Technical field
[0001] The present invention is in the field of dishwashing, in particular it relates to
a pack for the storage, distribution and display of a water soluble multi-compartment
pouch adapted to fit the dishwasher dispenser and to deliver product into the pre-wash,
main wash and/or post-rinse cycles of the dishwashing machine. The pouch contains
a cleaning composition for release on dissolution of the pouch.
Background of the invention
[0002] Unitised doses of dishwashing detergents are found to be more attractive and convenient
to some consumers because they avoid the need of the consumer to measure the product
thereby giving rise to a more precise dosing and avoiding wasteful overdosing or underdosing.
For this reason automatic dishwashing detergent products in tablet form have become
very popular. Detergent products in pouch form are also known in the art, they have
the advantage over tablets of avoiding the contact of the consumer fingers with the
dishwashing composition which may contain bleach and/or other irritant substances.
[0003] The automatic dishwashing process usually involves a initial pre-wash cycle, main-wash
cycle and several hot rinse cycles. Better performance is obtained when the detergent
is delivered at the beginning of the main-wash cycle than when the detergent is delivered
in the pre-wash cycle since it can be lost with the initial water. In laundry washing
machines the detergent can be placed in the drum or in the dispenser, however, in
dishwashers the detergent is generally delivered into the main wash via the dispenser
to avoid premature dissolution in the pre-wash. The amount of detergent is therefore
limited by the volume of the dispenser. Dispensers vary in volume and shape from manufacturer
to manufacturer. In the case of detergent in loose form (i.e., powders, paste and
liquids), the volume of the dispenser is a decisive factor. In the case of unit dose
forms, such as tablet, the geometry and shape of the dispenser plays also a very important
role.
[0004] Tablets can be designed to have a size and shape which fit all machines. One of the
drawbacks of detergent tablets is the fact that their manufacturing process requires
the additional step of powder compaction. This decreases enzyme activity and slows
down the dissolution rate of the ingredients forming the tablet, or requires the use
of complex and expensive disintegrant systems, or makes it difficult to achieve differential
dissolution of the detergent active ingredients.
[0005] Some detergent ingredients used in dishwashing detergent compositions are liquids.
These liquid ingredients can be difficult or costly to include in a solid detergent
composition. Also, certain ingredients are preferably transported and supplied to
detergent manufacturers in a liquid form and require additional, and sometimes costly,
process steps to enable them to be included in a solid detergent composition. An example
of these detergent ingredients is surfactant, especially nonionic surfactant which
are typically liquid at room temperature or are typically transported and supplied
to detergent manufacturers in liquid form. Another example is organic solvents.
[0006] Current methods of incorporating liquid ingredients into solid detergent compositions
include absorbing the liquid ingredient onto a solid carrier, for example by mixing,
agglomeration or spray-on techniques. Typically, solid detergent compositions comprise
only low amounts of these liquid detergent ingredients due to the difficulty and expense
of incorporating these liquid ingredients into a solid detergent. Furthermore, the
incorporation of liquid ingredients into solid detergent compositions can impact on
the dissolution characteristics of the composition (for example as the result of forming
surfactant gel phases), can increase the moisture pick-up by water sensitive ingredients
and can also lead to problems of flowability. It would be advantageous to have a detergent
composition which allows the different ingredients to be in their natural state i.e.,
liquid or solid. This would facilitate the manufacturing process, increase the component
stability and furthermore allow the delivery of liquid ingredients prior or post '
to the delivery of solid ingredients. For example differential dissolution of active
ingredients would be beneficial in the case of enzyme/bleach compositions to avoid
oxidation of enzymes by the bleach in the dishwashing liquor. It would also be advantageous
to separate bleach from perfume.
[0007] Another factor that can contribute to the inefficient delivery of actives to the
wash, in the case of tablets, is the need for adding carrier materials, as for example
porous materials able to bind active liquid materials, binders and disintegrants.
In particular, the incorporation of liquid surfactants to powder form detergent compositions
can raise considerable processing difficulties and also the problem of poor dissolution
through the formation of surfactant gel phases.
[0008] There is still the need for a multi-compartment unitised dose form capable of fitting
the dispensers of different dishwashing machine types and which allows for the simultaneous
delivery of incompatible ingredients and ingredients in different physical forms.
There is also need for a simplified manufacturing process for multi-compartment pouch
production and for multi-compartment pouches with improved strength, handling and
dissolution characteristics as well as excellent aesthetics.
[0009] WO97/26315 describes a tinted or untinted transparent container, such as a bottle, containing
a tinted cleaning liquid. In particular, it discloses a frilled package of blue or
violet tinted transparent liquid cleaning composition disposed in a transparent blue
or violet tinted or untinted container such that the appearance of the filled package
is substantially transparent and neutral in colour or slightly blue/green or slightly
yellow green in appearance.
[0010] GB2235206 describes a detergent system comprising two or more components each packaged and
dosed individually, and wherein each of the components have a distinctive colour to
distinguish them from one another.
[0011] EP0414462 discloses a laundry treatment product in the form of a single compartment or multi-compartment
sachet capable of releasing its contents into the wash liquor during the laundry process.
D4 also discloses a multi-compartment sachet; however, like
EP0414462 it is wholly silent about see-through packages for storing said sachets.
Summary of the invention
[0012] The present invention provides a display pack in accordance with claim 1 of the appended
claims and in accordance with claim 5 of the appended claims.
[0013] In a preferred embodiment there is provided a see-through, preferably transparent,
dishwashing detergent pack wherein the number of distinctive groups of pouches or
other unit doses is at least 2, preferably at least 3, more preferably at least 4,
and especially at least 6 and wherein the number of unit doses per pack is at least
10, preferably at least 16 an more preferably at least 20. The unit doses are multi-compartment
pouches, each compartment itself possibly being visually or otherwise distinctive
from the remainder of the compartments in an individual pouch. In a preferred embodiment,
groups of pouches are distinctive in terms of colour. At least one group of pouches
has one compartment which is visually distinctive, for example in terms of colour,
from the corresponding compartment in one or more other groups of pouches. Preferably
in such embodiments, all pouch groups have at least one 'common' compartment, i.e.
the appearance of which is the same from group to group. Preferably the visually distinctive
compartment contains a liquid, gel or paste; the common compartment contains a powder
or tablet. The pouches can be arranged in any form in the pack, either randomly or
following an order, for example suitable arrangements including layers wherein each
pouch comprises at least one compartment of a different colour to any of the compartments
of the remainder of the pouches on the same layer. The pack can be made of plastic
or any other suitable material, provided the material is strong enough to protect
the pouches during transport. This kind of pack is also very useful because the user
does not need to open the pack to see how many pouches there are left, the different
colour pouches are very easy to identify from the exterior.
[0014] Preferably in the invention of claim 1 and essentially in the invention of claim
5, the pouch has a volume of from 5 to 70 ml, preferably from 15 to 60 ml, more preferably
from 18 to 57 ml, and a longitudinal/transverse aspect ratio in the range from 2:1
to 1:8, preferably from 1:1 to 1:4. The longitudinal dimension is defined as the maximum
height of the pouch when the pouch is lying on one of the bases which has the maximum
footprint with the pouch compartments superposed in a longitudinal direction, i.e.
one over another, and under a static load of about 2 Kg. The transverse dimension
is defined as the maximum width of the pouch in a plane perpendicular to the longitudinal
direction under the same conditions. These dimensions are adequate to fit the dispensers
of the majority of dishwashers. Although the shape of the pouch can vary widely, in
order to maximise the available volume, preferred pouches have a base as similar as
possible to the footprint of the majority of the dispensers, that is generally rectangular.
[0015] In one embodiment the plurality of compartments of the water-soluble pouch are in
generally superposed relationship and the pouch comprises upper and lower generally
opposing outer walls, a skirt-like side walls, forming the sides of the pouch, and
one or more internal partitioning walls, separating different compartments from one
another, and wherein each of said upper and lower outer walls and skirt-like side
wall are formed by thermoforming, vacuum forming or a combination thereof.
[0016] In a preferred embodiment each internal partitioning wall of the water-soluble multi-compartment
pouch is secured to an outer or side wall of the pouch along a single seal line or
to both an outer and a side wall of the pouch along a plurality of seal lines that
are at least partially non-overlapping. Preferably each partitioning wall is secured
to one or more outer or sides wall by heat or solvent sealing.
[0017] In especially preferred embodiments at least one internal partitioning wall of the
multi-compartment pouch is secured to an upper or lower outer wall along a first continuos
seal line and one or both of said outer wall and said partitioning wall are secured
to the skirt-like side wall along a second continuous seal line and wherein the seal
lines in the case of heat seals are essentially non-overlapping and in the case of
solvent seals are at least partially non-overiapping.
[0018] Non-overlapping seal lines are particularly advantageous in the case of multi-compartment
pouches made by a process involving several non-simultaneous heat sealing steps. Without
wishing to be bound by theory, it is believed that the heat seal mechanism involves
the step of water evaporation from the film, therefore it is very difficult to achieve
a good overlapping seal unless the two seals are formed simultaneously. Heat sealing
is preferred in cases in which the pouches are filled with water sensitive components.
Solvent sealing can reduce processing cost, can produce stronger seals and can make
the process faster. Partially non-overlapping seals allow for the superposition of
a plurality of compartments of different sizes.
[0019] Preferably, at least one internal partitioning wall of the multi-compartment pouch
is secured to the upper outer wall along a first seal line defining the waist line
of the skirt-like wall and wherein the second non-overlapping or at least partially
non-overlapping seal is preferably off-set below the waist line-defining seal line
in the direction of the lower outer wall. The skirt-like side wall is also preferably
slightly gathered or puckered in the final pouch to provide a mattress-like appearance.
[0020] In another embodiment the water-soluble pouch comprises a plurality of compartments
in side-by-side but generally superposable relationship (for example, the compartments
can be folded over each other). The pouch comprises upper and lower generally opposing
outer walls, one or more skirt-like side walls and one or more external partitioning
walls, and wherein each of said upper and lower outer walls and skirt-like side walls
are formed by thermoforming, vacuum forming or a combination thereof.
[0021] In one embodiment at least one of the plurality of compartments of the water-soluble
pouch comprises a powder or densified powder composition. The powder composition usually
comprises traditional solid materials used in dishwashing detergent, such as builders,
alkalinity sources, enzymes, bleaches, etc. The powder composition can be in the form
of dry powder, hydrated powder, agglomerates, encapsulated materials, extrudates,
tablets or mixtures thereof. It is also useful to have water-soluble pouches with
several compartments comprising different powder compositions, usually compositions
in different compartments comprise incompatible actives or actives which need to be
delivered at different times of the dishwashing process. It is advantageous to have
bleach and enzymes in different compartments.
[0022] In a preferred embodiment at least one of the powder compartments comprises particulate
bleach. The bleach is preferably selected from inorganic peroxides inclusive of perborates
and percarbonates, organic peracids inclusive of preformed monoperoxy carboxylic acids,
such as phthaloyl amido peroxy hexanoic acid and di-acyl peroxides.
[0023] In the case of powder compositions differential dissolution can be obtained, for
example, by varying the degree of powder compression and/or particle size of the powder
compositions in the same or different compartments. Another way to obtain differential
dissolution is to use water-soluble films of different thickness or different degree
or rate of solubility under in-use conditions. Film solubility can be controlled by
for example pH, temperature, ionic strength or any other means. For purposes of achieving
phased or sequential delivery of detergent actives, it is preferred that each of the
compartments of the pouch have a different disintegration rate or dissolution profile
under in-use conditions.
[0024] In another embodiment at least one of the plurality of compartments of the water-soluble
pouch comprises a liquid composition. The liquid compositions comprise traditional
liquid materials used in dishwashing detergents, such as non-ionic surfactants or
the organic solvents described hereinbelow. In preferred embodiments the liquid composition
comprises detergency enzyme. Especially useful are water-soluble pouches having one
compartment comprising a liquid composition and another compartment comprising a solid
composition. In the case of liquid compositions, especially liquid compositions enclosed
within a secondary pack, it is desirable to have a water content in the composition
similar to the water content in the film in order to avoid transfer of water from
one to another. In cases in which the content of water is lower in the composition
than in the film, water can migrate from the film to the composition making the water-soluble
pouch brittle. For similar reasons, it is also desirable to have a similar amount
of plasticiser in the composition and in the film.
[0025] In another embodiment at least one of the plurality of compartments of the water-soluble
pouch comprises a composition in the form of a paste. The multi-compartment pouches
can also include compositions in the form of a gel or a wax.
[0026] In preferred embodiments at least one of-the plurality of compositions of the water-soluble
pouch comprises an organic solvent system compatible with the water-soluble pouch.
The organic solvent system can simply act as a liquid carrier, but in preferred compositions,
the solvent can aid removal of cooked-, baked- or burnt-on soil and thus has detergent
functionality in its own right. The organic solvent system (comprising a single solvent
compound or a mixture of solvent compounds) preferably has a volatile organic content
above 1 mm Hg and more preferably above 0.1 mm Hg of less than about 50%, preferably
less than about 20% and more preferably less than about 10% by weight of the solvent
system. Herein volatile organic content of the solvent system is defined as the content
of organic components in the solvent system having a vapor pressure higher than the
prescribed limit at 25°C and atmospheric pressure.
[0027] The organic solvent system for use herein is preferably selected from organoamine
solvents, inclusive of alkanolamines, alkylamines, alkyleneamines and mixtures thereof;
alcoholic solvents inclusive of aromatic, aliphatic (preferably C
4-C
10) and cycloaliphatic alcohols and mixtures thereof; glycols and glycol derivatives
inclusive of C
2-C
3 (poly)alkylene glycols, glycol ethers, glycol esters and mixtures thereof; and mixtures
selected from organoamine solvents, alcoholic solvents, glycols and glycol derivatives.
In one preferred embodiment the organic solvent comprises organoamine (especially
alkanolamine) solvent and glycol ether solvent, preferably in a weight ratio of from
about 3:1 to about 1:3, and wherein the glycol ether solvent is selected from ethylene
glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol monomethyl
ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene
glycol monoethyl ether, propylene glycol monobutyl ether, and mixtures thereof. Preferably,
the glycol ether is a mixture of diethylene glycol monobutyl ether and propylene glycol
butyl ether, especially in a weight ratio of from about 1:2 to about 2:1.
Detailed description of the invention
[0028] The invention envisages a detergent pack having improved display attributes and which
makes it very easy for the consumer to evaluate the amount of pouches in the pack.
[0029] The dishwashing composition, or components for use herein, are contained in the internal
volume space of the pouch, and are typically separated from the outside environment
by a barrier of water-soluble material. Typically, different components of the composition
contained in different compartments of the pouch are separated from one another by
a barrier of water-soluble material.
[0030] The compartments of the water-soluble pouch may be of a different colour from each
other, for example a first compartment may be green or blue, and a second compartment
may be white or yellow. One compartment of the pouch may be opaque or semi-opaque,
and a second compartment of the pouch may be translucent, transparent, or semitransparent.
The compartments of the pouch may be the same size, having the same internal volume,
or may be different sizes having different internal volumes.
[0031] Suitable water-soluble pouches include for example dual-compartment pouches comprising
loose powder, densified powder or a tablet in a first compartment and a liquid, paste,
or waxy or translucent gel detergent in a second compartment. The second liquid, paste
or gel compartment could also contain a separate packed powder, for example in the
form of micro-beads, noodles or one or more pearlized balls allowing a delayed or
sequential release effects. If the first compartment comprises a tablet, this tablet
can have a recess of a size and geometrical shape, (e.g. square, round or oval) so
as to partially or totally house the second compartment. In pouches comprising powder
in the first compartment, the powder can be arranged in layers that can be of different
colours.
[0032] Alternatively, dual compartment pouches can comprise powder of the same or different
colours in the two compartments, the powder comprising flecks of one or more colours
or having a uniform colour. One of the two compartments could also comprise a separate
densified powder phase (allowing delayed or controlled release), for example in the
form of micro-beads, noodles or one or more pearlized balls. Other dual compartment
pouches comprise a single or multi-phase liquid, paste or waxy or translucent gel
detergent in the two compartments, each compartment either comprising multi-phase
liquid or gels being of the same or different colour and/or density. Either or both
of these compartments can also comprise a separate densified powder phase (allowing
delayed or controlled release), for example in the form of micro-beads, noodles or
one or more pearlized balls. The compartments of all the above described dual compartment
pouches can be superposed or be in superposable (e.g. side by side) relationship.
[0033] Multi-compartment pouches, having three compartments, can have superposed compartments
of any geometrical shape in a sandwich like disposition, for example having either
loose or compacted powder in the two outer compartments and having a liquid, paste
or waxy or translucent gel in the middle compartment. Contrary, the liquid, paste
or waxy or translucent gel can be in the two outer compartments, perhaps containing
suspended solids and speckles, and the powder can be in the middle compartment. A
multi-compartment pouch can also have a tablet with more than one recess in the first
compartment and with multiple other compartments totally or partially housed in the
recesses of the tablet.
[0034] The pouches can be packed in a string, each pouch being individually separable by
a perforation line. Therefore, each pouch can be individually torn-off from the remainder
of the string by the end-user.
[0035] Especially suitable for use herein are multi-compartment pouches having a first compartment
comprising a liquid composition and a second compartment comprising a powder composition
wherein the weight ratio of the liquid to the solid composition is from about 1:30
to about 30:1, preferably form about 1:1 to about 1:25 and more preferably from about
1:15 to about 1:20.
[0036] For reasons of deformability and dispenser fit under compression forces, pouches
or pouch compartments containing a component which is liquid will usually contain
an air bubble having a volume of up to about 50%, preferably up to about 40%, more
preferably up to about 30%, more preferably up to about 20%, more preferably up to
about 10% of the volume space of said compartment.
[0037] The pouch is preferably made of a pouch material which is soluble or dispersible
in water, and has a water-solubility of at least 50%, preferably at least 75% or even
at least 95%, as measured by the method set out here after using a glass-filter with
a maximum pore size of 20 microns.
[0038] 50 grams ± 0.1 gram of pouch material is added in a pre-weighed 400 ml beaker and
245ml ± 1ml of distilled water is added. This is stirred vigorously on a magnetic
stirrer set at 600 rpm, for 30 minutes. Then, the mixture is filtered through a folded
qualitative sintered-glass filter with a pore size as defined above (max. 20 micron).
The water is dried off from the collected filtrate by any conventional method, and
the weight of the remaining material is determined (which is the dissolved or dispersed
fraction). Then, the % solubility or dispersability can be calculated.
[0039] Preferred pouch materials are polymeric materials, preferably polymers which are
formed into a film or sheet. The pouch material can, for example, be obtained by casting,
blow-moulding, extrusion or blown extrusion of the polymeric material, as known in
the art.
[0040] Preferred polymers, copolymers or derivatives thereof suitable for use as pouch material
are selected from polyvinyl alcohols, polyvinyl pyrrolidone, polyalkylene oxides,
acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose
amides, polyvinyl acetates, polycarboxylic acids and salts, polyaminoacids or peptides,
polyamides, polyacrylamide, copolymers of maleic/acrylic acids, polysaccharides including
starch and gelatine, natural gums such as xanthum and carragum. More preferred polymers
are selected from polyacrylates and water-soluble acrylate copolymers, methylcellulose,
carboxymethylcellulose sodium, dextrin, ethylcellulose, hydroxyethyl cellulose, hydroxypropyl
methylcellulose, maltodextrin, polymethacrylates, and most preferably selected from
polyvinyl alcohols, polyvinyl alcohol copolymers and hydroxypropyl methyl cellulose
(HPMC), and combinations thereof. Preferably, the level of polymer in the pouch material,
for example a PVA polymer, is at least 60%.
[0041] The polymer can have any weight average molecular weight, preferably from about 1000
to 1,000,000, more preferably from about 10,000 to 300,000 yet more preferably from
about 20,000 to 150,000.
[0042] Mixtures of polymers can also be used as the pouch material. This can be beneficial
to control the mechanical and/or dissolution properties of the compartments or pouch,
depending on the application thereof and the required needs. Suitable mixtures include
for example mixtures wherein one polymer has a higher water-solubility than another
polymer, and/or one polymer has a higher mechanical strength than another polymer.
Also suitable are mixtures of polymers having different weight average molecular weights,
for example a mixture of PVA or a copolymer thereof of a weight average molecular
weight of about 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.
[0043] Also suitable herein are polymer blend compositions, for example comprising hydrolytically
degradable and water-soluble polymer blends such as polylactide and polyvinyl alcohol,
obtained by mixing polylactide and polyvinyl alcohol, typically comprising about 1-35%
by weight polylactide and about 65% to 99% by weight polyvinyl alcohol.
[0044] Preferred for use herein are polymers which are from about 60% to about 98% hydrolysed,
preferably about 80% to about 90% hydrolysed, to improve the dissolution characteristics
of the material.
[0045] Most preferred pouch materials are PVA films known under the trade reference Monosol
M8630, as sold by Chris-Craft Industrial Products of Gary, Indiana, US, and PVA films
of corresponding solubility and deformability characteristics. Other films suitable
for use herein include films known under the trade reference PT film or the IC-series
of films supplied by Aicello, or VF-HP film supplied by Kuraray.
[0046] The pouch material herein can also comprise one or more additive ingredients. For
example, it can be beneficial to add plasticisers, for example glycerol, ethylene
glycol, diethyleneglycol, propylene glycol, sorbitol and mixtures thereof. Other additives
include functional detergent additives to be delivered to the wash water, for example
organic polymeric dispersants, etc.
[0047] The detergent and cleaning compositions herein can comprise traditional detergency
components and can also comprise organic solvents having a cleaning function and organic
solvents having a carrier or diluent function or some other specialised function.
The compositions will generally be built and comprise one or more detergent active
components which may be selected from bleaching agents, surfactants, alkalinity sources,
enzymes, thickeners (in the case of liquid, paste, cream or gel compositions), anticorrosion
agents (e.g. sodium silicate) and disrupting and binding agents (in the case of powder,
granules or tablets). Highly preferred detergent components include a builder compound,
an alkalinity source, a surfactant, an enzyme and a bleaching agent.
[0048] Unless otherwise specified, the components described hereinbelow can be incorporated
either in the organic solvent compositions and/or the detergent or cleaning compositions.
[0049] The organic solvents should be selected so as to be compatible with the tableware/cookware
as well as with the different parts of an automatic dishwashing machine. Furthermore,
the solvent system should be effective and safe to use having a volatile organic content
above 1 mm Hg (and preferably above 0.1 mm Hg) of less than about 50%, preferably
less than about 30%, more preferably less than about 10% by weight of the solvent
system. Also they should have very mild pleasant odours. The individual organic solvents
used herein generally have a boiling point above about 150°C, flash point above about
100°C and vapor pressure below about 1 mm Hg, preferably below 0.1 mm Hg at 25°C and
atmospheric pressure.
[0050] Solvents that can be used herein include: i) alcohols, such as benzyl alcohol, 1,4-cyclohexanedimethanol,
2-ethyl-1-hexanol, furfuryl alcohol, 1,2-hexanediol and other similar materials; ii)
amines, such as alkanolamines (e.g. primary allcanolamines: monoethanolamine, monoisopropanolamine,
diethylethanolamine, ethyl diethanolamine; secondary alkanolamines: diethanolamine,
diisopropanolamine, 2-(methylamino)ethanol; ternary alkanolamines: triethanolamine,
triisopropanolamine); alkylamines (e.g. primary alkylamines: monomethylamine, monoethylamine,
monopropylamine, monobutylamine, monopentylamine, cyclohexylamine), secondary alkylamines:
(dimethylamine), alkylene amines (primary alkylene amines: ethylenediamine, propylenediamine)
and other similar materials; iii) esters, such as ethyl lactate, methyl ester, ethyl
acetoacetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl
ether acetate, diethylene glycol monobutyl ether acetate and other similar materials;
iv) glycol ethers, such as ethylene glycol monobutyl ether, diethylene glycol monobutyl
ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene
glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol butyl
ether and other similar materials; v) glycols, such as propylene glycol, diethylene
glycol, hexylene glycol (2-methyl-2, 4 pentanediol), triethylene glycol, composition
and dipropylene glycol and other similar materials; and mixtures thereof.
Surfactant
[0051] In the methods of the present invention for use in automatic dishwashing the detergent
surfactant is preferably low foaming by itself or in combination with other components
(i.e. suds suppressers). Surfactants suitable herein include anionic surfactants such
as alkyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, alkyl glyceryl
sulfonates, alkyl and alkenyl sulphonates, alkyl ethoxy carboxylates, N-acyl sarcosinates,
N-acyl taurates and alkyl succinates and sulfosuccinates, wherein the alkyl, alkenyl
or acyl moiety is C
5-C
20, preferably C
10-C
18 linear or branched; cationic surfactants such as chlorine esters (
US-A-4228042,
US-A-4239660 and
US-A-4260529) and mono C
6-C
16 N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted
by methyl, hydroxyethyl or hydroxypropyl groups; low and high cloud point nonionic
surfactants and mixtures thereof including nonionic alkoxylated surfactants (especially
ethoxylates derived from C
6-C
18 primary alcohols), ethoxylated-propoxylated alcohols (e.g., BASF Poly-Tergent® SLF18),
epoxy-capped poly(oxyalkylated) alcohols (e.g., BASF Poly-Tergent® SLF18B - see
WO-A-94/22800), ether-capped poly(oxyalkylated) alcohol surfactants, and block polyoxyethylene-polyoxypropylene
polymeric compounds such as PLURONIC®, REVERSED PLURONIC®, and TETRONIC® by the BASF-Wyandotte
Corp., Wyandotte, Michigan; amphoteric surfactants such as the C
12-C
20 alkyl amine oxides (preferred amine oxides for use herein include C
12 lauryldimethyl amine oxide, C
14 and C
16 hexadecyl dimethyl amine oxide), and alkyl amphocarboxylic surfactants such as Miranol™
C2M; and zwitterionic surfactants such as the betaines and sultaines; and mixtures
thereof. Surfactants suitable herein are disclosed, for example, in
US-A-3,929,678,
US-A- 4,259,217,
EP-A-0414 549,
WO-A-93/08876 and
WO-A-93/08874. Surfactants are typically present at a level of from about 0.2% to about 30% by
weight, more preferably from about 0.5% to about 10% by weight, most preferably from
about 1% to about 5% by weight of composition. Preferred surfactant for use herein
are low foaming and include low cloud point nonionic surfactants and mixtures of higher
foaming surfactants with low cloud point nonionic surfactants which act as suds suppresser
therefor.
Builder
[0052] Builders suitable for use in detergent and cleaning compositions herein include water-soluble
builders such as citrates, carbonates and polyphosphates e.g. sodium tripolyphosphate
and sodium tripolyphosphate hexahydrate, potassium tripolyphosphate and mixed sodium
and potassium tripolyphosphate salts; and partially water-soluble or insoluble builders
such as crystalline layered silicates (
EP-A-0164514 and
EP-A-0293640) and aluminosilicates inclusive of Zeolites A, B, P, X, HS and MAP. The builder is
typically present at a level of from about 1% to about 80% by weight, preferably from
about 10% to about 70% by weight, most preferably from about 20% to about 60% by weight
of composition.
[0053] Amorphous sodium silicates having an SiO
2:Na
2O ratio of from 1.8 to 3.0, preferably from 1.8 to 2.4, most preferably 2.0 can also
be used herein although highly preferred from the viewpoint of long term storage stability
are compositions containing less than about 22%, preferably less than about 15% total
(amorphous and crystalline) silicate.
Enzyme
[0054] Enzymes suitable herein include bacterial and fungal cellulases such as Carezyme
and Celluzyme (Novo Nordisk A/S); peroxidases; lipases such as Amano-P (Amano Pharmaceutical
Co.), M1 Lipase
R and Lipomax
R (Gist-Brocades) and Lipolase
R and Lipolase Ultra
R(Novo); cutinases; proteases such as Esperase
R, Alcalase
R, Durazym
R and Savinase
R (Novo) and Maxatase
R, Maxacal
R, Properase
R and Maxapem
R (Gist-Brocades); α and β amylases such as Purafect Ox- Am
R (Genencor) and Termamyl
R, Ban
R, Fungamyl
R, Duramyl
R, and Natalase
R (Novo); pectinases; and mixtures thereof. Enzymes are preferably added herein as
prills, granulates, or cogranulates at levels typically in the range from about 0.0001
% to about 2% pure enzyme by weight of composition.
Bleaching agent
[0055] Bleaching agents suitable herein include chlorine and oxygen bleaches, especially
inorganic perhydrate salts such as sodium perborate mono-and tetrahydrates and sodium
percarbonate optionally coated to provide-controlled rate of release (see, for example,
GB-A-1466799 on sulfate/carbonate coatings), preformed organic peroxyacids and mixtures thereof
with organic peroxyacid bleach precursors and/or transition metal-containing bleach
catalysts (especially manganese or cobalt). Inorganic perhydrate salts are typically
incorporated at levels in the range from about 1% to about 40% by weight, preferably
from about 2% to about 30% by weight and more preferably from abut 5% to about 25%
by weight of composition. Peroxyacid bleach precursors preferred for use herein include
precursors of perbenzoic acid and substituted perbenzoic acid; cationic peroxyacid
precursors; peracetic acid precursors such as TAED, sodium acetoxybenzene sulfonate
and pentaacetylglucose; pernonanoic acid precursors such as sodium 3,5,5-trimethylhexanoyloxybenzene
sulfonate (iso-NOBS) and sodium nonanoyloxybenzene sulfonate (NOBS); amide substituted
alkyl peroxyacid precursors (
EP-A-0170386); and benzoxazin peroxyacid precursors (
EP-A-0332294 and
EP-A-0482807). Bleach precursors are typically incorporated at levels in the range from about
0.5% to about 25%, preferably from about 1% to about 10% by weight of composition
while the preformed organic peroxyacids themselves are typically incorporated at levels
in the range from 0.5% to 25% by weight, more preferably from 1% to 10% by weight
of composition. Bleach catalysts preferred for use herein include the manganese triazacyclononane
and related complexes (
US-A-4246612,
US-A-5227084); Co, Cu, Mn and Fe bispyridylamine and related complexes (
US-A-5114611); and pentamine acetate cobalt (III) and related complexes(
US-A-4810410).
Low cloud point non-ionic surfactants and suds suppressers
[0056] The suds suppressers suitable for use herein include nonionic surfactants having
a low cloud point. "Cloud point", as used herein, is a well known property of nonionic
surfactants which is the result of the surfactant becoming less soluble with increasing
temperature, the temperature at which the appearance of a second phase is observable
is referred to as the "cloud point" (See
Kirk Othmer, pp. 360-362). As used herein, a "low cloud point" nonionic surfactant is defined as a nonionic
surfactant system ingredient having a cloud point of less than 30° C., preferably
less than about 20° C., and even more preferably less than about 10° C., and most
preferably less than about 7.5° C. Typical low cloud point nonionic surfactants include
nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohol,
and polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverse block polymers.
Also, such low cloud point nonionic surfactants include, for example, ethoxylated-propoxylated
alcohol (e.g., BASF Poly-Tergent® SLF18) and epoxy-capped poly(oxyalkylated) alcohols
(e.g.,BASF Poly-Tergent® SLF18B series of nonionics, as described, for example, in
US-A-5,576,281).
[0057] Preferred low cloud point surfactants are the ether-capped poly(oxyalkylated) suds
suppresser having the formula:
![](https://data.epo.org/publication-server/image?imagePath=2015/27/DOC/EPNWB2/EP04030420NWB2/imgb0001)
wherein R
1 is a linear, alkyl hydrocarbon having an average of from about 7 to about 12 carbon
atoms, R
2 is a linear, alkyl hydrocarbon of about 1 to about 4 carbon atoms, R
3 is a linear, alkyl hydrocarbon of about 1 to about 4 carbon atoms, x is an integer
of about 1 to about 6, y is an integer of about 4 to about 15, and z is an integer
of about 4 to about 25.
[0058] Other low cloud point nonionic surfactants are the ether-capped poly(oxyalkylated)
having the formula:
R
IO(R
IIO)
nCH(CH
3)OR
III
wherein, R
I is selected from the group consisting of linear or branched, saturated or unsaturated,
substituted or unsubstituted, aliphatic or aromatic hydrocarbon radicals having from
about 7 to about 12 carbon atoms; R
II may be the same or different, and is independently selected from the group consisting
of branched or linear C
2 to C
7 alkylene in any given molecule; n is a number from 1 to about 30; and R
III is selected from the group consisting of:
(i) a 4 to 8 membered substituted, or unsubstituted heterocyclic ring containing from
1 to 3 hetero atoms; and
(ii) linear or branched, saturated or unsaturated, substituted or unsubstituted, cyclic
or acyclic, aliphatic or aromatic hydrocarbon radicals having from about 1 to about
30 carbon atoms;
(b) provided that when R2 is (ii) then either: (A) at least one of R1 is other than C2 to C3 alkylene; or (B) R2 has from 6 to 30 carbon atoms, and with the further proviso that when R2 has from 8 to 18 carbon atoms, R is other than C1 to C5 alkyl.
[0059] Other suitable components herein include organic polymers having dispersant, anti-redeposition,
soil release or other detergency properties invention in levels of from about 0.1%
to about 30%, preferably from about 0.5% to about 15%, most preferably from about
1% to about 10% by weight of composition. Preferred anti-redeposition polymers herein
include acrylic acid containing polymers such as Sokalan PA30, PA20, PA15, PA10 and
Sokalan CP10 (BASF GmbH), Acusol 45N, 480N, 460N (Rohm and Haas), acrylic acid/maleic
acid copolymers such as Sokalan CP5 and acrylic/methacrylic copolymers. Preferred
soil release polymers herein include alkyl and hydroxyalkyl celluloses (
US-A-4,000,093), polyoxyethylenes, polyoxypropylenes and copolymers thereof, and nonionic and anionic
polymers based on terephthalate esters of ethylene glycol, propylene glycol and mixtures
thereof.
[0060] Heavy metal sequestrants and crystal growth inhibitors are suitable for use herein
in levels generally from about 0.005% to about 20%, preferably from about 0.1% to
about 10%, more preferably from about 0.25% to about 7.5% and most preferably from
about 0.5% to about 5% by weight of composition, for example diethylenetriamine penta
(methylene phosphonate), ethylenediamine tetra(methylene phosphonate) hexamethylenediamine
tetra(rnethylene phosphonate), ethylene diphosphonate, hydroxyethylene-1,1-diphosphonate,
nitrilotriacetate, ethylenediaminotetracetate, ethylenediamine-N,N'-disuccinate in
their salt and free acid forms.
[0061] The compositions herein can contain a corrosion inhibitor such as organic silver
coating agents in levels of from about 0.05% to about 10%, preferably from about 0.1%
to about 5% by weight of composition (especially paraffins such as Winog 70 sold by
Wintershall, Salzbergen, Germany), nitrogen-containing corrosion inhibitor compounds
(for example benzotriazole and benzimadazole - see
GB-A-1137741) and Mn(ll) compounds, particularly Mn(II) salts of organic ligands in levels of
from about 0.005% to about 5%, preferably from about 0.01% to about 1%, more preferably
from about 0.02% to about 0.4% by weight of the composition.
[0062] Other suitable components herein include colorants, water-soluble bismuth compounds
such as bismuth acetate and bismuth citrate at levels of from about 0.01% to about
5%, enzyme stabilizers such as calcium ion, boric acid, propylene glycol and chlorine
bleach scavengers at levels of from about 0.01% to about 6%, lime soap dispersants
(see
WO-A-93/08877), suds suppressors (see
WO-93/08876 and
EP-A-0705324), polymeric dye transfer inhibiting agents, optical brighteners, perfumes, fillers
and clay.
[0063] Liquid detergent compositions can contain low quantities of low molecular weight
primary or secondary alcohols such as methanol, ethanol, propanol and isopropanol
can be used in the liquid detergent of the present invention. Other suitable carrier
solvents used in low quantities includes glycerol, propylene glycol, ethylene glycol,
1,2-propanediol, sorbitol and mixtures thereof.
[0064] The pouch, when used herein can be of any form, shape and material which is suitable
to hold the product prior to use, e.g. without allowing the release of the compositions
from the pouch prior to contact of the pouched composition to water. The exact execution
will depend on for example the type and amount of the compositions in the pouch, the
characteristics required from the pouch to hold, protect and deliver or release the
compositions, the number of compartments in the pouch.
[0065] Preferred herein are water-soluble pouches having one compartment comprising a liquid
composition and another compartment comprising a powder or densified powder composition.
During the manufacture of the liquid compartment an air bubble is typically formed.
This air bubble can reduce the compressibility of the pouch and therefore the ease
of closing the dispenser after placing the pouch therein. It has been found that ease
of closing is increased when the ratio of the air bubble diameter to the maximum lateral
dimension of the pouch footprint is from about 1:5 to about 1:2. Preferably, the bubble
has a diameter from about 9 to about 16 mm. The bubble dimension can be controlled
by process parameters.
[0066] In use, the water-soluble pouch is usually placed within the washing machine dispenser
and released during the main cycle of the dishwashing process. However, the dispensers
of some dishwashing machines are not completely water tight, mainly for two reasons,
either the dispenser has some apertures allowing water ingress or the dispenser is
sealed with a rubber band that can deform with time due to the high temperature of
the dishwashing process. Water ingress into the dispenser can cause premature leaking
of some of the pouch content which is thus lost at the end of the pre-wash. This problem
is especially acute in the case of pouches comprising liquid compositions having a
low viscosity wherein a considerable amount of the product can be lost before the
main-wash cycle. The problem can be overcome by making the pouch or at least the liquid
compartment thereof out of a film material which is designated to survive the pre-wash
and to release the pouch contents at or after the start of the main-wash cycle. In
European machines, the pre-wash is usually a cold water cycle (about 20°C or less)
without detergent and lasting for about 10 to 15 min.
[0067] Preferably the film material has a water solubility according to the hereinbelow
defined test of less than about 50%, more preferably less than about 20% and especially
less than about 5% under cold water conditions (20°C or below) when exposed to the
water for at least 10 minutes, preferably at least 15 minutes; and a water solubility
of at least about 50%, more preferably at least about 75% and especially at least
about 95% under warm water conditions (30°C or above, preferably 40°C or above) when
exposed to the water for about 5 minutes and preferably when exposed to the water
for about 3 minutes. Such film materials are herein referred to as being substantially
insoluble in cold water but soluble in warm water. Sometimes this is abbreviated simply
to "warm water soluble".
[0068] 50 grams ± 0.1 gram of pouch material is added in a pre-weighed 400 ml beaker and
245ml ± 1ml of distilled water is added. This is kept at the desired temperature,
by using a water bath, and stirred vigorously on a magnetic stirrer set at 600 rpm,
for the desired time. Then, the mixture is filtered through a folded qualitative sintered-glass
filter with a maximum pore size of 20 µm. The water is dried off from the collected
filtrate by any conventional method, and the weight of the remaining material is determined
(which is the dissolved or dispersed fraction). Then, the % solubility or dispersability
can be calculated.
[0069] Commercially available films insoluble in cold water and soluble in hot water include
BP26 available from Aicello, L10 and L15 available from Aquafilm, VF-M and VM-S available
from Kuraray and E-2060 available from Monosol.
[0070] In a preferred embodiment a multi-compartment pouch comprises a first compartment
comprising a liquid composition and a second compartment comprising a powder or densified
powder composition. Preferably, the liquid compartment is made of a warm water-soluble
material as described hereinabove and the powder or densified powder compartment is
made of cold water-soluble material, i.e., a material which is soluble to an extent
of at least 50%, preferably at least 75%, more preferably at least 95% by weight under
cold water conditions (20°C or below) when exposed to the water for about 5 minutes
and preferably when exposed to the water for about 3 minutes. Due to the way in which
European dishwashing machines operate (they are filled with cold water and the cold
water is heated by means of a heater), the compartment made of warm water-soluble
material takes longer to dissolve than the compartment made of cold water-soluble
material. This kind of pouch allows for a delayed release of the liquid composition
providing optimised use of the detergent composition. Preferably, the liquid composition
comprises detergency enzyme, this being advantageous from the enzyme storage stability
viewpoint, the enzyme being separated from the bleach and from highly alkaline materials
contained in the powder or densified powder composition. Furthermore, the liquid containing
compartment (substantially cold water-insoluble and warm water-soluble) will take
longer to dissolve or disintegrate than the solid containing compartment (cold water-soluble),
minimizing the negative interaction in the wash liquor between bleach and enzymes
and between surfactant and enzymes and providing improved protein soil removal and
spotting benefits in the later stages of the dishwashing process.
[0071] Pouch compartments containing solid compositions, in particular oxygen bleach comprising
compositions, are usually pin-pricked in order to allow the leakage of any formed
oxygen. The holes formed by pin pricking also allow the leakage of perfumes or malodors,
however. For example, surfactants often have an unpleasant smell associated with them
and when such pouches are packed within a secondary package, the unpleasant surfactant
smell can be concentrated into the package head space and released each time that
the user open the package. This problem can be avoided by including the surfactant
in the liquid composition, since liquid containing compartments must be made free
of pin holes. Thus, according to another embodiment, the liquid composition comprises
a surfactant. Another advantage of having the surfactant in the liquid phase is to
avoid problems of loading the surfactant onto the solid material. A further advantage
is that the surfactant is released with a certain delay with respect to the solid
composition, this allows better performance of the bleach and enzymes which can be
adversely affected by interaction between the surfactant and the table/dishware surfaces.
[0072] Preferably perfume is introduced in the solid composition, pin prickling allowing
for slow release of the perfume before the product is used in the dishwasher.
[0073] Films substantially insoluble in cold water and soluble in warm water have relatively
low moisture and plasticiser content, therefore the film would require a significant
time and temperature in order to seal by means of heat sealing. These requirements
can lead to damage of the film such as for example pin-holes at the point where the
film is stretched into the mould, causing leakage, especially problematic in the case
of pouches containing liquid. Therefore, it is preferred that compartments made of
films substantially insoluble in cold water and soluble in warm water and which house
liquids are sealed using solvent which partially hydrates the film prior to sealing,
lowering the time and temperature required for sealing, generating strong seals and
avoiding pin-hole formation. In the preferred embodiment of differential solubility
pouches having one compartment comprising a liquid composition and another compartment
comprising a powder composition wherein the liquid compartment is made of material
substantially insoluble in cold water and soluble in warm water and the powder compartment
is made of material which is soluble in cold water, it is preferred that the liquid
compartment be sealed by solvent-sealing while the liquid compartment is sealed to
the powder compartment by heat sealing.
[0074] The pouch can also be placed outside the dispenser, for example in the cutlery basket,
in a net or on the door of the dishwasher. In this case, it is preferred to make the
entire pouch of a film material, as for example the one described herein above, which
protects the pouch content until at least the start of the main-wash cycle.
[0075] Although the nature of the pouched products is such that it readily dissolves or
disperses into the water, it may be preferred that disintegrating agents such as effervescence
sources, water-swellable polymers or clays are present in the pouch itself, and/ or
in the product therein, in particular effervescence sources based on an acid and a
carbonate source. Suitable acids include the organic carboxylic acids such as fumaric
acid, maleic acid, malic acid, citric acid; suitable carbonate sources include sodium
salts of carbonate, bicarbonate, percarbonate. Preferred levels for the disintegrating
aids or effervescence sources or both are from 0.05% to 15% or even from 0.2% to 10%
or even form 0.3 to 5% by weight of total pouched composition.
Examples: All of the examples are provided for illustrative purposes.
Abbreviations used in Examples
[0076] In the examples, the abbreviated component identifications have the following meanings:
- Carbonate :
- Anhydrous sodium carbonate
- STPP :
- Sodium tripolyphosphate
- Silicate :
- Amorphous Sodium Silicate (SiO2:Na2O = from 2:1 to 4:1)
- HEDP :
- Ethane 1-hydroxy-1,1-diphosphonic acid
- Perborate :
- Sodium perborate monohydrate
- Percarbonate :
- Sodium percarbonate of the nominal formula 2Na2CO3.3H2O2
- Carbonate :
- Anhydrous sodium carbonate
- Termamyl :
- α-amylase available from Novo Nordisk A/S
- Savinase :
- protease available from Novo Nordisk A/S
- FN3 :
- protease available from Genencor
- SLF18 :
- Poly-Tergent® available from BASF
- ACNI :
- alkyl capped non-ionic surfactant of formula C9/11 H19/23 EO8-cyclohexyl acetal
- C14AO :
- tetradecyl dimethyl amine oxide
- C16AO :
- hexadecyl dimethyl amine oxide
- Duramyl :
- α-amylase available from Novo Nordisk A/S
- DPM :
- dipropylene glycol methyl ether
- DPG :
- dipropylene glycol
- Methocel :
- cellulosic thickener available from Dow Chemical
[0077] In the following examples all levels are quoted as per cent (%) by weight.
Examples 1 to 8
[0078] The compositions of examples 1 to 4 are introduced in a two compartment layered PVA
rectangular base pouch. The dual compartment pouch is made from a Monosol M8630 film
as supplied by Chris-Crafl Industrial Products. 17.2 g of the particulate composition
and 4 g of the liquid composition are placed in the two different compartments of
the pouch. The pouch dimensions under 2 Kg load are: length 3.7 cm, width 3.4 cm and
height 1.5 cm. The longitudinal/transverse aspect ratio is thus 1.5:3.2 or 1:2.47.
The pouch is manufactured using a two-endless surface process, both surfaces moving
in continuous horizontal rectilinear motion as herein described. According to this
process a first web of pouches is prepared by forming and filling a first moving web
of open pouches mounted on the first endless surface and closing the first web of
open pouches with the second web of filled and sealed pouches moving in synchronism
therewith.
[0079] The pouch is introduced in the 25 ml dispenser compartment of a Bosch Siemens 6032
dishwashing machine, the dispenser is closed and the washing machine operated in its
normal 55°C program.
![](https://data.epo.org/publication-server/image?imagePath=2015/27/DOC/EPNWB2/EP04030420NWB2/imgb0003)