Note: Descriptions are shown in the official language in which they were submitted.
1
A WATER-SOLUBLE UNIT DOSE ARTICLE COMPRISING AN ETHYLENE OXIDE-
PROPYLENE OXIDE-ETHYLENE OXIDE (E0/PO/E0) TRIBLOCK COPOLYMER
FIELD OF THE INVENTION
Use of an ethylene oxide-propylene oxide-ethylene oxide (E0/PO/E0) triblock
copolymer in said water-soluble unit dose articles.
BACKGROUND OF THE INVENTION
Water-soluble unit dose articles comprising liquid laundry detergent
compositions are
liked by consumers as being convenient and efficient to use.
Such water-soluble unit dose articles comprise water-soluble films, preferably
made of
polyvinyl alcohol. In order to prevent the film from becoming too brittle
and/or splitting prior to
use, the internal liquid laundry detergent composition needs to be formulated
with non-aqueous
solvents. Such non-aqueous solvents keep the film plasticized, i.e. prevent
film plasticizer
migration out of the film into the liquid laundry detergent composition,
therefore, ensuring the
film does not become too brittle. The non-aqueous nature of the solvent also
prevents premature
dissolution of the film, contrary to when formulating highly aqueous
compositions. The non-
aqueous solvents also provide physical stabilization of the liquid laundry
detergent composition
and control of liquid product viscosity. However, often a problem encountered
is that the film
can become over-plasticized due to absorption of a too high quantity of these
non-aqueous
solvents from the liquid laundry detergent composition by the film, leading to
swelling of the
film. Such swelling of the film results in the unit dose article overall
lacking structural integrity,
meaning the unit dose articles look 'floppy' which consumers find undesirable.
Therefore, there exists a need in the art for a water-soluble unit dose
article which
comprises a water-soluble film which does not suffer from brittleness and has
improved
structural integrity.
It was surprisingly found that the use of an ethylene oxide-propylene oxide-
ethylene
oxide (E0/PO/E0) triblock copolymer in a water-soluble unit dose article
improved the
structural integrity of the water-soluble film, i.e. minimised film swelling,
whilst still minimising
film brittleness.
SUMMARY
Certain exemplary embodiments provide use of an ethylene oxide-propylene oxide-
ethylene oxide (E0/PO/E0) triblock copolymer, wherein the copolymer comprises
a first EO
Date Recue/Date Received 2022-03-01
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block, a second EO block and PO block and wherein the first EO block and the
second EO block
are linked to the PO block, to improve the strength of a water-soluble unit
dose article compared
to a unit dose article that does not comprise the triblock co-polymer, wherein
the unit dose article
comprises a water-soluble film and a liquid laundry detergent composition
wherein the liquid
laundry detergent composition comprises the ethylene oxide-propylene oxide-
ethylene oxide
(E0/PO/E0) triblock copolymer.
A first aspect of the present invention is the use of an ethylene oxide-
propylene oxide-
ethylene oxide (E0/PO/E0) triblock copolymer, wherein the copolymer comprises
a first EO
block, a second EO block and PO block and wherein the first EO block and the
second EO block
are linked to the PO block, to improve the strength of a water-soluble unit
dose article,
preferably minimised film swelling of a water-soluble unit dose article,
wherein the unit dose
article comprises a water-soluble film and a liquid laundry detergent
composition wherein the
liquid laundry detergent composition comprises the ethylene oxide-propylene
oxide-ethylene
oxide (E0/PO/E0) triblock copolymer.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1: Schematic illustration of the basic configuration of the unit dose
article strength test.
FIG. 2: is a water-soluble unit dose article according to the present
invention.
DETAILED DESCRIPTION OF THE INVENTION
Use
The present invention relates to the use of an ethylene oxide-propylene oxide-
ethylene
oxide (E0/PO/E0) triblock copolymer to improve the strength of a water-soluble
unit dose
article according to the present invention, wherein the unit dose article
comprises a water-soluble
film and a liquid laundry detergent composition wherein the liquid laundry
detergent
composition comprises the ethylene oxide-propylene oxide-ethylene oxide
(E0/PO/E0) triblock
copolymer. Most preferably the copolymer has a molecular weight between 2500
and 3000, a
propylene oxide content between 25 and 35 propylene oxide units, and an
ethylene oxide content
of between 10 and 15 ethylene oxide units per ethylene oxide block.
Water-soluble unit dose article
The present invention is related to a water-soluble unit dose article
comprising a water-
soluble film and a liquid laundry detergent composition. The water-soluble
film and the liquid
laundry detergent composition are disclosed in more detail below.
Date Recue/Date Received 2022-03-01
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The water-soluble unit dose article comprises the water-soluble film shaped
such that the
unit-dose article comprises at least one internal compartment surrounded by
the water-soluble
film, and wherein the laundry detergent composition is present within said
compartment. The
unit dose article may comprise a first water-soluble film and a second water-
soluble film sealed
to one another such to define the internal compartment. The water-soluble unit
dose article is
constructed such that the laundry detergent composition does not leak out of
the compartment
during storage. However, upon addition of the water-soluble unit dose article
to water, the
water-soluble film dissolves and releases the contents of the internal
compartment into the wash
liquor.
The compartment should be understood as meaning a closed internal space within
the unit
dose article, which holds the detergent composition. During manufacture, a
first water-soluble
film may be shaped to comprise an open compartment into which the detergent
composition is
added. A second water-soluble film is then laid over the first film in such an
orientation as to
close the opening of the compartment. The first and second films are then
sealed together along
a seal region.
The unit dose article may comprise more than one compartment, even at least
two
compartments, or even at least three compartments. The compartments may be
arranged in
superposed orientation, i.e. one positioned on top of the other. In such an
orientation the unit
dose article will comprise three films, top, middle and bottom. Alternatively,
the compartments
may be positioned in a side-by-side orientation, i.e. one orientated next to
the other. The
compartments may even be orientated in a 'tyre and rim' arrangement, i.e. a
first compartment is
positioned next to a second compartment, but the first compartment at least
partially surrounds
the second compartment, but does not completely enclose the second
compartment.
Alternatively, one compartment may be completely enclosed within another
compartment.
Wherein the unit dose article comprises at least two compartments, one of the
compartments may be smaller than the other compartment. Wherein the unit dose
article
comprises at least three compartments, two of the compartments may be smaller
than the third
compartment, and preferably the smaller compartments are superposed on the
larger
compartment. The superposed compartments preferably are orientated side-by-
side.
In a multi-compartment orientation, the laundry detergent composition
according to the
present invention may be comprised in at least one of the compartments. It may
for example be
comprised in just one compar ______________________________________________
intent, or may be comprised in two compar intents, or even in three
compartments.
Date Recue/Date Received 2022-03-01
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Each compartment may comprise the same or different compositions. The
different
compositions could all be in the same form, or they may be in different forms.
The water-soluble unit dose article may comprise at least two internal
compartments, wherein the
liquid laundry detergent composition is comprised in at least one of the
compartments,
preferably wherein the unit dose article comprises at least three
compartments, wherein the
detergent composition is comprised in at least one of the compartments.
The water-soluble unit dose article according to the invention comprises at
least one
compartment comprising a liquid detergent composition. The liquid detergent
composition
according to the invention comprises an ethylene oxide-propylene oxide-
ethylene oxide
(E0/PO/E0) triblock copolymer. Without wishing to be bound by theory, it is
believed that the
ethylene oxide-propylene oxide-ethylene oxide (E0/PO/E0) triblock copolymer
reduces film
swelling which results in increased film tightness, and hence unit dose
article tightness and
overall strength. A further benefit of the present invention is it allows for
overall reduced levels
of non-aqueous solvent whilst still ensuring unit dose article strength and
minimized film
brittleness, and minimized instability of the liquid laundry detergent
composition. Yet a further
benefit, is that the ethylene oxide-propylene oxide-ethylene oxide (E0/PO/E0)
triblock
copolymer provides non-ionic surfactant cleaning benefits, especially grease
cleaning benefits.
This is especially beneficial in the compacted liquid laundry detergent
compositions in a water-
soluble unit dose article. Hence the ethylene oxide-propylene oxide-ethylene
oxide (E0/PO/E0)
triblock copolymer provides a double benefit of improving water-soluble unit
dose article
strength and providing non-ionic surfactant cleaning benefits. This means that
non-aqueous
solvent and/or fatty alcohol ethoxylate levels in the water-soluble unit dose
article can be
reduced without compromise on unit dose article strength, film brittleness or
cleaning
performance.
Water-soluble film
The film of the present invention is soluble or dispersible in water. The
water-soluble
film preferably has a thickness of from 20 to 150 micron, preferably 35 to 125
micron, even
more preferably 50 to 110 micron, most preferably about 76 micron.
Preferably, the film has a water-solubility of at least 50%, preferably at
least 75% or even
at least 95%, as measured by the method set out here after using a glass-
filter with a maximum
pore size of 20 microns:
5 grams 0.1 gram of film material is added in a pre-weighed 3L beaker and 2L
5m1 of
distilled water is added. This is stirred vigorously on a magnetic stirrer,
Labline model No. 1250
Date Recue/Date Received 2022-03-01
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or equivalent and 5 cm magnetic stirrer, set at 600 rpm, for 30 minutes at 30
C. Then, the
mixture is filtered through a folded qualitative sintered-glass filter with a
pore size as defined
above (max. 20 micron). The water is dried off from the collected filtrate by
any conventional
method, and the weight of the remaining material is determined (which is the
dissolved or
dispersed fraction). Then, the percentage solubility or dispersability can be
calculated.
Preferred film materials are preferably polymeric materials. The film material
can, for
example, be obtained by casting, blow-moulding, extrusion or blown extrusion
of the polymeric
material, as known in the art.
Preferred polymers, copolymers or derivatives thereof suitable for use as unit
dose article
material are selected from polyvinyl alcohols, polyvinyl pyrrolidone,
polyalkylene oxides,
acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters,
cellulose amides, polyvinyl
acetates, polycarboxylic acids and salts, polyaminoacids or peptides,
polyamides,
polyacrylamide, copolymers of maleic/acrylic acids, polysaccharides including
starch and
gelatine, natural gums such as xanthum and carragum. More preferred polymers
are selected
from polyacrylates and water-soluble acrylate copolymers, methylcellulose,
carboxymethylcellulose sodium, dextrin, ethylcellulose, hydroxyethyl
cellulose, hydroxypropyl
methylcellulose, maltodextrin, polymethacrylates, and most preferably selected
from polyvinyl
alcohols, polyvinyl alcohol copolymers and hydroxypropyl methyl cellulose
(HPMC), and
combinations thereof Preferably, the level of polymer in the film material,
for example a PVA
polymer, is at least 60%. The polymer can have any weight average molecular
weight,
preferably from about 1000 to 1,000,000, more preferably from about 10,000 to
300,000 yet
more preferably from about 20,000 to 150,000.
Mixtures of polymers can also be used as the pouch material.
Preferably, the water-soluble film comprises polyvinyl alcohol polymer or
copolymer,
preferably a blend of polyvinylalcohol polymers and/or polyvinylalcohol
copolymers, preferably
selected from sulphonated and carboxylated anionic polyvinylalcohol copolymers
especially
carboxylated anionic polyvinylalcohol copolymers, most preferably a blend of a
polyvinylalcohol
homopolymer and a carboxylated anionic polyvinylalcohol copolymer.
Preferred films exhibit good dissolution in cold water, meaning unheated
distilled water.
Preferably such films exhibit good dissolution at temperatures of 24 C, even
more preferably at
10 C. By good dissolution it is meant that the film exhibits water-solubility
of at least 50%,
preferably at least 75% or even at least 95%, as measured by the method set
out here after using
a glass-filter with a maximum pore size of 20 microns, described above.
Date Recue/Date Received 2022-03-01
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Preferred films are those supplied by Monosol under the trade references
M8630, M8900,
M8779, M8310.
The film may be opaque, transparent or translucent. The film may comprise a
printed
area.
The area of print may be achieved using standard techniques, such as
flexographic
printing or inkjet printing.
The film may comprise an aversive agent, for example a bittering agent.
Suitable
bittering agents include, but are not limited to, naringin, sucrose octa-
acetate, quinine
hydrochloride, denatonium benzoate, or mixtures thereof. Any suitable level of
aversive agent
may be used in the film. Suitable levels include, but are not limited to, 1 to
5000ppm, or even
100 to 2500ppm, or even 250 to 2000rpm.
Liquid laundry detergent composition
The water-soluble unit dose article comprises a liquid laundry detergent
composition.
.. The term 'liquid laundry detergent composition' refers to any laundry
detergent composition
comprising a liquid capable of wetting and treating a fabric, and includes,
but is not limited to,
liquids, gels, pastes, dispersions and the like. The liquid composition can
include solids or gases
in suitably subdivided form, but the liquid composition excludes forms which
are non-fluid
overall, such as tablets or granules.
The liquid detergent composition can be used in a fabric hand wash operation
or may be
used in an automatic machine fabric wash operation.
The liquid laundry detergent composition comprises an ethylene oxide-propylene
oxide-
ethylene oxide (E0/PO/E0) triblock copolymer, wherein the copolymer comprises
a first EO
block, a second EO block and PO block wherein the first EO block and the
second EO block are
.. linked to the PO block. In other words, the PO block is positioned between
the two EO blocks.
The copolymer may consist of a first EO block, a second EO block and PO block
wherein the
first EO block and the second EO block are linked to the PO block. By 'linked
to the PO block',
we herein the EO-PO-E0 blocks have the following structure;
-CH3
HO, CH2 CH2 0 - .. CHICH20- - CH2CH20-----H
EO J,PO EO
- X2
Date Recue/Date Received 2022-03-01
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wherein Xi is preferably on average is between 2 and 90, preferably 3 and 50
more
preferably between 4 and 20, even more preferably between 5 and 15, most
preferably between
and 15;
X2 is preferably on average is between 2 and 90, preferably 3 and 50 more
preferably
5 between 4 and 20, even more preferably between 5 and 15, most preferably
between 10 and 15;
Y is preferably on average between 15 and 70, preferably between 20 and 60,
more
preferably between 25 and 50, even more preferably between 25 and 40, most
preferably
between 25 and 35.
Preferably, the liquid laundry detergent composition comprises between 1% and
10%,
10 preferably between 2% and 8% by weight of the liquid laundry detergent
composition of the
ethylene oxide-propylene oxide-ethylene oxide (E0/PO/E0) triblock copolymer.
Preferably, the ethylene oxide-propylene oxide-ethylene oxide (E0/PO/E0)
triblock
copolymer has an average propylene oxide chain length of between 15 and 70,
preferably
between 20 and 60, more preferably between 25 and 50, even more preferably
between 25 and
40, most preferably between 25 and 35 propylene oxide units.
Preferably, the ethylene oxide-propylene oxide-ethylene oxide (E0/PO/E0)
triblock
copolymer has an average molecular weight of between 1000 and 10,000,
preferably between
1500 and 5000 more preferably between 2000 and 4500, even more preferably
between 2500 and
4000, most preferably between 2500 and 3000.
Preferably, each ethylene oxide chain independently has an average chain
length of
between 2 and 90, preferably 3 and 50 more preferably between 4 and 20, even
more preferably
between 5 and 15, most preferably between 10 and 15 ethylene oxide units.
Preferably, the copolymer comprises on average between 10% and 90%, preferably
between 20% and 70%, most preferably between 30% and 50% by weight of the
copolymer of
the combined ethylene-oxide blocks. Most preferably the total ethylene oxide
content is split
over the two ethylene oxide blocks such that each ethylene oxide block
comprises on average
between 40% and 60% preferably between 45% and 55%, even more preferably
between 48%
and 52%, most preferably 50% of the total number of ethylene oxide units,
wherein the
percentage of both ethylene oxide blocks accounts for 100% of the ethylene
oxide units present.
Most preferably the copolymer has an average molecular weight between 2500 and
3000,
an average propylene oxide content between 25 and 35 propylene oxide units,
and an average
ethylene oxide content of between 10 and 15 ethylene oxide units per ethylene
oxide block.
Without wishing to be bound by theory, a further benefit of the ethylene oxide-
propylene oxide-
ethylene oxide (E0/PO/E0) triblock copolymer is that they exhibit good safety
profiles. Most
Date Recue/Date Received 2022-03-01
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preferred are copolymers having an average molecular weight between 2500 and
3000, an
average propylene oxide content between 25 and 35 propylene oxide units, and
an average
ethylene oxide content of between 10 and 15 ethylene oxide units per ethylene
oxide block as
these have the best safety profile of this class of copolymers wherein they
especially exhibit
minimal skin and eye irritation if accidentally contacted with skin or eye.
Suitable ethylene oxide ¨ propylene oxide ¨ ethylene oxide triblock copolymers
are
commercially available under the Pluronic PE series from the BASF company, or
under the
Tergitol L series from the Dow Chemical Company. A particularly suitable
material is Pluronic
PE 6400 or Tergitol L64.
Without wishing to be bound by theory, a further benefit of the ethylene oxide-
propylene
oxide-ethylene oxide (ED/PO/ED) triblock copolymer is that they exhibit good
safety profiles
wherein they especially exhibit minimal skin and eye irritation if
accidentally contacted with
skin or eye.
Preferably, the liquid laundry detergent composition comprises a non-soap
anionic
surfactant, preferably wherein the non-soap anionic surfactant comprises
linear alkylbenzene
sulphonate, alkoxylated alkyl sulphate or a mixture thereof, more preferably a
mixture thereof
wherein the ratio of linear alkylbenzene sulphonate to alkoxylated alkyl
sulphate preferably the
ratio of linear alkylbenzene sulphonate to ethoxylated alkyl sulphate is from
1:2 to 20:1,
preferably from 1.1:1 to 15:1, more preferably from 1.2:1 to 10:1, even more
preferably from
1.3:1 to 5:1, even more preferably from 1.4:1 to 3:1, most preferably from
1.4:1 to 2.5:1.
Preferably the ethoxylated alkyl sulphate is an alkyl ethoxy sulphate
comprising a mol average
of 1 to 5, preferably 2 to 4, most preferably 3 ethylene oxide units per alkyl
chain.
The liquid laundry detergent composition may comprise between 10% and 60%,
preferably between 15% and 50% by weight of the liquid laundry detergent
composition of
surfactant. In terms of the present invention, the ethylene oxide-propylene
oxide-ethylene oxide
(ED/PO/ED) triblock copolymer of the present invention is not defined as a
surfactant and so
does not contribute to the total level of surfactant. More preferably, the
liquid laundry detergent
composition comprises between 5% and 50%, preferably between 15% and 45%, more
preferably between 25% and 40%, most preferably between 30% and 40% by weight
of the
detergent composition of the non-soap anionic surfactant.
Preferably, the liquid laundry detergent composition comprises less than 10%
preferably
less than 5%, preferably less than 3%, more preferably less than 2.5% by
weight of the laundry
detergent composition of a fatty alcohol ethoxylate non-ionic surfactant.
Preferably, the liquid laundry detergent composition comprises between 1.5%
and 20%,
Date Recue/Date Received 2022-03-01
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more preferably between 2% and 15%, even more preferably between 3% and 10%,
most
preferably between 4% and 8% by weight of the liquid detergent composition of
soap, preferably
a fatty acid salt, more preferably an amine neutralized fatty acid salt,
wherein preferably the
amine is an alkanolamine more preferably selected from monoethanolamine,
diethanolamine,
triethanolamine or a mixture thereof, more preferably monoethanolamine.
The liquid laundry detergent composition preferably comprises a non-aqueous
solvent
preferably selected from 1,2-propanediol, dipropylene glycol,
tripropyleneglycol, glycerol,
sorbitol or a mixture thereof More preferably the liquid laundry detergent
composition
comprises between 10% and 40%, preferably between 15% and 30% by weight of the
liquid
laundry detergent composition of the non-aqueous solvent. Preferably, the
weight ratio of non-
aqueous solvent selected from 1,2-propanediol, dipropylene glycol,
tripropyleneglycol, glycerol,
sorbitol or a mixture thereof to the ethylene oxide-propylene oxide¨ethylene
oxide tri-block
copolymer is between 1:1 and 10:1 more preferably between 2:1 and 5:1.
The liquid laundry detergent composition preferably comprises an alkanolamine
preferably selected from monoethanolamine, triethanolamine, and mixtures
thereof, preferably
monoethanolamine. The alkanolamine preferably is present between 5% and 15% by
weight of
the liquid laundry detergent composition.
Preferably, the liquid laundry detergent composition comprises between 0.5%
and 15%,
preferably between 5% and 13% by weight of the liquid laundry detergent
composition of water.
The liquid laundry detergent composition may comprise an enzyme. Preferably,
the
enzyme is selected from the group comprising hemicellulases, peroxidases,
proteases, cellulases,
xylanases, lipases, phospholipases, esterases, cutinases, pectinases,
keratanases, reductases,
oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases,
pentosanases,
malanases, B-glucanases, arabinosidases, hyaluronidase, chondroitinase,
laccase, and amylases,
or mixtures thereof, preferably proteases, amylases, lipases, cellulases and
mixtures thereof,
preferably lipases.
The liquid laundry detergent composition may comprise a further polymer
selected from
the group comprising an alkoxylated polyethyleneimine, preferably an
ethoxylated
polyethyleneimine, a cationically modified polysaccharide, preferably a
canonically modified
hydroxyethylcellulose, a carboxymethylcellulose, preferably a hydrophobically
modified
carboxymethylcellulose, a polyester terephthalate soil release polymer,
preferably an anionic
polyester terephthalate soil release polymer, and an amphiphilic graft soil
release polymer,
preferably a polyethylene glycol graft polymer comprising a polyethylene
glycol backbone and
hydrophobic vinyl acetate side chains, or a mixture thereof Preferably, the
liquid laundry
Date Recue/Date Received 2022-03-01
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detergent composition comprises independently between 0.1% and 10%, preferably
between
0.25% and 7%, more preferably between 0.5% and 5% by weight of the liquid
laundry detergent
composition of each of these polymers.
The liquid laundry detergent composition may further comprise an adjunct
ingredient
selected from builders, dye transfer inhibiting agents, dispersants, enzymes,
enzyme stabilizers, catalytic materials, bleach, bleach activators, polymeric
dispersing agents,
antiredeposition agents, suds suppressors, aesthetic dyes, pacifiers,
perfumes, perfume delivery
systems, structurants, hydrotropes, processing aids, pigments and mixtures
thereof
Preferably, the liquid laundry detergent composition has a pH between 6 and
10, more
preferably between 6.5 and 8.9, most preferably between 7 and 8. The pH of the
liquid laundry
detergent composition may be measured as a 10% dilution in demineralized water
at 20 C.
The liquid detergent composition preferably has a viscosity of between 100 and
1000
cPa.s, measured at a shear rate of 20/s at 20 C on a TA instruments AR-G2 or
AR2000 using a
40mm plate geometry and a 500 micron gap size.
Without wishing to be bound by theory, low viscosity allows higher
manufacturing line
speed, however, there is an increased risk of 'splashing' and 'stringing' in
which liquid detergent
accidentally contaminates the seal area and so results in seal defects. Such
seal defects affects
the structural integrity of the unit dose article. Increasing the viscosity
avoids the issues of seal
contamination but reduces manufacturing line speed. The preferred viscosity of
the present
invention allows for efficient manufacture line speed whilst minimizing seal
contamination.
Method of washing
A further aspect of the present invention is a method of washing comprising
the steps of
adding the water-soluble unit dose article according to the present invention
to sufficient water to
dilute the liquid laundry detergent composition by a factor of at least 300
fold to create a wash
liquor and contacting fabrics to be washed with said wash liquor.
Without wishing to be bound by theory, when the water-soluble unit dose
article is added
to water, the water-soluble film dissolves releasing the internal liquid
laundry detergent
composition into the water. The liquid laundry detergent composition disperses
in the water to
create the wash liquor.
Preferably the wash liquor may comprise between IL and 64L, preferably between
2L and
32L, more preferably between 3L and 20L of water.
Date Recue/Date Received 2022-03-01
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Preferably, the wash liquor is at a temperature of between 5oC and 90oC,
preferably
between 10oC and 60oC, more preferably between 12oC and 45oC, most preferably
between
15oC and 40oC.
Preferably, washing the fabrics in the wash liquor takes between 5 minutes and
50 minutes,
preferably between 5 minutes and 40 minutes, more preferably between 5 minutes
and 30
minutes, even more preferably between 5 minutes and 20 minutes, most
preferably between 6
minutes and 18 minutes to complete.
Preferably, the wash liquor comprises between lkg and 20 kg, preferably
between 3kg and
15kg, most preferably between 5 and 10 kg of fabrics.
The wash liquor may comprise water of any hardness preferably varying between
0 gpg to
40gpg.
The dimensions and values disclosed herein are not to be understood as being
strictly
limited to the exact numerical values recited. Instead, unless otherwise
specified, each such
dimension is intended to mean both the recited value and a functionally
equivalent range
surrounding that value. For example, a dimension disclosed as "40 mm" is
intended to mean
"about 40 mm."
EXAMPLES
Example 1
The impact of partially replacing the non-aqueous solvent system within a
water soluble
unit dose liquid laundry detergent formulation by an ethylene oxide-propylene
oxide-ethylene
oxide (E0/PO/E0) triblock copolymer according to the invention, has been
studied on overall
film swelling and linked unit dose article strength and tightness properties.
From the data
tabulated below it can clearly be seen that reduced film swelling and hence
stronger and tighter
unit dose articles are obtained with the compositions according to the
invention comprising the
ethylene oxide-propylene oxide-ethylene oxide (E0/PO/E0) triblock copolymer
(Compositions
1 to 3) compared to Comparative Composition A lacking the ethylene oxide-
propylene oxide-
ethylene oxide (E0/PO/E0) triblock copolymer.
Date Recue/Date Received 2022-03-01
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Test compositions:
Comparative
Composition Composition Composition Composition
100% wt active A 1 2 3
Water 11.0 10.9 10.9 10.8
1,2-Propanediol 14.7 16.0 13.2 11.6
DiPropyleneGlycol 3.9 0.08 0.08 0.08
Glycerine 3.8 3.9 4.0 3.9
Sorbitol 0.05 0.05 0.05 0.05
HLAS 21.7 22.1 22.5 22.0
C24 HAE3S 14.9 15.1 15.4 15.1
Nonionic alcohol
1.8 1.9 1.9 1.9
ethoxylate (C24E07)
Lutensol XL100 0.5 0.5 0.5 0.5
Citric Acid 0.7 0.7 0.7 0.7
TPK Fatty Acid 4.4 4.5 4.6 4.5
HEDP chelant 2.3 2.0 2.1 2.0
Ethoxylated
poly ethyleneimine 3.3 3.4 3.5 3.6
(PEI600E020)*
Amphiphilic graft
2.6 2.6 2.6 2.6
polymer**
(E0-PO-E0) triblock
copolymer (Pluronic 2.1 4.0 6.8
PE9200)
Sodium Formate
0.1 0.1 0.1 0.1
(HCOONa)
Magnesium Chloride
0.33 0.34 0.36 0.36
(MgCl2)
Potassium Sulfite
0.4 0.4 0.4 0.4
(K2S03)
Hydrogenated Castor Oil 0.09 0.09 0.09 0.09
Brightener 49 0.4 0.4 0.4 0.4
Date Recue/Date Received 2022-03-01
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Monoethanolamine
10.0 10.3 10.4 10.8
(MEA)
Minors (enzymes, anti-
Balance to Balance to Balance to Balance to
foam, perfume,
100% 100% 100% 100%
preservative, dye)
*ethoxylated polyethyleneimine having an average degree of ethoxylation of 20
per EO chain
and a polyethyleneimine backbone with MW of about 600
**polyethylene glycol graft polymer comprising a polyethylene glycol backbone
(Pluriol E6000)
and hydrophobic vinyl acetate side chains, comprising 40% by weight of the
polymer system of
a
polyethylene glycol backbone polymer and 60% by weight of the polymer system
of the grafted
vinyl acetate side chains
Test methods:
Film swelling:
A film sample was prepared of a water soluble PVOH film intended to be used to
form a
sealed compartment enclosing the comparative composition and liquid household
detergent
compositions according to the invention described above. The film/juice ratio
in the immersion
is about 1:100; we typically use 5 replicates/test. The bottom of a clean
inert glass recipient was
covered with a thin layer of liquid and the film to be tested was spread on
the liquid; air bubbles
trapped under the film were gently pushed towards the sides. The remaining
liquid was then
gently poured on top of the film, in such a way that the film was fully
immersed into the liquid.
The film should remain free of wrinkles and no air bubbles should be in
contact with the film.
The film stayed in contact with the liquid and was stored under closed vessel
conditions for 5
days at 50 C and 1 night at 21 C. A separate glass recipient was used for each
test. The film was
then removed from the storage vessel, and the excess liquid was removed from
the film. A piece
of paper was put on the film which was laid on top of a bench paper, and then
the film was
wiped dry thoroughly with thy paper. The weight of the film was measured pre
and post
immersion testing, and the relative gain weight has been calculated and
expressed as a % change
according to below folinula ;
% change = (end-weight/starting weight)*100.
Date Recue/Date Received 2022-03-01
14
Unit dose article Strength:
This test method describes the practice for determining the unit dose article
strength
using the Instron Universal Materials Testing instrument (Instron Industrial
Products, 825
University Ave., Norwood, MA 02062-2643) with a load cell of maximum 100 kN
(kilo
Newton). Via compression of a unit dose article, this method determines the
overall strength (in
Newtons) of the unit dose article by putting pressure on the film and seal
regions. Unit dose
article strength (in Newtons) is defined as the maximum load a unit dose
article can support
before it breaks. Unit dose articles opening at the seal area at a pressure
lower than 250N are
reported as seal failures, and are not taken into account when determining
average unit dose
article strength.
The liquid detergent compositions have been enclosed in a water soluble PVA
film, more
particularly a PVA film comprising a blend of a polyvinylalcohol homopolymer
and a
carboxylated anionic polyvinylalcohol copolymer resin, to obtain a water
soluble unit dose
article for pouch strength / tightness testing, the water soluble unit dose
article matching the
Ariel 3-in-1 Pods design, as commercially available in the UK in January 2018
and visualized in
Figure 2, having filled all 3 compai iments therein by one of the test
compositions described
above respectively (i.e. each of the three compartments had the same
composition). The same
water soluble PVA film has been used for the film swelling experiment. The
water soluble film
has been pre-heated and drawn into a cavity through vacuum to form a first
open compartment
into which the test detergent composition has been dosed. In parallel the 2
top side by side
compartments have been formed by drawing a pre-heated water soluble film in a
second side by
side cavity to form 2 side by side open compartments into which the same test
detergent is
dosed, followed by closing and sealing these filled side by side compartments
by a second film.
The closed side by side compartments are consequently added and sealed on top
of the first open
and filled cavity to obtain the superposed multi-compartment water soluble
article being tested.
The unit dose article strength was measured no sooner than two hours after
unit dose
article production so that the film/unit dose articles had time to set after
converting. The method
was performed in a room environment between 40-50% relative humidity (RH) and
22-24 C.
Stored unit dose articles were allowed to re-equilibrate to the testing room
environment for one
hour prior to testing.
FIG. 1. shows a schematic illustration of the basic configuration of the unit
dose article
strength test. To measure unit dose article strength, a unit dose article 510
was enclosed in a
plastic de-aerated bag 500 (150 mm by 124 mm with closure, 60 micron thick -
e.g. Raja grip
RGP6B) to prevent contamination of working environment upon unit dose article
rupture. After
Date Recue/Date Received 2022-03-01
15
enclosure in the bag, the unit dose article 510 was centered between two
compression plates 520,
530 of the instrument. The unit dose article 510 was placed in an upright
position, so that the
width seal dimension 540 (e.g. smallest dimension within a defined rectangular
plane just
encompassing the seal area, 41mm in actual unit dose articlees tested) was
between the
compression plates (x-direction) such that the stress was applied on the width
seal. For the
compression, the speed of decreasing the distance between the plates 520 and
530 is set at 60
min/min. Ten replicates were conducted per test leg, and average unit dose
article strength data,
excluding seal failures as defined above, are reported (the higher the
stronger the unit dose
article).
Unit dose article Tightness: (the higher the better)
This test method describes the practice for determining the unit dose article
tightness
using the Instron Universal Materials Testing instrument (Instron Industrial
Products, 825
University Ave., Norwood, MA 02062-2643) with a load cell of maximum 100 kN
(kilo
Newton). Via compression of a unit dose article, this method determines the
residual distance
between compression plates when applying a load of ION.
The unit dose article tightness was measured no sooner than two hours after
unit dose
article production so that the film/unit dose articles had time to set after
being made. The
method was performed in a room temperature environment between 30% and 60%
relative
humidity and 18-25 C, most preferred between 40% and 50% relative humidity and
22-24 C.
Stored unit dose articles were allowed to re-equilibrate to the testing room
environment for one
hour prior to testing.
The test set-up is similar as in the unit dose article strength test and as
shown in FIG. 1
with the exception that the unit dose article has now been positioned with the
surrounding seal
plane horizontal, rather than vertical as in the unit dose article strength
test, between the two
compressions plates 520,530 of the instrument. To measure unit dose article
tightness, a unit
dose article 510 was enclosed in a plastic de-aerated bag 500 (150 mm by 124
mm with closure,
60 micron thick - e.g. Raja grip RGP6B) to prevent contamination of working
environment upon
accidental unit dose article rupture. After enclosure in the bag, the unit
dose article 510 was
centered between two compression plates 520, 530 of the instrument. The unit
dose article 510
was placed in a horizontal position, so that the outer seal / flange dimension
was horizontally
oriented between the compression plates (y,z-direction). For the compression,
the speed of
decreasing the distance between the plates 520 and 530 is set at 60 mm/min,
and the instrument
is set for the compression plate to stop when a pressure of 0.01 kN (1 Kg) is
reached. The unit
Date Recue/Date Received 2022-03-01
16
dose article tightness can hence be read from the instrument display as the
end distance in
between the two compression plates (mm).
Test results:
Film Swelling:
A decreased degree of film swelling is observed for the compositions
comprising the
ethylene oxide-propylene oxide-ethylene oxide (ED/PO/ED) triblock copolymer
(Compositions
1 to 3) compared to Comparative Composition A lacking the ethylene oxide-
propylene oxide-
ethylene oxide (ED/PO/ED) triblock copolymer.
Weight Film Fresh (g) Weight after ageing (g) % change
Comparative 2.208 2.34 106.0
composition A
Composition 1 2.126 2.212 104.0
Composition 2 2.197 2.269 103.3
Composition 3 2.052 2.083 101.5
Unit dose article Strength & Tightness:
Stronger and tighter water soluble unit dose articles are obtained with the
compositions
comprising the ethylene oxide-propylene oxide-ethylene oxide (ED/PO/ED)
triblock copolymer
(Compositions 1 to 3) compared to Comparative composition A lacking the
ethylene oxide-
propylene oxide-ethylene oxide (ED/PO/ED) triblock copolymer.
Unit Dose Strength (N) Tightness (mm)
Comparative 680 20.4
composition A
Composition 1 686 20.5
Composition 2 685 20.7
Composition 3 770 21.3
Example 2
A range of different ethylene oxide-propylene oxide-ethylene oxide (ED/PO/ED)
triblock
copolymers according to the invention has been studied by substituting the
(ED/PO/ED) triblock
Date Recue/Date Received 2022-03-01
17
copolymer within Composition 3 on their ability to prevent film swelling,
according to the
protocol described herein.
Test results .=
A decreased degree of film swelling is observed across all ethylene oxide-
propylene
oxide-ethylene oxide (E0/PO/E0) triblock copolymers tested, varying in
molecular weight,
degree of ethylene oxide and propylene oxide units, compared to Comparative
composition A
lacking the ethylene oxide-propylene oxide-ethylene oxide (E0/PO/E0) triblock
copolymer.
Weight Film Weight after ageing (g) %
change
Fresh (g)
Comparative 2.01 2.07 103.0
composition A
Composition 3 E013P03oE013 1.99 2.00 100.5
with Pluronic MW 2900 - 40% EO
PE6400
Composition 3 E05P019E05 2.99 2.00 100.0
with Pluronic MW 1570 - 30wt% EO
PE4300
Composition 3 E03P040E03 2.02 2.02 100.0
with Tergitol MW 2550 - 10% EO
L81
Composition 3 E08P047E08 1.98 1.98 100.0
with Pluronic MW 3440 - 20w0/0 EO
PE9200
Composition 3 E02113047E021 2.00 2.02 101.0
with Pluronic MW 4580- 40w0/0 EO
PE9400
Example 3
FIG.2 discloses a water-soluble unit dose article (1) according to the present
invention.
The water-soluble unit dose article (1) comprises a first water-soluble film
(2) and a second water-
soluble film (3) which are sealed together at a seal region (4). The liquid
laundry detergent
composition according to the invention (5) is comprised within the water-
soluble soluble unit dose
article (1).
Date Recue/Date Received 2022-03-01
