EP1004661A1 - High density granule, method for production thereof, and its use as disintegrant in tablets - Google Patents

Abstract

Compressed granulate contains starch and/or starch derivative, finely-divided (co)polymer of (meth)acrylic acid or salt and liquid surfactant(s) that thickens or forms a gel with water. An Independent claim is also included for the production of the compressed granulate.

Description

The invention is directed to granules that are particularly good at water records and forwards inside, which in some cases increases the volume takes place, so that the granules as disintegrants for pressed moldings, such as tablets.

Disintegrants for tablets or granules are auxiliary substances that disintegrate tablets or granules in contact with liquids, in particular Influence water positively. The decay of Tablets in large parts and then a disintegration into smaller ones Particles are caused and accelerated.

A large number of inorganic and organic disintegrants for tablets are Substances known, for example inorganic substances such as bentonites, also persalts, acetates, alkali carbonates / hydrogen carbonates and citric acid. Known organic compounds include starch, modified Starch and starch degradation products, cellulose, cellulose ethers, such as Methyl cellulose hydroxypropyl cellulose and carboxymethyl cellulose, poly (meth) acrylates, Polyvinyl pyrrolidone and cross-linked polyvinyl pyrrolidone, Alginates, gelatin and pectins.

For tablets that are made from pre-made compounds the need to disintegrate into the original compounds and subsequent to accelerate even in individual components.

For tablets that are pressed from non-prefabricated compounds, A very high density often arises when pressing, that in contact delayed the desired disintegration of the tablet with water. This is common undesirable, because components then only come off with a delay.

From WO98 / 40463 an explosive granulate and its use in washing or cleaning-active moldings, such as tablets, known a high adsorption capacity for water and a grain size distribution in which at least 90% by weight has a particle size of at least 0.2 mm and a maximum of 3 mm. The granules preferably contain 25-100% by weight of disintegrants, such as starch, starch derivatives, cellulose, cellulose derivatives, Alginic acid, carboxylmethylamylopectin, polyacrylic acid, polyvinylpyrrolidone and polyvinyl polypyrrolidone. After teaching this Patentes affects the presence of anionic or nonionic Surfactants negatively affect the tablet disintegration time. The granules will made by conventional means such as spray drying. Hot steam drying aqueous preparations or by granulating, pelleting, Extrusion or roller compaction of powdery components.

WO 96/06156 describes a method for producing detergent tablets described. Citric acid is used as a disintegrant or citrates, bicarbonates and carbonates. Bisulfate and percarbonate, microcrystalline Cellulose, sugar, sorbitol or swellable layered silicates called the type of bentonite or smectite. The explosives are used in quantities of 1 to 25% by weight as a single raw material or as a compound.

DE-A-44 04 279 describes the following disintegrants for washing or cleaning tablets: Starch, starch derivatives, cellulose, cellulose derivatives, microcrystalline cellulose, salts of polymeric polyacrylates or polymethacrylates, Methyl celluloses, hydroxypropyl celluloses or methyl hydroxypropyl celluloses. Acetates or percarbonates are also considered Called explosives. The application amounts are up to 15% by weight. There as a builder water-soluble silicates can be used with a Combination of poly (meth) acrylates and non-ionic cellulose ethers Even quantities of 1% by weight lead to very good results.

Handbook of Pharmaceutical Excipients (1986) entnommen werden. Als Beispiele werden genannt: Stärke (modifizierte Stärke Natrium-Stärke-Gluconate), Gummi (Agar, Guar, und andere), Cellulose, Carboxymethylcellulose, Alginate, Siliziumdioxid, Ton, Polyvinylpyrrolidon, Polysaccharide und Ionenaustauscherharze.In European patent application EP 0 846 756 A1, tablet disintegrants are incorporated into the tablet and preferably into the outer, solid shell of the tablet. Combinations of soluble acids and alkali carbonates are preferably used. Other possible explosives can

Handbook of Pharmaceutical Excipients (1986). Examples include: starch (modified starch, sodium starch gluconate), rubber (agar, guar, and others), cellulose, carboxymethyl cellulose, alginates, silicon dioxide, clay, polyvinylpyrrolidone, polysaccharides and ion exchange resins.

Detergent tablets, the disintegrants, are known from EP-A-0 552 766 contain that work according to four different mechanisms: swelling, Porosity / capillary action, deformation and chemical reaction. Starch, starch derivatives, carboxymethyl starch, sodium starch glycolates, Cellulose and cellulose derivatives, carboxymethyl cellulose, cross-linked modified cellulose, microcrystalline cellulose and various organic polymers such as polyethylene glycol, and cross-linked polyvinypyrrolidones and inorganic swelling agents such as bentonites. Combinations of organic acids and bicarbonates are also mentioned the carbonates of alkali metals.

EP 0 628 627 A1 describes a water-soluble, water-softening agent Builder in the form of a tablet. Combinations are used as explosives from citric acid and / or partially neutralized polymers and carbonate and / or bicarbonate or an insoluble polyvinylpyrrolidone.

In another European patent application (EP 0 799 886 A2) Detergent tablets described as starch derivatives, Cellulose compounds, polyvinylpyrrolidone compounds, polyvinylpolypyrrolidone compounds, Contain bentonite compounds, alginate gelatin and pectins can. To further improve the solving time, the addition of a polyfunctional organic carboxylic acid, such as maleic acid, malic acid, Citric acid or tartaric acid together with carbonates or bicarbonates recommended.

No disintegrant is known from the prior art, which is characterized by is characterized by a non-linear source kinetics and the use is nowhere of surfactants, preferably gel-forming or water-thickening Surfactants, mentioned in the disintegrant. The prolongation of the tablet disintegration time Certain surfactants have so far been described as a disadvantage.

The object of the invention is to provide granules which swell rapidly and strongly in water, so that it is suitable as a disintegrant for pressed moldings in order to promote their disintegration on contact with water and the disadvantages described in the prior art, such as increasing the Correct tablet disintegration times using anionic and nonionic surfactants.
This object is achieved by a compacted granulate containing starch and / or starch derivatives and finely divided polymers / copolymers of (meth) acrylic acid or salts thereof and one or more liquid, gel-forming or thickening surfactants. The term "starch / starch derivatives" used here also includes the group of polygalactomannans.

In one embodiment of the invention, the starch / starch derivative is used in combination with water-swellable, high-purity cellulose / cellulose derivative.
Up to about 95% by weight of the starch can be replaced by cellulose and or cellulose derivatives. The weight ratio of starch / starch derivative: cellulose / cellulose derivative is preferably from 10: 1 to 1:10, weight ratios from 5: 1 to 1: 5 are very particularly preferred.
In this embodiment of the invention, the water-swellable, preferably high-purity cellulose is used in the form of microcrystalline structures, the super-molecular structural elements being in the form of fibrils, in the longitudinal direction of which crystalline and amorphous regions can alternate. Fibrils of native cellulose with a maximum length of 300 µm have proven to be particularly suitable. Both microcrystalline and amorphous finely divided cellulose / cellulose derivatives and mixtures thereof can be used.

The finely divided cellulose preferably has bulk densities of 40 g / l up to 300 g / l, very particularly preferably from 65 g / l to 170 g / l. Become already used granulated types, their bulk density is higher and can be from 350 g / l to 550 g / l. The bulk weights of the starch / starch derivatives can range from 50 g / l to 1000 g / l, preferably in Range from 100 g / l and 800 g / l.

The particle size of the finely divided cellulose can be between 30 μm and 200 µm, in the case of granulated types the average particle size is between 350 µm and 800 µm.

The polysaccharides of the starch / starch derivative type to be used according to the invention can be of different origins, for example Starch from rice, corn, wheat, potatoes and legumes. The corresponding ones too Flours with cellulosic plant components can be used become.

Cold-swelling or cold-soluble starches are preferably used. Polygalactomannans, such as guar or locust bean gum this property already in the native state and can directly or after slight modification.

Naturally starches that do not swell in cold water are preferred in the form of their derivatives used. Chemically derivatized starches preferably contain Substituents. those by ester or ether groups in sufficient Number attached to the polysaccharide chains to ensure cold water swellability to convey.

Starches modified with ionic substituents such as carboxylate, hydroxyalkyl or phosphate groups have proven to be particularly advantageous proven and are therefore preferred. Furthermore, cold water swelling Starches of the type of starches mined can be used, for example Acid, enzyme and oxidatively degraded starches or dextrinized Strengthen. It is often an advantage for the swelling property if the starch derivatives through a combination of degradation and chemical substitution be modified.

To improve the swelling behavior, the use of tried and tested crosslinked strengths. Also alkaline treated starches can be used because of their cold water solubility.

Another group of the cold water swellable which can be used according to the invention Strengths are the native strengths that result from physical treatment have acquired cold swellability. These include extruder starches, for example and drum dryer strengths.

In combination with starch (derivatives) and possibly cellulose (derivatives) are fine-particle polymers of (meth) acrylic acid or copolymers of (meth) acrylic acid or salts thereof or mixtures thereof Polymers or copolymers or salts thereof with high water absorption contained in the granulate. Have proven to be particularly suitable linear polymers of (meth) acrylic acid, copolymers of (meth) acrylic acid or salts thereof with weight average molecular weights of 5,000 up to 70,000 and cross-linked polymers of (meth) acrylic acid, copolymers of (meth) acrylic acid or salts thereof with weight average molecular weights proven from 1,000,000 to 5,000,000. For the copolymers it is preferably copolymers of (meth) acrylic acid and maleic acid or maleic anhydride, for example 40 to 90% by weight (Meth) acrylic acid and 60 to 10% by weight of maleic acid or maleic anhydride contain, whose relative molar mass, based on free acids, between 3,000 and 100,000, preferably 3,000 to 70,000 and very particularly preferred Is 5,000 to 50,000.

Ter- and quattropolymeric polycarboxylates have also proven to be very suitable proven, made from (meth) acrylic acid, maleic acid and vinyl alcohol or vinyl alcohol derivatives, or those of (meth) acrylic acid, ethylenically unsaturated sulfonic acids and sugar derivatives, or such (Meth) acrylic acid, maleic acid, vinyl alcohol derivatives and sulfonic acid groups Monomers

Salt formation is preferably carried out with cations of alkali metals, Ammonia and amines, or their mixtures.

The finely divided polymers / copolymers of (meth) acrylic acid or salts preferably have the same of the cross-linked derivatives described above an average particle size of 45 µm to 150 µm. Most notably particle sizes from 45 μm to 90 μm are preferred.

Particles with average particle sizes over 150 µm show a good one Explosive effects, but are too large after swelling, become when washing filtered off and are visually as particles on the textile after washing visible.

Starch (derivatives) and optionally cellulose (derivatives) are made with polymers / copolymers of (meth) acrylic acid or salts thereof in the granulate combined, the weight ratio can be from 100: 0.5 to 100: 30, preferably from 100: 1 to 100: 20, a is particularly preferred Weight ratio from 100: 1 to 100: 10, the most favorable is a weight ratio from 100: 3.

The granulate contains one or more other essential constituents liquid, water-forming or thickening surfactants from the group of nonionic, anionic or amphoteric surfactants.

The nonionic surfactants are selected from alkyl polyglucosides, fatty acid alkylolamides, Fatty acid polyethylene glycol esters, fatty amine oxethylates, Fatty alcohol ethoxylates with 3-15 mol ethylene oxide or propylene oxide, Fatty acid glycerides. Sorbitan esters, sucrose esters, e.g. Sucrose palmitate, Pentaerythritol partial esters, which can also be ethoxylated, as well as alkylphenol polyethylene glycol ethers and phenol poly - ethylene glycol ethers (if they can be used in the respective country)

The anionic surfactants are selected from alkyl sulfates, linear and branched alkylbenzenesulfonates, alkylglycerol ethers, fatty alcohol polyethylene glycol ether sulfates, Paraffin sulfonates, alpha olefin sulfonates, Sulfosuccinates. Phosphoric acid esters and fatty alcohol ether carboxylates.

The amphoteric surfactants are selected from coconut fatty acid amidopropyl betaine, modified imidazolines and fatty acid amide derivatives with betaine structure.

The quantitative ratio of starch (derivatives) and possibly cellulose (derivatives) and / or polymers / copolymers of (meth) acrylic acid or Salting the same: surfactant can range from 100: 1 to 10: 1. Prefers are quantitative ratios from 100: 2 to 100: 5.

Completely surprisingly, it was found that when the inventive compounds were added Starch surfactants (derivatives) and optionally cellulose (derivatives) the swelling effect of the disintegrant granules according to the invention clearly is improved. This is particularly surprising since many are concentrated Surfactants tend to gel on contact with water and wetting and swelling of the explosive granules should be rather impeded. Gelation or thickening effects e.g. for fatty alcohol ethoxylates, Soaps, fatty alkyl ether sulfates and fatty alkyl sulfates were observed.

The gel-forming or water-thickening surfactants can be anionic, be amphoteric or nonionic, particularly preferred are nonionic Surfactants.

It has therefore proven to be particularly advantageous to use the liquid Surfactants first in direct contact with the starch (derivatives) and if necessary to bring and add cellulose (derivatives) and then the finely divided polymers / copolymers of (meth) acrylic acid or to introduce their salts into the mixture in such a way that the polymer particles adhere to the fibrils of cellulose / starch (derivatives).

The mixture of the granulate components according to the invention, starch (derivatives) and optionally cellulose (derivatives) and polymers / copolymers of (Meth) acrylic acid and nonionic surfactants are then made using conventional methods granulated. For example, mixers from Vomm, Lödige, Schugi, Eirich, Henschel or Fukae can be used.

For the swelling and water absorption behavior of the granules according to the invention the final compression is essential. Compacting under Pressure can be applied in various ways.

Compaction on rolling mills has proven to be particularly suitable whose rollers run at different speeds, so that the pressure on the granules in the nip is still due to friction is added. This leads to the formation of a scale-like structure and alignment of the starch (derivatives) and optionally anisotropic cellulose (derivatives) in the granulate.

This orientation can be one of the reasons for the particularly cheap source kinetic behavior of this embodiment of the invention Be granules.

The compression of the granules should preferably be such that the compression Granules a bulk density of 100 g / l to 800 g / l, preferred from 200 g / l to 600 g / l, very particularly preferably from 300 g / l to 500 g / l having.

The disintegrant granules according to the invention are in the moldings in Contain amounts of 0.5 wt.% To 10 wt.%, Preferably 2 wt.% To 7 % By weight and particularly preferably 3% by weight to 6% by weight.

The specific water absorption capacity of the granules according to the invention can be determined gravimetrically as follows:

A defined amount of granulate (e.g. 2.00 g) is placed in a thin paper bag, sealed like a teabag and in a jar with one Excess water submerged. After 3 minutes of immersion, the bag removed from the water and hung for 10 minutes to drain. The bag is weighed and from the weight difference of a wet bag determines the water absorption with and without granules. For the determination can use distilled water or water of defined hardness become.

The water absorption which can be determined in this way is preferably 500 until 2000 %

The compacted granulate according to the invention is distinguished by a special one Swelling kinetics, the expansion changes depending on the Time is not linear and should reach a certain level after the shortest possible time to reach. The swelling behavior in the first 10 seconds after contact with water when the granules as Explosives should be used for moldings.

The increase in volume after 5 seconds is preferably 55% by volume to 225% by volume, the increase in volume being greater with higher compaction, ie higher bulk density.
After 10 seconds, the increase in volume is preferably 75% by volume to 270% by volume, the increase in volume likewise increasing with increasing bulk density.

With a bulk density of 250 g / l to 350 g / l, the volume increases after 5 seconds contact with water from 55 vol.% to 100 vol.% and after 10 seconds from 75 vol.% to 130 vol.% With a bulk density of 400 g / l to 500 g / l, the volume increase of 200 after 5 seconds Vol.% To 225 vol.% And after 10 seconds from 230 vol.% To 270 vol.%.

To determine the swelling speed and the swelling height under load 3.00 g of granules are placed in a cylindrical plastic container with a Given an inner diameter of 60 mm and with a water-permeable Fleece covered. The layer thickness of the granules is depending on the bulk density 1-3 mm. A movable, pierced stamp is placed on the fleece put on with a weight of 58 g and with a displacement measuring instrument connected that records the path of the stamp depending on the time. The granules are made to swell by adding 50 ml of water and the resulting displacement of the stamp (path length) in Determined as a function of time and evaluated graphically.

Figure 1 shows a diagram for the swelling kinetics of known explosives and granules according to the invention.

Table 1 contains the corresponding measured values. Swelling kinetics of different materials Bulk density [g / l] 70 90 90 300 300 450 450 Cellulose V 1 M1 V2 M2 V3 M3 Time [sec] Way [mm] Way [mm] Way [mm] Way [mm] Way [mm] Way [mm] Way [mm] 0 0 0 0 0 0 0 0 1 0.10 0.20 0.35 0.30 0.70 0.80 1.30 2nd 0.20 0.40 0.50 0.60 1.40 1.20 2.00 3rd 0.30 0.60 0.75 0.90 1.70 1.50 2.30 4th 0.35 0.70 0.95 1.00 1.90 1.60 2.45 5 0.40 0.85 1.10 1.10 2.10 1.70 2.50 6 0.42 1.00 1.40 1.15 2.30 1.72 2.60 7 0.44 1.10 1.50 1.20 2.40 1.80 2.70 8th 0.46 1.20 1.65 1.25 2.45 1.82 2.75 9 0.48 1.35 1.80 1.40 2.48 1.83 2.80 10th 0.48 1.40 1.95 1.50 2.50 1.85 2.90 11 0.49 1.45 1.98 1.60 2.50 1.90 2.90 12th 0.50 1.50 2.00 1.65 2.52 1.92 3.00

The composition of the samples V1 to V3 is as in Table 3, example 1.

The composition of the samples M1 to M3 is as in Table 3, Example 6. Volume expansion in vol.% Cellulose V1 M1 V2 M2 V3 M3 Bulk density in g / l 70 90 90 300 300 450 450 Volume increase after 5 sec vol.% 5 14 18th 61 110 210 240 after 10 sec vol.% 6 23 35 83 140 242 270

Formulation V1 has the composition of Example 1 in undensified form. Formulation M1 has the composition of Example 6 in undensified form.
V2, M2 denote samples that were compressed to a bulk density of 300 g / l after mixing in a roller press. V3 and M3 refer to samples which, after mixing, were compressed to a bulk density of 450 g / l using a roller press.

You can clearly see the improved performance of the compressed samples, the increase in volume after 5 seconds is preferably at least 95%, particularly preferably ≥ 150%.

Another object of the invention is a method for manufacturing a compacted granulate, the starch (derivatives) and optionally water-insoluble but swellable high-purity cellulose and fine particles Polymers / copolymers of (meth) acrylic acid or its salts and one or contains several liquid surfactants, by mixing starch (derivative) and optionally high purity cellulose with the surfactant (s) and mixing in Polymers / copolymers, granulation and subsequent compression of the granulate with alignment of the starch (derivatives) and optionally cellulose (derivatives).

The first step of the process involves a mixing and granulation process. in the pre-compounds produced by agglomeration processes become. These precompounds form a free-flowing and coarse-grained Goods that have a certain degree of moisture. The next step will be these precompounds are mechanically compressed. The products can be between two pressure areas in roller compressors, e.g. B. smooth or profiled, compressed become. If certain sliding properties are available, the Compression in extruders or flat die presses to form dies. The compactate is ejected as a strand. Compression methods in Matrices with stamps or pillow rollers produce compact forms such as tablets or briquettes. Roller compactors, Extruders, roller or cube presses, but also granulating presses be used. Below are the coarse, densified particles crushed, e.g. Suitable for mills, shredders or roller mills are.

The granulate according to the invention takes this quickly in contact with water with volume increase and is therefore suitable as a so-called Disintegrant for pressed moldings so that they quickly disintegrate in water.

The invention includes the use of the compacted granules as Disintegrants for pressed molded articles, for example tablets, cubes, Bullets and the like.

The use as disintegrant for detergent formulations is particularly preferred, Detergent formulations, stain salts, water softeners in tablet or cube form.

Detergent tablets and detergent tablets for different Purposes, in the sanitary area or for dishwashers are generally known.

Such moldings must have sufficient stability and strength to enable handling, packaging and storage however, quickly disintegrate on contact with water, so that the components can have the desired effect.

For this reason, the pressed moldings often contain so-called Disintegrants that due to the swelling behavior and the increase in volume Remove the cohesion of the shaped bodies and accelerate the disintegration.

Such designed as shaped bodies, such as tablets Detergent formulations usually contain builders, bleaches and bleach activators, surfactants, tabletting aids, disintegrants and other common additives and auxiliaries.

Polyphosphates, pyrophosphates, metaphosphates or come as builders Phosphonates, layered silicates, amorphous silicates, amorphous disilicates and Zeolite into consideration. Fillers can also form part of the builder system such as alkali carbonates, bicarbonates e.g. Sodium carbonate or sodium hydrogen carbonate, Sesquiocarbonates, sodium sulfate, magnesium sulfate, or citrate, citric acid, succinic acid, tartaric acid and malic acid his. Cobuilders and dispersants are often used as auxiliary builders. Such cobuilders or dispersants can be polyacrylic acids and their sodium salts.

Copolymers of (meth) acrylic acid and maleic acid, terpolymers and Quattropolymers of (meth) acrylic acid, maleic acid, vinyl alcohol and sulfo groups Vinyl compounds can be used.

Ter- and quattropolymeric polycarboxylates are also particularly preferred, made from (meth) acrylic acid, maleic acid and vinyl alcohol or Vinyl alcohol derivatives (as described in DE 43 00 772 C2) or those from (meth) acrylic acid, 2-alkylallylsulfonic acid and sugar derivatives (as described in DE 42 21 381 C1) or those made from (meth) acrylic acid, Maleic acid, vinyl alcohol derivatives and monomers with sulfonic acid groups (described in DE 19 516 957 A).

There are also polyethylene glycol and / or polypropylene glycol with a Molecular weight of 900 - 30,000 suitable, as well as carboxylated polysaccharides, Polyaspartates and polyglutamate.

Mixtures with various organic builders such as citric acid are possible.

Customary bleaching agents are sodium perborate tetrahydrate and sodium perborate monohydrate, sodium percarbonate, peroxypyrophosphates, citrate perhydrates, as well as H ₂ O ₂ providing peracid salts, peracids, such as perbenzoates. Peroxyphthalates, diperazelaic acid and diperdodecanedioic acids. The bleach content in tablets is preferably 10-60% by weight and in particular 15-50% by weight.

In order to achieve a good bleaching effect when washing below 60 ° C and below, activators can be incorporated. Suitable bleach activators are the N-acyl and O-acyl compounds forming with H ₂ O ₂ organic peracids, preferably N, N'-tetraacylated diamines, carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. Acetylated mixtures of sorbitol and mannitol can also be used. Particularly suitable bleach activators are N, N, N ', N' -tetraacetylethylenediamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,2,5-triazine (DADHT) and acetylated sorbitol mannitol Mixtures (SORMAN).

In addition to nonionic, anionic and amphoteric surfactants, cationic surfactants can also be present in detergent formulations, for example quaternary ammonium compounds with C ₈ -C ₁₆ N-alkyl or N-alkenyl groups and N-substituents such as methyl, hydroxyethyl or hydroxypropyl groups.

Polyalkylene glycols and magnesium stearates come as tableting aids into consideration.

Examples of other common detergent additives and auxiliaries are Enzymes, magnesium silicates, aluminum aluminates, benzotriazole, glycerin, Magnesium stearate, polyalkylene glycols, hexametaphosphate, phosphonates, bentonites, Soil release polymers, carboxymethyl celluloses.

Dishwashing tablets as an educational form of detergent formulations usually contain polyphosphates, pyrophosphates, Metaphosphates or phosphonates, layered silicates, amorphous silicates, amorphous disilicates and zeolites, as well as fillers such as sodium carbonate, Sodium sulfate, magnesium sulfate, sodium hydrogen carbonate, citrate as well Citric acid, succinic acid, tartaric acid and malic acid. Frequently are also used as auxiliary builders, cobuilders and dispersants. Such Cobuilders or dispersants can be polyacrylic acids or copolymers with polyacrylic acid and its sodium salts.

Customary bleaching agents are sodium perborate tetrahydrate and sodium perborate monohydrate, sodium percarbonate, peroxypyrophosphates, citrate perhydrates, as well as H ₂ O ₂ providing peracid salts, peracids, such as perbenzoates. Peroxyphthalates, diperazelaic acid and diperdodecanedioic acids. The content in the tablets is preferably 10-60% by weight and in particular 15-50% by weight.

Low-foaming non-ionic surfactants of the polyalkylene glycol and alkyl polyglucoside type are also used.

Examples of other common detergent additives and auxiliaries are here too enzymes, magnesium silicates, aluminum aluminates. Benzotriazole, Glycerin, magnesium stearate, polyalkylene glycols, hexametaphosphate as well Phosphonates.

Water softening tablets usually consist of builders such as Layered silicates, amorphous silicates, amorphous disilicates and zeolites, as well as fillers such as sodium carbonate, sodium sulfate, magnesium sulfate, Sodium bicarbonate, citrate and citric acid. Often called Auxiliary builders cobuilders and dispersants also used. Such cobuilders or dispersants can be polyacrylic acids or copolymers with polyacrylic acid and their sodium salts.

Low-foaming non-ionic surfactants of the polyalkylene glycol and alkyl polyglucoside type are also used.

Examples of other common detergent additives and auxiliaries are Magnesium silicates, polyalkylene glycols and phosphonates.

The invention is further elucidated below on the basis of exemplary embodiments explained. All data refer to weight, unless it something else is specified in individual cases.

Examples Examples 1-8

Examples of disintegrant compositions according to the teaching of the patent (all amounts in% by weight) . example 1 comparison 2 comparison 3rd 4th 5 6 7 8th Component: Cellulose 80 50 80 48 85 70 80 105 Linear PAA 20th 5 10th 5 12th 8th 8th 7 Networked PAA - - - - 1 - - - Carboxymethyl starch - - - - - - 10th - Hydroxyethyl starch - - - - - - - 10th Guar - - - - - 20th 1 - Microcrystalline cellulose - - - - - - - 23 Nio surfactant - - 10th 5 2nd 2nd 2nd 2nd Water ad 100% - 45 - 42 - - - -

Example 9: Detergent tablet containing phosphate: strength of the tablet and its Disintegration time using the granules of the above examples:

Phosphate-containing detergent tablets with the composition described in Table 3 were examined for their disintegration time and strength. Composition of detergent tablet: raw material Amount used in% Sodium tripolyphosphate 35 Sodium percarbonate 19th TAED 4th Fatty alcohol sulfate 14 Linear alkyl benzene sulphonate 4th soda 8th Defoamer, optical brightener, CMC, phosphonate 6 Microcrystalline cellulose (200 µm) 2nd Enzyme mix 1 Fatty alcohol ethoxylate (C12 / 14, EO = 4.7) 2nd Disintegrant preparation according to Examples 1 to 8 5

Table 5 shows the strength and disintegration time of the individual detergent tablets when using the different explosives:

Disintegrant composition according to example Disintegration time in sec Strength in N 1 35 62 2nd 25th 63 3rd 22 53 4th 21 64 5 19th 58 6 18th 56 7 18th 59 8th 17th 61

Example 10: Phosphate-free detergent tablet: strength of the tablet and its disintegration time using one of the granules of the aforementioned examples: 10.1 .: Granules from example 6 in zeolite-based formulations

raw material Amount used in% a) b) Zeolite P 39 35 Fatty alcohol ethoxylate (C12 / 14, EO = 4.7) 4th 7 Sodium percarbonate 16 16 TAED 4th 4th Fatty alcohol sulfate 10th 11 Linear alkyl benzene sulphonate 3rd 3rd soda 4th 4th Defoamer, optical brightener, CMC, phosphonate 5 5 Enzyme mix 1 1 Microcrystalline cellulose (200 µm) 4th 4th Disintegrant preparation according to example 6 5 5 Sodium citrate 5 5 Recipe Disintegration time in sec Strength in N a) 30th 59 b) 35 51

10.2: Granules from formulations based on disilicate

raw material Amount used in% a) b) Amorphous disilicate 36 30th Fatty alcohol ethoxylate 2nd 7 Fatty alcohol sulfate 11 15 Linear alkyl benzene sulphonate 4th 2nd Sodium percarbonate 16 16 TAED 4th 4th Acrylate-maleate copolymer - 3rd soda 7 4th Sodium citrate 5 5 Microcrystalline cellulose (200 µm) 4th 4th Defoamer, optical brightener, CMC, phosphonate 5 4th Enzyme mix 1 1 Disintegrant preparation according to example 6 5 5 Recipe Disintegration time in sec Strength in N a) 40 68 b) 15 48

Example 11: Pressed molded articles with the intended use as a) Stain remover of the following composition:

raw material Amount used in% Soda disilicate cogranulate 20th soda 41 Nonionic surfactant 4th TAED 7 Enzyme mix 1 Sodium percarbonate 24th Disintegrant preparation according to example 4 3rd

b) water softener of the following composition:

raw material Amount used in% Zeolite 15 Sodium bicarbonate 32 citric acid 20th Polycarboxylate 17th Layered silicate 8th Process aids 5 Disintegrant preparation according to example 7 3rd

c) Machine dishwashing detergent of the following composition:

raw material Amount used in% Soda disilicate cogranulate 20th Tripolyphosphate 35 soda 20th Sodium perborate 12th TAED 4th Enzyme mix 2nd Process aids 3rd Perfume, dyes 2nd Disintegrant preparation according to example 8 2nd

Results on the strength and disintegration time of the cleaning tablets

Physical parameters Stain remover according to composition a) Water softener according to composition b) Cleaning machine according to composition c) Strength in N 170 200 180 Disintegration time without explosives 224 s 147 s 240 s Disintegration time with disintegrant 100 s 70 s 60 s

Claims (26)

Compacted granules containing starch and / or starch derivatives and finely divided polymers / copolymers of (meth) acrylic acid or salts the same and one or more liquid, gel-forming with water or thickening surfactants. Granules according to claim 1, characterized in that it is additionally not water-soluble, water-swellable high-purity cellulose and / or cellulose derivatives. Granules according to claim 1 or 2, characterized in that compacting an alignment of starch / starch derivatives and anisotropic cellulose or cellulose derivatives was generated. Granules according to one of claims 1 to 3, characterized in that the weight ratio of the combined starch / starch derivatives and optionally the water-swellable cellulose / cellulose derivatives and polymers / copolymers of (meth) acrylic acid: liquid surfactant (s) from 100: 1 to 10: 1. Granules according to one of claims 1 to 4, characterized in that that the surfactants are nonionic and / or anionic and / or amphoteric Are surfactants. Granules according to one of claims 1 to 5, characterized in that that starch / starch derivatives and optionally swellable in water high-purity cellulose / cellulose derivatives and finely divided polymers / copolymers of (meth) acrylic acid in a weight ratio of 100: 0.5 to 100: 30, preferably from 100: 1 to 100: 20, very particularly preferably in a weight ratio of 100: 1 to 100: 10 available. Granules according to one of claims 1 to 6, characterized in that that the bulk density is from 100 g / l to 800 g / l, preferably 200 g / l to 600 g / l and particularly preferably 300 g / l to 500 g / l. Granules according to one of claims 1 to 7, characterized in that that the specific water absorption is 500 to 2,000% by weight. Granules according to one of claims 1 to 8, characterized in that that it has non-linear swelling kinetics. Granules according to one of claims 1 to 9, characterized in that that the finely divided polymers / copolymers selected from (meth) acrylic acid are made of linear polymers / copolymers of (meth) acrylic acid, cross-linked polymers / copolymers of (meth) acrylic acid, Copolymers of (meth) acrylic acid and maleic acid, ter- and quattropolymer Copolymers made from (meth) acrylic acid, maleic acid and vinyl alcohol or vinyl alcohol derivatives, or such (Meth) acrylic acid, ethylenically unsaturated sulfonic acid and sugar derivatives, or from (meth) acrylic acid, maleic acid or maleic anhydride, Vinyl alcohol derivatives and sulfonic acid groups Monomers, and mixtures thereof. Granules according to one of claims 2 to 10, characterized in that that the finely divided cellulose / cellulose derivatives have a medium Has particle size between 30 microns and 300 microns and / or a bulk density from 40 g / l to 300 g / l, preferably from 65 g / l to 170 g / l. Granules according to one of claims 1 to 11, characterized. that the starch is selected from the group of starches soluble in cold water is. Granules according to one of claims 1 to 12, characterized in that the starch / starch derivatives chemically and / or physically modified Strength is. Granules according to one of claims 1 to 13, characterized in that that the starch from galactomannans, carboxymethyl starches, hydroxyethyl starches and dextrins is selected. Granules according to one of claims 1 to 14, characterized in that that the liquid anionic or nonionic surfactant (s) are selected from 3 to 15 moles of fatty alcohol ethoxylates Ethylene oxide, anionics of the type fatty alcohol sulfate and linear alkylbenzenesulfonates, as well as alkyl ether sulfates and mixtures thereof. Process for producing a compacted granulate according to a of claims 1 to 15 by mixing the starch (derivatives) and optionally of high purity cellulose / cellulose derivatives with the (the) nonionic, anionic and amphoteric surfactant (s) and Mixing in the finely divided polymer (s) from (Meth) acrylic acid or salts thereof and granulation and subsequent Compacting the granulate. The method of claim 16, wherein compacting the granules under Alignment of starch (derivatives) and, if necessary, anisotropic Cellulose / cellulose derivatives. Method according to one of claims 15 or 16, characterized in that that the compaction is carried out by means of rollers with friction. Method according to one of claims 15 or 16, characterized in that that compacting by means of roller compactors, roller or cube presses or extruding. Use of the granulate according to one of claims 1 to 15 or obtained according to claims 16 to 19 as a disintegrant for pressed Molded body. Use according to claim 20, wherein the granules in amounts of 0.5 % By weight to 10% by weight, preferably 2% by weight to 7% by weight and particularly preferably 3% by weight to 6% by weight is used. Use according to claim 20 or 21 as disintegrant for detergent tablets. Use according to claim 20 or 21 as a disintegrant for detergent tablets. Use according to claim 23 as a disintegrant for detergent tablets for dishwashers. Use according to claim 20 or 21 as disintegrant for water softening tablets. Use according to claim 20 or 21 as disintegrant for stain remover tablets.

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