CZ397699A3 - Compacted granulation product, process for producing thereof and its use as swelling agent for pressed shaped bodies - Google Patents

Abstract

Densified granules containing starch and / or a derivative thereof a optionally water swellable cellulose and / or derivatives thereof; fine-grained polymers and / or copolymers of acrylic acid or methacrylic or a salt thereof and one or more liquid surfactants for use as a disintegrant for tablets detergent, detergent tablets, tablets a water-softening composition, salt-removing tablets blemishes, and which is produced by blending ingredients, granulating a compaction

Description

Field of the invention

The invention relates to a granulate which receives particularly well and conducts water inside, thereby partially expanding the volume, so that the granulate is suitable as a disintegrating agent for molded articles such as tablets.

BACKGROUND OF THE INVENTION

Tablet or granulate disintegrants are excipients which have a positive effect on the disintegration of tablets or granules in contact with liquids, especially water. In doing so, they are intended to cause and accelerate the disintegration of the tablets into coarse parts as well as their subsequent disintegration into smaller particles.

Numerous inorganic and organic substances are known as tablet disintegrating agents, for example inorganic substances such as bentonites, also peroxy salts, acetates, alkali carbonates and / or bicarbonates and citric acid. Known organic substances include starches, modified starches and starch degradation products, cellulose, cellulose ethers such as methylcellulose, hydroxypropylcellulose and carboxymethylcellulose, polyacrylates, polymethacrylates, polyvinylpyrrolidone and cross-linked polyvinylpyrrolidone, alginates, gelatin and pectins.

For tablets that are compressed from preformed compositions, there is a need to accelerate the disintegration of the original compositions, and thereafter their individual components.

For tablets which are not compressed from preformed compositions, compression often results in a very high density which retards the desired disintegration of the tablet upon contact with water. This is often undesirable since the components dissolve with delay.

WO98 / 40463 discloses a disintegrant granulate and its use in laundry or cleaning moldings, for example tablets, which have a high adsorption capacity for water and which exhibits a particle size distribution at which at least 90 wt. has a particle size of at least 0.2 mm and at most 3 mm. The granulate preferably contains 25 to 100 wt. disintegrating agents such as starch, starch derivatives, cellulose, cellulose derivatives, alginate acid, carboxymethylamylopectins, polyacrylic acid, polyvinylpyrrolidone and polyvinylpolypyrrolidone. According to the contents of this patent, the presence of anionic or nonionic surfactants has a negative effect on the disintegration time of the tablets. The granulate is produced in a conventional manner, such as by spray drying, hot steam drying of aqueous preparations, or by granulating, pelletizing, extruding or rolling the powdered components.

WO96 / 06156 discloses a process for the manufacture of detergent or detergent tablets. As disintegrating agents citric acid or citric acid are mentioned. citrates, bicarbonates and carbonates, hydrosulphates and percarbonates, microcrystalline cellulose, sugar, sorbitol or layered silicates, capable of

swelling such as bentonite or smectite. The disintegrants are used in amounts of 1 to 25 wt. as individual raw materials or as compositions.

DE-A-44 04 279 discloses the following disintegrating agents for washing or cleaning tablets: starch, starch derivatives, cellulose, cellulose derivatives, microcrystalline cellulose, salts of polymeric polyacrylates or polymethacrylates, methylcellulose, hydroxypropylcellulose and the like. methylhydroxypropylcellulose. Acetates or percarbonates are also mentioned as disintegrating agents. Their amounts are up to 15% by weight. Since water-soluble silicates are used as components, they can, in combination with polyacrylates or polymethacrylates and non-ionic cellulose ethers, lead to very good results already in an amount of 1% by weight.

According to European patent application EP 0 846 756 A1, tablet disintegrants are incorporated into tablets, preferably into their outer solid coating. Preferably, combinations of soluble acids and alkali carbonates are used. Other possible disintegrants are evident from the Handbook of Pharmaceutical Excipients, (1986). Examples include starches (modified starches, resins (agar, guar and carboxymethylcellulose, alginate, polyvinylpyrrolidone oxide, resin polysaccharides).

sodium starch gluconate), others), cellulose, silica, clays, and ion exchange

From EP-A-0 522 766 detergent tablets are known which contain disintegrating agents which function on the basis of four different mechanisms: swelling, porosity and capillary action,

deformation and chemical reactions. Starches, starch derivatives, carboxymethyl starches, sodium starch glycolates, cellulose and cellulose derivatives, carboxymethylcellulose, cross-linked modified cellulose, microcrystalline cellulose and various organic polymers such as polyethylene glycol, and cross-linked polyvinylpyrrolidone and inorganic swelling agents such as bentonite are described. Combinations of organic acids and alkali metal bicarbonates or carbonates are also disclosed.

EP 0 628 627 discloses a water-soluble, water-softening component in the form of a tablet. Combinations of citric acid and / or partially neutralized polymers and carbonate and / or bicarbonate or insoluble polyvinylpyrrolidone are used as disintegrants.

In another European patent application (EP 0 799 886 A2) detergent tablets are described which may contain as disintegrating agents starch derivatives, cellulose compounds, polyvinylpyrrolidone compounds, bentonite compounds, alginates, gelatin and pectins. To further improve the dissolution time, it is recommended to add a polyfunctional organic carboxylic acid, such as maleic, malic, citric or tartaric acids, together with carbonates or bicarbonates.

There is no prior art disintegrant known to exhibit nonlinear swelling kinetics, and there is no mention of the use of surfactants, preferably water-gelling or water-thickening surfactants, in the disintegrant. The prolongation of tablet disintegration time by certain surfactants has been described as a disadvantage.

-5Podgtata vynalezu

SUMMARY OF THE INVENTION It is an object of the present invention to provide a water-swellable granulate which is rapidly and strongly swellable, suitable as a disintegrant for compressed moldings, causing their disintegration upon contact with water, and eliminating the disadvantages described in the prior art such as prolonging tablet disintegration time.

This object is achieved by a compacted granulate comprising starch and / or starch derivatives and fine-grained polymers and / or copolymers of acrylic or methacrylic acid or salts thereof and one or more liquid, water-gelling or thickened surfactants. The term "starch and / or starch derivatives" also includes a group of polygylactomannan.

According to one embodiment of the invention, the starch and / or starch derivative is used in combination with high purity cellulose and / or a water swellable cellulose derivative. Up to about 95 wt. starch cellulose. Preferably, the weight ratio of starch and / or starch derivative to cellulose and / or cellulose derivative is 10: 1 to 1:10, particularly preferably the weight ratio is 5: 1 to 1: 5.

In this embodiment of the invention, the water swellable, preferably highly pure cellulose is used in the form of a microcrystalline structure, wherein the supermolecular structural elements have the shape of fibrils in which the crystalline and amorphous regions can alternate in the longitudinal direction. Particularly

4445 4 4

Natural cellulose fibrils with a maximum length of 300 µm have proved to be suitable. Both microcrystalline and amorphous fine-grained celluloses and / or cellulose derivatives and mixtures thereof can be used.

The fine-grained cellulose preferably has a bulk density of 40 g / l to 300 g / l, particularly preferably 65 g / l to 170 g / l. If granular types are used, their bulk density is higher, and may be 350 g / l to 550 g / l. The bulk density of the starch and / or starch derivatives may be 50 to 1000 g / l, preferably 100 g / l to 800 g / l.

The particle size of the fine-grained cellulose may be between 30 µm and 200 µm, in the case of granular types the mean particle size is between 350 µm and 800 µm.

The polysaccharides used according to the invention are of the type starch and / or starch derivatives and may be of different origin, for example starches from rice, maize, wheat, potatoes and legumes. Appropriate flour from cellulose parts of plants can also be used.

Advantageously, they can be used to swell or swell. cold soluble starches. Polygalactomannan, such as guar or locust bean flour, have these properties already in their natural state and can be used directly or after slight modification.

Starches, which are not cold swellable in nature, are preferably used in the form of their derivatives. Chemically substituted starches preferably contain substituents which

7 • · ···· β · «<· · 4 · · ·

99 are attached, via ester or ether groups, to the polysaccharide chain in sufficient quantity to provide swellability in water.

Starches modified with ionic substituents such as carboxyl, hydroxyalkyl or phosphate groups have proven particularly advantageous and are therefore preferred. It is furthermore possible to use starches swellable in cold water of the type of degraded starches, for example acids, enzymes and oxidatively degraded starches, respectively. dextrinated starches. It is often advantageous for swellability when starch derivatives are modified by a combination of degradation and chemical substitution.

The use of slightly cross-linked starches has also proven useful in improving swelling. Due to their solubility in cold water, alkali-treated starches are also used.

Another group of cold water swellable starches useful in the present invention are natural starches which are given cold swellability by physical processing. These include extruded starches and starches processed in a roller dryer.

In combination with starches (or derivatives thereof) and, optionally, cellulose (or derivatives thereof), fine-grained acrylic or methacrylic acid polymers or acrylic or methacrylic acid copolymers or salts thereof or mixtures of such polymers or copolymers or salts thereof with high water-absorption capacity are contained in the granulate. . Linear • 9 proved to be particularly suitable

-8 polymers of acrylic acid, methacrylic acid, copolymers of acrylic or methacrylic acid or their salts with a weight average molecular weight of 5000 to 70 000, and cross-linked polymers of acrylic acid, methacrylic acid, copolymers of acrylic or methacrylic acid or their salts with a weight average molecular weight of 1 The copolymers are preferably copolymers of acrylic or methacrylic acid and maleic acid or maleic anhydride, which contain, for example, 40 to 90% by weight. % acrylic or methacrylic acid and 60 to 10 wt. maleic acid or maleic anhydride whose relative molecular weight, based on free acids, is 3000 to 100,000, preferably 3000 to 70,000, most preferably 5000 to 50,000.

Terpolymeric and quaternary polymeric polycarboxylates formed from acrylic or methacrylic acid, maleic acid and vinyl alcohol or vinyl alcohol derivatives, or formed from acrylic or methacrylic acid, ethylenically unsaturated sulfonic acids and sugar derivatives, or formed from acrylic or methacrylic acid have also proven suitable. maleic, vinyl alcohol derivatives and sulfone-containing monomers.

The salt is preferably formed with an alkali metal cation, ammonia or amines, respectively. mixtures thereof.

Fine-grained polymers or copolymers of acrylic or methacrylic acid or its salts of the abovementioned crosslinked derivatives preferably have a mean particle size

• · · · · · · · · · ·

-945 to 150 μπι. Particularly preferred are particle sizes of 45 to 90 microns.

Particles with an average particle size of over 150 μπι show good swelling, but are too large after swelling, they are filtered off and are visible as particles on the textile after washing.

Starches or derivatives thereof and optionally cellulose or derivatives thereof are combined in the granulate with polymers or copolymers of acrylic or methacrylic acid or their salts in a weight ratio of 100: 0.5 to 100: 30, preferably 100: 1 to 100: 20, particularly preferred the weight ratio is 100: 1 to 100: 10, most preferably the weight ratio is 100: 3.

As a further essential component, the granulate comprises one or more liquid, water-gelling or thickened surfactants selected from the group of nonionic, anionic or amphoteric surfactants.

Nonionic surfactants are selected from the group consisting of alkylpolygucosides, fatty acid alkylolamides, polyethylene glycol esters of fatty acids, fatty amine oxoethylates, fatty alcohol ethoxylates with 3 to 15 moles of ethylene oxide or propylene oxide, fatty acid glycerides, sorbitan esters, sucrose esters, sucrose esters, e.g. pentaerythritol ester, which may also be ethoxylated, such as alkylphenolpolyethylene glycol ethers and phenolpolyethylene glycol ethers (if applicable).

· 9 9 ···· · ·>

• 999 9999

The anionic surfactants are selected from the group consisting of alkyl sulfates, linear and branched alkyl benzene sulfonates, alkyl glycerol ethers, sulfates of ethylene glycol ethers of fatty alcohols, sulfonates of paraffins, sulfonates of alpha-olefins, sulfosuccinates, esters of phosphoric acid and carboxylates of fatty alcohol ethers.

The amphoteric surfactants are selected from the group consisting of betaine coconut propylamide, modified imidazoles and fatty acid amide derivatives with a betaine structure.

The amount ratio of starch or its derivatives and optionally cellulose or its derivatives and / or polymers or copolymers of acrylic or methacrylic acid or its salts to the surfactant may be 100: 1 to 10: 1. The amount ratios are 100: 2 to 100: 5.

Surprisingly, it has been found that by depositing the surfactant of the invention on starch or a derivative thereof and optionally on cellulose or a derivative thereof, the swelling effect of the disintegrant granulate of the invention has been clearly improved. This is particularly surprising since numerous concentrated surfactants tend to gelatinize and crosslink when in contact with water and should therefore tend to reduce the swelling of the disintegrant granulate. Gelatinization or thickening effects have been observed, for example, with fatty acid ethoxylates, soaps, fatty alkyl ether sulfates and fatty alkyl sulfates.

The water gelling or thickened surfactants may be anionic, amphoteric or nonionic, nonionic surfactants being particularly preferred.

It has proven particularly advantageous to bring the liquid surfactants first into direct contact with starch or its derivatives and optionally cellulose or its derivatives, and then to add to this mixture fine-grained polymers or copolymers of acrylic or methacrylic acid or their salts, so that the polymer particles adhere to cellulose or starch fibrils or derivatives thereof.

The mixture of the components of the granulate according to the invention, namely starch or its derivatives and, if appropriate, the starch. cellulose or its derivatives and polymers or copolymers of acrylic or methacrylic acid and non-ionic surfactants are granulated by conventional methods. Mixers from Vomm, Lodige, Schugi, Eirich, Henschel or Fukae can be used.

Subsequent compaction is essential for the swelling and water uptake properties of the granules of the invention. The compaction can be carried out in various ways using pressure.

It has proved to be particularly advantageous to compact by means of a rolling device, the rolls of which rotate at different speeds, so that, in addition to the pressure effect, a friction force is exerted on the granulate in the rolling gap. This leads to the formation of a scaly structure and an arrangement of the structure of the starch or its derivatives and optionally anisotropic cellulose or its derivatives in the granulate.

This arrangement of the structure may cause a particularly advantageous swelling behavior in this embodiment of the granulate according to the invention.

* 4

-12 • 44 · 4 ··· · 4 · · · ·

4 4

The compacting of the granulate may be such that the compacted granulate has a bulk density of 100 to 800 g / l, preferably 200 to 600 g / l, most preferably 300 to 500 g / l.

The disintegrant granules according to the invention are present in the moldings in amounts of 0.5 to 10% by weight, preferably 2 to 7% by weight, particularly preferably 3 to 6% by weight.

The specific water absorption capacity of the granulate of the invention can be determined gravimetrically as follows:

A defined amount (e.g., 2.00 g) of the granulate is sealed in a thin paper bag, such as a tea bag, and immersed in a container with excess water. After three minutes of immersion time, the bag is removed from the water and suspended for 10 minutes to drain. The bag is weighed and the amount of water received is determined from the weight difference of the wet bag with and without granulate. Distilled water or water of defined hardness is used for the determination.

The amount of water absorbed in this manner is preferably 500 to 2000%.

The compacted granulate according to the invention is characterized by excellent swelling kinetics, its expansion varies with time in a non-linear manner and can reach a certain level in the shortest time. Of particular interest is the swelling in the first 10 seconds after contact with water when using granules as disintegrants for moldings.

-13···· · · • ·· ··· ·· "·

The volume increase is preferably 55 to 225% by weight after 5 seconds. higher bulk density, the volume increase is usually greater. After 10 seconds, the volume increase is preferably 75 to 270% by volume, and the volume increase also increases with increasing bulk density.

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

To determine the swelling rate and the swelling rate under load, 3.00 g were placed in a cylindrical plastic container with an inner diameter of 60 mm and covered with a water-permeable fleece. Depending on the bulk density, the thickness of the granulate layer is 1 to 3 mm. A movable, pre-drilled punch weighing 58 g was placed on the web and coupled to a path measuring device showing the punch travel versus time. By adding 50 ml of water, the granulate is swollen and the displacement (travel length) of the punch thus determined and graphically evaluated as a function of time.

Giant. 1 is a diagram of the swelling kinetics of known disintegrants and granulates according to the invention.

· 99 99 • 9 99 9 9 9 9

9 9 9 9 9

9 9 9 9 99 99 9 • · 999 9999 _{λ t} ··· · · 99999 99 99

-14 Table 1 contains the corresponding measured values.

Table 1: Kinetics of swelling different materials Sypná 70 90 90 300 300 450 450 mass (g / D celu- VI Ml V2 M2 V3 M3 time (s) lóza path path path English Translation: path path (mm) (mm) (mm) (mm) (mm) (mm) (mm)

0 0 0 0 0 0 0 0 1 0.10 0.20 0.35 0.30 0.70 0.80 1.30 2 0.20 0.40 0.50 0.60 1.40 1.20 2.00 3 0.30 0.60 0.75 0.90 1.70 1.5o 2.30 4 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 8 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 10 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 12 0.50 1.50 2.00 1.65 2.52 1.92 3.00 Composition of samples VI Example 1. to V3 is the same not like in Table 3, Sample composition Ml to M3 is the same as in Table 3,

Example 6.

-15 · * · · 99 99

999 9 9 «* 9 9 9 9 9

9,999 99 9

9 9 9 9 9

999 99 99

Table 2: Volume expansion in% vol

Cellulose M1 V2 M2 V3 M3 Lose Bulk Weight 70 (g / D volume expansion after 5 s (ob%) 5 after 10 s (ob%) 6

90 90 300 14 18 61 23 35 83

300 450 450 110 210 240 140 242 270

Composition VI has the composition of Example 1 form. Composition M1 has the composition of Example 6 form. V2, M2 denote samples that were compacted in a roller press to a bulk density of 300 denote samples that were compacted after blending to a bulk density of 450 g / l.

v uncompacted v uncompacted after mixing g / 1. V3, M3 in cylindrical

An improved efficiency of the compacted samples is evident, with a volume expansion of 5 preferably at least 95%, particularly preferably> 150%.

A further object of the invention is also a process for the production of a compacted granulate comprising starch or derivatives thereof, and optionally. water-insoluble but swellable high purity cellulose and acrylic or methacrylic acid polymers or copolymers or their salts and one or more non-ionic surfactants by mixing starch or its derivatives and optionally high purity cellulose with one or more surfactants and blending polymers or copolymers , granulating and subsequently compacting the granulate in arranging the structure of the starch or its derivatives and optionally cellulose or its derivatives.

-16 * »» · «16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 16 ·>

• ♦ · • * * * *

The first step of the process comprises a mixing and granulating process in which a masterbatch is produced by agglomeration. These premixes form a loose coarse-grained material having a certain moisture content. In the next step, these masterbatches are mechanically compacted. The product may be compacted between the pressing surfaces of the rolling device, eg smooth or profiled. If certain shear properties are present, compaction can be performed in extruders or in molds on presses. The compacted material extrudes as a string. Molding by means of punches or punch rollers provides compact shapes such as tablets or briquettes. Roller compactors, extruders, roller presses or cube presses, but also granulation presses can be used as compaction machines. Subsequently, the coarse compacted particles are crushed, for example mills, cutters or rolling mills are suitable.

The granulate according to the invention, in contact with water, rapidly absorbs water with an increase in volume and is therefore suitable as a so-called disintegrant for molded bodies, so that they disintegrate rapidly in water.

The invention encompasses the use of compacted granules as disintegrants for compressed moldings, for example tablets, cubes, spheres and the like.

Especially preferred is its use as disintegrants for detergent compositions, detergent compositions, stain removal salts and water softening compositions in tablet or bar form.

-17 • 9 · 9 · 9 · 9 · 9 9 9 9 9 9

9

999 99 99

Detergent tablets and detergent tablets for various purposes, in the sanitary field or for dishwashers, are known in principle.

Such shaped bodies must have sufficient stability and strength to allow handling, packaging and storage, but must disintegrate rapidly in contact with water so that their components can exert the desired effect.

For this reason, molded moldings often contain so-called disintegrating agents which, by virtue of their swellability and volume expansion, disrupt the cohesion of the molded bodies and accelerate disintegration.

Such detergent compositions formed as shaped bodies, such as tablets, generally contain bases, bleaching agents and bleach activators, surfactants, tabletting ingredients, disintegrating agents, and other ingredients and excipients.

Polyphosphates, diphosphates, metaphosphates or phosphites, flake silicates, amorphous silicates, amorphous di-silicates and zeolites can be used as bases. Other components of the building component system may be fillers such as alkali metal carbonates or bicarbonates, such as sodium carbonate or sodium bicarbonate, sesquicarbonates, sodium sulfate, magnesium sulfate, citrates, citric acid, succinic acid, tartaric acid and malic acid. Builders and dispersants are often used as auxiliaries.

Such builders or dispersants may be polyacrylic acids and their sodium salts.

It is also possible to use copolymers of acrylic or methacrylic acid and maleic acid, terpolymers and quaternary polymers of acrylic or methacrylic acid, maleic acid, vinyl alcohol and vinyl compounds with a sulfo group.

Especially preferred are also terpolymer and quaternary polycarboxylates made from acrylic or methacrylic acid, maleic acid and vinyl alcohol or vinyl alcohol derivatives (as described in DE 43 00 772), or from acrylic or methacrylic acid, 2-alkylalyl sulfonic acid and sugar derivatives (such as are described in DE 42 21 381) or from acrylic or methacrylic acid, maleic acid, vinyl alcohol derivatives and sulfo group monomers (as described in DE 19 516 957).

Further suitable are polyethylene glycol and / or polypropylene glycol having a molecular weight of 900 to 30,000, as well as polysaccharides, polyapartates and polyglutamate.

Mixtures with various builders, such as citric acid, are also possible.

Typical bleaching agents are sodium perborate tetrahydrate and sodium perborate monohydrate, sodium percarbonate, perphosphate, citrate perhydrate, as well as peracid salts and

Peroxyacids, providing peroxybenzoates, peroxophthalates, diperoxododecanoic acid. in tablets preferably 10 is 15 to 50 wt.

H ₂ O ₂ , such as diperoxoazolaic acid Bleaching agents up to 60% by weight, in particular

Activators can be incorporated to achieve good bleaching performance in washes up to 60 ° C. Suitable bleaching activators are N-acyl and O-acyl compounds forming with H ₂ O _2, organic peracid, preferably N, N-tetraacyldiaminy, carboxylic acid anhydrides and esters of polyols, such as glucose pentaacetate. Acetylated mixtures of sorbitol and mannitol may also be used. Particularly suitable as bleach activators are Ν, Ν, Ν '', N'-tetraacetylethylenediamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,2,5-triazine (DADHT) and acetylated sorbitol mixtures and mannitol (SORMAN).

In addition to nonionic, anionic and amphoteric surfactants, cationic surfactants, for example quaternary ammonium compounds with _C8- C16 N-alkyl or cationic surfactants, may also be present in the detergent compositions. N-alkenyl groups; hydroxypropyl groups.

Suitable tabletting additives are polyalkylene glycols and magnesium stearate.

Examples of other conventional additives and excipients are enzymes, magnesium silicate, aluminum aluminate, benzotriazole, glycerin, magnesium stearate,

-20 polyalkylene glycols, hexametaphosphate, phosphonates, bentonium, soil releas polymers and carboxymethylcellulose.

Dishwashing detergent tablets as one embodiment of the detergent composition typically comprise as builders polyphosphates, diphosphates, metaphosphates or phosphonates, flakes, amorphous silicates, amorphous silicates and zeolites, as well as fillers such as sodium carbonate, sodium sulfate, magnesium sulfate , sodium bicarbonate, citrates as well as citric acid, centenaric acid, tartaric acid and malic acid. Builders and dispersants are often used as auxiliaries. Such builders or dispersants may be polyacrylic acids or polyacrylic acid copolymers and their sodium salts.

bleaching agents are sodium perborate sodium perborate monohydrate,

Conventional tetrahydrate and percarbonate or trishydrates, peroxyacids, peroxybenzoates, sodium, as well as providing perphthalate, peroxydisulfate, peroxyacid salts and H ₂ O ₂ , such as diperoxoazolaic acid diperoxododecanoic acid. Their content in the tablets is preferably 10 to 60% by weight, particularly preferably 15 to 50% by weight.

Non-foaming nonionic surfactants such as polyalkylene glycol and alkyl polyglucosides are also used.

• ·

-21 * · · · · · · · · · · 4 4 4

4444 44 4 44 44 4

4,444,444 «

444 4 «444 44 44

Examples of other conventional additives and excipients are enzymes, magnesium silicate, aluminum aluminate, benzotriazole, glycerin, magnesium stearate, polyalkylene glycols, hexametaphosphate and phosphonates.

Water softener tablets generally consist of building materials such as flake silicates, amorphous silicates, amorphous silicates and zeolites, as well as fillers such as sodium carbonate, sodium sulfate, magnesium sulfate, sodium bicarbonate, citrates, and citric acid. Builders and dispersants are often used as auxiliaries. Such builders or dispersants may be polyacrylic acids and their sodium salts.

Non-foaming nonionic surfactants such as polyalkylene glycol and alkyl polyglucosides are also used.

Examples of other conventional additives and excipients are magnesium silicate, polyalkylene glycols, and phosphonates.

DETAILED DESCRIPTION OF THE INVENTION

The invention will be explained in more detail with reference to the following exemplary embodiment. All data are by weight unless otherwise indicated on a case-by-case basis.

Examples 1-8 • ·

Table 3: Examples of disintegrant compositions according to the idea of the invention (all amounts in% by weight)

example component: 1 cf. 2 cf. 3 . cf. 4 5 cf. cf. 6 7 8 cellulose 80 50 80 48 85 70 80 55 linear PAA ^v) 20 May 5 10 5 12 8 8 10 cross-linked PAA - - - - 1 - - - carbomethyl ^{starch Vli)} - - - - - - 10 - hydroxyethyl starch ^vii) - - - - - - - 10 (vii) guar - - - - - 20 May 1 - microcrystalline cellulose - - - - - - - 23 Ni-surfactant ^iv) - - 10 5 2 2 2 2 water up to 100% - 45 - 42 - - - - (x) figures in% se concern i folders in commercially available form

with a typical water content of xx) cellulose with a fiber length of 150 μπι xxx) microcrystalline cellulose with a particle size of about 200 μπι iv) fatty alcohol surfactant (C12 / 14, EO04,7)

(v) linear polyacrylic acid with an average molecular weight of 40 000; vi) crosslinked polyacrylic acid with a wiping, molecular weight of 2 000 000; (vii) commercially available material

Example 9

Detergent tablets: Tablet strength and disintegration time using the granules of the above examples.

23 Detergent tablet compositions of Table 3 were tested for disintegration time and strength.

Table 4: detergent tablet composition substance% sodium tripolyphosphate 35 sodium percarbonate 19

TAED 4 fatty alcohol sulphate 14 linear alkylbenzene sulphonate 4 soda 8 defoamer, optical brightener, CMC, phosphite 6 microcrystalline cellulose (200 μιη) 2 enzyme mixture 1 fatty alcohol ethoxylate (C12 / 14, EO = 4,7) 2 disintegrant according to examples 1 to 8

Table 5: Strength and disintegration time of individual detergent tablets using different disintegrants

the composition of the disintegrant according to example no. 1 disintegration time (s) 35 strength (N) 62 2 25 63 3 22nd 53 4 21 64 5 19 Dec 58 6 18 56 7 18 59 8 17 61

Example 10

Phosphate-free detergent tablets: tablet strength and disintegration time using the granulate of the above examples

10.1 .: Granulate of Example 6 in a zeolite-based composition

-25Table 6

substance amount and) (b) zeolite P 39 35 fatty alcohol ethoxylate (C12 / 14, EO = 4.7) 4 7 sodium carbonate 16 16 TAED 4 4 fatty alcohol sulfate 10 11 linear alkylbenzenesulfonate 3 3 soda 4 4 antifoam, optical brightener, CMC, phosphite 5 5 mixture of enzymes 1 1 microcrystalline cellulose (200 pm) 4 4 the disintegrant of Example 6 5 5 sodium citrate 5 5

Table 6.1

composition disintegration time (s) strength (N) and) 30 59 (b) 35 51 10.2 .: Granulate from a composition based on of silicate

-26Table 7 amorphous fatty alcohol polysilicate fatty alcohol ethoxylate fatty alcohol sulphate linear alkylbenzene sulphonate sodium percarbonate

TAED acrylate / maleate copolymer sodium sodium citrate microcrystalline cellulose (200 μτη) antifoam, optical brightener, CMC, phosphonate enzyme mixture disintegrant according to example 6 amount% a) b)

30

7

15 Dec

2

16

4

4

5

4

4

1

5

Table 7.1

Composition disintegration time (s) strength (N) and) 40 68 (b) 15 Dec 48

Example 11: Molded moldings intended for use as

(a): stain-removing salt of the following composition:

-27 • 0 * 0 00 00 • · · 0 · 000 0 · · · · 000 ···· · · · 0 0 0 0 0 0

00 0 0000 * · · · · · · · ·

Table 8 Substance Amount% Mixed soda-silicate granulate 20 Soda 41 Non-ionic surfactant 4

TAED 7 enzyme mixture 1 sodium percarbonate 24 disintegrant according to example 4 3

(b): stain-removing salt of the following composition:

Table 9 Substance% zeolite 15 sodium bicarbonate 32 citric acid 20 polycarboxylate 17 flake silicate 8 excipients 5 disintegrant according to example 7 3

(c): dishwasher detergent of the following composition:

-28 • · «· 9 ···

9 · · 9 ··· <

9 · 9 9 9999 ···· · · · 999 99 9

98 9 · 9 9 9

99,999 9 · 99

Table 10 substance quantity% mixed granulate soda-disilicate 20 tripolyphosphate 35 soda 20 sodium perborate 12

TAED 4 enzyme mixture 2 processing aids 3 perfume, dyes 2 disintegrant according to example 8 3

Strength and disintegration values of detergent tablets

Table 11

Physical Salt for Product for Product for parameter removal softening washing dishes stains o water composition in the dishwasher o composition according to according to b) composition according to and) (b) Strength (N) 170 200 180 Disintegration time 224 147 240 without a hammer Disintegration time 100 ALIGN! 70 60 with a bubbler

BB Β ·

Claims (23)

PATENT CLAIMS A compacted granulate comprising starch and / or starch derivatives and fine-grained polymers and / or copolymers of acrylic or methacrylic acid or their salts and one or more liquid, water-gelling or thickened surfactants. The granulate according to claim 1, characterized in that it further comprises a water-insoluble, water-swellable, highly pure cellulose and / or a cellulose derivative. Granulate according to claim 1 or 2, characterized in that it has an ordered structure formed by compacting starch and / or its derivatives and anisotropic cellulose or its derivatives. Granulate according to one of Claims 1 to 3, characterized in that the weight ratio of the combination of starch and / or its derivatives and optionally water-swellable cellulose and / or its derivatives with polymers and / or copolymers of acrylic or methacrylic acid to liquid surfactants or surfactants is 100: 1 to 10: 1. Granulate according to one of Claims 1 to 4, characterized in that the surfactants are nonionic and / or anionic and / or amphoteric surfactants. Granulate according to one of claims 1 to 5, characterized in that the starches and / or their derivatives and -30 ··· · f · · · ♦ · • · • · • · • · · · · popřípadě popřípadě popřípadě water-swellable high purity cellulose and / or derivatives thereof and fine-grained polymers or copolymers of acrylic or methacrylic acid are present in a weight ratio of 100: 0.5 to 100: 30, preferably 100: 1 to 100: 20, particularly preferably in a weight ratio of 100 : 1 to 100: 10. 7. Granulate according to any of the claims 1 to 6, characterized by that has bulk density to i 800 g / i, preferably 200 to 600 g / 1, no ! more preferably 300 to 500 g / i • 8. Granulate according to any of the claims 1 in az 7, characterized by that has ability hold 500 az 2000 wt. % water. 9. Granulate according to any of the claims 1 to 8, characterized in that it has nonlinear swelling kinetics. Granulate according to one of claims 1 to 9, characterized in that the fine-grained polymers and / or copolymers of acrylic or methacrylic acid are selected from the group consisting of linear polymers and / or copolymers of acrylic or methacrylic acid, crosslinked polymers and / or copolymers of acid. acrylic or methacrylic, copolymers of acrylic or methacrylic acid and maleic acid, terpolymeric and quaternary polymeric copolymers, formed from acrylic or methacrylic acid, maleic acid and vinyl alcohol or vinyl alcohol derivatives, or formed from acrylic or methacrylic acid, ethylenically unsaturated sulphonic acids and formed from acrylic or methacrylic acid, pi / / 993-39¾ • 94 · 9 9 9 9 9 9949 9994 • 9 94 9 9944 444494 9 4 45 44 4 -31 maleic or maleic anhydride, vinyl alcohol derivatives and sulfone-containing monomers, and mixtures thereof. Granulate according to one of claims 2 to 10, characterized in that the fine-grained cellulose and / or cellulose derivatives have a mean particle size of 30 to 300 μτη and / or have a bulk density of 40 g / l to 300 g / l, preferably 65 g / l to 170 g / l. Granulate according to any one of claims 1 to 11, characterized in that the starch is selected from the group consisting of cold water-soluble starches. Granulate according to one of claims 1 to 12, characterized in that the starch and / or starch derivatives are chemically and / or physically modified starches. Granulate according to any one of claims 1 to 13, characterized in that the starch is selected from the group consisting of galactomannans, carboxymethyl starches, hydroxyethyl starches and dextrins. Granulate according to one of claims 1 to 14, characterized in that the liquid anionic or nonionic surfactants, one or more, are selected from the group consisting of fatty alcohol ethoxylates with 3 to 15 moles of ethylene oxide, anionic type of fatty alcohol sulfates and linear alkylbenzene sulfonates. as well as alkyl ether sulfates, and mixtures thereof. -32 • φ · · · φ · · · · · · · · · · · · 99 ΦΦ φφ 99 Method for producing a compacted granulate according to any one of claims 1 to 15 by mixing starch or its derivatives and optionally high purity cellulose and / or its derivatives with one or more non-ionic, anionic and amphoteric surfactants and admixing fine-grained polymers and / or copolymers of acrylic or methacrylic acid or a salt thereof, by granulating and subsequently compacting the granulate. Method according to claim 16, characterized in that the compaction of the granulate is arranged in the structure of starch or its derivatives and optionally anisotropic cellulose and / or its derivatives. Method according to claim 15 or 16, characterized in that the compaction is carried out by means of a rolling device with the simultaneous effect of a friction force. Method according to claim 15 or 16, characterized in that the compaction is carried out by means of a roller compactor, a roller press or a die press, or an extruder. Use of the granulate according to any one of claims 1 to 15, optionally obtained by the process according to any one of claims 16 to 19, as a disintegrant for molded moldings. Use according to claim 20, wherein the granulate is used in an amount of 0.5 to 10% by weight, preferably 2 to 7% by weight, in particular 3 to 6% by weight. Use according to claim 20 or 21 as disintegrant for detergent tablets. -339 9 99 99 99 9 9 9 • 9 9 9 9 9 9 9 9 9 9 999 99 99 Use according to claim 20 or 21 as disintegrant for detergent tablet. Use according to claim 23 as disintegrating agent for dishwasher detergent tablets. Use according to claim 20 or 21 as disintegrant for water softening tablets. Use according to claim 20 or 21 as disintegrating agent for stain removal salts tablets. 555ΘΑΜ6Ι, Dalli / StoekhaHSQO-