Note: Descriptions are shown in the official language in which they were submitted.
CA 02293969 2000-O1-OS
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Additive Granules for Detersive Shaped Bodies
Field of the Invention
This invention relates generally to disintegrating aids for compact
shaped bodies having detersive properties. More particularly, the invention
relates to so-called disintegrator granules for use in detersive shaped
bodies such as, for example, laundry detergent tablets, dishwasher tablets,
stain remover tablets or water softening tablets for use in the home, more
particularly, in machines.
Background of the Invention
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 transportation. As a result, detergent shaped bodies are
also comprehensively 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 compressing 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.
According to the teaching of European patent EP-B-0 523 099, the
disintegrators known from the production of phamaceuticals are also
suitable for use in detergents. The disintegrators mentioned include
swellable layer silicates, such as bentonites, starch- and cellulose-based
natural materials and derivatives thereof, alginates and the like, potato
starch, methyl cellulose and/or hydroxypropyl cellulose. These
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disintegrators may be mixed with, or even incorporated in, the granules to
be compressed.
According to International patent application WO-A-96106156 also, it
can be of advantage to incorporate disintegrators in detergent or
dishwasher tablets. Microcrystalline cellulose, sugars, such as sorbitol,
and also layer silicates, more particularly fine-particle swellable layered
silicates of the bentonite and smectite type, are again mentioned as typical
disintegrators. Substances which contribute towards gas formation, such
as citric acid, bisulfate, bicarbonate, carbonate and percarbonate, are also
mentioned as possible 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 fine-particle form.
According to EP-A-0 711 827, the use of particles consisting
predominantly of citrate, which has a certain solubility in water, also leads
as a secondary effect to accelerated disintegration of the tablets. It is
assumed that the dissolution of the citrate locally increases the ion strength
over a transitional period so that the gelling of surfactants is suppressed
and, as a result, the disintegration of the tablet is not impeded. According
to this patent application, therefore, citrate is not a disintegrating agent
in
the accepted sense, but acts as an anti-gelling agent.
The proposed solutions mentioned above produce the required
result in the production of pharmaceutical tablets. Although, in the field of
detergents, they lead to an improvement in the disintegration properties of
detersive tablets, the improvement achieved is inadequate in many cases.
In addition, the use of the disintegrators in detersive shaped bodies leads
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to specific problems which are entirely unknown in the case of
pharmaceuticals.
One particular problem arises out of the use of cellulose as a
disintegration aid in detersive tablets. If the primary particle size of the
cellulose is too large, residues of cellulose are left on the treated
textiles.
With dark-colored textiles in particular, deposits of the comparatively large
primary cellulose particles, which are released in the wash liquor from the
disintegrator compactate after disintegration of the shaped body, are
clearly visible after drying. In order to avoid the formation of residues on
textiles, it is advisable to use a finer-particle cellulose which does not
create any of these problems. However, even fine-particle celluloses can
only be incorporated in certain quantities because otherwise visible
residues are left on the textiles.
Accordingly, the problem addressed by the present invention was to
provide additive granules for detersive shaped bodies which, on the one
hand, would not be attended by the residue problem, but which on the
other hand could be incorporated in granular form in the mixtures to be
compressed without losing their effective shape. Compared with the
disintegrators described in the prior art, effectiveness would be further
improved for the same amount of cellulose so that the detergent shaped
bodies containing the additive granules could be dosed via the dispensing
compartment of domestic washing machines. In addition, it would be
possible by virtue of the invention either to reduce the percentage content
of cellulose or cellulose-containing disintegration aids or to dispense with
them altogether. Accordingly, the disintegration aid to be provided by the
invention would be substantially free or even completely free from
cellulose. Another problem addressed by the invention was to provide a
process for the production of such disintegrator granules for incorporation
in detergent shaped bodies.
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Summary of the Invention
Additive granules which support conventional cellulose-based
disintegration aids in their disintegrating effect, but which themselves may
be cellulose-free, have now been found.
In a first embodiment, therefore, the present invention relates to
additive granules for detersive shaped bodies which are characterized by a
content of
a) 50 to 99% by weight of one or more polymers having a molecular
weight of at least 1000 gmole)' and
b) 1 to 50% by weight of one or more solubilizers having a solubility of
more than 200 g per liter of water at 20°C and/or one or more sub-
stances having an oil adsorption capacity of more than 20 g per 100 g.
Detailed Description of the Invention
In the context of the present invention additive granules are
understood to be any auxiliaries and, more particularly, disintegrators
which are present per se in fine-particle powder form and which have been
converted into a coarser particle form by a spray drying, granulation,
agglomeration, compacting, pelleting or extrusion process.
The additive granules according to the present invention have a
number of advantages which set them apart from conventional
disintegrators. Thus, they may be formulated, if required, entirely free from
cellulose so that residue problems on laundry washed with detergent
shaped bodies containing the additive granules according to the invention
are not in evidence. In combination with conventional cellulose-containing
disintegration aids, they support them in their disintegrating effect and lead
to improved disintegration of tablets without further increasing the cellulose
content of the tablets.
The additive granules according to the invention contain as
component a) one or more polymers having molecular weights of at least
CA 02293969 2000-O1-OS
1000 gmole)'. In the context of the present invention, the expression
"polymer" characterizes products which consist of a group of
macromolecules (polymer molecules) which, although chemically uniform,
generally differ from one another in regard to their degree of
5 polymerization/molecular weight/chain length. Polymers in the context of
the present invention may be regarded as substances made up of
molecules in which one type or several types of atoms or groups of atoms
are repeatedly strung together. The polymers suitable for use as
component a) in accordance with the invention may be of natural or
synthetic origin. Natural polymers are naturally occurring polymers
including, for example, polysaccharides, such as cellulose, galacto-
mannans and starch, and proteins, nucleic acids, lignins and natural
rubber. Since the problem addressed by the present invention was to
provide substantially or completely cellulose-free additive granules, the use
of cellulose and cellulose derivatives is undesirable for the purposes of the
present invention. Overall, the synthetic polymers are distinctly preferred
to the natural polymers, so that preferred additive granules are free from
natural polymers.
Synthetic polymers are industrially produced from smaller molecules
by polymerization, polyaddition or polycondensation reactions. Examples
of such synthetic polymers are polyethylene, polypropylene, polybutylene,
etc., polyvinyl alcohols, polyvinyl acetates, polyacrylic acids, polyvinyl
pyrrolidones and any other polymerization products of compounds
containing ethylenically unsaturated groups in the molecule. The most
important polymers produced by polyaddition are the polyurethanes and
the polyureas while the most important polycondensates are polyamides,
polyimides, polyesters, polycarbonates, aminoplastics, phenolics,
polysulfides or urea resins.
According to the present invention, water-soluble or swellable and
water-dispersible polymers are distinctly preferred to totally insoluble
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polymers, such as PVC for example, as component a).
The percentage content of component a) in the additive granules
according to the invention is in the range from 60 to 95% by weight,
preferably in the range from 65 to 90% by weight and more preferably in
the range from 70 to 85% by weight. In another preferred embodiment, the
molecular weight of the polymers used is above the lower limit mentioned
above, so that preferred additive granules are those in which the
polymers) has/have a molecular weight of at least 5000 gmole)',
preferably of at least 10,000 gmole)' and, more preferably, of at least
25,000 gmole)'.
Particularly preferred components a) are polymeric polycarboxy-
lates, more particularly the homopolymers and copolymers of acrylic acid
which are often collectively referred to as "polyacrylates".
Examples of such components are the alkali metal salts of
polyacrylic acid or polymethacrylic acid, for example those having a relative
molecular weight of 5000 to 70,000 gmole.
The molecular weights mentioned for polymeric polycarboxylates in
the context of the present invention are weight average molecular weights
MW of the particular acid form which, basically, were determined by gel
permeation chromatography (GPC) using a UV detector. The measure-
ment was made against an external polyacrylic acid standard which gives
realistic molecular weight values by virtue of its structural relationship to
the
polymers investigated. These data differ distinctly from the molecular
weight data where polystyrene sulfonic acids are used as standard. The
molecular weights measured against polystyrene sulfonic acids are
generally far higher than the molecular weights mentioned in this
specification.
Suitable polymers are, in particular, polyacrylates which preferably
have a molecular weight of 2000 to 20,000 gmole. By virtue of their
superior solubility, short-chain polyacrylates which have molecular weights
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of 2000 to 10,000 gmole and, more preferably, 3000 to 5000 gmole are
preferred within this group.
Copolymeric polycarboxylates, particularly those of acrylic acid with
methacrylic acid and those of acrylic acid or methacrylic with malefic acid,
are also suitable. Copolymers of acrylic acid with malefic acid which
contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of
malefic acid have proved to be particularly suitable. Their relative molecular
weight, based on free acids, is generally in the range from 2000 to 70,000
g/mole, preferably in the range from 20,000 to 50,000 gmole and more
preferably in the range from 30,000 to 40,000 gmole.
To improve their solubility in water, the polymers may also contain
allyl sulfonic acids, for example allyloxybenzenesulfonic acid, and methallyl
sulfonic acid as monomer. Biodegradable polymers of more than two
different monomer units, for example those which contain salts of acrylic
acid and malefic acid and also vinyl alcohol or vinyl alcohol derivatives as
monomers or those which contain salts of acrylic acid and 2-alkylallyl
sulfonic acid and sugar derivatives as monomer, are also particularly
preferred.
Other preferred copolymers are those which preferably contain
acrolein and acrylic acid/acrylic acid salts or acrolein and vinyl acetate as
monomers.
Another group of polymers which may advantageously be used as
component a) in accordance with the present invention are the polyvinyl
pyrrolidones [poly(1-vinyl-2-pyrrolidinones)] which are referred in short as
PVPs and which have the following general formula:
CH-CH2
N
~O
n
CA 02293969 2000-O1-OS
They are produced by radical polymerization of 1-vinyl pyrrolidone
by solution or suspension polymerization using radical formers as initiators.
The ionic polymerization of the monomers only gives products with low
molecular weights. Commercial polyvinyl pyrrolidones have molecular
weights of about 2500 to 750,000 g/mole. They are marketed as white
hygroscopic powders or as aqueous solutions. Polyvinyl pyrrolidones are
readily soluble in water and in a number of organic solvents. The
crosslinked polyvinyl pyrrolidones insoluble in water and in all other
solvents (abbreviation: crospovidon, formerly: polyvinyl pyrrolidone, PVPP),
which are formed as so-called popcorn polymers by heating vinyl
pyrrolidone with alkalis or divinyl compounds, may also be used for the
purposes of the present invention.
Preferred additive granules are characterized in that homopolymers
and copolymers of acrylic acid, preferably copolymers of acrylic acid with
methacrylic acid and of acrylic acid or methacrylic acid with malefic acid,
more especially copolymers of acrylic acid with malefic acid containing 50 to
90% by weight of acrylic acid and 50 to 10% by weight of malefic acid, and
polyvinyl pyrrolidones are used as polymers.
The additive granules according to the invention contain as their
second component 1 to 50% by weight of one or more solubilizers having a
solubility of more than 200 g per liter of water at 20°C and/or one or
more
substances having an oil absorption capacity of more than 20 g per 100 g.
The solubilizers suitable for use as component b) in the additive
granules in accordance with the present invention have solubilities above
200 grams of solubilizer in 1 liter of deionized water at 20°C.
According to
the invention, suitable solubilizers are various compounds which may
emanate both from the group of covalent compounds and from the group of
salts. The solubilizers preferably have even higher solubilities so that
preferred additive granules are those in which one or more solubilizers
having a solubility of more than 250 g per liter of water at 20°C,
preferably
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of more than 300 g per liter of water at 20°C and, more preferably, of
more
than 350 g per liter of water at 20°C is/are present as component b).
Solubilizers suitable for the purposes of the present invention are listed
below. The solubilities listed in this Table are the values at 20°C,
unless
other temperatures are explicitly mentioned:
Sodium carbonate monohydrate 210 g/I
_ 210 g/I
Sodium carbonate decahydrate
Lactose monohydrate (25C) 216 g/I
Disodium hydrogen phosphate dodecahydrate 218 g/I
Potassium dihydrogen phosphate 222 g/I
Potassium hydrogen carbonate 224 g/I
Sodium dithionite 224 g/I
Fumaric acid disodium salt (25C) 228 g/I
Calcium levulinate 250 g/I
Glycine (25C) 250 g/I
Potassium monopersulfate 256 g/I
Trisodium phosphate dodecahydrate 258 g/I
Ammonium iron(II) sulfate hexahydrate 269 g/I
Magnesium sulfate 269 g/I
Potassium hexacyanoferrate(II) trihydrate 270 g/I
(12C)
Disodium tartrate dehydrate 290 g/I
Calcium acetate hydrate 300 g/I
Potassium hexacyanoferrate(III) 315 g/I
Potassium nitrate 320 g/I
Manganese(II) acetate tetrahydrate 330 g/I
L(+) ascorbic acid 333 g/I
Potassium chloride 340 g/I
Lithium sulfate monohydrate 340 g/I
Zinc sulfate monohydrate 350 g/I
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Dipotassium oxalate monohydrate 360 g/I
Sodium chloride 360 g/I
L-(-)-malic acid 363 g/I
Sodium bromate 364 g/I
Ammonium chloride 370 g/I
Ammonium dihydrogen phosphate 370 g/I
Iron(II) sulfate heptahydrate 400 g/I
Sodium azide (17C) 417 g/I
L-lysine monohydrochloride 420 g/I
Magnesium nitrate hexahydrate 420 g/I
Zinc acetate dihydrate 430 g/I
Potassium hydrogen sulfate 490 g/I
Sodium acetate 490 g/I
Sodium sulfite (40C) 495 g/I
Magnesium perchlorate hydrate (25C) 500 g/I
Lithium nitrate 522 g/I
~-alanine (25C) 545 g/I
L-(-)-sorbose (17C) 550 g/I
Sodium peroxodisulfate 556 g/I
Sodium thiocyanate 570 g/I
Ammonium peroxodisulfate 582 g/I
Gluconic acid sodium salt (25C) 590 g/I
Ammonium bromide 598 g/1
Aluminium sulfate-18-hydrate 600 g/I
Aluminium sulfate hydrate (16-18 H20) 600 g/I
Potassium sodium tartrate tetrahydrate 630 g/I
Potassium bromide 650 g/I
Sodium hydrogen sulfate monohydrate 670 g/I
D(+)-galactose (25C) 680 g/I
Sodium thiosulfate pentahydrate 680 g/I
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Diammonium hydrogen phosphate 690 g/I
Magnesium sulfate heptahydrate 710 g/I
Calcium chloride 740 g/I
Trilithium citrate tetrahydrate (25C) 745 g/I
Ammonium sulfate 760 g/1
Manganese(II) sulfate monohydrate 762 g/I
Malefic acid (25C) 788 g/I
Ammonium carbamate 790 g/I
Sodium bromide 790 g/I
D(+) glucose monohydrate (25C) 820 g/I
Lithium chloride 820 g/I
Sodium formate 820 g/I
Saccharin sodium salt hydrate 830 g/I
Sodium nitrate 880 g/I
Tripotassium phosphate heptahydrate 900 g/I
Sodium sulfate decahydrate 900 g/I
Iron(III) chloride 920 g/I
Iron(III) chloride hexahydrate 920 g/I
Trisodium citrate-5,5-hydrate (25C) 920 g/I
Zinc sulfate heptahydrate 960 g/I
Ammonium carbonate 1000 g/I
Calcium chloride dehydrate 1000 g/I
Sodium chlorate 1000 g/I
Sodium polyphosphate 1000 g/I
Sodium salicylate 1000 g/I
Resorcinol 1000 g/I
Urea 1080 g/I
Sodium hydroxide 1090 g/I
Sodium dihydrogen phosphate monohydrate 1103 g/I
Potassium hydroxide 1120 g/I
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Ammonium nitrate 1183 g/I
Sodium acetate trihydrate 1190 g/I
Ammonium iron(III) citrate 1200 g/I
Manganese(II) chloride dehydrate 1200 g/I
Ammonium iron(III) sulfate dodecahydrate (25C)1240 g/I
Potassium iodide 1270 g/I
Malonic acid 1390 g/I
Manganese(II) chloride 1400 g/I
DL-malic acid (26C) 1440 g/I
Ammonium acetate 1480 g/I
Iron(II) chloride tetrahydrate (10C) 1600 g/I
Dipotassium hydrogen phosphate 1600 g/I
Citric acid monohydrate 1630 g/I
Ammonium thiocyanate (19C) 1650 g/I
Tripotassium citrate monohydrate (25C) 1670 g/I
Magnesium chloride hexahydrate 1670 g/I
Ammonium iodide 1700 g/I
Caesium sulfate 1790 g/I
Sodium iodide 1790 g/I
Caesium chloride 1800 g/I
Zinc nitrate hexahydrate 1800 g/I
Zinc nitrate tetrahydrate 1800 g/I
Ammonium amidosulfonate 1950 g/I
Sucrose (15C) 1970 g/I
Manganese(II) chloride tetrahydrate 1980 g/I
Dipotassium tartrate hemihydrate 2000 g/I
Sodium perchlorate monohydrate (15C) 2090 g/I
Potassium thiocyanate 2170 g/I
D(+)-mannose (17C) 2480 g/I
Melibiose monohydrate (25C) 2500 g/I
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Potassium acetate 2530 g/I
Caesium carbonate 2615 g/I
Zinc chloride 3680 g/I
D(-)-fructose 3750 g/I
Manganese(II) nitrate tetrahydrate 3800 g/I
Zinc iodide 4500 g/I
Calcium chloride hexahydrate 5360 g/I
In one preferred embodiment of the present invention, component b)
does not emanate from the groups of builders, bleaching agents and
bleach activators, foam inhibitors and soil release polymers.
In one particularly preferred embodiment, component b) is not a
typical ingredient of detergents. According to the invention, the following
substances are preferred as solubilizers (component b)):
Lactose monohydrate (25C) 216 g/I
Sodium dithionite 224 g/I
Fumaric acid disodium salt (25C) 228 g/I
Calcium levulinate 250 g/I
Glycine (25C) 250 g/I
Potassium monopersulfate 256 g/I
Ammonium iron(II) sulfate hexahydrate 269 g/I
Magnesium sulfate 269 g/I
Potassium hexacyanoferrate(III) trihydrate 270 g/I
(12C)
Disodium tartrate dehydrate 290 g/I
Calcium acetate hydrate 300 g/I
Potassium hexacyanoferrate(III) 315 g/I
Potassium nitrate 320 g/I
Manganese(II) acetate tetrahydrate 330 g/I
L(+) ascorbic acid 333 g/I
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Potassium chloride - 340 g/I
Lithium sulfate monohydrate 340 g/I
Zinc sulfate monohydrate 350 g/I
Dipotassium oxalate monohydrate 360 g/I
Sodium chloride 360 g/I
L-(-)-malic acid 363 g/I
Sodium bromate 364 g/I
Ammonium chloride 370 g/I
Ammonium dihydrogen phosphate 370 g/I
Iron(II) sulfate heptahydrate 400 g/I
Sodium azide (17C) 417 g/I
L-lysine monohydrochloride 420 g/I
Magnesium nitrate hexahydrate 420 g/I
Zinc acetate dehydrate 430 g/I
Potassium hydrogen sulfate 490 g/I
Sodium acetate 490 g/I
Sodium sulfite (40C) 495 g/I
Magnesium perchlorate hydrate (25C) 500 g/I
Lithium nitrate 522 g/I
~3-alanine (25C) 545 g/I
L(-)-sorbose (17C) 550 g/I
Sodium peroxodisulfate 556 g/I
Sodium thiocyanate 570 g/I
Ammonium peroxodisulfate 582 g/I
Gluconic acid sodium salt (25C) 590 g/I
Ammonium bromide 598 g/I
Aluminium sulfate-18-hydrate 600 g/I
Aluminium sulfate hydrate (16-18 H20) 600 g/I
Potassium sodium tartrate tetrahydrate 630 g/I
Potassium bromide 650 g/I
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Sodium hydrogen sulfate monohydrate 670 g/I
D(+) galactose (25C) 680 g/I
Sodium thiosulfate pentahydrate 680 g/I
Diammonium hydrogen phosphate 690 g/I
Magnesium sulfate heptahydrate 710 g/I
Calcium chloride 740 g/I
Trilithium citrate tetrahydrate 925C) 745 g/I
Ammonium sulfate 760 g/I
Manganese(II) sulfate monohydrate 762 g/I
Malefic acid (25C) 788 g/I
Ammonium carbamate 790 g/I
Sodium bromide 790 g/I
D(+) glucose monohydrate (25C) 820 g/I
Lithium chloride 820 g/I
Sodium formate 820 g/I
Saccharin sodium salt hydrate 830 g/I
Sodium nitrate 880 g/I
Iron(III) chloride 920 g/I
Iron (III) chloride hexahydrate 920 g/I
Zinc sulfate heptahydrate 960 g/I
Ammonium carbonate 1000 g/I
Calcium chloride dehydrate 1000 g/I
Sodium chlorate 1000 g/I
Sodium salicylate 1000 g/I
Resorcinol 1000 g/I
Urea 1080 g/I
Sodium hydroxide 1090 g/I
Potassium hydroxide 1120 g/I
Ammonium nitrate 1183 g/I
Sodium acetate trihydrate 1190 g/I
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Ammonium iron(III) citrate 1200 g/I
Manganese(II) chloride dihydrate 1200 g/I
Ammonium iron(III) sulfate dodecahydrate (25C)1240 g/I
Potassium iodide 1270 g/I
Malonic acid 1390 g/I
Manganese(II) chloride 1400 g/I
DL-malic acid (26C) 1440 g/I
Ammonium acetate 1480 g/I
Iron(II) chloride tetrahydrate (10C) 1600 g/I
Ammonium thiocyanate (19C) 1650 g/I
Magnesium chloride hexahydrate 1670 g/I
Ammonium iodide 1700 g/1
Caesium sulfate 1790 g/I
Sodium iodide 1790 g/I
Caesium chloride 1800 g/I
Zinc nitrate hexahydrate 1800 g/I
Zinc nitrate tetrahydrate 1800 g/I
Ammonium amidosulfonate 1950 g/I
Sucrose (15C) 1970 g/I
Manganese(II) chloride tetrahydrate 1980 g/I
Dipotassium tartrate hemihydrate 2000 g/I
Sodium perchlorate monohydrate (15C) 2090 g/I
Potassium thiocyanate 2170 g/I
D(+) mannose (17C) 2480 g/I
Melibiose monohydrate (25C) 2500 g/I
Potassium acetate 2530 g/I
Caesium carbonate 2615 g/I
Zinc chloride 3680 g/I
D(-) fructose 3750 g/I
Manganese(II) nitrate tetrahydrate 3800 g/I
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Zinc iodide 4500 g/I
Calcium chloride hexahydrate 5360 g/I
According to the invention, substances which have oil adsorption
capacities above 20 grams per 100 g may also be used in addition to or
instead of the solubilizers as component b) in the additive granules. The oil
adsorption capacity is a physical property of a substance which can be
measured by standardized methods. For example, British Standards BS
1795 and BS 3483: Part B7: 1092, which both refer to ISO 78715, are
available. In these test methods, a weighed sample of the particular
substance is applied to a dish and refined linseed oil (density: 0:93 gcm)3)
is added dropwise from a burette. After each addition, the powder is
intensively mixed with the oil using a spatula, the addition of oil being
continued until a paste of flexible consistency is obtained. This paste
should flow without crumbling. Now, the oil adsorption capacity is the
quantity of oil added dropwise, based on 100 g of adsorbent, and is
expressed in ml/100 g or g/100 g, conversions via the density of the linseed
oil readily being possible. According to the invention, various compounds
which may emanate both from the group of covalent compounds and from
the group of salts may be used as component b) or as an addition thereto.
The powder-form components preferaby have even higher oil adsorption
capacities, so that preferred additive granules are those in which one or
more substances(s) with an oil adsorption capacity of more than 25 g per
100 g, preferably more than 30 g per 100 g and more preferably more than
35 g per 100 g is/are present as component b). Examples of suitable sub-
stances are silicates, aluminium silicates and silicas.
Even in cases where substances having high oil adsorption
capacities are used, component b) preferably does not emanate from the
groups of builders, bleaching agents and bleach activators, foam inhibitors
and soil release polymers. In a particularly preferred embodiment,
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component b) is not a typical ingredient of detergents. According to the
invention, preferred substances having high oil adsorption capacities
suitable for use as component b) are, for example, silicon dioxide, more
particularly in the form of precipitated silica, silicates and aluminium
silicates which have little, if any, building effect and which, accordingly,
do
not count as builders.
In preferred additive granules, both substances of high solubility and
substances having a high oil adsorption capacity are used, so that
preferred additive granules are those in which one or more solubilizers
having a solubility of more than 250 g per liter of water at 20°C,
preferably
more than 300 g per liter of water at 20°C and, more preferably, more
than
350 g per liter of water at 20°C and one or more substances having an
oil
adsorption capacity of more than 25 g per 100 g, preferably more than 30 g
per 100 g and, more preferably, more than 35 g per 100 g are present as
component b).
Preferred additive granules contain component b) in quantities of 2
to 40% by weight, preferably 5 to 30% by weight and more preferably 10 to
25% by weight, based on the additive granules.
The additive granules according to the invention are preferably fine
particles. Particularly preferred additive granules are characterized in that
at least 50% by weight, preferably at least 60% by weight and more
preferably at least 70% by weight of the granules have particle sizes below
600 Nm.
In another embodiment, the present invention relates to a process
for the production of additive granules for detersive shaped bodies in which
a) 50 to 99% by weight of one or more polymers having a molecular
weight of at least 1000 gmole)' and
b) 1 to 50% by weight of one or more solubilizers having a solubility of
more than 200 g per liter of water at 20°C and/or one or more sub-
CA 02293969 2000-O1-OS
19
stances having an oil adsorption capacity of more than 20 g per 100 g
are granulated.
Granulation may be carried out by any of the processes familiar to
the expert, various machines being suitable for carrying out the process
according to the invention. In the context of the present invention,
granulation may be equated with such terms as fluidized-bed granulation,
agglomeration, compacting, extrusion and pelleting.
The foregoing observations on the additive granules according to
the invention apply equally to preferred embodiments of the process
according to the invention. Thus, preferred processes are those in which
polyvinyl pyrrolidones or homopolymers and copolymers of acrylic acid,
preferably copolymers of acrylic acid with methacrylic acid and of acrylic
acid or methacrylic acid with malefic acid, more particularly copolymers of
acrylic acid with malefic acid containing 50 to 90% by weight of acrylic and
50 to 10% by weight of malefic acid, which preferably have a molecular
weight of at least 5000 gmole)', more preferably of at least 10,000 gmole)'
and, most preferably, of at least 25,000 gmole)', are used as component a)
and one or more solubilizers with a solubility of more than 250 g per liter of
water at 20°C, preferably more than 300 g per liter of water at
20°C and,
more preferably, more than 350 g per liter of water at 20°C and/or one
or
more substances with an oil adsorption capacity of more than 25 g per 100
g, preferably more than 30 g per 100 g and, more preferably, more than 35
g per 100 g is/are used as component b).
In another embodiment, the present invention relates to the use of
additive granules for detergent shaped bodies as disintegration
accelerators in such shaped bodies, more particularly in detergent tablets.
Accordingly, the present invention also relates to detersive shaped
bodies, more particularly detergent tablets, which contain from 1 to 40% by
weight, preferably from 2.5 to 30% by weight and more preferably from 5 to
CA 02293969 2000-O1-OS
20% by weight of the additive granules according to the invention.
These shaped bodies are produced by mixing the additive granules
with the other ingredients of the detergent and then compressing the
resulting mixture in dies.
5 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
10 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
15 such units in a single shaped 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 shaped bodies as cylindrical or square tablets,
20 preferably with a 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
as 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
contact with water. However, it is of course readily possible - and preferred
in accordance with the present invention - to use the detergent shaped
CA 02293969 2000-O1-OS
21
bodies in conjunction with a dosing aid.
Another preferred shaped body which can be produced has a plate-
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 predetermined 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 comprise 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 may 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 outer 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 least three layers, i.e. two outer layers and at least one
inner
layer, a peroxy bleaching 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
from peroxy bleaching agent. In another possible embodiment, peroxy
bleaching agent and any bleach activators or bleach catalysts present
CA 02293969 2000-O1-OS
22
and/or enzymes may be spatially separated from one another in one and
the same shaped body. Multilayer shaped bodies such as these have the
advantage that they 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 the 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 by 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 detersive 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
performance point of view, it is preferred to use mixtures of anionic and
nonionic surfactants in which the percentage content of anionic surfactants
CA 02293969 2000-O1-OS
23
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
Cs-13 alkyl benzenesulfonates, olefin sulfonates, i.e. mixtures of alkene and
hydroxyalkane sulfonates, and the disulfonates obtained, for example, from
C~2_~a monoolefins with an internal or terminal double bond by sulfonation
with gaseous sulfur trioxide 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 suitable anionic surfactants are sulfonated fatty acid glycerol
esters. Fatty acid glycerol esters in the context of the present invention are
the monoesters, diesters and triesters and mixtures thereof which are
obtained where production 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 sodium salts of the sulfuric acid semiesters of C~2_~a fatty
alcohols, for example cocofatty alcohol, tallow fatty alcohol, lauryl,
myristyl,
cetyl or stearyl alcohol, or C~o_2o oxoalcohols and the corresponding
semiesters of secondary alcohols with the same chain lengths. Other
CA 02293969 2000-O1-OS
24
preferred alk(en)yl sulfates are those with the chain length mentioned
which contain a synthetic, linear alkyl chain based on a petrochemical and
which are similar in their degradation behavior to the corresponding
compounds based on oleochemical raw materials. C~z_~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
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 monoesters 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
C~2_~$ fatty alcohols containing 1 to 4 EO, are also suitable. In view of
their
high foaming capacity, they are only used in relatively small quantities, for
example in quantities of 1 to 5% by weight, in dishwasher detergents.
Other suitable anionic surfactants are the salts of alkyl sulfosuccinic
acid which are also known as sulfosuccinates or as 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 C8_~a 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
moieties are 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.
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
CA 02293969 2000-O1-OS
behenic acid, and soap mixtures derived in particular from natural fatty
acids, for example 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
5 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
10 carbon atoms and, 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
15 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,
20 C~2_~$ alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such
as mixtures of C~2_,a alcohol containing 3 EO and C,2_~$ 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
25 (narrow range ethoxylates, NRE). In addition to these nonionic surfactants,
fatty alcohols containing more than 12 EO may also be used, examples
including tallow fatty alcohol containing 14 EO, 25 EO, 30 EO or 40 EO.
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
CA 02293969 2000-O1-OS
26
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, fatty acid alkyl esters preferably containing 1 to 4 carbon
atoms in the alkyl chain, more especially the fatty acid methyl esters which
are described, for example, in Japanese patent application JP 58/217598
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 fatty acid alkanolamide type are also suitable. The
quantity in which these 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 formula (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
to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxyfatty acid
amides are known substances which may normally be obtained by
reductive amination of a reducing sugar with ammonia, an alkylamine or an
CA 02293969 2000-O1-OS
27
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-CO-N-[Z] (I I)
in which R is a linear or branched alkyl or alkenyl group containing 7 to 12
carbon atoms, R' is 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 which 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-alkoxy- or N-aryloxy-substituted compounds may then be
converted into the required polyhydroxyfatty acid amides by reaction with
fatty acid methyl esters in the presence of an alkoxide as catalyst, for
example in accordance with the teaching of International patent application
WO-A-95/07331.
Besides the detersive ingredients, builders are the most important
ingredients of detergents. In the detergent tablets according to the
invention, any of the builders normally used in detergents may be present
in the bed of solids, including in particular zeolites, silicates, carbonates,
organic co-builders and also - providing there are no ecological objections
to their use - the phosphates.
Suitable crystalline layer-form sodium silicates correspond to the
general formula NaMSiX02X+~A y H20, where M is sodium or hydrogen, x is
CA 02293969 2000-O1-OS
28
a number of 1.9 to 4 and y is a number of 0 to 20, preferred values for x
being 2, 3 or 4. Crystalline layer silicates such as these are described, for
example, in European patent 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 Na2Si205A y H20 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 have been treated to dissolve with delay and
which exhibit multiple wash cycle properties. The delay in dissolution in
relation to conventional amorphous sodium silicates can have been
obtained in various ways, for example by surface treatment, 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 silicate 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 a 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 such 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.
CA 02293969 2000-O1-OS
29
The finely crystalline, synthetic zeolite containing bound water used
in accordance with the invention is preferably zeolite A and/or zeolite P.
Zeolite MAP~ (Crosfield) is a particularly preferred P-type zeolite.
However, zeolite X and mixtures of A, X and/or P are also suitable.
According to the invention, it is also possible to use, for example, a
commercially obtainable co-crystallizate of zeolite X and zeolite A (ca. 80%
by weight zeolite X) which is marketed by CONDEA Augusta S.p.A. under
the name of VEGOGOND AX~ and which may be described by the
following formula:
nNa20 ~ (1-n)K20 ~ A1203 ~ (2 - 2.5)Si02 ~ (3.5 - 5.5) H20
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 tripolyphosphates are particularly suitable.
Organic co-builders which may be present in the detergent tablets
according to the invention include, in particular, polycarboxy-
lates/polycarboxylic acids, polymeric polycarboxylates, aspartic acid,
polyacetals, dextrins, other organic cobuilders (see below) and
phosphonates. These classes of organic co-builders are described in the
following.
Useful organic builders are, for example, the polycarboxylic acids
usable in the form of their sodium salts, polycarboxylic acids in the present
context being carboxylic acids which carry more than one acid function.
Such acids are, for example, citric acid, adipic acid, succinic acid, glutaric
CA 02293969 2000-O1-OS
acid, malic acid, tartaric acid, malefic acid, fumaric acid, sugar acids,
amino-
carboxylic acids, nitrilotriacetic acid (NTA), providing its use is not
ecologically unsafe, and mixtures thereof. Preferred salts are the salts of
the polycarboxylic acids, such as citric acid, adipic acid, succinic acid,
5 glutaric acid, tartaric acid, sugar acids and mixtures thereof.
The acids per se may also be used. Besides their building effect,
the acids typically have the property of an acidifying component and,
accordingly, are also used to adjust detergents to a lower and milder pH
value. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid
and
10 mixtures thereof are particularly mentioned in this regard.
Other suitable builders are polymeric polycarboxylates which were
described in detail earlier on as optional ingredients of the additive
granules according to the invention.
Other preferred builders are polymeric aminodicarboxylic acids, salts
15 or precursors thereof. Particular preference is attributed to polyaspartic
acids or salts and derivatives thereof which, according to German patent
application DE-A-195 40 086, are also said to have a bleach-stabilizing
effect in addition to their co-builder properties.
Other suitable builders are polyacetals which may be obtained by
20 reaction of dialdehydes with polyol carboxylic acids containing 5 to 7
carbon atoms and at least three hydroxyl groups. Preferred polyacetals
are obtained from dialdehydes, such as glyoxal, glutaraldehyde, terephthal-
aldehyde and mixtures thereof and from polyol carboxylic acids, such as
gluconic acid and/or glucoheptonic acid.
25 Other suitable organic builders are dextrins, for example oligomers
or polymers of carbohydrates which may be obtained by partial hydrolysis
of starches. The hydrolysis may be carried out by standard methods, for
example acid- or enzyme-catalyzed methods. The end products are
preferably hydrolysis products with average molecular weights of 400 to
30 500,000 g/mol. A polysaccharide with a dextrose equivalent (DE) of 0.5 to
CA 02293969 2000-O1-OS
31
40 and, more particularly, 2 to 30 is preferred, the DE being an accepted
measure of the reducing effect of a polysaccharide by comparison with
dextrose which has a DE of 100. Both maltodextrins with a DE of 3 to 20
and dry glucose sirups with a DE of 20 to 37 and also so-called yellow
dextrins and white dextrins with relatively high molecular weights of 2,000
to 30,000 g/mol may be used.
The oxidized derivatives of such dextrins are their reaction products
with oxidizing agents which are capable of oxidizing at least one alcohol
function of the saccharide ring to the carboxylic acid function. Dextrins
thus oxidized and processes for their production are known, for example,
from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-
A-0 472 042 and EP-A-0 542 496 and from International patent
applications WO 92118542, WO 93108251, WO 93116110, WO 94!28030,
WO 95107303, WO 95112619 and WO 95120608. An oxidized
oligosaccharide corresponding to German patent application DE-A-196 00
018 is also suitable. A product oxidized at C6 of the saccharide ring can be
particularly advantageous.
Other suitable co-builders are oxydisuccinates and other derivatives
of disuccinates, preferably ethylenediamine disuccinate. Ethylenediamine
N,N'-disuccinate (EDDS) is preferably used in the form of its sodium or
magnesium salts. The glycerol disuccinates and glycerol trisuccinates are
also particularly preferred in this connection. The quantities used in
zeolite-containing and/or silicate-containing formulations are from 3 to 15%
by weight.
Other useful organic co-builders are, for example, acetylated
hydroxycarboxylic acids and salts thereof which may optionally be present
in lactone form and which contain at least 4 carbon atoms, at least one
hydroxy group and at most two acid groups. Co-builders such as these are
described, for example, in International patent application WO-A-95120029.
Another class of substances with co-builder properties are the
CA 02293969 2000-O1-OS
32
phosphonates, more particularly hydroxyalkane and aminoalkane phos-
phonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-
diphosphonate (HEDP) is particularly important as a co-builder. It is
preferably used in the form of a sodium salt, the disodium salt showing a
neutral reaction and the tetrasodium salt an alkaline ration (pH 9).
Preferred aminoalkane phosphonates are ethylenediamine tetramethylene
phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate
(DTPMP) and higher homologs thereof. They are preferably used in the
form of the neutrally reacting sodium salts, for example as the hexasodium
salt of EDTMP and as the hepta- and octasodium salt of DTPMP. Within
the class of phosphonates, HEDP is preferably used as builder. The
aminoalkane phosphonates also show a pronounced heavy metal binding
capacity. Accordingly, it can be of advantage, particularly where the
detergents also contain bleaching agents, to use aminoalkane
phosphonates, more especially DTPMP, or mixtures of the phosphonates
mentioned.
In addition, any compounds capable of forming complexes with
alkaline earth metal ions may be used as co-builders.
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 griseus, are particularly suitable. Proteases of the subtilisin
type are preferred, proteases obtained from Bacillus lentus being
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 to protect them against premature decomposition.
CA 02293969 2000-O1-OS
33
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 5% by weight and is preferably from 0.1 to
about 2% 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 com-
pounds of similar composition which contain a diethanolamino group, a
methylamino group, 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-3-sulfostyryl)-diphenyl or 4-(4-chlorostyryl)-4'-(2-sulfo-
styryl)-Biphenyl, 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 improving 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 dust and which are adapted in their particle size
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
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
CA 02293969 2000-O1-OS
34
of the additive granules throughout the shaped body is achieved by the
compacting of the disintegration aid with a detergent ingredient. The
improved disintegration can be tested, for example, under critical
conditions in a normal domestic washing machine (bleach/detergent tablet
used directly in the wash 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
corresponding tests 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 test of less than 2 minutes and, more particularly,
less than 1 minute. Particularly advantageous embodiments even have
disintegration times of less than 30 seconds. Disintegration times of less
than 1 minute in the glass beaker test are generally sufficient to ensure
than the detergent shaped bodies or detergent additive shaped bodies are
flushed into the wash liquor from the dispensing compartment of
conventional domestic washing machines, including so-called "critical
machines" which use very little water for flushing. In another embodiment,
therefore, the present invention relates to a washing process using a
shaped body according to the invention, characterized in that the shaped
body is introduced into the wash liquor from the dispensing compartment of
a domestic washing machine.
The actual production of the shaped bodies according to the
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 der Technik" in SOFW Journal, Vol. 122, pages
CA 02293969 2000-O1-OS
1016-1021 (1996)).
Embodiments of the invention are described by reference to the
following examples which are not to be construed as limiting.
5 Examples
Additive granules (polymer compounds) according to the invention
differing from one another in their composition were produced in two
particle size ranges in a fluidized bed granulator with a grinding/sieving
circuit, the type of polymer, the particle size and the carrier material being
10 varied. The composition of the additive granules is shown in Table 1 and
their particle size distribution in Table 2. The additive granules according
to the invention obtained in this way were incorporated in detergent tablets
E1 a and E1 b and E2a and E2b. Detergent tablets V containing no polymer
compound were used for comparison. All the tablets additionally contained
15 a commercially available cellulose disintegrator (Arbocel~ TF 30 HG,
Rettenmaier).
Surfactant-containing granules (for composition, see Table 1) used
as the basis for a particulate premix were produced by granulation in a
Lodige 50-liter plowshare mixer. After granulation, the granules were dried
20 for 30 minutes in a Glatt fluidized bed dryer at a feed air temperature of
60°C. After drying, fine particles below 0.4 mm in size and coarse
particles
above 1.6 mm in size were removed by sieving.
This premix was produced by mixing the surfactant-containing
granules with bleaching agent, bleach activator and other aftertreatment
25 components. The additive granules according to the invention were
incorporated in the tablets E according to the invention as a further
aftertreatment component while the comparison tablets V were free from
the polymer compounds according to the invention.
The premixes were compressed in a Korsch eccentric press to form
30 tablets (diameter 44 mm, height ca. 22 mm, weight 37.5 g). The tabletting
CA 02293969 2000-O1-OS
36
pressure was adjusted in such a way that three series of tablets (E1a, E1a',
E1 a", E2a, E2a', E2a" with fine-particle polymer compound, E1 b, E1 b',
E1 b", E2b, E2b', E2b" with coarse-particle polymer compound and V, V', V"
without polymer compound), which differed in their hardness, were
obtained. The measured tablet hardness values and disintegration times
are the average values of a double determination, the individual values
varying by at most 2 N and 2 s, respectively, according to the type of tablet
(E1a, E1a', etc.). The composition of the premixes to be compressed (and
hence of the tablets) is shown in Table 3 while the particle size distribution
of the polymer compounds is shown in Table 2.
Table 1:
Composition of the surfactant granules and the additive granules
[°/a by
weight]
SurfactantAdditive Additive
granules granules granules
1 2
C9_~3 alkyl benzenesulfonate 19.4 - -
C~2_~s fatty alcohol + 7 EO 4.8 - -
C~2_~s fatty alcohol sulfate 5.2 - -
C~2-~s alkyl-1,4-glycoside 1.0 - -
1.6
Soap - -
Optical brightener 0.3 -~ -
Sodium carbonate 17.0 23.0 -
Sodium silicate 5.6 - -
Acrylic acid/maleic acid copolymer5.6 - -
Zeolite A (water-free active 28.5 - 11.0
substance)
Na hydroxyethane-1,1-diphosphonate0.8 - -
Sokalan~ CP 5* - - 85.0
Sokalan~ HP 53 ** - 75.0 -
Water, salts Balance Balance Balance
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37
* Acrylic acid/maleic acid copolymer, MW 70,000 gmole)' (BASF)
** Polyvinyl pyrrolidone, MW 40,000 gmole)' (BASF)
Table 2:
Particle size distribution of the additive granules according to the invention
[% by weight]
Particle size >1.6 >1,2 >0.8 >0.6 >0.4 >0.2 <0.2
distribution [mm]
Additive granules 0 0 0 5 32 46 17
1a
Additive granules1 3 59 31 6 1 0 0
b
Additive granules 0 0 0 9 74 17 0
2a
Additive granules 0 0 42 54 4 0 0
2b
Table 3:
Composition of the premixes [% by weight]
E1a E1b E2a E2b V
Surfactant granules (Table 57.55 57.55 57.55 57.55 62.55
1 )
Additive granules 1 a (fine)5.0 - - - -
Additive granules 1 b (coarse)- 5.0 - - -
Additive granules 2a (fine)- - 5.0 -
Additive granules 2b (coarse)- - - 5.0 -
Sodium perborate monohydrate17.4 17.4 17.4 17.4 17.4
TAED 7.3 7.3 7.3 7.3 7.3
Foam inhibitor 3.5 3.5 3.5 3.5 3.5
Repel-O-Tex~ SRP 4* 1.1 1.1 1.1 1.1 1.1
Enzymes 1.7 1.7 1.7 1.7 1.7
Perfume 0.45 0.45 0.45 0.45 0.45
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38
Wessalith~ P (zeolite 1.0 1.0 1.0 1.0 1.0
A)
Arbocel~ TF 30 HG 5.0 5.0 5.0 5.0 5.0
* Terephthalic acid/ethylene glycol/polyethylene glyco~ ester (Knoaia,
Rhone-Poulenc)
The hardness of the tablets was measured after storage for two
days by deforming the tablets until they broke, the force being applied to
the sides of the tablet and the maximum force withstood by the tablets
being determined.
To determine tablet disintegration, the tablets were placed in a glass
beaker filled with water (600 ml water, temperature 30°C) and the time
taken by the tablets to disintegrate completely was measured. The
experimental data are set out in Tables 4 and 5.
Table 4:
Detergent tablets containing additive granules 1 [physical data]
Tablets E1 a E1 V
b
Tablet hardness [N] 41 40 40
Tablet disintegration [secs.]16 16 20
Tablets E1 a' E1 V'
b'
Tablet hardness [N] 50 49 50
Tablet disintegration [secs.]19 23 31
Tablets E1 a" E1 V"
b"
Tablet hardness [N] 59 61 60
Tablet disintegration [secs.]26 46 >60
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Table 5:
Detergent tablets containing additive granules 2 [physical data]
Tablets E2a E2b V
Tablet hardness [N] 40 39 40
Tablet disintegration [secs.]13 19 20
Tablets E2a' E2b' V'
Tablet hardness [N] 49 52 50
Tablet disintegration [secs.]22 29 31
Tablets E2a" E2b" V"
Tablet hardness (N] 60 61 60
Tablet disintegration [secs.]25 35 >60
Tables 4 and 5 show that the disintegration times of detergent
tablets can be distinctly reduced by using the additive granules according
to the invention, irrespective of their particle size. Thus, the
disintegration
times of tablets of comparable hardness were all shorter where the additive
granules according to the invention were used than those of tablets which
did not contain the additive granules, this effect being more clearly
pronounced, the greater the tablet hardness (comparison of E1/2a or E1/2b
with V).
At high hardness levels in particular, it was also found that the use
of the additive granules according to the invention in fine-particle form (E1a
and E2a) produced a further improvement in the disintegration times in
relation to the tablets containing the coarser additive granules as additives
(E1b and E2b), the disintegration times of E1a and E2a being distinctly
shorter than those of the additive-free tablets V.
