Note: Descriptions are shown in the official language in which they were submitted.
CA 02290014 1999-11-17
1
Additive Granules fur Moulded Bodies Having a Detergent and
Cleaning Action
This invention relates generally to disintegration aids for compact
shaped bodies having detersive properties. More particularly, the invention
relates to so-called disintegrator granules for use in detergent shaped
bodies such as, for example, detergent tablets, dishwasher tablets, stain
remover tablets or water softening tablets for use in the home, more
particularly for uses in maclhines.
Detergent shaped bodies are widely described in the prior-art
literature and are enjoying increasing popularity among consumers
because they are easy to dose. Tabletted detergents have a number of
advantages over powder-form detergents: they are easier to dose and
handle and, by virtue of their compact structure, have advantages in regard
to storage and tr~~nsport~~tion. As a result, detergent shaped bodies are
also comprehensiively described in the patent literature. One problem
which repeatedly arises in the use of detergent shaped bodies is the
inadequate disintegrating and dissolving rate of the shaped bodies under
in-use conditions. Since sufficiently stable, i.e. dimensionally stable and
fracture-resistant, shaped bodies can only be produced by applying
relatively high pressures, the ingredients of the shaped body are heavily
compacted so that disintegration of the shaped body in the wash liquor is
delayed which results in excessively slow release of the active substances
in the washing process.
The problem of i:he overly long disintegration times of highly
compacted shaped bodiea is known in particular from the pharmaceutical
industry where certain disintegration aids, so-called tablet disintegrators,
have been used for some time in order to shorten the disintegration times.
According to Rompp (9th Edition, Vol. 6, page 4440) and Voigt "Lehrbuch
der pharmazeuti:~chen Technologie" (6th Edition, 1987, pages 182-184),
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2
tablet disintegrators or disintegration accelerators are auxiliaries which
provide for the rapid disintegration of tablets in water or gastric juices and
for the release of i:he pharmaceutical principles in an absorbable form.
"Hagers Handbuch der pharmazeutischen Praxis" (5th Edition,
1991, page 942) classifies the disintegration accelerators or disintegrators
according to their action mechanism, the most important action mechan
isms being the :>welling mechanism, the deformation mechanism, the
wicking mechanism, the repulsion mechanism and the evolution of gas
bubbles on contact with water (effervescent tablets). In the case of the
swelling mechanism, the particles swell on contact with water and undergo
an increase in volume. This produces local stresses which spread
throughout the tablet arnd thus lead to disintegration of the compacted
structure. The deformation mechanism differs from the swelling
mechanism in the fact that the swelling particles were previously
compressed during the tabletting process and now return to their original
size on contact with water. In the case of the wicking mechanism, water is
drawn into the intE~rior of l:he shaped body by the disintegration accelerator
and loosens the ~~inding forces between the particles which also results in
disintegration of the shaped body. The repulsion mechanism differs
additionally in the fact that the particles released by the water drawn into
the pores repel one another under the effect of the electrical forces
generated. A totally different mechanism forms the basis of "effervescent
tablets" which contain active substances or active-substance systems
which, on contact with water, release gases that cause the shaped body to
burst. In addition, it is known to use hydrophilicizing agents which provide
for better wetting of the compressed particles in water and hence for faster
disintegration.
Whereas substances which act by the last two of the above
mentioned mechanisms can easily be distinguished from other
disintegration mechanisrns, the effects on which the swelling and
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3
deformation mechanisms and the wicking and repulsion mechanisms are
based cannot always be clearly distinguished from one another, so that
classification into hydrophilicizing agents, gas-releasing systems and
swelling disintegra~tors is rnore appropriate for practical reasons.
The first group includes, for example, polyethylene glycol sorbitan
fatty acid esters vvhile thE~ second group includes systems of weak acids
and carbonate-containing disintegrators, more particularly citric acid and/or
tartaric acid in combination with hydrogen carbonate or carbonate.
However, magne~;ium peroxide which releases oxygen with water is also
used as a disintegrator.
By far the largest group of disintegrators acts by swelling and/or
wicking. These disintegrators include, in particular, starches, celluloses
and cellulose derivatives, alginates, dextrans, crosslinked polyvinyl
pyrrolidones, gelatine, formaldehyde casein and also typically inorganic
substances, such as the various clay minerals (for example bentonite) and
Aerosil~ (silica) and certain ion exchanger resins (Amberlit~.
According iro the teaching of European patent EP-B 0 523 099,
disintegrators known from the production of pharmaceuticals may also be
used in detergenia or clE~aning products. The disintegrators mentioned
include swellable Ilayer silicates, such as bentonites, natural materials and
derivatives thereof based on starch and cellulose, alginates and the like,
potato starch, mE~thyl cellulose and/or hydroxypropyl cellulose. These
disintegrators may be mixed with, or even incorporated in, the granules to
be compressed.
According t~o International patent application WO-A-96106156 also, it
can be of advantage to incorporate disintegrators in detergent or
dishwasher tablet:;. Once again, microcrystalline cellulose, sugars, such as
sorbitol, and also layered silicates, more particularly fine-particle
swellable
layered silicates of the bentonite and smectite type, are mentioned as
typical disintegratcrrs. Substances which contribute towards gas formation,
. CA 02290014 1999-11-17
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such as citric acid, bisulfate, bicarbonate, carbonate and percarbonate, are
also mentioned a~; possiblle disintegration aids.
Although neither of the last two prior-art documents cited above
specifies the exact particle size distribution which suitable disintegrators
are supposed to have, figures relating to the microcrystallinity of the
cellulose and the particlE~ fineness of the layer silicates suggest to the
expert, above all in connection with the literature known from the
production of pharmaceutical tablets, that conventional disintegrators are
supposed to be used in fiine-particle form. This is consistent with the fact
that, hitherto, relatively coarse products obtained, for example, by
granulation of fine powders, which are expressly marketed as tablet
disintegrators, have not bE:en commercially available.
European patent applications EP-A-0 466 485, EP-A-0 522 766, EP
A-0 711 827, EP-/~-0 711 828 and EP-A-0 716 144 describe the production
of detersive tableta 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, the surfactant- and builder-containing particles at least are
coated with a solution or dispersion of a binder/disintegration aid, more
particularly polyethylene glycol. Other binders/disintegration aids are the
already repeatedly described and known disintegrating agents, 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.
Other suitable coating materials are 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 disintegrating agents. In
these cases, too, no specific details are provided as to the particle size
distribution of they disintegrators. However, they are all applied to the
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surface of granules. This is done either - as mentioned - in liquid to
disperse form or in solid Norm. It is known to the expert in this connection
that fine-particle solids, i.e~. powder-like solids, which normally also
contain
relatively high per~centagE~s of dust, can be used for coating particles with
5 particulate solids, so-called "powdering".
The proposed solutions mentioned in the foregoing produce the
required result in the production of pharmaceutical tablets. Although, in the
field of detergents and cleaning products, they contribute towards an
improvement in the disintegration properties of washing- or cleaning-active
tablets, the improvement achieved is inadequate in many cases. This
applies in particular when the percentage of tacky organic substances in
the tablets, for example anionic and/or nonionic surfactants, increases. In
addition, the use of the diisintegration aids in detersive shaped bodies can
lead to specific problem: which are entirely unknown in pharmaceutical
products.
A particular problem arises from the use of cellulose as a
disintegration aid in shaped bodies of detergents. If the primary particle
size of the cellulose is too large, the problem of residue formation on the
treated fabrics ari;>es. One dark-colored fabrics in particular, deposits of
the
comparatively large cellulose primary particles, which are released from the
disintegrator compactate in the wash liquor after the disintegration of the
shaped body, can clearly Ibe seen after drying.
As already known from pharmaceutical applications, a weak
disintegrating effect is obtained where cellulose is incorporated in the
shaped bodies solely in i:he form of a fine powder, so that disintegration
aids and cellulosE: in particular are generally incorporated in the shaped
bodies both in granular form and in powder form (cf. "Angewandte
Biopharmazie" 'Vllissen:>chaftliche Verlagsgesellschaft mbH Stuttgart,
1973, page 382). In the production of detergent shaped bodies, however,
the additional incorporation of cellulose powder has proved unnecessary
_ CA 02290014 1999-11-17
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and, in some cases, has even been found to hinder the disintegration of the
shaped bodies. To produce cellulose-based granular disintegrators,
cellulose powders with particle sizes above 150 Nm are normally
compacted to foam granules between 0.4 and 2.0 mm in size and are
tabletted in this form with the other ingredients to form detergent shaped
bodies (tablets).
To prevent residue:; being left on fabrics, it is advisable to use a finer
particle cellulose where this problem does not arise. Unfortunately, a
cellulose with primary particle sizes below 100 Nm cannot be compacted
because the granules obtained are so unstable that they disintegrate on
mixing with the other ingredients of the detergent tablets so that,
ultimately,
cellulose powder which does not have any significant disintegrating effect
of its own is incorporated in the tablets.
Accordingly, the problem addressed by the present invention was to
provide additive granules for detergent shaped bodies which, on the one
hand, would not have the residue problem, but which on the other hand
could be incorporated in granular form in the mixtures to be compressed
without losing its effective shape. Another problem addressed by the
present invention was to provide a process for the production of such
disintegrator granules for incorporation in detergent shaped bodies.
It has now been found that the stability problems of disintegrator
granules based on cellullose with particle sizes below 100 Nm can be
avoided by granulating the cellulose together with microcrystalline cellulose
or other ingredients of detergents.
In a first embodiment, therefore, the present invention relates to
additive granules for detergent shaped bodies which contain
a) 10 to 95% by weight of cellulose with particle sizes below 100 Nm
and
b) 5 to 90% by weight of microcrystalline cellulose and/or one or more
CA 02290014 1999-11-17
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ingredients of detergents.
Substances from the group of builders, bleaching agents and bleach
activators, foam inhibitors and soil-release polymers are preferably used as
the ingredients of detergents.
In the context of the present invention, additive granules are
understood to be any additives and, in particular, disintegrators which are
present per se in the form of fine-particle powders and which can be
converted into a coarser particle form by spray drying, granulation,
agglomeration, compacting, pelletizing or extrusion. They include not only
disintegrators in granular form, but for example also those in co-granulated
form.
In the contE:xt of the present invention, the terms "particle size" and
"primary particle size" are synonymous where they are used to describe the
cellulose in powdler form. The granules obtained by granulation of the
cellulose powder do of course have particle sizes which are larger than the
primary particle sire of thE: cellulose powder used. The term "particle size"
or "primary particle size" in this regard means that the corresponding
powders completely pass through a sieve with the indicated mesh width
and leave behind less than 1 % by weight of residue, based on the sieved
powder, on the sieve.
The additive granules according to the present invention have a
number of advantages which set them apart from conventional
disintegrators. Thus, there are no residue problems on laundry which has
been washed with detergent tablets containing the additive granules
according to the invention. In quantitative terms also, laundry which has
been washed with corresponding detergent tablets produces better
reflectance values and is whiter and softer compared with laundry washed
with detergent tablets containing cellulose granules of cellulose with
primary particle sizes above 150 Nm as disintegrator for otherwise the
CA 02290014 1999-11-17
8
same composition.
The cellulose present as component a) in the additive granules
according to the invention has the formal empirical composition (C6H~o05)n
and, formally, is a ~i-1,4-polyacetal of cellobiose which, in turn, is made up
of two molecules of gluco;>e. Suitable celluloses consist of ca. 500 to 5,000
glucose units and, accordingly, have average molecular weights of 50,000
to 500,000. A particle size of the cellulose before granulation of less than
100 Nm is crucial to the iinvention, primary particle sizes below 70 Nm or
below 50 Nm being preferred. According to the invention, cellulose
derivatives obtainable frorn cellulose by polymer-analog reactions may also
be used as component a;~. These chemically modified celluloses include,
for example, products of esterification or etherification reactions in which
hydroxy hydrogen atoms have been substituted. However, celluloses in
which the hydroxy groups have been replaced by functional groups that are
not attached by an oxygen atom may also be used as cellulose derivatives.
The group of cellulose derivatives includes, for example, alkali metal
celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and
aminocelluloses.
The cellulose derivatives mentioned are preferably not used as
component a) on their own, but rather in the form of a mixture with
cellulose. The content of cellulose derivatives in mixtures such as these is
preferably below ~~0% by weight and more preferably below 20% by weight,
based on component a). In a particularly preferred embodiment, pure
cellulose free from cellulose derivatives is used as component a). In
another particularly preferred embodiment, the granules contain 15 to 80%
by weight, preferably 20 to 70% by weight and more preferably 25 to 60%
by weight of cellulose with a particle size of less than 70 Nm and preferably
less than 50 Nm as component a).
The additive granules according to the invention contain
microcrystalline cellulose and/or the ingredients of detergents in quantities
CA 02290014 1999-11-17
9
of 5 to 90% by weight, based on the additive granules. These ingredients
are preferably used in quantities of 10 to 70% by weight, more preferably in
quantities of 20 to 60% by weight and most preferably in quantities of 30 to
50% by weight.
Microcrysta,lline ceNlulose may be used as sole component b) or as
part of that component. This cellulose has primary particles sizes of ca. 5
Nm and was comb>acted to granules having an average particle size of 200
Nm. These comp~actates are stable, can be mixed with other substances
without disintegrating into the primary particles and are capable in
conjunction with the fine-particle cellulose {component a)} of forming stable
additive granules which remain stable when mixed with other substances.
In this way, it is possiblle in accordance with the present invention to
produce completely cellulose-based additive granules which are not
attended by the residue (problem of conventional cellulose disintegrators.
In the wash liquor, thesE~ additive granules disintegrate into the primary
particles so that no cellulose particles larger than 100 Nm in size remain in
the wash liquor. According to the present invention, preferred additive
granules are thosE~ which contain 5 to 70% by weight, preferably 10 to 60%
by weight and more preferably 20 to 50% by weight of microcrystalline
cellulose, based on the additive granules, as component b).
The additive granules according to the invention may contain any
typical detergent ingredients as the ingredients of detergents {sole
component b) or part of component b)~, the use of auxiliaries which,
besides their function of stabilizing the cellulose-containing granules, also
perform other functions in the washing process being preferred. The
detergent ingrediE~nts present in the additive granules according to the
invention are preferably selected from the group of builders, bleaching
agents and bleach activators, foam inhibitors and soil-release polymers.
Preferred components b) from this group are the bleaching agents
and bleach activators, additive granules containing 10 to 70% by weight,
. CA 02290014 1999-11-17
preferably 20 to 60% by weight and more preferably 30 to 50% by weight of
a bleaching agent or bleach activator as component b) being preferred.
Preferred additive granules contain the bleach activator tetraacetyl
ethylenediamine (~TAED) ;~s part of component b) or as the sole ingredient
5 of component b).
The additive granules according to the invention preferably contain
no particles smaller than 0.1 mm in size (fines) and, in one preferred
embodiment, contain in alll only 0 to 5% by weight of particles with particle
sizes below 0.2 mm. At least 90% by weight of preferred granules consist
10 of particles at least 0.3 mrn to at most 2.0 mm in size.
In another embodiment, the present invention relates to a process
for the production of the additive granules according to the invention in
which
a) 10 to 95% by weight of cellulose with particle sizes below 100 Nm
and
b) 5 to 90% byy weight of microcrystalline cellulose and/or one or more
ingredients of detergents
are granulated under compacting conditions.
To this end, components a) and b) are mixed, the cellulose having to
satisfy the above-mentioned particle size criteria in view of the residue
problem whereas. component b) is not subject to any particle size
limitations. In the interest of intensive and homogeneous mixing of the two
components, howE:ver, it can be of advantage to grind component b) before
the compacting step to particle size ranges below 1 mm, more particularly
below 500 Nm and, in one particularly preferred embodiment, below 200
Nm.
The granulation process under compacting conditions may be
carried out by any of the processes known to the expert, various machines
- CA 02290014 1999-11-17
11
being suitable for carrying out the process according to the invention. In
the context of the present invention, granulation under compacting
conditions may be~ equated with such terms as granulation, agglomeration,
compacting, extrusion and pelletizing.
Suitable machines for carrying out the process according to the
invention are, for examplE~, mixers of various types such as, for example,
Series R or RV f=irich~ mixers (trade marks of Maschinenfabrik Gustav
Eirich, Hardheim), Fukae'~ FS-G mixers (trade marks of Fukae Powtech,
Kogyo Co., Japan), Lodige~ FM, KM and CB mixers (trade marks of Lodige
Maschinenbau GmbH, Paderborn) and Series T or K-T Drais~ mixers
(trade marks of Drais-Werke GmbH, Mannheim). Other suitable
granulating machines are pellet presses which, in preferred embodiments,
are used as annular die presses. Roller compacting has proved to be
particularly advanltageous and is particularly preferred for the purposes of
the invention. In i~oller compacting, the dry mixture of components a) and
b) is compacted by two contrarotating rollers to form a sheet-form
compactate which is subsequently size-reduced by grinding and sieving to
form granules with particles sizes below 2 mm.
The ingredients of detergents preferably used as component b) are
briefly described in the following, the substances from the group of builders,
bleaching agents and bleach activators, foam inhibitors and soil-release
polymers being described in that order.
Silicates, aluminiunn silicates (especially zeolites), carbonates, salts
of organic di- and polycairboxylic acids and mixtures of these substances
are mentioned in particular as builders which may be present as sole
component b) or as an ingredient of component b) in the additive granules
according to the invention and in the process for producing them.
Suitable crystalline layer-form sodium silicates correspond to the
general formula Na2MSixCI2X+~~ H20, where M is sodium or hydrogen, x is a
number of 1.9 to 4 and y is a number of 0 to 20, preferred values for x
. CA 02290014 1999-11-17
12
being 2, 3 or 4. Crystalline layer silicates such as these are described, for
example, in European K>atent application EP-A-0 164 514. Preferred
crystalline layer silicates corresponding to the above formula are those in
which M is sodium and x assumes the value 2 or 3. Both Vii- and 8-sodium
disilicates Na2Si2~J5~ y H;zO are particularly preferred, ~3-sodium disilicate
being obtainable, for example, by the process described in International
patent application WO-A- 91108171.
Other useful builders are amorphous sodium silicates with a
modulus (Na20:Si02 ratio) of 1:2 to 1:3.3, preferably 1:2 to 1:2.8 and more
preferably 1:2 to '1:2.6 which dissolve with delay and exhibit multiple wash
cycle properties. The delay in dissolution in relation to conventional
amorphous sodium silicai:es can have been obtained in various ways, for
example by surface treatrnent, compounding, compacting or by overdrying.
In the context of the invention, the term "amorphous" is also understood to
encompass "X-ray amorphous". In other words, the silicates do not
produce any of the sharp X-ray reflexes typical of crystalline substances in
X-ray diffraction experiments, but at best one or more maxima of the
scattered X-radiation which have a width of several degrees of the
diffraction angle. However, particularly good builder properties may even
be achieved where the ~;ilicate particles produce crooked or even sharp
diffraction maxima in electron diffraction experiments. This may be
interpreted to mean that the products have microcrystalline regions
between 10 and 2i few hundred nm in size, values of up to at most 50 nm
and, more particularly, up to at most 20 nm being preferred. So-called X-
ray amorphous silicates :>uch as these, which also dissolve with delay in
relation to conventional waterglasses, are described for example in
German patent application DE-A-44 00 024. Compacted amorphous
silicates, compounded amorphous silicates and overdried X-ray-amorphous
silicates are particularly preferred.
The finely crystalline, synthetic zeolite containing bound water used
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13
in accordance wii:h the invention is preferably zeolite A and/or zeolite P.
Zeolite MAP~ (Crosfield) is a particularly preferred P-type zeolite.
However, zeolite .X and rnixtures of A, X and/or P are also suitable. The
zeolite may be used as a spray-dried powder or even as an undried
suspension still moist frorn its production. If the zeolite is used in the
form
of a suspension, the suspension may contain small additions of nonionic
surfactants as stalbilizers, for example 1 to 3% by weight, based on zeolite,
of ethoxylated C~2_~8 fatty alcohols containing 2 to 5 ethylene oxide groups,
C~2-~4 fatty alcohols containing 4 to 5 ethylene oxide groups or ethoxylated
isotridecanols. Suitable zeolites have a mean particle size of less than 10
~m (volume distribution, as measured by the Coulter Counter Method) and
contain preferably 18 to 22% by weight and more preferably 20 to 22% by
weight of bound water.
The generally known phosphates may of course also be used as
builders providing their use should not be avoided on ecological grounds.
The sodium salts of the orthophosphates, the pyrophosphates and, in
particular, the tripalyphos~>hates are particularly suitable.
Useful organic buiNders are, for example, the polycarboxylic acids
usable, for example, in the form of their sodium salts, such as citric acid,
adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, amino
carboxylic acids, nitrilotriacetic acid (NTA), providing their use is not
ecologically unsafe, and rnixtures thereof. Preferred salts are the salts of
the polycarboxylic acids, such as citric acid, adipic acid, succinic acid,
glutaric acid, tartaric acid, sugar acids and mixtures thereof.
Among the compounds yielding H202 in water which serve as
bleaching agents, sodium perborate tetrahydrate and sodium perborate
monohydrate are particularly important. Other useful bleaching agents are,
for example, sodium perc;arbonate, peroxypyrophosphates, citrate perhy-
drates and H2O2-yielding peracidic salts or peracids, such as
perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or
- CA 02290014 1999-11-17
14
diperdodecane dioic acid.
In order to obtain an improved bleaching effect where washing is
carried out at temperatures of 60°C or lower, bleach activators may be
incorporated as sole component b) or as an ingredient of component b).
The bleach activators may be compounds which form aliphatic
peroxocarboxylic acids containing preferably 1 to 10 carbon atoms and
more preferably 2 to 4 carbon atoms and/or optionally substituted
perbenzoic acid under perhydrolysis conditions. Substances bearing O-
and/or N-acyl groups with the number of carbon atoms mentioned and/or
optionally substituted benzoyl groups are suitable. Preferred bleach
activators are pol~~acylated alkylenediamines, more particularly tetraacetyl
ethylenediamine I;TAED), acylated triazine derivatives, more particularly
1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycol-
urils, more particularly te~traacetyl glycoluril (TAGU), N-acylimides, more
particularly N-nonanoyl succinimide (NOSI), acylated phenol sulfonates,
more particularly n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-
NOBS), carboxylic anhydrides, more particularly phthalic anhydride,
acylated polyhydric alcohols, more particularly triacetin, ethylene glycol
diacetate and 2,5-diaceto~;y-2,5-dihydrofuran.
In addition to or instead of the conventional bleach activators
mentioned above, so-called bleach catalysts may also be incorporated in
the shaped bodies. Bleach catalysts are bleach-boosting transition metal
salts or transition metal complexes such as, for example, manganese-,
iron-, cobalt-, ruthenium- or molybdenum-salen complexes or carbonyl
complexes. Manganese, iron, cobalt, ruthenium .....titanium, vanadium
and copper complexes with nitrogen-containing tripod ligands and cobalt-,
iron-, copper- and ruthenium-ammine complexes may also be used as
bleach catalysts.
Suitable foam inhibitors - which may form part of component b) or
may be used on their own as component b) - are, for example, soaps of
- CA 02290014 1999-11-17
natural or synthetic origin which have a high percentage content Of C~g_24
fatty acids. Suitable non-surface-active foam inhibitors are, for example,
organopolysiloxanes and mixtures thereof with microfine, optionally
silanized, silica or bis-stearyl ethylenediamide. Mixtures of different foam
5 inhibitors, for exarnple mixtures of silicones, paraffins and waxes, may
also
be used with advantage. The foam inhibitors are preferably fixed to a
granular water-solluble or water-dispersible support. Mixtures of paraffins
and bis-stearyl ethylenedi,amides are particularly preferred.
In addition, the detergents according to the invention may also
10 contain components with ;a positive effect on the removability of oil and
fats
from textiles by washing (so-called soil repellents) as component b) or as
part of componeni: b). Thiis effect becomes particularly clear when a textile
which has already been repeatedly washed with a detergent according to
the invention containing 'this oil- and fat-dissolving component is soiled.
15 Preferred oil- and fat-dissolving components include, for example, nonionic
cellulose ethers, such as methyl cellulose and methyl hydroxypropyl
cellulose containing 15 to 30% by weight of methoxyl groups and 1 to 15%
by weight of hydroxypropoxyl groups, based on the nonionic cellulose
ether, and the polymers of phthalic acid and/or terephthalic acid known
from the prior arlr or derivatives thereof, more particularly polymers of
ethylene terephthalates and/or polyethylene glycol terephthalates or
anionically and/or nonionically modified derivatives thereof. Of these, the
sulfonated derivatiives of phthalic acid and terephthalic acid polymers are
particularly preferred. According to the invention, carboxymethyl starch
(CMS) may also be used as component b) or as part of component b).
In another embodiment, the present invention relates to the use of
the additive granules according to the invention for detergent shaped
bodies as disintegration accelerators in such shaped bodies, more
particularly detergent tablets.
Accordingly, the present invention also relates to detergent shaped
CA 02290014 1999-11-17
16
bodies, more particularly detergent tablets, which contain from 1 to 40% by
weight, preferably from 2.;i to 30% by weight and more preferably from 5 to
20% by weight of i:he additive granules according to the invention.
These shaped bodies are produced by mixing the detergent
granules with the other ingredients of the detergent and then compressing
the resulting mixture in dies.
The shaped bodies can be made in predetermined three-
dimensional forms and predetermined sizes. Suitable three-dimensional
forms are virtually any easy-to-handle forms including, for example, slabs
or bars, cubes, squares and corresponding three-dimensional elements
with flat sides and., more particularly, cylindrical forms with a circular or
oval
cross-section. This particular three-dimensional form encompasses tablets
and compact cylinders with a height-to-diameter ratio of more than 1.
The portioned shaped bodies may be formed as separate individual
elements which correspond to a predetermined dose of the detergent.
However, it is also possible to form shaped bodies which combine several
such units in a single shad>ed body, individual portioned units being easy to
break off in particular through the provision of predetermined weak spots.
For the use of laundry detergents in machines of the standard European
type with horizontally arranged mechanics, it can be of advantage to
produce the portioned slhaped bodies as cylindrical or square tablets,
preferably with <~ diameter-to-height ratio of about 0.5:2 to 2:0.5.
Commercially available hydraulic presses, eccentric presses and rotary
presses are particularly suitable for the production of shaped bodies such
these.
The three-dimensional form of another embodiment of the shaped
bodies according to the invention is adapted in its dimensions to the
dispensing compartment of commercially available domestic washing
machines, so that the shaped bodies can be introduced directly, i.e. without
a dosing aid, into the dispensing compartment where they dissolve on
' CA 02290014 1999-11-17
17
contact with water. However, it is of course readily possible - and preferred
in accordance with the present invention - to use the detergent shaped
bodies in conjunction with a dosing aid.
Another preferred shaped body which can be produced has a plate-
s like or slab-like structure with alternately thick long segments and thin
short
segments, so that individual segments can be broken off from this "bar" at
the predeterminecl weak spots, which the short thin segments represent,
and introduced into the machine. This "bar" principle can also be
embodied in other geometric forms, for example vertical triangles which are
only joined to one another at one of their longitudinal sides.
In another possible embodiment, however, the various components
are not compressed to form a single tablet, instead the shaped bodies
obtained comprises several layers, i.e. at least two layers. These various
layers may have different. dissolving rates. This can provide the shaped
bodies with favorable performance properties. If, for example, the shaped
bodies contain components which adversely affect one another, one
component may be integrated in the more quickly dissolving layer while the
other component rnay be incorporated in a more slowly dissolving layer so
that the first component can already have reacted off by the time the
second component dissolves. The various layers of the shaped bodies can
be arranged in the form of a stack, in which case the inner layers) dissolve
at the edges of the shaped body before the other layers have completely
dissolved. Alternatively, however, the inner layers) may also be
completely surrounded by the layers lying further to the outside which
prevents constituents of the inner layers) from dissolving prematurely.
In another preferred embodiment of the invention, a shaped body
consists of at leash three layers, i.e. two outer layers and at least one
inner
layer, a peroxy blE~aching agent being present in at least one of the inner
layers whereas, in the case of the stack-like tablet, the two cover layers
and, in the case of the envelope-like tablet, the outermost layers are free
CA 02290014 1999-11-17
18
from peroxy bleaching agent. In another possible embodiment, peroxy
bleaching agent .and arn~ bleach activators or bleach catalysts present
and/or enzymes nnay be spatially separated from one another in one and
the same shaped body. IVlultilayer shaped bodies such as these have the
advantage that thE~y can be used not only via a dispensing compartment or
via a dosing unit which is added to the wash liquor, instead it is also
possible in cases such as these to introduce the shaped body into the
machine in direct contact with the fabrics without any danger of spotting by
bleaching agent or the like.
Similar effects can also be obtained by coating individual
constituents of they detergent composition to be compressed or the shaped
body as a whole. To this end, the shaped bodies to be coated may be
sprayed, for example, with aqueous solutions or emulsions or a coating
may be obtained ~~y the process known as melt coating.
In addition 'to the additive granules according to the invention which
facilitate and accelerate the disintegration of the detergent shaped bodies,
the shaped bodies according to the invention may contain all the usual
ingredients of detergents. If additive granules according to the invention
containing certain detergent ingredients as component b) are used, there is
no need to add those ingredients during the production of the shaped body.
However, it may even be preferred to incorporate those detergent
ingredients both as component b) in the additive granules and also in the
shaped body. Besides the ingredients already mentioned as part of the
additive granules, the shaped bodies according to the invention may
contain other components. which are not introduced into the shaped body
through the additive granules. Surfactants and enzymes in particular are
mentioned as detf:rsive substances which are incorporated in the shaped
bodies.
Anionic, nonionic, cationic and/or amphoteric surfactants may be
used in the detergent shaped bodies according to the invention. From the
" CA 02290014 1999-11-17
19
performance point of view, it is preferred to use mixtures of anionic and
nonionic surfactants in which the percentage content of anionic surfactants
should be greater than that of the nonionic surfactants. The total surfactant
content of the shaped bodies is between 5 and 60% by weight, based on
the weight of the shaped body, surfactant contents of more than 15% by
weight being preferred.
Suitable anionic surfactants are, for example, those of the sulfonate
and sulfate type. Suitable surfactants of the sulfonate type are preferably
C9_~3 alkyl benzen~esulfonates, olefin sulfonates, i.e. mixtures of alkene and
hydroxyalkane sulfonates, and the disulfonates obtained, for example, from
C~2_~$ monoolefin~; with an internal or terminal double bond by sulfonation
with gaseous sulfur trioxidle and subsequent alkaline or acidic hydrolysis of
the sulfonation products. Other suitable surfactants of the sulfonate type
are the alkane sulfonates obtained from C~2_~$ alkanes, for example by
sulfochlorination or sulfoxidation and subsequent hydrolysis or
neutralization. The esters of a-sulfofatty acids (ester sulfonates), for
example the a-sulfonated methyl esters of hydrogenated coconut oil, palm
kernel oil or tallow fatty acids, are also suitable.
Other suitalble anionic surfactants are sulfonated fatty acid glycerol
esters. Fatty acid glyceroll esters in the context of the present invention
are
the monoesters, ~diesters and triesters and mixtures thereof which are
obtained where pr~~duction is carried out by esterification of a monoglycerol
with 1 to 3 moles of fatty acid or in the transesterification of triglycerides
with 0.3 to 2 moles of glycerol. Preferred sulfonated fatty acid glycerol
esters are the sulfonation products of saturated fatty acids containing 6 to
22 carbon atoms, for example caproic acid, caprylic acid, capric acid,
myristic acid, lauric; acid, palmitic acid, stearic acid or behenic acid.
Preferred alk(en)yl sulfates are the alkali metal salts and, in
particular, the sodlium salts of the sulfuric acid semiesters of C,2_~$ fatty
alcohols, for example cocofatty alcohol, tallow fatty alcohol, lauryl,
myristyl,
CA 02290014 1999-11-17
cetyl or stearyl alcohol, or C~o_2o oxoalcohols and the corresponding
semiesters of secondary alcohols with the same chain length. Other
preferred alk(en)yl sulfates are those with the chain length mentioned
which contain a synthetic, linear alkyl chain based on a petrochemical and
5 which are similar in thE~ir degradation behavior to the corresponding
compounds based on olE~ochemical raw materials. C~2_~6 alkyl sulfates,
C~2-~5 alkyl sulfates and C:~4_~5 alkyl sulfates are preferred from the point
of
view of washing technology. Other suitable anionic surfactants are 2,3-
alkyl sulfates which may be produced, for example, in accordance with US
10 3,234,258 or US 5,075,041 and which are commercially obtainable as
products of the Shell Oil Company under the name of DAN~.
The sulfuric acid rnonoesters of linear or branched C~_2~ alcohols
ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched
C9_» alcohols containing ~on average 3.5 moles of ethylene oxide (EO) or
15 C~2_~8 fatty alcohols containing 1 to 4 EO, are also suitable. In view of
their
high foaming capacity, thE~y are only used in relatively small quantities, for
example in quantii.ies of 1 to 5% by weight, in detergents.
Other preiferred anionic surfactants are the salts of alkyl
sulfosuccinic acid which are also known as sulfosuccinates or as
20 sulfosuccinic acid esters and which represent monoesters and/or diesters
of sulfosuccinic acid with alcohols, preferably fatty alcohols and, more
particularly, ethoxylated fatty alcohols. Preferred sulfosuccinates contain
C$_~8 fatty alcohol residues or mixtures thereof. Particularly preferred
sulfosuccinates contain a fatty alcohol moiety derived from ethoxylated fatty
alcohols which, considered in isolation, represent nonionic surfactants (for
a description, see below). Of these sulfosuccinates, those of which the
fatty alcohol moiE~ties arse derived from narrow-range ethoxylated fatty
alcohols are particularly preferred. Alk(en)yl succinic acid preferably
containing 8 to 18 carbon atoms in the alk(en)yl chain or salts thereof may
also be used.
- CA 02290014 1999-11-17
21
Other suitable anionic surfactants are, in particular, soaps. Suitable
soaps are saturated fatty acid soaps, such as the salts of lauric acid,
myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and
behenic acid, and soap mixtures derived in particular from natural fatty
acids, for examples coconut oil, palm kernel oil or tallow fatty acids.
The anionic; surfactants, including the soaps, may be present in the
form of their sodium, potassium or ammonium salts and as soluble salts of
organic bases, such as mono-, di- or triethanolamine. The anionic
surfactants are preferably present in the form of their sodium or potassium
salts and, more preferably, in the form of their sodium salts.
Preferred nonionic: surfactants are alkoxylated, advantageously
ethoxylated, more especially primary alcohols preferably containing 8 to 18
carbon atoms andl, on average, 1 to 12 moles of ethylene oxide (EO) per
mole of alcohol, in which the alcohol radical may be linear or, preferably,
methyl-branched in the 2-position or may contain linear and methyl-
branched radicals in the form of the mixtures typically present in oxoalcohol
radicals. However, alcohol ethoxylates containing linear radicals of
alcohols of native origin with 12 to 18 carbon atoms, for example coconut
oil, palm oil, tallow fatty or oleyl alcohol, and on average 2 to 8 EO per
mole
of alcohol are particularly preferred. Preferred ethoxylated alcohols
include, for example, C~2_~4 alcohols containing 3 EO or 4 EO, C9_» alcohol
containing 7 EO, C~3_~5 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO,
C~2_~$ alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such
as mixtures of C~2-~4 alcohol containing 3 EO and C~2_~8 alcohol containing
5 EO. The degrees of ethoxylation mentioned represent statistical mean
values which, for a special product, can be a whole number or a broken
number. Preferred alcohol ethoxylates have a narrow homolog distribution
(narrow range ethoxylates, NRE). In addition to these nonionic surfactants,
fatty alcohols coni:aining more than 12 EO may also be used, examples
including tallow fatty alcohol containing 14 EO, 25 EO, 30 EO or 40 EO.
- CA 02290014 1999-11-17
22
In addition, alkyl glycosides corresponding the general formula
RO(G)X where R is a primary, linear or methyl-branched, more particularly
2-methyl-branched, aliphatic radical containing 8 to 22 and preferably 12 to
18 carbon atoms and G stands for a glycose unit containing 5 or 6 carbon
atoms, preferably glucose, may also be used as further nonionic
surfactants. ThE: degree of oligomerization x, which indicates the
distribution of monoglycosides and oligoglycosides, is between 1 and 10
and preferably between 1.2 and 4.
Another class of preferred nonionic surfactants which may be used
either as sole nonionic surfactant or in combination with other nonionic
surfactants are alkoxylated, preferably ethoxylated or ethoxylated and
propoxylated, fatt~~ acid alkyl esters preferably containing 1 to 4 carbon
atoms in the alkyl chain, nnore especially the fatty acid methyl esters which
are described, for example, in Japanese patent application JP 581217598
or which are preferably produced by the process described in International
patent application WO-A-90113533.
Nonionic surfactants of the amine oxide type, for example N-
cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethyl-
amine oxide, and the fatfi~ acid alkanolamide type are also suitable. The
quantity in which tlhese nonionic surfactants are used is preferably no more
than the quantity in which the ethoxylated fatty alcohols are used and,
more preferably, no more 'than half that quantity.
Other suitable surfactants are polyhydroxyfatty acid amides
corresponding to f~~rmula (I):
R'
R-CO-N-[Z] (I)
in which RCO is an aliphatic acyl group containing 6 to 22 carbon atoms,
R' is hydrogen, an alkyl or hydroxyalkyl group containing 1 to 4 carbon
atoms and [Z] is a linear ~or branched polyhydroxyalkyl group containing 3
' CA 02290014 1999-11-17
23
to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxyfatty acid
amides are known sub:;tances which may normally be obtained by
reductive aminatie~n of a reducing sugar with ammonia, an alkylamine or an
alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl
ester or a fatty acid chloride.
The group of polyhydroxyfatty acid amides also includes compounds
corresponding to formula (II):
R' -O-R2
R-C O-N-[Z] ( I I )
in which R is a lirnear or branched alkyl or alkenyl group containing 7 to 12
carbon atoms, R' lis a linear, branched or cyclic alkyl group or an aryl group
containing 2 to 8 carbon atoms and R2 is a linear, branched or cyclic alkyl
group or an aryl group or an oxyalkyl group containing 1 to 8 carbon atoms,
C~~ alkyl or phenyl groups being preferred, and [ZJ is a linear polyhydroxy-
alkyl group, of whlich the alkyl chain is substituted by at least two hydroxyl
groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives
of that group.
[Z] is preferably obtained by reductive amination of a reduced sugar,
for example glucose, fructose, maltose, lactose, galactose, mannose or
xylose. The N-allcoxy- or N-aryloxy-substituted compounds may then be
converted into the required polyhydroxyfatty acid amides by reaction with
fatty acid methyl esters iin the presence of an alkoxide as catalyst, for
example in accordance with the teaching of International patent application
WO-A-95107331.
Suitable enzymes are those from the class of proteases, lipases,
amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial
strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and
Streptomyces gris~eus, area particularly suitable. Proteases of the subtilisin
type are preferred, proteases obtained from Bacillus lentus being
CA 02290014 1999-11-17
24
particularly preferred. Enzyme mixtures, for example of protease and
amylase or protease and lipase or protease and cellulase or of cellulase
and lipase or of protease, amylase and lipase or of protease, lipase and
cellulase, but especially cellulase-containing mixtures, are of particular
interest. Peroxidases or oxidases have also proved to be suitable in some
cases. The enzymes may be adsorbed to supports and/or encapsulated in
shell-forming substances i;o protect them against premature decomposition.
The percentage content of the enzymes, enzyme mixtures or enzyme
granules in the shaped bodies according to the invention may be, for
example, from about 0.1 to 10% by weight and is preferably from 0.5 to
about 5% by weight.
The shaped bodies may contain derivatives of diamino-
stilbenedisulfonic .acid or alkali metal salts thereof as optical brighteners.
Suitable optical brighteners are, for example, salts of 4,4'-bis-(2-anilino-4-
morpholino-1,3,5-triazinyl-6-amino)-stilbene-2,2'-disulfonic acid or
compounds of similar composition which contain a diethanolamino group, a
methylamino grouip, an anilino group or a 2-methoxyethylamino group
instead of the morpholino~ group. Brighteners of the substituted diphenyl
styryl type, for example alkali metal salts of 4,4'-bis-(2-sulfostyryl)-
diphenyl,
4,4'-bis-(4-chloro-~s-sulfostyryl)-diphenyl or 4-(4-chlorostyryl)-4'-(2-
sulfostyryl)-diphenyl, may also be present. Mixtures of the brighteners
mentioned above may also be used.
The invention can also make use of the fact that acidifying agents,
such as citric acid, tartaric acid or succinic acid, and also acidic salts of
inorganic acids ("hydrogen salts"), for example bisulfates, above all in
combination with carbonate-containing systems, can also contribute
towards improvinc,~ the disintegration properties of the shaped bodies.
According to the invention, however, these acidifying agents are also used
in the form of coarse particles, more particularly granules, which are
substantially free from durst and which are adapted in their particle size
CA 02290014 1999-11-17
distribution to the additive granules. The granular acidifying agents may be
present in the shaped bodies, for example, in quantities of 1 to 10% by
weight.
The shaped bodies according to the invention, more especially the
5 hitherto poorly disintegrating and poorly soluble detergent tablets and
bleach tablets, have outstanding disintegration properties through the use
of the additive granules according to the invention. A broader distribution
of the additive gr<~nules throughout the shaped body is achieved by the
compacting of thE~ disintegration aid with a detergent ingredient. The
10 improved disintegration can be tested, for example, under critical
conditions
in a normal domestic washing machine (bleach/detergent tablet used
directly in the w~~sh liquor with the aid of a conventional dispenser,
delicates program or colors program, washing temperature max. 40°C) or
in a glass beaker .at a water temperature of 25°C. The carrying out of
the
15 corresponding tesis is described in the Examples. Under these conditions,
the shaped bodies according to the invention not only disintegrate
completely in 10 minutes, the preferred embodiments have disintegration
times in the glass beaker lest of less than 3 minutes and, more particularly,
less than 2 minutEa. Particularly advantageous embodiments even have
20 disintegration times of less than 1 minute. Disintegration times of less
than
3 minutes in the glass beaker test are sufficient to ensure than the
detergent shaped bodies or detergent additive shaped bodies are flushed
into the wash liquor fronn the dispensing compartment of conventional
domestic washings machines. In another embodiment, therefore, the
25 present invention relates to a washing process in which the shaped bodies
are introduced into the wash liquor from the dispensing compartment of a
domestic washing machine. The dissolving time of the shaped bodies in
the washing machine is preferably less than 8 minutes and more preferably
less than 5 minute;.
The actual production of the shaped bodies according to the
- CA 02290014 1999-11-17
26
invention is carried out by initially dry mixing the disintegrator granules
with
the other constituents and then shaping the resulting mixture, more
particularly by compression, into tablets using conventional processes (for
example as described in the conventional patent literature on tabletting,
above all in the field of detergents of cleaners, more particularly as
described in the above-cited patent applications and in the article entitled
"Tablettierung: Stand dE~r Technik" in SOFW Journal, Vol. 122, pages
1016-1021 (1996)..
Examples
Additive granules 1, 2 and 3 according to the invention and
comparison granules 4, 5 and 6, which had the composition shown in Table
1, were produced by roller compacting and subsequent grinding and
sieving.
The comparison granules contained either an unsuitable component
a) (overly large primary particle size, Example 4), unsuitable components
b) (Example 6: ~~dditiomal effervescent system which is not a typical
ingredient of detergents) or no component b) at all (Example 5).
In the case of Comparison Example 5, stable granules could not be
obtained. Even before the tabletting process, the "granules" obtained
disintegrated into the primary particles when mixed with the other
ingredients. In another comparison, non-granulated cellulose in the form of
a fine powder (~i0 pm), which produced completely the same tablet
hardness and disintegration time values (Table 3) as comparison granules
5, were used from the outset.
CA 02290014 1999-11-17
27
Table 1:
Additive granules [% by weight]
Additive granules 1 2 3 4 5 6
Cellulose (primary particle80% 50% 40% 100% 40%
size 50 Nm)
Cellulose (primary particle 100%
size 150 Nm)
Granules of microcr. cellulose 50% 10% 10%
(FMC)
NaHC03 28.2%
Citric acid, water-free 21.8%
Carboxymethyl starch 20%
TAED 50%
The additive granules produced in this way were mixed with other
components to form a detergent, a powder with the following composition
being used as the basic granules:
Table 2:
Basic granules [% by weight]
Quantity
Cs-~3 Alkyl benzernesulfonate 15.4
C13-15 Oxoalcohol ~ 3 to 7 EO 7.9
Soap 1.0
Optical brightener 0.2
Sodium carbonate 13.9
Sodium silicate 4.3
Co-builder H40 4.9
HEDP 0.6
Zeolite A (water-free active 25.5
substance)
Na perborate monohydrate 18.3
Water 8.0
CA 02290014 1999-11-17
28
Co-builder H40 i:~ an acrylic acid/maleic acid copolymer available from
Stockhausen.
HEDP is the sodium salt of hydroxyethane-1,1-diphosphonic acid.
The mixed detergEmts were then tabletted in a tablet press. The
hardness of the tablets was measured by deforming a tablet until it broke,
the force being applied to the sides of the tablet and the maximum force
which the tablet wlithstood being determined.
To determine tablE~t disintegration, a tablet was placed in a glass
beaker filled with water (600 ml water, temperature 25°C) and the time
which the tablet took to di;>integrate completely was measured.
The composition of the tablets and the experimental data are shown
in Table 3 below:
Table 3:
Detergent tablets ;composition in % by weight]
Tablet Ex.1 Ex.2 Ex.3 Ex.4 Ex.5 Ex.6
Additive 5% 4% 10% 4% 4% 8%
Basic granules 81.25%~82.25% 81.25% 82.25% 82.25% 78.25%
Enzyme 2.5% 2.5% 2.5% 2.5% 2.5% 2.5%
TAED 7% 7% 2% 7% 7% 7%
Foam inhibitor 3.5% 3.5% 3.5% 3.5% 3.5% 3.5%
Soil-release 0.75% 0.75% 0.75% 0.75% 0.75% 0.75%
polymer
Tablet hardness33 N 20 N 30-35 30-35 25 N 25 N
N N
Tablet disintegration20 sec:..58 sets.5-10 5-10 >5 mins.>5 mins.
sets. sets.
Comparison Example 4 produces results comparable with Examples
1, 2 and 3 according to the invention both in regard to tablet hardness and
CA 02290014 1999-11-17
29
in regard to disintegration time. To demonstrate the superiority of the
additive granules according to the invention in detergent shaped bodies,
the following washing test, were carried out:
Two 40 g tablets uvere placed in the dispensing compartment of a
washing machine. The machine was loaded with 3.5 kg of dark blue terry
towels and operated under the following conditions: tap water with a
hardness of 23°d (equivalent to 230 mg Ca0/I), washing temperature
60°C,
liquor ratio (kg washing : liter wash liquor in the main wash cycle) 1:5.7,
three rinses with tap water, spinning and drying. After 10 washes, the dried
towels were evaluated according to the following criteria:
score 1: satisfactory, no discernible residues
score 2: acceptable, iisolated, harmless residues
score 3: discE~rnible rasidues problematical on critical evaluation
score 4: clearly discernible and problematical residues in an increas-
ing number and quantity
In addition, the dispensing compartment was opened after the wash
process and visually evaluated with the following results:
score 1: satisfactory, no discernible residues, completely flushed in
score 2: acceptable, isolated, harmless residues, very finely distri-
buted
score 3: discernible residues problematical on critical evaluation
score 4: clearly discernible and problematical residues in an increas-
ing number <~nd quantity, agglomeration and lump formation
The individual detergent tablets were evaluated as follows:
CA 02290014 1999-11-17
Table 4:
Visual evaluation of residuie behavior
Tablet 1 2 3 4 5 6
Dried towel 2 2 2 5
Dispensing compartment1 1 1 1 >10 >10
Tota l 3 3 ( 3 6 > 10 > 10
Tablets 1, 2 and 3 according to the invention produce the best
residue results through the use of the fine-particle cellulose in conjunction
with very good tablet disintegration (see Table 3). Comparison Example 4,
which is also characterized by a good disintegration rate (see Table 3),
does not perform nearly as well as a result of the use of the cellulose with a
primary particle sire of 150 Nm. The cellulose residues on the towels can
clearly be seen as problematical residues.
*) Due to their extremely long disintegration times, tablets 5 and 6 do
not disintegrate in the dish>ensing compartment and cannot be flushed into
the wash procesa from the dispensing compartment of the washing
machine. After the washing process, the tablets are still present almost
intact in the dispensing compartment, with the result that no residues can
be seen on the washed to~nrels.
