Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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Method for TreatingStained Materials
Field of the Invention
This invention relates to method for treating material with a treatment
composition in a
water-soluble pouch, whereby firstly a part of the composition is applied to
the material
by partially opening the pouch to allow dispensing of part of the treatment
composition,
and subsequently the material and the remaining of the pouched composition are
washed
in water.
Background to the Invention
Cleaning products and fabric care products can be found on the market in
various forms,
such as granular compositions, liquid compositions and tablets.
Such liquid laundry compositions have been marketed to be used with a device
to hold an
amount of liquid, which can be used to firstly dispense small amount of the
liquid directly
onto stains, and then to be put in the washing machine with cloths. A known
example is
the so-called 'rollerball' container, which can be rolled over the stains,
thereby
dispensing product, and then added to the washing machine
The inventors have now found a new, even more convenient method of delivering
two-
step treatment with one device, namely a method whereby a treatment
composition, such
as a laundry detergent, is incorporated in a water-soluble pouch, which can be
opened by
the user to allow dispensing of a part of the composition onto the stained
material (for
example fabrics) where after the user can put the pre-treated material and the
remaining
of the water-soluble pouched composition in the wash water, for example in the
drawer or
drum of a laundry washing machine. The user can easily hold the pouched
composition
and rub it onto the stains. There is no need any longer to add the composition
to a
dispensing device such as a'rollerball', nor to retrieve this from the wash
after use.
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The pouch or multitude of pouches herein comprises typically (in total) an
amount
sufficient for a cleaning operation, for example one wash, so the user does
not have to
dose the product. The water-soluble pouch around the product also serves to
limit or
avoid direct contact with the product by the user, which makes this execution
more
desirable than a tablet unit dose form.
Typically, the pouched composition has at least two compartments with product,
whereof
only one or more is opened by the user to pre-treat the material and one or
more remain
closed until the pouched composition is dissolved in water. The user can hold
the closed
compartment(s) and rub the other compartment(s) over the (stains on the)
material
(optionally first wetted), to dispense the product in that opened compartment.
The
rubbing action may cause the compartment to open, or preferably the user opens
the
compartment before application onto the material. This is preferably done by a
cutting or
piercing device, such as a needle-shaped object.
Preferred is thus that the pouched compositions are packed in a container or
box which
contains such a cutting or piercing device, to facilitate easy opening of the
compartment
by the user.
Summarv of the Invention
The present invention relates to a method for treating material with a
treatment
composition which is comprised in a water-soluble pouch, involving the steps
of:
a) opening at least a part of the pouch and dispensing part of the treatment
composition onto the material ;
b) adding the material of step a) and the remaining of the pouched treatment
composition to an aqueous bath, thereby dispensing the remaining of the
pouched
treatment composition.
Preferred methods involve treating a material which is a hard-surface,
including dish-
ware, or more preferably which is a fabric (garment); then in the latter case,
preferred is
that the aqueous bath is a laundry washing machine.
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Preferred is that the part of the treatment composition dispensed in step a)
is in liquid
form.
The pouch may be opened in step a) by applying pressure such that the pouch
opens
(bursts). It may also be preferred that the material in step a) is wet and by
applying the
pouched treatment composition onto the material in step a), the water-soluble
pouch
material opens because it dissolves in the area in contact with the wet
material, thus
allowing release of part of the composition in step a).
Preferred is that the pouch is partially opened by cutting, or even more
preferred, piercing
the pouch and form a hole. Thereby, the composition can flow from the pouch
through
the narrow hole onto the material in a controlled manner, typically controlled
by
application of pressure by the user onto the pouch (for example by pressing
the pouched
composition onto the material, or rubbing it over the material or squeezing
the pouched
composition). Typically, the pouch has more than one compartment and at least
one, but
not all compartments are opened in step a).
The invention also relates to specific pouched unit-dose treatment
composition, which are
shaped to be easy to hold in step a) above and/ or which have an area of
weakness in the
pouch or a part of the pouch is removable, to allow the flow of liquid
composition form
the pouch in step a). The area of weakness may be achieved by providing a
pouch having
a compartment made of a film which is stretched and under tension, having thus
an weak
area where the film is most stretched.
A preferred pouched treatment composition herein, preferably a laundry
detergent, has at
least a first compartment comprising a liquid composition, preferably a
thixotropic liquid.
Preferred is also that the pouch has a second compartment, whereby the top
wall of the
second compartment is the bottom wall of the first compartment and the second
compartment has side wall or side walls connected to the top wall with an
internal angle
of 60 to 120 , preferably from 80 to 100 . This allows the user to hold this
latter, firm
compartment while opening the first compartment and it allows a good hold when
applying the liquid composition on the material (e.g. stained fabric).
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Preferred is that the liquid composition in the first pouch, to be opened in
step a), is
thixotropic and contains a solvent and at least 20% by weight of said liquid
composition
of surfactant, preferably including nonionic surfactant, the liquid preferably
having a pH
of3to7.5.
The pouched unit-dose treatment composition herein preferably has at least two
compartments whereby the first compartment has a different size, shape and/ or
colour
than the second compartment.
The invention also provides specific pouched treatment compositions whereby
the pouch
is made of a stretched film, preferably being a thermo-formed or more
preferably a
vacuum-formed pouch.
The invention also relates to a combination of a treatment composition in a
water-soluble
pouch as described herein and a cutting or piercing device, the water-soluble
pouch,
respectively, to be cut or pierced by the cutting or piercing device,
preferably, the
piercing device having a pin-shaped (or needle-shaped) part.
The invention also relates to a container comprising one or more pouched
treatment
compositions as described herein and a cutting or piercing device. The
piercing device
can be attached to the container or be present in the container as a separate
item.
Detailed Description of the Invention
Method of Treating Materials
The method of the invention involves at least two steps using a pouched
treatment
composition, namely first step a) opening at least a part of the pouch and
dispensing part
of the treatment composition onto the material; and then step b) adding the
material of
step a) and the remaining of the pouched treatment composition to an aqueous
bath,
thereby dispensing the remaining of the pouched treatment composition.
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When used herein, the remaining of the pouched treatment composition is what
remains
of the pouched treatment composition after step a), thus typically at least
part of the
pouch and at least part of the composition.
5 Typically, the first step is done without addition of water during that
step, in contrast with
the second step which involves adding the remaining pouch and material an
aqueous bath.
It may be useful that the material treated in the method of the invention is
wetted prior to
step a), so that in step a) part of the pouch dissolves upon contact with the
wet material
and thus releases part of the composition.
The aqueous bath can be any container suitable to hold water and suitable to
clean with or
in, or for example a automatic washing machine. Preferred is thus that the
first step is a
pre-treatment step done by hand and the second step is the main wash in a
washing
machine.
The dispensing in step b) preferably involves reaction of the remaining pouch
upon
contact with water, preferably dissolution of the pouch, and subsequently
dispersion and/
or dissolution of the remaining composition.
Preferably, the pouch is only partially opened to control dispensing of
treatment
composition in step a), for example to avoid too much treatment composition
leaving the
pouch in step a) or to avoid the treatment composition dispensing too quickly.
The pouch
may be opened by any method, including by partial dissolution (as mentioned
above),
applying pressure onto the pouch to rupture the pouch.
Preferred is that the pouch has an area of weakness or an area which is
removable. The
are of weakness is an area on the pouch which resist pressure of force less
than the
remaining of the pouch. Preferred may be that the area of weakness is achieved
by
making an area of the pouch of chemically or physically different material
than the rest,
preferably a thinner material. Preferably may be that the pouch is of
stretched film
whereby the area most stretched is typicality thinner and forms an area of
weakness.
Preferred may also be that the pouch has an area of weakness which is an area
surrounded
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by lines of weakness (perforations for example). The area of weakness may also
be a
removable area, for example a tear strip, flap.
The pouch may also be opened by removing part of the pouch; more preferred is
that the
pouch is opened by making a small opening in the pouch, typically by cutting
piercing the
pouch to form a hole. For example, the piercing can be done by a needle- or
pin-shaped
device, thus resulting in a small (pin) hole. It may be preferred that this is
done in an area
of weakness, for example a thinner part of the pouch, for example obtainable
by
stretching the material (preferably a film)used for making the pouch. Of
course, it may
be preferred that the pouch has an area of weakness which is to be cut or
pierced to be
opened.
Part of the treatment composition leaves the pouch through the opening, onto
the
material. Typically, this involved bringing the pouch with the opening in
close proximity
to the material, or typically stains on the material and dispensing some of
the treatment
composition throughout the opening. Preferred is that the pouched treatment
composition
is contacted with the material and the product is rubbed onto the material by
rubbing the
pouched treatment composition over the material.
The composition in step a may be solid or liquid. Preferably the composition
dispensed
in step a) is liquid, to allow a good flow through the opening onto the
material.
Preferably having a viscosity of the liquid is such that the liquid only
leaves the pouch
when a force is applied, for example the force applied by the user when
rubbing the
pouch onto the material, or for example by squeezing the opened pouch.
Preferred are
thus thixotropic liquid compositions. Preferred thixotropic compositions
comprise
structuring agents such as clays, preferably organically modified (hectorite)
clay.
Preferred may also be that the thixotropic liquid composition comprises
surfactants and
water, the surfactants gelling upon contact with said water.
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Preferred is that the liquid has a viscosity (at 25 C) of at least 200Pa.s or
even at least
50Pa.s or even at least 100Pa.s or even at least 150Pa.s, or even at least
200Pa.s, as
measured at a shear rate of 1.7 s-'.
The pouch herein is a closed structure, typically made of materials described
herein,
having an interior (a volume space) comprising therein a liquid and/ or solid
composition.
The exact execution will depend on, for example, the type and amount of the
composition
in the pouch, the number of compartments in the pouch and the characteristics
required
from the pouched composition to hold, protect and deliver or release the
compositions
and to be held and used in the method of the invention.
Preferred is that the pouched compositions are unit-dose compositions, e.g.
that a
multitude of pouches, but preferably two pouches or more preferably one pouch,
thus
holds sufficient composition for a single treatment operation.
Preferred treatment compositions are personal care compositions, personal
cleaning
compositions, hard-surface cleaning compositions, dish-washing detergent
compositions,
laundry detergent compositions, laundry and dish washing additive compositions
such as
fabric enhancers, bleach compositions. Most preferred are hard-surface
cleaners, laundry
detergents and dish washing detergents, most preferably laundry detergents.
Preferred is that the pouch has at least two compartments, preferably attached
to one
another. The pouch preferably contains different compartments. Preferably, the
different
compartments comprise different compositions and/ or preferably the
compartments are
visibly distinct, for example the compartments (or compositions) having a
different
colour, shape and/ or size, or comprising compositions with visibly different
properties,
for example physical states (liquid and solid), different density, viscosity,
colour, or
mixtures thereof.
Preferred may be that one compartment in the pouch (opened in step a) is
smaller than the
second compartment. Exact sizes will depend on how much each pouch need to
contain
and thus how much volume is required. For example, the first compartment (to
be opened
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in step a)) has a volume or comprises an amount of product (by weight ) which
is less
than 75% or even less than 60% of the volume of the second pouch or the amount
(by
weight) in the second compartment, and typically more than 10%, preferably
more than
15%.
Preferred is that the pouch has two or more compartments which are visually
distinct, so
the user knows which compartment(s) to open in the first step.
Preferred may be that one compartment comprises a solid composition and
another
compartment a liquid composition. It may be preferred that one compartment
comprises
a composition of a different viscosity, density, than the composition in the
other
compartment. Preferred may also be that the compositions or compartments or
part
thereof have different shades or colour, for example white and blue, or
comprising
speckle particles. Preferred may also be that one composition is a clear
liquid and
another an opaque liquid. It may also be preferred that one compartment is
smaller than
another compartment, typically such that the compartment to be opened in the
first step is
smaller than the other compartment.
Preferred is that the pouch is of such a shape that it is easy to hold by the
user, allowing a
hold even when some of the treatment composition is already dispensed in step
a).
Preferred is that the pouch comprises more than one compartment and that one
or more
compartments are opened in step a), but not all compartments. This allows the
user to
hold the pouch by the compartment which is not to be opened, whilst opening
one or
more of the other compartments and dispensing part of the treatment
composition thereof.
Preferred is that one of the compartments, not to be opened has a firm or even
rigid
structure. Hereto, this compartment is preferably made by vacuum-forming or
thermoforming, hereby stretching the pouch material to form a compartment
under
tension, as described herein after. Preferred is also that the compartment
(which is not to
be opened) comprises a solid composition, to further improve the grip by the
user.
Also preferred is that the pouch has at least one compartment which has walls
with a
height (distance from bottom to top, connected by said walls) of at least 1
cm, preferably
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at least 1.5 cm or even at least 2 cm, typically up to about 10 cm, or
preferably up to 6 cm
or even up to 5 cm, to allow a better grip for the user.
Typically, the width or diameter of the pouch or compartment thereof is
between 2 cm
and 12 cm, preferably 2.5 cm or even 3 cm to 10cm or even to 8 cm or even to 6
cm.
It may be preferred that the width or diameter of the first pouch, to be
opened in step a),
is smaller than the width or diameter of the other compartment, not opened in
step b.
Preferably is how ever that, when the first compartment is on top of the other
compartment, the surface area of the bottom of the first compartment is at
least 40% or
even at least 50% or even at least 60% of the surface area of the top of the
other
compartment. This further ensures that the user can apply enough pressure to
get the
composition out of the compartment, in step a) of the method of the invention.
Preferably, this compartment comprises a solid and is made of a film material
which is
under tension and/ or stretched. Preferred is also that the internal angle of
the walls with
the top of this compartment (being (connected to) the bottom of the other
compartment)
is between 60 to 120 , preferably 80 to 100 or even preferably about 90
(thus, the
slope of the side or walls of the pouch being of an angle as specified). This
allows a
better grip for the user. Preferred may be that the wall of at least one
compartment, to be
held by the user, is straight, rather than curved.
Preferred may be that the all compartments (preferably two) are made by
stretching the
material the compartments, e.g. film, to obtain compartments of stretched
material, under
tension . Hereby, the tension not only gives a good grip to one of the
compartments, but
facilitates opening of the other compartment.
Preferred pouched treatment compositions have at least one compartment of a
shape
having straight walls (connecting top and bottom of the pouch) rather than
curved walls,
thus preferred shapes include hexagonal shape, square shape, rectangular shape
or
cylindrical shape to allow a good hold and dispensing of the composition under
slight
pressure by the user (e.g. rubbing, squeezing):
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Preferred may be that the pouch herein comprises a skirt, typically around
part or all of
the pouch, typically an frill-shaped skirt extending from the pouch. Typically
the pouch is
made by filling an open pouch shape and closing the open pouch by sealing.
Then, the
5 skirt or frill may be the sealing area, extending from the pouch.
Preferred may be that the pouch has at least two compartments on top of
another and
separated by the material of the pouch/ compartments and that this material
extends from
the pouch, to thus form the skirt of the pouch. It may be preferred that it
extends such
10 that the thus formed skirt surrounds the pouch.
This edge or frill helps to prevent the user of the pouch in the method of the
invention
from getting in contact with the treatment composition in step a) , when it
leaves the
pouch and is rubbed unto the (stained) material, e.g. fabric.
The width of this frill or edge (i.e. distance from pouch to end of frill or
edge) is
preferably at least 0.2mm, more preferably at least 0.3 mm or even 0.5mm or it
may be
even 1.0cm or more, typically up to 3cm or even up to 2cm r even up to 1.5cm.
When the pouched composition is for use in a laundry washing or dish washing
machine
and may need to be dispensed to the water via a dispensing drawer, it may be
preferred
that the remaining pouched composition, or preferably the pouched composition
itself, is
of such a size that it can dispense into the wash water through the drawer.
However,
alternatively the pouch is added into the drum of the machine directly, so
that the size of
the pouched composition or remaining pouched composition is not determined by
the size
of dispensing drawers.
Piercing or Cutting Device
The cutting or piercing device can be any device suitable to cut or pierce the
pouch,
typically making a scission, cut or hole in the pouch. Preferred are piercing
devices
having a sharp part, preferably having a sharp edge or point, for example a
pin-shaped
part or a hook, or a chisel shaped part or knife-shaped part. Most preferred
are piercing
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devices, making a hole in the pouch. The size of the sharp edge or point of
the device can
be adjusted, depending on the size of the opening (hole, cut) required.
The cutting or piercing device may be attached to the container for the (unit-
dose)
pouched treatment compositions (e.g. box), or it may be a separate device.
Preferably the cutting or piercing device also has a also part suitable to be
held by the
user in the method of the invention. Preferred may be that the piercing or
cutting device
thus comprises a sharp part and a holder.
Preferred may be that the cutting or piercing device, typically the holder
thereof, has a
surface or volume capable to receive to pouched composition, typically such
that the
pouched composition to be opened by cutting or pierced matches the shape of
the surface.
For example it may be preferred that the pouched composition, or at least the
part to be
opened by cutting or piercing, has a round shape and that the cutting or
piercing device
has a hollow surface, wherein the pouch fits.
Container for Pouched Compositions
The pouched compositions are typically packed in a container. Typically, the
container
contains a number of pouched treatment compositions. Any container suitable
for
holding and storage of the pouched composition can be used.
Preferred are rigid containers, for example a box, having at least one wall,
bottom or top
which can be opened and closed. Typically, this is the top or lid of the
container.
Preferred may be that the cutting or piercing device is attached to the
container, for
example to the opening top or lid. Preferred may be that the cutting or
piercing device is
at the outside of the box, to avoid contact with the pouched compositions
during storage.
It may also be preferred that the cutting or piercing device is in the box,
preferably such
that contact with the pouched compositions can be avoided. For example, the
cutting or
piercing device may be attached so that it can be moved in a position that is
can be used
to pierce the pouch and that it can be moved back in a position that it can
not be used for
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piercing. For example the cutting or piercing device may be attached flat to a
wall, top
or bottom of the container and be moved to extend from that wall, top or
bottom.
Pouch and Pouch Material
At least the remaining pouch herein is made from a water-reactive material, to
provide a
water-soluble pouched treatment composition. Preferably the pouch as a whole
is made of
water-reactive material.
For the purpose of the invention, water-reactive material means material which
either
dissolves, disperses or disintegrates (or mixtures thereof) upon contact with
water,
releasing thereby the composition. Preferably, the material is water-soluble.
The remaining pouch will react in water to release its content. To achieve
sequential
release in the second step b), the remaining pouch may comprise different
compartments
whereof one may be more water-soluble than another. This can for example be
achieved
by using different type of material for one compartment than another, for
example,
material having a different type of polymer, different plasticiser, different
levels
components in the material, different coating of the film material, different
thickness of
the film material.
The water-soluble film for the pouch preferably has a solubility in water of
at least 50%,
preferably at least 75% or even at least 95%, as measured by the method set
out
hereinafter using a glass-filter with a maximum pore size of 50 microns,
namely:
Gravimetric method for determining water-solubility of the material of the
compartment
and/or pouch:
50 grams 0.1 gram of material is added in a 400 ml beaker, whereof the
weight has
been determined, and 245m1 lml of distilled water is added. This is stirred
vigorously
on magnetic stirrer set at 600 rpm, for 30 minutes. Then, the mixture is
filtered through a
folded qualitative sintered-glass filter with the pore sizes as defined above
(max. 50
micron). The water is dried off from the collected filtrate by any
conventional method,
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and the weight of the remaining polymer is determined (which is the dissolved
or
dispersed fraction). Then, the % solubility can be calculated.
Preferred materials for the pouch are films of polymeric materials, e.g.
polymers which
are formed into a film or sheet. The film can for example be obtained by
casting, blow-
moulding, extrusion or blow extrusion of the polymer material, as known in the
art.
Preferred polymers, copolymers or derivatives thereof 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 preferably the polymer is selected from
polyacrylates and
water-soluble acrylate copolymers, methylcellulose, carboxymethylcellulose
sodium,
dextrin, ethylcellulose, hydroxyethyl cellulose, hydroxypropyl
methylcellulose,
maltodextrin, polymethacrylates, most preferably polyvinyl alcohols, polyvinyl
alcohol
copolymers and hydroxypropyl methyl cellulose (HPMC). Most preferred is PVA
film;
preferably, the level of polymer in the film, 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, or even form 10,000 to 300,000 or even form 15,000 to 200,000 or
even
form 20,000 to 150,000.
Mixtures of polymers can also be used. This may in particular be beneficial to
control the
mechanical and/or dissolution properties of the compartments or pouch,
depending on the
application thereof and the required needs. For example, it may be preferred
that a
mixture of polymers is present in the film, whereby one polymer material has a
higher
water-solubility than another polymer material, and/or one polymer material
has a higher
mechanical strength than another polymer material. It may be preferred that a
mixture of
polymers is used, having different weight average molecular weights, for
example a
mixture of PVA or a copolymer thereof of a weight average molecular weight of
10,000-
40,000, preferably around 20,000, and of PVA or copolymer thereof, with a
weight
average molecular weight of about 100,000 to 300,000, preferably around
150,000.
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Also useful are polymer blend compositions, for example comprising
hydrolytically
degradable and water-soluble polymer blend such as polylactide and polyvinyl
alcohol,
achieved by the mixing of polylactide and polyvinyl alcohol, typically
comprising 1-35%
by weight polylactide and approximately from 65% to 99% by weight polyvinyl
alcohol,
if the material is to be water-soluble.
It may be preferred that the polymer present in the film is from 60% to 98%
hydrolysed,
preferably 80% to 90%, to improve the dissolution of the material, and/ or
that the levels
of plasticiser, including water, in the film are varied such that the
dissolution is adjusted
as required.
Most preferred are films which comprise a PVA polymer with similar properties
to the
film which comprises a PVA polymer and is known under the trade reference
M8630 or
CXP4087, as sold by Chris-Craft Industrial Products of Gary, Indiana, US.
Preferred
may be that the first pouch is made of a film material having the properties
of PVA
polymer-containing film M8630 and that the second pouch is made of material
having
similar properties as PVA-containing film CXP4087. Preferred are the materials
M8630
and/ or CXP4087 itself.
The film herein may comprise other additive ingredients than the polymer or
polymer
material. For example, it may be beneficial to add plasticisers, for example
water
glycerol, ethylene glycol, diethyleneglycol, propylene glycol, sorbitol and
mixtures
thereof, and other additives, for example stabilisers, disintegrating aids. It
may be useful
that the pouch material itself comprises a treatment composition ingredients,
for example
a cleaning ingredient, to be delivered to the wash water, for example organic
polymeric
soil release agents, dispersants, dye transfer inhibitors, surfactants.
Preferably, the pouch is made of a material which is stretchable, as set out
herein. This
for example facilitates the closure of the open pouch, when is filled for more
than 90% or
even 95% by volume or even 100% or even over filled. Moreover, the material is
preferably elastic, to for example to ensure a firmly formed pouch, preferably
rigid
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pouch, easy to pierce and to hold by the user, and to ensure tight packing and
fixation of
the composition therein during handling and use.-
Preferred stretchable materials have a maximum stretching degree of at least
150%,
5 preferably at least 200%, n1oi-e preferably of at least 400% as determined
by comparison
of the original length of a piece of material with the length of this piece of
material just
prior to rupture due to stretching, when a force of at least 1 Newton is
applied to a hiece
of filni with a width of I cin. Preferably, the material is such that it has a
stretching
degree as before, when a force of at least 2Newton, or even at least 3 Newton
is used.
10 Preferably, it has this stretching degree when a force of the above lower
limits is used,
but not more than 20 Newton, or even 12 Newton, or even 8 Newton. For example,
a
piece of film with a length of 10 cm and a width of 1 cm and a thickness of 40
microns is
stretched lengthways with an increasing stress, up to the point that it
ruptures. The extent
of elongation just before rupture can be determined by continuously measuring
the length
15 and the degree of stretching can be calculated. For example, this piece of
film with an
original length of 10 cm can be stretched with a force of 9.2 Newton to 52 cm
just before
breaking, and then is has a maximum stretching degree of 520%.
The force to stretch such a piece of film (10 cm x 1 cm x 40 microns) to a
degree of
200% should preferably be at least I Newton, preferably at least 2 Newton,
more
preferably at least 2.5 or even 3 Newton, and preferably no more than 20
Newton,
preferably less than 12 Newton, most preferably less than 8 Newton. This in
particular
ensures that the elastic force remaining in the film after forniing the pouch
or closing the
pouch is high enough to pack the composition tightly within the pouch (but not
so high
that the film cannot be drawn into a vacuum mould of reasonable depth, when
the pouch
is made by a process involving the use of vacuum, such as by vacuum-forming or
thermo-
forming).
As is clear form the definition herein, the stretchable material is defined by
a degree of
stretching measured when it is not present as a closed pouch. However, as said
above,
the material is preferably stretched when forming or closing the pouch. This
can for
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16
example been seen by printing a grid onto the material, e.g. film, prior to
stretching, then
forming a pouch; it can be seen that squares of the grid are elongated and
thus stretched.
The elasticity of the stretchable material of the can be defined as the
'elasticity recovery'.
This can be determined by stretching the material for example to an elongation
of 200%,
as set out above, and measuring the length of the material after release of
the stretching
force. For example a piece of film of a length of 10 cm and width 1 cm and
thickness of
40 microns is stretched lengthways to 20 cm (200% elongation) with a force of
2.8
Newtons (as above), and then the force is removed. The film snaps back to a
length of 12
cm, which means 80% elastic recovery.
Preferably, the pouch material has an elasticity such that the elastic
recovery is from 20%
to 100%, more preferably 50% or even from 60% or even from 75% or even 80% to
100%.
Typically and preferably, the degree of stretching in non-uniform over the
pouch, due to
the formation and closing process. For example, when a film is positioned in a
mould
and an open pouch is formed by vacuum forming, the part of the film in the
bottom of the
mould, furthest removed form the points of closing, will be stretched more
than in the top
part. Another advantage of using stretchable and preferably also elastic
material, is that
the stretching action stretches the material non-uniformly, which results in a
pouch which
has a non-uniform thickness. This allows control of the dissolution/
disintegration or
dispersion of the pouches herein. Preferably, the material is stretched such
that the
thickness variation in the pouch formed of the stretched material is from 10
to 1000%,
preferably 20% to 600%, or even 40% to 500% or even 60% to 400%. This can be
measured by any method, for example by use of an appropriate micrometer.
Process for Making the Pouched Treatment Compositions
The pouch can be made and filled by any process. When more than' compartment
is
present in the pouch, it may be preferred that each compartments is first
formed and then
sealed together. However, to reduce pouch material, it is more preferred that
one
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17
compartment is first made and used as part of the other compartment,
typically, one open
compartment being closed by a pre-formed, closed (sealed) compartment.
The pouch herein is preferably made by thermo-forming or even more preferred
by
vacuum-forming. Because vacuum-formed pouches, and thermo-formed pouches to a
lesser extend, have a number of advantages, as described above, it is
preferred to use such
a process for the formation of the pouches herein. Thermo-forming typically
involves the
step of formation of an open pouch in a mould under application of heat, which
allow-s
the material used for the pouch to take on the shape of the mould. Vacuum-
forming
typically involves the step of applying a (partial) vacuum (reduced pressure)
on a mould
which sucks the material into the mould and ensures the material adopts the
shape of the
mould. The pouch forming (or compartment forming) process may also be done by
first
heating the material and then applying reduced pressure, e,g. (partial)
vacuum.
For example, an open compartment is formed in a mould and then filled with the
required
composition then closed, typically with another piece of material or with
another
compartment, and sealed.
The sealing can be done by any known method, for example by heat sealing,
wetting, use
of gluing agent, compression, or combinations thereof.
The seal can extend from the pouch, forming a skirt around the pouch, as
described
herein before, and thereto it may be cut into the right width. Alternatively,
it may be
preferred that the seal does not extend from the pouch and then it may be cut-
off
completely.
Treatment Compositions
Preferred treatment compositions are compositions with a dual purpose, for
example pre-
treatment and cleaning, cleaning and fabric enhancing or softening, cleaning
and dyeing.
Preferred treatment compositions herein are useful in cleaning operations,
such as hand
and automatic laundry and dish washing, hard-surface cleaning, personal
cleaning, and
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18
specialised fabric treatment compositions such as bleach additives, dye
compositions, and
fabric care or enhancing compositions, such as fabric conditioners.
Preferably, the treatment composition is a cleaning composition and comprises
at least a
surfactant. Preferably, it comprises also builders, bleach, enzymes, chelating
agents
and/or perfumes.
Highly preferred is that the treatment compositions is divided over different
compartment
and that the compositions differ chemically per compartment.
Preferred is that the composition dispensed in step a) contains stain
treatment ingredients,
preferably comprising at least a surfactants, preferably at least a anionic
and/ or nonionic
surfactant, preferably also a chelanting agent and/ or enzymes and/ or soil
(clay)
dispersing agents, such as cationic alkoxylated amines, and/ or perfume. The
composition
dispensed in step a) may comprise bleaching agents, but it is preferred that
this is free of
bleaching agents, to avoid contact of bleach in undiluted form with the
stained material in
step a).
The composition to be dispensed in step a) preferably comprise at least
builders,
additional surfactant, bleaching agents, perfume, fabric softener or
conditioner, or
mixtures thereof.
Highly preferred in the fabric treatment composition herein are fabric
integrity polymers
as described herein after. Also highly preferred are fabric softening agents
as described
herein.
It may be preferred that the composition dispensed in step a) has a pH of 3.0
or even 3.5
to 7.5 or even 7.0 or even 6.5 or even 6Ø It may be preferred that the
composition
dispensed in step a) comprises acidic agents, to reduce the pH of the
composition.
It may be preferred that the composition dispensed in step a) comprises an
organic
carboxylic acid, such as citric acid, fumaric acid, maleic acid, or polymeric
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19
polycarboxylic acid. Highly preferred is citric acid. Preferred levels are
from 1% to 20%
or even 2% to 15% or even 3% to 12% by weight of the total treatment
composition.
Preferred may also be that a carbonate source is present, such as a salt of
carbonate or
bicarbonate, which can react upon contact with water, with the acid, t provide
effervescing and improved dissolution of the pouched treatment composition.
It may be preferred that the composition not dispensed in step a) has a pH
which is higher
than the pH of the composition dispensed in step a), for example from 7.5 or
even 8 or
even 9 or even 9.5 to 12 or even to 11 or even to 10.5.
It may be preferred that the first composition is liquid, including non-
aqueous liquids and
gels, which is transparent. It may also be preferred that the compositions
have a different
physical state, for example that the first composition is liquid and the
second composition
is solid. Then, it may be preferred that the first compartment comprises a
composition
containing liquid surfactants and solvent, preferably including at least
nonionic surfactant
and organic solvent, and preferably perfume oils, water and other solvents;
then, it may
also be preferred that the other composition, not dispensed in step a) but
only in step b),
comprises solid ingredients, for example actives which are not very soluble in
organic
solvent or water, or even insoluble, or which are more efficiently or
effectively delivered,
incorporated or performing in solid form: for example enzyme granules, bleach
granules,
insoluble builders and polymeric ingredients, salts of builders or
surfactants, perfume
granules, clay, effervescence sources.
Also preferred may be that the division of ingredients per composition is done
based on
their chemical or physical compatibility, for example that the composition;
for example,
one compartment may comprise a composition with bleach and the other
compartment a
composition with a bleach sensitive or reactive ingredient such as perfumes,
enzymes,
organic polymers, bleach catalysts.
As described above, preferred are effervescence sources, capable of producing
a gas upon
contact with water, typically CO2 gas, formed by reaction of a carbonate
source and an
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acid source, preferably a carbonate salt and an organic carboxylic acid, such
a citric acid,
malic acid, maleic acid, glutaric acid, fumaric acid. Also preferred are other
dissolution
or dispensing aids, as known in the art.
5 If a liquid composition is present, it preferably comprises one or more
solvent, preferably
from 1% to 60% or even 5% to 50% or even 8% to 40% by weight of the liquid
composition. Preferred are organic solvents such as methyl or ethyl or
methoxylated or
ethoxylated amines, alcohols, polyethylene glycol, glycerol, water and
mixtures thereof.
Preferred may be that only small amounts of water, up to 20% or even up to 10%
or up to
10 8% or even up to 4% by weight of the liquid composition. Preferably, other
solvents are
present, such as alcohols, glycerine, polyethylene glycol, paraffin.
Preferred Ingredients of Treatment Compositions
The preferred surfactants for the compositions herein are selected from
anionic, nonionic,
15 cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures
thereof.
Preferably the compositions comprise from 5% more preferably from 10%, yet
more
preferably from 15%, to 80%, more preferably to 50%, yet more preferably to
30% by
weight of the composition of surfactant.
20 Anionic sulfonate surfactants suitable for use herein include the salts of
C5-C20 linear
alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary
alkane
sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl
glycerol
sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates,
and any mixtures
thereof.
Anionic sulfate surfactants suitable for use herein include the linear and
branched
primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl
glycerol sulfates,
alkyl phenol ethylene oxide ether sulfates, the C5-C 17 acyl-N-(C 1-C4 alkyl)
and -N-(C I-
C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such
as the
sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being
described
herein).
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21
Alkyl sulfate surfactants are preferably selected from the linear and branched
primary
C 10-C 18 alkyl sulfates, more preferably the C 11-C 15 branched chain alkyl
sulfates and
the C 12-C 14 linear chain alkyl sulfates.
Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting of the
C 10-C 18 alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles
of
ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate
surfactant is a C 1
C 18, most preferably C 11-C 15 alkyl sulfate which has been ethoxylated with
from 0.5 to
7, preferably from 1 to 5, moles of ethylene oxide per molecule.
Essentially any alkoxylated nonionic surfactants are suitable herein. 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/propoxylate
condensates
with propylene glycol, and the nonionic ethoxylate condensation products with
propylene
oxide/ethylene diamine adducts.
The condensation products of aliphatic alcohols with from 1 to 25 moles of
alkylene
oxide, particularly ethylene oxide and/or propylene oxide, are suitable for
use herein. The
alkyl chain of the aliphatic alcohol can either be straight or branched,
primary or
secondary, and generally contains from 6 to 22 carbon atoms. Particularly
preferred are
the condensation products of alcohols having an alkyl group containing from 8
to 16
carbon atoms.
Highly preferred, in particular such that it is dispensed in step a) at least,
are alkoxylated,
preferably ethoxylated, cationic monoamines, diamines polyamines. The positive
charge
of the N+ groups is offset by the appropriate number of counter anions.
Suitable counter
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22
anions include Cl-, Br-, SO3?, P04 2, MeOSO3- and the like. Particularly
preferred counter
anions are Cl - and Br-.
Preferred are cationic amines substituted with one or more polyoxyalkylene
moieties -
[(R60)õ,(CH2CH2_Oõ)-]. The moieties -(R60)m- and -(CH2CH2O)n- of the
polyoxyalkylene
moiety can be mixed together or preferably form blocks of -(R60)m and -
(CH2CH20)õ-
moieties. R6 is preferably C3H6 (propylene); n is at least about 14; m is
preferably from 0 to
about 5 and is most preferably 0, i.e. the polyoxyalkylene moiety consists
entirely of the
moiety -(CH2CH20)n . The moiety -(CH2CH20)õ preferably comprises at least
about 85% by
weight of the polyoxyalkylene moiety and most preferably 100% by weight (m is
0).
The composition herein preferably comprises a bleaching agent, or even a
mixture of
bleaching agents. Preferably the treatment compositions comprise from 3% more
preferably
from 5%, yet more preferably from 10%, to 40%, more preferably to 25%, yet
more
preferably to 20% by weight of the composition of bleaching agent.
Suitable N-acylated lactam perbenzoic acid precursors have the formula:
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23
0
11
O C-CH2- i H2
R6-C-N-,
CH2-iCH2 ]n
wherein n is from 0 to 8, preferably from 0 to 2, and R6 is a benzoyl group.
A preferred class of substituted perbenzoic acid precursor compounds are the
amide
substituted compounds of the following general formulae:
Ri -C N R2-C-L Ri -N-C-R2-C L
O R5 0 or R5 O 0
wherein Rl is an aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is
an arylene,
or alkarylene group containing from 1 to 14 carbon atoms, and R5 is H or an
alkyl, aryl,
or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any
leaving
group. Rl preferably contains from 6 to 12 carbon atoms. R2 preferably
contains from
4 to 8 carbon atoms. Rl may be aryl, substituted aryl or alkylaryl containing
branching,
substitution, or both and may be sourced from either synthetic sources or
natural sources
including for example, tallow fat. Analogous structural variations are
permissible for
R2. The substitution can include alkyl, aryl, halogen, nitrogen, sulphur and
other typical
substituent groups or organic compounds. R5 is preferably H or methyl. Rl and
R5
should not contain more than 18 carbon atoms in total. Amide substituted
bleach
activator compounds of this type are described in EP-A-0170386.
The hydrophobic peroxy acid bleach precursor preferably comprises a compound
having
a oxy-benzene sulphonate group, preferably nonanoyl oxy-benzene sulphonate
(NOBS),
decanoyl oxy-benzene sulphonate (DOBS) and/ or comprising (6-nonamidocaproyl)
oxybenzene sulfonate (NACA-OBS).
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24
Also highly preferred are more hydrophilic peroxy acid bleach precursors or
activators
such as TAED.
Also preferred bleaching agent for use herein are particulate peracids. In an
even more
preferred embodiment the peracid is selected from the range of pre-formed mono
peroxycarboxylic acid. In an even more preferred embodiment the pre-formed
peracid is
phthaloyl amido peroxyhexanoic acid, known as PAP.
The bleach activator or precursor and/or the pre-formed peracid is preferably
used in
particulate form, or as a particle, suspended in a liquid matrix. The liquid
matrix where
present is substantially non-aqueous meaning that it does not comprise a level
of water
that would result in the dissolution of the bleach precursor or peracid.
Preferred
suspending agent used to suspend the bleach activator or precursor, or the
peracid are
solvents which do not either dissolve or damage the pouches. More preferably
the
suspending agent is a long chain, low polarity solvent. By long chain it is
meant solvents
comprising a carbon chain of greater than 6 carbon atoms and by low polarity
it is meant
a solvent having a dielectric constant of less than 40. Preferred solvents
include C12-14
paraffin and more preferably C12-14 isoparaffin.
Examples of inorganic perhydrate salts include perborate, percarbonate,
perphosphate,
persulfate and persilicate salts. The inorganic perhydrate salts are normally
the alkali
metal salts. The inorganic perhydrate salt may be included as the crystalline
solid
without additional protection. For certain perhydrate salts however, the
preferred
executions of such granular compositions utilize a coated form of the material
which
provides better storage stability for the perhydrate salt in the granular
product. Suitable
coatings comprise inorganic salts such as alkali metal silicate, carbonate or
borate salts or
mixtures thereof, or organic materials such as waxes, oils, or fatty soaps.
Sodium perborate (a perhydrate salt in the form of the monohydrate of nominal
formula
NaBO2H2O2 or the tetrahydrate NaBO2H2O2.3H20), may be used, but is not
compatible with certain pouch materials with -OH groups, such as PVA, and is
thus often
not preferred.
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Alkali metal percarbonates, particularly sodium percarbonate are preferred
perhydrates
herein. Sodium percarbonate is an addition compound having a formula
corresponding to
2Na2C03.3H202, and is available commercially as a crystalline solid.
5
Chloride bleaches may also be useful, in particle when the article is a bleach
additive or
hard surface cleaner. Suitable bleaches are hypochlorite species in aqueous
solution
include alkali metal and alkaline earth metal hypochlorites, hypochlorite
addition
products, chloramines, chiorimines, chloramides, and chlorimides. Specific
examples of
10 compounds of this type include sodium hypochlorite, potassium hypochlorite,
monobasic
calcium hypochlorite, dibasic magnesium hypochlorite, chlorinated trisodium
phosphate
dodecahydrate, potassium dichloroisocyanurate, sodium dichloroisocyanurate
sodium
dichloroisocyanurate dihydrate, trichlorocyanuric acid, 1,3-dichloro-5,5-
dimethylhydantoin, N-chlorosulfamide, Chloramine T, Dichloramine T, chloramine
B
15 and Dichloramine B. A preferred bleaching agent is sodium hypochlorite,
potassium
hypochlorite, or a mixture thereof.. A preferred chlorine-based bleach can be
Triclosan
(trade mark).
A preferred ingredients of the liquid compositions herein are opacifying
agents and. or
20 dyes, to dye the liquid composition, and dyed particles or speckles for
solid compositions
herein. The dye as used herein can be a dye stuff or an aqueous or nonaqueous
solution of
a dye stuff. It may be preferred that the dye is an aqueous solution
comprising a dyestuff
at any level, to add to liquid compositions or to obtain dyed particles by
applying the
solution onto granules, preferably such that levels of dye are obtained up to
5%, or even
25 up to 2% by weight of a composition. The dye may also be mixed with a non-
aqueous
carrier material or organic binder materials, which may also be a non-aqueous
liquid.
The dyestuff can be any suitable dyestuff. Specific examples of suitable
dyestuffs include
E 104 - food yellow 13 (quinoline yellow), E I 10 - food yellow 3 (sunset
yellow FCF),
E131 - food blue 5 (patent blue V), Ultra Marine blue (trade name), E133 -
food blue 2
(brilliant blue FCF), E140 - natural green 3 (chlorophyll and chlorphyllins),
E141 and
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26
Pigment green 7 (chlorinated Cu phthalocyanine). Preferred dyestuffs may be
Monastral
Blue BV paste (trade mark) and/or Pigmasol Green (trade mark).
Also useful herein are fabric substantive dyes (in contrast to the above dyes
which are not
fabric substantive), to provide dyeing of fabrics treated with the article of
the invention.
Another preferred ingredient of the compositions herein is a perfume oil or
perfume
composition. Any perfume oil or composition can be used herein. The perfumes
may
also be encapsulated. Preferred may be that the second pouch comprises the
perfume, so
that this is delivered a t a later stage, to ensure a more efficient delivery
of the perfume to
the fabric.
Preferred perfumes containing at least one component with a low molecular
weight
volatile component, e.g. having a molecular weight of from 150 to 450 or
preferably 350.
Preferably, the perfume component comprises an oxygen-containing functional
group.
Preferred functional groups are aldehyde, ketone, alcohol or ether functional
groups or
mixtures thereof.
Preferred aldehydes are selected from citral, 1-decanal, benzaidehyde,
florhydral, 2,4-
dimethyl-3-cyclobexen-l-carbox.aldehyde; cis/trans-3,7-dimethyl-2,6-octadien-
I -al;
heliotropin; 2,4,6-trimethyl-3-cyclohexene-l-carboxaldehyde; 2,6-nonadienal;
alpha n-
amyl cinnamic aldehyde, alpha-n-hexyl cinnatnic aldehyde, P.T. Bucinal, lyral,
cymal,
methyl nonyl acetaldehyde, trans-2-nonenal, LilialTm, trans-2-nonenal, lauric
aldehyde,
undecylenic aldehyde, mefloral and mixture thereof.
Preferably, the perfume ketone is selected from buccoxime; iso jasmone; methyl
beta
naphthyl ketone; musk indanone; TonalidTm/musk plus; Alpha-Damascone, Beta-
Damascone, Delta-Damascone, Iso-Damascone, Damascenone, Darnarose, Methyl-
Dihydrojasmonate, Menthone, Carvone, Camphor, Fenchone, Alpha-Ionone, Beta-
lonone, Gamma-Methyl so-called lonone, Fleuramone, Dihydrojasmone, Cis-
Jasmone,
Iso-E-Super, Methyl- Cedrenyl-ketone or Methyl- Cedrylone, Acetophenone,
Methyl-
Acetophenone, Para-Methoxy-Acetophenone, Methyl-Beta-Naphtyl-Ketone, Benzyl-
Acetone, Benzophenone, Para-Hydroxy-Phenyl-Butanone, Celery Ketone or
Livescone,
6-Isopropyldecahydro-2-naphtone, Dimethyl-Octenone, Freskomenthe, 4{1-
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27
Ethoxyvinyl)-3,3,5,5,-tetramethyl-Cyclohexanone, Methyl-Heptenone, 2-(2-(4-
Methyl-3-
cyclohexen-l-yl)propyl)-cyclopentanone, 1-(p-Menthen-6(2)-yl)-1-propanone, 4-
(4-
Hydroxy-3-methoxyphenyl)-2-butanone, 2-Acetyl-3,3-Dimethyl-Norbornane, 6,7-
Dihydro-1,1,2,3,3-Pentamethyl-4(5H)-Indanone, 4-Damascol, Dulcinyl or
Cassione,
Gelsone, Hexalon, Isocyclemone E, Methyl Cyclocitrone, Methyl-Lavender-Ketone,
Orivon, Para-tertiary-Butyl-Cyclohexanone, Verdone, Delphone, Muscone,
Neobutenone,
Plicatone, Veloutone, 2,4,4,7-Tetramethyl-oct-6-en-3 -one, Tetrameran,
hedione, and
mixtures thereof.
More preferably, for the above mentioned compounds, the preferred ketones are
selected
from Alpha Damascone, Delta Damascone, Iso Damascone, Carvone, Gamma-Methyl-
lonone, Iso-E-Super, 2,4,4,7-Tetramethyl-oct-6-en-3-one, Benzyl Acetone, Beta
Damascone, Damascenone, methyl dihydrojasmonate, methyl cedrylone, hedione,
and
mixtures thereof
Preferred are also perfume compositions comprising perfume oils and a carrier
material,
for example as described in JP-56075159, describing the combination of
methacrylonitrilebutadiene-styrene tertiary polymer with a liquid perfume;
GB2141726,
DE 3247709; WO 97/34982; WO 94/19449; WO 98/28398. Preferably, the carrier is
a
water-insoluble polymer, preferably selected from polymers which have
chemically
reacted with the perfume ingredient, to make the carrier as above mentioned.
Preferably the treatment compositions comprise from 0.05% more preferably from
1%,
yet more preferably from 3%, to 15%, more preferably to 10% by weight of the
composition of perfume oil or perfume composition.
The compositions herein preferably contain a heavy metal ion sequestrant or
chelant or
chelating agent. By heavy metal ion sequestrant it is meant herein components
which act
to sequester (chelate) heavy metal ions. These components may also have
calcium and
magnesium chelation capacity, but preferentially they show selectivity to
binding heavy
metal ions such as iron, manganese and copper.
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Heavy metal ion sequestrants are generally present at a level of from 0.005%
to 10%,
preferably from 0.1% to 5%, more preferably from 0.25% to 7.5% and most
preferably
from 0.3% to 2% by weight of the compositions.
Suitable heavy metal ion sequestrants for use herein include organic
phosphonates, such
as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-
hydroxy
disphosphonates and nitrilo trimethylene phosphonates.
Preferred among the above species are diethylene triamine penta (methylene
phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene
diamine
tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate, 1,1
hydroxyethane diphosphonic acid and 1,1 hydroxyethane dimethylene phosphonic
acid.
Other suitable heavy metal ion sequestrant for use herein include
nitrilotriacetic acid and
polyaminocarboxylic acids such as ethylenediaminotetracetic acid,
ethylenediamine
disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine
disuccinic
acid or any salts thereof.
Other suitable heavy metal ion sequestrants for use herein are iminodiacetic
acid
derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic
acid,
described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2-
hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-
hydroxypropyl-3-
sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein.
The (3-
alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N-
monoacetic
acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also
suitable.
EP-A-476,257 describes suitable amino based sequestrants. EP-A-510,331
describes suitable sequestrants derived from collagen, keratin or casein. EP-A-
528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic
acid
and 2-phosphonobutane-1,2,4-tricarboxylic acid are also suitable. Glycinamide-
N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and
2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.
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29
Especially preferred are diethylenetrianiine pentacetic acid, ethylenediamine-
N,N'-
disuccinic acid (EDDS) and 1,1 hydroxyethane diphosphonic acid or the alkali
metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof,
or
mixtures thereof.
In particular the chelating agents comprising a amino or amine group can be
bleach-sensitive and are suitable in the compositions of the invention.
Another highly preferred ingredient useful in the compositions herein is one
or more
additional enzymes.
Preferred additional enzymatic materials include the commercially available
lipases,
cutinases, amylases, neutral and alkaline proteases, cellulases, endolases,
esterases,
pectinases, lactases and peroxidases conventionally incorporated into
detergent
compositions. Suitable enzymes are discussed in US Patents 3,519,570 and
3,533,139.
Preferred connnercially available protease enzymes include those sold under
the
trade marks Alcalase, Savinase, Primase, Durazym, and Esperase by Novo
Industries A/S
(Denmark), those sold under the trade marks Maxatase, Maxacal and Maxapem by
Gist-
Brocades, those sold by Genencor International, and those sold under the trade
marks
Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incorporated
into
the compositions in accordance with the invention at a level of from 0.0001
1o to 4%
active enzyme by weight of the composition.
Preferred amylases include, for example, a amylases obtained from a special
strain of B
licheniformis, described in more detail in GB-1,269,839 (Novo). Preferred
commercially
available amylases include for example, those sold under the trade mark
Rapidase by
Gist-Brocades, and those sold under the trade marks Termamyl, Duramyl and BAN
by
Novo Industries A/S. Highly preferred amylase enzymes may be those described
in
W096/03276, and in W095/26397 and W096/23873.
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Amylase enzyme may be incorporated into the composition in accordance with the
invention at a level of from 0.0001 % to 2% active enzyme by weight.
Lipolytic enzyme may be present at levels of active lipolytic enzyme of from
0.0001% to
5 2% by weight, preferably 0.001% to 1% by weight, most preferably from 0.001%
to 0.5%
by weight.
The lipase may be fungai or bacterial in origin being obtained, for example,
from a lipase
producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp. including
10 Pseudomonas pseudoalcali enes or Pseudomas fluorescens. Lipase from
chemically or
genetically modified mutants of these strains are also useful herein. A
preferred lipase is
derived from Pseudomonas pseudoalcaiigenes, which is described in Granted
European
Patent, EP-B-0218272.
15 Another preferred lipase herein is obtained by cloning the gene from
Humicola
lanu 'nosa and expressing the gene in Asper gillus orvza, as host, as
described in
European Patent Application, EP-A-0258 068, which is commercially available
from
Novo Industri A/S, Bagsvaerd, Denmark, under the trade mark Lipolase. This
lipase is
also descn'bed in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7,
1989.
20 The phosphate-containing builder material preferably comprises tetrasodium
pyrophosphate or even more preferably anhydrous sodium tripolyphosphate.
Also preferred herein are builders, such as water-soluble and water-insoluble
builders.
Preferred water-insoluble builders, typically for solid compositions herein
are alumino
25 silicates such as zeolites (zeolite A, MAP, P, X) and layered silicates
such as known as
SKS-6TM, sold by Clariant.
Suitable water-soluble builder compounds include the water soluble monomeric
polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic
acids or their
30 salts in which the polycarboxylic acid comprises at least two carboxylic
radicals
separated from each other by not more that two carbon atoms, and mixtures of
any of the
foregoing.
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31
The carboxylate or polycarboxylate builder can be momomeric or oligomeric in
type
although monomeric polycarboxylates are generally preferred for reasons of
cost and
performance.
Suitable carboxylates containing one carboxy group include the water soluble
salts of
lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates
containing two
carboxy groups include the water-soluble salts of succinic acid, malonic acid,
(ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid,
tartronic acid and
fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
Polycarboxylates or their acids containing three carboxy groups include, in
particular,
water-soluble citrates, aconitrates and citraconates as well as succinate
derivatives sucb
as the carboxymethyloxysuccinates described in British Patent No. 1,379,241,
lactoxysuccinates described in British Patent No. 1,389,732, and
aminosuccinates
described in Canadian Patent No. 973771, and the oxypolycarboxylate materials
such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No.
1,387,447.
The most prefen-ed polycarboxylic acid containing three carboxy groups is
citric acid,
preferably present at a level of from 0.1 % to 15%, more preferably from 0.5%
to 8% by
weight.
Polycarboxylates containing four carboxy groups include oxydisuccinates
disclosed in
British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-
propane
tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates
containing
sulfo substituents include the sulfosuccinate derivatives disclosed in British
Patent Nos.
1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated
pyrolysed
citrates described in British Patent No. 1,439,000. Preferred polycarboxylates
are
hydroxycarboxylates containing up to three carboxy groups per molecule, more
particularly citrates.
The parent acids of the monomeric or oligomeric polycarboxylate chelating
agents or
mixtures thereof with their salts, e.g. citric acid or citrate%itric acid
mixtures are also
contemplated as useful builder components.
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32
Suitable examples of water-soluble phosphate builders are the alkali metal
tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and
potassium and ammonium pyrophosphate, sodium and potassium orthophosphate,
sodium
polymeta/phosphate in which the degree of polymerization ranges from about 6
to 21, and
salts of phytic acid.
Also preferred in treatment compositions hererin are fabric integrity polymers
such as cyclic
amine based polymers, including adducts of two or more compositions selected
from the group
consisting of piperazine, piperadine, epichlorohydrin, epichlorohydrin benzyl
quat,
epichlorohydrin methyl quat, morpholine and mixtures thereof.
Highly preferred cyclic amine based polymers herein are referred to as
Imidazole-epi
chlorohydrin copolymers. These cyclic amine based polymers can be linear or
branched. One
specific type of branching can be introduced using a polyfunctional
crosslinking agent. An
example of such polymer is exemplified below.
T
I
R2
% x
H
HO O OH
T~R2 W_~o,,,~ o,,~W - R T
x x
This material will generally be about 0.01% to about 10% by the weight of the
detergent
composition or component, more preferably from 0.05% to 6% or even from 0.05%
to 3%.
The treatment compositions herein may also comprise as soil release or fabric
integrity agents,
salt of an anionic cellulose material comprising an anionic substituent group
R - X - Z wherein R
is a saturated, unsaturated or aromatic hydrocarbon spacer group, X is oxygen,
nitrogen or
sulphur, Z is carboxylate, sulphonate, sulphate or phosphonate group. The
hydrocarbon spacer
group is preferably a C1-C18, more preferably a C1-C14, or even more
preferably a C1-C4 saturated,
unsaturated or aromatic group, preferably an alkylene group. The spacer group
may also be
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33
substituted with one or more hydroxy groups. he group X is preferably a
nitrogen, or even more
preferably an oxygen atom. The group Z is preferably a carboxylate group.
Highly preferred
hereon are the so-called salts of carboxyalkyl celluloses, whereby preferably
the alkylene group
(or the so-called alkyl group) comprises from 1 to 4 carbon atoms. Most
preferred herein is a salt
of carboxymethyl cellulose. The cation of the salt is preferably a potassium
ion or more
preferably a sodium ion.
Depending on the application of the composition, the amount of cellulose
material may very. The
anionic cellulose material will generally be about 0.01% to about 10% by the
weight of the
detergent composition or component, more preferably from 0.05% to 6% or even
from 0.05% to
3% by weight of a composition.
The softening ingredients useful herein may be selected from any known
ingredients that
provides a fabric softening benefit.
Clay minerals used to provide the softening properties of the instant
compositions can be
described as expandable, three-layer clays, i.e., alumino-silicates and
magnesium
silicates, having an ion exchange capacity of at least 50 meq/100g. of clay.
The term
"expandable" as used to describe clays relates to the ability of the layered
clay structure
to be swollen, or expanded, on contact with water. The three-layer expandable
clays used
herein are those materials classified geologically as smectites.
There are two distinct classes of smectite-type clays; in the first, aluminum
oxide is
present in the silicate crystal lattice; in the second class of smectites,
magnesium oxide is
present in the silicate crystal lattice. The general formulas of these
smectites are
Alz(Si205)z(OH)2 and Mg3(Si205) (OH)2 for the aluminum and magnesium oxide
type
clay, respectively. It is to be recognised that the range of the water of
hydration in the
above formulas can vary with the processing to which the clay has been
subjected. This is
immaterial to the use of the smectite clays in the present invention in that
the expandable
characteristics of the hydrated clays are dictated by the silicate lattice
structure.
Furthermore, atom substitution by iron and magnesium can occur within the
crystal
lattice of the smectites, while metal cations such as Na+, Ca++, as well as
H+, can be co-
present in the water of hydration to provide electrical neutrality. Except as
noted
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34
hereinafter, such cation substitutions are immaterial to the use of the clays
herein since
the desirable physical properties of the clays are not substantially altered
thereby.
However, smectites, such as montmorillonite and bentonite, having an ion
exchange
capacity of around 70 meq/100 g., and montmorillonite, which has an ion
exchange
capacity greater than 70 meq/100 g., have been found to be useful in the
instant
compositions in that they are deposited on the fabrics to provide the desired
softening
benefits. Accordingly, clay minerals useful herein can be characterised as
expandable,
three-layer smectite-type clays having an ion exchange capacity of at least
about 50
meq/100 g.
The smectite clays used in the compositions herein are all commercially
available. Such
clays include, for example, montmorillonite, volchonskoite, nontronite,
hectorite,
saponite, sauconite, and vermiculite. The clays herein are available under
various
trade marks, for example, Thixogel #1 and Gelwhite GP from Georgia Kaolin
Co.,
Elizabeth, New Jersey; Volclay BC and Volclay #325 , from American Colloid
Co.,
Skolde, Illinois; Black Hills Bentonite BH450 , from Interaational Minerals
and
Chemicals; and Veegum ProTm and Veegum FTM, from R.T. Vanderbilt. It is to be
recognized that such smectite-type minerals obtained under the forgoing trade
marks
can comprise mixtures of the various discrete mineral entities. Such mixtures
of the
smectite minerals are suitable for use herein.
While any of the smectite-type clays having a cation exchange capacity of at
least about
50 meq/100 g. are useful herein, certain clays are preferred. For example,
Gelwhite GP
is an extremely white form of smectite clay and is therefore preferred when
formulating
white granular detergent compositions. Voiclay BC , which is a smectite-type
clay
mineral containing at least 3% of iron (expressed as Fe=03) in the crystal
lattice, and
which has a very high ion exchange capacity, is one of the most efEcient and
effective
clays for use in laundry compositions and is preferred from the standpoint of
product
performance.
Appropriate clay minerals for use herein can be selected by virtue of the fact
that
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smectites exhibit a true 14A x-ray diffraction pattern. This characteristic
pattern, taken in
combination with exchange capacity measurements performed in the manner noted
above, provides a basis for selecting particular smectite-type minerals for
use in the
granular detergent compositions disclosed herein.
5
The clay is preferably mainly in the form of granules, with at least 50%,
preferably at
least 75%, and more preferable at least 90% being in the form of granules
having a size
of at least 0.1 mm up to 1.8 mm, preferably up to 1.18 mm, preferably from
0.15 mm to
0.85 mm. Preferably the amount of clay in the granules is at least 50%, more
preferably at
10 least 70% and most preferably at least 90% by weight of the granules.
Smectite clays are disclosed in the US Patents No.s 3,862,058, 3,948,790,
3,954,632 and
4,062,647. European Patents No.s EP-A-299,575 and EP-A-313,146 in the name of
the
Procter and Gamble Company describe suitable organic polymeric clay
flocculating
15 agents.
Other suitable softening ingredients are long chained polymers and copolymers
derived
from such monomers as ethylene oxide, acrylamide, acrylic acid, dimethylamino
ethyl
methacrylate, vinyl alcohol, vinyl pyrrolidone and ethylene imide. Preferred
are
20 polymers of ethylene oxide, acrylamide and acrylic acid. These polymers
preferably have
average molecular weight in the range of from 100 000 to 10 million, more
preferably
from 150 000 to 5 million. Average molecular weight of a polymer can be easily
measured using gel permeation chromatography, against standards of
polyethylene oxide
of narrow molecular weight distributions. The most preferred polymers are
polyethylene
25 oxides.
Other suitable softening ingredients include cationic fabric softening agents
can also be
incorporated into compositions in accordance with the present invention which
are
suitable for use in methods of laundry washing. Suitable cationic fabric
softening agents
30 include the water insoluble tertiary amines or dilong chain amide materials
as disclosed in
GB-A-1 514 276 and EP-B-0 011 340.
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36
Other preferred ingredients are neutralizing agents, buffering agents,
including (bi)
carbonate salts, phase regulants, hydrotropes, enzyme stabilizing agents,
polyacids, suds
regulants, anti-oxidants, bactericides, or mixtures thereof.
ExamDles
Ex le
A first pouch is made in a mould of a hollow shape. The mould has some holes
in the
mould material to allow a vacuum to be applied. A piece of (optionally heated)
Chris-
CraftTm M-8630 or CXP4087 film is placed on top of this mould. A vacuum is
applied to
pull the film into the mould and pull the film flush with the inner surface of
the mould.
Composition 1, 2 or 3 below is poured into the mould, preferably in an amount
to almost
or completely fill the mould. Then, another piece of the same film material is
placed over
the mould and sealed to the first piece of film by applying heat.
A second larger pouch is fonned in mould Qf a cylindrical shape, having a
diameter just
larger than the first pouch and a depth of 2.5 cm. The mould has some holes in
the mould
material to allow a vacuum to be applied. A piece of (optionally heated) Chris-
Craft M-
8630 fihn is placed over the top of this mould and a vacuum is applied to pull
the film
into the mould and pull the film flush with the inner surface of the mould.
Composition 4,
5 or 6 below is added into the mould, preferably in an amount to completely
fill the
mould. Then the first pouch is placed over the mould and sealed to the first
piece of film
by applying heat (typically with a temperature of from 135 C to 150 C and
applied for up
to 5 seconds.)
This process can be modified by using other methods of forming the shape of
the
pouches, other types of fihn, other sizes of mould, sealing methods, more
individual
pouches etc.
The following is an example of a PVA pouch made by vacuum forming or thermo-
fonning as described herein, having two compartments,, one compartment
comprising
liquid composition 1, 2 or 3 and one compartment comprising solid composition
4, 5 or 6.
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37
The weight ratio of the liquid composition to the solid composition may be
varied, but is
herein below typically about 1:3. The values are by weight of the specified
composition.
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38
1 2 3 4 5 6
LAS and/or 25.0 - 40.0 10.0 13.5 5.0
alkyl sulphate
surfactant
nonionic 45.0 50.0 3.0
surfactant
TAE 80 5.0 1.0 1.0
cationic 5.0 5.0 2.0
surfactant
Layered silicate 5.0
Zeolite A/ 15.0 15.0 22.0
phosphate
Citric acid 10.0 6.0 7.0
Sodium citrate 1.0 3.0 -
Sodium 10.0 9.0
bicarbonate
Sodium 10.0 10.0 14.0
carbonate
MEA 5.0 10.0 9.0
Fatty acid 10.0
Ethanol 15.0 10.0 10.0
Plasticiser 3.0 5.0 1.0 2.0
(PEG,
glycerol)
Percarbonate 18.0 10.0 15.0
Bleach activator 5.0 5.0 3.0
QEA# 5.0 10.0 5.0
Chelant (EDDS, 5.0 11.0 6.0 3.0 3.0 3.0
HEDP, DTPA)
Imidazole-based 2.0 2.0
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39
polymer
Maleic/ acrylic 2.0 2.0 4.0
acid or salt
copolymer
Brightener 1.0 1.0 1.0
Dye Transfer 2.0 2.0 2.0
inhibiting
polymer
protease 2.0 3.0 1.0 2.0 1.0
enzyme
Amylase 2.0 1.0 1.0 1.0
enzyme
Cellulase 2.0 1.0 1.0
enzyme
Cellulose-based 2.0 3.0 2.5
polymer
Perfume 2.0 0.5 2.0 2.0 2.0
Dye 2.0 1.0 0.5 0.5 0.5 0.5
Suds suppressor 2.0 1.0 2.0
Soap 1.0 0.5 0.5
Minors up to
total 100%
#QEA: bis((C2HSO)(C2H40)n)(CH3)-N+C6H12N+(CH3)bis((C2HSO)(C2H40)n),
wherein n is from 15 to 30, preferably 17 to 20.
