[0001] The present invention relates to a printed water-soluble package including a bittering
agent, in particular, packages containing dishwashing or laundry detergent compositions,
methods of producing such packages and their use in dishwashing or textile laundering.
[0002] Water-soluble packages known in the art typically include a composition, such as
a dishwashing or laundry detergent composition enclosed in a water-soluble film, container
or capsule. The detergent composition can therefore be released from the water-soluble
package on exposure to water during use. Such water-soluble packages provide the advantages
of providing single dosing packages, the user does not need to open the package and
the user is not exposed to the detergent composition before use.
[0003] Typically, the contents of such water-soluble packages must be released quickly and
completely during use in water, and without leaving a residue. As a result, the water-soluble
package is often a thin water-soluble film package or a thin walled water-soluble
capsule or container, and may have a high water solubility or reactivity.
[0004] However, such water-soluble package may be relatively fragile. In addition, the water-soluble
package may be susceptible to damage from environmental moisture. The structural integrity
of the water-soluble package may be weakened and/or the water-soluble packages may
have a tendency to stick together when a number of the packages are stored in close
proximity over a period of time.
[0005] WO 02/26896 and
JP/0129438 describe water-soluble package materials which are coated with a fine powder. Suitable
powders include calcium carbonate, magnesium carbonate, clay, talc, silicic acid and
kaolin. Such coating is said to provide excellent slip and anti-blocking properties.
[0006] More recently,
WO 2013/158364 describes a water-soluble packet comprising a water-soluble film coated by a powder
wherein the powder comprises a mixture of powdered lubricant and an active agent.
The combination of a powdered lubricant and an active agent is reported to be particularly
advantageous in providing the packet with additional functionality while improving
the feel of the packet surface, mitigating potential weeping of liquid products onto
the surface of the packet, and preventing the packets from sticking together, thereby
preventing possible failure during separation. The powdered lubricant is said to be
typically a starch, modified starch, silica, siloxane, calcium carbonate, magnesium
carbonate, clay, talc, silicic acid, kaolin, gypsum, zeolite, cyclodextrin, calcium
stearate, zinc stearate, alumina, magnesium stearate or zinc oxide. The active agent
is typically one or more of enzymes, oils, flavours, colorants, odour absorbers, fragrances,
pesticides, fertilisers, activators, acid catalysts, metal catalysts, iron scavengers,
bleaches, bleach components or fabric softeners.
[0007] Furthermore, it is often desirable to deter humans or animals from orally ingesting
the contents of water-soluble packages. Accordingly, it is known to include a bittering
agent in a water-soluble package in order to produce a bitter taste in the mouth if,
for example, a child attempts to eat the film package.
EP 0 700 989 A1 describes a unit packaged detergent for dish washing which may include an additive
which provides an unbearable bitter taste, such as denatonium (e.g. bitrex
™). The additive may be coated onto the unit package detergent in order to improve
the prevention that children may accidently ingest the package detergent.
[0008] WO 2008/034594 A1 and
EP 2 196 531 A1 describe coated detergent compositions, including a water-soluble coating. Both documents
note that the unit coated detergent can include a coating of an unbearable bitter
tasting additive, either as part of the water-soluble coating or as a separate layer.
[0009] More recently,
WO 2014/026856 A1 identifies that when the bittering agent is included in a water-soluble film at higher
doses, the bittering agent can be transferred to a user's hands when handling the
water-soluble film, thus leaving bitterness on the user's hands for several hours.
Accordingly,
WO 2014/026856 A1 describes a water-soluble package containing an agent and a water-soluble covering
wherein the water-soluble covering contains a bittering agent in a diluted state in
order to solve this problem.
[0010] Furthermore, water-soluble packages often include printed information, such as text
and/or pictures visible on an exterior surface of the package, in order to show the
nature of the contents, to provide any instructions and/or warn of any potentially
hazardous materials, for example, see
WO2014/016144 and
WO2008/073299.
[0011] Typically, a water-soluble film material is printed with one or more dye or pigment
layers on to the material using an ink, before adding a protective or lacquer layer
on top of the primer and ink or pigment layers. In some instances, the water-soluble
film material is printed with a primer layer first, then printed with the ink. The
printed water-soluble material may then be used to form a printed water-soluble package
enclosing a composition or material, such as a detergent composition.
SUMMARY OF THE INVENTION
[0012] The present inventors investigated ways of improving printed water-soluble packages
and, in particular, into including a bittering agent in a printed water-soluble package.
However, the present inventors have surprisingly discovered that containing a bitter
agent within or film-coated on a water-soluble substrate has adverse effects on the
appearance of the printed matter on the exterior surface of the water-soluble substrate
and wherein the bittering agent is substantially homogenously contained within the
water-soluble substrate.
[0013] The present inventors have thus sought to provide a printed water-soluble package
including a bittering agent with improved retention of printed information over time.
[0014] In a first aspect, the present invention provides a printed water-soluble package
according to claim 1.
[0015] As used herein, a printed region or regions has one or more layers of dye deposited
on the exterior surface of the water-soluble substrate. The layer or layers of dye
may be deposited directly or indirectly on the exterior surface of the water-soluble
substrate. For example, the printed region may include one or more primer layers between
the layer of dye and the exterior surface of the substrate. Alternatively or additionally,
the printed region may include a protective or lacquer layer on top of the layer or
layers of dye. In contrast, the unprinted region or regions of the water-soluble substrate
have an exterior surface substantially free of deposited dye.
[0016] In a further aspect, the present invention provides a method of producing a printed
water-soluble package according to claim 9.
[0017] In a further aspect, the present invention provides use of a printed water-soluble
package according to the first aspect for washing dishes or laundering textiles, wherein
the composition or material enclosed in the substrate is a dish-washing detergent
compositions or a laundry detergent composition.
Water-soluble package
[0018] "Water-soluble package" means any package construction that is suitable for enclosing
and/or containing the composition or material, such as a dishwashing or laundry detergent
composition. The water-soluble package can be in any packaging form, such as film
packaging, capsules, and containers. In particular embodiments, the water-soluble
package is a single dose water-soluble package.
[0019] The water-soluble package typically contains at least one compartment for containing
the composition. In some embodiments, the water-soluble package includes two or more
compartments. Each compartment can contain a different composition from another compartment.
Alternatively, each compartment may contain a different component (or mixture of components)
of a composition from another compartment. For example, the water-soluble package
may contain two compartments wherein each compartment is a different mixture of components
of a laundry or dishwashing composition.
[0020] When the water-soluble package includes two or more compartments for containing compositions
and/or composition component(s), a printed region may be on the exterior surface of
one or more of the compartments. In some embodiments, the water-soluble has two or
more compartments, the exterior surface of at least one compartment includes a printed
region and the exterior surface of at least one other compartment includes an unprinted
region.
Water-soluble substrate
[0021] The water-soluble substrate typically forms a wall or walls of the water-soluble
package for enclosing a composition. The exterior surface of the substrate is a surface
that is intended to be exposed to the environment during use. The exterior surface
typically opposes an interior surface intended to face or abut the composition or
material to be contained, encased or enclosed in the water-soluble package (such as
a dish-washing or laundry detergent composition).
[0022] Suitable water-soluble substrate materials are known. In particular, the water-soluble
substrate may include one or more water-soluble polymers. In one embodiment, the water-soluble
substrate includes polyvinyl alcohol, a modified polyvinyl alcohol, polyvinyl acetate,
polyacrylates, water-soluble acrylate copolymers, polyaminopropyl sulfonic acid and
salts thereof, polyitaconic acid and salts thereof, polyacrylamides, polyvinylpyrrolidone,
pullalan, cellulosics (such as carboxymethylcellulose and hydroxypropyl methyl cellulose),
water-soluble naturla polymers (such as guar gum, xanthan gum, carrageenan and starch),
water-soluble polymer derivatives (such as modified starches, including ethoxylated
starch and hydroxylated propylstarch, poly(sodium acryloamido-2-methylpropane sulfonate,
polymonomethylmaleate and salts thereof), copolymers thereof and combinations thereof.
In some embodiments, the water-soluble substrate includes, or consists essentially
of, polyvinyl alcohol, a modified polyvinyl alcohol, polyvinyl acetate, carboxymethylcellulose
or hydroxypropyl methyl cellulose.
[0023] In particular embodiments, the water-soluble substrate includes, or consists essentially
of, polyvinyl alcohol, polyvinyl acetate and/or a modified polyvinyl alcohol. Polyvinyl
alcohol, polyvinyl acetate and modified polyvinyl alcohols can provide stable water-soluble
substrates that have suitable dissolution rates.
[0024] The water-soluble substrate material may also contain one or more plasticizers. Examples
of plasticizers include, but are not limited to glycerol, glycerin, diglycerin, ethylene
glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, monopropylene
glycol, polyethylene glycol, neopentyl glycol, trimethylpropane polyether polyols,
sorbitol, ethanolamines and mixtures thereof. The plasticizer, when present, may be
included in the water-soluble substrate material in an appropriate amount, as generally
known.
[0025] The water-soluble package substrate encloses or contains a composition or material.
In use, the water-soluble substrate may dissolve in water to release the material
or composition enclosed within the substrate. Such materials and compositions particularly
include, but are not limited to, detergent compositions, such as dishwashing compositions
and laundry detergent compositions. The material or composition may be in solid, granular,
gel or liquid form.
Bittering agent
[0026] The water-soluble package of the present invention includes a bittering agent. Bittering
agents are generally known. In some embodiments, the bittering agent is selected from
benzoic benzylamine amide, denatonium benzoate, denatonium saccharide, trichloroanisole,
methyl anthranilate and quinine (and salts of quinine). Further examples of bittering
agents include naringin, sucrose octaacetate and agents derived from plant or vegetable
matter, such as chemical compounds derived from chilli pepper plants, those derived
from a plant species of the genus cynaro, alkaloids and amino acids.
[0027] In some embodiments, the bittering agent is selected from the group consisting of
denatonium benzoate, denatonium saccharide, quinine or a salt of quinine. The chemical
name of denatonium is phenylmethyl-[2-[(2,6-dimethylphenyl)amino]-2-oxoethyl]-diethylammonium.
In particular embodiments, the bittering agent is denatonium benzoate or denatonium
saccharide.
[0028] The bittering agent may be contained within (i.e. incorporated in or blended with)
or film-coated on at least part of the water-soluble substrate. The bittering agent
may be contained within or film-coated on the water-soluble substrate in the printed
region or regions. Additionally or alternatively, the bittering agent may be contained
within or film-coated on an unprinted region or regions when present. In preferred
embodiments, the bittering agent is contained within printed and unprinted regions
of the water-soluble substrate. It is preferred that the bittering agent is substantially
homogenously contained within the water-soluble substrate. The bittering agent can
be substantially homogenously mixed with the water-soluble substrate material before
water-soluble substrate is formed. In this way, the production of the water-soluble
package with the bittering agent is simplified.
[0029] The bittering agent may be incorporated into the matrix of a water-soluble polymer
included in the water-soluble substrate by dissolving the bittering agent in a water-soluble
polymer solution before the unprinted region of the water-soluble substrate is formed.
The bittering agent may be present in water-soluble substrate material in a range
of 100 to 5000 ppm, preferably 200 to 3000 ppm, more preferably 500 to 2000 ppm, based
on the weights of the bittering agent and water-soluble substrate. For example, 1
mg of bittering agent may be incorporated into 1 g of water-soluble substrate to provide
the bittering agent at 1000 ppm.
[0030] Film-coating of a bittering agent on the surface of the water-soluble substrate at
printed and/or unprinted regions can be performed by known techniques, such as spraying
or printing of a bittering agent solution onto the surface of the water-soluble substrate.
[0031] Additionally or alternatively, the bittering agent may be included in the printed
water-soluble package in the powder coating as a powdered bittering agent (described
in more detail herein).
Powder coating
[0032] The printed water-soluble package includes a powder coating on an exterior surface
of the water-soluble substrate, and the powder coating includes a powdered lubricating
agent. The powder coating, when present, may coat the printed region or regions and/or
the unprinted region or regions (if present) of the water-soluble substrate. In the
printed regions of the water-soluble substrate, the powder coating may be indirectly
on the exterior surface of the water-soluble substrate where there is a layer of dye
or pigment.
[0033] The powder coating typically is applied to least 50% by area of the exterior surface
of the water-soluble substrate. In some embodiments, the powder coating is applied
to 60% or more, 70% or more, 80% or more, or 90% or more by area of the exterior surface
of the water-soluble substrate. The powder coating can be applied by any known technique
such as spray-coating or passing the water-soluble substrate through a falling curtain
of powder coating composition.
[0034] The powder coating may be applied to the exterior surface of the water-soluble substrate
at a rate of 0.5 to 10mg per 100cm
2, in some embodiments not more than 5mg per 100cm
2, and in further embodiments in the range of 1.25 to 2.5mg per 100cm
2. Alternatively, the powder coating is applied to or present on the exterior surface
of the water-soluble substrate in an amount of 100 ppm or more, preferably 200 ppm
or more, more preferably 300 ppm or more, based on the weights of the powder coating
and the water-soluble substrate. For example, a 1 mg of powder coating may be applied
to a 1 g water-soluble substrate to provide a 1000 ppm coating on the substrate. In
certain embodiments, the powder coating is applied to or present on the exterior surface
of the water-soluble substrate in a range of 100 to 5000 ppm, preferably 200 to 3000
ppm, more preferably 300 to 2000 ppm.
[0035] The powder coating includes a powdered lubricating agent. Typical powdered lubricating
agents include oligosaccharide, polysaccharide and inorganic lubricating agents. The
powdered coating may include one or more of the group selected from starch, modified
starches (including, but limited to, corn starch, potato starch or hydroxyethyl starch)
silicas, siloxanes, calcium carbonate, magnesium carbonate, clay, talc, silicic acid,
kaolin, gypsum, zeolites, cyclodextrins, calcium stearate, zinc stearate, alumina,
magnesium stearate, sodium sulphate, sodium citrate, sodium tripolyphosphate, potassium
sulphate, potassium citrate, potassium tripolyphosphate and zinc oxide. In a preferred
embodiment, the powdered lubricating agent includes talc.
[0036] The powdered lubricating agent may form 10 wt.% or more of the powder coating based
on the total weight of the powder coating. In some embodiments, the powdered lubricating
agent forms 25 wt.% or more, 30 wt.% or more, 35 wt. % or more, 40 wt.% or more, or
45 wt.% or more of powder coating based on the total weight of the powder coating.
In some embodiments, the powdered lubricating agent forms 95 wt.% or less, 90 wt.
% or less, 85 wt.% or less, 80 wt.% or less, or 75 wt.% or less of the powder coating
based on the total weight of the powder coating.
[0037] In certain embodiments, the powdered lubricating agent forms in the range of 25 to
95 wt.%, 30 to 90 wt.%, 35 to 85 wt.%, 40 to 80 wt.%, or 45 to 75 wt.% of the powder
coating based on the total weight of the powder coating. In preferred embodiments,
the powder coating consists essentially of a powdered lubricating agent.
[0038] In alternative embodiments, the powdered lubricating agent forms 50 wt.% or more,
60 wt.% or more, or 70 wt.% or more of the powder coating based on the total weight
of the powder coating.
[0039] The powdered lubricating agent may have an average particle diameter of at least
about 0.1 microns. The powdered lubricating agent may have an average particle diameter
of about 200 microns or less. In some embodiments, the powdered lubricating agent
has an average particle diameter in the range of about 0.1 to 100 microns, in other
embodiments in the range of about 0.1 to 20 microns and in further embodiments in
the range of about 5 and 15 microns. Average particle diameter can be measured by
known optical imaging techniques. For example, the diameter of all particles within
a fixed area under a microscope (or other optical imaging device) can be measured
and the mean diameter calculated. The diameter can be taken as the major dimension
for irregularly shaped particles.
[0040] The powder coating can include a powdered bittering agent in addition to or as an
alternative to a bittering agent being present within or film-coated on the water-soluble
substrate. The powdered bittering agent may be a powdered form of any one of the bittering
agents described herein. In preferred embodiments, the powdered bittering agent is
selected from a powdered form of denatonium benzoate, denatonium saccharide, quinine
or a salt of quinine.
[0041] When a bittering agent is included in a powder coating, the powdered bittering agent
may form 5 wt.% or more of the powder coating based on the total weight of the powder
coating. In some embodiments, the powdered bittering agent forms 10 wt.% or more,
15 wt.% or more, 20 wt. % or more, or 25 wt.% or more of powder coating based on the
total weight of the powder coating. In some embodiments, the powdered bittering agent
forms 75 wt.% or less, 70 wt. % or less, 65 wt.% or less, 60 wt.% or less, or 55 wt.%
or less of the powder coating based on the total weight of the powder coating. In
further embodiments, the powdered bittering agent forms 5 to 75 wt.%, 10 to 70 wt.%,
15 to 65 wt.%, 20 to 60 wt.%, or 25 to 55 wt.% of the powder coating based on the
total weight of the powder coating. In alternative embodiments, the powdered bittering
agent forms 50 wt.% or less, 40 wt.% or less, 30 wt.% or less of the powder coating
based on the total weight of the powder coating. In these embodiments, it is advantageous
to include a relatively low amount of powdered bittering agent in the powder coating
while maintaining a bitter taste when a user tries to ingest the water-soluble package.
[0042] The powdered bittering agent, when present, may have an average particle diameter
of at least about 0.1 microns. The powdered bittering agent may have an average particle
diameter of about 200 microns or less. In some embodiments, the powdered bittering
agent has an average particle diameter of in the range of about 0.1 to 100 microns,
in other embodiments in the range of about 0.1 to 20 microns and in further embodiments
in a range of about 5 and 15 microns. Average particle diameter can be measured by
known optical imaging techniques.
[0043] In some embodiments, the powder coating further includes one or more additional active
agents. The additional active agent may be selected from one or more of the group
of enzymes, oils, odour absorbers, fragrances, bleaches, bleach components, cleaning
polymers, soil release polymers, EPEI, water softeners, dyes and fabric softeners.
Method of making a water-soluble package
[0044] The printed water-soluble packages of the present invention can be manufactured using
standard known techniques. For example, a sheet of water-soluble substrate (e.g. film)
may be printed with one or more layers of dye or pigment in a pattern. The pattern
may be indicia, such as words, symbols or drawings.
[0045] The layer or layers of dye or pigment are printed onto the water-soluble substrate
using a non-aqueous solvent-based inks (such as organic solvent-based inks).
[0046] The water-soluble substrate may be printed with a primer layer before printing of
the layer or layers of dye or pigment. After printing with the layer or layers of
dye or pigment, the water-soluble substrate may be printed with a protective or lacquer
layer. The printed layer or layers may be then dried, for example using heat and/or
air flow. The resulting printed water-soluble substrate may be stored, transported
or used immediately to form the printed water-soluble packages of the present invention.
[0047] When the bittering agent is contained within at least part of the water-soluble substrate,
the bittering agent is typically present in the water-soluble substrate before printing.
In one embodiment, the bittering agent is included at least on part of the exterior
surface of the water-soluble substrate as a film coating. The film coating of bittering
agent may be deposited on the water-substrate before, during or after the printing
of the printed regions.
[0048] The printed water-soluble substrate is typically formed (preferably thermoformed)
into a water-soluble substrate enclosure (e.g. a film pocket, open capsule or container).
The water-soluble substrate enclosure may then be filled with a composition such as
a dish-washing or laundry detergent composition. The water-soluble enclosure containing
the composition or material can then be sealed, for example by sealing the edges of
the enclosure or joining the enclosure with one or more additional pieces of water-soluble
substrate, in order to enclose the material or composition in the printed water-soluble
package.
[0049] The powder coating may then be applied to the exterior surface of the water-soluble
substrate. The powdercoating may be applied to the water-soluble substrate by any
known powder technique. Preferably, the powder is applied to the water-soluble substrate
using no solvent or a non-aqueous solvent. Such an application reduces the risk of
dissolving the water-soluble substrate.
[0050] The above optional and preferred features are equally combinable and applicable to
all aspects of the invention, unless indicated otherwise.
[0051] In a particular embodiment, the present invention provides a printed water-soluble
package comprising a bittering agent and a water-soluble substrate enclosing a composition,
the water-soluble substrate having an exterior surface with one or more printed regions
wherein the printed regions are printed with non-aqueous solvent-based ink, the bittering
agent is selected from the group consisting of denatonium benzoate, denatonium saccharide,
quinine or a salt of quinine and is substantially homogenously contained within the
water-soluble substrate, and wherein the water-soluble package further includes a
powder coating coated on the exterior surface of the water-soluble substrate, the
powder coating a including a powdered lubricating agent, the powdered lubricating
agent being talc.
DETAILED DESCRIPTION
[0052] The invention will be described in more detail with reference to specific embodiments
and examples.
Example 1 (Control)
[0053] A polyvinyl alcohol thin film (Solublon
™, available from Aicello) was printed with a primer, ink and lacquer combination.
After rewinding of the film and transportation, thin film capsules were produced from
the film, filled with two different commercially available laundry detergent compositions
and loaded into standard laundry detergent capsule containers.
[0054] The containers were placed in storage at a range of climatic conditions: 20°C & 65%
relative humidity (RH); 28°C & 70% RH; and 37°C & 70% RH. Such conditions simulate
west European ambient conditions and accelerated testing. The capsules were assessed
visually at various time points.
[0055] After 18 weeks under simulated conditions, there was some evidence that dye had transferred
to other capsules and a limited amount of fading of the colours existed. However,
there was no significant discolouration of the dyes.
Example 2 (Comparative)
[0056] A polyvinyl alcohol thin film (Solublon
™, available from Aicello) impregnated with bitrex
™ was printed with a primer, ink and lacquer combination. After rewinding of the film
and transportation, thin film capsules were produced from the film, filled with two
different commercially available laundry detergent compositions and loaded into standard
laundry detergent capsule containers.
[0057] The containers were placed in storage at a range of climatic conditions: 20°C & 65%
relative humidity (RH); 28°C & 70% RH; and 37°C & 70% RH. Such conditions simulate
west European ambient conditions and accelerated testing. The capsules were assessed
visually at various time points.
[0058] After 4 weeks under simulated conditions, there was some evidence that the dye had
transferred to other capsules and a limited amount of fading of the colours. However,
there was also evidence of significant discolouration of the dyes, in particular the
red dye.
Example 3
[0059] A polyvinyl alcohol thin film (Solublon
™, available from Aicello) impregnated with bitrex
™ is printed with a primer, ink and lacquer combination. After rewinding of the film
and transportation, thin film capsules are produced from the film, filled with two
different commercially available laundry detergent compositions and coated with a
powder coating including talc as a lubricating agent. The powder-coated capsules are
loaded into standard laundry detergent capsule containers.
[0060] The containers are placed in storage at a range of climatic conditions: 20°C & 65%
relative humidity (RH); 28°C & 70% RH; and 37°C & 70% RH. Such conditions simulate
west European ambient conditions and accelerated testing. The capsules were assessed
visually at various time points.
[0061] After some time, there was no evidence of print smearing and no evidence of print
transfer. The printed images appear clean and crisp as per at the beginning of the
test.
Example 4
[0062] A polyvinyl alcohol thin film (Solublon
™, available from Aicello) is printed with a primer, ink and lacquer combination. After
rewinding of the film and transportation, thin film capsules are produced from the
film, filled with two different commercially available laundry detergent compositions
and coated with a powder coating including a mixture of bitrex
™ and talc. The powder-coated capsules are loaded into standard laundry detergent capsule
containers.
[0063] The containers are placed in storage at a range of climatic conditions: 20°C & 65%
relative humidity (RH); 28°C & 70% RH; and 37°C & 70% RH. Such conditions simulate
west European ambient conditions and accelerated testing. The capsules were assessed
visually at various time points.
Example 5
[0064] A polyvinyl alcohol thin film (Solublon
™, available from Aicello) impregnated with bitrex
™ is printed with a primer, ink and lacquer combination. After rewinding of the film
and transportation, thin film capsules are produced from the film, filled with two
different commercially available laundry detergent compositions and coated with a
powder coating including a mixture of bitrex
™ and talc. The powder-coated capsules are loaded into standard laundry detergent capsule
containers.
[0065] The containers are placed in storage at a range of climatic conditions: 20°C & 65%
relative humidity (RH); 28°C & 70% RH; and 37°C & 70% RH. Such conditions simulate
west European ambient conditions and accelerated testing. The capsules were assessed
visually at various time points.