DE102008020274A1 - Preparing a cleaning agent tablet, useful for cleaning or washing e.g. moldings, comprises compressing a particulate premix containing zinc-containing granulates and other ingredients - Google Patents

Abstract

Process for preparing a cleaning agent tablet comprises compressing a particulate premix containing zinc-containing granulates and other ingredients, where the compression is carried out at a pressure of greater than 20 kNcm ->2>and the zinc-containing granulates have an average particle size of greater than 0.4 mm (determined by DIN 66145).

Description

The The present invention is more compact in the field of manufacture Shaped body, the washing and cleaning properties exhibit. Such detergent tablets comprise in particular Detergent tablets used to clean dishes used in a household dishwasher and short as detergent tablets or dishwasher tablets be designated, and method for their preparation.

Cleaning tablets are widely described in the art and enjoy the Consumers due to the simple dosage of increasing popularity. Tableted detergents have powdery over a number of advantages: they are easier to dose and to handle and have advantages due to their compact structure storage and transport. Also in the patent literature are Accordingly, detergent tablets are described comprehensively. A problem with the use of washing and cleaning active Moldings occurs again and again, the too low decomposition and dissolution rate of the molded articles under application conditions. Because sufficiently stable, d. H. resistant to deformation and breakage Shaped body only by relative high pressing pressures can be produced, it comes to a strong compaction of moldings components and to a resulting delayed disintegration of the molding in the aqueous liquor and thus too slow Release of the active substances in the washing or cleaning process.

To overcome the dichotomy between hardness, d. H. Transport and handling stability, and easy disintegration of the moldings are in the prior art Many solutions have been developed. One in particular from the pharmacy known and in the field of detergent tablets extended approach is the incorporation of certain disintegration aids, which facilitate the access of water or in the case of access of water swelling or gas-developing or disintegrating in another form Act. Other proposed solutions from the patent literature describe the compression of premixes of specific particle sizes, the separation of individual ingredients from certain other ingredients as well as the coating of individual ingredients or the whole Moldings with binders.

That's how it describes EP 687 464 (Allphamed Arzneimittel-Gesellschaft) Effervescent tablets, consisting of at least one active ingredient or combination of active ingredients, at least one binder, if necessary

excipients such as flavors, dyes, fragrances, plasticizers, bleaches and effervescent additives, wherein as a binder propylene glycol or glycerol, preferably in amounts of from 0.004 to 2.5% by weight become. Also claimed are methods of making this Effervescent tablets. After the statements of this writing leaves also with the teaching of the invention Make detergent effervescent tablets without the used Binder to a carbon dioxide loss in the effervescent additives would lead.

The European patent application EP 711 828 (Unilever) describes laundry detergent tablets containing surfactant (s), builder (s), and a polymer that acts as a binder and disintegration aid. The binders disclosed in this document should be solid at room temperature and fed to the premix to be compressed as a melt. Preferred binders are the relatively high molecular weight polyethylene glycols.

The use of solid polyethylene glycols is also disclosed in the German patent application DE 197 09 411.2 (Henkel). This document teaches synergistic effects between the polyethylene glycols and overdried amorphous silicates.

in the Framework of the development work underlying this application it was surprisingly found that the decay properties of detergent tablets except through the previously described compaction also by the incorporation of Zinc or zinc salts are adversely affected. This observation is for the production of detergent tablets in significance, as zinc and zinc salts in machine Dishwashing a beneficial effect on the during machine cleaning of glass surfaces have occurring glass corrosion processes and for this reason too in compacted automatic dishwashing detergents with preference be used.

For example, describe the international application WO 03/016444 A2 (Henkel KGaA) automatic dishwasher detergents which contain zinc salts of organic acids to inhibit glass corrosion.

Subject of the international application WO 03/104370 A1 (Henkel KGaA) are automatic dishwashing detergents which contain synergistic active substance combinations of zinc salts and crystalline sheet silicates as glass corrosion inhibitors.

In the German Offenlegungsschrift DE 10 2005 025 332 A1 (Henkel KGaA) zinc-containing surfactant compounds are described, through the use of which in particular an improved rinse effect can be achieved.

None of these documents discloses solutions for the improvement of the dissolution behavior zinciferous Cleaning tablets. The present invention The task was now based zinc-containing detergent tablets to provide that at given hardness through distinguish short disintegration times.

It has now been found that the dissolution and decay behavior zinc-containing detergent tablets on exposure high pressing pressures through the use of zinc-containing granules specific particle size can be improved.

A first subject of the present application is therefore a process for the preparation of a detergent tablet by compressing a particulate premix, which also contains a zinciferous granules in addition to other ingredients, characterized in that the pressing takes place with a compacting pressure above 20 kNcm ^-2 and the zinc-containing granules an average particle size (determined after DIN 66145 ) above 0.4 mm.

The Tabletting according to the invention is divided into four sections: metering, compaction (elastic deformation), plastic deformation and ejection. The tabletting takes place preferably on so-called rotary presses.

• – Verwendung von Kunststoffeinlagen mit geringen Dickentoleranzen
• – Geringe Umdrehungszahl des Rotors
• – Große Füllschuhe
• – Abstimmung des Füllschuhflügeldrehzahl auf die Drehzahl des Rotors
• – Füllschuh mit konstanter Pulverhöhe
• – Entkopplung von Füllschuh und Pulvervorlage

When tableting with rotary presses, it has proven to be advantageous to carry out the tableting with the lowest possible weight fluctuations of the tablet. In this way, the hardness fluctuations of the tablet can be reduced. Small variations in weight can be achieved in the following ways:

• - Use of plastic inserts with small thickness tolerances
• - Low number of revolutions of the rotor
• - Big filling shoes
• - Matching of the Füllschuhflügeldrehzahl on the speed of the rotor
• - filling shoe with constant powder height
• - Decoupling of filling shoe and powder template

to Reduction of Stempelanbackungen offer all Non-stick coatings known in the art. Especially advantageous are plastic coatings, plastic inserts or plastic stamps. Rotary stamps have proved to be advantageous, wherein if possible upper and lower punches rotatable should be. With rotating punches can on a plastic insert usually be waived. Here should be the stamp surfaces be electropolished.

Preferred methods in the context of the present invention are characterized in that the particulate material is compacted with a pressing force of more than 30 kNcm ^-2 , preferably above 35 kNcm ^-2 and in particular above 40 kNcm ^-2 .

Rotary presses can also increase with two to increase throughput Füllschuhen be provided, wherein for the production of a Only one semicircle must be passed through the tablet.

As mentioned above, the tablets can be in the context of also multiphase, in particular multi-layered, embellish. The moldings can be in a predetermined spatial form and predetermined size are made. When Raumform come practically all sensibly manageable configurations for example, the training as a blackboard, the staff or bar form, cube, cuboid and corresponding room elements with flat side surfaces and in particular cylindrical Embodiments with a circular or oval cross-section. This last embodiment detects the presentation form from the tablet to compact cylinder pieces with one Ratio of height to diameter above 1.

to Production of two- and multi-layered molded body several filling shoes arranged one behind the other, without the slightly pressed first layer before further filling is ejected. Through suitable process management In this way coat and point tablets can also be produced, which have a onion - bowl - like structure, in the case of the Punkttabletten the top of the core or the core layers not covered and thus remains visible. Also rotary tablet presses are Equipped with single or multiple tools, so that for example, an outer circle of 50 and a Inner circle with 35 holes used simultaneously for pressing become. The throughputs of modern rotary tablet presses are over one million moldings per hour.

After pressing, the detergent tablets have a high stability. The breaking strength of cylindrical shaped bodies can be detected by the measurand of the diametric breaking load. This is determinable σ = 2P πDt

Here in σ stands for the diametral breaking stress (diametrically fracture stress, DFS) in Pa, P is the force in N, the leads to the pressure exerted on the molding, which causes the breakage of the molded article, D is the molded article diameter in meters and t is the height of the moldings. Detergent tablets preferred according to the invention, especially detergent tablets, are characterized that the detergent molding or the detergent tablet a fracture hardness above 150 N, preferably above 200 N has.

The to tablets to be pressed, usually powdery or fine-grained material is, if not particularly expensive and the production hindering arrangements for a special Distribution are made when filling in the die distributed approximately evenly. As a consequence, that the material in the places where the profile of the embossing element the highest elevations, the strongest must be compressed. Although the material to be pressed the highest pressure peaks due to a movement in the direction of trying to avoid less highly stressed areas in the areas of the highest profile surveys also the highest specific area pressures.

One Tabletting punches whose embossing element described in the Form is executed, is advantageously anhaftverhütend or at least reducing adhesion. With such a Press tool can long tool life and flawless Tablet surfaces can be achieved.

The Coating the base of the embossing element should therefore be both tough and resilient against high surface loads, on the other hand also one have friction-reducing or lubricating property. For this have nickel-containing surface coatings as very suitable, in which the finest PTFE particles (Teflon) are included. These impart anti-adherence to the coating and material-seizure-preventing properties. alternative This has also become an embodiment for the Adhesion-reducing coating proven, at the base coating material instead of nickel from a nickel-phosphorus alloy consists. Preferred method according to the invention are characterized in that the pressing surface of the press ram coated to reduce adhesion.

When Another alternative for the surface coating with at least adhesion-reducing effect, however otherwise the requirements for hardness and durability has met, has a coating of diamond particles proven graphite containing. In doing so, the surface becomes the pin coated with a graphite layer, which as lubricating or slide-promoting, and here simultaneously serves as a binder for fixing diamond particles, which in turn give the surface the required hardness. Experiments with these surface coatings of the surveys for the reinforcement pits have shown that even with very long tool life no material buildup to be observed. It is therefore preferred that the at least Adhesion-reducing coating consisting essentially of carbon consists.

In Another preferred embodiment is the pressing surface the press ram at least partially made of plastic, preferably a polyamide.

• – Grundfläche und Mulde sind aus dem gleichen Material gefertigt;
• – Grundfläche und Mulde sind aus unterschiedlichem Material gefertigt, wobei das zur Fertigung der Grundfläche eingesetzte Material eine höhere Härte und geringere Walkbarkeit aufweist als das zur Fertigung der Mulde eingesetzte Material, wobei sich diese Variante insbesondere in Bezug auf die Haltbarkeit und der Prägeelemente als vorteilhaft erwiesen hat;
• – Grundfläche und Mulde sind aus unterschiedlichem Material gefertigt, wobei das zur Fertigung der Grundfläche eingesetzte Material eine geringere Härte und höhere Walkbarkeit aufweist als das zur Fertigung der Mulde eingesetzte Material, wobei sich diese Variante insbesondere in Bezug auf das Auflösungsverhalten der resultierenden Wasch- oder Reinigungsmittelformkörper als vorteilhaft erwiesen hat

For the design of the embossing element of the upper punch there are three alternatives with regard to the execution of the base and the trough:

• - Base and trough are made of the same material;
• - Base and trough are made of different materials, which is the reason for manufacturing the reason surface used material has a higher hardness and lower Walkability than the material used for the production of the trough, this variant has proven to be particularly advantageous in terms of durability and the embossing elements;
• - Base and trough are made of different materials, the material used for the production of the base material has a lower hardness and higher Walkbarkeit than the material used for the production of the trough, this variant is particularly in relation to the dissolution behavior of the resulting detergent tablets has proved to be advantageous

The term "hardness" is in the context of the present invention, the term for the resistance that opposes a solid body to the penetration of another body. While, for example, for minerals the so-called scratch hardness (hardness to Mohs) is measured, technically different methods for hardness testing have prevailed. Brinell, Rockwell and Vickers methods (especially for steel and other metals) are most commonly used. To determine the Brinell hardness (HB, ball hardness, DIN 50351 ) standardized steel or Widia balls with 10 mm diameter and a test load P (in terms of N) pressed bumplessly in the substances to be tested and determines the surface 0 (in mm ² ) of the indented dome of diameter d. The Brinell hardness is then given by:

In the determination of the Rockwell hardness (HR) suitable for higher degrees of hardness, either a diamond cone (HRC) or steel balls of different diameters (HRB) are pressed into the material. When determining the Vickers hardness (HV), a diamond pyramid with an area opening angle of 136 ° is used; Here, too, the hardness is defined as the load in relation to the impression surface (N / mm ² ). In this test method, the impressions are very small, so you can also determine the hardness of very thin layers. Similarly, this also applies to the Knoop hardness (HK), in the determination of which a diamond pyramid with a rhombic ground plan is used. In the determination of impact hardness, the diameter of a ball impression, which was generated by impact with the hand hammer (Poldihammer, scleroscope) or by a tensioned spring, serves as a basis for calculation. Another dynamic method of determining hardness is the return method. The Shore hardness determined in this way is determined in the case of steel by the ball impact test as rebound hardness or, in the case of rubber and other elastomers, as penetration resistance against a truncated cone.

at harder plastics, eg. B. hard thermoplastics and especially with thermosets, one measures the ball pressure hardness as quotient of test load and surface of the Impression of a steel ball (5 mm diameter) after 10, 30 or 60 Seconds under load.

to Production of pressing surfaces with special high hardnesses In particular, metals are suitable, which is why processes in which the pressing surface of the ram at least partially is made of metal, according to the invention preferred become.

When Walkable material for the formation of the base has been described above. Experiments have shown that for example, with the polyurethane material Vulkollan or the PVC material Mipolam very good results could be achieved. about Operating times of several thousand pressures were no attachments detected on the base material.

Preferred processes according to the invention are characterized in that the compression of the particulate material takes place in a tablet press. To prepare the tablets, the premix is compressed in a so-called matrix between two punches to form a solid compressed product. As stated at the beginning, the tablet hardness and the tablet disintegration properties are surprisingly influenced by the particle size of the zinc-containing granules contained in the particulate premix according to the invention. In this case, it is preferred according to the invention that the zinc-containing granules have an average particle size (determined by DIN 66145 ) above 0.5 mm, preferably above 0.6 mm and in particular above 0.8 mm.

The detergent tablets produced according to the invention consist of compressed, particulate material. Examples of such shaped bodies are tablets or extrusion molded bodies. The particulate material on which the shaped body is based in turn comprises the abovementioned specific zinc-containing granules based on a carrier material from the group of builders. In this case, the claimed detergent molding may consist entirely of the zinc-containing granules, comprises in a be preferred alternative embodiment, however, in addition to the zinc-containing granules further particulate detergent-active substances or mixtures of substances.

The detergent tablets produced in preferred processes are characterized in that the detergent tablets, in each case based on the total weight of the detergent tablet, 0.1 to 50 wt .-%, preferably 0.2 to 40 wt .-% of zinc-containing Contain granules.

The Shaped bodies can have one, two or more phases exhibit. As the "phase" of this one, two or more phases Detergent tablets are within the scope of this application macroscopically visible areas of these dosing units called. In the case of tableted detergent or detergent dosing units These are, for example, layers or cores.

The individual phases of a preferred two or more phase tablet are preferably in layers or as a combination of layer (s) and core (s) arranged. The weight fraction of the smallest phase is preferably, based on the entire tablet at least 5 wt .-%, preferably at least 10 wt .-% and in particular at least 20% by weight. The weight fraction of the phase with the highest Weight fraction of the tablet is two-phase Tablets preferably not more than 90% by weight, preferably not more than 80 wt .-% and in particular between 55 and 70 wt .-%. at three-phase tablets is the weight fraction of the phase preferably with the highest proportion by weight of the tablet not more than 80% by weight, preferably not more than 70% by weight and in particular between 35 and 60% by weight.

In In a preferred embodiment, the inventively produced one-, two- or multi-phase moldings of compressed particulate material next to the compressed phases furthermore also not compressed phases. These phases are for example, layers or cores based on solidified Melting or gelatinized solutions or dispersions. Particularly preferred embodiments are mortar tablets made of pressed particulate material with an in the trough inlaid non-compressed core.

The produced by the process according to the invention Shaped bodies preferably contain one for implementation adequate cleaning and washing cycles cleaning-active substances. Corresponding shaped bodies preferably have a weight between 8 and 35 g, preferably between 10 and 30 g and in particular between 12 and 25 g. The volume the shaped body is usually in the range between 5 and 40 ml, preferably between 8 and 30 ml and in particular between 12 and 20 ml.

The produced by the process according to the invention Detergent tablets preferably have dimensions in the range 5 cm × 3 cm × 3 cm, preferably in Range 4.5 cm × 2.5 cm × 2.5 cm, particularly preferred in the range 4 cm × 2 cm, 2 cm up.

a first essential part of the invention used zinc-containing granules form those contained in these granules Zinc compounds. Preferred inventive Processes are characterized in that the zinc-containing Granules, in each case based on its total weight, 10 to 70 wt .-%, preferably 12 to 60 wt .-% of a zinc compound.

In the context of the present application, the group of zinc compounds includes both organic and inorganic zinc salts. A non-exhaustive list of some preferred zinc salts is shown in the following table: zinc salt solubility Zinc acetate dihydrate 430 g / l (20 ° C) zinc acetylacetonate 4 g / l (20 ° C) zinc bromide 820 g / l (25 ° C) zinc chloride 4320 g / l (25 ° C) zinc gluconate 100 g / l (20 ° C) zinc hydroxycarbonate Almost insoluble (20 ° C) zinc iodide 4500 g / l (20 ° C) Zinc nitrate hexahydrate 1843 g / l (20 ° C) Zinc nitrate tetrahydrate Slightly soluble (20 ° C) zinc oxide Insoluble zinc stearate 0.9 mg / l (20 ° C) Zinc sulfate Heptahydat 960 g / l (20 ° C) Zinc sulphate monohydrate ~ 350 g / l (20 ° C)

Next the insoluble inorganic zinc salts, ie salts, which has a solubility below 1 g / L (20 ° C) have (for example: zinc oxide), are within the scope of the present application the soluble inorganic interest salts, that is Salts having a solubility above 1 g / L in water, preferred ingredient of granules according to the invention. Among the preferred soluble inorganic salts include zinc bromide, zinc chloride, zinc iodide and zinc nitrate. With particular preference, however, the zinc sulfate is used.

The Spectrum of the invention preferred zinc salts organic acids, preferably organic carboxylic acids, ranges from salts that are not soluble in water, so have a solubility below 1 g / L, up to such Salts which have a solubility above 1 g / L in water, (all solubilities at 20 ° C water temperature). For example, the first group of zinc salts include the zinc nitrate, the zinc laureate, the zinc oleate, the zinc oxalate, the Zinktartrat and the zinc stearate, to the group of soluble organic zinc salts include, for example, zinc acetate, the zinc acetylacetonate, the zinc benzoate, the zinc formate, the zinc lactate, the zinc gluconate, the zinc valerate and the zinc salt of p-toluenesulfonic acid. From the group of organic zinc salts is with particular preference the zinc acetate used.

Of course may preferably zinc-containing according to the invention Granules also mixtures of organic and / or inorganic zinc salts contain.

preferred Variants of the method according to the invention are characterized in that the zinc-containing Cogranualte a zinc compound selected from the group zinc sulfate, zinc acetate, zinc chloride, zinc hydroxide, Contains zincate and zinc oxide.

In With respect to the corrosion-inhibiting effect produced according to the invention Detergent tablet has it to be advantageous proven, water-soluble zinc compounds, ie zinc compounds with a water solubility above 1 g / L (20 ° C) use. Preferred manufacturing methods are for this reason characterized in that the zinc-containing granules are a water-soluble Contains zinc compound.

a second essential ingredient of the invention in the Method used zinciferous granules form the in these Granules contained carrier materials b). preferred Processes are characterized in that the zinc-containing granules, in each case based on its total weight, 30 to 90 wt .-%, preferably 40 to 88 wt .-% of a carrier material, preferably from the group of builders.

To the builders include in particular the phosphates, Silicates, carbonates and the organic co-builders such as the phosphonates.

The group of suitable silicates includes in particular crystalline layer-form silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is an integer from 1.9 to 22, preferably from 1.9 to 4, Particularly preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. The crystalline layered silicates of the formula NaMSi _x O _{2x + 1} · yH ₂ O are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ .xH ₂ O, Kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ .xH ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ O ₁₇ .xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ .xH ₂ O, Makatite).

Particularly suitable for the purposes of the present invention are crystalline phyllosilicates of the formula NaMSi _x O _{2x + 1} .yH ₂ O, in which x is 2. In particular, both β- and δ-sodium disilicates are Na ₂ Si ₂ O ₅ .yH ₂ O and furthermore especially Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O _5, natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ · H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ · 3H ₂ O, kanemite), Na-SKS-11 (t- Na ₂ Si ₂ O ₅ ) and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ).

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.

The produced by the process according to the invention Detergent tablets and zinc-containing granules are preferably free of water-insoluble aluminum silicates such as natural water softening or synthetic zeolites.

Of course it is also possible to use the generally known phosphates as builders, if such use is not for environmental reasons should be avoided. Among the variety of commercially available Phosphates have the alkali metal phosphates, with particular preference of Pentasodium or pentakalium triphosphate (sodium or potassium tripolyphosphate) the largest in the detergents and cleaners industry Importance.

Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts and also contribute to the cleaning performance.

Technically particularly important phosphates are the pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate). The sodium potassium tripolyphosphates are also preferably used according to the invention.

Further Builders are the alkali carriers. As alkali carrier For example, alkali metal hydroxides, alkali metal carbonates, Alkali metal bicarbonates, alkali metal sesquicarbonates, the mentioned alkali metal silicates, alkali metal silicates, and mixtures of aforementioned substances, wherein for the purposes of this invention preferably the Alkali carbonates, especially sodium carbonate, sodium bicarbonate or sodium sesquicarbonate.

When Organic co-builders are in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, Dextrins to name other organic cobuilders and phosphonates. These Substance classes are described below.

useful Organic builders are, for example, those in Usable form of the free acid and / or its sodium salts Polycarboxylic acids, wherein among polycarboxylic acids Such carboxylic acids are understood to be more than one Wear acidity. For example, these are citric acid, Adipic acid, succinic acid, glutaric acid, Malic acid, tartaric acid, maleic acid, fumaric acid, Sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use is for environmental reasons not to complain about, as well as mixtures of these. The free Acids typically also have, in addition to their builder effect the property of an acidifying component and thus serve also for setting a lower and milder pH of Detergents or cleaners. In particular, here are citric acid, Succinic acid, glutaric acid, adipic acid, Gluconic acid and any mixtures of these.

When Builders are further suitable polymeric polycarboxylates, These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70000 g / mol.

Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, this group can turn into the short chain polyacrylates having molecular weights of from 2,000 to 10,000 g / mol, and more preferably from 3,000 to 5,000 g / mol, may be preferred.

Suitable are furthermore copolymeric polycarboxylates, especially those of Acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As special suitable copolymers of acrylic acid with maleic acid proven, the 50 to 90 wt .-% acrylic acid and 50 to 10 Wt .-% maleic acid. Your molecular weight, based on free acids, is generally 2000 to 70000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The Complexing phosphonates include, in addition to 1-hydroxyethane-1,1-diphosphonic acid a number of different compounds such as diethylenetriamine penta (methylenephosphonic acid) (DTPMP). In this application, in particular hydroxyalkane or Aminoalkanephosphonates. Among the hydroxyalkane phosphonates is the 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a co-builder. It is preferably used as the sodium salt, wherein the disodium salt is neutral and the tetrasodium salt is alkaline (pH 9) reacts. Ethylenediamine tetramethylene phosphonates are preferably used as aminoalkane phosphonates (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher Homologous in question. They are preferably in the form of neutral reacting Sodium salts, e.g. B. as hexasodium salt of EDTMP or hepta- and octa-sodium salt of DTPMP. As a builder will be there from the class of phosphonates preferred HEDP used. The aminoalkane phosphonates also have a pronounced Schwermetallbindeabmögen. Accordingly, it may, especially if the means also bleach be preferred, Aminoalkanphosphonate, in particular DTPMP, to use or mixtures of the phosphonates mentioned.

in the With regard to the improvement of the decay and dissolution characteristics Inventive detergent tablet produced according to the invention have carrier materials from the group of carbonates (including bicarbonates and sesquicarbonates) and the phosphonates the other builders proved superior. When using this particularly preferred Backing materials are the clearest improvements of mold body decay and mold dissolution observed.

Especially preferred methods of the invention are characterized in that the zinc-containing granules a carrier material from the group of carbonates and phosphonates contains.

The for the preparation of zinc-containing granules used water-soluble or water-insoluble zinc salts may be dependent from the chemical nature of the likewise used carrier materials and optional binder in the course of the production process of the granules or the subsequent storage and processing with these Support materials and / or binders react.

• a) 8 bis 80 Gew.-% einer oder mehrerer Zinkverbindung(en);
• b) 20 bis 92 Gew.-% Trägermaterial aus der Gruppe der Carbonate und Phosphonate

umfasst, sind besonders bevorzugt.Process according to the invention, characterized in that the particulate premix, based in each case on its total weight, contains 0.1 to 60% by weight of a zinc-containing granulate

• a) 8 to 80 wt .-% of one or more zinc compound (s);
• b) 20 to 92 wt .-% support material from the group of carbonates and phosphonates

are particularly preferred.

When another optional, in the context of the present application However, preferred additives include those in the inventive Method used zinciferous granules a binder. The in preferred variants of the invention Used zinc-containing granules are characterized in that that the zinc-containing granules, in each case based on its total weight, 0.1 to 15, preferably 0.5 to 12 wt .-% of a binder.

By the addition of the binder will not be just the physical Properties such as hardness or abrasion behavior of zinc-containing Granules improved, furthermore, is surprisingly by the addition of the binder also the hardness and the decay behavior of this Granules produced tablets improved. This is especially true for the addition of aqueous binders such as water or aqueous solutions or dispersions.

• a) 8 bis 79 Gew.-% einer oder mehrerer Zinkverbindung(en);
• b) 20 bis 91,9 Gew.-% Trägermaterial aus der Gruppe der Carbonate und Phosphonate
• c) 0,1 bis 20 Gew.-% eines Bindemittels

umfasst.Preferred processes according to the invention are characterized in that the particulate premix, based in each case on its total weight, contains from 0.1 to 60% by weight of a zinc-containing granulate

• a) 8 to 79 wt .-% of one or more zinc compound (s);
• b) 20 to 91.9 wt .-% of carrier material from the group of carbonates and phosphonates
• c) 0.1 to 20 wt .-% of a binder

includes.

A first group, with particular preference used binder comprises Water and aqueous solutions or dispersions, in particular aqueous polymer solutions or aqueous Polymer dispersions or aqueous surfactant solutions or aqueous surfactant dispersions but also aqueous Silkatlösungen.

In dissolved or dispersed form are preferably in particular organic polymers from the group of polyvinyl alcohols, acetalated polyvinyl alcohols, polyvinylpyrrolidones and polyalkylene glycols, in particular polyethylene oxides. Preferred polyvinyl alcohols and acetalated polyvinyl alcohols have molecular weights in the range from 10,000 to 100,000 gmol ^-1 , preferably from 11,000 to 90,000 gmol ^-1 , particularly preferably from 12,000 to 80,000 gmol ^-1 and in particular from 13,000 to 70,000 gmol ^-1 . Preferred polyethylene oxides have molecular weights in the range of about 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n of about 5 to> 100,000.

Of the Water content of the solutions used with particular preference or dispersions is preferably between 5 and 95 Wt .-%, preferably between 10 and 90 wt .-% and in particular between 20 and 80 wt .-%, each based on the total weight of the solution or Disperison.

Of the Water content of the process according to the invention used zinc-containing granules is preferably between 1 and 15 wt .-%, preferably between 2 and 12 wt .-% and in particular between 4 and 10 wt .-%, each based on the total weight of the granules.

preferred Process variants are further characterized in that the zinc-containing granules, in each case based on its total weight, 0.1 to 20 wt .-%, preferably 0.2 to 15 wt .-% and in particular 0.5 to 10 wt .-% of a binder, preferably a fusible Contains binder with a melting point below 50 ° C.

preferred inventive methods are characterized that the zinc-containing granules used in this process a binder, preferably a binder from the group water, contain organic polymers and surfactants.

Preferred processes according to the invention are characterized in that the compression takes place at a pressure above 20 kNcm ^-2 and the zinc-containing granules have an average particle size (determined after DIN 66145 ) above 0.4 mm, wherein the zinc-containing granules in a pressing process upstream of step a) is prepared by addition of a binder by wet granulation, compaction, fluidized bed granulation, extrusion or pelletization. The process step of wet granulation, compaction, fluidized-bed granulation, extrusion or pelletization preceding the compression is preferably used to adjust the mean particle size of the zinc-containing granules used in the process according to the invention.

A process for the preparation of a detergent tablet by compressing a particulate premix, which also contains a zinciferous granules in addition to other constituents, characterized in that the pressing takes place with a compacting pressure above 20 kNcm ^-2 and the zinc-containing granules produced by compaction an average particle size (determined by DIN 66145 ) above 0.4 mm, are preferred according to the invention.

Some exemplary, according to the invention preferred process variants for process step a) are listed in the following tables: Table 1 No. granulation support material binder 1 mixer granulation carbonate water 2 aqueous silicate solution 3 aqueous polymer solution 4 aqueous polymer dispersion 5 Polyethylene glycol with melting point <50 ° C 6 aqueous surfactant solution 7 aqueous surfactant dispersion 8th Surfactant with melting point <50 ° C 9 phosphonate water 10 aqueous silicate solution 11 aqueous polymer solution 12 aqueous polymer dispersion 13 Polyethylene glycol with melting point <50 ° C 14 aqueous surfactant solution 15 aqueous surfactant dispersion 16 Surfactant with melting point <50 ° C Table 2 No. granulation support material binder 1 fluidized bed granulation carbonate water 2 aqueous silicate solution 3 aqueous polymer solution 4 aqueous polymer dispersion 5 Polyethylene glycol with melting point <50 ° C 6 aqueous surfactant solution 7 aqueous surfactant dispersion 8th Surfactant with melting point <50 ° C 9 phosphonate water 10 aqueous silicate solution 11 aqueous polymer solution 12 aqueous polymer dispersion 13 Polyethylene glycol with melting point <50 ° C 14 aqueous surfactant solution 15 aqueous surfactant dispersion 16 Surfactant with melting point <50 ° C Table 3 No. granulation support material binder 1 extrusion carbonate water 2 aqueous silicate solution 3 aqueous polymer solution 4 aqueous polymer dispersion 5 Polyethylene glycol with melting point <50 ° C 6 aqueous surfactant solution 7 aqueous surfactant dispersion 8th Surfactant with melting point <50 ° C 9 phosphonate water 10 aqueous silicate solution 11 aqueous polymer solution 12 aqueous polymer dispersion 13 Polyethylene glycol with melting point <50 ° C 14 aqueous surfactant solution 15 aqueous surfactant dispersion 16 Surfactant with melting point <50 ° C Table 4 No. granulation support material binder 1 compacting carbonate water 2 aqueous silicate solution 3 aqueous polymer solution 4 aqueous polymer dispersion 5 Polyethylene glycol with melting point <50 ° C 6 aqueous surfactant solution 7 aqueous surfactant dispersion 8th Surfactant with melting point <50 ° C 9 phosphonate water 10 aqueous silicate solution 11 aqueous polymer solution 12 aqueous polymer dispersion 13 Polyethylene glycol with melting point <50 ° C 14 aqueous surfactant solution 15 aqueous surfactant dispersion 16 Surfactant with melting point <50 ° C Table 5 No. granulation support material binder 1 pelleting carbonate water 2 aqueous silicate solution 3 aqueous polymer solution 4 aqueous polymer dispersion 5 Polyethylene glycol with melting point <50 ° C 6 aqueous surfactant solution 7 aqueous surfactant dispersion 8th Surfactant with melting point <50 ° C 9 phosphonate water 10 aqueous silicate solution 11 aqueous polymer solution 12 aqueous polymer dispersion 13 Polyethylene glycol with melting point <50 ° C 14 aqueous surfactant solution 15 aqueous surfactant dispersion 16 Surfactant with melting point <50 ° C

The Preparation of the zinc-containing granules can, as stated above, done by a number of different methods. In a first variant of the method are used to produce the zinc-containing Cogran granules used in a mixer granulated. Suitable mixers are both high shear mixers and free fall mixers or fluidized bed apparatus.

High shear mixer usually have a stationary housing and movable agitator located in this housing and / or cutting tools. In the stirring and / or cutting tools it may be one- or biaxial devices which For example, have knives, rods or blades. The tool-guiding axes can be horizontal or oriented vertically.

The process control in this mixer can be carried out continuously or in a batch process. The preferably used in the present application, high shear mixer include, for example Lödige ^® Recycler KM "Pfugschar" mixer, Lödige ^® CB mixer, the mixer of Drais ^® KT series and other mixers of the company Fukae (Fukae FS-G series) Dierks & Sons (Diosna ^® V Series), Fuji (Fuji ^® VG-C Series), Fielder (Pharma Matrix ^® ) or Schugi (Schugi ^® Granulator, Schugi ^® Flexomix)

In the context of the present invention, such free-fall mixers are those mixers which are characterized by a movable or rotating reactor housing or a moving mixing vessel. Such reactors can furthermore comprise static and / or mobile mixing and / or cutting tools, but preference is given to rotating reactors in which the mixture is taken up by wall friction and then falls freely through the mixer space due to its own gravitational force. As a container of such a free-fall mixer are those with simple geometric shapes (cylinder, single or double cone, cube, etc.) Preferred mixing containers also have as obtuse-angled inner corners, as this both the free movement of the mix than The movement of the container is preferably transferred to the mix in the interior, that as irregular as possible cluttering and loosening up of the reaction mixture occurs Continuous method according to the invention on a directed component of motion in order to ensure the continuous mass transfer. The types of movement for the free-fall mixer are, in particular, rotation about a container axis (drum or rotary tube mixer) or about axes that do not coincide with geometric axes of the container or perpendicular to its symmetry planes (tumble mixer), or vibrate, preferably with high amplitude and low frequency as well as changing directions of the rashes, so the irregularly protective tumbling or staggering movements occur.

In a preferred embodiment of the invention Process forms the moving in the rotating reactor solid support material a falling powder curtain, the preferably introduced Binders preferably sprayed onto this powder curtain becomes.

When Fluidized bed apparatus can be both mechanical and also act as pneumatic equipment. invention Process in which the preparation of zinc-containing granules is done in a pneumatic fluidized bed, but are preferred.

In the pneumatic fluidized bed apparatus is the movement of the mixture components by blowing air into the initially stationary mixture generated. The operation of these fluidized bed apparatuses can be continuous and discontinuous. The injection of air is preferably carried out through the porous floor provided with holes. The bulk density of the partially granulated mixture at Entry into the pneumatic fluidized bed is preferred between 300 and 700 g / l, more preferably between 350 and 650 g / l and in particular between 400 and 600 g / l. The air comes through preferably the porous soil having at least the loosening speed one.

From the initial fixed bed is formed the fluidized bed, the fluidized bed, which due to the easy mobility of the particles has continuum properties similar to a liquid. The mix is preferably almost cohesive. Intensive mixing is - depending on the fineness of the mix - only given at 2 to 6 times the relaxation rate; Gas inflow rates which have at least 2 times, preferably at least 4 times, more preferably at least 6 times and in particular at least 8 times the value of the rate of loosening, are therefore preferred in the context of the method according to the invention. The loosening speed w _L can be calculated from the equilibrium of forces between the weight F _{g of} the bed and the compressive force F _p - the pressure drop Δ _p multiplied by the green area A above the flow-through layer - with the aid of the Ergun equation. It follows: W 1 = 42.9 · (1 - ε L ) · Ν / d p · {(1 + 3,11 · 10 -4 [ε L / (1 - ε L ) 2 ] * G * d p 3 · [Ρ s / ρ f ] / Ν 2) 0.5 - 1}

ε_L

die Porosität der Schicht vor der Lockerung,

ν

die kinematische Zähigkeit der Luft,

d_p

der Sauterdurchmesser d₃₂ der Partikel in der Schicht

ρ_s, ρ_f

Die Feststoff- bzw. bzw. die Luftdichte

Are in it

ε _L

the porosity of the layer before loosening,

ν

the kinematic viscosity of the air,

d _p

the Sauter diameter d _{32 of} the particles in the layer

ρ _s , ρ _f

The solid or the air density

In preferred fluidized bed mixers are the soils in sectors divided, the periodically more or less strongly ventilated become. As a result, changing upheavals occur larger Areas of the vortex. Further preferred are inventive Process in which the temperature of the incoming air is controllable, wherein in particularly preferred process variants the temperature deviates from the outside temperature, either colder or warmer than the temperature of the surrounding outside air and / in different areas of the fluidized bed different temperatures for the incoming Air to be selected.

The Binder is preferably by means of a spray device sprayed onto the fluidized bed formed in the fluidized bed. The spraying can be carried out by means of single-component or high-pressure spray nozzles, Two-substance spray nozzles or three-component spray nozzles respectively.

In a particularly preferred variant of the invention Method is the spray head of the sprayer above the surface of the fluidized bed.

Of the Drop diameter of the sprayed liquid Binder is preferably between 1 and 100 microns, more preferably between 2 and 80 microns, especially preferably between 4 and 70 microns and in particular between 8 and 60 μm. The temperature of the sprayed Binder is preferably between 20 and 70 ° C, preferably between 25 and 60 ° C, more preferably between 30 and 55 ° C and especially between 40 and 50 ° C.

In a further preferred embodiment of the method according to the invention, the Be Constituents of the zinc-containing granules preferably continuously fed to a planetary roller extruder or a 2-shaft extruder or 2-screw extruder with concurrent or counter-rotating screw guide, the housing and the extruder pelletizing head can be heated to the predetermined extrusion temperature. Under the shearing action of the extruder screws, the premix under pressure, which is preferably at least 25 bar, at extremely high throughputs depending on the apparatus used but also may be below, compacted, plasticized, extruded in the form of fine strands through the hole die plate in the extruder head and finally Preferably, the extrudate is reduced by means of a rotating doctor blade to approximately spherical to cylindrical granules. The hole diameter of the hole nozzle plate and the strand cut length are matched to the selected granule dimension. In this embodiment, it is possible to produce zinc-containing granules of a substantially uniformly predeterminable particle size, wherein in detail the absolute particle sizes can be adapted to the intended use. Important embodiments provide here for the production of uniform granules in the millimeter range, for example in the range of 0.4 to 5 mm and in particular in the range of about 0.5 to 3 mm. The length / diameter ratio of the chopped primary granules in one important embodiment is in the range of about 1: 1 to about 3: 1. Furthermore, it is preferable to supply the still plastic primary granules to a further shaping processing step; At the same time, edges present on the raw extrudate are rounded, so that ultimately spherical to approximately spherical extrudate grains can be obtained. If desired, small amounts of dry powder, for example, zeolite powder, such as zeolite NaA powder, may be included in this stage. This shaping can be done in commercially available Rondiergeräten. Care should be taken to ensure that only small amounts of fine grain content are produced in this stage. Drying of the resulting extrudates is unnecessary in the context of the present invention, since the process according to the invention is essentially anhydrous, ie without the addition of free, non-bound water.

alternative Extrusions / Pressings can also be used in low-pressure extruders, be carried out in the Kahl press or Bextruder.

In a further preferred embodiment of the invention Process takes place the production and shaping of zinc-containing Granules by means of a Kompaktierverfahrens, preferably a Walzenkompaktierverfahrens. Here, the zinc-containing premix is targeted between two smooth or metered with recesses of defined shape provided rollers and between the two rollers under pressure to form a sheet Kompaktat, the so-called Schülpe, rolled. Practice the rollers on the premix a high line pressure and can additionally heated or cooled as needed become. When using smooth rolls, one obtains smooth, unstructured sling belts while structured by the use of structured rolls Slugs can be generated in which, for example specified certain forms of the later zinc-containing granules can be. The scarf band will be below by a tee and crushing process into smaller pieces broken and can be processed in this way to granules be obtained by further known per se surface treatment methods further tempered, in particular in approximately spherical Shape can be brought.

In a further preferred embodiment of the invention Process is the zinc-containing granules by means of a pelleting process produced. Here, the zinc-containing premix is on a perforated Surface applied and by means of a pressure-giving body Pressed through the holes under plasticization. In conventional embodiments of pellet presses the premix is compacted under pressure, plasticized, by means of a rotating roller in the form of fine strands through a pressed perforated surface and finally comminuted to granules with a stripping device. Here are the most varied configurations of pressure roller and perforated die conceivable. For example, find flat perforated plates as well as concave or convex ring matrices, through which the material is pressed by means of one or more pressure rollers becomes. The press rollers can be used with the plate devices also be conically shaped, in the annular devices can co-matrices and press roll (s) or have opposite directions of rotation. Of course but can also be heated or cooled during pelleting Rolls are worked to a desired temperature to adjust the premix.

The zinc-containing granules become the particulate material mixed before pressing. For this purpose, the granules, for example with further particulate solid components Material mixed and subsequently with the addition of a granulating agent be granulated. Alternatively, the addition of the zinc-containing Granules to the particulate material in a Postadditionsschritt without subsequent granulation.

Examples

• * anionisches Polymer
• ** amphoteres Polymer
• *** Kompaktat mit mittlerer Teilchengröße (bestimmt nach DIN 66145 ) unterhalb 0,4 mm
• **** Kompaktat mit mittlerer Teilchengröße (bestimmt nach DIN 66145 ) oberhalb 0,8 mm

To demonstrate the advantageous effect of zinc granules of the invention on the hardness and the disintegration of detergent tablets, the particulate premixes listed in the table below were monolayered with a pressing force of 35 kNcm ^-2 (V1 and E1) and 50 kNcm ^-2 (V2 and E2) Compressed tablets. V1 [% by weight] E1 [% by weight] V2 [% by weight] E2 [% by weight] phosphate 60.0 55.0 60.0 55.0 surfactant 3.0 3.0 3.0 3.0 Polymer 1 * 5.0 5.0 5.0 5.0 Polymer 2 ** 1.0 1.0 1.0 1.0 enzyme 15.0 15.0 15.0 15.0 TAED 9.0 9.0 9.0 9.0 binder 0.7 0.7 0.7 0.7 perfume 0.2 0.2 0.2 0.2 dye 0.2 0.2 0.2 0.2 Zinc acetate *** 2.50 - 2.50 - Zinc acetate **** - 2.50 - 2.50 Misc Add 100 Add 100 Add 100 Add 100

• * anionic polymer
• ** amphoteric polymer
• *** Kompaktat with average particle size (determined after DIN 66145 ) below 0.4 mm
• **** Kompaktat with average particle size (determined after DIN 66145 ) above 0.8 mm

After 5 days (V1 and E1) and 6 days (V2 and E2) storage, the hardness and dissolution times of the resulting tablets were determined V1 E1 V2 E2 tablet hardness 350 N 350 N 460 460 dissolution time 40 min 15 minutes 46 min 38 min

this Data show that by packing the into the Tablets contained zinc salt in the form of a builder-based zinc-containing granules with constant hardness of the tablets Decay and dissolution behavior can be significantly improved can.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - EP 687464 [0004]
• - EP 711828 [0006]
• - DE 19709411 [0007]
• WO 03/016444 A2 [0009]
• WO 03/104370 A1 [0010]
• DE 102005025332 A1 [0011]

Cited non-patent literature

• - DIN 66145 [0014]
• - DIN 50351 [0030]
• - DIN 66145 [0035]
• - DIN 66145 [0079]
• - DIN 66145 [0080]
• - DIN 66145 [0100]
• - DIN 66145 [0100]

Claims (15)

Process for producing a detergent tablet by compressing a particulate premix which, in addition to other constituents, also contains a zinc-containing granulate, characterized in that the compression takes place with a compacting pressure above 20 kNcm ^-2 and the zinc-containing granules have an average particle size (determined to DIN 66145) above 0.4 mm. A method according to claim 1, characterized in that the particulate material is pressed with a pressing force above 30 kNcm ^-2 and in particular above 40 kNcm ^-2 . Method according to one of the preceding claims, characterized in that the zinc-containing granules have a mean Particle size (determined according to DIN 66145) above 0.5 mm, preferably above 0.6 mm and in particular above 0.8 mm. Method according to one of the preceding claims, characterized in that the zinc-containing granules in one of Pressing upstream process step by wet granulation, Compaction, fluidized bed granulation, extrusion or pelletizing will be produced. Method according to one of the preceding claims, characterized in that the detergent tablet, respectively based on their total weight, 0.1 to 50 wt .-%, preferably 0.2 contains up to 40 wt .-% of zinc-containing granules. Method according to one of the preceding claims, characterized in that the zinc-containing granules, respectively on its total weight, 10 to 70 wt .-%, preferably 12 to 60 Wt .-% of a zinc compound. Method according to one of the preceding claims, characterized in that the zinc-containing granules are a water-soluble Contains zinc compound. Method according to one of the preceding claims, characterized in that the zinc-containing cogranulate is a zinc compound selected from the group of zinc sulfate, zinc acetate, zinc chloride, Zinc hydroxide, zincate and zinc oxide. Method according to one of the preceding claims, characterized in that the zinc-containing granules, respectively on its total weight, 30 to 90 wt .-%, preferably 40 to 88 Wt .-% of a carrier material. Method according to one of the preceding claims, characterized in that the zinc-containing granules are a carrier material from the group of builders. Method according to one of the preceding claims, characterized in that the zinc-containing granules are a carrier material from the group of carbonates and phosphonates. Method according to one of the preceding claims, characterized in that the zinc-containing granules, respectively on its total weight, 0.1 to 20, preferably 0.5 to 12 wt .-% containing a binder. Method according to one of the preceding claims, characterized in that the zinc-containing granules are a binder from the group containing water, organic polymers and surfactants. Method according to one of the preceding claims, characterized in that the particulate premix in each case based on its total weight, 0.1 to 60 wt .-% of a zinc-containing granules containing a) 8 to 80 wt .-% of a or more zinc compound (s); b) 20 to 92 wt .-% carrier material from the group of carbonates and phosphonates includes. Method according to one of the preceding claims, characterized in that the particulate premix in each case based on its total weight, 0.1 to 60 wt .-% of a zinciferous granules containing a) 8 to 79 wt .-% of one or more zinc compound (s); b) from 20 to 91.9% by weight of carrier material from the group of carbonates and phosphonates c) from 0.1 to 20% by weight of a binder.