[0001] The present invention provides a detergent tablet comprising a compressed/compacted
portion and a meltable and/or dissolvable non-compressed portion.
[0002] Detergent compositions in tablet form are known in the art. It is understood that
detergent compositions in tablet form hold several advantages over detergent compositions
in particulate form, such as ease of handling, transportation and storage. To ease
the use for the consumer and/or to improve the stability detergents are often applied
in the form of a shaped body. Commonly this is a single or multi layer tablet. However,
to make a composition for detergents suitable for pressing tablets some restrictions
concerning the composition have to be regarded.
[0003] Detergent tablets are most commonly prepared by pre-mixing particular components
of a detergent composition and forming the pre-mixed detergent components into a tablet
using a tablet press. Tablets are typically formed by compression of the particular
components of the detergent composition into a tablet.
[0004] Further, a tablet should disintegrate quickly but should also have a firm body that
does not break easily during the whole route from tabletting-machine up to washing
machine. Also some (performance) ingredients are limited in use in the composition
in order not to disturb the tabletting/compressing process.
[0005] Furthermore as the components of the detergent composition are compressed, the components
are brought into close proximity with each other. A result of the close proximity
of the components can be that certain of the components react with each other, becoming
unstable, inactive or exhausted. A solution to this problem, as seen in the prior
art, has been to separate components of the detergent composition that may potentially
react with each other when the detergent composition is compressed into tablet form.
Separation of the components has been achieved in the art by, for example, preparing
multiple-layer tablets wherein the components that may potentially react with each
other are contained in different layers of the tablet.
[0006] Multiple-layer tablets are commonly prepared using multiple compression steps. Layers
of the tablet that are subjected to more than one compression step are subjected to
a cumulative and potentially greater overall compression pressure. An increase in
compression pressure of the tabletting press is known to decrease the rate of dissolution
of the tablet with the effect that such multiple layer may not dissolve satisfactorily
in use.
[0007] Other methods of achieving separation of detergent components have been described.
One way to partly overcome the restrictions concerning the detergent composition is
to provide a so called 'tab in tabs'. In
EP0979865 is described that a compressed body is attached inside the cavity of another compressed
body. In another embodiment a cavity of a compressed body can also be filled with
an uncompressed body as described in
EP1184450. Producing a 'tab in tab' to increase the freedom in the detergent composition however
requires a significant change in the common production process when compared to the
process of standard single or multi layer detergent tablet.
[0008] Another approach for example is described in
EP-A 0,224,135 disclosing a dishwashing detergent in a form which comprises a warm water-soluble
melt, into which a cold water-soluble tablet is pressed.
[0009] The object of the present application is to provide a detergent shaped body which
is stabile during handling and dissolvable in a liquid. The compressed part of the
shaped body can contain a smaller amount of ingredients that disturb the compressing
step in production. The non-compressed part of the shaped body does contain atleast
one ingredient that should disturb in the compressing step in production.
[0010] Said object is met by a detergent shaped body without any cavity comprising a compressed
portion and at least one non-compressed portion in form of at least one strand(s),
stripe(s), extruded line(s), dot(s), a pattern or at least one layer and a process
for preparing same.
[0011] According to the present invention "any cavity" comprises any depression on the surface
of the shaped body provided intentionally during pressing of the body or any mould
or hole in the shaped body.
[0012] Thus, in accordance with the present invention it has been found that active detergent
components of a detergent tablet which impair processability of the detergent composition
for example due to high mechanical action inside the tabletting machine the component
can melt or become waxy and thus leave a solid deposit on the inside of the tabletting
machine that increases over the time and disturb the mechanical movement in the machine.
Therefore there is a restriction to the detergent composition concerning the ingredients
and therefore the composition may only contain limited amounts of those ingredients
that do impair with the processability. Examples of these components include several
types of surfactants impairing the ability of a particulate detergent composition
to be compressed without leaving deposits inside of the tabletting machine if included
in a high amount. Examples are listed below as well as sensitive compounds like for
example bleaching agents and enzymes.
[0013] In addition, in accordance with the present invention, it has been found that active
detergent components of a detergent tablet may be separated from one another by having
one or more compatible components contained in a compressed portion and one or more
compatible components contained in a non-compressed portion of the tablet. Examples
for components restricting processability of the detergent composition, e.g. ability
to be compressed are surfactants shown below as suitable raw materials for the non-compressed
portion or polyalkylene glycols. Examples of components that may interact and therefore
preferably are separated include bleaching agents, bleach activators or catalyst and
enzymes; bleaching agents and bleach catalysts or activators; bleaching agents and
surfactants; alkalinity sources and enzymes.
[0014] Separating at least a part of the ingredients impairing processability of the detergent
composition by including at least a part of them in a non-compressed portion allows
that part of the composition not containing or only partly containing such ingredients
to be easily formed into a tablet and thereafter to be combined with the remainder
of the desired composition by applying the non-compressed portion including the remaining
desired ingredients e.g. on the surface of the formed tablet.
[0015] Furthermore, it may be advantageous to provide the compressed and the non-compressed
portions such that they dissolve in wash water with different dissolution rates. Therefore
the compressed and the non-compressed portions might be formulated in a way that the
ingredients are released or dissolved at different time ranges in a washing or cleaning
process. By controlling the rate of dissolution of each portion relative to one another,
and by selection of the active detergent components in the respective portions, their
order of release into the wash water can be controlled and the cleaning performance
of the detergent tablet may be improved. For example it is often preferred that enzymes
are delivered to the wash prior to bleaching agent and/or bleach activator, or different
types of surfactants are provided in a determined order.
[0016] It may also be preferred that a source of alkalinity is released into the wash water
more rapidly than other components of the detergent tablet. It is also envisaged that
it may be advantageous to prepare a detergent tablet according to the present invention
wherein the release of certain components of the tablet is delayed relative to other
components.
[0017] It is also possible that the tablet may comprise a plurality of compressed and/or
non-compressed portions. For example, a plurality of compressed portions may be arranged
in layers and/or a plurality of non-compressed portions may be present as discrete
stripes/strands/extruded lines/dots or layers on the tablet. Thus, there may be a
first and a second and optional subsequent compressed layers and/or non-compressed
portions, each comprising an active detergent component and where at least the first
and second portions may comprise different active detergent components or mixtures
of components. Such a plurality of compressed and/or non-compressed portions may be
advantageous, enabling a tablet to be produced which has for example, a first and
second and optional subsequent portions so that they have different rates of dissolution.
Such performance benefits might be achieved by selectively delivering active detergent
components into the wash water at different times.
[0018] The detergent tablets described herein are preferably between 6g and 80g in weight,
more preferably between 7g and 60g in weight, even more preferably between 8g and
50g in weight.
The detergent tablet described herein that are suitable for use in automatic dishwashing
methods are most preferably between 8g and 30g in weight.
Detergent tablets suitable for use in fabric laundering methods are most preferably
between 30g and 50g. The weight ratio of compressed portion to non-compressed portion
is generally greater than 0.5: 1, preferably greater than 1: 1, more preferably greater
than 2: 1, even more preferably greater than 3: 1 or even 4: 1, most preferably at
least 5: 1.
Compressed portion
[0019] The compressed portion of the detergent tablet comprises at least one active detergent
component but may comprise a mixture of more than one active detergent components,
which are compressed. Any detergent tablet component conventionally used in known
detergent tablets is suitable for incorporation into the compressed portion of the
detergent tablets of this invention. Suitable active detergent components are described
hereinafter. Preferred active detergent components include builder compound(s), surfactant(s),
bleaching agent(s), bleach activator(s), bleach catalyst(s), enzyme(s) and an alkalinity
source(s).
[0020] Active detergent component(s) present in the compressed layer may optionally be prepared
in combination with a carrier and/or a binder for example water, polymer (e. g. PEG),
liquid silicate. The active detergent components are preferably prepared in particulate
form (i. e. powder or granular form) and may be prepared by any known method, for
example conventional spray drying, granulation, pelletting or agglomeration. The particulate
active detergent component(s) are then compressed using any suitable equipment suitable
for forming compressed tablets, blocks, bricks or briquettes. The form of the compressed
portion is not limiting the invention, however, according to the invention the form
should be one which can be easily pressed and doesn't include any cavity provided
to be filled with a further portion of a detergent composition.
Non-Compressed Portion
[0021] The non-compressed portion comprises at least one active detergent component, but
may comprise a mixture of more than one active detergent components.
[0022] Active detergent components suitable for incorporation into the non-compressed portion
include components that either give restrictions to the formulation of the detergent
composition of the tablet, for example due to high mechanical action inside of the
tabletting machine the component can melt or become waxy and thus leave a solid deposit
on the inside of the tabletting machine that increases over time and impairs the mechanical
movement in the machine or they might interact with one or more of the detergent components
present in the compressed portion.
[0023] In particular, preferred components of the non-compressed portion are some types
of surfactants, which are mentioned below as preferably included at least partially
into the non-compressed portion or those that are adversely affected by the mechanical
forces on detergent powder or tablets that are present inside of a tabletting machine.
Examples of the later mentioned active detergent components include, but are not limited
to, bleaching agent(s), bleach activator(s), bleach catalyst(s), enzyme(s), corrosion
inhibitor(s), perfume and an alkalinity source(s). These components are described
in more detail below. The active detergent component(s) may be in any form for example
particulate (i. e. powder or granular), gel or liquid form.
[0024] The non-compressed portion either comprises an active detergent compound which itself
is solid at room temperature (about 15 to 30°C) but becomes liquid at increased temperature
(above ca. 40°C). Preferably the component(s) melt(s) in a temperature range of 35°C
to 150°C. Such materials are called "hot melt materials".
[0025] Or the non-compressed portion in addition to comprising any active detergent component
might comprise at least one carrier component or a mixture of carrier components.
The active detergent component may be present in the form of a solid, gel or liquid,
prior to combination with said carrier component(s). In a preferred embodiment the
carrier component (composition) is solid at room temperature (about 15 to 30°C) but
becomes liquid or flowable at increased temperature (above ca. 40°C). Preferably the
component(s) melt(s) in a temperature range of 35°C to 150°C. Such materials as well
are "hot melt materials". Preferably the hot melt material(s) are water soluble or
water dispersible.
[0026] Examples of active detergent raw materials suitable to be used as or in a hot melt
and having according physical properties are
- non-ionic surfactants with ethylene oxide and/or propylene oxide and/or butylene oxide
groups,
- anionic surfactants, with carboxylate, sulphonate, sulphate or phosphate end groups.
- cationic surfactants,
- amphoteric surfactants, like betaines, glycinates, amino propionates,
- polyalkene glycols, like polyethylene glycol.
Such types of surfactants according to any of the present groups usable as or in a
hot melt are described below as optional active ingredients in more detail.
[0027] Further all these materials can be used as carrier for any (further) active detergent
compound which preferably is included into the non-compressed portion of the shaped
body. Further as carriers preferably can be used waxes of any origin, like Fischer-Tropsch,
paraffin and microcrystalline waxes. However, the carriers are not restricted to these
materials, but any hot melt material according to the definition above can be included
as carrier material into the non-compressed portion of the detergent shaped body.
[0028] The non-compressed portion of the detergent tablet may be in solid, gel or paste
form. In a preferred embodiment the non-compressed portion is solid or pasty at room/ambient
temperature, more preferred it is solid at room/ambient temperature.
[0029] According to the present invention the non-compressed portion be delivered to the
compressed portion such that the compressed portion and non-compressed portion contact
each other. The non-compressed portion may be delivered to the compressed portion
in flowable, solid, gelly or pasty form. Where the non-compressed portion is in solid
form, it is pre-prepared, optionally shaped and then delivered to the compressed portion.
The non-compressed portion is then affixed to a pre-formed compressed portion, for
example by adhesion of the non-compressed portion to a co-operating surface of the
compressed portion. In a particularly preferred embodiment the non-compressed portion
is delivered or extruded from at least one nozzle or gun or dye in form of at least
one strand, extruded line, dot or stripe(s) onto the surface of the shaped body.
[0030] Preferably the compressed portion doesn't comprise a pre-prepared depression or mould
into which the non-compressed portion is delivered, but the non-compressed portion
is delivered onto the surface of the compressed portion.
[0031] The non-compressed portion is preferably delivered to the compressed portion in flowable
or pasty extrudable form, and solidifies by cooling. The non-compressed portion is
affixed to the compressed portion for example by adhesion, by forming a coating over
the non-compressed layer to secure it to the compressed portion, or by hardening,
for example
- (i) by cooling to below the melting point where the flowable composition becomes a
solidified melt;
- (ii) by evaporation of a solvent;
- (iii) by crystallisation;
- (iv) by polymerisation of a polymeric component of the flowable non-compressed portion;
- (v) through pseudo-plastic properties where the flowable non-compressed portion comprises
a polymer and shear forces are applied to the non-compressed portion;
- (vi) combining a binding agent with the flowable non-compressed portion.
[0032] In a preferred embodiment the flowable non-compressed portion may be an extrudate
that is affixed to the compressed portion by for example any of the mechanism described
above or by expansion of the extrudate.
[0033] Further a coating material can also be applied on the non-compressed portion to make
the not yet hardened surface less sticky. The powder or granular shaped coating material
is preferably provided on the not yet solidified non-compressed part of the detergent
tablet.
The remainder of the powder or granular shaped coating material that does not stick
to the non-compressed part is preferably removed from the detergent tablet. Possibilities
for said remove is by means of air, pressure or vacuum.
In case that such a coating material is used the following production steps do not
have to be postponed until the non-compressed portion is hardened. The powder or granular
shaped coating material that can be used is any suitable material, e.g. a detergent
ingredient, a mixture of various detergent ingredients or a detergent composition.
[0034] Preferably the compressed portion doesn't comprise any pre-prepared depression, cavity,
hole or mould into which the non-compressed portion is delivered.
[0035] The non-compressed portion may comprise particulates. The particulates may be prepared
by any known method, for example conventional spray drying, granulation, encapsulation
or agglomeration. Particulates may be affixed to the compressed portion by incorporating
a binding/fixing agent or by forming a coating layer over the non-compressed portion.
[0036] Where the detergent tablet comprises more than one non-compressed portion, the first
and second and optional further non-compressed portions may comprise the same or different
ingredients of the detergent composition.
[0037] Tablets in which one or more of the non-compressed portions comprise different ingredients
are as well an embodiment according to the invention, where the first and second and
optionally subsequent non-compressed portions are desired to have different rates
of dissolution.
[0038] Preferably the non-compressed portion comprises a solidified melt. The melt is prepared
by heating at least a part of an active detergent composition which preferably should
not be included into the portion to be compressed, like e.g. the hot melt raw materials
mentioned above, or by heating a composition comprising a detergent active component
and (an) optional carrier component(s) to above its melting point to form a pasty,
flowable or extrudable melt. The melt preferably is extruded from at least one nozzle
or gun or die onto at least one surface of the shaped body and allowed to cool. As
the melt cools it becomes preferably solid at ambient temperature. Where the composition
comprises one or more carrier components, the carrier component(s) may be heated to
above their melting point, and then an active detergent component may be added. Carrier
components suitable for preparing a solidified melt can be active detergent components,
e.g. the components cited above as hot melt material, or non-active components that
can be heated to above melting point to form a liquid and cooled to form an intermolecular
matrix that can effectively trap active detergent components. One preferred non-active
carrier component is an organic polymer that is solid at ambient temperature. Preferably
the non-active detergent component is polyethylene glycol (PEG) or any of the waxes
mentioned above.
[0039] Further the flowable/pasty non-compressed portion may be in a form (additionally)
comprising a dissolved or suspended active detergent component. The non-compressed
portion may harden over time to form a solid non-compressed portion by any of the
methods described above. In particular, the flowable/pasty non-compressed portion
may harden by evaporation of a solvent. Solvents suitable for use herein may include
any known solvent in which a binding agent is soluble.
[0040] Preferred solvents may be polar or non-polar and may include water, alcohol, (for
example ethanol, acetone) and alcohol derivatives. In an alternative embodiment more
than one solvent may be used.
[0041] The non-compressed portion may comprise one or more binding agents.
[0042] Any binding agent that has the effect of causing the composition to become solid
over time and preferably to attach the non-compressed portion to the compressed portion
is envisaged for use herein. Although not wishing to be bound by theory, it is believed
that mechanisms by which the binding agent causes a non-solid composition to become
solid include: chemical reaction (such as chemical cross linking), or effect interaction
between two or more components of the compositions or portions either; chemical or
physical interaction of the binding agent with a component of the composition.
[0043] Preferred binding agents include a sugar/gelatine combination, starch, glycerol and
organic polymers. The sugar may be any monosaccharide (e. g. glucose), disaccharide
(e. g. sucrose or maltose) or polysaccharide (e.g. xanthan gum). The most preferred
sugar is commonly available sucrose. For the purposes of the present invention type
A or B gelatine may be used, available for example from Sigma. Type A gelatine is
preferred since it has greater stability in alkaline conditions in comparison to type
B.
[0044] Preferred organic polymers include polyethylene glycol (PEG) of molecular weight
from 600 to 12,000 preferably from 1000 to 12,000 (e.g. available from BASF).
[0045] Where the non-compressed portion is an extrudate, the extrudate is prepared by premixing
the active detergent components with optional carrier components to form a viscous
paste. The viscous paste is then extruded using any suitable commonly available extrusion
equipment such as for example a single or twin screw extruder available from for example
APV Baker, Peterborough, U. K.
[0046] The non-compressed portion applied can be a suitable raw material or a blend of 2
or more suitable materials. Optionally a dye or pigment can be used to give any desired
colour.
[0047] The applied amount of hot melt material might have a height of 0.1 mm up to 10mm
and a weight of 0.025% to 10% of the weight of the total tablet.
[0048] The non-compressed portion of the detergent composition preferably is provided on
at least one surface of the compressed portion in form of for example at least one
strand, (extruded) line, dot, stripe or combinations thereof , e.g. as well in form
of a pattern like e.g. a lattice parallel stripes or lines or similar or as at least
one layer, wherein it is preferred that the non-compressed part is delivered as at
least one strand, (extruded) line, dot or stripe.
In a preferred embodiment the non-compressed portion is solid at ambient temperature
(about 15 to 35°C) but becomes liquid at increased temperature (higher than about
at least 40°C).
The application of a non-compressed portion in form of at least one strand, line,
dot or stripe, preferably in form of a pattern, provides the possibility to prepare
a detergent shaped body with less restrictions with regard to all the desired ingredients,
even in case that some of the ingredients cannot be included in their full amount
into the particular part of the composition without providing some restrictions to
said composition, e.g. impairing their further processability like shaping. By the
present inventions the ingredients restricting the formulation of the detergent composition
can be easily added by applying them in an "on-line" process after pressing the compressed
portion.
[0049] Additionally the application of the non-compressed portion in form of at least one
strand, line, dot or stripe, preferably in form of a pattern increases the stability
to the shaped body, particularly in case that these strand(s), line(s), dot(s) or
stripes(s) (e.g. as a pattern) is/are provided on more than one side of the shaped
body. In a preferred embodiment the strand(s), line(s) or stripes(s) are delivered
to the shaped bodies after pressing the bodies (e.g. in form of tablets) by passing
the bodies under at least one nozzle or gun or dye or extruding device delivering
the non-compressed portion continuously, e.g. on a conveyor belt, thereby applying
the non-compressed portion during the passage of the bodies under the nozzle or gun
or dye /extruding device. Of course a skilled person understands that as well the
nozzle(s)/dye(s)/device(s) can be passed over the shaped bodies. By this method typically
at least three surfaces of the bodies are applied with the non-compressed portion,
which are at least two side surfaces and the upper surface passing under the nozzle/dye/device.
In case in a further step the bodies are turned by 90° and thereafter are passed a
second time under a delivering nozzle/dye/device (e.g. resulting in a lattice pattern
on the upper surface) at least the other two side surfaces can be provided with the
non-compressed portion. After solidification of the non-compressed portion the shaped
body is somehow protected by the non-compressed portion and stability of the whole
body is increased. On the other hand the strand(s), line(s) or stripes(s) or the pattern
provide enough uncovered areas allowing the fast disrupture/dissolution of the shaped
body after contact with water, resulting (at least nearly) the same dissolution time
as a conventional pressed detergent shaped body.
[0050] The non-compressed portion may be coated with a coating layer. The coating may support
attachment of the non-compressed portion to the compressed portion. This may be particularly
advantageous where the non-compressed portion comprises flowable particulates, a paste
or gel.
[0051] The coating layer preferably comprises a material that becomes solid on contacting
the compressed and/or the non-compressed portions within preferably less than 15 minutes,
more preferably less than 10 minutes, even more preferably less than 5 minutes, most
preferably less than 60 seconds. Preferably the coating layer is water-soluble. Preferred
coating layers comprise materials selected from the group consisting of fatty acids,
alcohols, diols, esters and ethers, adipic acid, carboxylic acid, dicarboxylic acid,
polyvinyl acetate (PVA), polyvinyl pyrrolidone (PVP), polyacetic acid (PLA), polyethylene
glycol (PEG), gelatine and mixtures thereof. Preferred carboxylic or dicarboxylic
acids comprise an even number of carbon atoms. Preferably carboxylic or dicarboxylic
acids comprise at least 4, more preferably at least 6, even more preferably at least
8 carbon atoms, most preferably between 8 and 13 carbon atoms. Preferred dicarboxylic
acids include adipic acid, suberic acid, azelaic acid, subacic acid, undecanedioic
acid, dodecandioic acid, tridecanedioic and mixtures thereof. Preferred fatty acids
are those having a carbon chain length of from C 12 to C22, most preferably from C
18 to C22. The coating layer may also preferably comprise a disrupting agent. Where
present the coating layer generally present at a level of at least 0.05%, preferably
at least 0.1 %, more preferably at least1%, most preferably at least 2% or even at
least 5% of the detergent tablet.
[0052] As an alternative embodiment the coating layer may encapsulate the whole detergent
tablet.
[0053] If present, the coating layer is at a level of at least 1 %, preferably 3%, more
preferably at least 5%, most preferably at least 10% of the detergent tablet.
[0054] In a preferred embodiment, but not necessarily, the compressed and/or non-compressed
portions and/or coating layer additionally comprise a disrupting agent. The disrupting
agent may be a disintegrating or effervescing agent. Suitable disintegrating agents
include agents that swell on contact with water or facilitated water influx and/or
efflux by forming channels in compressed and/or non-compressed portions. Any known
disintegrating or effervescing agent suitable for use in laundry or dishwashing applications
is envisaged for use herein. Suitable disintegrating agent include starch, starch
derivatives, alginates, carboxymethylcellulose (CMC), CMC-based polymers, sodium acetate,
aluminium oxide. Suitable effervescing agents are those that produce a gas on contact
with water. Suitable effervesing agents may be oxygen, nitrogen dioxide or carbon
dioxide evolving species. Examples of preferred effervesing agents may be selected
from the group consisting of perborate, percarbonate, carbonate, bicarbonate and carboxylic
acids such as citric or maleic acid. Preferably at least the compressed portion comprises
a disintegrating agent.
Process
[0055] According to the present invention there is also provided a process for preparing
a detergent shaped body comprising the steps of : a) compressing a composition comprising
at least an active detergent component to form a compressed portion in form of a shaped
body without any cavity; and b) delivering a non-compressed portion comprising at
least one active detergent component to the compressed portion.
[0056] As described above, the detergent tablets described herein are prepared by separately
preparing the composition of active detergent components and forming the respective
compressed portion and thereafter applying the non-compressed portion onto at least
one surface of the compressed portion.
[0057] The compressed portion is prepared by providing at least one active detergent component
and optionally premixing with other detergent composition ingredients and/or carrier
components. Any pre-mixing can be carried out in a suitable mixer; for example a pan
mixer, rotary drum, vertical blender or high shear mixer. Preferably dry particulate
components are admixed in a mixer, as described above, and liquid components are applied
to the dry particulate components, for example by spraying the liquid components directly
onto the dry particulate components. The resulting composition is then formed into
a compressed portion in a compression step using any known suitable equipment. Preferably
the composition is formed into a compressed portion using a tablet press, wherein
the tablet is prepared by compression of the composition between an upper and a lower
punch. According to the present invention it is not necessary to provide any modified
punch, since in none of the surfaces of the produced shaped body any cavity has to
be contained.
[0058] The non-compressed portion preferably comprises at least another active detergent
component and preferably at least one carrier material as described above, preferably
a "hot melt" material. In case that the active ingredient itself is such a hot melt
material no further carrier is necessary.
[0059] The components of the non-compressed portion can be pre-mixed using any known suitable
mixing equipment. In addition the non-compressed portion may optionally comprise any
further carrier with which the active detergent components are combined. The blend
of the non-compressed portion may be prepared in solid form, like, flakes, granulates,
powders or in a pasty, gelly or flowable form or in a combination thereof.
[0060] The temperature which is necessary to provide the melt depends on the hot melt material
and the other used ingredients, but is preferably above from 30°C, more preferred
above 40°C and usually below 150°C, preferably below 100°C. Once prepared the composition
is delivered to the compressed portion. The non-compressed portion may be delivered
to the compressed portion by manual delivery or using a nozzle feeder, dye, gun or
extruder.
[0061] Where the applied non-compressed portion is affixed to the compressed portion by
hardening, the process comprises a delivery step in which the pasty/gelly/flowable
non-compressed portion is delivered to the compressed portion and an optional subsequent
conditioning step, wherein the non-compressed portion hardens. Such a conditioning
step may comprise drying, cooling, binding, polymerisation etc. of the non-compressed
portion, during which the non-compressed portion becomes solid, semi-solid or pasty.
Heat may be used in a drying step. Heat, or exposure to radiation may be used to effect
polymerisation in a polymerisation step. In a preferred embodiment the non-compressed
portion comprises a hot-melt material which hardens by cooling.
[0062] In another optional subsequent conditioning step the stickiness of non-compressed
portion is neutralized or reduced. This can be obtained by providing a powder or granular
shaped coating material on the non-compressed portion of the detergent tablet. Said
coating material sticks to the not hardened non-compressed part of the detergent tablet
and remains its surface less sticky.
[0063] The following described detergent components are commonly used detergent ingredients.
These ingredients are examples of preferably used ingredients according to the invention,
however, should neither be considered as limiting the invention, nor as an exhausting
list of possible ingredients usable in the inventive detergent shaped bodies. Particularly
adaption of the detergent composition to new ingredients or to national rules in a
special country might result in replacement or deletion of some of the ingredients
listed below. Such a replacement or deletion is not intervening with the invention
as long as the resulting detergent shaped body has a compressed and a non-compressed
part as described above and claimed in the claims.
Active Detergent Components
OPTIONAL INGREDIENTS
[0064] The detergent composition(s) of the present invention may also comprise optional
ingredients like e.g. builders, surfactants, enzymes, dyes, perfume, polymers, complexing
agents, bleaching agents, bleach activators, bleach catalysts, dispersing agents,
optical brighteners, process aids and anti corrosion agents, without any restriction.
[0065] All of the optional active ingredients known in the state of the art to be effective
or usable in detergents might be included. Highly preferred active detergent components
include a builder compound, a surfactant, an enzyme and a bleaching agent.
BUILDERS
[0066] The composition of the present invention may optionally comprise one or more builders,
typically present at a level of from 1 % to 80% by weight.
[0067] The main functions of the builders are to soften the washing water, to provide alkalinity
and a buffering capacity to the washing liquid and to have an anti redeposition or
dispersing function in the detergent composition. The physical properties of the detergent
composition are also depending on the builders that are used.
[0068] Inorganic non-phosphate builders include, but are not limited to, phosphonates, silicates,
carbonates, sulphates, citrate, citric acid and aluminosilicates.
[0069] Organic builders include, but are not limited to, a wide variety of (poly)carboxylated
compounds. As used herein polycarboxylate refers to compounds having a plurality of
carboxylate groups, preferably at least three carboxylates. Polycarboxylates can generally
be added to the composition in acid form, but can also be added in the form of neutralized
salt or in a partly neutralized form. When used in a partly or completely neutralized
form alkali metals like sodium, potassium and lithium or alkanolammonium salts are
preferred.
[0070] Phosphoric builders include, but are not limited to, various alkali metal phosphates
such as tripolyphosphate, pyrophosphate, orthophosphate, etc.
SURFACTANTS
[0071] The composition of the present invention may optionally comprise one or more surfactant(s).
[0072] The main functions of surfactants are: changing the surface tension, dispersing,
foam controlling and surface modification. A special type of surfactants used in ADD
compositions is the 'carry over' surfactant. The 'carry over' surfactant has the property
that some amount of the surfactant used remains in the machine after the rinsing cycles
to give a performance during the final rinsing cycle and the (optional) drying phase
of the whole washing cycle of the dishwashing machine. This type of surfactant is
described in
EP-A 1 524 313 in more detail.
[0073] For ADD compositions alkoxylated nonionic surfactants and Gemini surfactants are
commonly used. The alkoxy groups mostly exist of ethyleneoxide, propyleneoxide and/or
butyleneoxide. Also amphoteric surfactants are known to be used in ADD compositions.
Nonionic surfactant
[0074] Essentially any nonionic surfactants useful for detersive purposes can be included
in the detergent tablet. Preferred, non-limiting classes of useful nonionic surfactants
are listed below.
Nonionic ethoxylated alcohol surfactant
[0075] The alkyl ethoxylate condensation products of aliphatic alcohols with from 1 to 25
moles of ethylene 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 20 carbon atoms with from 2 to
10 moles of ethylene oxide per mole of alcohol.
End-capped alkylalkoxylate surfactant
[0076] A suitable endcapped alkyl alkoxylate surfactant is the epoxy-capped poly (oxyalkylated)
alcohols represented by the formula:
R1 0 [CH2CH (CH3)O]x [CH2CH20]y [CH2CH (OH) R2](I) wherein R1 is a linear or branched, aliphatic hydrocarbon radical having
from 4 to 18 carbon atoms;R2 is a linear or branched aliphatic hydrocarbon radical
having from 2 to 26 carbon atoms; x is an integer having an average value of from
0.5 to 1.5, more preferably 1; and y is an integer having a value of at least 15,
more preferably at least 20.
[0077] Preferably, the surfactant of formulal, at least 10 carbon atoms in the terminal
epoxide unit [CH
2CH (OH) R2]. Suitable surfactants of formula I, according to the present invention,
are Olin Corporation'sPOLY-TERGENTO SLF-18B nonionic surfactants, as described, for
example, in
WO 94/22800, published October 13,1994 by Olin Corporation.
Ether-capped poly (oxyalkylated) alcohols
[0078] Preferred surfactants for use herein include ether-capped poly (oxyalkylated) alcohols
having the formula:
R1 O [CH2CH (R3) 0]x [CH2]kCH(OH) [CH2]jOR2 wherein R1 and R2 are linear or branched, saturated or unsaturated, aliphatic
or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms; R3 is H, or a linear
aliphatic hydrocarbon radical having from 1 to 4 carbon atoms; x is an integer having
an average value from 1 to 30, wherein when x is 2 or greater R3 may be the same or
different and k and j are integers having an average value of from 1 to 12, and more
preferably 1 to 5.
R1 and R2 are preferably linear or branched, saturated or unsaturated, aliphatic or
aromatic hydrocarbon radicals having from 6 to 22 carbon atoms with 8 to 18 carbon
atoms being most preferred. H or a linear aliphatic hydrocarbon radical having from
1 to 2 carbon atoms is most preferred for R3. Preferably, x is an integer having an
average value of from 1 to 20, more preferably from 6 to 15.
[0079] As described above, when, in the preferred embodiments, and x is greater than 2,
R3 may be the same or different. That is, R3 may vary between any of the alklyeneoxy
units as described above. For instance, if x is 3,R3may be be selected to form ethlyeneoxy
(EO) or propyleneoxy (PO) and may vary in order of (EO) (PO) (EO), (EO) (EO) (PO);
(EO) (EO) (EO); (PO) (EO) (PO); (PO) (PO) (EO) and (PO) (PO) (PO).
[0080] Of course, the integer three is chosen for example only and the variation may be
much larger with a higher integer value for x and include, for example, mulitple (EO)
units and a much small number of (PO) units.
[0081] Particularly preferred surfactants as described above include those that have a low
cloud point of less than20 C. These low cloud point surfactants may then be employed
in conjunction with a high cloud point surfactant as described in detail below for
superior grease cleaning benefits.
[0082] Most preferred ether-capped poly (oxyalkylated) alcohol surfactants are those wherein
k is 1 and j is 1 so that the surfactants have the formula:
R1 O [CH2CH (R3)0]xCH2CH(OH)CH20R2 whereR1, R2 and R3 are defined as above and x is an integer with an average value
of from 1 to 30, preferably from 1 to 20, and even more preferably from 6 to 18.
[0083] Most preferred are surfactants wherein RI and R2 range from 9 to 14, R3 is H forming
ethyleneoxy and x ranges from 6 to 15.
[0084] The ether-capped poly (oxyalkylated) alcohol surfactants comprise three general components,
namely a linear or branched alcohol, an alkylene oxide and an alkyl ether end cap.
The alkyl ether end cap and the alcohol serve as a hydrophobic, oil soluble portion
of the molecule while the alkylene oxide group forms the hydrophilic, water-soluble
portion of the molecule.
[0085] These surfactants exhibit significant improvements in spotting and filming characteristics
and removal of greasy soils, when used in conjunction with high cloud point surfactants,
relative to conventional surfactants.
[0086] Generally speaking, the ether-capped poly (oxyalkylene) alcohol surfactants of the
present invention may be produced by reacting an aliphatic alcohol with an epoxide
to form an ether which is then reacted with a base to form a second epoxide. The second
epoxide is then reacted with an alkoxylated alcohol to form the novel compounds of
the present invention. Examples of methods of preparing the ethercapped poly (oxyalkylated)
alcohol surfactants are described below:Preparation of C12/I/I alkyl glycidyl ether
AC12/14 fatty alcohol (100.00 g, 0.515 mol.) and tin (IV) chloride (0.58 g, 2.23 mmol,
available from Aldrich) are combined in a 500 mL three-necked roundbottomed flask
fitted with a condenser, argon inlet, addition funnel, magnetic stirrer and internal
temperature probe. The mixture is heated to60 C. Epichlorhydrin (47.70 g, 0.515 mol,
available from Aldrich) is added dropwise so as to keep the temperature between60-65
C. After stirring an additional hour at60 C, the mixture is cooled to room temperature.
The mixture is treated with a 50% solution of sodium hydroxide (61.80 g, 0.773 mol,
50%) while being stirred mechanically.
[0087] After addition is completed, the mixture is heated to90 C for 1.5 h, cooled, and
filtered with the aid of ethanol. The filtrate is separated and the organic phase
is washed with water (100 mL), dried overMgSO4, filtered, and concentrated.
[0088] Distillation of the oil at 100-120 C (0.1 mm Hg) providing the glycidyl ether as
an oil.
Preparation of C12/14 alkyl-Cg/1 l ether capped alcohol surfactant
[0089] Neodol 91-8 (20.60 g, 0.0393 mol ethoxylated alcohol available from the Shell chemical
Co.) and tin (IV) chloride (0.58 g, 2.23 mmol) are combined in a 250 mL three-necked
round-bottomed flask fitted with a condenser, argon inlet, addition funnel, magnetic
stirrer and internal temperature probe. The mixture is heated to 60 C at which pointC12/14
alkyl glycidyl ether (11.00 g, 0.0393 mol) is added dropwise over 15 min. After stirring
for 18 h at60 C, the mixture is cooled to room temperature and dissolved in an equal
portion of dichloromethane. The solution is passed through a 1 inch pad of silica
gel while eluting with dichloromethane. The filtrate is concentrated by rotary evaporation
and then stripped in a Kugelrohr oven(100 C, 0.5 mm Hg) to yield the surfactant as
an oil.
Nonionic ethoxylated/propoxylated fatty alcohol surfactant
[0090] The ethoxylatedC6-C 18 fatty alcohols andC6-C 18 mixed ethoxylated/propoxylated fatty
alcohols are suitable surfactants for use herein, particularly where water soluble.
Preferably the ethoxylated fatty alcohols are the C 1 o-C 18 ethoxylated fatty alcohols
with a degree of ethoxylation of from 3 to 50, most preferably these are the C 12-c
18 ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40.
[0091] Preferably the mixed ethoxylated/propoxylated fatty alcohols have an alkyl chain
length of from 10 to 18 carbon atoms, a degree of ethoxylation of from 3 to 30 and
a degree of propoxylation of from 1 to 10.
Nonionic EO/PO condensates with propylene glycol
[0092] The condensation products of ethylene oxide with a hydrophobic base formed by the
condensation of propylene oxide with propylene glycol are suitable for use herein.
[0093] The hydrophobic portion of these compounds preferably has a molecular weight of from
1500 to 1800 and exhibits water insolubility. Examples of compounds of this type include
certain of the commercially-available PluronicTM surfactants, marketed by BASF.
[0094] Nonionic EO condensation products with propylene oxide/ethylene diamine adducts The
condensation products of ethylene oxide with the product resulting from the reaction
of propylene oxide and ethylenediamine are suitable for use herein. The hydrophobic
moiety of these products consists of the reaction product of ethylenediamine and excess
propylene oxide, and generally has a molecular weight of from 2500 to 3000. Examples
of this type of nonionic surfactant include certain of the commercially availableTetronic
compounds, marketed by BASF.
Mixed Nonionic SurfactantSvstem
[0095] In a preferred embodiment of the present invention the detergent tablet comprises
a mixed nonionic surfactant system comprising at least one low cloud point nonionic
surfactant and at least one high cloud point nonionic surfactant.
[0097] As used herein, a "low cloud point" nonionic surfactant is defined as a nonionic
surfactant system ingredient having a cloud point of less than30 C, preferably less
than20 C, and most preferably less than10 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., Olin Corporation's Poly-TergentSLF 18), epoxy-capped
poly (oxyalkylated) alcohols (e. g., Olin Corporation's Poly-Tergent O SLF 18B series
of nonionics, as described, for example, in
WO 94/22800, published October 13,1994 by Olin Corporation) and the ether-capped poly (oxyalkylated) alcohol surfactants.
[0099] Low cloud point nonionic surfactants additionally comprise a polyoxyethylene, polyoxypropylene
block polymeric compound. Block polyoxyethylene-polyoxypropylene polymeric compounds
include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane
and ethylenediamine as initiator reactive hydrogen compound. Certain of the block
polymer surfactant compounds designatedPLURONIC@, REVERSEDPLURONICO, and TETRONICO
by the BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable in ADD compositions
of the invention. Preferred examples include REVERSEDPLURONIC@ 25R2 and TETRONICO
702, Such surfactants are typically useful herein as low cloud point nonionic surfactants.
[0100] As used herein, a "high cloud point" nonionic surfactant is defined as a nonionic
surfactant system ingredient having a cloud point of greater than40 C, preferably
greater than50 C, and more preferably greater than60 C. Preferably the nonionic surfactant
system comprises an ethoxylated surfactant derived from the reaction of a monohydroxy
alcohol or alkylphenol containing from 8 to 20 carbon atoms, with from 6 to 15 moles
of ethylene oxide per mole of alcohol or alkyl phenol on an average basis. Such high
cloud point nonionic surfactants include, for example, Tergitol15S9 (supplied by Union
Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc), and Neodol 91-8 (supplied
by Shell).
[0101] It is also preferred for purposes of the present invention that the high cloud point
nonionic surfactant further have a hydrophile-lipophile balance("HLB" ; see Kirk Othmer
hereinbefore) value within the range of from 9 to 15, preferably 11 to 15.
[0102] Such materials include, for example, Tergitol 15S9 (supplied by Union Carbide), Rhodasurf
TMD 8.5 (supplied by Rhone Poulenc), and Neodol 91-8 (supplied by Shell).
[0103] Another preferred high cloud point nonionic surfactant is derived from a straight
or preferably branched chain or secondary fatty alcohol containing from 6 to 20 carbon
atoms(C6-C20 alcohol), including secondary alcohols and branched chain primary alcohols.
Preferably, high cloud point nonionic surfactants are branched or secondary alcohol
ethoxylates, more preferably mixed C9/11 or Cl 1/15 branched alcohol ethoxylates,
condensed with an average of from 6 to 15 moles, preferably from 6 to 12 moles, and
most preferably from 6 to 9 moles of ethylene oxide per mole of alcohol. Preferably
the ethoxylated nonionic surfactant so derived has a narrow ethoxylate distribution
relative to the average.
[0104] Preferably the low cloud point surfactant is present in the compressed portion and
the high cloud point surfactant is present in the non-compressed portion of the detergent
tablet of the present invention.
Anionic surfactant
[0105] Essentially any anionic surfactants useful for detersive purposes are suitable. These
can include salts (including, for example, sodium, potassium, ammonium, and substituted
ammonium salts such as mono-, di-and triethanolamine salts) of the anionic sulfate,
sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are
preferred.
[0106] Other anionic surfactants include the isethionates such as the acyl isethionates,
Nacyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates,
monoesters ofsulfosuccinate (especially saturated and unsaturated C 12-C 1 g monoesters)
diesters of sulfosuccinate (especially saturated and unsaturatedC6-C14 diesters),
N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such
as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present
in or derived from tallow oil.
Anionic sulfate surfactant
[0107] 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-C17 acyl-N-(C1-C4 alkyl)and-N-
(C 1-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such
as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described
herein).
[0108] Alkyl sulfate surfactants are preferably selected from the linear and branched primary
C 1 o-C 18 alkyl sulfates, more preferably the C 11-C 15 branched chain alkyl sulfates
and the C12-C14 linear chain alkyl sulfates.
[0109] Alkyl ethoxysulfate surfactants are preferably selected from the group consisting
of the C I O-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 aC 11-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.
[0110] A particularly preferred aspect of the invention employs mixtures of the preferred
alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed
in
PCT Patent Application No. WO 93/18124.
Anionic sulfonate surfactant
[0111] Anionic sulfonate surfactants suitable for use herein include the salts ofCs-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 carboxylate surfactant
[0112] Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the
alkyl polyethoxy polycarboxylate surfactants and the soaps('alkyl carboxyls'), especially
certain secondary soaps as described herein.
[0113] Suitable alkyl ethoxy carboxylates include those with the formula RO (CH2CH20)x CH2COO-M+
wherein R is a C6 toC 1 g alkyl group, x ranges from O to 10, and the ethoxylate distribution
is such that, on a weight basis, the amount of material where x is 0 is less than
20 % and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include
those having the formulaRO- (CHR1-CHR2-O)-R3 wherein R is a C6 toC1 g alkyl group,
x is from 1 to 25, R1 and R2 are selected from the group consisting of hydrogen, methyl
acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof,
and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted
hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.
[0114] Suitable soap surfactants include the secondary soap surfactants which contain a
carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants
for use herein are water-soluble members selected from the group consisting of the
water-soluble saltsof 2-methyl-1-undecanoic acid,2-ethyl-1-decanoic acid, propyl-1-nonanoic
acid,2-butyl-1-octanoic acid and2-pentyl-1-heptanoic acid.
[0115] Certain soaps may also be included as suds suppressors.
Alkali metal sarcosinate surfactant
[0116] Other suitable anionic surfactants are the alkali metal sarcosinates of formula R
CON(RI) CH2 COOM, wherein R is aCs-C17 linear or branched alkyl or alkenyl group,
RI is aC1-C4 alkyl group and M is an alkali metal ion. Preferred examples are the
myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.
Amphoteric surfactant
[0117] Suitable amphoteric surfactants for use herein include the amine oxide surfactants
and the alkyl amphocarboxylic acids.
Suitable amine oxides include those compounds having the formula
[0118] R3(OR4) XN0 (R5) 2 wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl
and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms;
R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or
mixtures thereof ; x is from 0 to 5, preferably from 0 to 3; and eachR5 is an alkyl
or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing
from 1 to 3 ethylene oxide groups. Preferred are C 1 o-C 18 alkyl dimethylamine oxide,
and C 10-18 acylamido alkyl dimethylamine oxide.
[0119] A suitable example of an alkyl aphodicarboxylic acid is Miranol (TM) C2MConc. manufactured
by Miranol, Inc., Dayton, NJ.
Zwitterionic surfactant
[0120] Zwitterionic surfactants can also be incorporated into the detergent compositions
hereof. These surfactants can be broadly described as derivatives of secondary and
tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives
of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine
and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
[0121] Suitable betaines are those compounds having the formula R (R')2N+R2COO-wherein R
is aC6-C 18 hydrocarbyl group, eachR1 is typicallyC1-C3 alkyl, and R2 is aCl-C5 hydrocarbyl
group. Preferred betaines areC12-18 dimethyl-ammonio hexanoate and the C 10-18 acylamidopropane
(or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable
for use herein.
Cationic surfactants
[0122] Cationic ester surfactants used in this invention are preferably water dispersible
compound having surfactant properties comprising at least one ester (i. e.-COO-) linkage
and at least one cationically charged group. Other suitable cationic ester surfactants,
including choline ester surfactants, have for example been disclosed in
US Patents No. s 4228042,
4239660 and
4260529.
[0123] Suitable cationic surfactants include the quaternary ammonium surfactants selected
from monoC6-C16, preferably C6-C1 o N-alkyl or alkenyl ammonium surfactants wherein
the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl
groups.
[0124] Further all surfactants commonly known to be used in detergent compositions can be
part of the composition, this includes all anionic, non-ionic, cationic and amphoteric
surfactants known in the art.
ENZYMES
[0125] The composition of the present invention may optionally comprise one or more enzymes.
[0126] Enzymes are often used to aid the removal of stains. Enzymes react with the soiling
and "break it down" into (smaller) particles that have increased water solubility
or are easier to disperse in the washing liquid.
[0127] The enzymes that can be used in detergent compositions include, but are not limited
to, proteases, amylases, lipases, cellulases, mannanase, peroxidase, oxidase, xylanase,
pullulanase, glucanase, pectinase, cutinase, hemicellulases, glucoamylases, phospholipases,
esterases, keratanases, reductases, phenoloxidases, lipoxygenases, ligninases, tannases,
pentosanases, malanases, arabinosidases, hyaluronidase, chondroitinase, laccase or
mixtures thereof. These enzymes are known to the skilled artisans and can be used
in common amounts.
ANTI CORROSION AGENTS
[0128] The detergent composition of the present invention may optionally comprise one or
more anticorrosion agents.
[0129] The main function of anticorrosion agents is to minimize the amount of material damage
caused on glass and metal during automatic dishwashing.
[0130] Glass corrosion occurs because metal ions are dissolved out of the glass surface.
This happens more intensively when few hardness ions are present in the water to be
bound by the builders or complexing agents present in the ADD composition that is
used. Also of influence are the washing temperature, the quality of the glassware
and the duration of the cleaning program.
[0131] Glass corrosion becomes visible in white lines or white clouds on the glass surface.
The glass corrosion damage can be "repaired" or the glassware can be protected, in
both cases by anti corrosion agents. The amount of the corrosion can be reduced by
using less strong builders and/or complexing agents.
[0132] Metal corrosion occurs mainly when oxide, sulfide and/or chlorides are present in
the washing liquid (witch normally is a mixture of tab water, soil and a detergent
composition) and do react with the metal surface of items that are in the dishwashing
machine. In the case of silver the silver metal salts that occur give a discoloration
of the silver metal surface that becomes visible after one or more cleaning cycles
in an automatic dishwashing machine.
[0133] The occurrence of metal corrosion can be slowed down by use of detergent ingredients
that give the metal a protective layer or ingredients that bounds with the oxide,
sulfide and/or chlorides to prevent them from reacting with the metal surface. The
metals can be silver, copper, stainless steel, iron, brass, etc.
[0134] The types of anti corrosion agents that often are used in detergent compositions
or are described in literature include, but are not limited to, triazole-based compounds
(like 1,2,3-benzotriazole), polymers with an affinity to attach to glass surfaces,
strong oxidizers (like permanganate), silicates, organic or inorganic metal salts,
or metal salts of biopolymers. The metal can be selected e.g. from the group aluminum,
strontium, barium, titanium, zirconium, manganese, lanthanum, bismuth, zinc, wherein
the latter is most commonly applied for the prevention of glass corrosion. Further
compounds to be added e.g. are manganese compounds as described in
WO 2005/095570.
POLYMERS
[0135] The composition of the present invention may optionally comprise one or more polymers.
[0136] The main function of polymers are acting as a dispersing agent or builder. As a dispersing
agent the polymer disperses (inorganic) insoluble particles, like calciumphosponate.
[0137] The polymers that often are used in detergent compositions include, but are not limited
to, homo-, co- or a terpolymers of or based on acrylic acid, methacrylic acid or maleic
acid. Such polymers are often combined with monomers that give the polymer a special
function. Such polymers are commonly known and are described e.g. in
EP-A 1 363 986,
EP-A 1 268 729,
EP-A1 299 513 and
EP-A 0 877 002.
COMPLEXING AGENTS
[0138] The composition of the present invention may optionally comprise one or more complexing
agent(s).
[0139] The main function of complexing agents is to capture trace metal ions like, Cu(II),
Fe(II), Fe(III), Mn(II), Cd(II), Co(II), Cr(III), Hg(II), Ni(II), Pb(II), Pd(II),
Zn(II). These ions can interfere with or disturb certain processes of the detergent
in the washing machine, like e.g. the bleach performance.
[0140] The complexing agent(s) that are known to be used in detergent compositions include,
but are not limited to, S,S-ehtylenediamine-N,N'-disuccinic acid (S,S-EDDS), ethylenediaminetetraacetic
acid (EDTA), diethylenediaminepentamethylene phosphonate (DETPMP), nitrilotriacetic
acid (NTA), iminodisuccinic acid (IDS), methylglycinediacetic acid (MGDA), diethylenetriaminepentaacetic
acid (DTPA), ethylenediaminedihydroxyacetic acid (EDDHA), N(hydroxyethyl)ethylenediaminetriacetic
acid (HEDTA), diethylenetriaminepentamethylene phosphonic acid (DTPMPA), hydroxyethylidene-1,1-diphosphonic
acid (HEDP), phytic acid, triethylenetetramine (TETA), tetraethylenepentamine (TEPA),
aminoethylethanolamine (AEEA), diethylenetriamine (DETA), dipicolinic acid, ethylene
diamine tetra (methylene phosphonic) acid or the salts thereof.
DISPERSING AGENTS
[0141] The composition of the present invention may optionally comprise one or more dispersing
agents.
[0142] The main functions of dispersing agents are to inhibit crystal growth and disperse
insoluble materials in the washing liquor, this can be a (fatty) soil, inorganic or
organic salts, etc. Dispersing agents often have a polymeric character and are at
least partly hydrophilic.
[0143] For dispersing a fatty soil surfactants are commonly used. Due to their hydrophilic
and hydrophobic parts the can form micelles with the fatty soil and thus keep is dispersed
in the washing liquor.
[0144] Polymers most commonly based on acrylic acid, methacrylic acid and/or maleic acid
can be used to prevent crystal growth from water insoluble salts and aid for the salts
to be dispersed. These polymers often also contain monomers with various properties,
like sulphonated styrene, styrene, 2-acrylamido-2-methyl propane sulponic acid (AMPS),
methallyl sulphonic acid, acryl amide, etc.
ANTIREDEPOSITION AGENTS
[0145] The composition of the present invention may optionally comprise one or more antiredeposition
agents.
[0146] The main functions of antiredeposition agents is that when a washing liquor shows
insufficient soil antiredeposition capacity it aids to prevent the soil from redepositioning
on the washing substrate.
[0147] The antiredeposition agent can exercise their effect by becoming adsorbed irreversibly
to the soil particles and/or to the substrate. This way the soil becomes better dispersed
in the washing liquor and/or the substrate is occupied with antiredeposition agent
on those places the soil could redeposit.
[0148] The antiredeposition agent(s) that are known to be used in detergent compositions
include, but are not limited to, carboxymethyl cellulose, polyester-PEG co-polymer,
etc.
BLEACHING AGENTS
[0149] The composition of the present invention may optionally comprise one or more bleaching
agents.
[0150] Bleaching agents can be used in a detergent either alone or in combination with an
bleach activator and/or a bleach catalyst. The function of the bleaching agent is
the removal of bleachable stains and to achieve an antibacterial effect on the load
and inside of the (dish)washing machine.
[0151] The bleaching agents used as a sole bleaching ingredient in detergents react with
the substrate that should be cleaned.
[0152] When an inorganic oxygen based bleaching agent is used in combination with a bleach
activator it does react with the bleach activator. One of the reaction product provides
the actual performance.
[0153] When an inorganic oxygen based bleaching agent is used in combination with a bleach
catalyst it does react with the bleach catalyst. A bleach activator can optionally
be present. The oxidized bleach catalyst provides the actual bleach performance.
[0154] Bleaching agents that can be used in detergent compositions include, but are not
limited to,
- active chlor compounds
- inorganic peroxygen compounds
- organic peracids.
Examples are sodium percarbonate, sodium perborate monohydrate, sodium perborate tetrahydrate,
hydrogen peroxide, hydrogen peroxide based compounds, peroxymonosulphate, e-phthalimid-peroxo-capronic
acid, benzoyl peroxide, sodium hypochlorite, sodium dichloroisocyanurate, etc.
[0155] Bleaching agents are often applied in a way that separates them from the chemically
fragile ingredients of the composition that can be deactivated. This can be obtained
by coating the material, dose the material in separate layers in a compressed body
or separated chambers in pouches in a water soluble sachet or form, or separate chambers
in a bottle, complexing the bleaching agent with cyclodextrin, etc.
BLEACH ACTIVATORS
[0156] The composition of the present invention may optionally comprise one or more bleach
activators.
[0157] When inorganic peroxygen based bleaching agents are applied a bleach activator provides
the possibility to use a reduced temperature to achieve the desired bleaching performance.
The bleach activator reacts with the peroxygen to form an organic peracid. Depending
from the used bleach activator these peracids can have a hydrophobic or a hydrophilic
character.
[0158] Bleaching agents that can be used in detergent compositions include, but are not
limited to, tetraacetylethylenediamine (TAED), sodium nonanoyloxybenzene sulphonate
(NOBS), acetyl caprolactone, and N-methyl morpholinium acetonitrile and salts thereof
(such as Sokalan BMG from BASF).
BLEACH CATALYSTS
[0159] The composition of the present invention may optionally comprise one or more bleach
catalysts.
[0160] A bleaching catalyst can be used besides to or instead of a bleach activator. Most
activators used are complexes with transition metal ions with organic ligands. Some
metal ions that are applied in catalysts are Mn, Fe, Cu, CO, Mo. Complexes with these
metals can interact with inorganic and organic peroxygen compounds to form reactive
intermediates.
[0161] Use of bleach catalyst can result in achieving the desired bleaching performance
at an even lower temperature than needed for bleach activators.
[0162] Bleaching catalysts that can be used in detergent compositions are intensively described
in the state of the art. These include, but are not limited to, a complex of manganese(IV)
with 1,4,7-trimethyl-1,4,7-triazacyclononane (MnMeTACN), tris[2-(salicylideneamino)ethyl]amine
manganese(III), etc.
OPTICAL BRIGHTENERS
[0163] The composition of the present invention may optionally comprise one or more optical
brighteners.
[0164] An optical brightener do via the washing liquor attach to the substrate to be cleaned.
An optical brightener does convert invisible ultraviolet radiation into visible radiation
with a longer wave length. Most commonly this becomes visible as a blue light that
make the substrate appear to be whiter.
[0165] For different substrate there are different optical brighteners available. Optical
brighteners that can be used in detergent compositions are intensively described in
the state of the art and include, but are not limited to, stilbene-, pyrazolin-, cumarin-,
benzoxazol-, naphthalimide-, distyrilbiphenyl sulphonate-, pyren-, methyl umbelliferon-
and dihydroxyquinolin-derivates.
DYES
[0166] The composition of the present invention may optionally comprise one or more dyes.
[0167] The dye is used to color the detergent, parts of the detergent or speckles in the
detergent. This will make the product more attractive to the consumer.
[0168] Dyes that can be used in detergent compositions include, but are not limited to,
Nylosan yellow N-7GL, Sanolin brilliant flavine 8GZ, Sanolin yellow BG, Vitasyn quinoline
yellow 70, Vitasyn tartrazine X90, Puricolor yellow AYE23, Basacid yellow 232, Vibracolor
yellow AYE17, Simacid Eosine Y, Puricolor red ARE27, Puricolor red ARE14, Vibracolor
red ARE18, Vibracolor red ARE52, Vibracolor red SRE3, Basacid red 316, Ponceau SX,
Iragon blue DBL86, Sanolin blue EHRL, Sanolin turquoise blue FBL, Basacid blue 750,
Iragon blue ABL80, Vitasyn blue AE90, Basacid blue755, Vitasyn patentblue V 8501,
Vibracolor green AGR25. These dyes are available at the firms Clariant, Basf, Ciba.
PERFUME
[0169] The composition of the present invention may optionally comprise one or more perfumes.
[0170] The perfume(s) is added to the detergent to improve the sensorial properties of the
product or of the machine load after cleaning.
[0171] The perfume can be added to the detergent as a liquid, paste or as a co-granulate
with a carrier material. To improve the stability of the perfume it can be e.g. used
in an encapsulated form or as a complex like for example a perfume-cyclodextrine complex.
[0172] Also perfumes that have a deodorizing effect can be applied. These perfumes encapsulate
malodors by binding to their sulfur groups.
PROCESS AIDS
[0173] The composition of the present invention may optionally comprise one or more process
aids. Process aids are used to improve certain product properties.
[0174] The process aids used in detergent compositions commonly are used for various purposes
often depending of the physical form of the final product. Process aids for example
can optimize compressibility, friability, toughness, disintegration speed, hygroscopicity,
density, free flowing properties, stickiness, etc. of an detergent product in a certain
physical shape.
[0175] Process aids that can be used in detergent compositions include, but are not limited
to, polyalkylene glycols, sorbitol, starch derivates, disintegration agents (e.g.
polyvinylpyrrolidone derivates, cellulose derivates, etc.), acetate salts, soda ash,
sodium sulphate, talc, silicates, glycerin, water, stearates, etc.
PHYSICAL SHAPES
Pre-dose
[0176] In the pre-dosed system the consumer has more convenience since he/she only has to
dose (one) unit(s) of a pre-dosed detergent composition. There can be any limitations
due to the conditions the dose functions most optimal. These are usually communicated
via the package of the detergent. The pre-dosed detergent unit can be provided e.g.
in the form of a tablet, a bar, a pouch or a container. The pre-dosed detergent unit
can have a weight that most commonly varies between 5 and 80 grams.
Tablet
[0177] A tablet can have various shapes where droplet, rectangular, rhomboidal, circular,
cylindrical, round, cubic, square and oval are examples of the possibilities. Tablets
can be provides as mono layer or as multilayer tablets. The tablets can also be cored,
e.g. a tablet within a tablet. For example Linotech Mercury tabletting presses can
be provided with a system to produce cored tablets.
[0178] Tablets are often wrapped in a foil. This foil can be water soluble like polyvinyl
alcohol or copolymers based on it. The foil can also be not water soluble. Than the
base of the most commonly used foils is (bi)oriented polypropylene or high density
polyethylene.
Mixture of self-dose and pre-dosed
[0179] When detergent compositions are provided as a mixture of self-dose and pre-dosed
systems one should self dose a number of pre-dosed units. The dosing advise is often
provided on the package of the detergent. Dependent from the conditions (like amount
of soil, water hardness, etc.) the consumer should decide to dose one, two, three
or more of the pre-dosed units in the (dish)washing machine.
Example 1
[0180] Onto the surface of at least 50 pressed detergent tablets several compositions as
shown in the table below were delivered.
Apparatus
[0181] An apparatus used to provide the hot melt material in a desired way on the surface
of the tablet consists at least of the following parts;
- Melter or container with heating
- Hose with heating
- Nozzle or gun with heating and a valve
- Pump
[0182] Such types of apparatus are available as "hot melt systems", for example offered
by the following companies: Nordson, ITW Dynatec, Axco Adhesive Systems Company, Slautterback,
Hot Melt Technologies or Melton.
Applying
[0183] The hot melt material composition is provided in the container of the apparatus.
The container and its content is heated to the desired temperature.
[0184] Detergent tablets are transported on a conveyor belt. The nozzle or gun of the apparatus
is located above this conveyor belt oriented towards the tablets on the belt. The
nozzle is heated to the desired temperature, that is above the melting point/traject
of the hot melt material composition, so that the composition to be applied is flowable/pasty/liquid.
[0185] A pump transports the fluid hot melt material composition from the container through
a heated hose to the nozzle and keeps the molten hot melt under pressure. A valve
is used to close or open the nozzle.
[0186] A detector detects a tablet coming in the direction of the nozzle. At the desired
moment the valve opens and closes the nozzle in order to put the desired amount of
hot melt material in the desired shape or pattern on the detected tablet. This shape
or pattern can for example be one or more lines, stripes or areas that are situated
for example straight, diagonal, S-shaped, etc on the tablet.
[0187] The described system can be applied with one or more nozzles or one or more hot melt
systems to give the tablet the desired amount of hot melt material.
Solidification
[0188] After the hot melt material is provided on the tablet it is still flowable/pasty/liquid
and should solidify before the tablet continues the steps in the production process.
In this test the hot melt was solidified by cooling with dried and cooled air.
Table 1: Examples of different hot melt compositions
Composition |
1 |
2 |
3 |
4 |
5 |
|
|
|
|
|
|
PEG200 |
4.75% |
2.9% |
3.6% |
3.8% |
3.8% |
Dye |
0.25% |
0.1 % |
0.4% |
0.2% |
0.2% |
PEG9000 |
95% |
- |
48% |
32% |
70% |
PEG6000 |
- |
- |
- |
16% |
- |
Dipropionate |
- |
- |
- |
- |
26% |
C16-18 +25EO |
- |
- |
- |
16% |
- |
C16-18+80EO |
- |
97% |
48% |
32% |
- |
Total |
100% |
100% |
100% |
100% |
100% |
|
|
|
|
|
|
Composition |
6 |
7 |
8 |
9 |
10 |
|
|
|
|
|
|
PEG200 |
- |
2.9% |
3.6% |
2.9% |
2.7% |
Dye |
- |
0.1 % |
0.4% |
0.1 % |
0.3% |
PEG9000 |
- |
- |
66% |
- |
- |
Sodiumcitrate |
- |
10% |
30% |
- |
- |
Dipropionate |
- |
4% |
- |
- |
25% |
pAA/AMPS copolymer |
|
- |
- |
30% |
- |
C16-18 +80E0 |
100% |
83% |
- |
67% |
72% |
Total |
100% |
100% |
100% |
100% |
100% |
[0189] PEG200, PEG 6000, PEG9000 are polyethylene glycols with an avarage molairweight of
respectively 200, 6000 and 9000 and is available at BASF in the Pluriol product range.
Dipropionate is for example available at Lakeland Laboratories as AMA100.
C16-18+25E0 and +80EO are fatty alcohol ethoxylates with a carbon chain of 16 to 18
carbon atoms and respectively averagely 25 and 80 ethylene oxide groups. Such products
are available at BASF in the Lutensol AT product range.
pAA/AMPS copolymer is copolymer of acrylic acid and AMPS. Such a product is for example
available at Alco Chemicals as Alcoguard4100.
Example 2
[0190] Onto the surface of at least 50 pressed detergent tablets a hot melt composition
is applied in a way and with an apparatus as described in example 1. The hot melt
compositions used in this test are the compositions 1, 3 and 6 as described in table
1.
[0191] Onto the not yet cooled hot melt surface on the tablet an excessive amount of powder
or granulate was provided. The remaining amount not contacting the non-compressed
portion was removed by means of pressurized air or by suction of a vacuum. The portion
of the powder or granulate contacting the hot melt surface remaind on the sticky hot
melt surface.
The powders/granulates used in this test were soda, sodium citrate and a state-of-art
dishwashing detergent powder composition.
[0192] After this treatment stickiness of the coated surface of the hot melt was lowered
in amount that it was possible to continue with the following steps of the production
process without any delay due to the solidification of the hot melt material.