Note: Descriptions are shown in the official language in which they were submitted.
1
USE OF POLYESTER TEREPHTHALATE TO REDUCE MALODOUR ON FABRICS
FIELD OF THE INVENTION
Use of a polyester terephthalate and use of a wash liquor containing said
polyester
terephthalate to reduce malodour on fabrics.
BACKGROUND OF THE INVENTION
Consumers use laundry detergent compositions during the laundry process. Such
laundry
detergent compositions provide cleaning, freshness and/or care benefits to the
fabrics during the
laundry operation.
Recently, of particular concern to some consumers, a developing need for
laundry
detergents is ensuring that malodours on fabrics are reduced to a minimum
during the laundry
process. Malodours are typically caused by adherence of hydrophobic soils such
as body soils,
cooking oils, and non-food oils onto fabrics, especially onto hydrophobic
fabrics, followed by,
optionally bacterial induced, chemical degradation, generating, and hence,
releasing bad smelling
volatiles materials.
However, achieving reduction of malodours onto fabrics during a washing
process
traditionally has required the addition of specific malodour reducing
technologies to the detergent
composition. Due to environmental appreciation and a desire to reduce carbon
footprints, there is
a trend to compact detergent formulations so to reduce resources required for
shipping and
packaging. This requirement for compaction is especially true in water-soluble
unit dose articles.
Therefore, traditionally formulators often face a trade-off of one benefit for
another due to a
required prioritization call of one active versus the other due to space
constraints for actives within
the formulation. Additionally, such malodour reducing technologies are added
to fabric softening
compositions which are added in the rinse step of a wash operation after the
main wash operation.
This has the disadvantage of requiring the user to use both a detergent
composition for the main
wash and a subsequent softener composition in the rinse step to achieve the
malodour reduction
benefits.
Therefore, there is a desire in the art to formulate actives that provide
multiple benefits in
laundry detergent compositions especially in compacted compositions such as
water-soluble unit
dose articles, with reduced or no trade-off of one benefit in preference of
another.
Anionic polyester terephthalates are known as soil release (whiteness
boosting) polymers
on fabrics. However, it was surprisingly found, both under single as well as
under multi-cycle
Date Recue/Date Received 2020-11-20
2
testing, that anionic polyester terephthalates can also be used to reduce
malodours on fabrics.
Without wishing to be bound by theory, it is believed that the ethoxylate
groups of the polyester
terephthalate polymer are thought to create a hydrophilic layer on the fabric
surface, especially on
hydrophobic fabrics such as polyester, resulting in reduced (re-) adherence of
hydrophobic soils
on fabrics during the wash cycle or during subsequent use of the fabrics.
Also, it was surprisingly
found that anionic polyester terephthalates are less sensitive than other
polyester terephthalates to
being washed off again during the same or subsequent wash operation. Without
wishing to be
bound by theory, it is believed the anionic polyester terephthalate has a
repulsive effect on the
mainly anionically charged detergent surfactant system, so reducing instances
of the polyester
terephthalate being washed off the fabrics.
Therefore, the use according to the present invention provides the dual
benefit of reduced
malodour on fabrics and soil release (whiteness) benefits whilst minimizing
the addition of actives.
Furthermore, the malodour benefit was achieved without the additional use of a
fabric softener.
SUMMARY OF THE INVENTION
A first aspect of the present invention is the use of a polyester
terephthalate polymer to
reduce malodour on a fabric, wherein the polyester terephthalate comprises a
polyester
terephthalate backbone and the polyester terephthalate backbone is grafted
with one or more
anionic groups.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG.1 is a water-soluble unit dose article according to the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Use of a polyester terephthalate polymer
An aspect of the present invention is the use of a polyester terephthalate
polymer to reduce
malodour on a fabric, wherein the polyester terephthalate comprises a
polyester terephthalate
backbone and the polyester terephthalate backbone is grafted with one or more
anionic groups.
The polyester terephthalate is described in more detail below.
A 'malodour' is any odour that a user finds unpleasant or undesirable.
Preferably, the
malodour comprises body soils, cooking oils and chemical degradation products
thereof, non-food
oils and chemical degradation products thereof, or mixtures thereof,
preferably hydrolysable fatty
acid esters and chemical degradation products thereof, hydrolysable
triglyceride esters and
Date Recue/Date Received 2020-11-20
3
chemical degradation products thereof or a mixture thereof. By 'degradation
products thereof', we
herein mean preferably aldehydes, ketones, epoxides, hydroxy compounds or a
mixture thereof.
Without wishing to be bound by theory, oils, especially vegetable oils are
composed of glycerol
molecules esterified by three fatty acids molecules. Each type of vegetable
oils is characterized by
its own specific fatty acids ratio content. Predominantly, fatty acids have 16
or 18 carbon atoms in
straight aliphatic chains, and these chains can undergo degradation changes
due to high levels of
double bonds presented. They are quite sensitive to oxidative conditions and
generate many
degradation products including aldehydes, ketones, epoxides, hydroxy
compounds, or mixtures
thereof. Oxidative stress can also cause conjugated double bond system
formation as well as of
trans fatty acids.
The malodour may comprise body soils, cooking oils, non-food oils, or mixtures
thereof,
preferably hydrolysable fatty acid esters, hydrolysable triglyceride esters or
a mixture thereof.
Those skilled in the art will be aware of suitable fabrics. Preferably, the
fabrics comprise
cotton, polycotton, polyester, or mixtures thereof, preferably the fabric
comprises polyester.
The polyester terephthalate may be used to;
a. reduce malodour on fabrics during a laundry wash operation, wherein the
polyester
terephthalate polymer is comprised within a wash liquor and the wash liquor is
in
contact with the fabric;
b. reduce malodour on fabrics during use of said fabrics following a wash
operation,
wherein in the wash operation the polyester terephthalate polymer is comprised
within a wash liquor and the wash liquor is in contact with the fabric and
following
contact the polyester terephthalate polymer is deposited onto the fabrics;
c. reduce malodour on fabrics during a laundry wash operation, wherein the
polyester
terephthalate polymer is comprised on the fabric prior to the fabric being
contacted
with a wash liquor;
d. or a mixture thereof.
Those skilled in the art will be aware of standard laundry wash operations.
The wash
operation may be a manual wash operation, an automatic wash operation, a semi-
automatic wash
operation or a mixture thereof. Without wishing to be bound by theory, a
laundry wash operation
involves making a wash liquor which is contacted with fabrics to be washed.
The wash liquor may
be prepared first and the fabrics then added, or the wash liquor can be
created in a suitable container
Date Recue/Date Received 2020-11-20
4
or drum of an automatic washing machine in which the fabrics have been placed
first, i.e. the wash
liquor is created around the fabrics.
Preferably the wash liquor may comprise between 1L and 64L, preferably between
2L and
32L, more preferably between 3L and 20L of water.
Preferably, the wash liquor is at a temperature of between 5 C and 90 C,
preferably
between 10 C and 60 C, more preferably between 12 C and 45 C, most preferably
between 15 C
and 40 C.
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.
Without wishing to be bound by theory, the polyester terephthalate polymer may
be used
to reduce malodours on fabrics during the wash operation, or on fabrics when
in use following a
wash operation (e.g. as they are being worn) or both. In the wash operation,
the polyester
terephthalate polymer may be added to the wash liquor separately to that of
the fabrics, or may be
present on the fabrics prior to them being contacted with the wash liquor, or
both.
Preferably, the polyester terephthalate is present in the wash liquor,
preferably at a
concentration between 1ppm and 200ppm, preferably between 5ppm and 150ppm,
most preferably
between lOppm and 100ppm.
Those skilled in the art will be aware of ways to prepare a wash liquor.
Preferably, the
wash liquor is prepared by diluting a laundry detergent composition in water,
diluting a fabric
softening composition in water, or a mixture thereof, and wherein the laundry
detergent
composition, the fabric softening composition, or a mixture thereof, comprises
the polyester
terephthalate polymer. Preferably, the polyester terephthalate polymer is
comprised within a wash
liquor and the wash liquor is in contact with the fabric. Those skilled in the
art will be aware of
how to make laundry detergent and fabric softening compositions. Preferred
laundry detergent
and fabric softening compositions are described in more detail below.
Preferably, the wash liquor comprises a non-soap surfactant, preferably
wherein the non-
soap surfactant is present at a concentration of between lOppm and 2000ppm,
preferably between
Date Recue/Date Received 2020-11-20
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50ppm and 1500ppm, most preferably between 100ppm and 1000ppm. Where the wash
liquor is
prepared by diluting a laundry detergent composition, a fabric softening
composition or mixture
thereof in water, the non-soap surfactant may be present in the laundry
detergent composition,
fabric softening composition or mixture thereof.
Preferably, the non-soap surfactant comprises a non-soap anionic surfactant, a
non-ionic
surfactant or a mixture thereof, preferably wherein the weight ratio of the
non-soap anionic
surfactant to non-ionic surfactant is between is from 1:2 to 20:1, preferably
from 1:1 to 15:1, more
preferably from 1.5:1 to 15:1, most preferably from 3:1 to 15:1.
Preferably, the non-soap anionic surfactant comprises linear alkylbenzene
sulphonate,
alkyl sulphate, alkoxylated alkyl sulphate or a mixture thereof, preferably
wherein the weight ratio
of linear alkylbenzene sulphonate to alkoxylated alkyl sulphate is between
15:1 and 1:15,
preferably 10:1 and 1:10, more preferably 5:1 and 1:5, even more preferably
4:1 and 1:4.
The non-ionic surfactant may be selected from a fatty alcohol alkoxylate, an
oxo-
synthesised fatty alcohol alkoxylate, Guerbet alcohol alkoxylates, alkyl
phenol alcohol alkoxylates
or a mixture thereof. The non-ionic surfactant may be added to the wash liquor
via the laundry
detergent composition, the fabric softening composition or a mixture thereof.
Preferably, the wash liquor comprises between 1 ppm and 1000 ppm, preferably
between
5 ppm and 500 ppm, most preferably between 10 ppm and 250 ppm 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.
Preferably, the wash liquor comprises an adjunct ingredient selected from
hueing dyes,
polymers, builders, dye transfer inhibiting agents, dispersants, enzyme
stabilizers, catalytic
materials, bleach, bleach activators, polymeric dispersing agents, anti-
redeposition agents, suds
suppressors, aesthetic dyes, opacifiers, perfumes, perfume delivery systems,
structurants,
hydrotropes, processing aids, pigments, amphoteric surfactants, cyclic
diamines, zwitterionic
polyamines, anti-oxidants, preservatives and mixtures thereof, preferably
selected from fatty acid,
neutralised fatty acid salt, carboxymethylcellulose, amphiphilic graft co-
polymer, hydroxyethyl
cellulose, modified hydroxethylcellulose, an enzyme, sulphite, or a mixture
thereof. The adjunct
ingredient may be added to the wash liquor via the laundry detergent
composition, the fabric
softening composition or a mixture thereof.
Preferably, the enzyme is selected from protease, amylase, lipase, cellulase,
mannanase,
pectate lyase, xyloglucanase, keratinase or a mixture thereof.
Date Recue/Date Received 2020-11-20
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The wash liquor may comprise a further polymer selected from the group
comprising an
alkoxylated polyethyleneimine, preferably an ethoxylated polyethyleneimine, a
cationically
modified polysaccharide, preferably a cationically modified
hydroxyethylcellulose, a
carboxymethylcellulose, preferably a hydrophobically modified
carboxymethylcellulose, 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 wash liquor comprises a chelant, an anti-oxidant or a mixture
thereof.
Laundry detergent composition
The polyester terephthalate polymer may be comprised in a laundry detergent
composition.
The laundry detergent composition may be a powder, a liquid or a mixture
thereof.
The solid laundry detergent composition may comprise solid particulates or may
be a single
homogenous solid. Preferably, the solid laundry detergent composition
comprises particles. This
means the solid laundry detergent composition comprises individual solid
particles as opposed to
the solid being a single homogenous solid. The particles may be free-flowing
or may be
compacted, preferably free-flowing.
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 powders, tablets or granules.
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.
The laundry detergent composition may be present in a water-soluble unit dose
article and
the water-soluble unit dose article comprises a water-soluble film.
The water-soluble unit dose article comprises a water-soluble film and a
laundry detergent
composition. The laundry detergent composition and the water-soluble film are
described in more
detail below.
Date Recue/Date Received 2020-11-20
7
The water-soluble unit dose article comprises the water-soluble film shaped
such that the
unit-dose article comprises at least one internal compai ___________________
tment surrounded by the water-soluble film,
and wherein the laundry detergent composition is present within said compai __
anent. 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 compai ____________________________ anent.
The water-soluble unit dose article is constructed
such that the laundry detergent composition does not leak out of the compai __
anent 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 compai __________ anent, even
at least two
compai __ intents, or even at least three compai ___________________________
intents. 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 compai __ intent, but the first compai _________________________
intent at least partially surrounds the second
compai __ anent, but does not completely enclose the second compai _________
anent. Alternatively, one
compai __ anent may be completely enclosed within another compai anent.
Wherein the unit dose article comprises at least two compai ________________
intents, one of the
compai __ intents may be smaller than the other compai __________________
anent. Wherein the unit dose article
comprises at least three compai ____________________________________________
intents, two of the compai intents may be smaller than the third
compai __ anent, and preferably the smaller compai _________________________
intents are superposed on the larger compartment.
The superposed compartments preferably are orientated side-by-side.
In a multi-compai __________________________________________________________
intent orientation, the laundry detergent composition according to the
present invention may be comprised in at least one of the compai _____
intents. It may for example be
comprised in just one compai _______________________________________________
anent, or may be comprised in two compaitments, or even in three
compai __ intents.
Date Recue/Date Received 2020-11-20
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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
compaatitents,
wherein the liquid laundry detergent composition is comprised in at least one
of the compar intents,
preferably wherein the unit dose article comprises at least three
compartments, wherein the
detergent composition is comprised in at least one of the compartments.
FIG.1 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 laundry
detergent composition
(5) is comprised within the water-soluble soluble unit dose article (1).
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, LablineTM
model No. 1250 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 solution 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
pouch 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 acry late copolymers, methylcellulose, carboxymethylcellulose
sodium, dextrin,
Date Recue/Date Received 2020-11-20
9
ethylcellulose, hy droxy ethyl cellulose, hy droxypropyl methy lcellulo se,
malto dextrin,
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 pouch 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 and/or copolymers can also be used as the pouch material,
especially
mixtures of polyvinylalcohol polymers and/or copolymers, especially mixtures
of
polyvinylalcohol homopolymers and/or anionic polyvinylalcohol copolymers
preferably selected
from sulphonated and carboxylated anionic polyvinylalcohol copolymers
especially carboxylated
anionic polyvinylalcohol copolymers. Most preferably the water soluble film
comprises 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.
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 octaacetate, 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.
Alternatively, the polyester terephthalate may be present in a fabric
softening composition.
which is diluted by a factor of between 300 and 3000 fold in water to create
the wash liquor.
Fabric softening composition
The softening composition may be in any suitable form. The softening
composition may
be a powder, a liquid or a mixture thereof.
Date Recue/Date Received 2020-11-20
10
The softening composition may comprise solid particulates or may be a single
homogenous
solid. Preferably, the solid softening composition comprises particles. This
means the solid
softening composition comprises individual solid particles as opposed to the
solid being a single
homogenous solid. The particles may be free-flowing or may be compacted,
preferably free-
flowing.
The term 'liquid laundry softening composition' refers to any laundry
softening
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 powders, tablets or granules.
The fabric softening composition may comprise a softening active selected from
quaternary
ammonium compounds, amines, fatty esters, sucrose esters, silicones,
dispersible polyolefins,
polysaccharides, fatty acids, softening oils, polymer latexes, softening clays
and combinations
thereof, preferably wherein the fabric softening active is selected from the
group consisting of
quaternary ammonium compounds and mixtures thereof, more preferably ester
quats, most
preferably wherein the fabric softening active is selected from the group
consisting of diester quats,
more preferably Diethylester Dimethyl Ammonium Chloride (DEEDMAC).
When formulated in a fabric softening composition, preferably, the softening
composition
comprises between 2% and 25%, preferably between 4% and 20%, more preferably
between 5%
and 15%, most preferably between 5% and 13% by weight of the softening
composition of the
softening active.
The laundry softening composition preferably further comprises perfume or
perfume
capsule technology, aiming at delivering scent to the treated fabrics. The
laundry softening
composition may comprise further ingredients, as typically recognized by a
skilled person in the
art.
Polyester terephthalate polymer
The polyester terephthalate is a polyester terephthalate backbone grafted with
one or more
anionic groups, more preferably, an anionic polyester of propylene
terephtalate.
Suitable anionic polyesters are those that are derived from terephtalic acid,
5-
sulfoisophtalic acid or the salt of 5-sulfoisophtalic acid, from ethylene
glycol or polyethylene
glycol, propylene glycol or polypropylene glycol and polyalkyleneglycol
monoalky 1 ether, and
Date Recue/Date Received 2020-11-20
11
optionally from further monomers having 3 to 6 functions capable of
polycondensation, in
particular acid, alcohol or ester functions.
Preferably, the polyester terephthalate comprises the combination of
structural units (I) to
(III):
-[(OCHR1-CHR2)a-0-0C-Ar-00-1d
(II) -[(OCHR3-CHR4)b-0-0C-sAr-CO-le
(III) -[(OCHR5-CHR6)e-OR71e
wherein:
a, b and c are from 1 to 200;
d, e and fare from 1 to 50;
Ar is a 1,4-substituted phenylene;
sAr is 1,3-substituted phenylene substituted in position 5 with SO3Me;
Me is Li, K, Mg/2, Ca/2, A1/3, ammonium, mono-, di-, tri-, or
tetraalkylammonium wherein the alkyl groups are (Ci-C22) alkyl or (C2-Cto)
hydroxyalkyl, or mixtures thereof;
le, R2, R3, R4, R5 and R6 are independently selected from H or (Ci-C18)n- or
iso-
alkyl preferably methyl; and R7 is a linear or branched (Ci-C18) alkyl, or a
linear
or branched (C2-C30) alkenyl, or a cycloalkyl group with 5 to 9 carbon atoms,
a
(C6-C30) aryl group or a (C6-050) arylalkyl group preferably phenyl or benzyl.
Preferably, the polyester terephthalate comprises the structural units (I) to
(III) wherein;
RI- to R6 independently are H or methyl,
R7 is methyl,
a, b and c are a number from 1 to 20, preferably a and b are 1 and c is a
number from 2 to
10,
d is a number between 1 and 25, preferably between 1 and 10, more preferably
between 1
and 5,
e is a number between 1 and 30, preferably between 2 and 15, more preferably
between 3
and 10, and
Date Recue/Date Received 2020-11-20
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f is a number between 0.05 and 15, preferably between 0.1 and 10, more
preferably between
0.25 and 3.
The polyester terephthalates according to the invention generally have a
number average
molecular weight in the range of 700 to 50000 g/mol, preferably 800 to 25000
g/mol, more
preferably 1000 to 15000 g/mol, most preferably 1200 to 12000 g/mol.
Suitable anionic polyester terephthalate soil release polymers are sold by
Clariant under
the TexCare series of polymers, e.g. TexCare0 SRA300.
The laundry detergent preferably comprises between 0.1% and 10% preferably
between
0.5 and 5% by weight of the detergent composition of the anionic polyester
terephthalate soil
release polymer. The anionic polyester terephthalate is present in the wash
liquor, preferably at a
concentration between 1ppm and 200ppm, preferably between 5ppm and 150ppm,
more preferably
between lOppm and 100ppm.
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
Examples:
The impact of a single variable addition of an anionically modified polyester
terephthalate
soil release polymer (Texcare0 SRA300) according to the invention on top of a
non-aqueous
soluble unit dose laundry detergent, towards amount of remaining malodor at
the end of a full scale
washing test has been assessed according to the protocol described herein.
Test Products:
The following compositions were prepared by mixing of the individual
components,
followed by enclosing in a water soluble PVA film, supplied by the Monosol
company, to obtain
water soluble unit dose laundry pouches. Each unit dose laundry pouch
comprised 29.932g of the
detergent compositions. Texcare0 SRA300 was added separately to the wash as a
20% active
aqueous solution.
Date Recue/Date Received 2020-11-20
13
Wt% Comparative Example 1A Example 1B Example
1C
Example 1
C1415E07 3.0 3.0 3.0 3.0
C1214E09 0.9 0.9 0.9 0.9
HLAS 22.8 22.8 22.8 22.8
C1215AE2.5S 15.5 15.5 15.5 15.5
Citric acid 0.9 0.9 0.9 0.9
C1218 Fatty acid 6.3 6.3 6.3 6.3
Enzymes 0.1 0.1 0.1 0.1
(amylase,
protease,
mannanase)
Ethoxylated 3.4 3.4 3.4 3.4
polyethyleneimine
(PEI600E020)*
Amphiphilic graft 2.3 2.3 2.3 2.3
polymer**
DTPA chelant 0.9 0.9 0.9 0.9
Brightener 49 0.2 0.2 0.2 0.2
Hueing dye 0.03 0.03 0.03 0.03
1,2-propanediol 11.9 11.9 11.9 11.9
glycerol 4.0 4.0 4.0 4.0
dipropyleneglycol 4.2 4.2 4.2 4.2
MEA 8.4 8.4 8.4 8.4
water 10.6 10.6 10.6 10.6
Hydrogenated 0.1 0.1 0.1 0.1
Castor Oil
Perfume, dye & Balance till 100 Balance till 100 Balance till 100 Balance
till 100
minors
Texcare0 - 0.1g active in 0.5g active in lg
active in
SRA300 wash wash wash
added separately
Date Recue/Date Received 2020-11-20
14
Wt% Comparative Example 2A Example 2B Example
2C
Example 2
C1415E07 3.0 3.0 3.0 3.0
C1214E09 0.9 0.9 0.9 0.9
HLAS 22.8 22.8 22.8 22.8
C1215AE2.5S 15.5 15.5 15.5 15.5
Citric acid 0.9 0.9 0.9 0.9
C1218 Fatty acid 6.3 6.3 6.3 6.3
Enzymes 0.1 0.1 0.1 0.1
(amylase,
protease,
mannanase)
Ethoxylated 3.4 3.4 3.4 3.4
polyethyleneimine
(PEI600E020)*
Amphiphilic graft 2.3 2.3 2.3 2.3
polymer**
DTPA chelant 0.9 0.9 0.9 0.9
Brightener 49 0.2 0.2 0.2 0.2
Hueing dye 0.03 0.03 0.03 0.03
1,2-propanediol 11.9 11.9 11.9 11.9
glycerol 4.0 4.0 4.0 4.0
dipropyleneglycol 4.2 4.2 4.2 4.2
MEA 8.4 8.4 8.4 8.4
water 10.6 10.6 10.6 10.6
Hydrogenated 0.1 0.1 0.1 0.1
Castor Oil
Perfume, dye & Balance to Balance to Balance to Balance to
minors 100% 100% 100% 100%
Texcare0 - 0.25g active in 0.33g
active in 0.41g active in
SRA300 wash wash wash
added separately
*ethoxylated polyethyleneimine having an average degree of ethoxylation of 20
per EO chain
and a polyethyleneimine backbone with MW of about 600
Date Recue/Date Received 2020-11-20
15
**polyethylene glycol graft polymer comprising a polyethylene glycol backbone
(Pluriolim
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
Malodor cocktail:
The following malodor cocktail compositions were prepared by mixing of the
individual
components (supplied by Sigma Aldrich, purity grade >95% ¨ Artificial Body
Soil by Accurate
Product Development). The malodor cocktail is stored at a temperature below 0
C. Malodor
cocktails are re-equilibrated at room temperature prior to application on test
swatches.
Malodor Premix:
Material CAS # % Composition
Iso Valeric acid 503-74-2 12.00
Undecanal 112-44-7 0.20
Undecanoic Acid 112-37-8 62.80
Skatole 83-34-1 1.00
Decanoic Acid 334-48-5 22.00
Ethyl
undecanoate 627-90-7 2.00
COMPONENT WEIGHT NEEDED (g)
Malodor Premix 11.7
Artificial Body Soil 17.55
Squalene (cas # 111-02-4) 17.55
After weighing add 135 mL Di-propylene glycol monomethyl
ether (CAS: 34590-94-8) using a glass graduated cylinder
Testing Protocol:
Wash Test:
2x5 inch de-sized polycotton (50/50) test swatches, as supplied by Accurate
Product
Development, global materials supplier located in Cincinnati, Ohio, are pre-
conditioned with test
product prior to soiling. Herefore a single unit dose of the test product is
placed first towards the
Date Recue/Date Received 2020-11-20
16
back of the drum of a DuetTM 9200 front-loading washing machine, followed by
addition of half
of the ballast load size (1.95kg), the test swatches (16 pieces) and the
remaining half of the ballast
load size (1.95kg). A normal cycle is run at 77 F washing temperature, 60 F
rinsing temperature
and 7 gpg water hardness. This pre-conditioning step is repeated 4 times,
followed by drying the
test swatches together with 4 clean, dry hand towels for 20 minutes in a
MaytagTM Double Stack
dryer.
Malodour sensors are freshly prepared by applying the malodour cocktail to the
pre-
conditioned test swatches, using an Integra ViafloTM Automatic Pipette
attached with a 96-channel
head (8x12) and 300p1 pipette tips. 3 rows of 12 tips are filled with product,
each tip providing
15p1 of malodour cocktail on the pre-conditioned test swatches). 16 soiled
swatches, i.e. the
malodour sensors, are placed together and wrapped up in an Aluminium foil
straight after
completion of the malodour cocktail addition. These malodour sensors are
stored at room
temperature under a fume hood for use on the same day in a washing test.
For the washing test a single unit dose of the test product is placed first
towards the back
of the drum of a Duet 9200 front-loading washing machine, followed by addition
of half of the
ballast load size (1.95kg), the malodour soiled test swatches (16 pieces) and
the remaining half of
the ballast load size (1.95kg). A normal cycle is run at 77 F washing
temperature, 60 F rinsing
temperature and 7 gpg water hardness, followed by drying the malodour soiled
test swatches
together with 4 clean, dry hand towels for 20 minutes in a MaytagTM Double
Stack dryer. 10
malodour sensor swatches are consequently stored overnight in a heat-sealed
mylar bag for sensory
evaluation, 6 malodour sensor swatches are equally stored overnight and sent
for analytical
evaluation. This washing test is repeated 4 times, such that 64 test swatches
are obtained.
Evaluation:
Sensory Evaluation:
The 40 malodour sensor swatches per test leg (10 internal replicates per wash
x 4 external
replicate washes) are consequently assessed for remaining malodour intensity.
One of the test
designs recommended by ASTM (E1958) for finding differences in measurable
attributes is using
a trained sensory expert panel, also called descriptive analysis panel. The
malodour sensor
swatches are assessed by 9 trained external (i.e. non-employees) sensory
expert panellists, who
grade on malodour intensity and were trained on how to grade the prepared
fabrics for dry fabric
malodour intensity using their typical 0 (no malodour left) -100 (strong
malodour left) scale. The
malodour assessment is conducted 2-fold, i.e. before and after rubbing the
malodour sensor
Date Recue/Date Received 2020-11-20
17
swatches. All samples were labelled with a blinded 3-digit code, and
presentation order was
randomized.
Pre-rub assessment:
The test swatches are folded in 2 and opposite ends of the half-folded
swatches are
stretched with 2 hands. The left and right side of the test swatch are
consequently sniffed, prior to
flipping over the top end of the test swatch to assess the opposite side of
the test swatch by sniffing
again the left and right side. A remaining malodour intensity grade on a zero
(no malodour left) to
100 (strong malodour left) scale is consequently provided. All 40 test
swatches are assessed first
for pre-rub, prior to move to post-rub assessment. A break of 2 minutes is
provided in-between
different test swatch evaluations. The average pre-rub malodour intensity
grade of the 40 test
swatches and the 9 panellists is calculated and recorded.
Post-rub Assessment:
The test swatches are folded in 2 and opposite ends of the half-folded
swatches are
stretched with 2 hands.
The 2 hands are consequently brought together and with pressure rubbed
together up and
down 5 times, at a trained and calibrated pressure of 1.2 to 2.4 psi. The
rubbed area of the test
swatch is consequently sniffed and a remaining malodour intensity grade on a
zero (no malodour
left) to 100 (strong malodour left) scale is again provided. All 40 test
swatches are assessed for
post-rub. A break of 2 minutes is provided in-between different test swatch
evaluations. The
average post-rub malodour intensity grade of the 40 test swatches and the 9
panellists is calculated
and recorded.
Analytical Evaluation:
Analytical evaluation of remaining malodour actives on test swatches after a
laundry wash
test has been conducted through a headspace measurement above test fabrics.
Herefore a Gas
Chromatograph 7890B equipped with a Gerstel Multi-Purpose sampler equipped
with a solid
phase micro-extraction (SPME) probe
(Divinylbenzene/Carboxen/Polydimethylsiloxane SPME
fiber from Supelco part# 57298-U), DB-FFAP column Agilent part# 122-3232 (30
m, 0.25 mm,
0.25 gm), a Mass Selective Detector (5977B), and ChemstationTM quantitation
package was used.
Test swatches were cut in 2x2.5 inch pieces and placed in a 10 ml headspace
crimp vial, and
allowed to equilibrate for 12 hours prior to running the analytical
measurement. Test results were
compared versus malodour standards to quantify amount of remaining malodour.
Malodour
standards for analysis were prepared by pipetting 1.18 mL of the malodour
standard at room
Date Recue/Date Received 2020-11-20
18
temperature into 10 mL deactivated headspace vials and equilibrated in an oven
g 80 C for 90
minutes and allowed to sit overnight before analysis.
Gerstel auto sampler parameters:
= SPME: from Incubator
= Incubation Temperature : 80 'C
= Incubation Time : 90.00 min SAMPLE PARAMETERS
= Sample Tray Type : VT32-10
= Vial Penetration : 22.00 mm
= Extraction Time : 20.00 min
= Inj. Penetration : 54.00 mm
= Desorption Time : 300 s
GC oven parameter:
= Front SS Inlet He
= Mode Split
= Heater On 250 C
= Pressure On 11.962 psi
= Total Flow On 79.5 mL/min
= Septum Purge Flow On 3 mL/min
= Split Ratio 50 :1
= GC Run Time 22.5 min
= Oven
= (Initial) 40 C
= Hold Time 0 min
= Heating Program
= Rate 12 C/min
= Temp 250 C
= Hold Time 5
Date Recue/Date Received 2020-11-20
19
MSD parameters:
= Run in scan mode with a minimum range of 40 to 350 m/z (range may be
greater). A target
ion for quantification is determined for each malodour component along with a
minimum
of 1 qualifier ion, preferably 2. The defined target and qualifier ions for
each component
must be based on an MSD compound library or standard.
= Calibration curves are generated from the standards in mineral oil for
each malodour
material. Utilizing the calibration headspace response, the integration of the
extracted ion
(EIC) for each malodour components in the samples are plotted or recorded.
Test Results :
It is clear from both the sensory panel as from the analytical data tabulated
below (the lower the
better) that single variable addition of Texcare0 SRA300 technology on top of
unit dose liquid
laundry detergent formulation results in a reduction of remaining malodour on
fabric.
Sensory Panel Analytical data
Water
Post- Total Gen V
Pre-Rub Squalene Soluble
Rub Markers Markers
Acids
Comparative 27.0 18.1
206.4 173.8 17.8 32.6
Example 1
Example 1A 28.5 17.4 173.6 138.1 23.7 35.5
Example 1B 22.8 12.5 69.7 49.8 5.6 19.9
Example 1C 20.4 9.8 39.3 22.4 1.3 17.0
Sensory Panel Analytical data
Water
Post- Total Gen V
Pre-Rub Squalene Soluble
Rub Markers Markers
Acids
Comparative 33.3 23.4
94.0 56.6 22.3 37.4
Example 2
Example 2A 27.0 17.4 60.5 33.2 15.8 27.4
Example 2B 24.3 15.0 49.8 26.7 10.5 23.2
Example 2C 24.3 16.1 39.6 20.3 7.2 19.4
Date Recue/Date Received 2020-11-20
