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Patent 2273168 Summary

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(12) Patent Application: (11) CA 2273168
(54) English Title: IMPROVEMENTS RELATING TO BLEACHING COMPOSITIONS COMPRISING HYDROGEN PEROXIDE
(54) French Title: AMELIORATIONS CONCERNANT DES COMPOSITIONS DE BLANCHIMENT CONTENANT DU PEROXYDE D'HYDROGENE
Status: Deemed Abandoned and Beyond the Period of Reinstatement - Pending Response to Notice of Disregarded Communication
Bibliographic Data
(51) International Patent Classification (IPC):
  • C11D 3/39 (2006.01)
(72) Inventors :
  • THOMPSON, KATHERINE MARY (United Kingdom)
  • THORNTHWAITE, DAVID WILLIAM (United Kingdom)
(73) Owners :
  • UNILEVER PLC
(71) Applicants :
  • UNILEVER PLC (United Kingdom)
(74) Agent: SMART & BIGGAR LP
(74) Associate agent:
(45) Issued:
(86) PCT Filing Date: 1997-10-31
(87) Open to Public Inspection: 1998-06-04
Examination requested: 2002-09-09
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/EP1997/006164
(87) International Publication Number: WO 1998023717
(85) National Entry: 1999-05-28

(30) Application Priority Data:
Application No. Country/Territory Date
9624840.6 (United Kingdom) 1996-11-29

Abstracts

English Abstract


The invention provides a bleaching composition of pH 10-14 which comprises an
oxygen transfer agent and hydrogen peroxide. It is believed that the reaction
of hydrogen peroxide with the imine quat. oxygen transfer agents proceeds
through a different route than that of the organic and inorganic peroxides. As
a consequence, the formation of acyl hydroxamate is significantly reduced.
Furthermore it is believed that when hydrogen peroxide is used as the
bleaching agent in the pH range indicated, a surprising improvement in the
efficacy of the bleaching system occurs and it is possible to formulate
peroxide based systems which have efficacy approaching or exceeding that of
hypochlorite without the disadvantages associated with hypochlorite. A further
aspect of the present invention provides a method for bleaching a stained
substrate which comprises the step of treating the substrate with a bleaching
composition of pH 10-14, which bleaching composition comprises an oxygen
transfer agent and hydrogen peroxide.


French Abstract

L'invention concerne une composition de blanchiment de pH 10 à 14 contenant un agent de transfert d'oxygène et du peroxyde d'hydrogène. Selon l'invention, la réaction du peroxyde d'hydrogène avec les agents de transfert d'oxygène de l'imine quat. s'opère à travers un parcours différent de celui des peroxydes organiques ou inorganiques. Il en résulte une formation d'hydroxamate d'acyle sensiblement réduite. De plus, selon l'invention, en utilisant le peroxyde d'hydrogène comme l'agent de blanchiment, dans la gamme de pH indiquée, on constate une amélioration surprenante de l'efficacité du système de blanchiment, ce qui permet d'élaborer des systèmes à base de peroxyde ayant une efficacité approchant ou dépassant celle de l'hypochlorite sans les inconvénients liés à l'hypochlorite. Un autre aspect de la présente invention est un procédé de blanchiment d'un substrat taché qui consiste à traiter ledit substrat avec une composition de blanchiment de pH 10 à 14 contenant un agent de transfert d'oxygène et du peroxyde d'hydrogène.

Claims

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


-24-
CLAIMS
1. An aqueous liquid bleaching composition of pH
10-14 characterized in that it comprises hydrogen
peroxide and an imine quat oxygen tranfer agent
comprising ions of the general structure:
(R1)(R2)C=N+(R3)(R4)
wherein:
R1 and R4 are in a cis- relation and are
substituted or unsubstituted radicals selected
from the group consisting of hydrogen, phenyl,
aryl, heterocyclic ring, alkyl and cycloalkyl
radicals;
R2 is a substituted or unsubstituted radical
selected from the group consisting of hydrogen,
phenyl, aryl, heterocyclic ring, alkyl,
cycloalkyl, nito, halo, cyano, alkoxy, keto,
carboxylic acid and carboalkoxy groups; and,
R3 is a substituted or unsubstituted radical
selected from the group consisting of hydrogen,
phenyl, aryl, heterocyclic ring, alkyl,
cycloalkyl, nito, halo and cyano groups.
2. A bleaching composition according to claim 1
wherein hydrogen peroxide is present at a level
of 0.5-l0%wt on product.

-25-
3. A bleaching composition according to claim 1
wherein the weight ratio of the hydrogen peroxide
to the oxygen transfer agent falls in the range
5:1 to 20:1.
4. A bleaching composition according to claim 3
wherein the oxygen transfer agent is a
substituted or unsubstituted isoquinolinium salt.
A bleaching composition according to claim 1
having a pH of 10-12, said composition being an
aqueous liquid and comprising:
a) hydrogen peroxide at a level of 0.5-10%wt on
product,
b) 0.001-10%wt on product of an isoquinolinium
salt,
c) 0.01 to 30%wt on product of at least one
nonionic surfactant, and,
d) optional minors selected from the group
consisting of metal ion sequestering agents,
solvents and perfumes.
6 A method for bleaching a stained substrate which
comprises the step of treating the substrate with
a bleaching composition as defined in any one of
claims 1-5.

Description

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


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The present invention relates to aqueous liquid
bleaching compositions comprising hydrogen peroxide.
In household cleaning, fabric washing and in many
other areas there is a general need for agents which
can ~bleach~ unsightly materials, i.e. which can react
with these materials to decolourise them. One of the
commonest of such bleaching agents is sodium
hypochlorite, which is widely used in cleaning
compositions to decolourise soils, to assist in
cleaning through its reaction with soils and to kill
micro-organisms.
Sodium hypochlorite is a powerful oxidising agent,
which can decolourise a very large number of coloured
compounds found in soils but which has significant
limitations when used to bleach certain fatty and
pyrolised soils. Many consumers prefer not to use
chlorine-based bleach compounds due the characteristic
and pungent smell of chlorine. In some circumstances
the use of a chlorine containing bleaching composition
must be avoided due to the possibly adverse effects of
mixing such compositions with acidic bathroom cleaners
and the resulting release of chlorine gas.
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CA 02273168 1999-OS-28
WO 98/23717 PCT/EP97/06164
- 2 -
There is a need for an alternative to chlorine-based
bleaching and bleaching/cleaning agents. One well
known class of alternatives are the peroxygen
compounds. While these have been used extensively as
bleaching and cleaning agents, the efficacy of
peroxygen compounds as bleaching agents falls short of
that of hypochlorite. There is therefore a general
need to find new alternatives to chlorine based
bleaching agents and to improve the properties of
these towards that of hypochlorite.
It is known to use oxygen transfer agents such as
'imine quat' compounds to promote the bleaching
activity of peroxygen compounds. In the context of
the present invention, an oxygen transfer agent is a
species which reacts with a peroxygen compound such as
hydrogen peroxide to form an oxidative bleaching
species which oxidative bleaching species,
subsequently reacts with a substrate to regenerate the
oxygen transfer agent.
Such oxygen transfer agents include N-methyl-3.4-
dihydroisoquinolinium salts. US 5360569 discloses
that imine quat molecules can be used to promote the
activity of TAED/perborate bleaching compositions.
These systems are believed to work by generating per-
acetic acid in situ. This organic peroxide is
believed to interact with the imine quat. to bring
about the bleaching activity. US 5360568 discloses
that imine quat molecules can be used to promote the
activity of monopersulphate (an inorganic peroxygen
compound) and peroxy-adipyl-phthalimide (PAP) (an the
organic peracid).

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In the above-mentioned compositions the imine quatlis
believed to be converted, by reaction with the peracid
into an oxaziradinium salt which can act as an oxygen
donor (i.e. a bleaching species) and which is
converted back into the imine goat. The oxaziradinium
ion is however unstable at high pH in the compositions
described above, where it is believed to be converted
into an acyl hydroxamate thereby preventing the
bleaching cycle from working efficiently. As a
result, compositions have been limited in pH range and
it has proved difficult to formulate compositions
which are effective against the more recalcitrant
stains particularly hydrophobic and/or pyrolised
stains.
It is believed that the above-mentioned problem is
overcome by the use of hydrogen peroxide, rather than
an organic peracid or an inorganic peroxide, as the
source of oxidising equivalents. This enables the
formulation of compositions to bleach at relatively
high pH~s where some of the more difficult stains are
soluble and hence accessible to the formulation.
Other, hitherto unsuspected benefits arise from the
use of hydrogen peroxide as are described below.
Accordingly, the present invention provides an aqueous
liquid bleaching composition of pH 10-14 which
comprises an oxygen transfer agent and hydrogen
peroxide.
Without wishing to limit the scope of the present
specification by reference to some theory of
operation, it is believed that the reaction of
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hydrogen peroxide with the imine goat. oxygen transfer
agents proceeds through a different route than that of
the organic and inorganic peroxides mentioned above.
As a consequence, the formation of acyl hydroxamate is
significantly reduced. Furthermore it is believed
that when hydrogen peroxide is used as the bleaching
agent in the pH range indicated, a surprising
improvement in the efficacy of the bleaching system
occurs and it is possible to formulate peroxide based
systems which have efficacy approaching or exceeding
that of hypochlorite without the disadvantages
associated with hypochlorite.
A further aspect of the present invention provides a
method for bleaching a stained substrate which
comprises the step of treating the substrate with an
aqueous liquid bleaching composition of pH 10-14 which
bleaching composition comprises an oxygen transfer
agent and hydrogen peroxide.
As noted above, hydrogen peroxide is an essential
component of the compositions according to the present
invention. As hydrogen peroxide is a reactive
species, this will place some limitations on the other
components which can be present. These are described
in greater detail below.
Hydrogen peroxide is preferably present at a level of
0.5-10%wt on product, more preferably 1-5owt on
product. In typical embodiments of the invention the
weight ratio of the hydrogen peroxide to the oxygen
transfer agent falls in the range 5:1 to 20:1.

CA 02273168 1999-OS-28
WO 98/23717 PCT/EP97/06164
-
Oxvaen Transfgr Aaents
Oxygen transfer agents for use in the present
invention, include, but are not limited to, the imine
5 quat. N-methyl-3.4-dihydroisoquinolinium salts. Where
these salts are used, suitable counter-ions include
halides, sulphate, methosulphate, sulphonate,
p-toluene sulphonate and phosphate. Oxygen transfer
agents which comprise a quaternary nitrogen atom are
preferred.
A broad class of oxygen transfer agents suitable for
use in embodiments of the present invention are
compounds comprising ions of the general structure:
C Rl ) ( R., ) C=N C R3 ) C RQ )
Wherein:
R1 and Rq are in a cis- relation and are substituted or
unsubstituted moieties selected from the group
consisting of hydrogen, phenyl, aryl, heterocyclic
ring, alkyl and cycloalkyl radicals:
RZ is a substituted or unsubstituted moiety selected
from the group consisting of hydrogen, phenyl, aryl,
heterocyclic ring, alkyl, cycloalkyl, nito, halo,
cyano, alkoxy, keto, carboxylic acid and carboalkoxy
groups:
R~ is a substituted or unsubstituted moiety selected
from the group consisting of hydrogen, phenyl, aryl)
heterocyclic ring, alkyl, cycloalkyl, nito, halo and
cyano groups:
SUBSTITUTE SHEET (RULE 26)

CA 02273168 1999-OS-28
WO 98/23717 PCT/EP97/06164
- 6 -
Preferably, R1 with Rz and R3 respectively together form
a moiety selected from the group consisting of
cycloalkyl, polycyclo, heterocyclic and aromatic ring
systems.
Heterocyclic rings according to the present specifi-
cation include cycloaliphatic and cycloaromatic type
radicals incorporating an oxygen, sulphur and/or
nitrogen atom within the ring system. Representative
nitrogen heterocycles include pyridine, pyrrole, imi-
dazole, triazole, tetrazole, morpholine, pyrrolidone,
piperidene and piperazine. Suitable oxygen hetero-
cycles include furan, tetrahydrofuran and dioxane.
Sulphur heterocycles may include thiophene and
tetrahydrothiophene.
The term substituted as used in relation to R1, R." R3
and R4 includes a substituent which is nitro, halo,
cyano, C1-C20 alkyl, amino, aminoalkyl, thioalkyl,
sulphoalkyl, carboxyester, hydroxy, C1-C20 alkoxy,
polyalkoxy, or C1-C40 quaternar~r di- or tri-alkyl
ammoni um .
Preferred oxygen transfer agents are quaternary imine
salts, particularly those set forth in US patent
specification 5,360,568 (Madison and Coope), more
particularly the substituted or unsubstituted
isoquinolinium salts, preferably the 3,4 di-hydro
isoquinolinium salts and more preferably the N-methyl
3,4 di-hydro-isoquinolinium salts. N-methyl 3,4 di-
hydro-isoquinolinium p-toluene sulphonate is a
particularly preferred oxygen transfer agent.
Typically, the oxygen transfer agents are present of
levels of 0.001-10%wt on product. Preferably) the
SUBSTITUTE SHEET (RULE 26)
_._.. T

CA 02273168 1999-OS-28
WO 98/23717 PCT/EP97/06164
oxygen transfer agents are present at levels of 0.01-
l~wt on product, more preferably 0.1-0.5~wt on
product.
It is preferred that the compositions according to the
invention further comprise one or more surfactant
species. Surfactants can be nonionic, anionic,
cationic, amphoteric or zwitterionic provided that
they, and where appropriate their counter-ions, do not
react substantially with the oxygen transfer agent or
the hydrogen peroxide.
Suitable nonionic detergent active compounds can be
broadly described as compounds produced by the
condensation of alkylene oxide groups, which are
hydrophilic in nature, with an organic hydrophobic
compound which may be aliphatic ar alkyl aromatic in
nature. The length of the hydrophilic or
polyoxyalkylene radical which is condensed with any
particular hydrophobic group can be readily adjusted
to yield a water-soluble compound having the desired
degree of balance between hydrophilic and hydrophobic
elements.
Particular examples include the condensation product
of aliphatic alcohols having from $ to 22 carbon atoms
in either straight or branched chain configuration
with ethylene oxide, such as a coconut oil ethylene
oxide condensate having from 3 to 10 moles of ethylene
oxide per mole of coconut alcohol; condensates of
alkylphenols whose alkyl group contains from 6 to 12

CA 02273168 1999-OS-28
WO 98/23717 PCT/EP97/06164
g
carbon atoms with 3 to 10 moles of ethylene oxide per
mole of alkylphenol.
The preferred alkoxylated alcohol nonionic surfactants
are ethoxylated alcohols having a chain length of
C9-C11 and an EO value of at least 3 but less than 10.
Particularly preferred nonionic surfactants include
the condensation products of Clo alcohols with 3-8
moles of ethylene oxide. The preferred ethoxylated
alcohols have a calculated HLB of 10-16. An example
of a suitable surfactant is 'IMBENTIN 91-35 OFA' (TM,
ex. Kolb AG) a C9_11 alcohol with five moles of
ethoxylation.
Alternative surfactants include amine oxides, amines
and/or ethoxylates thereof. Amine oxides with a
carbon chain length of C12-C14 are particularly
preferred.
When present, the amount of nonionic detergent active
to be employed in the composition of the invention
will generally be from 0.01 to 30%wt, preferably from
0.1 to 20%wt, and most preferably from 3 to 10%wt for
non-concentrated products. Concentrated products will
have 10-20%wt nonionic surfactant present, whereas
dilute products suitable for spraying will have
0.1-5%wt nonionic surfactant present.
As noted above the pH of compositions according to the
present invention falls in the range 10-14. pH of
compositions is preferably 10-12, more preferably
10-11. At these higher pH's we have found that the
composition penetrates more readily into the soils.
SUBSTfTUTE SHEET (RULE 26)
___.___._~.~__...~ __-.__~.. _..._...~_._..

CA 02273168 1999-OS-28
WO 98/23717 PCT/EP97/06164
_ g -
As is noted in the illustrative examples given below,
the use of oxygen transfer agents at high pH is
contra-indicated by their tendency to increase the
colour of a stain rather than reduce it.
Minor components of compositions according to the
present invention include those typically present in
cleaning compositions.
In compositions which contain hydrogen peroxide it is
useful to include a metal ion complexing agent to
retard decomposition of the peroxide by any metal ions
which may be present as contaminants or such as are
introduced during processing. Again, these components
should be selected such that they do not react do not
react substantially with the oxygen transfer agent or
the hydrogen peroxide.
Preferably, cleaning and/or disinfecting compositions
according to the invention will further comprise metal
ion sequestrants such as ethylene-diamine-tetra-
acetates, amino-polyphosphonates (such as those in the
DEQUEST (TM) range) and phosphates and a wide variety
of other poly-functional organic acids and salts, can
also optionally be employed. Preferred metal ion
sequesterants are selected from dipicolinic acid)
ethylene diamine tetra acetic acid (EDTA) and its
salts, hydroxy-ethylidene diphosphonic acid (bequest
2010, RTM), ethylene diamine tetra (methylene
phosphonic acid) (bequest 2040, RTM), diethylene
triamine penta(methylene phosphonic acid) (bequest
2060, RTM), amino tri(methylene phosphonic acid)

CA 02273168 1999-OS-28
WO 98/23717 PCT/EP97/06164
- 10 -
(bequest 2000, RTM). The phosphonic acid derivatives
are particularly preferred. It is preferred that the
level of phosphonic acid derivative metal ion
complexing agent should fall into the range 0.05-50.
Preferably, cleaning and/or disinfecting compositions
according to the invention will further comprise at
least 1% of a solvent of the form R1-O- (EO) m- ( PO) n-R2,
wherein R1 and R, are independently C2-6 alkyl or H,
but not both hydrogen, m and n are independently 0-5.
More preferably, the solvent is selected from the
group comprising di-ethylene glycol mono n-butyl
ether, mono-ethylene glycol mono n-butyl ether,
propylene glycol n-butyl ether, isopropanol, ethanol,
butanol and mixtures thereof. Typically, the level of
solvent in cleaning and disinfecting compositions is
1-100, with a solvent. nonionic ratio of 1:3-3:1 being
particularly preferred.
Where compositions according to the present invention
are liquids, they can be water-thin or thickened.
Thickened compositions are advantageous in that they
cling to sloping surfaces and find particular utility
in toilet cleaners. Slight thickening of the
composition is desirable for applications in which the
composition is sprayed, so as to reduce the extent to
which small droplets are produced which might
otherwise cause respiratory irritation to the user.
Suitable thickening agents include amine oxide and
soap and systems based on nonionic surfactants.
Compositions according to the invention can also
contain, in addition to the ingredients already
mentioned, various other optional ingredients such as,
colourants, optical brighteners, soil suspending
SUBSTITUTE SHEET (RULE 26)

CA 02273168 1999-OS-28
WO 98/23717 PCT/EP97/06164
- 11 -
agents, detersive enzymes, gel-control agents, freeze-
thaw stabilisers, further bactericides, perfumes and
opacifiers .
A particularly preferred compositions according to the
present invention comprises a bleaching composition
having a pH of 10-12, said composition being an
aqueous liquid and comprising:
a) hydrogen peroxide at a level of 0.5-10%wt on
product,
b) 0.001-10%wt on product of an isoquinolinium salt,
c) 0.01 to 30%wt on product of at least one nonionic
surfactant, and,
d) optional minors selected from the group
consisting of metal ion sequestering agents,
solvents and perfumes.
Product form
Products according to the present invention are
generally liquids and preferably aqueous. However,
other product forms including pastes and solids are
also envisaged.
As will be appreciated, the product form is largely
determined by the end use and consequently liquids are
generally suitable for use as hard surface cleaners,
including cleaners for industrial, institutional and
domestic cleaning and/or disinfection of hard surfaces

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including metal, plastics materials or other polymers,
ceramic, and glass surfaces.
It is envisaged the method of the present invention
can be applied in the cleaning of surfaces used for
the preparation of food and beverages (e. g. worktops,
conveyor systems and utensils) or other industrial,
institutional and domestic surfaces such as sanitary
ware, industrial, institutional and domestic fluid
supply applications, for disinfection of medical,
surgical or dental apparatus, equipment, facilities or
supplies, catheters, contact lens , surgical dressings
or surgical instruments, in horticultural
applications, e.g. for sterilising the surfaces of
greenhouses, for soft surfaces including fabrics
(including in dressings, wipes and cloths), and non-
living materials of biological origin (such as wood).
Solid product forms are suitable for use as toilet and
urinal blocks and other uses where slow or delayed
release of the components is required.
In order that the present invention may be further
understood it will be described hereinafter by
reference to illustrative and non-limiting examples
and comparisons.
The following examples were performed using model
kitchen soils and a soiling procedure as described
below. The soils were chosen to have recalcitrant
stains, which would be difficult to bleach due to the
hydrophobic or pyrolised nature of the stain.
..
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CA 02273168 1999-OS-28
C3751' (C)
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Flat tiles, measuring 4" x 4~~ (10 x 10 cm), are cut
from white Formica sheeting and their surfaces
thoroughly cleaned using a commercially available
liquid abrasive cleaner, ~Jif~ (TM). After rinsing
with demineralised water, the tiles are allowed to dry
at room temperature.
The curcumin/oil stain is prepared by mixing 19 g of
vegetable oil and 180 g of ethanol and then adding 1 g
of pure curcumin (a pigment found in curry powder).
After thorough stirring, the resulting solution is
sprayed onto the tiles using an airbrush propellant
canister so as to give a uniform surface coverage.
The tiles are left to dry for a minimum of 10 minutes,
during which time the ethanol evaporates leaving a
bright yellow, slightly sticky, oily stain, which
cannot be removed by wiping or rinsing with water.
Curcumin is susceptible to photo-oxidation and stained
tiles should not be stored for periods exceeding 2
hours before use.
Experiments were performed with hydrogen peroxide, PAP
(peroxy-adipoyl-phthalimide), peroxymonosulphate and
sodium hypochlorite (a well known inorganic bleaching
agent ) .
Bleach solutions are prepared by dissolving the
peroxide co-oxidant in demineralised water and, where
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necessary, adding the oxygen transfer agent. Sodium
hydroxide solution (5 mol dm 3) is added dropwise to
adjust the pH to the desired value, as determined
using a pH meter. Further demineralised water is
added to the solution to give the desired final
volume.
In the examples described the oxygen transfer agent
was N-methyl 3,4 di-hydro isoquinolinium p-toluene
sulphonate. The preparation of this material is
described in US 5360569 and US 5360568 which are
incorporated herein by reference. The material is
referred to below as the 'Imine Quat'.
Hydrogen peroxide solutions are prepared to achieve a
final concentration of 3 w/w % (0.88 mol dm 3) and
used in conjunction with a 1°s molar equivalency of the
Imine Quat catalyst (0.0088 mol dm 3, 0.30 w/w %).
Solutions of potassium Caroate (TM: 6 w/w°s, equivalent
to 3 w/wo, 0.1 mol dm 3 peroxomonosulphate) and PAP
(6-[N-phthalimido]-perhexanoic acid: 2 w/ws, 0.012 mol
dm 3) were examined in combination with the same level
of Imine Quat. The potassium peroxymonosulphate
system was examined at pH 8.5 (but higher pH values
were used for hydrogen peroxide (which has a higher
pK~) and PAP (which is relatively insoluble at lower
alkalinities). Addition of a wetting agent (lo butyl
digol (TM): diethylene glycol mono n-butyl ether)
further increases the PAP solubility.
I~,'."~~~'~=n ~~~ET

CA 02273168 1999-OS-28
WO 98/23717 PCT/EP97/06164
- 15 -
(TM), di-ethylene glycol mono-n-butyl ether, was added
or used for comparison.
Soil removal experiments
Examples were performed at room temperature. A glass
ring, of diameter 50 mm and height 15 mm, is placed
over the centre of the stained tile and 5 cm' of the
aqueous bleach or surfactant solution is pipetted
within the annulus of the ring. The solution is
allowed to remain in contact with the stained tile
surface for 30 seconds, after which the glass ring is
removed and the solution poured away. The tile is
immediately rinsed with demineralised water for a
further 30 seconds and then allowed to dry. Each
solution is used to treat two tiles.
The extent of stain removal is assessed visually by a
panel of at least 15 people, using a standard scale.
Tiles are graded on an integer scale ranging from 0 to
5, where 0 denotes no visible soil removal and 5
corresponds to total removal. A minimum of two
stained tiles are treated with each bleach solution
and mean scores for each system are calculated by
averaging the scores from both tiles.
Results are shown in TABLE 1 below. From the results
presented in TABLE 1, it can be seen that a
significant improvement as regards hydrogen peroxide
bleaching is obtained in the presence of the Imine
Quat at both pH 10 and pH 10.5. A similar increase is
not seen for either the organic or inorganic peroxy
acid.

CA 02273168 1999-OS-28
WO 98123717 PCT/EP97/06164
- 16 -
Comparing the results with conventional
cleaning/bleaching systems. It can be seen that use
of an oxygen transfer agent together with hydrogen
peroxide provides results which are very favourably
comparable with hypochlorite, and significantly better
than alkali and surfactant based systems.
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CA 02273168 1999-OS-28
WO 98/23717 PCT/EP97/06164
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a w ~ ~ ~ r'
. o ~ Q
~ w
m ~ ~ n~ a
0 ~
0 ,-~ ~, a ~
'LS'~ a' ~ ~ I'-iH
w rtS.-1 ,-i
x x x z z ~a ~a
x x rl
ow ono ~a ow .-~ ,-,
M M N M r-1 r-irQ',Q,' O O

CA 02273168 1999-OS-28
WO 98/23717 PCT/EP97/06164
- 18 -
Example 2: Baked fat/flour on enamel
Soil nre~aration
Oleic acid (1 g), stearic acid (1 g) and Friol (TM)
Italian Oil (38 g) are mixed in a metal beaker and
directly heated, using a hotplate, to a temperature of
60°C, so that the mixture liquifies. Demineralised
water (100 g) is boiled and allowed to cool to 60°C
before mixing with Italian flour (40 g) to make a
thick paste.
The organic acid-oil mixture and the flour paste are
placed in a liquidiser jug and demineralised water
(280 g) added. The fat-flour mixture is blended for 5
seconds, allowed to stand for 10 seconds and then
blended for a further 5 seconds. The contents of the
liquidiser are then transferred to a glass beaker and
gent~.y warmed by direct heating over a hot-plate. The
mixture is allowed to simmer for five minutes with
constant agitation from an overhead stirrer. The
mixture must not be allowed to stick to the beaker or
excessive cross-linking will occur, resulting in a
soil that is overly resistant to removal. The mix is
then transferred to a polythene beaker and allowed to
cool before use.
Soil ao~lication
White enamel tiles (100 mm x 100 mm) are cleaned using
a commercially available liquid abrasive cleaner
('Jif' [TM]), rinsed in demineralised water and
allowed to dry. The tiles are then coated with a thin
(c.a. 0.5 mm) layer of the fat/flour mix using a

CA 02273168 1999-OS-28
WO 98/23717 PCT/EP97/06164
- 19 -
screen printing technique. A flexible rubber paddle
is used to spread the mix onto the tile surface,
through a thin plastic mesh, taking care to achieve a
uniformly thin coverage. The soiled tiles are allowed
to stand overnight in the open air, acquiring a
uniform matt finish. The tiles are baked on the
middle shelf of an oven at 190~C for one hour,
developing a light brown colouration, and allowed to
cool for 2 hours before cleaning. As there is
expected to be variation between batches of these
tiles soiled and subsequently pyrolised, it is
important that comparisons are performed with tiles
taken from the same batch.
Preparation of Bleach and Surfactant Solutions
Solutions are prepared as described for the curcumin-
oil soil removal experiments described above with
reference to TABLE 1 using the formulations listed in
TABLE 2 below. Detergency effects have been studied
using Neodol 91-5 (TM) nonionic surfactant, a
commercially available, slightly less pure, version of
the Imbentin 91-35 OFA (TM) surfactant used in the
curcumin/oil experiments above. Admox 10 (TM) is a C1~
amine oxide surfactant.
Peracetic acid is used at a concentration equal to
that of the HOO active oxidising species present in
the 3% hydrogen peroxide solution at the same pH
(10.0).
SUBSTITUTE SHEET (RULE 26)

CA 02273168 1999-OS-28
WO 98/23717 PCT/EP97106164
- 20 -
Soil removal experiments
Soil removal is carried out using a standard Wool
Industries Research Association Abrasion Tester (WIRA:
TM) apparatus. Two soiled tiles are cleaned
simultaneously with the same solution, to provide
duplicate results. The bleach or surfactant solution
3
(20 cm ) is poured onto the surface of the tile, and
rubbed using a cleaning head covered with two layers
of clean 'J'-cloth (TM) material. Each tile is
cleaned using 51 strokes of the head. The tiles are
then immediately removed from the apparatus, rinsed
under running water and patted dry using paper
tissues.
As noted above, although the colouration and ease of
soil removal is uniform for tiles coated with a
specific fat-flour mixture, there is some variability
between different batches of soil. Consequently, the
results shown below in TABLE 2 are grouped in sets
(TABLE 2a, 2b and 2c), each carried out using a
different batch of fat-flour soiled tiles.
Experiments using Jif (TM) liquid abrasive cleaner and
Domestos Multi-Surface Cleaner (TM), a commercial
hypochlorite hard surface cleaning product, are
included in each series of runs to provide reference
standards. The extent of soil removal is assessed
visually by a panel of at least 5 people, using a
standard scale. Tiles are graded on a scale ranging
from 0 to 10, and panellists award integer or half-
integer scores to each tile. A score of 0 denotes no
visible soil removal and 10 corresponds to total soil
removal. Mean scores for each soil removal system are
calculated by averaging scores from both replicates.
SUBSTITUTE SHEET (RULE 26)
r ... ..__.....~

CA 02273168 1999-OS-28
WO 98/23717 PCT/EP97106i64
- 21 -
Comparing the results with conventional
cleaning/bleaching systems, it can be seen that use of
an oxygen transfer agent together with hydrogen
- peroxide provides results which are very favourably
comparable with hypochlorite and commercial products
based on hypochlorite, and which are significantly
better than alkali and surfactant based systems. It
can be seen from table 2d that while the imine quat
shows a reduced effect in the presence of surfactant,
the improvement over systems which do not contain the
imine quat. is still measurable.
TABLE 2a
System Without With
Irvine 0 . 3~
Quat. Irvine
Quat
3o Hydrogen Peroxide at g.5 9.0
pH 10.5
3o K-monoperoxysulphate 5.6 5.6
at pH 8.5
Domestos Multi Surface 10 -
Cleaner at pH 21.5
JIF at pH 11.0 5.8 -
Alkali at pH 20.5 6.4 -
0.1% Neodol at pH 10.5 3.5 -

CA 02273168 1999-OS-28
WO 98/23717 PCT/EP97/06164
- 22 -
TABLE 2b
System Without With
Irvine 0.3%
Quat. Irvine
Quat.
3o Hydrogen Peroxide at 3.9 4.9
pH 10.0
0.12% peracetic acid 2.9 3.8
at pH 10.0
Domestos Multi Surface 9.1 -
Cleaner at pH 11.5
JIF at pH 11.0 3.6 -
TABLE 2C
System Without With
Irvine 0. 3 %
Quat. Irvine
Quat
3% Hydrogen Peroxide at 7.2 9.1
pH 10.0
Domestos Multi Surface 20 -
Cleaner at pH 11.5
3o NaOCl at pH 10.0 8.1 -

CA 02273168 1999-OS-28
WO 98/23717 PCT/EP97/06164
- 23 -
TABLE 2d
System Without With
Irvine 0 . 3s i
Quat. Irvine
Quat
3o Hydrogen Peroxide at 7.5 8.0
pH 10.0
3a Hydrogen Peroxide & 7.3 7.9
0.1s Admox 10 at pH
10.0
Domestos Multi Surface 9.4 -
Cleaner at pH 11.5
JIF at pH 11.0 4.3 -

Representative Drawing

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Administrative Status

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Event History

Description Date
Time Limit for Reversal Expired 2004-11-01
Application Not Reinstated by Deadline 2004-11-01
Deemed Abandoned - Failure to Respond to Maintenance Fee Notice 2003-10-31
Letter Sent 2002-10-15
Request for Examination Received 2002-09-09
Request for Examination Requirements Determined Compliant 2002-09-09
All Requirements for Examination Determined Compliant 2002-09-09
Letter Sent 1999-08-31
Inactive: Cover page published 1999-08-23
Inactive: Single transfer 1999-08-09
Inactive: First IPC assigned 1999-07-26
Inactive: Courtesy letter - Evidence 1999-07-13
Inactive: Notice - National entry - No RFE 1999-07-08
Application Received - PCT 1999-06-30
Application Published (Open to Public Inspection) 1998-06-04

Abandonment History

Abandonment Date Reason Reinstatement Date
2003-10-31

Maintenance Fee

The last payment was received on 2002-10-09

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  • the reinstatement fee;
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  • additional fee to reverse deemed expiry.

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Fee History

Fee Type Anniversary Year Due Date Paid Date
Basic national fee - standard 1999-05-28
MF (application, 2nd anniv.) - standard 02 1999-11-01 1999-05-28
Registration of a document 1999-08-09
MF (application, 3rd anniv.) - standard 03 2000-10-31 2000-09-18
MF (application, 4th anniv.) - standard 04 2001-10-31 2001-09-17
Request for examination - standard 2002-09-09
MF (application, 5th anniv.) - standard 05 2002-10-31 2002-10-09
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
UNILEVER PLC
Past Owners on Record
DAVID WILLIAM THORNTHWAITE
KATHERINE MARY THOMPSON
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
Documents

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Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Description 1999-05-28 23 824
Abstract 1999-05-28 1 63
Claims 1999-05-28 2 56
Cover Page 1999-08-20 1 55
Reminder of maintenance fee due 1999-07-06 1 112
Notice of National Entry 1999-07-08 1 194
Courtesy - Certificate of registration (related document(s)) 1999-08-31 1 140
Reminder - Request for Examination 2002-07-03 1 128
Acknowledgement of Request for Examination 2002-10-15 1 176
Courtesy - Abandonment Letter (Maintenance Fee) 2003-12-29 1 177
PCT 1999-05-28 21 769
Correspondence 1999-07-13 1 31