine 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
composition
Laponite clay 1.0 1.25 0.8 0.3
Xanthan gum 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
MgC12 1.00
C12A0 1.00 1.0 1.5 1.5
SLF18 1.5
ACNI 1.5
Cyclodextrin 1.00 1.00
Masking perfume 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%.

CA 02416327 2003-01-07
WO 02/08373 PCT/US00/34907
37
The masking perfume composition is given in the following table:
Ingredient %
Allyl amyl glycolate 0.5
Alvanone extra 2.0
Benzaldehyde 0.5
Cassis base 345 3.0
Cis-3-hexenyl acetate 1.0
Decyl aldehyde 01.0
Dihydro Myrcenol 63.0
Exaltolide 4.50
Habanolide 10.50
Ionone gamma methyl 3.0
Irisia base 10.00
Orivone 1.0

Representative Drawing

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Administrative Status

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Please note that "Inactive:" events refers to events no longer in use in our new back-office solution.

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Event History

Description Date
Appointment of Agent Requirements Determined Compliant 2017-01-04
Inactive: Office letter 2017-01-04
Inactive: Office letter 2017-01-04
Revocation of Agent Requirements Determined Compliant 2017-01-04
Appointment of Agent Request 2016-12-01
Change of Address or Method of Correspondence Request Received 2016-12-01
Revocation of Agent Request 2016-12-01
Inactive: Adhoc Request Documented 2016-11-28
Revocation of Agent Request 2016-11-03
Appointment of Agent Request 2016-11-03
Time Limit for Reversal Expired 2011-12-21
Letter Sent 2010-12-21
Grant by Issuance 2008-07-22
Inactive: Cover page published 2008-07-21
Pre-grant 2008-04-24
Inactive: Final fee received 2008-04-24
Notice of Allowance is Issued 2008-03-18
Letter Sent 2008-03-18
Notice of Allowance is Issued 2008-03-18
Inactive: IPC removed 2008-02-28
Inactive: IPC removed 2008-02-28
Inactive: IPC removed 2008-02-28
Inactive: IPC removed 2008-02-28
Inactive: IPC removed 2008-02-28
Inactive: IPC removed 2008-02-28
Inactive: IPC removed 2008-02-28
Inactive: IPC removed 2008-02-28
Inactive: IPC removed 2008-02-28
Inactive: IPC removed 2008-02-28
Inactive: IPC removed 2008-02-28
Inactive: First IPC assigned 2008-02-28
Inactive: IPC removed 2008-02-28
Inactive: Approved for allowance (AFA) 2007-12-31
Amendment Received - Voluntary Amendment 2007-05-02
Inactive: S.30(2) Rules - Examiner requisition 2006-11-02
Amendment Received - Voluntary Amendment 2006-04-11
Inactive: IPC from MCD 2006-03-12
Inactive: IPC from MCD 2006-03-12
Inactive: IPC from MCD 2006-03-12
Inactive: IPC from MCD 2006-03-12
Inactive: IPC from MCD 2006-03-12
Inactive: IPC from MCD 2006-03-12
Inactive: IPC from MCD 2006-03-12
Inactive: S.30(2) Rules - Examiner requisition 2005-10-12
Inactive: Cover page published 2003-03-10
Letter Sent 2003-03-06
Inactive: First IPC assigned 2003-03-06
Inactive: Acknowledgment of national entry - RFE 2003-03-06
Letter Sent 2003-03-06
Application Received - PCT 2003-02-19
Request for Examination Requirements Determined Compliant 2003-01-07
National Entry Requirements Determined Compliant 2003-01-07
All Requirements for Examination Determined Compliant 2003-01-07
Application Published (Open to Public Inspection) 2002-01-31

Abandonment History

There is no abandonment history.

Maintenance Fee

The last payment was received on 2007-09-25

Note : If the full payment has not been received on or before the date indicated, a further fee may be required which may be one of the following

  • the reinstatement fee;
  • the late payment fee; or
  • additional fee to reverse deemed expiry.

Please refer to the CIPO Patent Fees web page to see all current fee amounts.

Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
THE PROCTER & GAMBLE COMPANY
Past Owners on Record
BRIAN XIAOQING SONG
CARL-ERIC KAISER
HOWARD DAVID HUTTON
LUCIO PIERONI
PETER ROBERT FOLEY
YONG ZHU
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
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Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Description 2003-01-07 37 1,921
Claims 2003-01-07 8 325
Abstract 2003-01-07 1 58
Cover Page 2003-03-10 1 33
Description 2006-04-11 37 1,887
Claims 2006-04-11 6 193
Description 2007-05-02 37 1,886
Claims 2007-05-02 6 182
Cover Page 2008-07-08 1 35
Acknowledgement of Request for Examination 2003-03-06 1 185
Notice of National Entry 2003-03-06 1 225
Courtesy - Certificate of registration (related document(s)) 2003-03-06 1 130
Commissioner's Notice - Application Found Allowable 2008-03-18 1 164
Maintenance Fee Notice 2011-02-01 1 171
PCT 2003-01-07 6 196
PCT 2003-01-08 1 37
PCT 2003-01-08 2 77
Correspondence 2008-04-24 1 35
Correspondence 2016-11-03 3 139
Correspondence 2016-11-28 138 7,761
Correspondence 2016-12-01 3 128
Courtesy - Office Letter 2017-01-04 2 385
Courtesy - Office Letter 2017-01-04 2 388