EP1043389B1 - Detergent tablets containing a granular disintegrant - Google Patents

Abstract

A detergent and/or cleansing composition is in the form of a pressed article containing fine (co)granulated active agents, builders, auxiliaries, additives and 3-15 wt.% of a densified disintegrant granulate (I) comprising (A) water-insoluble, water-swellable cellulose and (B) binder(s) selected from (meth)acrylic acid (co)polymers and their salts. A detergent and/or cleansing composition is in the form of a pressed article containing fine (co)granulated active agents, builders, auxiliaries, additives and 3-15 wt.% of a densified disintegrant granulate (I) having moisture content 2-8 wt.% and porosity 600-1000 mg/kg and comprising (A) water-insoluble, water-swellable cellulose and optionally other modified water-swella polysaccharide derivatives and (B) binder(s) selected from (meth)acrylic acid (co)polymers and their salts.

Description

The invention is directed to pressed molded articles of washing and or Detergent compositions which, due to the contained explosive granules, which absorbs water particularly well while increasing the volume and passes on to the inside, quickly disintegrate on contact with water.

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, e.g. microcrystalline cellulose, CMC, MC, alginic acid, carboxylmethylamylopectin, Polyacrylic acid, polyvinyl pyrrolidone and polyvinyl polypyrrolidone. The granules are made by conventional means, such as spray drying, hot steam drying of aqueous preparations or by granulation, pelleting, extrusion or roller compaction powder components. The dust-free nature of the explosive granules and the other constituents to be pressed into shaped bodies is shown in this document expressly emphasized. The pressed moldings are said to Laboratory test in contact with water without mechanical action quickly disintegrate.

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 mentioned as disintegrants. The application amounts are up to 15% by weight. Since water-soluble silicates are used as builders, a combination of poly (meth) acrylates and nonionic cellulose ethers can lead to very good results even in amounts of 1% by weight.
In EP-A-846 756, tablet disintegrants are incorporated into the tablet and preferably into the outer hard shell of the tablet. Combinations of soluble acids and alkali carbonates are preferably used. Further possible disintegrants can be found in the "Handbook of Pharmaceutical Excipients (1986). Examples are: 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 containing disintegrants are known from EP-A-522 766. that work according to four different mechanisms: swelling, Porosity / capillary action, deformation and chemical reaction. Described 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. As well Combinations of organic acids and alkali bicarbonates are mentioned and alkali carbonates.

EP-A-628 627 describes a water-soluble, water-softening builder in the form of a tablet. Combinations of explosives are used Citric acid and / or partially neutralized polymers and carbonate and / or bicarbonate or an insoluble polyvinylpyrrolidone.

EP-A-799 886 describes detergent tablets which are used as disintegrants Starch derivatives, cellulose compounds, polyvinylpyrrolidone compounds, Polyvinyl polypyrrolidone compounds, bentonite compounds, alginates May contain gelatin and pectins. To further improve the Dissolving time is 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.

DE-A-197 09 991 describes a disintegrant for pressed molded articles powder or granular ingredients, this disintegrant compacted, finely divided cellulose material, possibly in combination with Contains surfactants. The volume of the disintegrant with a particle size from 0.2 to 6 mm increases on contact with water and thereby unfolds in compressed moldings explosive effect, which leads to the faster disintegration of the Shaped body contributes.

In total, the state of the art shows a pronounced optimization of the Disintegrant for selected formulations.

When formulating detergents and cleaning agents is also on the difficulty of using nonionic surfactants. The commercial products of these surfactants are liquid to highly viscous and tend to gel when diluted.

In WO 90/02165 this problem is solved by the production of two components solved before the pressing to a shaped body, in one Component the total amount of anionic surfactants in the other component most of the nonionic surfactants are included.

In EP-A 711 827, the use of citrate, which is a specific The tablet disintegrates in water in the presence of accelerated non-ionic surfactants.

To solve this problem, WO 95/21908 shows an approach in which amorphous, partially crystalline and / or crystalline layered silicates in the tablets are incorporated, and the tablets water up to a maximum Contain an amount that the ingredients can bind as crystal water.

This document also specifically emphasizes the need for assembly of the wording highlighted.

A treatment of the is also described in WO 98/40463 already mentioned above remaining ingredients of the formulation before mixing with the Disintegrant granules described, with a preferably anhydrous Treatment is pointed out. This special type of treatment requires in this case that dust particles below 0.2 mm before mixing with the Disintegrant granules should be separated as completely as possible since it otherwise deterioration of the disintegration properties of the tablets is coming.

The prior art uses many approaches to optimize the decay properties proposed by active washing and cleaning tablets, however, most of the improvements are very formulation-specific and therefore hardly universally applicable. It also helps to optimize formulation properties often used materials that themselves little contribute to the washing performance of the formulations.

The object of the invention is to produce pressed molded articles of washing and cleaning formulations to provide that no special treatments require before pressing and included when used in dosing chambers domestic or commercial washing machines disintegrate quickly and effectively.

This object is achieved by washing and / or cleaning compositions in the form of pressed bodies, containing in relatively fine form, as granules and / or cogranules, customary washing and / or cleaning substances, builders, auxiliaries and additives and 3 to 15% by weight. , based on the total weight of the compositions, compressed disintegrant granules of (a) water-insoluble cellulose which is water-soluble and optionally other modified water-swellable polysaccharide derivatives and (b) one or more polymers / copolymers of (meth) acrylic acid or salts thereof , and (a) and (b) are present in a weight ratio of 50: 1 to 2: 1 , and wherein the disintegrant granules have a moisture content of 2 to 8% by weight and a specific porosity of 600 to 1000 ml / kg (in terms of a specific time of 1 Kg of solids absorbed amount of organic liquid).

The disintegrant granulate preferably also contains one or more liquid, surfactants that gel or thicken with water.

The water-swellable cellulose is used in the disintegrant granulate in the form of cellulose fibers or microcrystalline cellulose, the super-molecular structural elements being in the form of fibrils, in the longitudinal direction of which crystalline and amorphous areas can alternate. Fibrils of native cellulose with a maximum length of 300 µm have proven to be particularly suitable. Both microcrystalline and amorphous cellulose and mixtures thereof can be used.
The cellulose preferably has bulk densities from 40 g / l to 300 g / l, very particularly preferably from 65 g / l to 170 g / l. If already granulated types are used, their bulk density is higher and can range from 350 g / l to 550 g / l. The bulk weights of the cellulose derivatives can be in the range from 50 g / l to 1000 g / l, preferably in the range from 100 g / l and 800 g / l.

The particle size of the cellulose can be between 30 µm and 400 µm, in the case of granulated types, the average particle size is between 350 µm and 800 µm. The particle size of the cellulose derivatives can be between 30 µm and 3000 µm.

The proportion of cellulose in the disintegrant granulate is between 60 to 99 % By weight, preferably between 60 to 95% by weight.

In a special embodiment of the explosive granules are also regenerated celluloses, such as viscose.

Due to their water absorption capacity, cellulose derivatives that are swellable in water, such as cellulose ethers and cellulose esters and mixed modifications the same can also be used. Suitable cellulose ethers are e.g. Methyl cellulose, hydroxypropyl cellulose and carboxymethyl cellulose, as well modified carboxymethyl cellulose. In addition, the granules in Water-swellable cellulose derivatives and starch or starch derivatives as well contain other swellable polysaccharides and polygalactomannans, for example ionically modified celluloses and starches such as carboxymethyl-modified Cellulose and starch, non-ionically modified celluloses and starches such as alkoxylated celluloses and starches such as hydroxypropyl and hydroxyethyl starch or hydroxypropyl and hydroxyethyl cellulose and alkyl etherified products such as methyl cellulose as well mixed modified celluloses and starches from the above modifications, that leads to networking. Suitable strengths are also cold swelling starches, which are caused by mechanical or degrading reactions Starch grain are formed. Above all, this includes swelling starches from extruder and drum drying processes as well as enzymatic, oxidizing or acid-degrading modified products. Contain chemically derivatized starches preferably substituents, which by ester and ether groups in sufficient number are attached to the polysaccharide chains.

Starches containing ionic substituents such as carboxylate, hydroxyalkyl or modified phosphate groups have proven to be particularly advantageous proven. The has also improved the swelling behavior Proven use of slightly cross-linked starches. Also treated with alkaline Starches can be used because of their good cold water swellability become.

In an advantageous embodiment, the combination of cellulose with cellulose derivatives and / or starch and / or starch derivatives proven. The quantitative ratios can vary within a wide range the proportion of cellulose derivatives and / or on the combination Starch and / or starch derivatives preferably 0.1 to 85% by weight, particularly preferably 5 to 50% by weight.

Pure cellulose and cellulose derivatives can also be used together with others modified water-swellable polysaccharide derivatives such as e.g. Strength and / or starch derivatives present in the granules to be used according to the invention his.

In combination with cellulose and possibly other modified ones water-swellable polysaccharide derivatives are polymers of (Meth) acrylic acid or copolymers of (meth) acrylic acid or salts thereof or mixtures of such polymers or copolymers or salts the same with high water absorption capacity in the granules. The Polymers can be used as finely divided polymers and / or as soluble polymers be used in aqueous solution. 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 ethylenic unsaturated dicarboxylic acids or their anhydrides, e.g. 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 Examples of suitable polymers can be found in DE 43 00 772, DE 42 21 371 and WO 95/17444.

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

The polymeric binders are preferred in the manufacture of the granules used in the form of their aqueous solutions, but can also in the form finely divided powder can be used.

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.

The proportion of polymers / copolymers in the disintegrant is between 1 and 40% by weight, preferably between 1 and 20% by weight, particularly preferably between 5 and 15% by weight.

Suitable co-binders that are also surfactant-type are also so-called polymer surfactants. These are reaction products understood, in addition to the typical polymer structures of the aforementioned Binder polymers additional structural elements that develop a surfactant effect exhibit. Examples of these are graft polymers with alkoxylated Fatty alcohol or carboxylate-containing polymers with methoxyalkylene oxide monomer units, also maleic acid / vinyl ether / longer chain fatty amine copolymers as well as half-amides of maleic acid copolymers and copolymers of Acrylic acid with long chain acrylates. In a preferred embodiment contain the polymeric surfactants alkylene oxide units. The polymer surfactants can also be used alone, i.e. without polymeric binder components and without Surfactant components are incorporated into the disintegrant granules. As The polymer surfactants with an amount of up to 30 become additional components % By weight can be contained in the disintegrant granulate as a single component with 1 to 40% by weight, preferably 5 to 20% by weight.

The cellulose and optionally other modified water-swellable polysaccharide derivatives are combined with polymers / copolymers of (meth) acrylic acid or salts thereof in the granulate, the weight ratio is from 50: 1 to 2: 1, preferably from 20: 1 to 5: 1, very particularly preferably is a weight ratio of 10: 1.
The cellulose and optionally other modified water-swellable polysaccharide derivatives, together with the polymers / copolymers of (meth) acrylic acid or salts thereof, are predispersed in water, wet-compacted and granulated and then dried. The wet granulation and the subsequent evaporation of the water to a residual water content of 2 to 8% by weight, based on the weight of the granulate, gives it a specific porous structure in which the polymer / copolymer of (meth) acrylic acid or its salt on the surface of the cellulose and optionally further modified water-swellable polysaccharide derivatives with incrustation of the surface.

The porous structure results in a particularly favorable absorption behavior for Liquids, in the case of water with rapid volume increase.

As specific porosity in the present invention, the under absorption of organic liquid determined under certain test conditions, which is understood without sources. The specific porosity of the The explosive granulate to be used according to the invention is 600 up to 1000 ml / kg, preferably 700 to 900 ml / kg, particularly preferably 850 ml / kg granules.

The preparation of the disintegrant granules to be used according to the invention is carried out first by mixing the granulate components according to the invention with usual mixing methods. For example, mixers from the company Vomm, Lödige, Schugi, Eirich, Henschel or Fukae can be used. At This first step of mixing and granulating becomes pre-compounds produced by agglomeration processes. These pre-compounds form one pourable goods that have a water content between 10 and 80% by weight. The required water content in the premix depends on the one used Compression device. A water content of at least 10% by weight, preferably 20% by weight is required in order to achieve good compaction. and a high fluid intake in the later dry granulate to guarantee. With water contents between 60 and 80% by weight, this is the case make sure that it is used with certain compactors, such as the ring die press during the pressing process, the water can can be pressed out of the mixture, whereas none in extruders Phenomena can be observed. I.e. the compression technology must ultimately be adjusted to the water content of the premix. For ring die presses and pelleting presses has a water content of 20 to 60% by weight, preferably from 20 to 40% by weight.

In the next step, these pre-compounds are mechanically compressed. For the swelling and water absorption behavior of the one to be used according to the invention The final compaction is essential for granules. The condensing using pressure can be done in several ways. The Products can be placed between two pressure surfaces in roller compressors, e.g. smooth or profiled. The compactate is ejected as a strand. Compaction methods in dies with punches or cushion rollers result in forms of copactate such as tablets or briquettes. As compaction machines can compactors, extruders, roller or cube presses, but also pelletizing presses are used.

Compression with pelleting presses has proven to be particularly suitable, granules are obtained by suitable process control, which can be dried without further crushing. Suitable Pelleting presses are e.g. from the companies Amandus Kahl and Fitzpatrick manufactured.

In the drying process, the water content of 2 to 8% by weight is preferred 2.5 to 7% by weight and particularly preferably 3 to 5% by weight. Therefor are common dryers such as Roller dryer (temperatures e.g. from 95 to 120 ° C) or fluid bed dryer (temperatures e.g. from 70 to 100 ° C).

The coarse, compacted particles are crushed, e.g. Mills, Carvers or roller mills are suitable. The crushing can be done before or after drying. The granules to a particle size distribution of 0.05 to 3 mm, preferably 0.1 to 1.5 mm set. The removal of dust particles below 0.1 mm can e.g. be carried out with conventional screening devices.

For use as a disintegrant for pressed molded articles of washing and / or cleaning compositions have grain fractions with average Grain size 0.5 to 3 mm, preferably 1 to 2 mm as special proven suitable. These fractions can be sieved or using a cyclone sifter are obtained, taking care that the proportion of Oversize and fines (undersize) is as low as possible. The shares 5% by weight of oversize or undersize should be used for process engineering reasons based on the weight of the grain fraction. Granules with Larger grain sizes are fed to breaking again, more formed Fine dust is returned to the wet mix and again together with a following wet approach compacted.

By wet compacting the granules to be used according to the invention and the subsequent drying forms a "crust" of the polymer / copolymer on the cellulose fibers or on the microcrystalline Cellulose or the cellulose derivative from the points of contact of the individual fibers for a stable juxtaposition of the individual fibrils leads. "Crust" does not mean a in the present invention uniform coating, which may be irregularly thick or thin, or on individual Places may be missing. The attachment of the polymer / copolymer to the Cellulose fibrils take place when applied and by drying the wet compacted granules.

For the swelling and water absorption behavior of the one to be used according to the invention Disintegrant granules have become wet compacting and subsequent Drying proved essential.

Completely surprisingly, it was found that the wet compaction and then drying them in water together with the polymer / copolymer predispersed cellulose / cellulose derivatives and / or starch / starch derivatives a granulate is obtained that is characterized by a specific Porosity characterizes the explosive effect of the granulate effective. The efficiency is probably due to the capillary action the pores and the resulting rapid penetration of the granules reached with water. Moldings of various compositions of washing or cleaning formulations containing such a mixture according to the invention Granules to be used are used in dosing chambers of domestic or commercial washing machines quickly and effectively blown up.

As a further component, the granulate can contain one or more liquid Water-forming or thickening surfactants selected from the group contain the nonionic, anionic or amphoteric surfactants, wherein nonionic surfactants are particularly preferred.

When using liquid surfactants to produce the granulate can also the cellulose and optionally other modified water-swellable Polysaccharide derivatives with the liquid surfactant / surfactant mixture mixed and then the polymer / copolymer of (meth) acrylic acid or its Salt can be mixed in. Then granulate with water usual facilities, the adjustment of a moisture content of 2 to 8% by weight has proven to be particularly favorable, and after known working methods with subsequent compacting by means of rolling mills. The desired grain fractions are made in the same way as for wet granulation described, received. Undersize and oversize are in the granulation stage or crushing stage.

The structure of the granules obtained in this way is that of wet granulation available similar, but the specific porosity is somewhat lower than with the wet granulation described. The water absorption and swelling behavior is very good, however, because water absorption and Volume increases very quickly.

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

Suitable anionic surfactants are, for example, 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 cellulose and any other modified water-swellable polysaccharide derivatives and / or polymers / copolymers of (meth) acrylic acid or salts thereof: surfactant can from 100: 1 to 10: 1. Quantities of 100: 1 are preferred up to 100: 5.

The disintegrant granules to be used according to the invention have bulk densities from 100 g / l to 500 g / l, preferably 150 g / l to 450 g / l, whole particularly preferably 250 g / l to 400 g / l and are in the moldings in Contain amounts of 3 wt.% To 15 wt.%, Preferably 5 wt.% To 10 % By weight and particularly preferably with 7% by weight.

The determination of the specific porosity (liquid absorption) of the Disintegrant granules are made using a known standard method Determination of the degree of porosity of solids:

Principle of the measurement method: The solid is mixed with dibutyl phthalate (or 2-propanol) completely soaked and then the one absorbed in the pores Liquid after a defined time under defined conditions removed by centrifugation. The amount of dibutyl phthalate absorbed (or 2-propanol) is a measure of the porosity of the solid.

Precise procedure: 3 to 4 g of the sample are placed in a commercially available Tared glass filter crucible G3 weighed in and with 10 ml dibutyl phthalate (or 2-propanol) added. You put these crucibles in a beaker, the bottom of which is lined with filter paper so that it drains better of excess solvent can take place. After exactly 5 minutes the glass filter crucibles are weighed, then placed in Teflon inserts and 5 min at 1800 rpm (with dibutyl phthalate) or 800 rpm (with 2-propanol) centrifuged. After centrifugation, the crucibles are Teflon inserts removed and weighed again.

P = Absorptionsvermögen in ml Lösemittel je kg Feststoff (Porosität)

M2 = Gewicht des Tiegels mit feuchter Probe nach Zentrifugieren in g

M1 = Gewicht des Tiegels mit trockener Probe mit Lösemittel in g

δ = Dichte des eingesetzten Lösemittels (0,786 g/ml für 2-Propanol 1,050 g/ml für Dibutylphthalat)

E = eingewogene Probenmenge in g

The porosity is determined according to the following formula (1): P = (M 2 - M 1) * 1000 δ * E

P = absorption capacity in ml of solvent per kg of solid (porosity)

M2 = weight of the crucible with wet sample after centrifugation in g

M1 = weight of the crucible with dry sample with solvent in g

δ = density of the solvent used (0.786 g / ml for 2-propanol, 1.050 g / ml for dibutyl phthalate)

E = weighed sample amount in g

The specific porosity of the explosive granules determined using this method is 600 to 1000 ml / kg, preferably 700 to 900 ml / kg, whole particularly preferably 850 ml / kg.

The specific water absorption capacity of the explosive granules can be determined gravimetrically as follows:
A defined amount of granules (eg 2.00 g) is sealed in a thin paper bag, such as a tea bag, and immersed in a vessel with an excess of water. After 3 minutes of immersion, the bag is removed from the water and hung for 10 minutes to drain. The bag is weighed and the water absorption is determined from the weight difference of a wet bag with and without granules. Distilled water or water with a defined hardness can be used for the determination.

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

The compacted granulate is characterized by special swelling kinetics off, the expansion does not change linearly depending on the time and should reach a certain level as soon as possible. Especially the swelling behavior in the first 10 seconds is of interest after contact with water if the granules are used as disintegrants for molded articles should be used.

When in contact with water, the granules rapidly take up volume and is therefore suitable as a so-called explosive for pressed moldings so that they quickly disintegrate in water.

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.

Tablets can be used with the disintegrant granules to be used according to the invention with a strength not known from the prior art of more than 50 N and effectively blown up.

The invention is directed to pressed molded articles of washing and / or Cleaning compositions, especially tablets. The moldings can but also cubes, cuboids, balls and the like, in which the Granules are included as a disintegrant.

The spatial shape of the molded body can in its dimensions of the induction chamber be adapted to the washing machine, but all reasonable manageable Design shapes. These include e.g. also cylindrical configurations with oval or circular cross-section and molded body with a plate-like structure. A preferred molded body consists of alternately thick long and thin short segments, so that individual segments of such a bolt at predetermined breaking points through the short thin segments are shown, broken off and into the Detergent dispenser of the machine can be entered. This principle of bar-shaped body can also be in other geometric polygonal shapes be realized.

A tablet produced in this way preferably has a weight of 10 to 120 g, particularly preferably from 20 to 100 g, the diameter the tablet is usually less than 100 mm. Preferred detergent tablets have a maximum diameter of 80 mm, in particular between 30 and 80 mm. However, it is also possible and in particular preferred in terms of better solubility, several, so at least two tablets with the same or different composition to use. In this case the tablets preferably have a weight from 10 to 40 g, with diameters from 20 to 50 mm being preferred.

Such washing and / or cleaning agent compositions designed as shaped articles usually contain builders, bleach and Bleach activators, surfactants, tabletting aids, disintegrants and others usual additives and auxiliary substances.

A preferred embodiment of the invention is a phosphate-containing detergent tablet, based on total weight: 53 to 20% by weight Sodium tripolyphosphate, 0 to 5% by weight other organic builders, 12 to 20% by weight Peroxide bleach, 2 to 6% by weight Bleach activator (s), 8 to 20% by weight Surfactant (s), 15 to 5% by weight Na carbonate / Na bicarbonate, 3 to 15% by weight compacted explosive granules and 7 to 9% by weight usual auxiliaries and additives.

In another embodiment, the shaped body is a phosphate-free detergent tablet, containing, based on the total weight: 45 to 20% by weight Zeolite and / or amorphous and / or crystalline disilicates, 2 to 6% by weight other organic builders, 12 to 20% by weight Peroxide bleach, 2 to 6% by weight Bleach activator (s), 8 to 20% by weight Surfactant (s), 15 to 4% by weight Na carbonate / Na bicarbonate, 3 to 15% by weight compacted explosive granules and 13 to 9% by weight usual auxiliaries and additives.

In a further embodiment, the shaped body is a water softening tablet, based on total weight: 10 to 30% by weight Zeolite, 20 to 5% by weight Disilicate 5 to 15% by weight polymeric organic builders, 10 to 35% by weight Na bicarbonate, 30 to 0% by weight Citric acid / Na citrate dihydrate, 3 to 12% by weight compacted explosive granules and 22 to 3% by weight other usual auxiliaries and additives.

According to another embodiment of the washing and / or cleaning composition, the shaped body is a bleach tablet, containing, based on the total weight: 65 to 20% by weight Na carbonate / disilicates, 15 to 30% by weight Peroxide bleach, 4 to 9% by weight Bleach activator (s), 5 to 10% by weight Surfactant (s), 3 to 15% by weight compacted explosive granules and 8 to 16% by weight other usual auxiliaries and additives

For all embodiments, both mono-, as well as double or triple tablets prefers.

Inorganic substances such as polyphosphates, pyrophosphates, Metaphosphates or phosphonates, layered silicates, amorphous silicates, amorphous disilicates and zeolite. Other components The builders system can fillers such as alkali carbonates, bicarbonates e.g. Sodium carbonate or sodium hydrogen carbonate, sesquiocarbonate, sodium sulfate, Magnesium sulfate, or citrate, citric acid, succinic acid, Be tartaric acid and malic acid. Often used as auxiliary builders Co-builders and dispersants also used. Such cobuilders or dispersants can be polyacrylic acids and their sodium salts.

Other organic builders are copolymers of (meth) acrylic acid and Maleic acid, terpolymers and quattropolymers from (meth) acrylic acid, maleic acid, Vinyl alcohol and vinyl compounds containing sulfo groups.

The used fine crystalline, synthetic and bound water containing Zeolite is preferably zeolite NaA in detergent quality. However, zeolite NaX, zeolite P and mixtures of A, X and P. The zeolite can either be spray-dried powder or granular compound, for example up to about 50% by weight of other components such as nonionic surfactants, cellulose ethers and / or polymers Contains polycarboxylates. Suitable powdered zeolites have an average particle size of less than 10 µm (volume distribution; Measurement method: Coulter counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Polycarboxylates and / or polymers are used as organic builder substances Polycarboxylates, as well as their acids used. To the polycarboxylic acids and the polycarboxylates in particular include those in the form of their sodium salts polycarboxylic acids such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids and mixtures of these. Suitable polymeric polycarboxylates are, for example, the sodium salts polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 800 to 150,000 (sourced from acid). Suitable copolymeric polycarboxylates are, in particular, those of Acrylic acid with methacrylic acid and acrylic acid and methacrylic acid with Maleic acid. The copolymers of acrylic acid have proven particularly suitable proven with maleic acid, the 50 to 90 wt.% Acrylic acid and 50 to Contain 10% by weight of maleic acid. Their relative molecular mass, based on Acids are generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.

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-C-43 00 772) or those from (meth) acrylic acid, 2-alkylallylsulfonic acid and sugar derivatives (as described in DE-C-42 21 381) or those made from (meth) acrylic acid, Maleic acid, vinyl alcohol derivatives and monomers with sulfonic acid groups (described in DE-A-19 516 957).

The (co) polymeric polycarboxylates are preferably used either as a powder or used as granular compounds. Suitable as granular compounds For example, such as in the international patent application WO-A 92/13937 are described.

Other suitable builder systems are oxidation products of carboxyl-containing ones Polyglucosans and / or their water-soluble salts, as for example in the international patent application WO 93/08251 are described or their manufacture, for example, in the international patent application WO 93/16110.

Other suitable organic builders are polyacetals, which can be obtained by reacting dialdehydes with polycarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, as described, for example, in European patent application EP-A-280 223. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
Polyethylene glycol and / or polypropylene glycol with a molecular weight of 900 to 30,000 are also suitable, as are carboxylated polysaccharides, polyaspartates and polyglutamate.

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

Customary peroxide bleaching agents are sodium perborate tetrahydrate and sodium perborate monohydrate, sodium percarbonate, peroxypyrophosphates, citrate perhydrates, as well as H ₂ O ₂ delivering peracidic salts, peracids such as perbenzoates, peroxyphthalates, diperazelaic acid and diperdodecanedioic acids.

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'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,2,5-triazine (DADHT) and acetylated sorbitol mannitol Mixes (SORMAN).

Bleaching detergent tablets contain peroxy bleach in quantities from 12 to 20% by weight. Tablets in addition to detergent formulations used as bleach tablets, however, contain peroxy bleach preferably in amounts of 15 to 30% by weight. A can Percarbonate content in amounts of 10 to 20% by weight is particularly advantageous if, in particular, at low percarbonate contents below 20 % By weight, further peroxy bleaching agents can be used.

Bleaching tablets are preferably characterized in that they are 20 to 65% by weight, preferably 30 to 40% by weight, of amorphous, partially crystalline and / or crystalline layered sodium silicates and 15 to 30 % By weight of peroxy bleach, but no zeolite.

Anionic, nonionic or amphoteric surfactants are used as surfactants Commitment. These can either be in the explosive granules as described above be incorporated, or added to the detergent formulation. In the cleaning formulation, surfactants are either available for purchase Granules can be used, or they can be in liquid form on individual components the formulation are applied, preferably to the builders. The liquid surfactants are preferably incorporated into the formulation Spraying introduced on the solids, spraying either on individual components, e.g. on soda, cellulose, silicate, zeolite, Phosphates can be made, or after mixing the solids of the formulation on the solid mixture.

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.

In addition to the anionic surfactants mentioned above, the surfactants of the sulfonate type are preferably C ₉ to C ₁₃ alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained, for example, from C ₁₂ -C ₁₈ monoolefins with end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C ₁₂ -C ₁₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.

Also suitable are the esters of sulfo fatty acids (ester sulfonates), e.g. the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or Tallow fatty acids.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Among fatty acid glycerol esters are the mono-, di- and triesters as well as their Mixtures to understand how they are made by esterification can be obtained by a monoglycerol with 1 to 3 moles of glycerol. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example the Caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, Stearic acid or behenic acid. Assuming fat and Oils, i.e. natural mixtures of different fatty acid glycerol esters off, it is necessary to start the feed products before sulfonation to become saturated with hydrogen to a large extent, i.e. on Harden iodine numbers less than 5, advantageously less than 2. Typical Examples of suitable feedstocks are palm oil, palm kernel oil, palm stearin, Olive oil, rape oil, coriander oil, sunflower oil, cottonseed oil, peanut oil, Linseed oil, lard oil or lard. Because of their high natural Proportion of saturated fatty acids, however, it has proven to be particularly advantageous proven to start from coconut oil, palm kernel oil or beef tallow. The Sulfation of saturated fatty acids with 6 to 22 carbon atoms or the mixtures from fatty acid glycerol esters with iodine numbers less than 5, the fatty acids containing 6 to 22 carbon atoms, is preferably carried out by reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous bases, as described in international patent application WO-A 91/09009 is specified.

Preferred alk (en) yl sulfates are the sulfuric acid semiesters of the C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half esters of secondary alcohols of this chain length. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. C ₁₆ -C ₁₈ alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with such anionic surfactants which have a lower Krafft point and have a low tendency to crystallize at relatively low washing temperatures from, for example, room temperature to approx show, deploy. In a preferred embodiment, the compositions contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C12-C14 fatty alkyl sulfates or C ₁₂ -C ₁₈ fatty alkyl sulfates with C ₁₆ -C ₁₈ fatty alkyl sulfates and in particular C ₁₂ -C ₁₆ fatty alkyl sulfates with C ₁₆ -C ₁₈ fatty alkyl sulfates . In a further preferred embodiment, however, not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C ₁₆ to C ₂₂ are used. Mixtures of saturated sulfated fatty alcohols predominantly consisting of C ₁₆ and unsaturated sulfated fatty alcohols predominantly consisting of C ₁₈ are particularly preferred, for example those. which are derived from solid or liquid fatty alcohol mixtures of the HD-Ocenol (R) type. Weight ratios of alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and in particular from about 5: 1 to 1: 1 are preferred.

The sulfuric acid monoesters of the straight-chain or branched C ₇ -C ₂₁ alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl branched C ₉ -C ₁₁ alcohols with an average of 3.5 moles of ethylene oxide (EO) or C12-C18 fatty alcohols with 2 to 4 EO are suitable. Because of their high foaming behavior, they are only used in relatively small amounts in detergents, for example in amounts of 1 to 5%.

Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, also known as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid Alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols represent. Preferred sulfosuccinates contain C8 to C18 Fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue that differs from ethoxylated Derives fatty acids, which are non-ionic surfactants (See description below). Here again are sulfosuccinates, whose fatty alcohol residues differ from ethoxylated fatty alcohols with restricted Deriving homolog distribution is particularly preferred. It is the same possible alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the Use alk (en) yl chain or its salts.

Preferred anionic surfactant mixtures contain combinations of Alk (en) yl sulfates, especially mixtures of saturated and unsaturated Fatty alk (en) yl sulfates, and alkylbenzenesulfonates, sulfated fatty acid glycerol esters and / or α-sulfofatty acid esters. In particular are preference is given to mixtures which contain alk (en) yl sulfates as anionic surfactants and alkylbenzenesulfonates, alk (en) ylsulfates and α-sulfofatty acid methyl esters and / or contain sulfated fatty acid glycerol esters.

Other suitable anionic surfactants are, in particular, soaps, preferably in amounts of 0.1 to 5% by weight. For example, saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. Soap mixtures are particularly preferred which are composed of 50 to 100% by weight of saturated C ₁₂ -C ₂₄ fatty acid soaps and 0 to 50% by weight of oleic acid soap.

The anionic surfactants and soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, Di- or triethanolamine are present. The anionic are preferably located Surfactants in the form of their sodium or potassium salts, especially in the form their sodium salts.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be methyl or linearly branched in the 2-position , or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example coconut oil, palm oil, tallow oil or oleyl alcohol and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ alcohols with 7 EO, C ₁₃ -C ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 Eo, C ₁₂ -C ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 EO and C ₁₂ -C ₁₈ alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO, for example those with up to about 80 EO, can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 E0.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G represents a symbol for a glycose unit with 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may be suitable. The amount of these nonionic surfactants is preferably no more than that of ethoxylated fatty alcohols, particularly preferably not more than half of these.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I), R ² -CO-NR ³ - [Z] in the R ² -CO for an aliphatic acyl radical with 6 to 22 C atoms, R ³ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 C atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 C -Atoms and 3 to 10 hydroxyl groups.
In a preferred embodiment, the detergent formulations contain the nonionic surfactants in amounts of up to 20% by weight.

Other preferred ingredients are alkaline in water inorganic salts, preferably up to 15% by weight in the tablets are included. To these inorganic alkaline salts belong in particular to bicarbonates, carbonates or mixtures thereof. Alkali carbonate and especially sodium carbonate are preferably used.

Other customary auxiliaries and additives in the compositions according to the invention are:
Inorganic salts which react neutral in water, preferably sulfates and chlorides, in particular in the form of their sodium and / or calcium salts; their content in the finished detergent formulation is preferably up to about 20% by weight.
Tableting aids, for example polyalkylene glycols and magnesium stearates.
Enzymes, magnesium silicates, aluminum aluminates, benzotriazole, glycerol, magnesium stearate, polyalkylene glycols, hexametaphosphate, phosphonates, bentonites, soil release and soil repellant compounds, carboxymethyl celluloses, solubility improvers, graying inhibitors, foam inhibitors and color softeners, optical brighteners, optical brighteners, optical brighteners, optical brighteners, optical brighteners, optical brighteners, optical brighteners, optical brighteners, optical brighteners, optical brighteners, and optical brighteners, optical brighteners, optical brighteners, optical brighteners, optical brighteners, optical brighteners, optical brighteners, and optical brighteners, as well as optical brighteners, optical brighteners, and optical brighteners, as well as optical brighteners, optical brighteners, and optical brighteners. Their content preferably does not exceed 10% by weight.

The compositions may also contain components that include the oil and Grease washability from textiles has a positive effect ("Soil Release Compounds "). These oil and fat dissolving components include e.g. nonionic cellulose ethers such as methyl hydroxypropyl cellulose with a Proportion of methoxyl groups from 15 to 30% by weight and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and the polymers known from the prior art Phthalic acid and / or terephthalic acid or their derivatives, in particular Polymers made from ethylene terephthalates and / or polyethylene glycol terephthalates.

The detergent formulations may also contain ingredients which improve the solubility of individual formulation components and thus increasing the dissolution rates of the tablets. About these ingredients belong to the described fatty alcohols with 10 to 80 Moles of ethylene oxide per mole of fatty alcohol, in particular polyethylene glycols relative molar masses between 200 and 6000.

Suitable foam inhibitors are, for example, natural or soaps synthetic origin, which have a high proportion of C18-C24 fatty acids. Suitable non-surfactant foam inhibitors are e.g. Organopolysiloxanes and their mixtures with microfine, possibly silanized silica as well as paraffins, waxes, microcrystalline waxes and mixtures thereof with silanized silica or bistearylethylenediamide. Mixtures too various foam inhibitors can be used, e.g. such out Silicones, paraffins or waxes. The foam inhibitors, in particular paraffin and silicone-containing foam inhibitors a granular, water-soluble or dispersible carrier substance bound. Mixtures of paraffins and bistearylethylenediamine are particularly preferred.

Enzymes come from the class of proteases, lipases, amylases and cellulases or mixtures thereof. Particularly suitable are enzymes derived from battery strains or fungi, e.g. Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus can be obtained. Proteases of the subtilisin type and in particular proteases are preferred, which are obtained from Bacillus lentus. Here are enzyme mixtures, for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from Protease, amylase and lipase or protease, lipase and cellulase, in particular however, cellulase-containing mixtures of particular interest. Peroxidases or oxidases are also found to be suitable in some cases. The enzymes can also be attached to and / or in vehicles Envelopes are embedded to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can e.g. about 0.1 to 5% by weight, preferably 0.1 to 2% by weight.

The stabilizers come in particular for per-compounds and enzymes Salts of polyphosphonic acids, especially 1-hydroxyethane-1,1-diphosphonic acid (HEDP), diethylenetriaminepentamethylenephosphonic acid (DETPMP) or ethylenediaminetetramethylenephosphonic acid.

Graying inhibitors serve to replace those of the laundry fiber To keep dirt in the wash liquor in suspension and so the graying to prevent laundry. Water-soluble colloids are usually more organic for this Suitable in nature, for example the water-soluble polymeric salts Carboxylic acids, glue, gelatin, salts of ether carboxylic acids or Ether sulfonic acids of starch or cellulose or salts of acidic Sulfuric acid esters of cellulose or starch. Also water-soluble, acidic Group-containing polyamides are suitable for this purpose. Furthermore soluble starch preparations and other than those mentioned above Use starch products, e.g. degraded starch, aldehyde starches, etc. Polyvinyl pyrrolidone can also be used. However, cellulose ethers are preferred, such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroypropylcellulose, Methyl carboxymethyl cellulose and mixtures thereof, and polyvinylpyrrolidone in amounts of, for example, 0.1 to 5 % Used.

The formulations can be derivatives of diaminostilbenedisulfonic acid as optical brighteners or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similar connections, which instead of the morpholino group is a diethanolamino group, a Methalamino group, an anilino group or a 2-methoxyethylamino group wear. In addition, brighteners of the substituted diphenylstyryl type be included, e.g. Alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the above Brighteners are used.

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 the above-mentioned polyacrylic acids or Copolymers with polyacrylic acid and its sodium salts.

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

The invention is further elucidated below on the basis of exemplary embodiments explained without being limited to this. All information refer to weight, unless it is something in individual cases otherwise stated.

Examples 1 to 5 Examples of compositions of phosphate-free detergent tablets (all amounts in% by weight). example 1 2 3rd 4th 5 Component: Zeolite 2.0 1.0 1.0 26.0 31.0 Disilicate 35.0 35.0 30.0 2.0 2.0 soda 4.2 9.3 10.2 8.6 10.8 Na citrate dihydrate - - 5.0 5.0 - Copolymer Na salt 3.5 3.0 3.0 2.3 3.5 Na percarbonate 19.0 16.0 17.0 19.0 17.0 TAED 5.0 4.0 4.0 5.0 4.5 Alkyl benzene sulfonate 2.5 - 2.5 7.0 6.8 Fatty alcohol sulfate 10.5 12.0 10.0 8.0 7.0 Fatty alcohol ethoxylate 5.0 4.0 4.5 3.5 4.4 Defoamer 1.5 1.4 1.5 1.5 1.4 Phosphonate 0.7 0.7 0.7 1.0 0.7 Enzymes 1.5 1.0 1.0 1.5 1.3 Soil release polymer 1.0 - 1.0 1.0 1.0 Carboxymethyl cellulose 1.0 1.0 1.0 1.0 1.0 Disintegrant granules 7.0 7.0 7.0 7.0 7.0 optical brighteners 0.3 0.3 0.3 0.3 0.3 Perfume 0.3 0.3 0.3 0.3 0.3

The nonionic surfactants are in liquid form in the detergent formulation by spraying onto the disilicate or the zeolite, as well as some of the anionic surfactants. More anionic Surfactants are used as granules.

Examples 6 to 10

Examples of compositions of phosphate-containing detergent tablets (all amounts in% by weight). example 6 7 8th 9 10th Component: Na tripolyphosphate 35.0 35.0 32.0 37.0 33.0 Zeolite A 3.0 2.0 2.0 2.0 1.5 silicate - 3.0 2.0 1.5 - soda 18.0 10.5 12.0 18.9 10.5 Na citrate dihydrate - - 5.0 - 7.0 Na percarbonate 15.0 17.0 16.0 14.0 18.0 TAED 3.0 4.0 4.0 2.0 4.0 Alkyl benzene sulfonate 5.0 3.0 4.0 2.4 - Fatty alcohol sulfate 8.0 11.0 9.0 11.0 14.0 Fatty alcohol ethoxylate 2.0 2.0 2.0 1.0 2.0 Defoamer 1.4 1.5 1.4 1.3 1.5 Phosphonate 2016 D 1.0 1.0 1.0 0.5 - Soil release polymer - 1.0 0.6 - - Carboxymethyl cellulose 1.0 1.4 1.4 1.0 1.0 Disintegrant granules 7.0 8.0 6.0 7.0 7.0 optical brighteners 0.3 0.3 0.3 0.2 0.3 Perfume 0.3 0.3 0.3 0.2 0.2

The nonionic surfactants are in liquid form in the detergent formulation by spraying on the tripolyphosphate, the soda or the Carboxymethyl cellulose introduced.

Examples 11 to 14: Pressed molded articles with the intended use as a) water softener of the following composition: quantity used in%

example 11 12th 13 14 Raw material: Zeolite A 16.0 16.0 16.0 16.0 Acrylic acid-maleic acid copolymer, 14.5 14.5 14.5 14.5 Na salt Layered silicate SKS-6 7.0 7.0 7.0 7.0 soda - - 27.5 28.0 Sodium bicarbonate 33.0 34.0 - - Sodium citrate dihydrate - - 24.5 25.0 citric acid 19.0 19.0 - - Polyethylene glycol 4000 to 6000 2.5 2.5 2.5 2.5 Paraffin oil 1.0 - 1.0 - Disintegrant granules 7.0 7.0 7.0 7.0

Example 15: Determination of the strength and disintegration time of a phosphate-containing one Detergent tablet with explosive granules used according to the invention.

The tablet breaking strength tester is used to determine the tablet strength type TB30 / TBH30MD from Erweka. Doing so the breaking strength by means of a strain gauge with a load cell certainly. The measuring accuracy is +/- 1N. After corresponding Programming, the tablet is placed in the measuring device and the Measuring process started. The device shows the value of the breaking strength.

The tablet disintegration time is determined as follows:

500 ml of soft water at a temperature of 23 ° C are placed in a beaker given. A metal sieve with a mesh size of 4 is placed at a height of 10 cm mm attached. A magnetic stirring bar with approx. 200 is placed in the beaker U / min set in motion and a tablet placed on the sieve from above. The time from the start of tablet addition until the tablet disintegrates is measured with the stopwatch. The disintegration is achieved when all Parts of the tablet have fallen through the sieve.

The detergent formulation given in Table 4 is compressed into tablets with the disintegrant granules M1 to M7 according to Table 5. The strength and disintegration time of these tablets are determined. raw material Quantity in% by weight Na tripolyphosphate 35 Na percarbonate 19th TAED 4th Alkyl benzene sulfonate 4th Fatty alcohol sulfate 14 soda 8th Defoamer, optical brightener, CMC , Phosphonate 6 Microcrystalline cellulose (200 µm) 2 Enzymes 1 Fatty alcohol ethoxylate (C12 / C14, E0 = 4.7) 2 Explosive preparation M1-M7 or V1 5 Explosives M1 M2 M3 M4 M5 M6 M7 Cellulose 50 50 45 50 47 40 50 Linear PAA 12.5 12.5 10 10 12.5 10 - Networked PAA - - - 2 - - - Carboxymethyl cellulose - - 15 5 10 20th - Nio surfactant 0.5 0.5 0.5 0.5 - 0.5 - Polymeric surfactant - - - - - - 12.5 Water for compact. (% By weight) 37 37 29.5 29.5 30.5 29.5 37.5 Bulk density (g / l) 335 335 335 335 335 335 335 Humidity (% by weight) 6 4th 3rd 3rd 4th 5 3rd Dust content (wt.%) 7 8th 6 5 5 5 7

A roller-compacted cellulose from Degussa serves as comparison V1 AG with the trade name Elcema G 250 (5% moisture, bulk density 400 g / l).

The tablet strengths and disintegration times obtained are shown in Table 6. Explosives Humidity [% by weight] Strength [N] Disintegration time [s] V1 5 58 52 M1 6 62 12th M2 4th 65 9 M3 3rd 57 8th M4 3rd 63 10 M5 4th 58 9 M6 5 59 7 M7 3rd 58 9

Table 6 shows that both the composition and - at the same Composition - the moisture content of the disintegrant granules clearly. influence the tablet disintegration time. Explosives with the preferred content of 3 to 5% by weight of moisture shows the best tablet disintegration times.

Claims (9)

1. Detergent and/or cleansing compositions in the form of pressed bodies containing in relatively fine form, as granules and/or co-granules, conventional substances having a detergent and/or cleansing action, builders, auxiliary substances and additives and

   from 3 to 15 wt.%, in relation to the total weight of the compositions, of compressed granular disintegrant prepared from (a) non-water-soluble, water-swellable cellulose and optionally additional modified water-swellable polysaccharide derivatives and (b) one or more polymers/copolymers of (meth)acrylic acid or salts thereof, and (a) and (b) are present in a ratio by weight of from 50 : 1 to 2 : 1, and

   wherein the granular disintegrant has a moisture content of from 2 to 8 wt.% and a specific porosity of from 600 to 1,000 ml/kg (expressed as the quantity of organic liquid absorbed by 1 kg of solid within a specified time).
2. Detergent and/or cleansing composition according to Claim 1, characterised in that the granular disintegrant also contains one or more liquid surfactants which gel or thicken with water.
3. Detergent and/or cleansing composition according to Claim 1 or 2, characterised in that in the granular disintegrant the water-swellable cellulose and optional additional modified water-swellable polysaccharide derivatives and polymers/copolymers of (meth)acrylic acid are present in a ratio by weight of from 20 : 1 to 5 : 1.
4. Detergent and/or cleansing composition according to Claim 1 or 2, characterised in that in the granular disintegrant the water-swellable cellulose and optionally additional modified water-swellable polysaccharide derivatives and polymers/copolymers of (meth)acrylic acid are present in a ratio by weight of 10 : 1.
5. Detergent and/or cleansing composition according to one of Claims 2, 3 or 4, characterised in that the ratio by weight of the combined water-swellable cellulose and optionally additional modified water-swellable polysaccharide derivatives and polymers/copolymers of (meth)acrylic acid : liquid surfactant(s) is from 100 : 1 to 10 : 1.
6. Detergent and/or cleansing composition according to one of the preceding claims, characterised in that it is a one- to three-phase phosphate-containing detergent tablet containing, in relation to the total weight: 53 to 20 wt.% sodium tripolyphosphate, 0 to 5 wt.% other organic builders, 12 to 20 wt.% peroxide bleach, 2 to 6 wt.% bleach activator(s), 8 to 20 wt.% surfactant(s), 15 to 5 wt.% Na carbonate/Na hydrogencarbonate, 3 to 15 wt.% compressed granular disintegrant and 7 to 9 wt.% conventional auxiliary substances and additives.
7. Detergent and/or cleansing composition according to one of the preceding Claims 1 to 5, characterised in that it is a one- to three-phase phosphate-free detergent tablet containing, in relation to the total weight: 45 to 20 wt.% zeolite and/or amorphous and/or crystalline disilicates, 2 to 6 wt.% other organic builders, 12 to 20 wt.% peroxide bleach, 2 to 6 wt.% bleach activator(s), 8 to 20 wt.% surfactant(s), 15 to 4 wt.% Na carbonate/Na hydrogencarbonate, 3 to 15 wt.% compressed granular disintegrant and 13 to 9 wt.% conventional auxiliary substances and additives.
8. Detergent and/or cleansing composition according to one of the preceding Claims 1 to 5, characterised in that it is a one- to three-phase water-softening tablet containing, in relation to the total weight: 10 to 30 wt.% zeolite 20 to 5 wt.% disilicate, 5 to 15 wt.% polymeric organic builder, 10 to 35 wt.% Na hydrogencarbonate, 30 to 0 wt.% citric acid/Na citrate dihydrate, 3 to 12 wt.% compressed granular disintegrant and 22 to 3 wt.% other conventional auxiliary substances and additives.
9. Detergent and/or cleansing composition according to one of the preceding Claims 1 to 5, characterised in that it is a one- to three-phase bleach tablet containing, in relation to the total weight: 65 to 20 wt.% Na carbonate/disilicates, 15 to 30 wt.% peroxide bleach, 4 to 9 wt.% bleach activator(s), 5 to 10 wt.% surfactant(s), 3 to 15 wt.% compressed granular disintegrant and 8 to 16 wt.% other conventional auxiliary substances and additives.