CA 02298948 2000-02-28
1
Dishwasher Detergent Shaped Bodies with Specific Solubility_
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 dimensiional 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 tabllets often show inadequate storage stability in regard to
sensitive ingrediE:nts (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 ca:;es, 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 ta~~lets for use in the home, more particularly for use in
CA 02298948 2000-02-28
2
machines, with hi~~h storage stability, minimal packaging volume, a good
fragrance profile <~nd 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
dissolving more quickly than the other regions) of the shaped body.
Accordingly, the present invention relates to a shaped body
containing builders, bleaching agents and surfactants, characterized in that
at least one 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, which 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, is present.
The shapedl body according to the invention consists of several, i.e.
at least two, regions which have different compositions and which therefore
dissolve at different rates when the shaped body is introduced into water.
The regions may assume various three-dimensional forms and may be
embodied, for example, in layers. However, so-called "ring/core" tablets or
"core/jacket" tableia may also be produced with the features according to
the invention, one region being formed by the core and the other region by
the ring or jacket: surrounding the core. Besides the shaped bodies
mentioned, which consist of two regions, it is of course also possible to
produce shaped bodies of three or four regions. One example of a shaped
body of three regions - besides the simplest embodiment, the three-layer
tablet - is a two-layer tablet into which a recess to be subsequently filled
with the third region is pressed. Shaped bodies consisting of three regions
can be industrially produced by means of suitable tabletting machine
providing the press. has three filling stations.
More than .B0% by weight, preferably more than 90% by weight,
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more preferably more than 95% by weight and most preferably 100% by
weight is present in the faster dissolving region according to the invention.
This means that at least 80% by weight of the total quantity of a certain
ingredient referred to herein as "ingredient (I)" is present in the faster
dissolving region. If, for example, a two-layer detergent shaped body
contains in all (i.e. based on the weight of the shaped body) 10 g of an
ingredient I (for example chlorine bleaching agent), shaped bodies
according to the invention are characterized in that more than 8 g of the
chlorine bleaching agent (preferably more than 9 g, more preferably more
than 9.5 g and most preferably 10 g) is present in the faster dissolving
layer.
The faster dissolving region of the shaped body according to the
invention dissolves more than 5%, preferably more than 10%, more
preferably more than 25%, most preferably more than 50% and, in one
particularly advani:ageous embodiment, more than 100% faster than the
remaining region and/or regions of the shaped body. In the case of a two-
layer tablet, this may be illustrated by the following example: if the slower
dissolving layer has a solubility of 20 grams per liter and hour [gl-'h-'],
for
example at a given temperature, the faster dissolving region - in
accordance with the present invention - has a solubility of more than 21 gl-
'h-' (105%, based on the basic value of 20). In this example, the solubility
of the faster dissolving region is more than 22 gl-'h-', preferably more than
gl-'h-', more preferably more than 30 gl-'h-' and most preferably more
than 40 gl-'h-'. Since the solubility of the individual regions of the shaped
25 body is also temperature-dependent and since the expression "faster
dissolving" is based on the dissolving time of the slower dissolving region
and can shift with temperature, the solubility values used in the context of
the present invention are based on a water temperature of 20°C. If a
shaped body accoirding to the invention consists of more than two regions,
two cases are ba:>ically possible: the faster dissolving region dissolves
faster than the other two regions which have the same solubility values or
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the solubility valuE~s of the two slower dissolving regions are different. In
the latter case, the expression "faster dissolving" is based on the total
solubility of the other regions, i.e. in a given volume on the effective
reduction in the tablet weight (residual weight without the faster dissolving
region) per unit of time. If a constant volume (for example one liter) is
used, the dissolving rate in grams per unit of time is directly obtained from
the reduction in weight of the shaped body. The above-mentioned unit gl-
'h-' is not normally used, instead the unit of measure is minutes or
seconds.
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 ~~Iso be a mixture of these components.
In one parlricularly 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 the region
containing the ingredient (I) makes up no more 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
shaped body.
It can also he very favorable if 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% by volume of the shaped body.
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Solubility
The solubility can be influenced by components and/or compounds
for accelerating solubility (disintegrators) or retarding solubility.
5 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, crosslinH;ed 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.
According to International patent application WO-A-96106156 also, it
can be of advantage to incorporate disintegrators in detergent tablets. In
this case, too, typical disintegrators are said to include microcrystalline
cellulose, sugars, ouch as sorbitol, and layered silicates, more particularly
fine-particle and s~wellable layered silicates of the bentonite and smectite
type. Effervescent substances, such as citric acid, bisulfate, bicarbonate,
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 20CI0 pm 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
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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 disintegrai:ors, may also be used as a coating material.
Particular rE~ference 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 disintegrato~r 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. Detergent shaped
bodies containing granular or optionally co-granulated disintegrators are
also described in German patent application DE 197 09 991 (Stefan
Herzog) and in International patent application W098140463 (Henkel).
These documents also contain details of the production of granulated,
compacted or co-granulated cellulose disintegrators. The particle sizes of
such disintegrators is generally above 200 Nm, at least 90% by weight of
the disintegrators preferably being between 300 and 1600 Nm in size and,
more preferably, between 400 and 1200 um in size. The relatively coarse
cellulose-based disintegrators mentioned above and described in detail in
the cited documents are preferably used as disintegrators in accordance
with the present invention and are commercially available, for example,
under the name of Arbocel~ TF-30-HG from Rettenmaier.
Disintegrators belonging to the group of organic acids, for example
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
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conventional dishwashing machine, i.e. shorter than 40 mins., preferably
shorter than 30 rains., more preferably shorter than 20 rains., and most
preferably shorter than 10 rains.
In a particularly preferred embodiment of the invention, the faster
dissolving region contains at least one acidifying agent. Suitable acidifying
agents are, for example, boric acid and alkali metal hydrogen sulfates,
alkali metal dihydrogen phosphates and other inorganic salts. However,
organic acidifying ~~gents are preferably used, citric acid being a
particularly
preferred acidifying agent. However, other solid mono-, oligo- and
polycarboxylic acids in particular may also be used. Within this group,
tartaric acid, succinic acid, malonic acid, adipic acid, malefic acid, fumaric
acid, oxalic acid and polyacrylic acid are preferred. Organic sulfonic acids,
such as amidosulfonic acid, may also be used. Sokalan~ DCS (trademark
of BASF), a mixture of succinic acid (max. 31 % by weight), glutaric acid
(max. 50% by uveight) and adipic acid (max. 33% by weight), is
commercially obtainable and may also be used with advantage as an
acidifying agent for the purposes of the present invention.
According t~~ the invention, preferred detergent shaped bodies are
those in which an acidifying agent selected from the group of organic di-,
tri- and oligocarboxylic acids or mixtures thereof is present in the faster
dissolving region, citric acid being particularly preferred. The acidifying
agents mentioned are preferably either sole components I or at least a part
thereof. Accordincaly, in a preferred embodiment of the invention, at least
80% by weight, preferably more than 90% by weight, more preferably more
than 95% by weight and, most preferably, 100% by weight of the acidifying
agent present in the shaped body is present in the faster dissolving region.
In preferred embodiments of the present invention, the faster
dissolving region may contain - besides the acidifying agent - other
ingredients to which the criterion relevant to the ingredient I may also be
advantageously applied, i.e. at least 80% by weight, preferably more than
90% by weight, rnore preferably more than 95% by weight and most
CA 02298948 2000-02-28
preferably 100% by weight of these ingredients, too, is contained in the
faster dissolving region. These other ingredients are, for example,
carbonates and/or hydrogen carbonates of which the use in combination
with an acidifying ~~gent leads to the evolution of gas on contact with water
which further reduces the dissolving times. An effervescent system such
as this may be formulated with an excess of acidifying agent, so that an
acidic prerinse cycle is possible, although other ingredients may also be
incorporated in they faster dissolving region, so that the effervescent system
releases the other' ingredients more quickly. If effervescent systems are
used, the dissolving time of the faster dissolving region is still preferably
below the values mentioned above, i.e. below 10 mins., preferably below 5
mins. and more preferably below 2 mins. Quick-dissolving regions such as
these can produce distinct advantages in regard to cleaning performance.
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 1!~7 27 073, of which the disclosure is hereby specifically
included as part of the present disclosure, is particularly suitable for the
purposes of the prE~sent 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 mins. and preferably
longer than 10 mins. In cases such as these, a relatively small region of
the shaped body rnay be dissolution-retarded, so that the greater part of
the shaped body makes up the faster dissolving region. By adopting such
measures for delaying dissolution, certain ingredients, for example, are
only released in the final rinse cycle which affords further advantages in
regard to cleaning performance.
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General forms of presentation
The shaped body may assume any of the various three-dimensional
forms which are li;>ted inter alia in patents belonging to the prior art and
in
the standard work, of the specialist literature (for example: Riedel, "Die
Tablette"). The rE~gion 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 prefE~rred embodiment, the invention provides homogeneous
or heterogeneous ;shaped bodies of known construction.
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, :square, rectangular, trapezoidal, oval and irregularly
shaped bases many 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 ak>ove 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.
CA 02298948 2000-02-28
A homogeneous shaped body in the context of the present invention
is understood to he one in which the ingredients of the shaped body -
except for the rE~gion containing ingredient (I) - are homogeneously
distributed in such a way that differences between ingredients and/or active
5 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, heterogeneous shaped bodies in the context of the
10 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
giving the various ingredients different colors and/or by providing them with
different fragrance components.
Another ca;>e which, according to the invention, counts as a non-
homogeneous (hel:erogeneous) 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 favorak>le if the ratios by volume of the other two phases are
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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
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 jaclket-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
especially 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 solubilifiy is made up together with enzymes. Another favorable
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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 l:he component, for controlling solubility is made up
together with the silver protector component. Another favorable and
preferred embodinnent of the invention is characterized in that one of the
components, or i:he component, for controlling solubility is made up
together with at least 50% by weight, preferably more than 70% by weight
and, more prefer~~bly, 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
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 aolution and/or melt), optionally at elevated temperature,
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, moat preferably between 2,500 and 7,000 mPas and, in a
particularly advani:ageous 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 (CutinaC~~ GMS), and also thickened caustic soda and fusible
salts, such as ;odium carbonate decahydrate, have proved to be
CA 02298948 2000-02-28
13
particularly suitable carrier materials. The advantages and disadvantages
of the individual in~~redients 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 bod~,r 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.
Specific in req dients
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 al:;o 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 m<~y also be used.
Other preferred ingredients (I) are other bleaching agents, for
example the haloc,~en bleaching agents mentioned above, among which
dichloroisocyanuric; acid (DICA) is particularly preferred for the purposes of
the invention.
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
CA 02298948 2000-02-28
14
anhydrides, ester:., 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 ~~cids 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), acylatE~d glycolurils, more especially tetraacetyl glycoluril
(TAGU), N-acyl imides, more especially N-nonanoyl succinimide (NOSI),
acylated phenol sulfonates, more particularly n-nonanoyl or
isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides,
more especially phthalic anhydride, acylated polyhydric alcohols, more
especially triace~tin, 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 76'7 and also acetylated sorbitol and mannitol and mixtures
thereof (SORMAN), acylated sugar derivatives, more especially
pentaacetyl gluco;>e (PAG), pentaacetyl fructose, tetraacetyl xylose and
octaacetyl lactose and acetylated, optionally N-alkylated, glucamine and
gluconolactone, and/or N-acylated lactams, for example N-benzoyl
caprolactam. Combinations of conventional bleach activators 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
CA 02298948 2000-02-28
detergent/cleaner as a whole.
In addition to or instead of the conventional bleach activators
mentioned above, so-called bleach catalysts may also be incorporated in
the shaped bodif~s. These substances are transition metal salts or
5 transition metal complexes such as, for example, manganese-, iron-,
cobalt-, rutheniurn- or molybdenum-salen or -carbonyl complexes.
Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and
copper complexes with nitrogen-containing tripod ligands and cobalt-, iron-,
copper- and ruthenium-ammine complexes may also be used as bleach
10 catalysts.
Bleach activators from the group of polyacylated alkylenediamines,
more particularly tetraacetyl ethylenediamine (TAED), N-acyl imides, more
particularly N-non~~noyl succinimide (NOSI), acylated phenol sulfonates,
more particularly n-nonanoyl or isononanoyloxybenzenesulfonate (n- or
15 iso-NOBS), n-methyl morpholinium acetonitrile methyl sulfate (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 selectecl 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,
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
CA 02298948 2000-02-28
16
corrosion inhibitor; 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 411 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 particul~~r oxygen- and nitrogen-containing organic redox-active
compounds, such as dihydric and trihydric phenols, for example
hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloro-
glucinol, 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 ~>referred, 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
compounds).
The soil-relE:ase compounds used in accordance with the invention
include any of the compounds known from the prior art. Particularly
suitable are cationic polymers such as, for example, hydroxypropyl
trimethyl ammonium guar; copolymers of aminoethyl methacrylate and
acnylamide and copolymers of dimethyl diallyl ammonium chloride and
CA 02298948 2000-02-28
17
acrylamide, polymers containing imino groups, cationic cellulose
derivatives, cationic homopolymers and/or copolymers (monomer units:
quaternized ammonium alkyl methacrylate groups).
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
ium groups; quaternary ethylene imine polymers and polyesters and poly-
amides containing quaternary lateral groups as soil-release compounds.
Natural polyuronic 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 i:o improve performance or guarantee the same quality of
cleaning under milder conditions. The most commonly used enzymes
include lipases, annylases, cellulases and proteases. Preferred proteases
are, for example, E3LAP~ 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
CA 02298948 2000-02-28
18
the condition of the region according to the invention be fulfilled by other
ingredients.
Water-soluk>le 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-
polymeric and copolymeric polycarboxylic acids and salts thereof, the car-
bonates, phosphates and silicates. Water insoluble builders include the
zeolites, which many 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 andlor 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 prevferably 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
CA 02298948 2000-02-28
19
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 relatiively long-chain alcohols (C~o to C~8, preferably between
C~2 and Cps such as, for example, C», C~2, C~3, C~4, C15, Cps, C17 and C1g
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
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 ethoxylate~s, which may also be used in accordance with the
invention, may al:~o be obtained by etherification with short-chain alkyl
groups, preferably butyl groups, in a concluding step. According to the
invention, highly e~thoxylated fatty alcohols or mixtures thereof with end-
capped fatty alcohol ethoxylates are particularly preferred for the purposes
of the invention.
Alkyl polygNycosides 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 lone-chain fatty alcohols while the degree of oligomerization
of the sugars is beilvveen 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
CA 02298948 2000-02-28
reduction process., as described for example in SOFW Journal, 119,
(1993), 794-808. Carbon chain lengths of C6 to C~2 are preferably used in
the fatty acid moiety.
The region:. of the shaped body may be colored. In one particularly
5 preferred embodinnent, 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
10 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%
15 and preferably belween 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 weiglht, most preferably no more than 20% by weight and, in
one particularly advantageous embodiment, no more than 10% by weight
20 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 day:. 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 aalvantageous 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
CA 02298948 2000-02-28
21
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 more than 20 wave numbers and, in one particularly
advantageous embodiment, no more than 10 wave numbers and, in the
most favorable care, no more than 5 wave numbers.
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
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 regians), it was reduced in accordance with the
invention or left oust altogether before the studies were carried out.
Possible starting formulation (Ra) and test formulations (Va) (figures =
by weight):
CA 02298948 2000-02-28
22
-~ ,
,. , f.
F ,.
, ~
~,': ',",~i':
~~w.. ~, x Y
x.
.:. '~-' . .,~ ~ ~~ ~~ ~-'r
,ai. G
a
5 , ' ~~
a 6 e..e::~
~ r.,. . .
f" "~ ,... .
;, . . ...; _ .,- ' . '_ ..,. , -
_' : ..; ,., :; s.; ,
.,3,>..:. ~,.... s ,
~z. , . ,
, " ,~ >
~',.
,
"
Phosphate (sodium tripolypho;>phate)30-60 54.856.4 30.543 48 48 47
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 CP5) 0-10 2.2 2.2 1 5
Sodium metasilicate 0-10 1.8 0
Sodium hydrogen carbonate 0-10 1 3
Bleach (sodium perborate) 2-20 9.0 9.0 6.7 15 10 12 9
Bleach activator (TAED) 0-5 2.1 2.1 3 2 1 1.5
(co-
pentammine-CI)
Enzyme (amylase) (Duramyl 0-5 2.0 2.0 0.7 3 3 3 2.5
60 T)
Enzyme (protease) (Blap 0-5 1.8 1.8 1.0 2 2 3 2.5
200 S)
Phosphonate or phosphonic 0-5 0.9 0.9 2 1.5
acid
Nonionic surfactant (Dehypon0-5 2.0 2.0 2.0 2 4 3 1.5
LS 54)
Silver protector (benzotriazole;~0-3 0.3 0.3 0 0.3 0.2 0.5
Tabletting aid (polyethylene0-10 6
gl~rcol)
Paraffn (Mp.: 53C) 0-10 2.0 1.0 3
Perfume 0-1 0.2 0.2 0.2 1 0.4 1 0.5
Dye 0-4 1.4 1.3 1.4 0.7 0.4 1.5
The builder system of the above starting formulation may also have the
following composition (all other ingredients same as for a).
. . ' fit llt~ y y k~ l~b~'~ltti7
s~ r 9 ' ~~ ~ ''
tart - :,
d t >~
.. , .
~.. .. . ~ .
. , . . , . ,
f ~
..
~
s.
Phosphate (sodium phate) 30-60 59 56 53 48 48 48 47
tripolyphos
Carbonate (sodium 5-25 21.220.322.7 17 20 16 24
carbonate)
Polymer (Sokalan 0-10 2 10 5 4 5
CP5)
Sodium metasilicate 0-10 1.8
Sodium hydrogen carbonate 0-10 1 3
Examples of another starting formulation (R) according to the present
invention and test formul~~tions (V) (% by weight) are shown in the following
Table:
CA 02298948 2000-02-28
23
r ;..
,, W, f'
Vie, Y
6 , ~ , ,6...~
",r~r 4 e ,g' 3f
6.- F"-
. ' i ,_ 3 6 ~I , ~ '
,..~66C fir...- ,
i e'~fF . 6 k r. .S
.3.
f" , a d.. . ~E :.'k
T.az,~. a ~.s.: .x
",...,~ $s-r ;.
P.~. T s$~
E , "., ;~ "
T ,,>,~, ~a ~.
,
i .., /
'~?-s 6
Y ;,
5 s,x S 's:::
3 ~E ..TsFi '~....Y.
'T i, 6E;, , ,.,~,~..,
R ~ " y~ , . '~'.;
,.r.6. , .E'"", , S, . _u,<.
. h.
Phosphate (sodium tripolyphoaphate)15-35 30 21 35 40
Carbonate (sodium carbonate) 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
.S)
Phosphonate or phosphonic 0-5 0 0 0 0
acid
Nonionic surfactant (Dehypon 0-5 2 1 1 1
LS 54)
Silver protector (benzotriazolej0-3 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:
Tk M"n:'. f ~ri;
/ E'.
/~~f ' t y
,
T ' -' / , r.. E6
r.; V.
~ > i
.63~ Y ,...
r' ;3 ~r.". .,. q~ ,..,
3. ..
~.,
~.. w 4f ~ $ ,., e~
,s.,.
d ~i
N,: J e> f f >r a
r... r'/-r'-~,
'S~.. s f
, ,a Z...
, w,....,. ...$a',.
.,:: ~ ~w..
( , P ,,... ~ 6
-a.. 7 ' :
,~s%: , t :aE~<
>., r ~,~,.,., _~es~, '3K , "" ,.?. " '
~". ,
. " ..k..
~hv, ., ~9'.~~~,
, 9.~t
,
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 200 0.4-5 2 3 1 5
S)
Phosphonate or phosphonic 0-5 1.5 2.3 2
acrid
Nonionic surfactant (Dehypon 0-5 2.5 1.7 2 1
ILS 54)
Silver protector (benzotriazole)0-3 0.5 0.5
CA 02298948 2000-02-28
24
H f3.
/' 4 ~? .F."
~ ~ 6 ,.. "'
f " /f , E, 2~
, ,3.;:
3 ,t NE , f : ~ ; ~
~ . d s ~i~r-
,_,~ .:., _ f
:.....:.i 1'P ;3 .
' ~r.
.,~ E l
r..u , ~ :
, ,:'m'
T. ,3.,.~,,~g~..-
i z
"~'f
:,. ~ d. s': , i.
( ~r, ,,9.~.,:;:
, , :
6 _ s ~,.~..:~~",> f. ,
F "~' r~~s
~ .. , r..~~ " i~ ::...-
t, ast . . . ,,..
v, a ~ d,,r
dr'E R , ~,r..,::.. ., ...
E;e , _~", _._. ". ~'
a ~ a ~
", ~F ~ "~, :~;.'.,.:
,ate,. ..._-..,,
":''... ._ .~-..:
Paraffin (Mp.: 0-10 3 1.5
53C)
Perfume 0-1 0.9 0.5 1 1
Dye 0-4 0.1 1.5 ~ I 2
Further examples of a starting formulation (R) according to the present
application and test formulations (V) (% by weight) are shown in the following
Table:
:; I it d ,
3,, ~
i , , i ,
', 5 t H. 1,,
~ o :I
:4 .:., C ,~-,a,
!!
9 Ef "F- .,. at.d,
a~ ~ ~ ~~ ;,:
is ~ -' - ~~ 5
v"3 -. _
, ., a . W~
~ . 3 sD 9Z7 ,.,. "':r ~i,~,~ e..:
, , ,
_ i a.'r.
,YS.fai,a
Citrate (trisodium citrate) 20-55 32 36 38 24
Phosphate (trisodium polyphosphate)20-55 26 23 24 24
Carbonate (sodium carbonate) 1-15 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
E~0 T)
Enzyme (protease) (Blap 200 0-5 5 0.5 2
S)
Phosphonate or phosphonic 0-5 2 2 2
acid
Tabletting aid (polyethylene 0-10 6 4 5 0.8
glycol)
- 0-5 2.5 2.8 2
Nonionic surfactant (Dehypon
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 (V) (% by weight) are shown in the following
Table:
&,t -
E 6.
$ ~ %, ",
~~' a , ,,
~_. ,~=
": 6..
~~.:"". F&. , u.': g....,/i P;
Bs F, ak, ' >LI
S".,
(...r.,.M . ~ _ avy ,.1 -__
F..t.. .. ~. -tea. ; ~..,.7. b~..-
8, ~, $ a ~.,
~dt .,.u..,.
a k
3~ s~ .:.: ~ ~' ,t.
r z d ,."".~ . ., ,t.
,_eG rr,&:';.i
A.._ ft ,~> ~ ",..<aa,.
-'fE;'E. ~. . ,. 3s 'f ,~t , t7.,."
r ~. , .
. ;,.~.,
:t fi3,...".. i..~T/~ ~.t 3s:r
~.". ..,.,.. ,.... ,...,. , .% ;
a , a , t ,8 'fee_ a~.~.t:3
,. :Y: ,Et ,." s ,.,e.~ ,~
,.t . .~<,.,..,..t ~~~.,
k .,:,96,"
>,neYy
Phosphate (trisodium polyphosphate)40-60 49 49 49 50
Carbonate (sodium carbonate) 0-20 17 19 5
Polymer (Sokalan CP5) 0-15 2 4 1 6
Silicate (sodium disilicate) 0-30 24 6 5 10
CA 02298948 2000-02-28
~. ,;n
~, ~
, .k E . ~_ .:., ;.~ f
v:
,. a
~E n.. s >,:?
L...~. . &
~r> , a f...... :n . t ~~,.ys
ai .d, , . .arc.
,"~~~ ~.
E,
, .>:~,
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 200 0-5 3.9 2 1.5 2.5
S)
Phosphonate or phosphoric 0-8 0.8 1 1 2
a~~id
Tabletting aid (polyethylene 0-10 0.2 4 3.7 5
glycol)
Nonionic surfactant (Dehypon 0-8 1.5 2 4 3
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 0-4 3 2 0.5 1
Further examples of a starting formulation (R) according to the present
application and test formulations (V) (% by weight) are shown in the following
Table:
.st y
.h l I i . ~: y ~,~
, ;,
P. E ~ &. ; ':
.9 ; Yep
.., ; -
a~
.n
';
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 (amylase) (Duramyl 0-5 2.0 2.0 0.7 2.5
60 T)
Enzyme (protease) (Blap 200 0-5 1.8 1.8 1.0 2.5
S)
Phosphonate or phosphoric 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
CA 02298948 2000-02-28
26
application and test formulations (V) (% by weight) are shown in the following
Table:
a" , ~~. .3
7..: ik ,R ,
, . d..n,1 ','r,3
~ Y 3 H i .< ".,.,.
fir. z
,
t: ' , .. "~, : >..:N$
3
S "r&c,... ~~,
,> . ~ 3i.,
1 ~.
~ii e,::
$
~~
,?.,r...:
"
I,
Phosphate (sodium tripolyphosphate)30-60 40 40 40 45 45 50 35
Sodium metasilicate (5-hydratE~)5-45 45 10 40 10 30 20 35
Sodium metasilicate (0-hydratE:)5-40 10 10 8 10 8 5 10
Sodium disilicate 0-40 0 30 0 15 10 5 0
Paraffin oil 0-10 4 5 5 5 6 5 0
Bleach (trichloroisocyanuric0.5-101 2 2 3 1 5 5
acid)
Enzyme (amylase) (Duramyl 0-5 1 2 2 2
60 T)
Enzyme (protease) (Blap 0-5 1 2 2 2
200 S)
Nonionic surfactant (Dehypon0-5 2 2 2 2 3
LS 54)
Tabletting aid (polyethylene0-10 1 4 2 4
glycol)
Perfume 0-1 0.3 0.3 1 1 0.5
Dye 0-4 0.7 0.7 1 1 2.5
CA 02298948 2000-02-28
27
Another starting formulation (R) (% by weight) and test formulations
(V) were tested:
Soi~ b' ~,,~,~~~~~ 3a: ~; % L ,. ~' ~ ,
k ';ry 9 ~ ~ ',, -a~ ~ , e,~.~
r~~ ",'. ' S~ ~3~er/ ",r /, ~ g3~ "a'~,~~~~ &
sS. ; ~ 'f 3 : ~ ~7,3i , f; '.
. . ,. -, .. ~ : , .. . , sl
, , a,~
, r
Sodium carbonate 35-55 43.5 45 55
Sodium hydrogen carbonate 15-35 15 25 34
Polymer (Sokalan CP;S) 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 200 0.4-2 1 1 0.5
S)
Phosphonate or phosphonic 0-5 0 2 0
acid
Nonionic surfactant (C~ehypon0-5 1 2 1
LS 54)
Tabletting aid (polyethylene 0-5 3
glycol)
Silver protector (benzotriazole)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 words 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 ~;hould 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 ~~ recess in a tablet, this recess containing the ingredient
CA 02298948 2000-02-28
28
(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 mi:~ture of paraffin and an active substance (I) was then
poured in and allowed 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 deter~gents/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 frorn 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 02298948 2000-02-28
29
way. This comparison test produced particularly good results. The
cleaning results wE~re 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 progr~~m 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 tablet;.
The effect was discernible even with paraffins having a melting point
of 40 to 44°C. l-he effect is more pronounced with paraffins having a
melting point of 4Ei to 48°C. The cleaning effect is particularly
pronounced
with paraffins haviing a melting point of 57 to 60°C.
In another washing test, samples (according to Ra) containing small
CA 02298948 2000-02-28
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
5 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 cases of the homogeneous tablet, so that the cleaning effect
against milk and si:arch-relevant stains was far from satisfactory.
10 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 usE~d in a standard program at 55°C. The cleaning
results
were better even immediately after production. The effect improved with
15 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.
20 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 4Ei to 48°C. The cleaning effect is also clearly
discernible
with paraffins having a melting point of 57 to 60°C.
In another i:est, samples containing surfactants on the one hand in
25 homogeneous di:~tribution 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
30 those obtained wii:h tablets without a region (I), i.e with a homogeneously
distributed component (I), and commercially available dishwasher tablets.
CA 02298948 2000-02-28
31
The results clearly show that the tablets according to the invention
are superior to conventional dishwasher tablets.
In order further to illustrate the advantages of shaped bodies
according to the invention, shaped bodies with three regions were
produced, the two slower dissolving regions assuming the form of layers.
The faster dissolving region according to the invention was obtained by
forming the two-layer tablet with a recess, into which the premix for the
faster dissolving rE:gion was pressed, with the aid of a top punch provided
with a projection. Accordingly, the three-phase shaped body according to
the invention was produced by the two process steps "formation of two-
layer recessed shaped badies" and "filling of the recess (formation of the
faster dissolving rE~gion)".
Process stew): formation of recessed shaped bodies:
Two-layer rectangular shaped bodies (weight 20 g) with a recess in
the shape of a semiellipse were made by compressing two different
premixes. 75% b~~r weight of the shaped bodies consisted of lower phase
and 25% by weight of upper phase. The composition in % by weight
(based on the particular premix) of the two premixes and hence the two
different phases of the recessed shaped body is shown in Table 1 below:
CA 02298948 2000-02-28
32
Table 1: compositions of the premixes for the upper and lower phases (%
by weight)
k 39~ b E' e
~.. is F ,~ ,t,"aj. ~ .'. sE4Ei,,ifI
' 6~ F ~ i ,~'.,
iefg ~' ~ ~Y,I~~,,. , f ~P ~~ r~ ~
/J. ~~' ,~c
~ f ~ 4
1 "
~ ..P
P6f&'.
,
'.a'"I~
~i~E
'
f
~~
~~~
~
~ .
f II , f. . .,
t n.~i , "
h B ' 'E
~ t
e
(: ~ f4~
i3 ~R ''. ~ ~~.,
~ '. ( ..E v.t
E, f ~ ~ sE~, ~ ~~' ~ P;"t,.
. FS ' 3~k <> ,~~ 1 ~: $ , .~
'',.. f k :: ~~~ ~. ;
r ca~'~ ~,F~T kJ,k a ~ ~~~ , ~:'k'.
'' t .'e
':
f er ,I~,~
r'~s>4 .ES s ;, w
Sodium carbonate 33.0 -
Sodium tripolypho:~phate 52.0 94.4
Sodium perborate 10.0 -
Tetraacetyl ethylenediamine 1.5 -
Benzotriazole 1.0
C~2 fatty alcoho1~3E0 2.5 -
Dye 0.2
Enzymes 3.0
Perfume 0.4
Silicone oil 2.0
If shaped bodies with the composition shown above are introduced
into 1 liter of water at 20°C, they dissolve in 20 minutes.
In shaped bodies E according to the invention, citric acid was
pressed into the recess of the shaped body as ingredient I. This "citric acid
core" formed the faster dissolving region. In Example E1, 1 g citric acid, in
Example E2 3 g citric acid and in Example E3 5 g citric acid were pressed
into the recess. Since the two layers of the recessed shaped body are free
from citric acid, ingredient I is 100% present in the faster dissolving
region.
Shaped bodies E1, E2 and E3 were each introduced into a glass
beaker filled with 1 liter of water at 20°C. The faster dissolving
region
dissolved completely in 3 minutes. In order to demonstrate the superiority
CA 02298948 2000-02-28
33
of the shaped tablets according to the invention, the detergents E1, E2 and
E3 were compared with commercially available dishwasher tablets. To this
end, tableware was soiled with tea and the removability of this soil was
tested in a 55°C program of a dishwashing machine.
(1) Preparation of the tea soil
In a water purification kettle, 16 liters of cold local water
(16°d) were
briefly brought to the boil. 96 g of black tea in a nylon net were allowed to
draw for 5 minutes with the lid on, after which the tea was transferred to a
heated and stirred immersion tank.
60 Tea cues are immersed 25 times at 1-minute intervals in the
prepared tea at a temperature of 70°C. The cups are then removed from
the hooks and placed face down on a draining board to dry.
(2) Test results
The cleaning performance of the tablets against the tea soil
prepared as described in (1) was visually scored by experts on a scale of 1
to 10 where 0 = no cleaning and 10 = complete stain removal.
The tea scores were awarded for washing conditions of
55°C/16°d
water hardness in the main wash cycle (i.e. "hard conditions"). The
dishwashing machine used was a Miele G 590 (universal program). Table
2 below shows tree pH value of the wash liquor after dissolution of the
faster dissolving region (*) and after dissolution of the entire tablet (**)
and
the tea stain removal achieved:
CA 02298948 2000-02-28
34
Table 2: removal of tea stains
a ~ '. a ~ f '': '. i F .~ ' .' a ~ 2. '
~s t r~~ , aye t E(id ~ ~ ''.,...
' E"~" ~ .e b! h t ~IEF ~: " 5~c~t~~-
a ~ ~ f 43
~~ bad ~>. ;
~ ~~'~~~~
~
,
f~
,e
-
~if
~
~~~
, , ~ ,,
,', (, ~ L , ~ F y, , ~,Y " ., ; I
8 ~
R.
,
E1 8.0 9.5 6.8
E2 7.0 9.5 7.5
E3 3.0 9.5 9.5
Commercially available dishwasher - 9.5 5.5
tablets
In other slhaped bodies according to the invention, the faster
dissolving region was formulated as an effervescent system. To this end,
the compositions :shown in Table 3 were selected for the faster dissolving
region (figures = %~ by weight):
Table 3: composition of the faster dissolving region (% by weight)
3~~e ~~~E~ ~ ~~ ~ , ~~ ~ ~~ '~ '
: z
v k
,~y,i I , T s r " s , , ~fi ", .~~,.,~k,. :.
,, " ,.. ", " ,. ,: , .. ,....:,..,: , . . ,.
.a.; , " : , ."", ,: .v ,,,.,: a , ,.
.. . , , , . , . , , f~',.
, .. . , ,
. ,
Citric acid 33.3 37.5 10.0 10.0
Sodium hydrogen carbonate 26.7 37.5 10.0 10.0
Enzymes 40.0 - - -
TAED - 25.0 - -
Sodium perborate monohydrate - 80.0 -
Sokalan~ BM-1
* n-methyl morpholinium acetonitrile methyl sulfate (MMA), ca. 50% on a
support (BASF)
Three-phase tablets were produced similarly to the preceding
Example. The percentages of the individual regions (upper and lower
CA 02298948 2000-02-28
phases and faster dissolving region) were selected as follows:
Table 4: compositiion of the shaped bodies E4-E6 (% by weight)
frfr.' ;;.~~ ~ fry 4 y,. ~ (E
~ "; W ~, ~ ~ - 9 '. ' ~ ~ , ~T ~
;. '. ~' ~ , , 3~9~~ ( ', ufr
Rxp 4, (- ~
~
~' ~
'
'
k g f E~" ,~ ,~E
~~.. , fi ~ ~. 'y ~ j
i .
3 9
;a';3~5 ~ -, '~ /'' ,
. F 2~ , ,
Lower phase* 61.8 63.0 61.1 63.0
Upper phase* 29.1 29.6 28.8 29.6
Faster dissolving region** 9.1 7.4 10.1 7.4
* see Table 1
** see Table 2.
In the case of shaped bodies E4 to E7, therefore, the ingredient I
confined to the faster dissolving region was always both citric acid and
sodium hydrogen carbonate. In the shaped bodies E4, 80.7% of the total
enzyme present in the shaped body was contained in the faster dissolving
region; in the shaped bodies E7, all the MMA in the shaped body was
contained in that r~sgion.
In every case, the faster dissolving region dissolved completely in
less than 120 seconds, the rest of the tablet taking another 15 minutes in
all to dissolve.
The cleaning performance against tea stains in the test described
above was also deaermined for the shaped bodies E4 to E7 by comparison
with conventional dishwasher tablets. The results are set out in Table 5.
CA 02298948 2000-02-28
36
Table 5: removal of tea stains
~C E~ ~3 J~~2' E ~ ~ ~E ~ /1~~k ~
i
~
~ ~
P& ~' ~ f5,3
.~Tc < " i'7 =s~
E4 7.8
E5 8.3
-
E6 7.8
E7 10.0
Commercially available dishwasher ~5
tablets
In further tEats, the bleach activator MMA (n-methyl morpholinium
acetonitrile methyl! sulfate) preferably used in the faster dissolving region
was made up as ingredient (I) in shaped bodies differing in composition in
which it was 100% present in the faster dissolving region. To this end,
one-phase rectan~~ular shaped bodies (weight 24 g) with a recess in the
form of a semie~llipse were prepared by compressing two different
premixes. The composition (in % by weight, based on the particular
premix) of the two premixes and hence of the two different recessed tablets
is shown in Table ~6 below:
Table 6: compositions of the premixes for the upper and lower phases (%
by weight)
CA 02298948 2000-02-28
37
~~ ~~~ ~ , , ~~ ~"r~i~~ P
f ~ f
~ P
3
1 3.
s ~ P ~p
'r~ '~ fi
~ f f ~ F f T ~ ~ ~ ~e 3
P
8~<"
',.
8
. o f,( .~~ F~(~ ~ 3..
3~~~ ~. i ~~~~ E '''. ~~~~~~ ~
~I'. f~ :
~
,, " , ~. ,'~ .. ~ :::~
3 .;:. . , "
, , r;':.,.. ; , f ~F~ "~/r ",.
~ ~ ~ ' f , "
", ' _ ,'z>s
. '' 3s.:
~'
".. , . 5.0
. ",
.>"" 5.0
Polycarboxylates
Phosphonates 1.0 1.0
Benzotriazole 0.1 -
C~2 fatty alcohol~31=O 2.0 2.0
Enzymes 3.0 3.0
The bleach-containing recessed tablets made from premix 3 were
filled with cores e~~ch weighing 1.3 g. The recessed tablets were filled by
melting PEG, incorporating the solids and pouring the melt into the
preformed recesses or pressing in the pure substances (E12, E13). The
composition of the various powder mixtures and hence of the cores is
shown in Table 7 which also shows the cleaning performance of the filled
core/recess tablet, against tea stains prepared in accordance with (1) {for
test conditions, see (2)}. The cleaning performance of an unfilled recessed
tablet was also determined for comparison (V1 ). A direct comparison with
an ingredient of which no more than 80% was contained in the faster
dissolving region of the shaped body was also made (V2). The cores
based on pure substances dissolved completely in one minute, the cores
based on PEG 1550 took 2 minutes and the cores based on PEG 3000 4
minutes to dissolve completely. The dissolving time of the recess base
(rest of the tablet 'without the dissolved core) was more than 20 minutes in
every test.
CA 02298948 2000-02-28
38
Table 7: composii;ion of the cores (faster dissolving region, % by weight)
and cleaning performance of the core/recess shaped bodies
3 E~.- 3..
~ , f- E
,. ~ . ~~~1 y ~ ~ ~_~ ~E~, ! ~, ltd
. ~~~~ !~ y
. ~ ~ ~:~~...:.
,
MMA* - - - - - - - 100
Sokalan~ BM-1 ** - - 50 25 44 60 100 -
TAED - 5- - - - - - -
Sodium perborate - - - 25 - - - -
PEG 1550 - 50 50 50 44 - - -
PEG 3000 - - - - - 40 - -
PEG 4000 - - - - - - - -
Citric acid - - - - 4.8 - - -
NaHC03 - - - - 7.2 - - -
Tea score (55C/16dhi)4.7 6.3 6.8 7.5 7.0 8.0 10.0 10.0
Tea score (55C/3dH;l7.0 *** 9.5 *** 10.0 9.7 10. 10.0
* n-methyl morpholinium acetonitrile hydrogen sulfate, pure substance
** n-methyl morpholinium acetonitrile hydrogen sulfate (MMA), ca. 50%
on a support (BASF)
*** not measured
Table 7 shows that confining an ingredient to the faster dissolving
region is particularly effective if more than 80% of that ingredient is
contained in the faster dissolving region (comparison of V2 with E8). It can
also be seen that tea stain removal is better, the more quickly the faster
dissolving region dissolves compared with the rest of the shaped body.
