Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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CONTAINER
The present invention relates to a container.
Inorganic peroxygen compounds, especially hydrogen
peroxide and solid peroxygen compounds which dissolve in
water to release hydrogen peroxide, such as sodium
perborate and sodium carbonate perhydrate, have long
been used as oxidizing agents for purposes of
disinfection and bleaching. The oxidizing action of
these substances in dilute solutions is heavily
dependent on the temperature; for instance, with H202 or
perborate in alkaline bleaching liquors, sufficiently
rapid bleaching of soiled textiles is obtained only at
temperatures above about 80 C. At lower temperatures
the oxidizing action of the inorganic peroxygen
compounds can be enhanced by adding what are called
bleach activators, for which numerous proposals have
been disclosed in the literature, principally from the
classes of the N-acyl or 0-acyl compounds, examples
being polyacylated alkylenediamines, especially
tetraacetylethylenediamine, acylated glycolurils,
especially tetraacetylglycoluril, N-acylated hydantoins,
hydrazides, triazoles, hydrotriazines, urazoles,
diketopiperazines, sulfurylamides and cyanurates, and
also carboxylic anhydrides, especially phthalic
anhydride, carboxylic esters, especially sodium
nonanoyloxybenzenesulfonate, sodium
isononanoyloxybenzenesulfonate and acylated sugar
derivatives, such as pentaacetylglucose. By addition of
these substances the bleaching action of aqueous
peroxide liquors can be increased to such an extent that
even at temperatures around 60 C essentially the same
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activities occur as with the peroxide liquor alone at
95 C.
Given the concern for energy-saving laundering and
bleaching methods, in recent years application
temperatures well below 60 C have gained in importance,
in particular below 45 C down to the cold water
temperature, below 20 C.
Previously the use of transition metal salts and
transition metal complexes has been described, for
example in European patent applications EP 392 592, EP
443 651, EP 458 397, EP 544 490, EP 549 271 and WO
01/48138, referred to as bleaching catalysts.
It has now been observed that textiles, particularly
coloured textiles, fade after a number of washes in the
presence of a bleach catalyst. It is theorised that
some catalysts previously used not only catalyze the
activity of the peroxygen compound but also remain at
least partly on their surfaces being bleached, and even
when the cleaning operation has ended. These transition
metal salts can then be oxidized and so cause colour
damage, and, in extreme cases, the risks of oxidative
damage to the textiles since they directly contact the
textile. As an example a deposit of Mn (II), is readily
oxidized to Mn (IV) dioxide, which is a very strong
oxidizing agent, particularly toward easily oxidizable
substances, such as organic dye compounds.
All of the bleaching catalysts known have the
disadvantage that they are brought into intimate contact
with the surfaces of the articles being treated and as
such typically a portion of the catalyst adheres to
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those surfaces or even penetrate those surfaces. This
gives rise to a risk of unwanted colour changes and in
rare cases; there may even be holes / tears, as a result
of fibre damage.
According to a first aspect of the invention there is
provided a container comprising a detergent formulation,
the container including a primary enclosing wall which
is permeable to water and a secondary enclosing wall
which comprises a bleaching catalyst admixture and a
support material.
It has been found that the container of the present
invention has a number of advantageous properties. The
principle advantageous property is that the bleach
catalyst, particularly the transition metal thereof when
present (when used in a washing / bleaching operation)
is not substantive upon an item being washed or
bleached. Thus detrimental damage to the item is
drastically reduced.
Another advantage of the present invention (when used in
a washing / bleaching operation) is the catalysis of the
oxidizing action and bleaching action of inorganic
peroxygen compound at low temperatures. Effective
catalysis is observed below 80 C and in particular from
about 12 C to 40 C.
Another advantage of the present invention (when used in
a washing / bleaching operation) is to allow for
reduction of peroxygen amount and / or bleach activator
(e.g. TAED) in a cleaning formulation while maintaining
bleaching performance, thus allowing for cost reduction.
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Preferably the bleach catalyst comprises a transition
metal compound based upon one or more of manganese,
copper, iron, silver, platinum, cobalt, nickel,
titanium, zirconium, tungsten, molybdenum, ruthenium,
cerium, lanthanum or vanadium. Most preferably the
bleach catalyst comprises a transition metal compound
based upon manganese.
The manganese bleach catalyst may be selected from wide
range of manganese compounds. Suitable inorganic
compounds (often salts) of manganese (e.g. Mn (II))
include hydrated / anhydrous halide (e.g. chloride /
bromide), sulphate, sulphide, carbonate, nitrate, oxide.
Further examples of suitable compounds (often salts) of
manganese (e.g. Mn (II)) include hydrated / anhydrous
acetate, lactate, acetyl acetonate, cyclohexanebutyrate,
phthalocyanine, bis (ethylcyclopentadienyl), bis
(pentamethylcyclopentadienyl).
Most preferably the bleach catalyst comprises manganese
(II) acetate tetrahydrate and/or manganese (II) sulphate
monohydrate.
Alternatively the bleach catalyst may comprise:-
4.r.~;3aaaas=
(1, 8 - diethyl-1, 4, 8, 11-TetraAzaCycloTetraDecane)
manganese (II) chloride [Mn-TACTD].
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Alternatively the bleach catalyst may comprise:-
Manganese (III) Catalyst with an
organic tripodal ligand. /-\
(nb "
Mn
5 \ \
Alternatively the bleach catalyst may comprise:-
O
Generally the bleach catalyst comprises from 0.001% to
10.00%, preferably from 0.01% to 5.00% more preferably
from 0.15% to 2.5% of the second enclosing wall, with
the remainder of the composition comprising the support
matrix.
A mixture of two or more bleach catalysts listed above
can be used.
The secondary wall is preferably in the form of a film.
The preferred film thickness is in the range of from
0.10mm to 1.0mm, more preferably from 0.20 to 0.40mm.
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The particle size of the catalyst used in the production
of the secondary wall is preferably between 50 micron
and 125 micron.
The support matrix of the secondary wall generally
comprises a polymeric material. Suitable polymeric
materials may be selected from the group of
polyurethanes; polyolefins / hydrocarbons, e.g.
polypropylene (PP), poly propylene containing maleic
anhydride, poly propylene mixed with poly ethylene,
polyethylene (PE), PE mixed with ethylene vinyl acetate
(PE/VA), poly ethylene copolymer with ethylene ethyl
acrylate, (PE/EEA) polystyrene, polybutadiene;
polyamides; polyvinyl chloride; polyesters, e.g. poly
methyl methacrylate, poly vinyl acetate, ethylene vinyl
acetate; phenolic resins; copolymers, e.g.
polymethylmethacrylate with n-butylacrylate and styrene;
natural / modified natural polymers, e.g. cellulose,
rubber, latex, styrene-butadiene rubber, butyl rubber,
chlorinated / hydrochlorinated rubber, nitrile rubber,
vulcanized rubber, siliconised rubber; polycarbonates;
silicone resins; fluorinated resins, e.g. PTFE.
A mixture of two or more plastic materials listed above
can also be used for the matrix.
The film may be made in any suitable method. Preferred
methods include casting and extrusion. Further
treatment such as a roller hot press bending machine may
be used.
Preferably casting involves dissolution of the support
in a suitable solvent, followed by suspension /
dispersion of the solid catalyst in fine powder into the
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solvent and support mixture. This is preferably
followed by deposition of the dispersion onto a surface
(e.g. stainless steel or semiconductor material) and
evaporation of the solvent (at room temperature or at an
elevated temperature). Suitable solvents include:
chlorinated organic solvents (e.g. chloroform), ketones
(e.g. acetone or methyl ethyl ketone), dimethylsulfoxide
(DMSO), alcohols, aliphatic or aromatic hydrocarbons,
glycol ethers or organic acids, (e.g. acetic acid or
formic acid), tetra hydro furan (THF).
Preferably extrusion and co-extrusion involves passing a
composition comprising the support and the catalyst
through an extrusion machine or a press machine. The
extrusion is preferably performed at an elevated
temperature which may be affected by heating or by the
pressure applied by the extruder.
The extrusion conditions depend to a degree upon the
exact nature of the composition being extruded and by
the type of machine used. A suitable extrusion
operating temperature is, for example, 90-260 C. A
suitable extrusion operating screw velocity is, for
example, 25-250 rpm (rotation per minute), preferably
50-125 rpm. A suitable extrusion operating pressure is,
for'example, 30-250 bar. A suitable torque force for an
extrusion process, is in the range 10-100 Ampere. The
extrudate is preferably in the form of film, pellets or
strand or noodles.
The primary wall is water permeable.
By water permeable we mean that the material allows
water to pass through, under the conditions in which the
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product is used. Suitably the material has an air
permeability of at least 1000 1/m2/s at 100 Pa according
to DIN EN ISO 9237. In addition the web must not be so
permeable that it is not able to hold a granular dye
transfer inhibition composition (e.g. greater than 150
microns).
Conventional materials used in tea bag manufacture or in
the manufacture of sanitary or diaper products may be
suitable for the primary wall. Preferred materials
includes polymeric fibres such as polyolefins
(particularly polyethylene and polypropylene),
poly(haloolefins), poly(vinylalcohol), polyesters such
as ethylene vinyl acetate, polyamides, polyacrylics,
protein fibres and cellulosic fibres (for example
cotton, viscose and rayon).
Conveniently the primary wall comprises a non-woven
material. Processes for manufacturing non-woven fabrics
can be grouped into four general categories leading to
four main types of non-woven products, textile-related,
paper-related, extrusion-polymer processing related and
hybrid combinations
Textiles. Textile technologies include garneting,
carding, and aerodynamic forming of fibres into
selectively oriented webs. Fabrics produced by these
systems are referred to as dry laid nonwovens, and they
carry terms such as garneted, carded, and air laid.
fabrics. Textile-based nonwoven fabrics, or fibre-
network structures, are manufactured with machinery
designed to manipulate textile fibres in the dry state.
Also included in this category are structures formed
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with filament bundles or tow, and fabrics composed of
staple fibres and stitching threads.
In general, textile-technology based processes provide
maximum product versatility, since most textile fibres
and bonding systems can be utilised.
Paper. Paper-based technologies include dry laid pulp
and wet laid (modified paper) systems designed to
accommodate short synthetic fibres, as well as wood pulp
fibres. Fabrics produced by these systems are referred
to as dry laid pulp and wet laid nonwovens. Paper-based
nonwoven fabrics are manufactured with machinery
designed to manipulate short fibres suspended in fluid.
Extrusions. Extrusions include spun bond, melt blown,
and porous film systems. Fabrics produced by these
systems are referred to individually as spun bonded,
melt blown, and textured or apertured film nonwovens, or
generically as polymer-laid nonwovens. Extrusion-based
nonwovens are manufactured with machinery associated
with polymer extrusion. In polymer-laid systems, fibre
structures simultaneously are formed and manipulated.
Hybrids. Hybrids include fabric/sheet combining
systems, combination systems, and composite systems.
Combining systems employs lamination technology or at
least one basic nonwoven web formation or consolidation
technology to join two or more fabric substrates.
Combination systems utilize at least one basic nonwoven
web formation element to enhance at least one fabric
substrate. Composite systems integrate two or more
basic nonwoven web formation technologies to produce web
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structures. Hybrid processes combine technology
advantages for specific applications.
The primary wall of the container may itself act as a
further means for modifying the water, for example by
5 having the capability of capturing undesired species in
the water and/or releasing beneficial species. Thus,
the wall material could be of a textile material with
ion-capturing and/or ion-releasing properties, for
example as described above, such a product may be
10 desired by following the teaching of WO 02/18533 that
describes suitable materials. Alternatively and more
preferably the wall may be modified to provide a dye /
dirt catching function. Such a function may be provided
by physically / chemically incorporating a dye / dirt
catching agent into / onto the fabric of the wall. A
preferred example of such a material is a quaternary
ammonium based compound.
The product may comprise an indication means which
serves to show the extent of performance of the dye
transfer inhibition function. A preferred example of
such an indication means is a colour change within the
product. This colour change may occur on the sachet and
/ or on the body contained within the sachet. A
preferred way of achieving the colour change is to use a
colour catching compound which is attached to the sachet
and / or to the body within the sachet.
Container forming can be done in an horizontal or in a
vertical plane from two or more rolls of material that
are joined together to form the walls of the sachet.
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Machine assemblies for sachet forming, filling and
sealing can be sourced from, VAI, IMA, Fuso for vertical
machines; Volpack, Iman Pack for horizontal sachet
machines; Rossi, Optima, Cloud for horizontal pod
machines.
The open container is preferably configured as a pocket
or pouch, preferably sealed or otherwise closed on three
edges, and which can be filled through an edge, for
example the fourth, open, side.
Filling of the open container can be done with a variety
of volumetric devices, such as a dosing screw or as a
measuring cup. Typical dosing accuracy required at
constant product density is +/-1% wt preferably, +/-5%
wt minimum.
Filling devices are supplied by the companies mentioned
above as part of the machine package.
Feedback control mechanisms acting on the speed of the
dosing screw or on the volume of the measuring cup can
be installed to maintain high dosing accuracy when the
product density changes.
Seal strength is important, as the container must not
open during the wash cycle or other type of cleaning or
water-softening operation, otherwise any water insoluble
ingredients might soil the items washed.
A seal strength of at least 5N / 20mm, preferably at
least 1ON / 20mm and most preferably at least 15N / 20mm
according to test method ISO R-527 measured before the
wash sealed sachet is subjected to a wash. The strength
of any seal is very much dependent on the materials used
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and the conditions of the sealing process, for example
the following conditions are used to generate good
quality seals
= heat sealing, preferably using flat sealing bars, 5mm
by 100mm, Teflon coated stainless steel, typically 1 sec
at 150 C +/-1 C at 20kg/cm2 actual sealing pressure, as
achieved on a bench scale Kopp heat sealer and on the
heat sealing devices of most of the machine suppliers
mentioned before;
= ultrasound sealing, preferably using grooved sealing
bars, 5mm by 150mm, pattern with diagonal grooves at 45
degrees to the side of the seal, pitch of 15mm and bar
width of 5mm with a nominal seal area coverage of 33%,
0.1 to 0.3 s at 20kHz and 70 microns vibration
amplitude, actual sealing pressure between 10 and 60
kg/cm2, typical absorbed power 300 to 1200W, typical
absorbed energy 30 to 180W, using ultrasound sealing
equipment produced by companies like Mecasonic or
Branson or Herrmann or Sonic or Dukane or Sonobond.
= glue sealing, e.g. applying lOg/m2 of hot melt glue
like Prodas 1400, PP, from Beardow Adams. Polyethylene
(PE) or polyamides or polyurethanes or UV curable
acrylics glues or epoxy resins can be used as well.
Thus overall the process may comprise:
a) forming an open container from two or more webs;
b) filling the open container with a dye transfer
inhibition composition; and
c) sealing the container.
The container is preferably flat, i.e. with one
dimension, the thickness of the container, at least 5
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times smaller preferably at least 10 times smaller,
ideally at least 30 times smaller than the other two,
the width and the length of the sachet (which are the
same as each other, corresponding to the diameter of the
sachet, should it be circular in plan). Preferred
thicknesses are in the range of 10 - 20mm, e.g. 10mm,
15mm or 20mm.
Preferably the- container covers a surface (i.e. the
product of width and length (when the sachet is
rectangular) of between 80 to 300 cm2, ideally 100 to 200
cm2. Preferred lengths/widths are in the range of 5 -
30cm, e.g. 6cm, 10cm, 12cm, 15cm, 20cm, 25cm or 30cm.
The container may comprise a flexible body of at least
10mm in one dimension and 10mm in another direction.
Preferably the body is such that no dimension is greater
than 20mm. Ideally each dimension is between 10 - 20mm,
e.g. 12mm, 15mm or 18mm.
The body may be configured to provide a volume adding
function e.g. by being resilient so it expands on
removal of compression forces. The inclusion of such a
volume adding member has been shown [when used in an
automatic washing operation] to decrease the incidence
of lodging of the device within the door seal, posting
of the device in the door seal, facilitate the finding
of the device after a washing operation, and can favour
water flow through the device.
This in turn has a positive environmental impact by
reducing the amount of packaging material required for
each pack. When great numbers of packs are produced and
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sold, this has also positive influence on transport
costs.
In a preferred embodiment the body comprises a foam
material which may comprise any suitable material such
as polypropylene, polyester and / or PE/EVA. The body
may comprise a number of separate elements each being
formed of a different material.
Preferably the detergent composition is a dishwashing,
laundry, hard surface cleaning and / or disinfecting
composition. Generally the composition is for use in
the appropriate washing operation in a washing machine
or other washing vessel such as a sink, bucket, etc.
Alternatively the composition may be used in an additive
(e.g. additives which are complementary to a detergent
product used in a washing operation) or in addition to a
product which contains a bleach.
The detergent composition may comprise a homogenous
product, e.g. a uniform powder / liquid or alternatively
the detergent composition may have a plurality of
individual phases, e.g. such as a multi-phase tablet.
The detergent composition typically comprises at least
one of surfactant (anionic, non-ionic, cationic or
amphoteric), builder, bleach, bleach activator, bleach
stabilizer, bleaching catalyst, enzyme, polymer, co-
builder, alkalizing agent, acidifying agent, anti-
redeposition agent, silver protectant, colourant,
optical brightener, UV stabilizer, fabric softener,
fragrance, soil repellent, anticrease substance,
antibacterial substance, colour protectant,
discolouration inhibitor, vitamin, phyllosilicate,
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odour-complexing substance, rinse aid, foam inhibitor,
foaming agent, preservative, or auxiliary.
According to a second aspect of the invention there is
provided the use of a container according to the first
5 aspect of the invention in a dishwashing, laundry and /
or hard surface cleaning operation and/ or a
sanitizer/disinfectant operation.
The container may be placed with the items to be washed
in an automatic washing machine.
10 Alternatively the container may pack into the flow
pathway for the rinse or wash water of a ware washing
machine such that the water is compelled to flow through
it.
The invention is now illustrated by reference to the
15 following non-limiting examples.
Example 1: Film Production
Key Equipment Used:
= Mono screw extruder Brabender PL 2000 PLE 650
attached to the Brabender Plasti-Corder.
= Brabender Bending Machine T' 300A Electronic- Roller
Hot Press.
Raw Materials Used
Ingredient Commercial Name Supplier Physical Aspect
Catalyst Manganese Acetate Kemira Pink fine powder 50-
(CH3000)2Mn.4 H2O Tetra Hydrate 125 pm
Catalyst Manganese Acetate Aldrich Pink.very fine powder
(CH3000)2Mn Anhydrous
Catalyst Manganese Sulfate Fluka Pink very fine powder
MnSO4.1 H2O Mono Hydrate, 99% 50-125 pm
Support PMMA VM 100ALTUGLAS Arkema Pellet 3x3x2.5mm,
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Poly Methyl brilliant transparent
Methacrylate PMMA
Support PP401-CA20 BP Pellet 3x3x2.5mm,
Poly Propylene copolymer white/ opaque
copolymer
Support Fusabond PP MD-511D Du Pont Pellet 3x3x2.5mm,
Poly Propylene + white
maleic anhydride
Lubricant Vaseline A. Sella Viscous oil
Paraffin Oil transparent
Phase 1: Raw Material Preparation
Manganese acetate tetra hydrate from Kemira was milled
into a fine powder using the laboratory grinder. After
sieving, a granulometry of 50-125 pm was selected for
film production.
Manganese sulphate monohydrate from Fluka was also
sieved, a granulometry of 50-125 pm was selected for
film production.
PMMA VM 100 was heated in an over for 2 hours at 80 C to
remove traces of water.
PP poly propylene was used as supplied, without being
dried.
Phase 2: Pre-Mix preparation
Several pre-mixes of 500g were prepared. The ratio /
amount of raw materials was selected in order to have
parity molar concentration of manganese in final film
prototypes (calculated Manganese concentration = 4800
ppm Mn).
Ingredient Pre Mix Pre Mix Pre Mix Pre Mix Pre Mix Pre Mix
(g) 3 4 5 6 7 8
(CH3COO)2Mn -- -- 7.6 7.6 -- --
MnSO4.1 H2O 7.3 7.6 -- -- -- --
(CH3COO)2Mn.4 -- -- -- -- 11.0 11.0
H2O
PMMA VM 100 492.4 492.4 492.2 492.2 489.0 489.0
dried dried dried dried dried dried
Paraffin Oil 0.3 0.3 0.3 0.3 0.3 0.3
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Ingredient (g) Pre Mix 9 Pre Mix Pre Mix Pre Mix Pre Mix
11 12 13
MnSO4.1 H2O 7.7 -- 7.7 -- --
(CH3000)2Mn.4 -- 11.0 -- 11.1 --
H20
(CH3000)2Mn -- -- -- -- 7.8
Anhydrous
PP Poly PP401 PP401 Fusabond Fusabond Fusabond
Propylene CA20 CA20 492.5 489.0 492.2
492.4 489.0
Paraffin Oil 0.3 0.3 0.3 0.3 0.3
Phase 3: Extrusion
The three heating zones of the extruder were set up as
5 follows:
Heating Zone Heating Zone Heating Zone Head T4
Ti T2 T3
Temperature 170 175 180 184-185
OC
Average screw velocity was 30 rpm. The head opening was
set up at 0.3mm.
The bending machine was set up at 60 C with a velocity
of 2.2 metres per minute.
10 These process parameters were set up at the beginning of
the trial and maintained constant throughout production
using PMMA. Summary of trials and film produced in the
table below:
Trial CATALYST SUPPORT Torque Observation
Ampere
Opaque-white smooth film
FILM 3 MnSO4.1 H2O PMMA 60 Good salt distribution.
Average thickness 0.18-0.22mm
Opaque-white smooth film
FILM 4 MnSO4.1 H2O PMMA 60 Good salt dispersion.
Average thickness 0.18-0.22mm
(CH3COO)2Mn 60 Translucent-pink rough film
FILM 5 PMMA Good salt distribution.
Average thickness 0.25mm
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(CH3COO)2Mn 60 Translucent-pink rough film
FILM 6 PMMA Good salt distribution.
Average thickness 0.25mm
(CH3COO)2Mn. 55 Translucent beige film
FILM 7 4 H20 PMMA Rough surface.
Average thickness 0.35mm
(CH3COO) 2Mn. 55 Translucent beige film
FILM 8 4 H20 PMMA Rough surface.
Average thickness 0.35mm
Average production capacity was 2 kg / hour.
Example 2: Chemical characterization of film produced
Chemical analyses were conducted on film 4, film 6 and
film 8 to assess the level of manganese present in the
solid film. Analytical results confirmed the
theoretical/calculated amount of manganese added by
weight in the premix is found in the final solid
prototype:
Film ppm Mn (metal)
FILM 4 4545
FILM 6 4721
FILM 8 4838
PMMA alone (no catalyst added) <0.005 (beneath detection limit)
Example 3: Oxidation Catalysis Study
The following reagents and solution were prepared, in
deionised water.
Solution Reagent g/L
A PCB Sodium Percarbonate (2Na2CO3.3H202)+ 1.38
TAED Tetra Acetyl Ethylene Diamine 0.30
+Saffron 0.035
B PCB + TAED + (CH3COO) 2Mn x4 H2O 0.005
+Saffron
C PCB + TAED + MnSO4. 1 H20+ 0.0034
+Saffron
D PCB + TAED + Film 4 (from example 1) 0.25
+Saffron
E PCB + TAED + Film 6 (from example 1) 0.25
+Saffron
F PCB + TAED + Film 8 (from example 1) 0.25
+Saffron
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A solution containing sodium percarbonate and TAED was
compared with a solution containing PCB, TAED and a
catalyst in homogeneous phase (manganese acetate OR
manganese sulphate) and with a solution containing PCB +
TAED + the corresponding catalysts in solid film format
(film 4, or film 6 or film 8).
Protocol Used: Saffron Beaker Test
Saffron solution (fresh, protected from light)
Deionised water
Temperature: 20 C
Reaction studied over 30 minutes.
UV/VIS Abs at 430 nm to monitor the oxidation rate on
substrate, via measurement of de-colouration of saffron
solution.
Results from laboratory experimental measurement of
absorbance residue after 30 minutes are summarized in
the following table
A B C D E F
Absorbance 70 58 62 66 65 62
Residue (%)
Data reported are the average of two
measurement/experimental run.
The results show that film 4, film 6 and film 8 are
effective as oxidation catalysts (vs. no catalyst), with
film 8 delivering the highest catalyses efficiency on
the bleaching of saffron.
Example 4: Analysis of Washing Liquors
The saffron solution from the above oxidative study
(example 3) were filtered to remove the solid catalyst,
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acidified and analysed via atomic absorption for
manganese presence to assess if any metal (Mn) was
released from the solid film to the water solution.
Results summarised as follows:
5
A B C D E F
ppm Mn 0.042 0.775 0.573 0.057 0.050 0.074
Analytical data for Mn presence shows there is no
significant release of Mn from the solid film: the level
found is in line with the Mn found in the solution A
10 containing the traditional bleach system PCB/TAED and
the substrate saffron (saffron used as oxidative
substrate).
Example 5: Performance under Washing Conditions.
Film 8 was used in a washing machine. test to assess the
15 catalytic activity on the bleaching of standard soils.
A test under consumer relevant washing condition was
conducted comparing the cleaning performance delivered
by a compact laundry detergent alone (Tandil Ultra Plus
dose at 68 g/wash, containing a traditional bleach
20 system based on percarbonate and TAED) with the
performance delivered by the same detergent plus the
addition in wash of the solid catalyst in film format
(film 8, dosed at 5 g/wash).
The following test protocol was used.
Water Hardness: 25 F
Temperature: 30 C
Program: Cotton cycle (heavy soil)
Load: 3.5kg new cotton
Washing machine: EU front load; 14.5 litre wash
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Replications: 4
Drying: RT, linen
Ironing: Domestic Iron
Evaluation: Datacolour 650 spectrophotometer
The following results were achieved:
Ultra Plus Detergent 68 g
Y-values-Instrumental Evaluation Ultra Plus Detergent + solid bleach catalyst
(5 g)
Stains 68 /wash FILM in PMMA + Mn Acetate
Tea on cotton empa 167 63,8 67,7
Tea PES/Cotton empa 168 64,9 67,3
Red wine cotton WFK IOLI 76,6 78,3
Coffee on cotton WFK 1OK 80,7 81,1
Ribes on cotton CFT CS-12 63,1 65,2
Blueberry Juice on cotto CFT CS-15 72,4 73,4
Peach Juice on cotton CFT CS-19 81,2 82,2
Tea on cotton BC-01 62,2 63,0
Tea on PES/cotton BC-03 58,4 59,0
Spinach on cotton CFT CS-25 83,9 84,3
These performance test results clearly shows that the
addition of solid catalyst in film format increase and
improves significantly the performance results/cleaning
action.
Example 6: Film Production
Key Equipment Used:
= Mono screw extruder Brabender PL 2000 PLE 650
attached to the Brabender Plasti-Corder.
= Brabender Bending Machine T 300A Electronic- Roller
Hot Press.
Raw Materials Used
Ingredient Commercial Name Supplier Physical Aspect
Catalyst Manganese Aldrich Pink very fine
(CH3000) 2 Mn Acetate powder, below 50
Anhydrous micron
Catalyst Cyclam type, Mn Clariant Very fine beige
CAT 3657 powder
Support LOTRIL Arkema Pellet 3x3x2.5mm,
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EEA Ethylene white
Ethyl Acrylate
(PE/EEA)
Support OREVAC, ESCORENE Arkema, Exo Pellet 3x3x2.5mm,
EVA (PE/EVA) Mobil white
Lubricant Vaseline A. Sella viscous oil
Paraffin Oil transparent
Phase 1: Raw Material Preparation
EEA was pre-dried in oven at 90 C for 2-4 hours.
PE / EVA was not pre-dried.
Phase 2: Pre-Mix
Several pre-mixes of 500g were prepared. The ratio /
amount of raw materials was selected in order to have
parity molar concentration of manganese in final film
prototypes (calculated Manganese concentration = 4800
ppm Mn).
Ingredient Pre Mix Pre Mix Pre Mix Pre Mix Pre Mix
(g) 20 21* 22 23 23 bis
(CH3COO)2Mn 7.6 -- -- 7.6 7.6
Anhydrous
CAT 3657 -- 7.0 -- -- --
EEA 492.1 184.0 -- -- --
EVA -- -- 100 492.1 491.7
Paraffin 0.3 0.3 0.3 0.3 0.4
Oil
The pre-measured plastic pellets were inserted into a
plastic PE bag. The Vaseline oil was added via pipette.
The admixture was agitated manually until the oil was
homogeneously distributed onto the pellets. The
manganese catalyst was added into the bag and mixing was
resumed.
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Phase 3: Extrusion:
The three heating zone of the extruder were set up as
follows:
Head T4 Heating Zone Heating Zone Heating Zone
T3 T2 Ti
Temperature 180 175 173 170
C
Average screw velocity was 30 rpm. The head opening was
set up at 0.3mm.
The bending machine was set up at 60 C with a velocity
of 3.0 metres per minute.
Trial CATALYST SUPPORT Torque Observation
Ampere
(CH3CO0)2Mn Smooth and soft film,
FILM 20 EEA 14 homogeneous catalyst
dispersion.
Good catalyst dispersion
FILM 21 CAT 3657 EEA 14
Good catalyst dispersion
FILM 22 (CH3COO)2Mn EVA 16 Elastic transparent film
Good catalyst dispersion
FILM 23 (CH3000)2Mn EVA 13
Average production capacity was 2 kg / hour. The
cleaning procedure was applied after each trial/each
film production.
