CA2293969A1 - Additive granules for detersive shaped bodies - Google Patents

Abstract

Detersive shaped bodies, more particularly tablets, such as laundry detergent tablets, dishwasher tablets, stain remover tablets or water softening tablets, meet the requirements for use in domestic dishwashing machines in regard to their disintegration rate through the use of the additive granules according to the invention. The additive granules according to the invention contain 50 to 99% by weight of one or more polymers with a molecular weight of at least 1000 gmole)1 and 1 to 50% by weight of one or more solubilizers with a solubility of more than 200 g per liter water at 20°C and/or one or more substances with an oil adsorption capacity of more than 20 g per 100 g and are superior to conventional cellulose-based disintegration aids in regard to their physical and detersive properties.

Description

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 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 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.

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 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 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 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:

N
~O
n 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 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

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

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

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

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

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

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

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

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, 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-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 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 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 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 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 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 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 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 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 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.

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 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 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 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.

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 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 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 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 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 * 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 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 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.

Claims (17)

1. Additive granules for detersive shaped bodies, 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)1 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 substances having an oil adsorption capacity of more than 20 g per 100 g.

2. Additive granules as claimed in claim 1, characterized in that one or more solubilizers with a solubility of more than 250 g per liter water at 20°C, preferably more than 300 g per liter water at 20°C and more preferably more than 350 per liter water at 20°C is/are present as component b).

3. Additive granules as claimed in claim 1, characterized in that one or more substance(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).

4. Additive granules as claimed in claim 1, characterized in that one or more solubilizers with a solubility of more than 250 g per liter water at 20°C, preferably more than 300 g per liter water at 20°C and, more particularly, more than 350 g per liter water at 20°C and one or more substance(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 are present as component b).

5. Additive granules as claimed in any of claims 1 to 4, characterized in that they 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.

6. Additive granules as claimed in any of claims 1 to 5, characterized in that component b) does not emanate from the groups of builders, bleaching agents and bleach activators, foam inhibitors and soil-release polymers.

7. Additive granules as claimed in any of claims 1 to 6, characterized in that component b) is not a typical ingredient of detergents.

8. Additive granules as claimed in any of claims 1 to 7, characterized in that 60 to 95% by weight, preferably 65 to 90% by weight and more preferably 70 to 85% by weight of one or more polymers with a molecular of at least 1000 gmole)1 is used as component a).

9. Additive granules as claimed in any of claims 1 to 8, characterized in that the polymer(s) has/have a molecular weight of at least 5000 gmole)1, preferably of at least 10,000 gmole)1 and more preferably of at least 25,000 gmole)1.

10. Additive granules as claimed in any of claims 1 to 9, 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 particularly 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, are used as the polymers.

11. Additive granules as claimed in any of claims 1 to 9, characterized in that polyvinyl pyrrolidones are used as the polymers.

12. Additive granules as claimed in any of claims 1 to 11, 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 a particle size below 600 µm.

13. A process for the production of additive granules for detersive shaped bodies, characterized in that a) 50 to 99% by weight of one or more polymers having a molecular weight of at least 1000 gmole)1 and b) 1 to 50% by weight of one or more solubilizers with a solubility of more than 200 g per liter water at 20°C and/or one or more substances having an oil adsorption capacity of more than 20 g per 100 g are granulated.

14. A process as claimed in claim 13, characterized in that 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 acrylic acid/maleic acid copolymers containing 50 to 90% by weight of acrylic acid and 50 to 10%
by weight of malefic acid, which have a molecular weight of preferably at least 5000 gmole)1, more preferably at least 10,000 gmole)1 and most preferably at least 25,000 gmole)1 are used as component a) and in that one or more solubilizers with a solubility of more than 250 g per liter water at 20°C, preferably more than 300 g per liter water at 20°C and more preferably more than 350 g per liter 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).

15. The use of the additive granules for detersive shaped bodies claimed in any of claims 1 to 12 as disintegration accelerators in detergent tablets, more particularly laundry detergent tablets.

16. Detergent tablets, more particularly laundry detergent tablets, containing 1 to 40% by weight, preferably 2 to 30% by weight and more preferably 2.5 to 20% by weight of the additive granules claimed in any of claims 1 to 12.

17. A washing process using the tablets claimed in claim 16, characterized in that the tablet is introduced into the wash liquor from the dispensing compartment of a domestic washing machine.