Note: Descriptions are shown in the official language in which they were submitted.
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DISHWASHER DETERGENT SHAPED BODIES WITH SPECIFIC
GEOMETRY
This invention relates to detersive shaped bodies, primarily tablets,
such as dishwasher tablets, laundry detergent tablets, bleach tablets, stain
remover tablets or water softening tablets, for use in the home, more
particularly for use in machines, to a process for their production and to
their use.
Detersive shaped bodies, more particularly tablets, have a number
of advantages over powder-form compositions, such as easy handling,
simple dosage and low packaging volumes.
Unfortunately, problems arise out of the fact that, to achieve
adequate dimensional stability and fracture resistance, relatively high
pressures have to be applied in the compression of the powder-form
ingredients. In view of the heavy compaction which they undergo,
corresponding tablets often show inadequate storage stability in regard to
sensitive ingredients (bleaching agent, perfume, enzymes, silver
protectors, dyes, surfactants), reduced performance (particularly against
such soils as tea, milk, starch) by comparison with comparable amounts of
active ingredient made up in another form, occasionally inadequate
protection of sensitive materials to be cleaned and impaired disintegration
and dissolving properties in use.
According to some patents belonging to the prior art, some of these
problems are said to have been solved.
In many cases, however, the consumer is unable to reproduce the
performance advantages described in those documents. Accordingly, an
important problem confronting manufacturers of detersive shaped bodies is
to satisfy the consumer.
Accordingly, the problem addressed by the present invention was to
provide high-performance, easy-to-handle detersive shaped bodies, above
all dishwasher tablets, laundry detergent tablets, stain remover tablets or
water softener tablets for use in the home, more particularly for use in
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2
machines, with high storage stability, minimal packaging volume, a good
fragrance profile .and a defined solubility profile which, above all, would
guarantee high consumer satisfaction.
This problem has surprisingly been solved by a shaped body in
which an ingredient (I) is mainly located in a defined region, this region
being surrounded by other ingredients in exactly three directions in space.
Accordingly, the present invention relates to a shaped body
containing builders, bleaching agents and surfactants, characterized in that
a region containing more than 80% by weight, preferably more than 90%
by weight, more preferably more than 95% by weight and, most preferably,
100% by weight of an ingredient (I) present is surrounded by other
ingredients of the shaped body in exactly three directions in space.
The ingredient (I) may be a bleaching agent from the group of
chlorine and/or oxygen bleaching agents, a bleach activator, a silver
protector and/or a soil-release compound, an enzyme, a surfactant or a
component or a compound for controlling solubility. However, the
ingredient (I) may also be a mixture of these components.
In one particularly preferred embodiment, the ingredient (I) is a
mixture of a component or a compound for controlling solubility and at least
one other ingredient from the group consisting of bleaching agent and/or
bleach activator .and/or silver protector and/or soil-release compound
and/or enzyme and/or a surfactant.
The volume of the region containing the ingredient (I), the solubility,
the surface and the nature of the compression can also have a critical
bearing on the properties of the tablet.
According to the invention, it can also be favorable if more than 80%
by weight, preferably more than 90% by weight, more preferably more than
95% by weight and most preferably 100% by weight of an ingredient (I)
present is contained in the region of no greater than 40% by volume,
preferably between 1 and 30% by volume, more preferably between 2 and
25% by volume and more preferably between 3 and 20% by volume of the
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3
shaped body.
The overall result can also be desirably influenced if the region
containing more than 80% by weight, preferably more than 90% by weight,
more preferably more than 95% by weight and most preferably 100% by
weight of an ingredient (I) present dissolves more than 5%, preferably more
than 10%, more preferably more than 25%, most preferably more than 50%
and, in one particularly advantageous embodiment, more than 100% faster
than the remaining region and/or regions of the shaped body.
In another very favorable embodiment, the region containing the
ingredient (I) occupies no more than 40% of the surface, preferably
between 5 and 30%, more preferably between 10 and 25% and most
preferably between 15 and 20% of the shaped body and more than 80% by
weight, preferably more than 90% by weight, more preferably more than
95% by weight and most preferably 100% by weight of an ingredient (I)
present is contained in that region.
Solubili
The solubility can be influenced by components and/or compounds
for accelerating solubility (disintegrators) or retarding solubility.
Suitable disintegrators are any of the disintegrators known from the
prior art. Particular reference is made in this regard to Rompp (9th
Edition, Vol. 6, page 4440) and Voigt "Lehrbuch der pharmazeutischen
Technologie" (6th Edition, 1987). Particularly suitable disintegrators are
such materials as starch, cellulose and cellulose derivatives, alginates,
dextrans, crosslinked polyvinyl pyrrolidones and others; systems of weak
acids and carbonate-containing disintegrators, more particularly citric acid
and tartaric acid in combination with hydrogen carbonate or carbonate and
polyethylene glycol sorbitan fatty acid ester.
The use of disintegrators is also known from the patent literature.
Thus, according to German patent application DE 938 566, acetyl salicylic
acid is converted into granular form before compression, carefully but
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4
completely dried and then coated with highly disperse silica. The acetyl
salicylic acid granules powdered with highly disperse silica may then be
mixed with other tablet ingredients present in powder form or granular form
and compressed to tablets. The barrier layer of highly disperse silica not
only acts as an insulating layer and affords protection against unwanted
reactions, it also contributes towards the rapid disintegration of the
tablets,
even after prolonged storage.
German patent application DE 12 28 029 describes the production
of tablets in which powder mixtures are mixed with cellulose powder and
optionally highly disperse silica without preliminary granulation and the
resulting mixture is compressed, preferably after grinding.
According to German patent application DE 41 21 127, a particularly
effective auxiliary in the production of pharmaceutical tablets comprises
cellulose particles with a coating material fixed to their surface. The
auxiliary is used in fine-particle form, mean particle sizes below 200 Nm
being said to be particularly advantageous. Normally, therefore, traditional
tablet disintegrators belonging to the first class of substances mentioned
are either mixed in very fine-particle form with the other tablet ingredients,
which may be present as fine-particles or granules, before the compression
step or the other tablet ingredients are coated or powdered with the tablet
disintegrator.
According to the teaching of European patent EP-B-0 523 099,
disintegrators known from the production of pharmaceuticals may also be
used in detergents or cleaning compositions. The disintegrators mentioned
include swellable layered silicates, such as bentonites, starch- and
cellulose-based natural materials and derivatives thereof, alginates and the
like, potato starch, methyl cellulose and/or hydroxypropyl cellulose. These
disintegrators may be mixed with the granules to be compressed or may
even be incorporated therein.
According to International patent application WO-A-96106156 also, it
can be of advantage to incorporate disintegrators in detergent tablets. In
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this case, too, typical disintegrators are said to include microcrystalline
cellulose, sugars, such as sorbitol, and layered silicates, more particularly
fine-particle and swellable layered silicates of the bentonite and smectite
type. Effervescent substances, such as citric acid, bisulfate, bicarbonate,
5 carbonate and percarbonate, are also mentioned as possible disintegration
aids.
European patent applications EP-A-0 466 485, EP-A-0 522 766, EP-
A-0 711 827, EP-A-0 711 828 and EP-A-0 716 144 describe the production
of detersive tablets in which compacted particulate material with a particle
size of 180 to 2000 Nm is used. The resulting tablets may have both a
homogeneous structure and a heterogeneous structure. According to EP-
A-0 522 766, at least those particles which contain surfactants and builders
are coated with a solution or dispersion of a binder/disintegration aid, more
particularly polyethylene glycol. Other binders/disintegration aids are -
again - the already repeatedly described and known disintegrators, for
example starches and starch derivatives, commercially available cellulose
derivatives, such as crosslinked and modified cellulose, microcrystalline
cellulose fibers, crosslinked polyvinyl pyrrolidones, layered silicates, etc.
Weak acids, such as citric acid or tartaric acid which, in conjunction with
carbonate-containing sources, lead to effervescent effects on contact with
water and which, according to Rompp's definition, belong to the second
class of disintegrators, may also be used as a coating material.
Particular reference is made to hitherto unpublished DE 197 10 254
which describes disintegrators of which the particle size distribution (sieve
analysis) is such that at most 1 % by weight, preferably less, of dust is
present and a total (including any dust present) of less than 10% by weight
of the disintegrator granules are smaller than 0.2 mm. At least 90% by
weight of the disintegrator granules advantageously have a particle size of
at least 0.2 mm and at most 3 mm. These disintegrators are particularly
suitable for the purposes of the present invention.
Disintegrators belonging to the group of organic acids, for example
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6
citric acid, or a citric acid/bicarbonate mixture and/or the celluloses and
cellulose derivatives are also suitable. If a disintegrator is present in the
shaped body, the dissolving time of the shaped body as a whole is
preferably shorter than the duration of the main wash cycle of a
conventional dishwashing machine, i.e. shorter than 40 rains., preferably
shorter than 30 rains., more preferably shorter than 20 rains., and most
preferably shorter than 10 rains.
In general, paraffins and/or microwaxes and/or the high molecular
weight polyethylene glycols described in detail in the prior art are normally
used as dissolution retarders. The use of mixtures mentioned in hitherto
unpublished DE 197 27 073, of which the disclosure is hereby specifically
included as part of the present disclosure, is particularly suitable for the
purposes of the present application.
If the shaped body contains a component for retarding solubility, the
dissolving time of the shaped body as a whole in cold (20°C) water - in
one
preferred embodiment - is longer than the prerinse cycle of a commercially
available dishwashing machine, i.e. longer than 5 rains. and preferably
longer than 10 rains.
General forms of presentation
The shaped body may assume any of the various three-dimensional
forms which are listed inter alia in patents belonging to the prior art and in
the standard works of the specialist literature (for example: Riedel, "Die
Tablette"). The region in which the ingredient (I) is contained is also not
confined to any particular three-dimensional form. However, a dimension
in one direction in space of more than 5 mm is preferred for practical
reasons.
Specific forms of presentation
In one preferred embodiment, the invention provides homogeneous
or heterogeneous shaped bodies of known construction.
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7
These include in particular cylindrical tablets which preferably have
a diameter of 15 to 60 mm and, more particularly, 30 t 10 mm. The height
of these tablets is preferably from 5 to 30 mm and more preferably from 15
to 28 mm. Shaped bodies with a diameter of 32, 33, 34, 35, 36, 37, 38 and
39 mm have proved to be particularly favorable. In particular
embodiments, the height is 24, 25, 26, 27 or 28 mm.
However, aquare, rectangular, trapezoidal, oval and irregularly
shaped bases may also be used with advantage. The edge lengths are
preferably between 15 and 60 mm and more preferably 30 t 10 mm.
The weight of the individual shaped bodies, more particularly tablets,
is preferably 15 to 60 g and more preferably 20 to 40 g per shaped body or
tablet. By contrast, the density of the shaped bodies or tablets normally
assumes values above 1 kg/dm3 and preferably in the range from 1.1 to 1.4
kg/dm3.
One or more shaped bodies, for example 2 to 4 shaped bodies,
more particularly tablets, may be used according to the particular
application, the water hardness range and the nature of the soils to be
removed. Other shaped bodies according to the invention may have even
smaller diameters or dimensions, for example around 10 mm.
A homogeneous shaped body in the context of the present invention
is understood to be one in which the ingredients of the shaped body -
except for the region containing ingredient (I) - are homogeneously
distributed in such a way that differences between ingredients and/or active
substances are not visible to the naked eye. The granular structure of the
solids used is of course still discernible. In one preferred embodiment of
the invention, only one other region (phase) is present besides the region
containing the ingredient (I).
Accordingly, heterageneous shaped bodies in the context of the
present invention are those in which the ingredients present besides the
ingredient (I) do not have to be homogeneously distributed. In one simple
case, heterogeneous shaped bodies may be produced, for example, by
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giving the various ingredients different colors and/or by providing them with
different fragrance components.
Another case which, according to the invention, counts as a non-
homogeneous (heterogeneous) shaped body is an embodiment in which a
shaped body comprising several layers (phases), i.e. at least two layers,
besides the region containing the ingredient (I) is compressed. For
example, these various layers may have different disintegration and
dissolving rates and/or may contain different ingredients. This can result in
advantageous performance properties of the shaped bodies. If, for
example, ingredients which adversely affect one another are present in the
shaped bodies, they can be separated. If a particular sequence of cleaning
conditions is to be created in a machine, one (or more) components) may
be integrated in a (or the) faster disintegrating and/or faster dissolving
layer
while the other components) is incorporated in a (or the) more slowly
dissolving layer, so that one component can act in advance or can have
already reacted off by the time another component dissolves.
In one preferred embodiment of the invention, another two phases
are present besides the region containing the ingredient (I): It is
particularly favorable if the ratios by volume of the other two phases are
between 10:1 and 1:10, preferably between 5:1 and 1:5 and more
preferably between 2:1 and 1:2.
Another particularly preferred embodiment is characterized in that
three or more other phases are present.
The layered structure of the shaped bodies may be stack-like, in
which case the inner layers) dissolves) at the edges of the shaped body
before the outer layers have completely dissolved or disintegrated.
However, the inner layers) may also be completely and/or partly
surrounded by the layers situated further to the outside which prevents
and/or retards the early dissolution of constituents of the inner layer(s).
In another preferred embodiment of the invention, a tablet consists
of at least three layers, i.e. two outer layers and at least one inner layer,
at
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9
least one of the inner layers) containing a peroxy bleaching agent
whereas, in the case of the stack-like tablet, the two cover layers and - in
the case of the jacket-like tablet - the outermost layers are free from peroxy
bleaching agent. Peroxy bleaching agent and any bleach activators or
bleach catalysts and/or enzymes present can also be separated from one
another in one and the same tablet and/or shaped body. Embodiments
such as these have the advantage that there is no danger of any unwanted
interactions in the shaped bodies according to the invention.
In another favorable and preferred embodiment of the present
invention, one of the bleach components or the bleach component, more
especialty the chlorine component, is not made up in one phase with the
perfume component. Another favorable and preferred embodiment of the
invention is characterized in that the silver protector component is not
made up with (any of) the bleach component(s). In another favorable and
preferred embodiment of the invention, one of the components, or the
component, for controlling solubility is made up together with the bleach
activator. Another favorable and preferred embodiment of the invention is
characterized in that one of the components, or the component, for
controlling solubility is made up together with enzymes. Another favorable
and preferred embodiment of the invention is characterized in that one of
the components, or the component, for controlling solubility is made up
together with the bleaching agent. Another favorable and preferred
embodiment of the invention is characterized in that one of the
components, or the component, for controlling solubility is made up
together with the silver protector component. Another favorable and
preferred embodiment of the invention is characterized in that one of the
components, or the component, for controlling solubility is made up
together with at least 50% by weight, preferably more than 70% by weighf
and, more preferably, more than 90% by weight of a surfactant or the
surfactant mixture as a whole.
The shaped bodies according to the invention are produced by any
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of the methods normally used for producing shaped bodies.
In some embodiments, it has proved to be particularly favorable to
introduce the region containing the ingredients) (I) in the form of a liquid
(quite generally a solution and/or melt), optionally at elevated temperature,
5 into a preformed recess of the surrounding ingredients and then to allow
this region to solidify by applying conventional technical measures (quite
generally drying and/or cooling). A viscosity of more than 1,500 mPas,
preferably more than 2,000 mPas, more preferably between 2,000 and
15,000 mPas, most preferably between 2,500 and 7,000 mPas and, in a
10 particularly advantageous embodiment, between 3,000 and 4,000 mPas,
has proved to be particularly effective.
It has proved to be particularly effective to combine the ingredient (I)
with fusible carrier materials. These include in principle any substances
which solidify at or particularly above room temperature.
According to the invention, nonionic surfactants (Dehypon~ LT 104,
Dehypon~ LS 54, Dehydol~ LS 30, Lutensol~ AT 80), polyethylene glycols
with various molecular weights (PEG 400, 12000), soaps (Lorol~ C 16),
stearates (Cutina43~ GMS), and also thickened caustic soda and fusible
salts, such as sodium carbonate decahydrate, have proved to be
particularly suitable carrier materials. The advantages and disadvantages
of the individual ingredients can be reproduced by the expert in tests.
The use of mixtures mentioned in hitherto unpublished DE 197 27
073, of which the disclosure is hereby specifically included as part of the
present disclosure, is particularly suitable for the purposes of the present
application.
In other embodiments, parts of the shaped body and/or components
of the shaped body are treated by exposure to microwave radiation in order
positively to influence their strength, moisture content and solubility.
However, the constituents may also be simply compressed. In this
case, microtabs and shaped bodies smaller in their dimensions than the
final shaped body may be used in addition to powders and granules.
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11
Specific ingredients
Particular ingredients (I) used in accordance with the invention are
oxygen bleaching agents, preferably the alkali metal perborates and
hydrates thereof and alkali metal percarbonates, sodium perborate
(monohydrate or tetrahydrate) or sodium percarbonate and hydrates
thereof preferably being used in accordance with the invention. The
persulfates may also be used.
However, other typical oxygen bleaching agents are the organic
peracids. Organic acids preferably used include above all the extremely
effective phthalimidoperoxycaproic acid although, in principle, any other
known peracids may also be used.
Particular ingredients (I) used in accordance with the invention are
bleach activators. Known bleach activators are compounds which contain
one or more N- or O-acyl groups, such as compounds from the class of
anhydrides, esters, imides and acylated imidazoles or oximes. Examples
are tetraacetyl ethylenediamine (TAED), tetraacetyl methylenediamine
(TAMD) and tetraacetyl hexylenediamine (TAHD) and also pentaacetyl
glucose (PAG), 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine (DADHT)
and isatoic anhydride (ISA).
The bleach activators used may be compounds which form aliphatic
peroxocarboxylic acids preferably containing 1 to 10 carbon atoms and,
more particularly, 2 to 4 carbon atoms and/or optionally substituted
perbenzoic acid under perhydrolysis conditions. Suitable bleach activators
are substances which carry O- and/or N-acyl groups with the number of
carbon atoms mentioned and/or optionally substituted benzoyl groups.
Preferred bleach activators are polyacylated alkylenediamines, more
especially tetraacetyl ethylenediamine (TAED), acylated triazine
derivatives, more especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
(DADHT), acylated glycolurils, more especially tetraacetyl glycoluril
(TAGU), N-acyl imides, more especially N-nonanoyl succinimide (NOSI),
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12
acylated phenol sulfonates, more particularly n-nonanoyl or
isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides,
more especially phthalic anhydride, acylated polyhydric alcohols, more
especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-
dihydrofuran, n-methyl morpholinium acetonitrile methyl sulfate (MMA) and
the enol esters known from German patent applications DE 196 16 693
and DE 196 16 767 and also acetylated sorbitol and mannitol and the
mixtures thereof (SORMAN) described in European patent application EP 0
525 239, acylated sugar derivatives, more especially pentaacetyl glucose
(PAG), pentaacetyl fructose, tetraacetyl xylose and octaacetyl lactose and
acetylated, optionally N-alkylated, glucamine and gluconolactone, and/or
the N-acylated lactams, for example N-benzoyl caprolactam, which are
known from International patent applications WO 94/27970, WO 94128102,
WO 94128103, WO 95100626, WO 95/14759 and WO 95117498. The
hydrophilically substituted acyl acetals known from German patent
application DE 196 16 769 and the acyl lactams described in German
patent application DE 196 16 770 and in International patent application
WO 95114075 are also preferably used. The combinations of conventional
bleach activators known from German patent application DE 44 43 177
may also be used. Bleach activators such as these are present in the
usual quantities, preferably in quantities of 1 % by weight to 10% by weight
and more preferably in quantities of 2% by weight to 8% by weight, based
on the detergent/cleaner as a whole.
In addition to or instead of the conventional bleach activators
mentioned above, the sulfonimines known from European patents EP 0
446 982 and EP 0 453 003 and/or bleach-boosting transition metal salts or
transition metal camplexes may be present as so-called bleach catalysts.
Suitable transition metal compounds include in particular the manganese-,
iron-, cobalt-, ruthenium- or molybdenum-salen complexes known from
German patent application DE 195 29 905 and the N-analog compounds
thereof known from German patent application DE 196 20 267, the
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manganese-, iron-, cobalt-, ruthenium- or molybdenum-carbonyl complexes
known from German patent application DE 195 36 082, the manganese,
iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper
complexes with nitrogen-containing tripod ligands described in German
patent application DE 196 05 688, the cobalt-, iron-, copper- and
ruthenium-ammine complexes known from German patent application DE
196 20 411, the manganese, copper and cobalt complexes described in
German patent application DE 44 16 438, the cobalt complexes described
in European patent application EP 0 272 030, the manganese complexes
known from European patent application EP 0 693 550, the manganese,
iron, cobalt and capper complexes known from European patent EP 0 392
592 and/or the manganese complexes described in European patent EP 0
443 651 or in European patent applications EP 0 458 397, EP 0 458 398,
EP 0 549 271, EP 0 549 272, EP 0 544 490 and EP 0 544 519.
Combinations of bleach activators and transition metal bleach catalysts are
known, for example, from German patent application DE 196 13 103 and
International patent application WO 95127775. Bleach activators from the
group of polyacylated alkylenediamines, more particularly tetraacetyl
ethylenediamine I;TAED), N-acyl imides, more particularly N-nonanoyl
succinimide (NOSI), acylated phenol sulfonates, more particularly n-
nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), MMA are
preferably used, preferably in quantities of up to 10% by weight, more
preferably in quantities of 0.1 % by weight to 8% by weight, most preferably
in quantities of 2 to 8% by weight and, with particular advantage, in
quantities of 2 to 6% by weight, based on the detergent/cleaner as a whole.
Bleach-boosting transition metal complexes, more particularly
containing the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and/or Ru,
preferably selected from the group of manganese and/or cobalt salts and/or
complexes, more preferably the cobalt (ammine) complexes, cobalt
(acetate) complexes, cobalt (carbonyl) complexes, chlorides of cobalt or
manganese and manganese sulfate, are also present in typical quantities,
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14
preferably in a quantity of up to 5% by weight, more preferably in a quantity
of 0.0025% by weight to 1 % by weight and most preferably in a quantity of
0.01 % by weight to 0.25% by weight, based on the detergent/cleaner as a
whole. In special cases, however, more bleach activator may even be
used.
Dishwasher detergents according to the invention may contain
corrosion inhibitors as ingredient (I) to protect the tableware or the machine
itself, silver protectors being particularly important for dishwashing
machines. Known corrosion inhibitors, for example those described in DE
43 25 922, DE 41 28 672 and DE 43 38 724, may be used. Above all,
silver protectors selected from the group of triazoles, benzotriazoles,
bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and the transition
metal salts or complexes may generally be used. Benzotriazole and/or
alkylaminotriazole is/are particularly preferred. In addition, dishwashing
formulations often contain corrosion inhibitors containing active chlorine
which are capable of distinctly reducing the corrosion of silver surfaces.
According to the above documents, chlorine-free dishwashing detergents
contain in particular oxygen- and nitrogen-containing organic redox-active
compounds, such as dihydric and trihydric phenols, for example
hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid,
phloroglucinol, pyrogallol and derivatives of these compounds. Salt-like
and complex-like inorganic compounds, such as salts of the metals Mn, Ti,
Zr, Hf, V, Co and Ce are also frequently used. Of these, the transition
metal salts selected from the group of manganese and/or cobalt salts
and/or complexes are preferred, cobalt(ammine) complexes,
cobalt(acetate) complexes, cobalt(carbonyl) complexes, chlorides of cobalt
or manganese and manganese sulfate being particularly preferred. Zinc
compounds may also be used to prevent corrosion of tableware.
Particular ingredients (I) used in accordance with the invention are
substances which prevent the resoiling of surfaces and/or which facilitate
the separation of soil after a single application (so-called soil-release
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compounds).
The soil-release compounds used in accordance with the invention
include any of the compounds known from the prior art. Cationic polymers
known, for example, from the following documents are particularly suitable:
5 According to EP-A-0 167 382, EP-A-0 342 997 and DE-OS 26 16
404, cationic polymers are added to cleaning compositions to obtain
streak-free cleaning of the surfaces.
EP-A-0 167 382 describes liquid cleaning compositions which may
contain cationic polymers as thickeners. Hydroxypropyl trimethyl ammoni-
10 um guar; copolymers of aminoethyl methacrylate and acrylamide and
copolymers of dimethyl diallyl ammonium chloride and acrylamide are
described as particularly suitable cationic polymers.
EP-A-0 342 997 describes multipurpose cleaners which may contain
cationic polymers" polymers containing imino groups in particular being
15 used.
DE-OS 26 16 404 describes cleaning compositions for glass
containing cationic cellulose derivatives. The addition the cationic cellulose
derivatives to the compositions ensures better drainage of the water so that
streak-free glass is obtained.
EP-A-0 467 472, for example, describes cleaning compositions for
hard surfaces which contain cationic homopolymers and/or copolymers as
soil-release polymers. These polymers contain quaternized ammonium
alkyl methacrylate groups as monomer units. These compounds are used
to finish the surfaces in such a way that the soils can be removed more
easily the next time the surfaces are cleaned.
Particular preference is attributed to the cationic polymers selected
from cationic polymers of copolymers of such monomers as trialkyl am-
monium alkyl (meth)acrylate or acrylamide; dialkyl diallyl diammonium
salts; polymer-analog reaction products of ethers or esters of poly-
saccharides with lateral ammonium groups, more particularly guar, cel-
lulose and starch derivatives; polyadducts of ethylene oxide with ammon-
CA 02299831 2000-03-07
16
ium groups; quaternary ethylene imine polymers and polyesters and poly-
amides containing quaternary lateral groups as soil-release compounds.
Natural palyuronic acids and related substances and also
polyampholytes and hydrophobicized polyampholytes and mixtures of
these substances are also particularly preferred for the purposes of the
present invention.
According to the invention, between 0 and 5% by weight of
enzymes, based on the composition as a whole, may be added to the
detergent/cleaner to improve performance or guarantee the same quality of
cleaning under milder conditions. The most commonly used enzymes
include lipases, amylases, cellulases and proteases. Preferred proteases
are, for example, BLAP~ 140 (Biozym), Optimase~ M-440 and Opticlean~
M-250 (Solvay Enzymes); Maxacal~ CX and Maxapem~ or Esperase~
(Gist Brocades) and even Savinase~ (Novo). Particularly suitable
celluloses and lipases are Celluzym~ 0,7 T and Lipolase~ 30 T (Novo
Nordisk). Particularly suitable amylases are Duramyl~ and Termamyl~ 60
T and Termamyl~ 90 T (Novo), Amylase-LT~ (Solvay Enzymes) and
Maxamyl~ P5000 (Gist Brocades). Other enzymes may also be used.
Other ingredients
In the shaped bodies according to the invention, all ingredients (I)
described above can also perform the function of other ingredients should
the condition of the region according to the invention be fulfilled by other
ingredients.
Water-soluble and water-insoluble builders may be used in the
detergents/cleaners according to the invention, above all to bind calcium
and magnesium. Water-soluble builders are preferred because, in general,
they tend less to form insoluble residues on tableware and hard surfaces.
Typical builders which may be present in quantities of 10 to 90% by weight,
based on the composition as a whole, in accordance with the invention are
the low molecular weight polycarboxylic acids and salts thereof, the homo-
CA 02299831 2000-03-07
17
polymeric and copolymeric polycarboxylic acids and salts thereof, the car-
bonates, phosphates and silicates. Water-insoluble builders include the
zeolites, which may also be used, and mixtures of the builders mentioned
above.
Trisodium citrate and/or pentasodium tripolyphosphate and/or
sodium carbonate and/or sodium bicarbonate and/or gluconates and/or
silicate builders from the class of disilicates and/or metasilicates are
preferably used.
Alkali sources may be present as further ingredients. Alkali sources
are alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen
carbonates, alkali metal sesquicarbonates, alkali metal silicates, alkali
metal metasilicates and mixtures of the substances mentioned above.
According to the invention, alkali metal carbonates, more particularly
sodium carbonate, sodium hydrogen carbonate or sodium sesqui
carbonate, are preferably used.
A builder system containing a mixture of tripolyphosphate and
sodium carbonate is particularly preferred.
Another particularly preferred builder system contains a mixture of
tripolyphosphate and sodium carbonate and sodium disilicate.
In principle, any surfactants may be used as surfactants. Nonionic
surfactants, above all low-foaming nonionic surfactants, are preferred
although other low-foaming surfactants may also be used. Alkoxylated
alcohols, especially ethoxylated and/or propoxylated alcohols, alkyl
polyglycosides, and alkyl polyglucamides are particularly preferred.
Alkoxylated alcohols are generally understood by the expert to be
the reaction products of alkylene oxide, preferably ethylene oxide, with
alcohols, the relatively long-chain alcohols (C~o to C~8, preferably between
C~2 and C~6 such as, for example, C», C,2, C~3, C~4, C~5, C,6, C~~ and C,8
alcohols) being preferred for the purposes of the present invention. In
general, a complex mixture of addition products differing in their degree of
ethoxylation is formed from n moles of ethylene oxide and 1 mole of
CA 02299831 2000-03-07
18
alcohol, depending on the reaction conditions. Another embodiment is
characterized by the use of mixtures of alkylene oxides, preferably a
mixture of ethylene oxide and propylene oxide. If desired, "end-capped"
alcohol ethoxylates, which may also be used in accordance with the
invention, may also be obtained by etherification with short-chain alkyl
groups, preferably butyl groups, in a concluding step. According to the
invention, highly ethoxylated fatty alcohols or mixtures thereof with end-
capped fatty alcohol ethoxylates are particularly preferred for the purposes
of the invention.
Alkyl polyglycosides are surfactants which may be obtained by
reacting sugars and alcohols using the relevant methods of preparative
organic chemistry, a mixture of monoalkylated oligomeric or polymeric
sugars being obtained according to the particular method of production
used. Preferred alkyl polyglycosides are alkyl polyglucosides. In a
particularly preferred embodiment, the alcohol is a long-chain fatty alcohol
or a mixture of long-chain fatty alcohols while the degree of oligomerization
of the sugars is between 1 and 10.
Fatty acid polyhydroxylamides (glucamides) are acylated reaction
products of the reductive amination of a sugar (glucose) with ammonia,
long-chain fatty acids, long-chain fatty acid esters or long-chain fatty acid
chlorides generally being used as acylating agents. Secondary amides are
formed if methyl amine or ethyl amine is used instead of ammonia for the
reduction process, as described for example in SOFW Journal, 119,
(1993), 794-808. Carbon chain lengths of Cs to C~2 are preferably used in
the fatty acid moiety.
The regions of the shaped body may be colored. In one particularly
preferred embodiment, one or more regions in the shaped body or all the
regions in the shaped body are differently colored. In one special
embodiment of the shaped body, the color is red. In another special
embodiment of the shaped body, the color is green. In another special
embodiment of the shaped body, the color is yellow. In another special
CA 02299831 2000-03-07
19
embodiment of the shaped body, the color is a mixture of different colors.
The storage stability of the shaped body is particularly important. In
one particularly preferred embodiment of the invention, the increase in
weight of the region of the ingredient (I) during storage under normal
domestic conditions, i.e. between 15 and 30°C and between 5 and 55%
and preferably between 15 and 35% air humidity for a period of 30 days,
preferably 60 days and more preferably 90 days is no more than 50% by
weight, preferably no more than 40% by weight, more preferably no more
than 30% by weight, most preferably no more than 20% by weight and, in
one particularly advantageous embodiment, no more than 10% by weight
and, in the most favorable case, no more than 5% by weight:
In another particularly preferred embodiment of the invention, the
loss of active substance of the ingredient (I) during storage under
normal domestic conditions, i.e. between 15 and 30°C and between 5 and
55% and preferably between 15 and 35% air humidity for a period of 30
days, preferably 60 days and more preferably 90 days is no more than 50%
by weight, preferably no more than 40% by weight, more preferably no
more than 30% by weight, most preferably no more than 20% by weight
and, in one particularly advantageous embodiment, no more than 10% by
weight and, in the most favorable case, no more than 5% by weight.
In another particularly preferred embodiment of the invention, the
absorption maximum of a 1% solution of a colored region or a colored
component during storage under normal domestic conditions, i.e. between
15 and 30°C and between 5 and 55% and preferably between 15 and 35%
air humidity for a period of 30 days, preferably 60 days and more preferably
90 days is no more than 100 wave numbers, preferably no more than 50
wave numbers, more preferably no more than 30 wave numbers, most
preferably no mare than 20 wave numbers and, in one particularly
advantageous embodiment, no more than 10 wave numbers and, in the
most favorable case, no more than 5 wave numbers.
CA 02299831 2000-03-07
Examples
The following formulations were mixed and compressed to shaped
bodies. The ingredients shown in brackets are examples of the class of
compounds in question, but may be replaced by other substances listed in
5 the application. The starting formulations represent preferred ranges of the
invention.
In the measurement of effectiveness, the particular ingredient (I)
selected was transferred to the region according to the invention. In the
other region (other regions), it was reduced in accordance with the
10 invention or left out altogether before the studies were carried out.
Possible starting formulation (Ra) and test formulations (Va) (figures =
by weight):
CA 02299831 2000-03-07
21
Phosphate (sodium 30-60 54.856.4 30.543 48 48 47
tripolyphosphate)
Sodium carbonate 5-25 15.913.2 21.57 20 12 24
Sodium disilicate 0-40 7.3 7.5 33.720 3 14
Polymer (Sokalan 0-10 2.2 2.2 1 5
CP5)
Sodium metasilicate 0-10 1.8 0
Sodium hydrogen 0-10 1 3
carbonate
Bleach (sodium 2-20 9.0 9.0 6.7 15 10 12 9
perborate)
Bleach activator 0-5 2.1 2.1 3 2 1 1.5
(TAED) (co-
pentammine-CI)
Enzyme (amylase) 0-5 2.0 2.0 0.7 3 3 3 2.5
(Duramyl 60 T)
Enzyme (protease) 0-5 1.8 1.8 1.0 2 2 3 2.5
(Blap 200 S)
Phosphonate or 0-5 0.9 0.9 2 1.5
phosphonic acid
Nonionic surfactant 0-5 2.0 2.0 2.0 2 4 3 1.5
(Dehypon LS 54)
Silver protector 0-3 0.3 0.3 0 0.3 0.2 0.5
(benzotriazole;l
Tabletting aid 0-10 6
(polyethylene
glycol)
ParafFn (Mp.: 0-10 2.0 1.0 3
53C)
Perfume 0-1 0.2 0.2 0.2 1 0.4 1 0.5
Dye I O-4 1.4 1.3 1.4 -0.7 0.4 ~ 1.5
~ I I ~ I ~
The builder system of the above starting formulation may also have the
following composition (all other ingredients same as for a).
Phosphate (sodium tripolyphosphate) 30-60 59 56 53 48 48 48 47
Carbonate (sodium carbonate} 5-25 21.220.3 22.717 20 16 24
Polymer (Sokalan CP5) 0-10 2 10 5 4 5
Sodium metasilicate 0-10 1.8
Sodium hydrogen carbonate ~0-10 I I I I 3
I 1
I
Examples of another starting formulation (R) according to the present
invention and test formulations (~ (% by weight) are shown in the following
Table:
CA 02299831 2000-03-07
22
~d, l..
~~ ~iy
~ i
i
yY
i Ij
~ Y
4 io-:,
Phosphate (sodium tripolyphosphate)15-35 30 21 35 40
Carbonate (sodium carbonates 25-55 39 50 40 35
Sodium hydrogen carbonate 10-20 14 19 15 12
Polymer (Sokalan CP5) 0-10 3 0
Sodium disilicate 0-10
Sodium disilicate 0-10 0 0 0 5
Bleach (sodium perborate) 2-10 7 8 5 5
Bleach activator (TAED) 0-5 1 0 1 1
Enzyme (amylase) (Duramyl 0.4-2 1 0.5 0.5 0.5
60 T)
Enzyme (protease) (Blap 200 0.4-2 1 0.5 0.5 0.5
5)
Phosphonate or phosphonic 0-5 0 0 0 0
acid
Nonionic surfactant (Dehypon 0-5 2 1 1 1
LS 54)
Silver protector (benzotriazole;i0-3 0.5 0 0.3 0
Paraffin (Mp.: 53C) 0-10 0 0 0
Perfume 0-1 0 0 0.7 0
Dye 0-4 0.5 0 1 0
Further examples of a starting formulation (R) according to the present
application and test formulations (V) (% by weight) are shown in the following
Table:
Trisodium citrate 20-55 44 34 44 44
Sodium hydrogen carbonate 5-35 24 9 34 20
Carbonate (sodium carbonate) 0-10 7
Polymer (Sokalan CP5) 0-10 6
Sodium disilicate 0-25 20
Bleach (sodium perborate) 0-22 9 16 17
Bleach activator (TAED) 0-25 3 1 0 20
Enzyme (amylase) (Duramyl 0.4-5 2.5 3 1 5
60 T)
Enzyme (protease) (Blap 0.4-5 2 3 1 5
200 S)
Phosphonate or phosphonic 0-5 1.5 2.3 2
acrid
Nonionic surfactant 0-5 2.5 1.7 2 1
(Dehypon LS 54)
Silver protector (benzotriazole) 0-3 0.5 0.5
CA 02299831 2000-03-07
23
Paraffin (Mp.: 53C) 0-10 3 1.5
Perfume 0-1 0.9 0.5 1 1
Dye 0-4 0.1 1.5 2
Further examples of a starting formulation (R) according to the present
application and test formulations (~ (% by weight) are shown in the following
Table:
,.
Citrate (trisodium citrate) 20-55 32 36 38 24
Phosphate (trisodium polyphosphate)20-55 26 23 24 24
Carbonate (sodium carbonate;l1-15 11 10 11 15
Polymer (Sokalan CP5) 0-10 5 1.5 6
Silicate (sodium disilicate) 0-25 3 6
Bleach (sodium perborate) 2-20 16 3 12 9
Bleach activator (TAED) 0-5 0.5 5 2 3
Enzyme (amylase) (Duramyl 0-5 5 3 2
60 T)
Enzyme (protease) (Blap 200 0-5 5 0.5 2
.5)
Phosphonate or phosphonic 0-5 2 2 2
acid
Tabletting aid (polyethylene 0-10 6 4 5 0.8
glycol)
Nonionic surfactant (Dehypon 0-5 2.5 2.8 2
LS 54)
Silver protector (benzotriazole)0-3 0.2 ~ 0.2
Paraffin (Mp.: 53C) 0-10
Perfume 0-1 1 1 1
Dye 0-4 0 1 1
Further examples of a starting formulation (R) according to the present
application and test formulations (~ (% by weight) are shown in the following
Table:
Phosphate (trisodium 40-60 49 49 49 50
pol phosphate)
Carbonate (sodium 0-20 17 19 5
carbonate)
Polymer (Sokalan 0-15 2 4 1 6
CP5)
Silicate (sodium 0-30 24 6 5 10
disilicate)
CA 02299831 2000-03-07
24
Bleach (sodium perborate) 0-15 10 8 10 8
Bleach activator (TAED) 0-5 1.5 2 3 2
Enzyme (amylase) (Duramyl 0-5 2 2 1.5 2.5
60 T)
Enzyme (protease) (Blap 0-5 3.9 2 1.5 2.5
200 S)
Phosphonate or phosphonic 0-8 0.8 1 1 2
acid
Tabletting aid (polyethylene 0-10 0.2 4 3.7 5
lycol)
Nonionic surfactant 0-8 1.5 2 4 3
(Dehypon LS 54)
Silver protector (benzotriazole) 0-5 0.1 0.5 0.3 0.5
Perfume 0-2 1 0.5 0.5 0.5
-
Dye ~ 0~ ~3 ~ 2 0.5 1
Further examples of a starting formulation (R) according to the present
application and test formulations (~ (% by weight) are shown in the following
Table:
Phosphate (trisodium polyphosphate)30-60 55.7 59.6 46.5 47
Sodium disilicate 5-40 22.3 17.5 39.2 24
Polymer (Sokalan CP5) 0-10 2.2 2.2 5
Sodium metasilicate 0-10 1.8
Sodium hydrogen carbonate 0-10
Bleach (sodium perborate) 2-20 10 10 6.7 10
Bleach activator (co-catalyst)0-2 1.1 1.1 0.5
Enzyme (am lase) (Duramyl 0-5 2.0 2.0 0.7 2.5
6~0 T)
Enzyme (protease) (Blap 200 0-5 1.8 1.8 1.0 2.5
S)
Phosphonate or phosphonic 0-5 0.9 0.9 1.5
acid
Nonionic surfactant (Dehypon 0-5 2.0 2.0 2.0 1.5
LS 54)
Silver protector (benzotriazole)0-3 0.3 0.3 0 0.5
Tabletting aid (polyethylene 0-10
glycol)
Paraffin (Mp.: 53C) 0-10 2.0 1.0 3
Perfume 0-1 0.2 0.2 0.2 0.5
Dye 0-4 1.4 1.3 1.4 1.5
Further examples of a starting formulation (R) according to the present
application and test formulations (~ (% by weight) are shown in the following
Table:
CA 02299831 2000-03-07
Phosphate 30-60 40 40 40 45 45 50 35
(sodium tripolyphosphate)
Sodium metasilicate 5-45 45 10 40 10 30 20 35
(5-hydrate)
Sodium metasilicate 5-40 10 10 8 10 8 5 10
(0-hydrate)
Sodium disilicate 0-40 0 30 0 15 10 5 0
Paraffin oil 0-10 4 5 5 5 6 5 0
Bleach (trichloroisocyanuric 0.5-10 1 2 2 3 1 5 5
acid)
Enzyme (amylase) 0-5 1 2 2 2
(Duramyl
60 T)
Enzyme (protease) 0-5 1 2 2 2
(Blap 200
.5)
Nonionic surfactant 0-5 2 2 2 2 3
(Dehypon
LS 54)
Tabletting 0-10 1 4 2 4
aid (polyethylene
glycol)
Perfume 0-1 0.3 0.3 1 1 0.5
Dye ~ ~0.7~7 1 1 2.5
CA 02299831 2000-03-07
26
Another starting formulation (R) (% by weight) and test formulations
(V) were tested:
.9
Sodium carbonate 35-55 43.5 45 55
Sodium hydrogen carbonate 15-35 15 25 34
Polymer (Sokalan CP;i) 3-10 5 3 0
Sodium metasilicate 0-10 3 2 0
Bleach (sodium perborate) 5-12 6 10 8
Bleach activator (TAED) 0-5 1 2 0
Enzyme (amylase) (Duramyl 0.4-2 1 1 0.5
60 T)
Enzyme (protease) (Blap 0.4-2 1 1 0.5
200 S)
Phosphonate or phosphonic 0-5 0 2 0
acid
Nonionic surfactant (Dehypon 0-5 1 2 1
LS 54)
Tabletting aid (polyethylene 0-5 3
glycol)
Silver protector (benzatriazole) 0-3 0.5 1 0
Paraffin (Mp.: 53C) 0-10 0 2 0
Perfume 0-1 0 1 0
Dye 0-4 1 1 1
Should a shaped body according to the invention contain several
phases, each formulation may also be the constituents of an individual
phase, in other wards the percentages are then not based - as usual - on
the formulation as a whole, but rather on the composition of individual
phase.
Each of the formulations may of course also contain other
ingredients typical of MDWM (for example fillers, preservatives and the like)
in extremely small quantities, in which case the percentage contents of the
other ingredients should be varied accordingly.
The production of the shaped bodies according to the invention
involves steps which are known to the expert in this field in another
connection. A preferred embodiment of the shaped body according to
claim 1 contains a recess in a tablet, this recess containing the ingredient
CA 02299831 2000-03-07
27
(I). Production is preferably carried out by forming a depression in a
shaped body and filling the depression thus formed. The depression may
be formed in a Korsch rotary press. In the present case, a Fette tablet
press was used. A round tablet die (26 x 36 mm) was selected and, using
a punch, a 5 mm deep recess was formed in one side, the base of the
recess being selected so that a volume of 1 ml could be poured in, the
surface of the tablet thereafter becoming smooth again.
A liquid mixture of paraffin and an active substance (I) was then
poured in and allawed to cool. The cooling process may be assisted by
conventional methods and equipment.
As already mentioned, the ingredient (I) was quantitatively reduced
beforehand in accordance with the invention in the corresponding
formulation surrounding the filled region and, in the present Examples and
studies, was left out in the surrounding regions.
In comparisons with homogeneous tablets (where ingredient (I) does
not correspond to the invention) and a few commercially available tablets,
the tablets according to the invention proved to be superior.
The particular properties of the detergents/cleaners according to the
invention were tested by comparison with known detergents/cleaners using
storage stability as an example. The particular properties of the
detergents/cleaners according to the invention were tested in comparison
with known detergents/cleaners using the removal of tea stains as an
example. The particular properties of the detergents/cleaners according to
the invention were tested by comparison with known detergents/cleaners
using the removal of enzyme-relevant stains as an example.
In addition, the particular properties of the detergents/cleaners
according to the invention were tested by technically untrained people
under simulated practical conditions in comparison with homogeneous
tablets. Apart from dosing instructions and general safety instructions, the
handling of the detergents/cleaners by the people in question in
commercially available dishwashing machines was not influenced in any
CA 02299831 2000-03-07
28
way. This comparison test produced particularly good results. The
cleaning results were evaluated as particularly favorable.
Particularly good results were obtained when a soil release
compound was used as ingredient (I). In a mixture corresponding to
formulation Ra or Va1, up to 2% by weight of polyuronic acids, cationic
polymers and hydrophobicized polyampholytes were used independently of
one another, builder being omitted. The cleaning performance against milk
and starch-containing soils in a following wash cycle was between 10 and
30% better than in the case of untreated samples.
In another 'washing test, samples according to starting formulation
Ra which contains active chlorine (dichlorocyanurate) as bleaching
component on the one hand in homogeneous distribution in the tablet and,
on the other hand, in accordance with claim 1, so that the active chlorine
was largely separated from the other (particularly enzyme-containing)
components, were used. Storage stability after 2 weeks was distinctly
poorer in the case of the homogeneous tablet so it was not possible to
obtain a satisfactory cleaning effect against milk and starch-relevant stains.
This applies to the entirely normal making-up of the bleach component in
region (I) which, in the present case, represented a recess. The effect is
even clearer where a mixture of chlorine component and paraffin is used in
a standard program at 55°C. The cleaning results were better even
immediately after production. The effect improved with storage. Tea, milk,
burnt-on meat, burnt-in meat, egg and starch mixtures in particular were
removed far more effectively than by tablets without a region (I), i.e. with a
homogeneously distributed component (I), and commercially available
dishwasher tablets.
The effect was discernible even with paraffins having a melting point
of 40 to 44°C. The effect is more pronounced with paraffins having a
melting point of 46 to 48°C. The cleaning effect is particularly
pronounced
with paraffins having a melting point of 57 to 60°C.
In another washing test, samples (according to Ra) containing small
CA 02299831 2000-03-07
29
quantities of metal catalysts (Mn catalyst, cobalt catalyst (cobalt-
pentammine-chloro complex) and, in one case, n-methyl morpholinium
acetonitrile methyl sulfate (MMA) as bleach activator component on the
one hand in homogeneous distribution in the tablet and on the other hand
in accordance with claim 1, so that the activator component was largely
separated from other components (particularly enzyme-containing
components), were used. The storage stability after 2 weeks was distinctly
poorer in the case of the homogeneous tablet, so that the cleaning effect
against milk and starch-relevant stains was far from satisfactory.
This applies to the entirely normal making-up of the bleach activator
component in region (I) which, in the present case, represented a recess.
The effect is even clearer where a mixture of activator component
and paraffin is used in a standard program at 55°C. The cleaning
results
were better even immediately after production. The effect improved with
storage. Improvements in the removal of tea stains in particular were
obtained and milk, burnt-on meat, burnt-in meat, egg and starch mixtures
were also removed more effectively than by tablets without a region (I), i.e.
with a homogeneously distributed component (I), and commercially
available dishwasher tablets.
The effect was even discernible with paraffins having a melting point
of 40 to 44°C. The effect was more pronounced with paraffins having a
melting point of 4C to 48°C. The cleaning effect is also clearly
discernible
with paraffins having a melting point of 57 to 60°C.
In another test, samples containing surfactants on the one hand in
homogeneous distribution in the tablet and, on the other hand, in
accordance with claim 1, so that the surfactant component was largely
separated from other components, were used. In this case, the final rinse
results were evaluated. Where a mixture of surfactant and paraffin was
used in a standard program at 55°C, the results obtained were better
than
those obtained with tablets without a region (I), i.e with a homogeneously
distributed component (I), and commercially available dishwasher tablets.
CA 02299831 2000-03-07
30
The results clearly show that the tablets according to the invention
are superior to conventional dishwasher tablets.
