Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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PRODUCT
The present invention relates a detergent dispensing cartridge for use with a
washing machine.
The washing of clothes in automatic washing machines is well known and is
practised extensively.
Ways are often sought to improve the washing action by modification of the
detergent used, the nature of the washing cycle and the machine itself.
There is an ever increasing need to modify washing processes such that
external resources (especially water and electricity) are used more
effectively. Also there is increasing environmental pressure on the reduction
of excessive chemical use in cleaning.
Further consumers are more
demanding in terms of the time that they must spend in performing
household chores.
According to a first aspect of the present invention there is provided a
detergent dispensing cartridge for use in a washing machine, wherein the
washing machine is for cleaning a soiled substrate, comprising the treatment
of the moistened substrate with a formulation comprising a multiplicity of
polymeric particles, the cartridge having multiple compartments; a first
compartment holds a first detergent formulation; and a second compartment
holds a second detergent formulation or a formulation, wherein a portion of
the contents of the first compartment are released before a portion of the
contents of the second compartment.
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According to a second aspect of the present invention there is provided a
detergent dispensing cartridge for use in a washing machine, wherein the
washing machine is for cleaning a soiled substrate, comprising the treatment
of the moistened substrate with a formulation comprising a multiplicity of
polymeric particles, wherein said formulation is free of organic solvents, the
cartridge having multiple compartments; a first compartment holds a first
detergent formulation; and a second compartment holds a second detergent
formulation, wherein a portion of the contents of the first compartment is
released before a portion of the contents of the second compartment is
released.
According to a third aspect of the present invention there is provided a
detergent dispensing cartridge for use in a washing machine, wherein the
washing machine is for cleaning a soiled substrate, comprising the treatment
of the moistened substrate with a formulation comprising a multiplicity of
polymeric particles, wherein said formulation comprises an organic solvent,
the cartridge having multiple compartments; a first compartment holds a
first detergent formulation; and a second compartment holds a second
detergent formulation, wherein a portion of the contents of the first
compartment is released before a portion of the contents of the second
compartment is released.
The cartridge has been found to be highly efficient and effective at providing
in an accurate way the (very small) detergent doses required by the type of
machine which is most suitable for use with the cartridge. It has been
observed that the same accuracy of dosing cannot be reached with a
traditional, hand-loaded, drawer.
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By washing machine any vessel / machine (whether manually operated or
fully / partially automated) which is capable of being used in a washing
operation is intended. The washing machine is preferably an automatic
clothes washing machine. Most preferably the washing machine is one
which has been modified such that it operates using the technology of one or
more of the co-pending patent applications W02007/128962, GB 0902619.6,
GB 0907943.5, GB 0916249.6, GB 0916250.4, GB 0920565.9, GB
1002245.7, and GB 1006076.2; the disclosures of which are incorporated by
reference.
Preferably the ratio of beads to substrate is generally in the range of from
30:1 to 0.1:1 w/w, preferably in the region of from 10:1 to 1:1 w/w, with
particularly favourable results being achieved with a ratio of between 5:1
and 1:1 w/w, and most particularly at around 2:1 w/w. Thus, for example,
for the cleaning of 5 g of fabric, 10 g of polymeric particles would be
employed
The polymeric particles are of such a shape and size as to allow for good
flowability and intimate contact with the textile fibre. A variety of shapes
of
particles can be used, such as cylindrical, spherical or cuboid; appropriate
cross-sectional shapes can be employed including, for example, annular ring,
dog-bone and circular. The particles may have smooth or irregular surface
structures and can be of solid or hollow construction.
Particles are
preferably of such a size as to have an average mass in the region of 5 to
100 mg, preferably from 10 to 30 mg. In the case of the most preferred
beads, the preferred average particle diameter is in the region of from 0.5 to
6.0 mm, more preferably from 1.0 to 5.0 mm, most preferably from 2.5 to
4.5 mm, and the length of the beads is preferably in the range from 0.5 to
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6.0 mm, more preferably from 1.5 to 4.5 mm, and is most preferably in the
region of 2.0 to 3.0 mm.
Said polymeric particles may comprise any of a wide range of different
polymers.
Specifically, there may be mentioned polyalkenes such as
polyethylene and polypropylene, polyesters and polyurethanes, which may
be foamed or unfoamed. Preferably, however, said polymeric particles
comprise polyamide or polyester particles, most particularly particles of
nylon, polyethylene terephthalate or polybutylene terephthalate, most
preferably in the form of beads. Said polyamides and polyesters are found
to be particularly effective for aqueous stain/soil removal, whilst
polyalkenes
are especially useful for the removal of oil-based stains.
Optionally,
copolymers of the above polymeric materials may be employed.
Various nylon or polyester homo- or co-polymers may be used including, but
not limited to, Nylon 6, Nylon 6,6, polyethylene terephthalate and
polybutylene terephthalate.
Preferably, the nylon comprises Nylon 6,6
homopolymer having a molecular weight in the region of from 5000 to
30000 Daltons, preferably from 10000 to 20000 Daltons, most preferably
from 15000 to 16000 Daltons. The polyester will typically have a molecular
weight corresponding to an intrinsic viscosity measurement in the range of
from 0.3-1.5 dl/g, as measured by a solution technique such as ASTM D-
4603.
Generally the polymeric particles comprise nylon chips, e.g. Nylon 6 or Nylon
6,6.
It has been found that with the use of a cartridge great benefits are provided
to a consumer in terms of ease of use. The use of a cartridge allows
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discharge of a detersive composition into a washing machine (over multiple
wash cycles) where the consumer has no need to measure the detersive
composition or come into contact with same yet have the security of
knowing that the correct detersive composition has been applied to the wash
load of the machine.
Separate containment and release has been found to be useful for many
reasons including storage stability of compartment components, particularly
for antagonistic components. For example the antagonist interaction
between bleach and enzyme may be obviated. Thus the enzyme based
formulation has time to fully perform on enzyme based stains before any
detrimental interaction with any bleach related species occurs.
A further example is the reduction / elimination of components that have
opposite ionic charges. In this regard most dye fixatives / dye transfer
inhibitors (e.g. such as PVP, PVP-VI, PVNO based compounds or derivates
thereof) (hereafter DTIs) have a positive charge. The presence of this
positive charge brings about a detrimental interaction between anionic
surfactants which are typically employed in detergents (especially laundry
detergents to provide cleaning function). The dye fixatives / DTIs and the
anionic surfactants "couple" together because of their opposing charges,
compromising their respective functions. One way to avoid this problem is
to replace the anionic surfactants with nonionic surfactants which avoids the
coupling effect however typically nonionic surfactants provide a poorer
cleaning function that anionic surfactants. By the placement of the dye
fixatives / DTI in a compartment separate from any anionic surfactant the
coupling problem may be obviated.
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Preferably the cartridge has one or more further compartments. Generally
each compartment may be activated separately such that the contents of
each compartment may be released separately / sequentially.
Each
compartment may be designed such that it holds a bespoke complete
detergent formulation or a formulation that focuses upon a single active
component of a detergent formulation. It
is preferred that each
compartment may be activated separately; either in completely individual
activation or in a "program" that activates one or more compartments at
pre-defined portions of a wash cycle so that a portion of the compartment
content may be released. In this way it has been found that the detergent
release can be tailored to suit a particular wash load in terms of its size,
compositions and type of staining present thereon. Clearly it is envisaged
that a particular compartment may be activated once, not at all or a plurality
of occasions in a wash cycle.
Additionally with the containment / release in separate compartments, the
temperature / heating of the wash liquor may be tailored such that it is
optimized to work with the contents of the compartment being released at
that juncture. As an example when a bleach / bleach activator composition
is released heating of the wash liquor (e.g. to around 40-60 C) may be
appropriate to ensure that optimal functioning of the bleach / bleach
activator composition occurs. In contrast many of the other detergent
components require no wash liquor heating to achieve their optimal function.
In this aspect it is to be understood that the entire wash liquor or a portion
thereof may be heated. Where only a portion of the wash liquor is heated
the portion may be a portion of the wash liquor which is passing through r
adjacent to the cartridge or the portion passing through or adjacent to any
wash liquor circulation system.
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Moreover the containment / release in separate compartments allows the pH
of the wash liquor may be tailored such that it is optimized to work with the
contents of the compartment being released at that juncture. As an
example when a bleach / bleach activator composition is released raising of
the pH of the wash liquor (e.g. to an alkaline pH by release of a suitable pH
modifying agent) may be appropriate to ensure that optimal functioning of
the bleach / bleach activator composition occurs. In contrast many of the
other detergent components require no pH adjustment to achieve their
optimal function.
Plus with the containment / release in separate compartments, release of
individual detergent actives may be tailored such that it is optimized to work
with the system of W02007/128962.
In this regard it has been found that one preferred release profile is in the
following order:-
a) Release of an enzyme containing formulation;
b) Release of an oxidising formulation;
c) Release of a builder / fabric conditioner containing formulation.
Another preferred release profile is in the following order:-
a) Release of an enzyme containing formulation;
b) Release of a oxidising formulation;
c) Release of a builder / fabric conditioner containing formulation.
d) Release of a dye fixative / DTI containing formulation.
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Composition (a) and / or (b) and / or (c) may also contain a surfactant. The
oxidising formulation may contain a bleach and / or a bleach activator /
catalyst.
Preferably step (d) occurs at the end of the washing machine cycle, during
the rinse phase. This for two reasons: dye fixative / DTI are generally
"quaternary" molecules (i.e. including at least one N+ moiety), as such they
could cause precipitation in presence of anionic surfactants. Also if added
before the cleaning phase, dye fixative / DTI could fix the stains (e.g. to
the
material being cleaned).
In accordance with the method of W02007/128962 the polymeric particles
used may be present throughout the entire laundry washing cycle or only for
a portion thereof. Where the polymeric particles are only present for a
portion of the washing cycle it is preferred that the polymeric particles are
removed form the washing area of the washing machine at a rinse cycle
(preferably a final rinse cycle) of the washing machine operation.
The cartridge may comprise compartments for release of some detersive
components in a pre-wash cycle (which may be before the beads are added
to the machine) of the washing machine operation. This has been found to
be beneficial with certain detergent components, the activity of which may
be compromised by adsorption on the polymeric particles.
Additionally or alternatively the cartridge may comprise compartments for
release of some detersive components in a rinse cycle (preferably a final
rinse cycle) of the washing machine operation. This has been found to be
beneficial with certain detergent components, the activity of which may be
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compromised by adsorption on the polymeric particles. Preferred examples
of detersive components for release at this stage (and for which there is
preferably a compartment in the cartridge) are optical brighteners and
fragrances. The cartridge compartments may be modular, e.g. one or more
compartments of the cartridge may be replaceable without replacing the
entire cartridge. Equally it is preferred that a consumer may select which
compartments are most suitable for their kind of typical washing so that a
complete cartridge may be constructed using the compartments that they
are most like to require in their washing.
Each compartment may have a volume of from 1 to 5000 cc, more
preferably from 10 to 900 cc, more preferably from 20 to 600 cc, more
preferably from 20 to 400 cc, more preferably from 20 to 300 cc, more
preferably from 20 to 200 cc and most preferably from 20 to 100 cc.
The positioning of the cartridge in the washing machine is flexible. Clearly
it
is preferred that the cartridge is positioned such that the cartridge contents
can be dispensed into the area of washing of the washing machine. A
conduit may be present to connect the cartridge output to the washing area.
Alternatively and / or additionally the cartridge may be positioned such that
its output is adjacent to or connected to fresh incoming wash fluid (e.g.
water). The cartridge may be positioned / the washing machine may be
designed such that fresh incoming wash fluid / wash liquor flows over /
around the device.
The cartridge compartment activation may be operated by one or more of a
number of mechanisms. Different activation mechanisms may be used for
different compartments of the cartridge.
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Preferred operation mechanisms may be manual or non-manual
mechanisms. Preferred non-manual operation mechanisms include physical
and chemical activation triggers associated with changes within the washing
cycle). Preferred examples include time, temperature / temperature
changes, smell/ odour, humidity / water presence (or some other associated
property of the cleaning liquor, e.g. such as ionic strength or pH), drum
rotation / centrifugal force or other force. Other operation mechanisms may
arise from a result of a conduit from the cartridge to the washing machine
(particularly the washing machine operating schematics) such that the
operation of the washing machine, triggered by the schematics of the
washing machine, influences or causes operation of one or more of the
compartments or the cartridge at one or more time points within the
washing cycle. In this way different washing cycles may triggers different
activation / operation of the cartridge / compartments thereof. Additionally
different wash loads / conditions may trigger a differential degree of
operation of one or more compartments.
The cartridge may also have a manual override which can be accessed by a
consumer. This manual override may overcome any normal dispense
activity of the cartridge and influence the dispensing such that the release
of
one or more compartments is increased / reduced and / or the timing of the
release is affected.
The entire contents of a compartment may be discharged in a single wash
cycle, either in one part of a single wash cycle or at multiple parts thereof.
More preferably the contents of a compartment may be released over a
plurality of wash cycles, e.g. over 10-30 wash cycles (such as about 20 wash
cycles) for added convenience to a consumer. In this case the cartridge
contents may still be released at multiple points over a plurality of cycles.
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Preferably the cartridge and / or one or each compartment thereof may have
an "end-of-life" indicator to make sure that a consumer is aware that the
contents of one or more compartment has been exhausted and needs to be
replenished. The end-of-life" indicator may be triggered by or arise through
liaison with the schematics of the washing machine
Equally in one embodiment of the device the cartridge is intended for a
single washing cycle.
Compartment release operation may be by one or more of a number of
mechanisms. Preferred compartment release mechanisms include manual
release (e.g. opening, squeezing), gravitational release, active release (e.g.
by a motor / pump, such as a powered motor, wax motor, piezo, injection or
spray) and passive release driven by a flow or wash liquor / polymeric
particles through or adjacent to a compartment drawing the contents of the
compartment (or a portion thereof) there from. The release may be
combination of active and passive mechanisms, e.g. an access means to a
compartment may be opened under a certain condition to allow release of an
active from a compartment. A preferred example of such an activating
mechanism is a bimetallic driven opening means such that the opening
means is activated at a certain predetermined temperature to allow release
(by whatever mechanism) to occur.
For detersive components (and associated compartments) which make up a
smaller portion of the entire detersive formulation (e.g. fragrances, optical
brighteners) more active dispensing methods, e.g. spraying may be
preferred. For detersive components (and associated compartments) which
make up a larger portion of the entire detersive formulation (e.g.
surfactants, builders) more passive dispensing methods may be preferred.
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The compartment contents may be in any suitable physical form. Preferred
forms include liquids (dispersions, suspensions, pastes, solutions and
emulsions, gels) and solids (solidified gels, powders, tablets). In a
cartridge
the content of differing compartments may be in differing physical forms.
The compartment contents may be contained in a secondary packaging, e.g.
such as an encapsulation means, pouch or sachet.
The compartment contents may be refillable. The refill contents may be in
the form of granules, powders, or liquids / gel dependent on the chemical /
physical nature of the nature of the composition for the / each compartment.
The refill composition may be in the form of a "unit-dose" composition, e.g.
a compressed / solidified / moulded tablet or the refill may be package in a
film pouch wherein the film may be entirely water soluble / dispersible or
have a water soluble potion or pierce-able section to allow release of the
pouch contents. The film pouch may comprise a metallic foil or a plastics
material, e.g. polypropylene, polyethylene, polyvinylalcohol, ABS, PET,
polyamides, PMMA or PC. Clearly the unit dose composition will be sized to
fit the respective compartment and allow ease of refilling without exposing a
consumer to any harmful chemicals. A plurality of unit-dose entities may fit
in one compartment; such an arrangement may have a separate support
frame associated therewith.
As well as conventional detersive actives (see later) the cartridge may
contain one or more actives directed to increasing the activity of the
polymeric particles. In this regard one preferred active is a plasticiser for
the polymeric particles. It is postulated that with the use of such a
plasticiser the Tg of the polymeric particles would be lowered such that the
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polymeric particles would be more active at lower temperatures. The
formulation may include sacrificial agents that are absorbed onto sites on
the polymeric particles, wherein these sites would otherwise cause
detrimental adsorption of one or more detersive active.
The cartridge may include a compartment which contains (supplementary)
polymeric particles. These particles may be purely polymer or may have
been physical or chemically altered to affect their activity. Preferred means
of chemical alteration include polymeric particles into which a detersive
active has been reversibly / irreversibly adsorbed (e.g. enzyme, bleach
catalyst) or upon which a detersive active has been coated.
With the use of the cartridge of the invention it has been found that the
overall detersive formulation may be altered because of the presence of the
polymeric particles. One example of an alteration is that the overall amount
of detergent required per wash cycle is considerably lower. Indeed in this
regard it has been found that the amount of detergent required may be as
low as 50%, 40%, 30%, 20% or even 10% of the amount that would
ordinarily be expected for a clothes washing operation in an automatic
laundry washing machine. As an example it has been found that with the
use of the cartridge of the invention an equivalent washing standard can be
achieved for a 5kg load of laundry in an automatic laundry washing machine
using as little as 15g of a liquid detergent formulation (whereas in a
conventional washing process in an automatic laundry washing machine
150g of the same liquid formulation would be required).
Where a smaller amount of detergent is used it has been found that the
amount(s) of certain components typically found in a household laundry
detergent may be reduced. In particular it has been found that the amount
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of builder required may be lower. Another alteration is that it has been
found that the detersive surfactant may be altered (in terms of amount and
/ or nature thereof) because the polymeric particles may form a modified
detersive micelle with a polymeric particle at the centre of the micelle. A
further alteration is that (due to the lower amount of wash liquor the amount
of certain actives, e.g. such as fragrance, optical brightener, which would be
wasted by extraction with excessive rinse water, may be dramatically
reduced.
Since a smaller amount of detergent (than for conventional laundry washing)
is required it has been found that the overall size of the cartridge and the
individual compartments thereof may be small with enhanced convenience
for a consumer.
With the use of the cartridge of the invention it has been found that overall
washing cycle may be altered. One example of an alteration is that higher
temperatures may be used (on at least a portion of the wash liquor),
typically for brief periods, (with no detriment to the amount of energy used
since the amount of wash liquor in the machine is lower). This has been
found to be beneficial in that the action of certain detersive components,
e.g. bleaches, can be increased, often at a lower concentration of the active
and possibly without any co-active (for bleach a co-active would be a bleach
catalyst / bleach activator).
It is understood that generally the washing cycle temperature is from 0 C to
90 C, more preferably between 5 C and 90 C, more preferably between 5 C
and 70 C, more preferably between 15 C and 40 C, e.g. about 30 C.
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The washing cycle time is preferably between 15 and 150 minutes, more
preferably between 15 and 120 minutes, and most preferably between 20
and 40 minutes. The rinsing proportion of the cycle is preferably up to 50%
of the entire cycle time, more preferably up to 40%, more preferably up to
20%, more preferably up to 10%. The final spin may be around 5% of the
entire cycle time. Intermediate spins (e.g. between parts of the cycle) may
be (individually or collectively) around 1-2% of the entire cycle time.
The amount of washing water used in a wash cycle is preferably around 6
litres per kilo of wash load; with around 3 liters for the washing stage(s)
and
3 litres for the rinsing stage(s). The amount of water can be lower, e.g.
preferably between 2.5:1 and 0.1:1 litres per kilo of wash load; more
preferably, the ratio is between 2.0:1 and 0.8:1 litres per kilo of wash load,
with particularly favourable results having been achieved at ratios such as
1.5:1, 1.2:1 and 1.1:1 litres per kilo of wash load.
This compares to around 13 litres per kilo of wash load for a conventional
washing machine; with around 4 liters for the washing stage(s) and 9 litres
for the rinsing stage(s).
The cartridge may be designed to be placed at a suitable locus in or on the
washing machine, e.g. in the drum / drawer.
The cartridge may operate with a suitable cartridge receiving means within
or associated with the washing machine. The cartridge receiving means may
be entirely mechanical. Alternatively the cartridge receiving means may
include an electronic component with associates with a portion of the
cartridge (and optionally drives operation of a portion of the cartridge). The
cartridge receiving means may include a mechanism that identifies the
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presence of a cartridge (and / or individual compartments thereof), e.g. such
as a radio-frequency identification (RFID) mechanism, e.g. such as a bar
code on the cartridge.
The cartridge preferably comprises a plastics material, e.g. polypropylene,
polyethylene, ABS, PET, polyamides, PMMA or PC. The cartridge /
compartment material may be coated, e.g. with a barrier layer. Such a layer
may be used to allow more aggressive chemical inclusion (e.g. to aid the
prevention of polymer stress cracking).
In one embodiment of the invention it is preferred that a plurality of
separate cartridges may be used simultaneously in a washing machine /
washing machine cycle. Each cartridge may be disposed in a different part
of the washing machine or the same part of the washing machine. Each
cartridge may contain the same or a complementary detergent composition
or compositions (e.g. in a number of compartments).
A bead cleaning process may be carried out typically every 5-6 washes,
allows the surface of the beads to remain highly active in the washing
process. Preferably, bead cleaning is carried out by adding individual doses
of surfactants (non-ionic and/or anionic and/or cationic), and optionally
other more aggressive chemicals, selected from, for example,
sodium/potassium hydroxide, hypochlorates, hypochlorites or the other
bleaches and activators previously recited, to an amount of water, such that
the ratio of water to beads is preferably in the region of 0.5-3 litres
water/kg
of beads. The bead cleaning process may be facilitated by release of a
suitable cleaning composition from the cartridge.
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Preferred examples of surface active agents include anionic, non-ionic,
cationic, amphoteric or zwitterionic surface active agent or mixture thereof.
Examples of anionic surfactants are straight-chained or branched alkyl
sulfates and alkyl polyalkoxylated sulfates, also known as alkyl ether
sulfates. Such surfactants may be produced by the sulfation of higher C8-C20
fatty alcohols.
Examples of primary alkyl sulfate surfactants are those of formula:
ROS03-M+
wherein R is a linear C8-C20 hydrocarbyl group and M is a water-solubilising
cation.
Preferably R is C10-C16 alkyl, for example C12-C14, and M is alkali metal such
as lithium, sodium or potassium.
Examples of secondary alkyl sulfate surfactants are those which have the
sulfate moiety on a "backbone" of the molecule, for example those of
formula:
CH2(CH2)n(CHOS03-M+)(CH2)mCH3
wherein m and n are independently 2 or more, the sum of m+n typically
being 6 to 20, for example 9 to 15, and M is a water-solubilising cation such
as lithium, sodium or potassium.
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Especially preferred secondary alkyl sulfates are the (2,3) alkyl sulfate
surfactants of formulae:
CH2(CH2)x(CHOS03-M+)CH3 and
CH3(CH2)x(CHOS03-M+)CH2CH3
for the 2-sulfate and 3-sulfate, respectively. In these formulae x is at least
4, for example 6 to 20, preferably 10 to 16. M is cation, such as an alkali
metal, for example lithium, sodium or potassium.
Examples of alkoxylated alkyl sulfates are ethoxylated alkyl sulfates of the
formula:
RO(C2H40)nS03-M+
wherein R is a C8-C20 alkyl group, preferably C10-C18 such as a C12-C16, n is
at least 1, for example from 1 to 20, preferably 1 to 15, especially 1 to 6,
and M is a salt-forming cation such as lithium, sodium, potassium,
ammonium, alkylammonium or alkanolammonium. These compounds can
provide especially desirable fabric cleaning performance benefits when used
in combination with alkyl sulfates.
The alkyl sulfates and alkyl ether sulfates will generally be used in the form
of mixtures comprising varying alkyl chain lengths and, if present, varying
degrees of alkoxylation.
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Other anionic surfactants which may be employed are salts of fatty acids, for
example C8-C18 fatty acids, especially the sodium potassium or
alkanolammonium salts, and alkyl, for example C8-C18, benzene sulfonates.
Examples of nonionic surfactants are fatty acid alkoxylates. The ethoxylated
and propoxylated nonionic surfactants are preferred. Preferred alkoxylated
surfactants can be selected from the classes of the nonionic condensates of
alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/
propoxylated fatty alcohols, nonionic ethoxylate/ propoxylated condensates
with propylene glycol, and the nonionic ethoxylate condensation products
with propylene oxide/ethylene diamine adducts.
Preferred fatty acid
ethoxylates, are especially those of formula:
R(C2H40),OH
wherein R is a straight or branched C8-C16 alkyl group, preferably a Cg-C15,
for example C10-C14, or C12-C14 alkyl group and n is at least 1, for example
from 1 to 16, preferably 2 to 12, more preferably 3 to 10.
The alkoxylated fatty alcohol nonionic surfactant will frequently have a
hydrophilic-lipophilic balance (HLB) which ranges from 3 to 17, more
preferably from 6 to 15, most preferably from 10 to 15.
Examples of fatty alcohol ethoxylates are those made from alcohols of 12 to
15 carbon atoms and which contain about 7 moles of ethylene oxide. Such
materials are commercially marketed under the trademarks Neodol 25-7 and
Neodol 23-6.5 by Shell Chemical Company. Other useful Neodols include
Neodol 1-5, an ethoxylated fatty alcohol averaging 11 carbon atoms in its
alkyl chain with about 5 moles of ethylene oxide; Neodol 23-9, an
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ethoxylated primary C12-C13 alcohol having about 9 moles of ethylene oxide;
and Neodol 91-10, an ethoxylated C9-C11 primary alcohol having about 10
moles of ethylene oxide.
Alcohol ethoxylates of this type have also been marketed by Shell Chemical
Company under the Dobanol trademark. Dobanol 91-5 is an ethoxylated Cg-
C11 fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-
7 is an ethoxylated C12-C15 fatty alcohol with an average of 7 moles of
ethylene oxide per mole of fatty alcohol.
Other examples of suitable ethoxylated alcohol nonionic surfactants include
Tergitol 15-S-7 and Tergitol 15-S-9, both of which are linear secondary
alcohol ethoxylates available from Union Carbide Corporation. Tergitol 15-S-
7 is a mixed ethoxylated product of a C11-C15 linear secondary alkanol with 7
moles of ethylene oxide and Tergitol 15-S-9 is the same but with 9 moles of
ethylene oxide.
Other suitable alcohol ethoxylated nonionic surfactants are Neodol 45-11,
which is a similar ethylene oxide condensation products of a fatty alcohol
having 14-15 carbon atoms and the number of ethylene oxide groups per
mole being about 11. Such products are also available from Shell Chemical
Company.
Further nonionic surfactants are, for example, C10-C18 alkyl polyglycosides,
such s C12-C16 alkyl polyglycosides, especially the polyglucosides. These are
especially useful when high foaming is desired. Further surfactants are
polyhydroxy fatty acid amides, such as C10-C18 N-(3-methoxypropyl)
glycamides and ethylene oxide-propylene oxide block polymers of the
Pluronic type.
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Examples of cationic surfactants are those of the quaternary ammonium
type.
Preferred quaternary ammonium compounds have the formula (I) or (Ia), or
include a mixture thereof;
[R'-(C0)-0-R-N+(-R")(-(R0),-,1-1)(-R-0-(C0)-Rf)]X- (I)
[R'-(C0)-NH-R-N+(-R1)(-(R0),-,H)(-R-NH-(C0)-R'AX- (Ia)
wherein:
R is an alkylene or alkenylene group having 2 to 4 carbon atoms;
R' is an alkyl or alkenyl group having 8 to 22 carbon atoms;
n is an integer having a value of 1 to 4;
R" is an alkyl group having 1 to 4 carbon atoms; R1 is an alkyl group having
1 to 4 carbon atoms or hydrogen; and
X- is a softener-compatible anion.
Non-limiting examples of softener-compatible anions (V) include chloride,
formate, nitrate, sulfate or C1-4 alkyl sulfate, preferably methyl sulfate.
The alkyl or alkenyl R' ideally must contain at least 10 carbon atoms,
preferably at least 14 carbon atoms, more preferably at least 16 carbon
atoms. The group may be straight or branched.
A specific example of quaternary ammonium compound is di-(tallow
carboxyethyl)hydroxyethylmethyl ammonium X.
A cationic fabric co-softener may be present.
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Examples of amphoteric surfactants are C10-C18 amine oxides and the C12-
C18 betaines and sulfobetaines.
Suitable builders are alkali metal or ammonium phosphates, polyphosphates,
phosphonates, polyphosphonates, carbonates, bicarbonates, borates,
polyhydroxysulfonates, polyacetates, carboxylates such as citrates and other
polycarboxylates / polyacetyl carboxylates such as succinate, malonate,
carboxymethyl succinate.
There are three main types of method of action for water-softening agents,
described below.
1) Ion exchange agents - such agents include alkali metal (preferably
sodium) aluminosilicates either crystalline, amorphous or a mixture of the
two. Such aluminosilicates generally have a calcium ion exchange capacity of
at least 50 mg CaO per gram of aluminosilicate, comply with a general
formula:
0.8-1.5 Na20. A1203. 0.8-6 5i02
and incorporate some water. Preferred sodium aluminosilicates within the
above formula contain 1.5-3.0 5i02 units. Both amorphous and crystalline
aluminosilicates can be prepared by reaction between sodium silicate and
sodium aluminate, as amply described in the literature.
Suitable crystalline sodium aluminosilicate ion-exchange detergency builders
are described, for example, in GB 1429143 (Procter & Gamble). The
preferred sodium aluminosilicates of this type are the well known
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commercially available zeolites A and X, and mixtures thereof. Also of
interest is zeolite P described in EP 384070 (Unilever).
Another class of compounds are the layered sodium silicate builders, such as
are disclosed in US-A-4464839 and US-A-4820439 and also referred to in
EP-A-551375.
These materials are defined in US-A-4820439 as being crystalline layered,
sodium silicate of the general formula
NaMSix02x+i = YH20
wherein
M denotes sodium or hydrogen,
x is from 1.9 to 4 and y is from 0 to 20.
Quoted literature references describing the preparation of such materials
include Glastechn. Ber. 37,194-200 (1964), Zeitschrift fur Kristallogr. 129,
396-404 (1969), Bull. Soc. Franc. Min. Crist., 95, 371-382 (1972) and Amer.
Mineral, 62, 763-771 (1977). These materials also function to remove
calcium and magnesium ions from water, also covered are salts of zinc which
have also been shown to be effective water softening agents.
2) Ion capture agents - agents which prevent metal ions from forming
insoluble salts or reacting with surfactants, such as polyphosphate,
monomeric polycarboxylates, such as citric acid or salts thereof,
polycarboxylate polymers, such as polyacrylates, acrylic/maleic copolymers,
and acrylic phosphonates, EDTA, algins, alginates.
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3) Anti-nucleating agents - agents that prevent seed crystal growth, such as
polycarboxylate polymers, such as polyacrylates, acrylic/maleic copolymers,
and acrylic phosphonates, and sulfonates. Such polymers may also act as
ion capture agents as well.
Preferred organic water-soluble water softening agents which may be
present include polycarboxylate polymers, such as polyacrylates,
acrylic/maleic copolymers, and acrylic phosphonates, monomeric
polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol
mono- di- and trisuccinates,
carboxymethyloxysuccinates,
carboxymethyloxymalonates, dipicolinates, hyd roxyethyli mi nod iacetates,
phosphonates, iminodisuccinates, polyaspartic acids, BHT, phosphonate
stabilisers such as, diethylenetriaminepenta (methylene phosphonic acid and
its corresponding pentasodium salt) available under the trade names
Dequest 2060 and Dequest 2066 Monsanto Chemical Co), DTPMP and
DTPMA (Dequest 2010) and HEDP.
Preferably the water-soluble water softening agent is a neutralised or
partially neutralised carboxylic acid, such as citric acid, succinic acid or
maleic acid, and/or a neutralised or partially neutralised polycarboxylic
acid,
such as a polyacrylate of Mw: 4000-8000 (such as Acusol 445N (Rohm &
Haas) CAS REG Nr. 66019-18-9 or Sokalan from BASF).
Further examples of such suitable polymers include polymers based on an
unsaturated sulphonic acid monomer. The
unsaturated sulphonic acid
monomer is preferably one of the following: 2-acrylamido methyl-1-
propanesultonic acid, 2-methacrylamido-2-methyl-1-propanesulphonic acid,
3-methacrylamido-2-hydroxypropanesulphonic acid, allysulphonic acid,
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methallysulphonic acid, allyloxybenzenesulphonic
acid,
methallyloxybenzensulphonic acid, 2-
hyd roxy-3-(2-
propenyloxy)propanesulphonic acid, 2-methyl-2-propene-1-sulphonic acid,
styrene sulphonic acid, vinylsulphonic acid, 3-sulphopropyl acrylate, 3-
sulphopropyl methacrylate,
sulphomethylacrylamid,
sulphomethylmethacrylamide, and water soluble salts thereof.
The unsaturated sulphonic acid monomer is most preferably 2-acrylamido-2-
propanesulphonic acid (AMPS).
Suitable enzymes include peroxidises, proteases, lipases, amylases and
cellulase enzymes. Such enzymes are commercially available and sold, for
example, under the registered trade marks Esperase, Alcalase, Savinase,
Termamyl, Lipolase and Celluzyme by Nova Nordisk A/S. When present
desirably the enzymes are present (as a proportion of the cartridge
contents) in an amount of from 0.5 to 3 wt%, especially 1 to 2 wt%.
Suitable bleaches / oxidisng agents / bleaching agents usually compsies a
source of active oxygen, e.g. hydrogen peroxide; urea / hydrogen peroxide;
percarboxylic adds, peroxy / per- acids suich as phthalimido-peroxy-
hexanoic-acid (PAP); per-salts such as; perborate, perphosphate,
percarbonate, persulphate, perscate. The bleaching agent may be based
on alternative chemistry, e.g. chlorine based bleaching agents, such as
hypochlorite bleaches, sodium dichloro-isocyanurate or NaDCC.
Other examples of suitable bleaches include N-acyiated lactam bleach
precursors, perbenzoic add precursors, perbenzoic add derivative precursors
and cationic peroxyacid precursors, or mixtures thereof
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Suitable bleach activators include tetraacetylethylendiamine (TAED),
acetylated triazine derivatives, in particular 1,5-
Diacety1-2,4-
dioxohexahydro-1,3,5-triazine (DADHT), acetylated glycoluriles, in particular
Tetraacetylglycolurile (TAGU), acylimides, in particular n-
nonanoylsuccinimide (NOSI), acetylated phenolsulfonates, in particular n-
nonanoyloxi or n-lauroyloxibenzolsulfonate (NOBS and/or PRAISE),
acetylated phenol carbonic acids, in particular nonanoyloxi or
decanoyloxibenzoesaeure (NOBA and/or DOBA), carbonic acid anhydrides,
acetylated sugar derivatives, in particular pentaacetylglucose (PAG),
pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as
acetylated N-alkylated glucamine and gluconolactone, and/or N- acetylated
lactams, for example N-Benzoylcaprolactam. Hydrophilically substituted ecyl
acetals and ecyl lactams are likewise preferentially used. Particularly
preferential bleach activators are TAED and DOBA.
Bleaching catalysts may be present. Preferred examples include complexes
of manganese, iron, cobalt, ruthenium, molybdenum, titanium or vanadium.
When using metal salts in particular manganese salts are in the oxidation
state +2 or +3 preferentially, for example manganese halides, whereby the
chloride is preferential. Manganese sulfate, manganese salts of organic
acids such as manganese acetates, acetylacetonate, oxalates as well as
manganese nitrates are suitable.
Metal complexes with macromolecular ligands may be used such as1,4,7-
Trimethy1-1,4,7-triazacyclononane (me-TACN), 1,4,7-Triazacyclononane
(TACN), 1,5,9-Trimethy1-1,5,9-triazacyclododecane (me-TACD), 2-Methyl-
1,4,7 trimethy1-1,4,7-triazacyclononane (MeMeTACN) and/or 2-Methy1-1,4,7
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triazacyclononane (Me/TACN) or ligands such as 1,2-bis (4,7-Dimethyl
1,4,7-triazacyclonono-i-y1) ethane (Me4-DTNE).
A thickening agent or gelling agent may be used. Suitable thickeners are
polyacrylate polymers such as those sold under the trade mark CARBOPOL,
or the trade mark ACUSOL by Rohm and Hass Company. Other suitable
thickeners are xanthan gums.
The thickener, if present, is generally present in an amount of from 0.2 to 4
wt%, especially 0.2 to 2 wt%.
One or more additional ingredients may optionally be comprised. These
include conventional detergent components such as further surfactants,
bleaches, bleach enhancing agents, builders, suds boosters or suds
suppressors, anti-tarnish and anti-corrosion agents, organic solvents, co-
solvents, phase stabilisers, emulsifying agents, preservatives, soil
suspending agents, soil release agents, germicides, anti-microbial / anti-
bacterial agents, phosphates such as sodium tripolyphosphate or potassium
tripolyphosphate, pH adjusting agents or buffers, non-builder alkalinity
sources, chelating agents, clays such as smectite clays, enzyme stabilizers,
anti-limescale agents, colourants, dyes, hydrotropes, dye transfer inhibiting
agents, brighteners, and perfumes. If used, such optional ingredients will
generally constitute no more than 10 wt%, for example from 1 to 6 wt%,
the total weight of the cartridge contents.
Where an enzyme is present materials may optionally be present to maintain
the stability of the enzyme. Such enzyme stabilizers include, for example,
polyols such as propylene glycol, boric acid and borax. Combinations of
these enzyme stabilizers may also be employed. If utilized, the enzyme
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stabilizers generally constitute from 0.1 to 1 wt% the total weight of the
cartridge contents.
Materials which serve as phase stabilizers and/or co-solvents may be used.
Example are C1-C3 alcohols or diols such as methanol, ethanol, propanol and
1,2-propanediol. C1-C3 alkanolamines such as mono-, di- and
triethanolamines and monoisopropanolamine can also be used, by
themselves or in combination with the alcohols.
The detersive components, if in liquid form, may be anhydrous, or, for
example, contain up to 5 wt% water. Desirably the aqueous substances
contain more than 10 wt%, 15 wt%, 20 wt%, 25 wt% or 30 wt% water, but
desirably less than 80 wt% water, more desirably less than 70 wt%, 60
wt%, 50 wt% or 40 wt% water. They may, for example, contain from 30 to
65 wt% water.
Optionally components which adjust or maintain the pH levels may be used.
Examples of pH adjusting agents are NaOH and citric acid. The pH of the
cartridge contents / wash liquor may be from, for example, 1 to 13.
The invention is illustrated with referent to the following examples.
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Examples
SEQUENTIAL ADDITION OF CLEANING AGENTS FOR CLEANING
WASH LOADS
1. TESTED MATERIALS
Stains: See later
Nylon Beads: Du Pont
Detergents: Liquid Laundry Detergent
Liquid Laundry Additive
Laundry Additive
Laundry Detergent (Ava) % r.m. (Vanish) % r.m.
Water 45.9 Water 40.4
Na LAS 7.1 NaOH 50% 2.95
(Na + TEA) Soaps 12.4 BHT 0.025
NA ALKYLSULPHATE 5.0 Fragrance, Power Pink 0.3
ETHOXYLATED ALC 013-
15.0
C15+7E0 SANOLIN RED N-6B 0.8
TEA 1.7 012-016 ALCOHOLS
3E0 5.0
ALKYLETHOXYLATE
DTPMP 7Na 0.325
012-14, 7 EO 13.3
Na citrate 2.4 SULPHONIC ACID 96 /0 10.7
Purafect Prime 4000L 1.6 HEDP L 0.2
AMYLASE 12L 0.6 Lialet 125-5 0.7
Monopropylenglycol 5.0 Plurafac LF 300 2.3
BIT @20% 0.03 H202 50% 23.0
Sodium sulphite 0.1 pacifier 0P301 0.15
Sodium formate 0.5 TOTAL 100.000
Calcium chloride 0.006
CBS-X 0.12
Blue Patent 0.0003
Yellow Chinoline 0.001
Opacifier 0.100
Silicon antifoam DB30 0.040
Perfume 1.5
TOTAL 100.000
2. TEST CONDITIONS:
Xeros Machine: Generation 1.5
Water Hardness: 25 f
Water temperature: RT + 40 C
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Cycle Time: 1h 33 (wash + rinse/separate)
Spinning (RPM) 800
76L (15L cold wash, 21L hot wash + 40L rinses (10 + 15 +
Total Water Use (Xeros Plus Active):
15))
Fabric Load: 15 Kg
Bead Load: 30 Kg
Replication: 2 internal, 4 external
Spectrophotometer: X-rite 8400
3. PROCEDURE
- Cut stains in swatches of about 6 cm x 6 cm each
- Stitch the stains to the ballast (four swatches per stain)
- Run reference cycles loading the WM
and the XM with the ballast plus swatches
and detergents.
At the end of the cycle dry the ballast in
tumble dryer.
- Detach and iron swatches
- Conduct measurements on all washed and ironed swatches
4. PERFORMANCE EVALUATION
L*,a*,b* Measurement
- D65 illumination, UV calibrated
- 10 observer
- Measuring geometry: D/8
- Biggest available aperture
- Gloss excluded
Statistics:
- Two measurements per swatch front only
- Calculate Y values from above measurements
STAIN SET FOR PERFORMANCE ASSESSMENT
Manufacturer Stain Code Fabric Support Stain Composition Category
1 Empa 101 cot olive oil/carbon black Greasy
2 Empa 104 p/c olive oil/carbon black Greasy
3 Empa 141 cot lipstick Greasy
4 Empa 143 cot make up Greasy
5 WFK 10D cot skin grease/pigment Greasy
6 WFK 10TE cot clay Greasy
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7 WFK 10M cot motor oil/pigment Greasy
8 OFT CS08 cot grass Bleach/Enz.
9 WFK 10J cot tea Bleachable
WFK 10K cot coffee Bleachable
11 WFK 10LI cot wine Bleachable
12 OFT 0S02 cot cocoa Enzymatic
13 OFT 0S68 cot chocolate ice cream Bleach/Enz.
TEST LEGS
Washing Machine (program cotton 40 C)
Leg A
As per Test Protocol; wash water T:
- General Conditions:
40 C
-Detergents: Laundry Detergent 4.3g/Kg fabric load
Laundry Additive 7.8g/Kg fabric load
Results
1 2
Laundry
Laundry
Detervent
. ..., -
Detergent
Plus Laundry Plus
' Laundry
Additive
Auldit;Fkre
icirmilaors - ' ' ¨ = .
release)
'release")
Y values
Stains:
Greasy Empa 101 - olive oil/carbon black 23.6 29.9
Empa 104 - olive oil/carbon black 23.6 29.8
Empa 141 - lipstick 47.1 53.6
Empa 143 - make up 78.6 83.7
WFK 10D - skin grease/pigment 63.2 73.0
WFK 10TE - clay 81.8 83.7
WFK 10M - motor oil/pigment 50.6 50.3
Bleachable WFK 10J - tea 65.1 73.7
WFK 10K - coffee 82.4 83.6
WFK 10LI - wine 70.5 71.3
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Enzymatic OFT CS-08 - grass 75.8 75.2
OFT CS-68 - chocolate ice cream 70.0 72.0
OFT CS-02 - cocoa 49.6 48.4
Average 60.1 63.7
** Laundry detergent released at start of wash and laundry additive released 5
minutes into wash cycle.
The performance of sequential addition is overall superior vs. contemporary
addition.
