EP1043391A1 - High density disintegrating granulate for tablets; method for making it and its use - Google Patents

Abstract

In a densified disintegrant granulate for tablets, comprising (A) 60-99 wt.% water-insoluble, water-swellable cellulose and optionally other modified water-swellable polysaccharide derivatives, (B) 1-40 wt.% binder(s) selected from (meth)acrylic acid (co)polymers and their salts and (C) 0-7 wt. % liquid surfactant(s) forming a gel with water, the granulate has a moisture conte of 2-8 wt.%. Independent claims are also included for: (i) an alternative form of the disintegrant granules (also having moisture conten 2-8 wt.%), comprising (A) as above and 1-40 wt.% of at least one polymeric binder/surfactant; and (ii) the preparation of either for the granulate by forming a pre-mix of the components to be granulated then densifying the premix, where the premix is adjusted t moisture content of 10-80 wt.%, followed by drying to a moisture content of 2-8 wt.% after compacting and optionally obtaining t required granule size distribution by milling and screening.

Description

The invention relates to an auxiliary granulate, composed of cellulose and optionally cellulose / starch derivatives, polymeric binders and gel-forming surfactants, which are used as disintegrants for tablets in Washing and Detergent tablets is suitable. Furthermore, a method for Preparation of the granules and their use described.

Disintegrants for tablets or granules are auxiliary substances that disintegrate Tablets or granules in contact with liquids, especially water influence positively. It is said that both the disintegration of tablets into rough parts also a subsequent disintegration into smaller particles up to dissolution / Dispersion of all detergent components can be effected and accelerated.

Tablets are determined by pressing a starting granulate with Press produced, the bulk density, e.g. for compact detergents approx. 900g / l, after tabletting rises to 1200 g / l. Such tablets with higher densities than the starting granulate are naturally less soluble / separable as the starting granulate. Since they are in use in the However, the washing machine should dissolve quickly or should disintegrate and dissolve, it is appropriate to add disintegrants that promote decay.

Depending on the detergent and cleaning agent composition, they are different Compression pressures required for tableting. The type of Builders, for example phosphate, zeolite, disilicate or layered silicate, result in different required pressures and therefore different hard or compact tablets arise. To keep the tablets safe from outside mechanical influences, for example during transport or when falling against To protect them from breaking, they should have a strength of 50 N or higher exhibit.

There are usually two options for practical application the addition of the tablet in the washing machine, on the one hand in the dispenser and on the other hand into the washing drum. The requirements for tablet disintegration are different depending on the location.

The addition to the induction chamber is the most convenient for the user and for the user The safest quality of the washing process. However, will be very high Requirements for the tablet disintegration speed. Especially the The first step of disintegrating the tablet into large parts must be done very quickly go, because otherwise residues of the tablet remain in the dispenser and not can be used for washing. Usually stands for modern Washing machines take about 30 seconds to rinse the tablets over the induction bowl available. The tablets must be used when hot perform their function even with cold induction water. Lie in the washing drum other conditions for the disintegration of the tablet, since both mechanical Friction as well as rising water temperatures the dissolution process of the tablet influence.

The problem of the long disintegration times of highly compressed moldings is already known from pharmacy. A large number of connections and Mixtures are used as tablet disintegrants in pharmaceutical practice known. According to their mechanism of action are used for tablet disintegrants discussed several models, such as the development of gas bubbles (shower powder), mutual particle repulsion, water transport (wicking) and swelling / expansion due to water absorption.

Many compounds that swell strongly are known from the literature. Often is however the swelling speed is too slow. In addition to the swelling speed and the source volume, the source pressure is particularly important for the application.

Various methods are known for measuring these properties. Man can expand without back pressure or swell without Measure expansion. Combined measurement methods, whereby both the source pressure and the extent to be recorded are particularly suitable for predicting Suitability of explosives to be taken in tablets. One such method is Measurement of swelling kinetics. Here is the temporal dependence of the expansion determined under the load of an explosive. So it goes both Swell pressure as well as expansion in the result. It is known that as Products suitable for disintegrants become linear or swell during the swelling process can expand nonlinearly. The nonlinearly swelling explosives are because the faster action is much more suitable than linear swelling products.

The statements of WO 98/55575 relating to the prior art show that in the field of detergents and cleaning agents also the disintegrants can be used in the manufacture of pharmaceutical tablets are known.

In DE-OS 2 251 249 e.g. rapidly disintegrating pharmaceutical tablets described by pressing pharmaceutical granules and Disintegrant granules are produced. The use of granular Starting materials lead to a porous tablet structure. An example is Disintegrant granules based on starch with a particle size of 2.0 to 0.3 mm used.

From DE-OS 2 355 204 medicinal tablets are known which consist of granular Components are pressed, the granules for the sake of Tablet stability before compression to a moisture content of less than 2% can be set.

No. 3,629,393 claims pharmaceutical tablets with delayed release of the active ingredient, which are pressed from granular components, disintegrants from high-molecular, water-swellable compounds, such as cellulose derivatives, being used in the form of granules. The granule dimensions in the examples are around 0.84 mm.
US 4,072,535 describes the use of disintegrants made of precompacted starch for pharmaceuticals and detergents. The grain size of the compact is 0.05 mm to 0.42 mm, the moisture content is stated as 9-16%, preferably 11-13%. The disintegration times of the sample tablets are several minutes.

Detergent tablets are known from DE-OS 2 321 693, which contain 1 to 25% by weight. contain fibrous cellulose as a disintegrant. In the examples Tablets made with a strength of 15 to 19 N, being compacted Cellulose granules can be used.

In EP 0 170 791, tablet-like washing additives are described which consist of granular constituents are pressed, 1 to 5% by weight also being granular tablet disintegrant based on cross-linked Polyvinyl pyrrolidone and / or cellulose ethers are used. The granules should be free of dust. The tablets have a breaking strength of 50 up to 120 N and have long dissolving times of several minutes.

From W098 / 40463, washing or cleaning-active moldings are known which can be produced using an explosive granulate that has a high Has adsorption capacity for water and a grain size distribution in which at least 90% by weight a particle size of at least 0.2 mm and a maximum of 3 mm have. The dust content <0.1 mm is less than 1%. The explosive granules contains at least 20% by weight of disintegrants, such as starch, starch derivatives, Cellulose, cellulose derivatives. According to the teaching of this patent, this has an effect Presence of anionic or nonionic surfactants negatively affects the Tablet disintegration time. The granules are made in a conventional manner manufactured, such as spray drying, superheated steam drying of aqueous preparations or by granulation, pelleting, extrusion or roller compaction powder components. Detailed procedural information on Granulation process or further process steps after the granulation the explosive granules are not made. The example produced Detergent tablet contains a disintegrant based on compacted cellulose thermochemically treated wood pulp and has a tablet hardness of 45 N. on. Tablets of higher strength, i.e. above 50 N are not described.

WO 98/55575 describes an auxiliary granulate for washing and detergent active moldings. The claimed auxiliary granules contain 10 to 95% by weight cellulose with particle sizes below 0.1 mm and 5 to 90% by weight microcrystalline cellulose. According to the examples in the Aid granules, the celluloses partially with carboxymethyl cellulose, TAED and citric acid / bicarbonate combined. The grain sizes of the compact are more than 90% by weight from 0.3 to 2.0 mm, less than 5% by weight less than 0.2 mm and have no dust content. For the manufacture is the Roll compacting of the dry premix is preferred. Detailed Process details for the production of granules are not given. The below Use of the auxiliary granules produced by way of example Detergent tablets have low strengths of 35 N or less. More stable, more compact tablets with higher strength from 50N not described.

In unpublished European patent applications 98121397.8 and 98121392.9 are cellulose / cellulose derivatives or starch / starch derivatives together with thickening surfactants and finely divided polymers (Meth) acrylic acid in compressed, granulated form as disintegrant granules for Detergents and cleaning agents, water softeners and stain salts in tablet form claimed. The granules have a non-linear swelling kinetics, with in Reference to the entire swelling process in the initial phase of the swelling process a very large increase in volume occurs. About the dissolution behavior of the Tablets in the washing-up chamber of a washing machine are not specified made.

Patent application WO 98/40462 describes a compact made of powdered and / or granular ingredients, in particular detergent ingredients, which contains particles of cellulose-containing material acting as disintegrant, the can also be in a compact form. Particularly preferred as Cellulose components become thermomechanical (TMP) and chemical thermomechanical (CTMP) treated wood pulps. The particle size of the compacted explosives can range from 0.2 to 6 mm. About the Cellulose components can also add tenside raw materials to the compact be mentioned, with 0.5 - 5% surfactant / compact. That corresponds to one Surfactant content of approx. 14 - 45% by weight in the cellulose disintegrant if you take the mentioned use concentrations of compacted granulate of 3 to 6% / Pressing is based. Detailed procedural information on manufacturing of the disintegrant granulate or its effect in the compact in the form of Embodiments are not made.

According to EP 0 750 662 B1, cleaning tablets with high breakage and storage stability if you work water-free in the manufacture and hydrophobicizes the mixture components beforehand. The tablets do not contain any Disintegrant granules and have breaking strengths of> 150 N, that Dissolution behavior is greatly delayed.

The state of the art also includes sales products from Degussa AG with the designation Elcema G250 and Elcema G 400, which consists of compact Pure cellulose exist and have been used as a tablet disintegrant since 1971 become. These products are made by dry granulation and have a particle size of 0.03 to 0.40 mm. The moisture content is <6%.

The object of the invention is therefore one compared to the prior art to provide improved disintegrant granules for tablets. It should in particular so swell so quickly and strongly that tablets made therewith in the induction chamber of washing machines during the short water induction period largely resolved. Furthermore, the explosive granules are said to be high Have abrasion stability and its effect not through in the course of its Manufacturing process inevitably occurring fine and in particular Dust levels can be restricted. Furthermore, the explosives are said to be in tablets with high strength over 50 N a combination of good explosive effect and ensure good solubility and by storing the tablets over several Weeks only slight signs of aging in the form of a weakening of the Experience properties.

In addition, the task also includes the provision of a method for Production of the explosive granules and their use in tablets for Washing and cleaning processes.

A) 60 - 99 Gew.% nichtwasserlöslicher, in Wasser quellbarer Cellulose und gegebenenfalls weitere, modifizierte wasserquellbare Polysaccharidderivate,

B) 1 - 40 Gew.% mindestens eines polymeren Bindemittels in Form eines Polymerisates bzw. Copolymerisates der (Meth)acrylsäure und / oder deren Salze,

C) 0 - 7 Gew.% mindestens eines flüssigen, mit Wasser gelbildenden Tensides,

wobei sich die Summe aus A), B), und C) zu 100 Gew.% ergänzt, dadurch gekennzeichnet, daß das Sprengmittelgranulat einen Feuchtigkeitsgehalt von 2 bis 8 Gew. % aufweist.This object is achieved by means of a compressed disintegrant granulate for tablets, built up from

A) 60-99% by weight of non-water-soluble, water-swellable cellulose and optionally further, modified water-swellable polysaccharide derivatives,

B) 1-40% by weight of at least one polymeric binder in the form of a polymer or copolymer of (meth) acrylic acid and / or salts thereof,

C) 0 to 7% by weight of at least one liquid surfactant which forms water,

where the sum of A), B) and C) adds up to 100% by weight, characterized in that the disintegrant granules have a moisture content of 2 to 8% by weight.

It has surprisingly been found that the disintegrant compactates are more effective if they have a certain water content. According to the Teaching of the state of the art and practical experience was to be expected that the lowest possible water content in the finished granulate is the best Would cause swelling.

Component A:

Here, water-insoluble, swellable cellulose is used. As special fibrils of native cellulose with a maximum length of 0.30 mm proven. Both microcrystalline and amorphous fine particles can be used Cellulose and mixtures thereof are used.

The finely divided cellulose preferably has bulk densities of 40 g / l to 300 g / l, very particularly preferably from 65 g / l to 170 g / l. Are already granulated Types used, their bulk density is higher and can be beneficial Execution range from 350 g / l to 550 g / l. The bulk weights of the cellulose derivatives are typically 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 finely divided cellulose is preferably between 0.030 mm and 0.20 mm, in the case of granulated types, the preferred medium one Particle size between 0.350 mm and 0.800 mm. The particle size of the finely divided cellulose derivatives is preferably 0.030 mm to 3.0 mm.

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 invention, regenerated ones are also used Celluloses such as viscose are used. Particularly regenerated celluloses in Powder form are characterized by very good water absorption. The Viscose powder can be made from cut viscose fiber or by precipitation dissolved viscose. Also degraded by electron beam low molecular weight cellulose is for example for the production of Disintegrant granules suitable. In an advantageous embodiment softened regenerated fibers are used. As a typical plasticizer for such products may be mentioned here, for example, glycerol.

Furthermore, the granules according to the invention can be advantageous Embodiment water-swellable cellulose derivatives, such as cellulose ether and Cellulose esters and starch or starch derivatives and other swellable ones Contain polysaccharides and polygalactomannans, for example ionic modified celluloses and starches such as carboxymethyl modified cellulose and Starch, nonionically modified celluloses and starches such as alkoxylated celluloses and starches such as hydroxpropyl and hydroxyethyl starch or hydroxpropyl and hydroxyethyl cellulose and alkyl etherified products such as methyl cellulose as well as mixed modified celluloses and starches from the aforementioned Modifications, possibly combined with a modification to Networking leads. Suitable starches are also cold swelling starches that are caused by mechanical or degrading reactions are formed on the starch grain. For this count primarily swelling starches from extruder and drum dryer processes as well products modified enzymatically, oxidizing or acid-degrading. Chemically Derivatized starches preferably contain substituents which are substituted by ester and A sufficient number of ether groups are attached to the polysaccharide chains

Starches with ionic substituents such as carboxylate, hydroxyalkyl or Phosphate groups are modified, have proven to be particularly advantageous and are therefore preferred. To improve the swelling behavior has also proven the use of slightly cross-linked starches. Also alkaline Treated 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 have proven successful. The Quantities can fluctuate within wide limits, based on the Combination is the proportion of cellulose derivatives and / or starch and / or Starch derivatives preferably 0.1 to 85% by weight, particularly preferably 5 to 50% by weight.

Component B:

Polymers or copolymers of (meth) acrylic acid or Mixtures of such polymers or copolymers are used in the granulate. The polymers are selected from the group of homopolymers (Meth) acrylic acid, from the group of copolymers with the following Monomer components of ethylenically unsaturated dicarboxylic acids and / or their Anhydrides and / or ethylenically unsaturated sulfonic acids and / or acrylic esters and / or vinyl esters and / or vinyl ethers or their saponification products and / or crosslinkers and / or graft bases based on Polyhydroxy compounds.

Uncrosslinked polymers or copolymers of (Meth) acrylic acid, with weight average molecular weights of 5,000 to 70,000 proven. The copolymers are preferably copolymers of (Meth) acrylic acid and ethylenically unsaturated dicarboxylic acids or their Anhydrides, such as maleic acid or maleic anhydride, for example 40 to 90% by weight of (meth) acrylic acid and 60 to 10% by weight of maleic acid or Contain maleic anhydride, their relative molar mass, based on free Acids, between 3,000 and 100,000, preferably 3,000 to 70,000 and whole is particularly preferably 5,000 to 50,000. As a suitable binder ter- and quattropolymeric polycarboxylates have also proven to be built up from (meth) acrylic acid, maleic acid and optionally fully or partially saponified vinyl alcohol derivatives, or those of (meth) acrylic acid, ethylenically unsaturated sulfonic acids and polyhydroxy units, such as sugar derivatives, or from (meth) acrylic acid, maleic acid, vinyl alcohol derivatives and monomers containing sulfonic acid groups. Examples of suitable polymers are in the patents DE 43 00 772, DE 42 21 371 and WO 95/17444.

The polymeric binders are preferred in the form of their preparation aqueous solutions used, but can also be in the form of finely divided powders be applied. The binder polymers are preferably in part or fully neutralized form, the salt formation preferably with cations of Alkali metals, ammonia and amines, or mixtures thereof.

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. Polymer contents above 15% in the disintegrant lead to harder ones Disintegrant granules, while polymer contents below 1% softer to form Granules tend to be less resistant to abrasion.

Suitable polymer binders are also crosslinked polymers made from (meth) acrylic acid. They are preferably used as finely divided powders and are preferred average particle sizes from 0.045 mm to 0.150 mm and are preferred with 0.1 to 10 wt.% Used. Particles with average particle sizes over 0.150 mm also produce good disintegrant granules, but lead to the Dissolving the tablets made with the granules visually as particles visible swelling bodies, for example in the case of textile washes deposit clearly visible on the textile in a disturbing manner.

A special embodiment of the invention is the combination of soluble poly (meth) acrylate homo- and copolymers and the aforementioned finely divided crosslinked polymer particles.

A) 60 - 99 Gew.% nichtwasserlöslicher, in Wasser quellbarer Cellulose und gegebenenfalls weitere, modifizierte wasserquellbare Polysaccharidderivate,

D) 1 - 40 Gew.% mindestens eines polymeren Bindemittels

wobei sich die Summe aus A) und D) zu 100 Gew.% ergänzt, dadurch gekennzeichnet, daß das Sprengmittelgranulat einen Feuchtigkeitsgehalt von 2 bis 8 Gew. % aufweist und das polymere Bindemittel D) ein Polymertensid ist.Suitable co-binders, which also have a surfactant character, are also so-called polymer surfactants. These are understood to mean reaction products which, in addition to the typical polymer structures of the abovementioned binder polymers, have additional structural elements which have a surfactant effect. For example, graft polymers with alkoxylated fatty alcohol or carboxylate-containing polymers with methoxyalkylene oxide monomer units are to be mentioned, furthermore maleic acid / vinyl ether / longer-chain fatty amine copolymers and half-amides of maleic acid copolymers and copolymers of acrylic acid with long-chain acrylate units of a preferred embodiment contain the polymer surfactants alkylene oxide units. Polymeric surfactants can be present in the disintegrant granules with up to 30% by weight.
It has been shown that the abovementioned polymeric surfactants, when used alone, are suitable for producing the disintegrant granules according to the invention without the presence of polymeric binder components and without surfactant components. The required amounts of polymeric surfactant in the disintegrant granulate are in the range from 1 to 40% by weight, preferably 5 to 20% by weight.
Accordingly, a further solution to the problem is provided by a compacted granulate for tablets, composed of

A) 60-99% by weight of non-water-soluble, water-swellable cellulose and optionally further, modified water-swellable polysaccharide derivatives,

D) 1-40% by weight of at least one polymeric binder

the sum of A) and D) adding up to 100% by weight, characterized in that the disintegrant granules have a moisture content of 2 to 8% by weight and the polymeric binder D) is a polymeric surfactant.

Component C:

The explosive granules contain one or more further constituents liquid, gel-forming surfactants selected from the group of nonionic, anionic or amphoteric surfactants, which are used in amounts up to 7 % By weight, preferably up to 3.5% by weight are present. If the surfactant content in the explosive is too high, in addition to increased abrasion manufactured tablets also have poor swelling properties.

The nonionic surfactants can be, for example, alkyl polyglucosides, fatty acid alkylolamides, Fatty acid polyethylene glycol esters, fatty aminoxethylates, Fatty alcohol ethoxylates with 3-15 mol ethylene oxide or propylene oxide, Fatty acid glycerides, sorbitan esters, sucrose esters, e.g. Sucrose palmitate, Pentaaerythritol partial esters, which can also be ethoxylated, and alkylphenol polyethylene glycol ether or be phenol poly ethylene glycol ether.

The anionic surfactants can be, 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 or Be fatty alcohol ether carboxylates.

The amphoteric surfactants can, for example, coconut fatty acid amidopropyl betaine, modified imidazolines or fatty acid amide derivatives with betaine structure.

In a preferred embodiment of the invention, mixtures of Surfactants are used, in a further preferred embodiment only non-ionic surfactants used.

The compacted granulate according to the invention is distinguished by a special one Swelling kinetics, the expansion does not change depending on the time linear but reaches a very high level after a very short time. Of The swelling behavior in the first 10 seconds is of particular interest after contact with water. In the range of the water content according to the invention from 2 to 8% by weight there is an unexpectedly high volume expansion, a high rate of expansion and a high swelling pressure. This The combination of properties has a positive influence on those with the explosives tablets produced and leads to short tablet disintegration times and one very good flushing behavior in the dosing chambers of the washing machines. Both Wash-in tests show the superior effect of the agents according to the invention in that almost all tablets disintegrate and are washed away.

The specific water absorption capacity of the granules according to the invention is very high and can be determined gravimetrically. That way determinable water absorption is preferably 500 to 2000%

Surprisingly, it has also been found that a certain Proportion of dust, which according to the teaching of the prior art in granules for Detergent tablets should not be present in the inventive Disintegrant compact does not bother and also a good one Storage stability of the tablets produced with it contributes. Shares of a Fine dust content of less than 0.1 mm up to 10% by weight, preferably up to 8 % By weight can be present in the disintegrant granules according to the invention his.

The fluid intake (also called specific porosity) of the Disintegrant according to the invention is compared to products of the prior art Technology significantly increased and is in a range of over 750 ml / kg, preferably in the range 800 to 1000 ml / kg. This high fluid intake has a significant influence on the swelling effect and water transport in the Explosives. State of the art products have average Liquid absorption values of approx. 600 ml / kg.

The disintegrant granules according to the invention are first produced by mixing the granulate components according to the invention with conventional mixing methods. For example, mixers from Vomm, Lödige, Schugi, Eirich, Henschel or Fukae can be used. In this first step of Mixing and granulating are precompounds Agglomeration process produced. These precompounds form a free-flowing Goods with 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%, preferably 20% is required to achieve good compaction and high To guarantee liquid absorption in the later dry granulate. At Water contents between 60 and 80% by weight must be ensured that it is at certain compactors, such as the ring die press during can occur during the pressing process that the water from the Mixture can be pressed, whereas none in extruders Phenomena can be observed. I.e. the compression technology must ultimately Water content of the premix can be adjusted. For ring die press and Pelleting presses have a water content of 20 to 60% by weight, preferably of Proven 20 to 40 wt.%. It should also be out of economic Because of the water content of the pre-compound it should not be higher than required because this water in the later drying process using energy must be removed.

In the next step, these pre-compounds are mechanically compressed. For the The swelling and water absorption behavior of the granules according to the invention is final compaction essential. Compacting using Printing can be done in different ways. The products can be between two Printing areas in roller compressors, e.g. B. smooth or profiled. The compactate is ejected as a strand. Compression methods in Matrices with stamps or pillow rollers produce compact forms such as tablets or briquettes. Roll compactors, extruders, Roller or cube presses, but also pelletizing presses are used.

Compression with pelleting presses has proven to be particularly suitable, with a suitable process control granules are obtained without further size reduction can be dried. Suitable pelleting presses e.g. manufactured by Amandus Kahl and Fitzpatrick.

Due to the compression, an explosive granulate with a Bulk density from 100 g / l to 500 g / l, particularly preferably from 150 g / l to 450 g / l and very particularly preferably from 250 g / l to 400 g / l. Compliance A preferred limit of the bulk density of a maximum of 400 g / l has changed the particularly good swelling properties proved to be favorable. Surprisingly, it was found that the granules also in these Bulk densities have very good abrasion resistance.

The coarse, compacted particles are crushed, e.g. Mills, Carvers or roller mills are suitable. The shredding can take place before or after drying. The inventive Granules preferably with a particle size distribution of 0.05 to 3 mm, particularly preferably 0.1 to 1.5 mm.

A removal of dust components below 0.1 mm can e.g. with usual Screening devices are carried out. Since dust content up to 10 wt Use of the granules according to the invention predominantly does not interfere their separation is often omitted.

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

The invention includes the use of the compacted granules as Disintegrants for pressed molded articles, for example tablets, cubes, balls and the like. Use as a disintegrant for is particularly preferred Detergent formulations, detergent formulations, stain salts, Water softener in tablet or cube form.

The disintegrant granules according to the invention are in the molded articles in quantities from 0.5% by weight to 15% by weight, preferably 3% by weight to 8% by weight and particularly preferably contain 4% by weight to 7% by weight.

The moldings according to the invention have sufficient stability and Strength, and allow safe handling, packaging and Storage. Upon contact with water, however, they should disintegrate quickly, so that the Components can have the desired effect. Adequate Stability against mechanical influences is for molded articles from one Breaking strength of 50 N is given. Lend the granules according to the invention a decay and disintegration characteristic such as these highly compressed shaped bodies it is otherwise only given in the case of moldings of low strength.

The moldings for detergent formulations usually contain Builders, bleaching agents and bleach activators, surfactants, tableting aids, Disintegrants and other usual additives and auxiliaries.

Polyphosphates, pyrophosphates, metaphosphates or come as builders Phosphonates, layered silicates, amorphous silicates, amorphous disilicates and zeolite in Consideration. Other components of the builder system can include fillers such as Alkali carbonates, bicarbonates e.g. B. sodium carbonate or sodium hydrogen carbonate, Sesquiocarbonates, sodium sulfate, magnesium sulfate, or citrate, citric acid, Succinic acid, tartaric acid and malic acid. Often called Auxiliary builders cobuilders and dispersants also used. Such cobuilders or Dispersants can be polyacrylic acids and their sodium salts.

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 can be used. In particular ter- and quatropolymeric polycarboxylates made from are also preferred (Meth) acrylic acid, maleic acid and vinyl alcohol or vinyl alcohol derivatives (such as they are described in DE 43 00 772 C2) or those made from (meth) acrylic acid, 2-alkylallylsulfonic acid and sugar derivatives (as described in DE 42 21 381 C1) or from (meth) acrylic acid, maleic acid, vinyl alcohol derivatives and Monomers with sulfonic acid groups (described in DE 195 16 957 A).

Polyethylene glycol and / or polypropylene glycol are further components used with a molecular weight of 900 to 30,000, and carboxylated Polysaccharides, polyaspartates and polyglutamate. Mixtures with various organic builders such as Citric acid is possible.

The usual bleaching agents to be used are sodium perborate tetrahydrate and sodium perborate monohydrate, sodium percarbonate, peroxypyrophosphates, citrate perhydrates, as well as H ₂ O ₂ -producing peracid salts, peracids such as perbenzoates, peroxyphthalates, diperazelaic acid and diperdodecanedioic acids. The bleach content in tablets is preferably 10-60% by weight and in particular 15-50% by weight. In order to achieve a good bleaching effect when washing below 60 ° C and below, activators can be incorporated. Suitable bleach activators are the N-acyl and O-acyl compounds forming with H ₂ O ₂ organic peracids, preferably N, N'-tetraacylated diamines, carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. Acetylated mixtures of sorbitol and mannitol can also be used. Particularly suitable bleach activators are N, N, N ', N'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,2,5-triazine (DADHT) and acetylated sorbitol mannitol Mixtures (SORMAN).

In addition to nonionic, anionic and amphoteric surfactants, in Detergent formulations, cationic surfactants may also be present, for example quaternary ammonium compounds with C8 - C16 N-alkyl or N-alkenyl groups and N-substituents such as methyl, hydroxyethyl or Hydroxypropyl groups.

Tableting aids are also optionally used, for example Polyalkylene glycols and magnesium stearates.

Examples of other common detergent additives and auxiliaries are enzymes, Magnesium silicates, aluminum aluminates, benzotriazole, glycerin, Magnesium stearate, polyalkylene glycols, hexametaphosphate, phosphonates, Bentonites, soil release polymers, carboxymethyl celluloses.

Dishwashing tablets as a form of training Detergent formulations usually contain builders Polyphosphates, pyrophosphates, metaphosphates or phosphonates, Layered silicates, amorphous silicates, amorphous disilicates and zeolites, as well as fillers such as sodium carbonate, sodium sulfate, magnesium sulfate, sodium hydrogen carbonate, Citrate as well as citric acid, succinic acid, tartaric acid and malic acid. Cobuilders and dispersants are often used as auxiliary builders. Such cobuilders or dispersants can be polyacrylic acids or copolymers with polyacrylic acid and its sodium salts.

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

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

Examples of other common detergent additives and auxiliaries are also here Enzymes, magnesium silicates, aluminum aluminates, benzotriazole, glycerin, Magnesium stearate, polyalkylene glycols, hexametaphosphate and phosphonates.

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

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

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

In a preferred embodiment, it is with the invention Disintegrant granules possible, detergent tablets with disintegration times of up to 15 sec with a tablet breaking strength of up to 80 N.

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

Test methods Determination of the specific water absorption capacity

The specific water absorption capacity of the granules according to the invention 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 is used for the determination.

Determination of the swelling kinetics

To determine the swelling speed and the swelling height under load 3.00 g of granules are placed in a cylindrical plastic container with a Given an inner diameter of 60 mm and with a water-permeable fleece covered. The layer thickness of the granules is 1-3 depending on the bulk density mm. A movable, pierced stamp with a weight is placed on the fleece of 58 g and connected to a path measuring instrument that the way of the stamp depending on the time. By adding 70 ml Water causes the granules to swell and the resulting triggers Displacement of the stamp (path length) determined as a function of time and evaluated graphically.

Determination of liquid absorption (specific porosity)

The specific porosity of the disintegrant granules is determined using a known standard method for determining the degree of porosity of solids. Principle of the method:
The solid is completely impregnated with di-n-butyl phthalate (DBP) and then the liquid absorbed in the pores is removed after a defined time under defined conditions by centrifugation. The amount of DBP absorbed is taken as a measure of the porosity of the solid.

Execution:

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

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

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

Dichte = 1,050 g/ml DBP

E = eingewogene Probenmenge in g

3 g of the sample are weighed into a commercially available tared glass filter crucible G3 and mixed with 10 ml DBP. These crucibles are placed in a beaker, the bottom of which is lined with filter paper. After exactly 5 minutes, the glass filter crucibles are weighed, then placed in Teflon inserts and centrifuged at 1800 rpm for 5 minutes. After centrifugation, the crucibles are removed from the Teflon inserts and weighed again.
The porosity is calculated using the following formula: P = (M2 - M1) * 1000 Density * E

P = absorption capacity in ml DBP per kg 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

Density = 1.050 g / ml DBP

E = weighed sample amount in g

Method for determining tablet disintegration time

A washing and cleaning tablet containing 5% disintegrant is used for used the test. 500 ml of soft water with a Given temperature of 23 ° C. A metal sieve with a Mesh width of 4 mm attached. A magnetic stir bar is placed in the beaker set in motion at approx. 200 rpm and a tablet on top of the sieve hung up. The time from the start of tablet addition until the tablet disintegrates is measured with a stopwatch. The disintegration is achieved when all tablet parts fell through the sieve.

Test conditions for induction tests of detergent tablets in Washing machines:

3 tablets are placed in a row in the washing machine drawer set. The washing machine is connected to a pressure line with 5 bar city water connected and started in the 60 ° C normal program. The wash-in time is 30 seconds, the machine only taking water once. The attempt will carried out a total of four times, so 12 tablets are used. To The remaining tablets are counted for each induction cycle. The The total amount of tablets that have not been washed in is given.

Determination of tablet breaking strength

For the determination of the tablet breaking strength the Tablet breaking strength tester type TB30 / TBH30MD from Erweka used. The tensile strength is measured using a strain gauge a load cell. The measuring accuracy is +/- 1N. After appropriate programming, the tablet is placed in the measuring device inserted and the measuring process started. The device shows the value of the Breaking strength.

Abrasion test for explosive granules

In a 500 ml beaker, 100g of dried disintegrant granules are mixed with a Given particle size> 1 mm. A metal dissolver disc dips into the granulate with a diameter of 3.5 cm, which is connected to a stirring motor. The stirring motor is set to 800 rpm and stirred for one minute. The granulate experiences a more or less significant abrasion. After the time has elapsed, the fraction of the grain fraction is determined using sieve analysis <1 mm determined. The proportion <1 mm is given as a percentage of the total quantity.

Examples Examples M1-M7 and comparative examples V1-V5

The disintegrants used in the examples were produced by wet compaction on a pellet mill from Amandus Kahl. The degree of compaction was set to 1: 3. The water content of the mixtures before compression is shown in Table 1. After the compacting, the granules were dried to the specified moisture contents on a Babcok drum dryer. Comparative example V5 was produced on a WP 150 roller press from Alexanderwerke without additional water. The pressing pressure was set at 1.1 t / cm. The granules were crushed on a grater. Drying was also carried out on a belt dryer.
The granules have particle sizes between 0.3 and 2 mm, the dust content below 0.1 mm is given in the table. Recipes for the production of disintegrants in% by weight and properties of the granules Explosives V1 V3 V4 V5 M1 M2 M3 M4 M5 M6 M7 Cellulose 50 50 50 80 50 50 45 50 47 40 50 Linear PAA 12.5 12.5 12.5 20th 12.5 12.5 10th 10th 12.5 10th - Networked PAA 2nd - CMC 15 5 10th 20th - Nio surfactant 0.5 0.5 0.5 0 0.5 0.5 0.5 0.5 0 0.5 - Polymeric surfactant 12.5 Water for Compact. (Wt%) 37 37 37 0 37 37 29.5 29.5 30.5 29.5 37.5 Bulk density (g / l) 325 330 335 300 335 335 335 335 335 335 335 Moisture (wt ) 18th 10th 1 3rd 6 4th 3rd 3rd 4th 5 3rd Dust content (wt%) 2nd 4th 8th 5 7 8th 6 5 5 5 7

A roller-compacted cellulose from Degussa AG with the trade name Elcema G 250 was used as comparative example V2 . (5% moisture, bulk density 400 g / l

Liquid intake (specific porosity):

When comparing example M2 according to the invention with example V2 there are significant differences in fluid intake caused by Compacting process and the moisture content when compacting are justified. With the moisture content according to the invention when compacting and drying (M2) result in 950 ml / kg intake of DBP, the dry compact and thus compressed pattern (V2) in the capillary structure resulted in a Consumption of only 600 ml / kg DBP.

This shows that the receptivity of the invention Disintegrant granules are significantly increased compared to the comparative product.

Example 1:

Detergent tablet containing phosphate: strength of the tablet and induction tests using the granules of the aforementioned examples: Composition of detergent tablet: Raw material quantity in% by weight Sodium tripolyphosphate 35 Sodium percarbonate 19th TAED 4th Fatty alcohol sulfate 14 Linear alkyl benzene sulphonate 4th soda 8th Defoamer, optical brightener, CMC, phosphonate 6 Microcrystalline cellulose (200 µm) 2nd Enzyme mix 1 Fatty alcohol ethoxylate (C12 / 14, EO = 4.7) 2nd Disintegrant preparation according to Examples V1-V5 and M1-M7 5

Table 3 shows the strength and the results of the induction test of the individual detergent tablets when using the different disintegrants: Explosives according to example Humidity (%) Wash-in test (not disassembled tabl.) Strength [N] Disintegration time [sec] V1 18th 10th 61 50 V2 5 10th 58 52 V3 10th 6 60 40 M1 6 1 62 12th M2 4th 0 65 9 V4 1 3rd 58 25th M3 3rd 0 57 8th M4 3rd 1 63 10th M5 4th 1 58 9 M6 5 0 59 7 M7 3rd 0 58 9

Table 3 shows that both the composition and the same Composition the moisture content of the explosive granules one have a significant influence on the tablet disintegration time. Explosives with the preferred content of 3-5 wt% water as in M2 also show the best Disintegration times of the tablets. Are also suitable swellable Substances incorporated as a disintegrant component can Disintegration properties can be further increased.

Table 4 shows the influence of the storage time (4 weeks at 40 ° C / 60% relative humidity in the closed container) on the induction behavior of tablets with disintegrants. Detergent tablet containing phosphate according to Table 2 example Disintegrant moisture [%] Wash-in test immediately (Tablet) n. 4 weeks Swelling kinetics after 3 seconds [mm] V4 1 3rd 3rd 0.85 M1 6 1 1 0.90 M2 4th 0 1 0.97 V3 10th 6 7 0.80 V1 18th 10th 11 0.45 V2 6 10th 11 0.47 M3 3rd 0 - 2.0 M4 3rd 1 - 1.7 M5 4th 1 - 1.6 M6 5 0 - 2.2

Table 4 shows that the moisture content according to the invention in Disintegrant granules to superior properties of the manufactured Tablets in the important wash-in test leads or that the swellability with values of 0.9 and higher is superior to the comparison products. Tablets with Disintegrants according to the invention show good storage stability. Tablets with In addition to cellulose, M3-M6 also contain cellulose derivatives and show thereby further improved swelling kinetics.

Example 2:

Phosphate-free detergent tablet: strength of the tablet and wash-in test using one of the granules of the aforementioned examples: Granules from Example M6 / M7 in zeolite-based detergent formulations Raw material quantity in% by weight Recipe a) b) Zeolite P 39 36 Fatty alcohol ethoxylate (C12 / 14, EO = 4.7) 4th 7 Sodium percarbonate 16 16 TAED 4th 4th Fatty alcohol sulfate 10th 11 Linear alkyl benzene sulphonate 3rd 3rd soda 4th 4th Defoamer, optical brightener, CMC, phosphonate 5 5 Enzyme mix 1 1 Microcrystalline cellulose (200 µm) 4th 4th Disintegrant preparation according to - Example V1, V2, M6, M7 5 5 Sodium citrate 5 5 Recipe Explosives Wash-in test Strength [N] a) M6 1 57 b) M6 0 51 a) M7 0 73 b) M7 0 59 Commercial standard tablet 1 30th Commercial standard tablet 11 80 a) V1 10th 58 a) V2 12th 59

Here too, the comparative granules V1 and V2 show significantly less activity than the product according to the invention from example M6 / M7. Commercial tablets show different dissolving behavior. Low strength tablets dissolve faster than high strength tablets. Granules from Example M3 in disilicate-based detergent formulations Raw material quantity in% by weight Recipe a) b) Amorphous disilicate 36 30th Fatty alcohol ethoxylate 2nd 7 Fatty alcohol sulfate 11 15 Linear alkyl benzene sulphonate 4th 2nd Sodium percarbonate 16 16 TAED 4th 4th Acrylate-maleate copolymer - 3rd soda 7 4th Sodium citrate 5 5 Microcrystalline cellulose (200 µm) 4th 4th Defoamer, optical brightener, CMC, phosphonate 5 4th Enzyme mix 1 1 Disintegrant preparation according to Example M3 5 5 Recipe Wash-in test Strength [N] a) 0 65 b) 1 60

The granules from Example M3 led to very good disintegration times for disilicate tablets.

Example 3:

Pressed moldings for use as stain remover of the following composition: Raw material quantity in% by weight Recipe Soda disiklikat cogranulate 20th soda 41 Nonionic surfactant 4th TAED 7 Enzyme mix 1 Sodium percarbonate 24th Disintegrant preparation according to Example M2 or V2 3rd

Water softener with the following composition: Raw material quantity in% by weight Zeolite 15 Sodium bicarbonate 32 citric acid 20th Polycarboxylate 17th Layered silicate 8th Process aids 5 Disintegrant preparation according to Example M2 or V2 3rd

Machine dishwashing detergent of the following composition: Raw material quantity in% by weight Soda-silicate cogranulate 20th Tripolyphosphate 35 soda 20th Sodium perborate 12th TAED 4th Enzyme mix 2nd Process aids 3rd Perfume, dyes 2nd Explosives preparation according to example M2 or V2 2nd

Results on the strength and disintegration time of the cleaning tablets property Stain remover water softener Machine dish cleaner composition according to a) according to b) according to c) Strength [N] 175 210 185 Disintegration time [sec] with explosive V2 225 145 245 Disintegration time [sec] with explosive M2 85 68 58

The tablet disintegration time of highly compressed tablets with the inventive Disintegrant is superior to the comparison products.

Example 4 and V7:

Influence of a high surfactant content on the properties of the Disintegrant granules

Granules (M2) according to the invention containing nonionic surfactant of 0.5% by weight with a granulate of the same formulation and Manufacturing technology compared, the nio-surfactant content increased to 12 wt% was (V7).

The following Table 11 shows the swelling kinetics of these two granules after 3, 5 and 10 seconds of swelling time. Example swelling path in [mm] 3 sec 5 sec 10 sec M2 0.97 1.0 1.1 V7 0.33 0.42 0.44 In another test, the abrasion of the two samples M2 and V7 was compared. Abrasion test on samples M2 and V7 example Grain fraction <1 mm in% by weight M2 10th V7 35

The results make it clear that disintegrant granules with one Surfactant content outside of the inventive design both in Swelling behavior and abrasion resistance significantly worse Have property values.

Claims (25)

Compacted disintegrant granules for tablets, made up of A) 60-99% by weight of non-water-soluble, water-swellable cellulose and optionally further, modified water-swellable polysaccharide derivatives, B) 1-40% by weight of at least one polymeric binder in the form of a polymer or copolymer of (meth) acrylic acid and / or salts thereof, C) 0 to 7% by weight of at least one liquid surfactant which forms water, where the sum of A), B) and C) adds up to 100% by weight, characterized in that the disintegrant granules have a moisture content of 2 to 8% by weight. Disintegrant granulate according to claim 1, characterized in that it is 1-15 % By weight of polymeric binder and 0.1 to 3.5% by weight of surfactant. Disintegrant granules according to claim 1 to 2, characterized in that the Surfactants are nonionic and / or anionic and / or amphoteric surfactants. Disintegrant granules according to Claims 1 to 3, characterized in that the Surfactants are selected from fatty alcohol ethoxylates with preferably 3 to 15 moles Ethylene oxide, fatty alcohol sulfates, linear alkyl benzene sulfonates, alkyl ether sulfates, Alkyl polyglycosides and their mixtures. Disintegrant granules according to Claims 1 to 4, characterized in that up to Contain 10% by weight of cross-linked, finely divided polymers of (meth) acrylic acid are. Disintegrant granules according to Claims 1 to 5, characterized in that it Contains 0-30% by weight of at least one polymer surfactant. Compacted disintegrant granules for tablets, made up of A) 60-99% by weight of non-water-soluble, water-swellable cellulose and optionally further, modified water-swellable polysaccharide derivatives, D) 1-40% by weight of at least one polymeric binder the sum of A) and D) adding up to 100% by weight, characterized in that the disintegrant granules have a moisture content of 2 to 8% by weight and the polymeric binder D) is a polymeric surfactant. Disintegrant granules according to Claims 1 to 7, characterized in that it a moisture content of 2.5 to 7% by weight, preferably 3 to 5% by weight having. Disintegrant granules according to Claims 1 to 8, characterized in that based on the cellulose 0.1 to 85% by weight, preferably 5 to 50% by weight water-swellable polysaccharide derivatives are present. Disintegrant granules according to Claims 1 to 9, characterized in that the water-swellable polysaccharide derivatives anionic and / or nonionic and / or are physically and / or cross-linked modified and differ from cellulose, starch and Derive polygalactomannans. Disintegrant granules according to Claims 1 to 10, characterized in that Carboxymethyl cellulose, carboxymethyl starch, hydroxyalkyl cellulose, Hydroxyalkyl starch, alkyl cellulose, guar flour or locust bean gum is used. Disintegrant granules according to Claims 1 to 11, characterized in that at least one regenerated cellulose is used. Disintegrant granules according to Claims 1 to 12, characterized in that the celluloses and polysaccharide derivatives before their compression in the form of fine particles Particles with particle sizes between 0.03 and 3 mm were present. Disintegrant granules according to Claims 1 to 13, characterized in that the polymers or copolymers of (meth) acrylic acid are selected from the group of homopolymers of (meth) acrylic acid, from the group of Copolymers with the following monomer components ethylenically unsaturated Dicarboxylic acids and / or their anhydrides and / or ethylenically unsaturated Sulfonic acids and / or acrylic esters and / or vinyl esters and / or vinyl ethers or their saponification products and / or crosslinking agents and / or graft bases Basis of polyhydroxy compounds. Disintegrant granules according to Claims 1 to 14, characterized in that the particle size is between 0.05 and 3.0 mm, preferably 0.1 to 1.5 mm. Disintegrant granules according to Claims 1 to 15, characterized in that it has a porosity of 800 to 1000 ml / kg. Disintegrant granules according to Claims 1 to 16, characterized in that it up to 10% by weight, preferably up to 8% by weight of a fine dust fraction of less Contains 0.1 mm. Disintegrant granules according to Claims 1 to 17, characterized in that it a bulk density from 100 g / l to 500 g / l, preferably from 150 g / l to 450 g / l and particularly preferably from 250 g / l to 400 g / l. Disintegrant granules according to claims 6 to 18, characterized in that the polymer surfactants contain alkylene oxide units embedded in the polymer structure. Process for the preparation of the disintegrant granules according to Claims 1 to 19 by mixing the components to be granulated into a premix and then compressing the premix, characterized in that a moisture content of 10 to 80% by weight is set in the premix and after compacting to a moisture content of 2 to 8% by weight, and drying if necessary the desired particle size distribution is set by grinding and sieving. A method according to claim 20, characterized in that the compression by means of rollers with the same friction or by means of roller or cube presses or by means of an extruder or by means of ring die or pelletizing presses. A method according to claims 20 to 21, characterized in that with Ring die or pelletizing presses with a moisture content of 20 to 40 % Is compacted. A method according to claim 20 to 22, characterized in that the Moisture content after drying to 2.5 to 7% by weight, preferably to 3 to 5 % Is set. Use of an explosive granulate according to one of claims 1 to 19 as a disintegrant for tablets, in particular for washing, cleaning, Water softening and stain remover tablets. Use of an explosive granulate according to one of claims 1 to 19 as a disintegrant in detergent tablets with a breaking strength up to 80 N and a tablet disintegration time of at most 15 sec.