DE19941266A1 - Composite multiphase shaped detergents useful in textile washing machines and in dishwashers have one part with a conical cavity containing the other part, optionally with optical differentiation - Google Patents

Abstract

A composite multiphase shaped detergent comprises a pressed part (A) having a cavity containing a further solid part (B), the cavity being conical. A composite shaped detergent comprises a pressed (A) part having a cavity containing a further solid part (B), the cavity being conical. Also included is an Independent claim for production of the composite by (i) pressing a particulate pre-mix to give part (A) with a conical cavity and then (ii) placing the formed part (B) into the cavity, optionally followed by a post-treatment.

Description

The present invention relates to detergent tablets, processes for their manufacture and their application.

Detergent tablets are widely described in the prior art are becoming increasingly popular with consumers because of the simple dosage. Tableted detergents have a number of powdered products Advantages: They are easier to dose and handle and because of their compact structure Advantages in storage and transport. There is therefore one extremely broad state of the art for detergent tablets, which itself is also reflected in an extensive patent literature. The Ent is there early developers of tablet-shaped products came across the idea differently set areas of the molded body certain ingredients only under defined conditions release in the wash or cleaning cycle to improve cleaning success ser. In addition to the core / shell Tablets and ring / core tablets, in particular multilayered molded articles, which are offered today for many areas of washing and cleaning or hygiene become. The optical differentiation of products is also becoming increasingly important tion, so that single-phase and single-color moldings in the field of washing and Cleansing was largely replaced by multi-phase moldings. Common in the market are currently two-layer molded articles with a white and a colored phase or with two differently colored layers. There are also point tablets, ring core tablets, coated tablets, etc., which currently have a rather minor meaning.  

Multi-phase cleaning tablets for the toilet are described, for example, in EP 055 100 (Jeyes Group). This document discloses blocks of toilet cleaners that a molded body from a slowly soluble detergent composition comprise, in which a bleach tablet is embedded. This document immediately reveals different forms of multi-phase moldings. The Her position of the molded body is done according to the teaching of this document either by insertion a compressed bleach tablet in a mold and pour this tablet into the Detergent composition, or by pouring some of the detergent composition into the mold, followed by inserting the pressed bleach Ablette and possibly subsequent pouring together with other cleaning agents settlement.

EP 481 547 (Unilever) also describes multi-phase detergent tablets which to be used for automatic dishwashing. These moldings have the Form of core / shell tablets and are obtained by gradually compressing the loading components manufactured: First, a bleaching agent composition is pressed to a shaped body which in a matrix half-filled with a polymer composition is inserted, which is then filled with further polymer composition and into one provided with a polymer jacket molded bleach is pressed. The procedure is then repeated with an alkaline detergent composition, so that there is a three-phase molded body.

Another way of producing optically differentiated detergents and cleaning agents Shaped body is in the international patent applications WO 99/06522, WO 99/27063 and WO 99/27067 (Procter & Gamble). According to the teaching of these writings a molded body is provided which has a cavity with a solidifying Melt is filled. Alternatively, a powder is filled in and by means of a coating layer attached in the cavity. All three applications have in common that the cavity filling area should not be pressed, because in this way "pressure sensitive" In contents should be spared.  

The way described in the prior art to prepare melts into the tablets are placed or which are poured into moldings, includes a thermal loading load of the ingredients in the melts. In addition, the exact dosage requires flu siger to pasty media as well as the subsequent cooling a high technical Effort that depends in part on the composition of the melt Shrinkage when cooling and the resulting detachment of the filling is made. The filling of cavities with powdery ingredients and the fixie Coating is also complex and has similar stability problems is liable.

The conventional tableting of multilayer tablets takes place in the field of Detergent tablets also have their limits if only one layer should have a small proportion of the total molded body. If you fall below a be if the layer thickness was correct, then there is pressing of one adhering to the rest of the molded body Layer increasingly difficult.

With the help of special transfer and centering devices can be manufactured separately Tablets in larger matrices, in which there is already a particulate premix for large insert the larger tablets and mix them together with the premix to form the shell / core Compress tablets or tablets. This is double Loading the "core" with high pressing pressures is just as disadvantageous as the high equipment Expenditure.

The older German patent application DE 199 09 271.0 (Henkel) therefore suggests as Alterna tivverfahren a process for the production of multi-phase detergents and cleaning agents Shaped body in which a particulate premix is pressed into shaped bodies, on their surfaces optional adhesion promoters are applied, after which further active substances stamping, for example in the form of pre-compressed molded body, is applied. This font also describes the introduction of pre-tableted active substance (mixtures) into cavities of other moldings.  

The present invention was based on the object that in the older German Patent application DE 199 09 271.0 to further develop the method described. In particular it should be possible to dispense with the use of adhesion promoters. Another The object of the present invention was to provide moldings in which also temperature-sensitive ingredients can be brought into defined regions, the delimited region in terms of its size in relation to the overall shaped body should not be subject to any restrictions. On the one hand, an optical Differentiation from conventional two-layer tablets can be achieved, on the other hand should the production of the molded body in large quantities without great technical effort rie function safely without the moldings disadvantages in terms of stability indicate or inaccuracies in the dosage would be feared.

It has now been found that the disadvantages mentioned are avoided if "Ker ne "is pressed into a specially shaped cavity of a pre-compressed molded body In this way the adhesion of the filling is improved even without the use of adhesion promoters, the temperature load of the ingredients excluded and the expenditure on equipment minimized.

In a first embodiment, the present invention relates to detergent tablets which

• a) a pressed part; which has at least one cavity,
• b) a further solid part, which is at least partially enclosed in the cavity is present

the cavity in part a) is conical.

The cavity in the pressed part a) of the shaped bodies according to the invention can be any Have shape. You can cut through the molded body, d. H. an opening to various NEN sides, for example on the top and bottom of the molded body, they can but also a cavity that does not go through the entire molded body, the opening thereof is only visible on one side of the molding.  

The moldings according to the invention can take on any geometric shape where with in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthor hombic, cylindrical, spherical, segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, pentagonal, octagonal and octagonal prismatic and rhombohedral shapes are preferred. Completely irregular too Base areas such as arrow or animal shapes, trees, clouds, etc. can be realized. If the shaped bodies according to the invention have corners and edges, these are preferred wisely rounded. As an additional optical differentiation, an embodiment with rounded corners and chamfered ("chamfered") edges preferred.

Of course, the pressed parts a) of the moldings according to the invention can also be produced in multiple phases. For reasons of procedural economy here, two-layer moldings have proven particularly effective.

The cavity in part a) of the moldings according to the invention is preferably open on one side, so that part a) represents a "trough molding". Washing or cleaning agents according to the invention molded article in which the cavity in part a) has the shape of an open on one side conical hole are preferred. These moldings according to the invention can assume any geometric shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment ment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyrami dale, ellipsoidal, five-, seven- and octagonal-prismatic and rhombohedral shapes are preferred. Also completely irregular base areas such as arrow or animal shapes, trees, Clouds etc. can be realized. If the molding has corners and edges, see above they are preferably rounded. Off is an additional optical differentiation leadership form with rounded corners and chamfered ("chamfered") edges in front moves.

The shape of the trough can also be chosen freely, with molded bodies being preferred which at least one trough has a concave, convex, cubic, tetragonal, orthorhombi cal, cylindrical, spherical, segment-like, disc-shaped, tetrahedral, dode cathedral, octahedral, conical, pyramidal, ellipsoid, pentagonal, octagonal and octagonal  prismatic and rhombohedral shape can take. Completely irregular Mul too shapes such as arrow or animal shapes, trees, clouds, etc. can be realized. As with the molded bodies, troughs are with rounded corners and edges or with rounded corners and chamfered edges preferred.

In preferred embodiments of the present invention, part b) fills the cavity Part a) does not completely look. In such moldings, parts a) and b) remain a cavity that can be filled with additional active substance.

To improve the adhesion between parts a) and b) of the invention Detergent or cleaning product tablets can be in the embodiments with a trough in addition, a "plug-like principle" can be used. The floor surface of the trough provided with an elevation, which is reflected by a corresponding recess fung in the ram can be easily realized during manufacture. Let of course the bottom surfaces of the troughs are also made with several elevations. Washing or Detergent tablets, which are characterized in that the conical trough one or more elevations and / or depressions, preferably having, from ih protruding and / or protruding bottom are preferred embodiments of the present invention.

Part b), which can be inserted into the conical cavity of part a), can be implemented in such a way tion forms are provided with a recess that the from the trough bottom surface protruding pin. This way the liability between the two Sharing improved. Molded core body b) which have corresponding depressions in the simplest case (a depression) the shape of trough shaped bodies. Detergent tablets in which the part that can be inserted into the trough is a has the corresponding deepening / elevation corresponding to the elevation / deepening in part a) also preferred.

Regardless of the type of cavity (continuous or trough-like), washing or Preferred detergent tablets in which the cavity has a circular cross cut has.  

The cavity in part a) of the detergent tablets according to the invention is conical shape. The term "conical" in the context of the present invention to be understood to mean that the two opposite openings of the cavity or the opening the cavity and its horizontal bottom surface have different largest diameters sen. If a longitudinal section is made through the cavity, the length of the section is that connecting the two edges at the top, longer or shorter than the length of the ent speaking connecting line at the bottom. These lines are called straight lines measure up. So if the top or bottom have convex or concave curvatures, then the length of the line then the length of the imaginary straight line that the two outer edges would connect with each other. The easiest way to do this is in the case of the "classic" Explain the cone of a truncated cone with a circular base: the diameter one of the two circular horizontal boundaries is smaller than that of the other (Otherwise there would be a cylinder). This principle can of course be based on this apply all other geometries, for example to square, rectangular, pentagonal, hexagonal and pentagonal or completely irregular bases. You can of course, different geometries can be combined with each other, so that a horizontal boundary surface can be a circle, an ellipse or a diamond, while the other boundary surface is shaped differently, for example quadra table, octagonal or irregular. For non-circular surfaces, the criterion applies that one horizontal "edge connecting line" must be shorter than the other, preferably for each vertical section through the cavity. The conical shape can be clearly illustrated Explain the cavity as follows: take the larger "base area" (i.e. the larger opening area, in the case of troughs the opening area always must be the largest area, since overlaps cannot be pressed) and thinks a prism with this base. Once the real shape of the cavity in this prism "fits in", the cavity) is conical in the sense of the present invention. Is preferred here that the real shape of the cavity nowhere touches the wall of the imaginary price mas touches the criterion that a horizontal "edge connecting line" should be shorter must be considered the other, preferably for each vertical section through the cavity, as be has been carried out.  

With the sizes and masses of conventional detergent tablets, which in the Range from 5 to 100 mm, preferably in the range from 7.5 to 75 mm and in particular from 10 to 50 mm and between 10 and 120 g, preferably between 15 and 80 g and in particular between 20 and 50 g, are in particular washing or cleaning preferred shaped tablets, in which the smallest diameter of the conical Cavity in part a) maximum 3 mm, preferably maximum 2.5 mm and in particular maxi times 2 mm smaller than its largest diameter. The term "diameter" characterizes net here again the "shortest edge connection line" in longitudinal section, with in In the case of irregularly shaped cavities, this criterion is preferred for any ver tical cut applies.

Part b) of the shaped body according to the invention is at least partially in the conical Contain cavity of part a), the cavity is not completely filled and a Cavity in part a) remains. Depending on the design of the cavity in the pressed part a) part b) can completely close off the cavity, but it is also possible that part b) For example, only one side of a through hole in part a) closes and the the remaining cavity, which then forms a cavity, forms the cavity. Part B) can, on the other hand, also be inserted like a closure into a cavity open on one side in part a) are set, whereby a cavity is formed, which has no outer surfaces of the molded body contacted. Detergent tablets, in which part b) the cavity in part a) closes and the remaining cavity is thus completely enclosed by a) and b) are preferred according to the invention.

Of course, this embodiment is not for closing troughs moldings limited; rather, a continuous conical hole in the ver pressed part a) with a correspondingly shaped part b) or with two different Parts b) are closed so that a cavity is formed inside the tablet det. As a logical continuation of the principle mentioned, conical cavities can also be used close with several openings through one or more parts b). Washing or Detergent tablets, which are characterized in that the continuous ko African hole in part a) is closed with two parts b), especially before moves.  

The size of the trough or through hole compared to the overall shape body depends on the intended use of the molded body. Depending on with how much more active substance the remaining hollow volume is filled should and whether a smaller or larger amount of active substance should be contained the size of the cavity and the size of the part not completely filling the cavity b) vary. Detergent or cleaning agent forms are independent of the intended use body preferred, in which the weight ratio of part a) to part (s) b) 1: 1 to 100: 1, preferably 2: 1 to 80: 1, particularly preferably 3: 1 to 50: 1 and in particular 4: 1 is up to 30: 1.

In addition to the volume ratio mentioned, a mass ratio of the two can also be used Parts are specified, the two values on the densities of parts a) and b) correlate with each other. Regardless of the density of the individual part a) or b) are Detergent tablets according to the invention are preferred, in which the Weight ratio of part a) to part (s) b) 1: 1 to 100: 1, preferably 2: 1 to 80: 1, is particularly preferably 3: 1 to 50: 1 and in particular 4: 1 to 30: 1.

Analogous information can also be given for the surfaces, each of part a) or from part b) are visible. Here are detergent tablets before moves, in which the outwardly visible surface of part b) 1 to 25%, preferably 2 to 20%, particularly preferably 3 to 15% and in particular 4 to 10% of the total upper area of the filled molded body

Part b) does not completely fill the conical cavity in the pressed part a), so that in a cavity formed in the detergent tablets according to the invention becomes. This cavity can be filled with active substance, see below. The Cavity can itself be a cavity, i. H. be open to one or more sides, however, it is also possible and preferred that the cavity be completely separated from parts a) and b) is enclosed. Regardless of the design of the cavity, washing or detergent tablets preferred, in which the volume ratio from the parts a) and b) formed cavity to the overall molded body 1: 1 to 50: 1, preferably 2: 1 to 40: 1, particularly preferably 3: 1 to 30: 1 and in particular 4: 1 to 20: 1.  

Part b) and the base molding [part a)] with a conical cavity are preferably optical distinctively colored. In addition to the optical differentiation, application technology nical advantages due to the different solubilities of the various molded parts be achieved. Detergent tablets in which part b) dissolves faster than part a) are preferred according to the invention. Determine by incorporation ter components, the solubility of part b) can be accelerated in a targeted manner, on the other hand, the release of certain ingredients from part b) can have advantages in Carry out washing or cleaning process. Ingredients that are preferred at least partially in Part b) are localized, for example the disintegrations described below auxiliary agents, surfactants, enzymes, soil-release polymers, builders, bleaches, bleach activators, bleaching catalysts, optical brighteners, silver protection agents, etc.. The be accelerated release of one or more of the active substances mentioned can lead to lei performance increase can be used, for example, by enzymes in a washing or cleaning process earlier and therefore longer available. Even the premature release set Bleaching agents or acidic components can be used without any problems cleaning or cleaning often results in performance advantages.

Of course, detergent tablets according to the invention are also molded preferred, in which part b) dissolves more slowly than part a). Again, you can all or some of the ingredients commonly found in washing or cleaning agents be included in part b). Performance benefits from this delayed release can be seen achieve, for example, by using a slower soluble part b) Active substance (s) are only released in later rinses. For example, at machine dishwashing by slower soluble parts b) can be achieved in Rinse aid further active substance (s) is / are available. By additional Leave substances such as nonionic surfactants, acidifiers, soil release polymers, etc. the rinse aid results improve. Incorporation of perfume is also pro easily possible; due to its delayed release, dishwashers can the often occurring "lye smell" when opening the machine can be eliminated. Also at Textile laundry can use effects of the type mentioned, for example by delayed release of cationic surfactants or other textile softeners or Textile auxiliaries. In this way, the household can in the post-treatment course  Washing machine active substance can be applied to the textiles that precede the washing process is difficult or incomplete to apply. In addition to the above Fabric softeners are especially perfumes, optical brighteners, UV protection agents, skin care products, ironing aids, anti-crease agents, swelling and sliding agents, etc. call.

In preferred embodiments of the present invention, the base molding has a high specific weight. Detergent tablets, which are characterized in that the base tablet [part a)] has a density above 1000 kgdm ^-3 , preferably above 1025 kgdm ^-3 , particularly preferably above 1050 kgdm ^-3 and in particular above 1100 kgdm ^-3 , are preferred according to the invention.

Further details on physical parameters of the base molding or the finished one Detergent tablets and information on their manufacture can be found in white ter below. The preferred ingredients of the base tablet are shown below.

Preferred detergent and cleaning agent form in the context of the present invention bodies are characterized in that the basic shaped body builders in amounts of 1 to 100% by weight, preferably from 5 to 95% by weight, particularly preferably from 10 to 90 % By weight and in particular from 20 to 85% by weight, in each case based on the weight of the Basic molding, contains.

In the detergent tablets according to the invention, all the usual builders used in washing and cleaning agents, ins So especially zeolites, silicates, carbonates, organic cobuilders and - where no ecological there are prejudices against their use - including phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for × 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in the international patent application WO-A-91/08171 .

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compaction / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted in such a way that the products have microcrystalline ranges of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a release delay compared to the conventional water glass glasses, are described for example in German patent application DE-A-44 00 024. Particularly preferred are compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates.

Preferred detergent and cleaning agent form in the context of the present invention bodies are characterized in that the base molding silicate (s), preferably Alkali silicates, particularly preferably crystalline or amorphous alkali disilicates, in quantities from 10 to 60% by weight, preferably from 15 to 50% by weight and in particular from 20 to 40 wt .-%, each based on the weight of the base molding, contains.  

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X), which was developed by CONDEA Augusta S. p. A. is sold under the brand name VEGOBOND AX® and through the formula

nNa ₂ O. (1 - n) K ₂ O.Al ₂ O _3. (2 - 2.5) SiO _2. (3.5 - 5.5) H ₂ O

can be described. The zeolite can be used both as a builder in a granule Ren compound used, as well as a kind of "powdering" of the whole to be pressed Send mixture are used, usually both ways of incorporation of the zeolite can be used in the premix. Suitable zeolites have a medium one Particle size of less than 10 µm (volume distribution; measurement method: Coulter Coun ter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight bound water.

It goes without saying that the generally known phosphates are also used as buildersub punching possible, provided that such use is not avoided for ecological reasons should be. Among the large number of commercially available phosphates, the Alka limetal phosphates with particular preference for pentasodium or pentapotassium tri phosphate (sodium or potassium tripolyphosphate) in detergents and cleaning agents Industry the most important.

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

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; it occurs when phosphoric acid is adjusted to pH 4.5 with caustic soda and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt with a density of 2.33 gcm ^-3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is easily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 , melting point 48 ° with loss of 5H ₂ O) and 12 mol. Water (density 1.52 gcm ^-3 , melting point 35 ° with loss of 5H ₂ O), becomes anhydrous at 100 ° and changes to diphosphate Na ₄ P ₂ O ₇ when heated to a greater extent. Disodium hydrogen phosphate is produced by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm ^-3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (corresponding to 390% P ₂ O ₅ ) a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 gcm ^-3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises e.g. B. when He's heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) . Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed by heating disodium phosphate to <200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dehydrating the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6H ₂ O. -Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° about 32 g of the crystal water-free salt; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% by weight solution (<23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

According to the invention, these are exactly like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two can be used; also mixtures of sodium tripolyphos phate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and Sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tri Polyphosphate and sodium potassium tripolyphosphate can be used according to the invention.

Preferred detergent and cleaning agent form in the context of the present invention Bodies are characterized in that the base molding is preferably phosphate (s) Alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (Sodium or potassium tripolyphosphate), in amounts of 20 to 80 wt .-%, preferably from 25 to 75% by weight and in particular from 30 to 70% by weight, in each case based on the Weight of the base molding.

Alkali carriers can be present as further constituents. The following are considered to be alkali carriers for example alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, the alkali silicates mentioned, alkali metals silicates, and mixtures of the aforesaid substances, whereby in the sense of this invention adds the alkali carbonates, especially sodium carbonate, sodium hydrogen carbonate or Sodium sesquicarbonate can be used. A builder system is particularly preferred holding a mixture of tripolyphosphate and sodium carbonate. Also special a builder system containing a mixture of tripolyphosphate and natri is preferred umcarbonate and sodium disilicate.  

The base contains particularly preferred detergent tablets molded articles carbonate (s) and / or hydrogen carbonate (s), preferably alkali carbonates, particularly preferably sodium carbonate, in amounts of 5 to 50% by weight, preferably of 7.5 to 40 wt .-% and in particular from 10 to 30 wt .-%, each based on the Ge importance of the base molding.

As organic cobuilders in the washing and cleaning agents according to the invention telformkörper in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxy latex, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used. These classes of substances are described below ben.

Usable organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, with such carboxylic acids under polycarboxylic acids can be understood that carry more than one acid function. For example, these are Citro Nenoic acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, Fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if one such use is not objectionable for ecological reasons, as well as mixtures from these. Preferred salts are the salts of polycarboxylic acids such as citric acid, Adi Pinic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of the sen.

The acids themselves can also be used. The acids have besides their buil the effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or Detergents. In particular, citric acid, succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.

Polymeric polycarboxylates are also suitable as builders, for example those Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70,000 g / mol.  

For the purposes of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{W of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the investigated polymers. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2000 to 20,000 g / mol. Because of their superior solubility, the This group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, preferably his.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As a special copolymers of acrylic acid with maleic acid, 50 to Contain 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative mole Cooling mass, based on free acids, is generally from 2000 to 70,000 g / mol preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be either as a powder or as an aqueous solution be used. The content of (co) polymeric polycarboxylates in the agent is before preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

To improve water solubility, the polymers can also allylsulfonic acids, such as for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer ten.

Biodegradable polymers of more than two ver. Are also particularly preferred different monomer units, for example those that act as monomers salts of acrylic  acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives contain.

Further preferred copolymers are those which are described in German patent applications DE- A-43 03 320 and DE-A-44 17 734 are described and preferably as monomers Have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Likewise, further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors. Polyas are particularly preferred paraginic acids or their salts and derivatives, of which in the German patent application dung DE-A-195 40 086 discloses that, in addition to cobuilder properties, it also has a have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which are produced by the implementation of Dial dehyden with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl have groups that can be obtained. Preferred polyacetals are from Dialde hyden such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from Obtained polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be. The hydrolysis can be carried out according to conventional methods, for example acid or enzyme lysed procedures are carried out. It is preferably hydrolysis pro Products with average molecular weights in the range of 400 to 500,000 g / mol. There is a poly saccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30 preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and dry glu can be used cosesirupe with a DE between 20 and 37 as well as so-called yellow dextrins and White dextrins with higher molar masses in the range from 2000 to 30000 g / mol.  

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 and international patent applications WO 92/18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608 are known. An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Also oxydisuccinates and other derivatives of disuccinates, preferably ethylenedia mindisuccinate are other suitable cobuilders. Here, ethylenediamine-N, N'- disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and Gly are also preferred in this context cerintrisuccinate. Suitable amounts are in zeolite and / or silicate salts gene formulations at 3 to 15 wt .-%.

Other useful organic cobuilders are, for example, acetylated hydroxycarbon acids or their salts, which may optionally also be in lactone form, and which have at least 4 carbon atoms and at least one hydroxyl group and maxi contain two acid groups. Such cobuilders are used, for example, in the inter national patent application WO 95/20029.

Another class of substances with cobuilder properties are the phosphonates it is in particular hydroxyalkane or aminoalkanephosphonates. Under the hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) from of particular importance as a cobuilder. It is preferably used as the sodium salt the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). As Aminoalkane phosphonates preferably come from ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher Ho mologist in question. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP,  used. HEDP is preferred as a builder from the phosphonate class turns. The aminoalkanephosphonates also have a pronounced heavy metal bin de assets. Accordingly, it can, especially if the agent also ent bleach hold, be preferred to use aminoalkane phosphonates, in particular DTPMP, or To use mixtures of the phosphonates mentioned.

In addition, all compounds that are capable of complexing with alkaline earth train ions as cobuilders.

The amount of builder is usually between 10 and 70 wt .-%, preferably as between 15 and 60 wt .-% and in particular between 20 and 50 wt .-%. How therefore the amount of builders used depends on the intended use, so that Bleach tablets may have higher amounts of builders (for example between 20 and 70% by weight, preferably between 25 and 65% by weight and in particular re between 30 and 55 wt .-%), for example detergent tablets (usually 10 to 50 wt .-%, preferably 12.5 to 45 wt .-% and in particular between 17.5 and 37.5% by weight).

Preferred detergent tablets furthermore contain one or more Surfactant (s). Can in the detergent tablets according to the invention anionic, nonionic, cationic and / or amphoteric surfactants or Mi can be used from these. Are preferred from an application point of view for detergent tablets, mixtures of anionic and nonionic surfactants and for detergent tablets non-ionic surfactants. The total surfactant content of the form In the case of detergent tablets, the body is 5 to 60% by weight, based on the Molded body weight, with surfactant contents above 15% by weight being preferred, while Reini detergent tablets for automatic dishwashing, preferably below 5% by weight Contain surfactant (s).

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and disulfonates such as are obtained, for example, from C _12-18 monoolefins having a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfofatty acids (ester sulfonates), e.g. B. the α-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids is suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under fatty acid glyce The mono-, di- and triesters as well as their mixtures are to be understood as Rinestern, as in the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or obtained in the transesterification of triglycerides with 0.3 to 2 mol of glycerol. Before pulled sulfated fatty acid glycerol esters are the sulfonation products of saturated fat acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, Ca. pric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

The alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ -Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials. From the washing, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ are - C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates of preferably. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C _12-18 -Fatty alcohols with 1 to 4 EO, are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Soaps are particularly suitable as further anionic surfactants. Are suitable saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural Fatty acids, e.g. B. coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants including the soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or Triethanolamine. The anionic surfactants are preferably in the form of their Sodium or potassium salts, especially in the form of the sodium salts.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol residue is linear or preferably in the 2-position May be methyl branched or may contain linear and methyl branched radicals in the mixture, as are usually present in oxoalko radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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

Another class of preferred nonionic surfactants, which are used either as allei some nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and pro poxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as described, for example, in Japanese Pa tentanmeldung JP 58/2 17598 are described or which preferably according to the in ternational patent application WO-A-90/13533 who produced the.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N- dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alka nolamides may be suitable. The amount of these nonionic surfactants is before  preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of it.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),

in the RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for water, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups . The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

in the R for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ¹ for a linear, branched or cyclic alkyl radical or an asylum radical with 2 to 8 carbon atoms and R ² for a linear, branched or cyclic alkyl radical or represents an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C _1-4 alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example, according to the teaching of international application WO-A-95/07331 by reaction with fatty acid remethyl esters in the presence of an alkoxide as a catalyst in the desired polyhy droxy fatty acid amides are transferred.

In the context of the present invention, washing and cleaning agents are detergent tablets Preferred moldings, the anionic (s) and nonionic (s) surfactant (s) ent hold, with application technology advantages from certain proportions, in where the individual classes of surfactants are used can result.

For example, detergent tablets are particularly preferred which the ratio of anionic surfactant (s) to nonionic surfactant (s) between 10: 1 and 1:10 is preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2. Before Also included are detergent tablets, the surfactant (s), preferably anionic (s) and / or nonionic (s) surfactant (s), in amounts of 5 to 40 wt .-% before preferably from 7.5 to 35% by weight, particularly preferably from 10 to 30% by weight, in particular special from 12.5 to 25 wt .-%, each based on the weight of the molded article.

From an application point of view, it can be advantageous if certain classes of surfactants in some phases of the detergent tablets or in their entirety body, d. H. in all phases, are not included. Another important embodiment The present invention therefore provides that at least one phase of the shaped body is free of non-ionic surfactants.

Conversely, the content of individual phases or the entire form can also be used body, d. H. all phases, certain surfactants have a positive effect. The The introduction of the alkyl polyglycosides described above has been found to be advantageous have shown, so that detergent tablets are preferred, in which mind least one phase of the shaped body contains alkyl polyglycosides.  

Similar to the nonionic surfactants can also be left out of anioni tensides from individual or all phases of detergent tablets result that are more suitable for certain areas of application. It is therefore in Also within the scope of the present invention are detergent tablets bar, in which at least one phase of the shaped body is free of anionic surfactants.

As already mentioned, the use of surfactants in cleaning detergents for machine dishwashing is preferably limited to the use of nonionic surfactants in small amounts. In the context of the present invention, detergent tablets preferably to be used as detergent tablets are characterized in that the base tablet total surfactant contents are below 5% by weight, preferably below 4% by weight, particularly preferably below 3% by weight and in particular below 2 wt .-%, each based on the weight of the basic molded body. Only weakly foaming nonionic surfactants are usually used as surfactants in automatic dishwashing detergents. Representatives from the groups of anionic, cationic or amphoteric surfactants, on the other hand, are of lesser importance. The detergent tablets according to the invention for machine dishwashing particularly preferably contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, especially primary alcohols, preferably having 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or preferably in the 2-position May be methyl-branched or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and preferred by average 2 to 8 EO per mole of alcohol. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical mean values which can be an integer or a fractional number for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (nar row range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In particular with detergent tablets or cleaning agents according to the invention Shaped articles for automatic dishwashing, it is preferred that the washing and cleaning Detergent tablets contain a nonionic surfactant that has a melting point above room temperature. Accordingly, the washing agents according to the invention contain or detergent tablets preferably a nonionic surfactant with a melt point above 20 ° C. Non-ionic surfactants to be used preferably Melting points above 25 ° C, particularly preferred nonionic Surfactants have melting points between 25 and 60 ° C, especially between 26.6 and 43.3 ° C.

Suitable nonionic surfactants, the melting or softening points in the above Temperature range are, for example, low-foaming nonionic ten side, which can be solid or highly viscous at room temperature. Will be at room temperature rature highly viscous nonionic surfactants used, it is preferred that these have a viscosity above half of 20 Pas, preferably above 35 Pas and in particular above 40 Pas exhibit. Also non-ionic surfactants, which have a waxy consistency at room temperature, are preferred.

Preferred nonionic surfactants to be used as solid at room temperature originate from the group pen of the alkoxylated nonionic surfactants, especially the ethoxylated primary alcohols and Mixtures of these surfactants with structurally more complex surfactants such as Po lyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

In a preferred embodiment of the present invention, this is nonionic Surfactants with a melting point above room temperature an ethoxylated nonionic surfactant,  that from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 C- Atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has gone.

A particularly preferred nonionic surfactant which is solid at room temperature is made from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol, of ethylene oxide won. Among these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

The nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule. Such PO units preferably make up to 25% by weight, in particular more preferably up to 20% by weight and in particular up to 15% by weight of the total moles mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally contain polyoxyethylene Have polyoxypropylene block copolymer units. The alcohol or alkylphenol part such nonionic surfactant molecules preferably make up more than 30% by weight, especially be preferably more than 50% by weight and in particular more than 70% by weight of the total molma such nonionic surfactants.

Other nonionic surfactants to be used with particular preference with melting points above Room temperature contain 40 to 70% of a polyoxypropy len / polyoxyethylene / polyoxypropylene block polymer blends, the 75 wt .-% of a vice returned block copolymers of polyoxyethylene and polyoxypropylene with 17 moles of ethyl lenoxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of Po lyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles Ethylene oxide and 99 moles of propylene oxide per mole of trimethylol propane.

Nonionic surfactants, which can be used with particular preference, are from for example under the name Poly Tergent® SLF-18 from Olin Chemicals true.  

Another preferred surfactant can be represented by the formula

R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ]

describe in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1 , 5 and y stands for a value of at least 15.

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x ≧ 2, each R ³ in the above formula can be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred for the radical R ³ . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula can be different if x ≧ 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, when x is 3, the R ³ group can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which can be joined together in any order, for example (EO ) (PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO ) (PO) (PO). The value 3 for x has been chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa.

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula can be used

R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²

simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particular preference is given to surfactants in which the radicals R ¹ and R ^{2 have} 9 to 14 carbon atoms, R ^{3 is} H and x assumes values from 6 to 15.

In order to facilitate the disintegration of highly compressed moldings, it is possible to disintegrate on aids, so-called tablet disintegrants, to incorporate them into the disintegration to shorten times. Under tablet disintegrants or disintegrators according to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical Technologie "(6th edition, 1987, pp. 182-184) understood auxiliary substances that are necessary for the rapid Disintegration of tablets in water or gastric juice and for the release of the pharmaceuticals in provide resorbable form.

These substances, which are also referred to as "explosives" due to their effect, ver increase their volume when water enters, and on the one hand increases their own volume (Swelling), on the other hand, a pressure can be generated via the release of gases which can break the tablet into smaller particles. Well-known disintegration aid medium are, for example, carbonate / citric acid systems, but also other organic ones Acids can be used. Swelling disintegration aids are, for example synthetic polymers such as polyvinyl pyrrolidone (PVP) or natural polymers or mo  differentiated natural substances such as cellulose and starch and their derivatives, alginates or casein Derivatives.

Preferred detergent tablets contain 0.5 to 10% by weight preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disinfectants Gration aids, each based on the weight of the molded body. Contains only the base molded disintegration aids, the information given relates only to the weight of the base molding.

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred laundry detergents and cleaning agents form such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular Contain 4 to 6 wt .-%. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, formally speaking, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably used not only as cellulose-based disintegrants, but rather in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free from cellulose derivatives is particularly preferably used as a cellulose-based disintegrant.

The cellulose used as disintegration aid is preferably not finely divided form, but before mixing into the premixes to be pressed converted into a coarser form, for example granulated or compacted. Washing and Detergent tablets, the disintegrant in granular or optionally cogranu Contained form, are in the German patent applications DE 197 09 991 (Ste fan Herzog) and DE 197 10 254 (Henkel) and the international patent application WO 98/40463 (Henkel). These writings are also more detailed information on the Her position of granulated, compacted or cogranulated cellulose disintegrants men. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 µm and in particular to at least 90% by weight between 400 and 1200 µm. The above and in the writings cited described coarser disintegration aids on cellulose In the context of the present invention, bases are preferred as disintegration aids used and commercially, for example under the name Arbocel® TF-30-HG by available from Rettenmaier.

As a further disintegrant based on cellulose or as part of this compo microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions that only attack the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses and dissolve completely, but leave the crystalline areas (approx. 70%) undamaged. A subsequent disaggregation of the microfine cellulo produced by the hydrolysis sen supplies the microcrystalline celluloses, which have primary particle sizes of approx. 5 µm sen and, for example, to granules with an average particle size of 200 microns are pactable.

Preferred detergent and cleaning agent form in the context of the present invention Bodies additionally contain a disintegration aid, preferably a disintegration agent cellulose-based auxiliary agents, preferably in granular, cogranulated or compact tated form, in amounts of 0.5 to 10 wt .-%, preferably from 3 to 7 wt .-% and in particular from 4 to 6% by weight, in each case based on the weight of the shaped body.  

The detergent tablets according to the invention can moreover both in the base molding [part a)] and in part b) or in the filling of the cavity contain a gas-developing shower system. The gas-developing shower system can consist of a single substance that releases a gas when in contact with water. Under These compounds should be mentioned in particular the magnesium peroxide, which is in contact releases oxygen with water. The gas-releasing bubble system usually exists however, in turn, from at least two constituents, which together form gas react. While here a variety of systems is conceivable and executable, the at release nitrogen, oxygen or hydrogen, for example, that will be invented bubble system used according to the detergent tablets according to the invention read probably based on economic as well as ecological considerations sen. Preferred shower systems consist of alkali metal carbonate and / or hydrogen carbonate and an acidifying agent that is suitable from the alkali Release tall salts in aqueous solution carbon dioxide.

In the case of the alkali metal carbonates or bicarbonates, the sodium and potassium are salts are clearly preferred over the other salts for cost reasons. Self ver the pure alkali metal carbonates or -hydrogen carbonates are used; rather, mixtures of different car bonates and hydrogen carbonates may be preferred for washing technology reasons.

In preferred detergent tablets, 2 to 20 are used as the shower system % By weight, preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or bicarbonate and 1 to 15, preferably 2 to 12 and in particular special 3 to 10 wt .-% of an acidifying agent, based in each case on the total Shaped body, used.

As an acidifying agent that releases carbon dioxide from the alkali salts in aqueous solution are, for example, boric acid and alkali metal bisulfates, alkali metal dihy drug phosphates and other inorganic salts can be used. However, are preferred organic acidifiers are used, with citric acid being particularly preferred  added acidifier. However, the other fixed ones can also be used in particular Mono-, oligo- and polycarboxylic acids. Wine is preferred from this group acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid like polyacrylic acid. Organic sulfonic acids such as amidosulfonic acid are also a settable. Commercially available and as an acidifying agent in the context of the present Sokalan® DCS (trademark of BASF) is also preferably used according to the invention Mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adi pinic acid (max. 33% by weight).

In the context of the present invention, detergents and cleaning agents are preferred molded articles in which a substance from the group is used as an acidifying agent in the shower system the organic di-, tri- and oligocarboxylic acids or mixtures of these are used become.

In addition to the ingredients mentioned builder, surfactant and disintegration aid, The detergent tablets according to the invention are further used in detergents. and cleaning agents usual ingredients from the group of bleaching agents, bleaching agents gates, dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, Anti-redeposition agents, graying inhibitors, color transfer inhibitors and corro ion inhibitors included. In these as well as in the above-mentioned Aktivsub punching it is of course possible that they are both in the base molding [part a)], as well as in part b) and in an optionally available filling of the hollow volume are present, but it is also possible that only certain parts of the shaped body certain Contain active substances, see below.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other usable bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -supplying peracidic salts or peracids, such as per benzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Cleaning agents according to the invention can also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaches are the diacyl peroxides, such as. B. dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimoxyhexanoic acid (peroxyiminoperacid acid) PAP)], o-carboxybenzamido peroxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacassyl acid, diperoxy acid, diperoxy acid -1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

As a bleach in the detergent tablets according to the invention for the machine Dishwashing can also use chlorine or bromine-releasing substances. Suitable chlorine or bromine releasing materials include, for example heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, Tribromo isocyanuric acid, dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

The bleaches are usually used in machine dishwashing detergents in amounts of 1 up to 30% by weight, preferably from 2.5 to 20% by weight and in particular from 5 to 15% by weight, each based on the agent used. In the context of the present invention the proportions mentioned on the weight of the base molding [part a)], so that Detergent tablets are preferred in which the base tablet Bleaching agents from the group of oxygen or halogen bleaching agents, in particular the Chlorine bleach, with particular preference for sodium perborate and Sodium percarbonate, in amounts of 2 to 25% by weight, preferably 5 to 20% by weight and in particular from 10 to 15 wt .-%, each based on the weight of the Basic molding, contains.  

Bleach activators that support the action of the bleach can also be be part of the base molding. Known bleach activators are compounds that contain one or more N- or O-acyl groups, such as substances from the class of Anhydrides, the esters, the imides and the acylated imidazoles or oximes. examples are Tetraacetylethylenediamine TAED, Tetraacetylmethylenediamine TAMD and Tetraacetylhe xylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexa hydro-1,3,5-triazine DADHT and isatoic anhydride ISA.

As bleach activators can be compounds that are under perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms and / or optionally substituted perbenzoic acid are used become. Substances which contain O- and / or N-acyl groups of the C- Bear atomic number and / or optionally substituted benzoyl groups. Are preferred multiple acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADH 99999 00070 552 001000280000000200012000285919988800040 0002019941266 00004 99880T), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), Carboxylic anhydrides, especially phthalic anhydride, acylated polyvalent Alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), and those from the German Patent applications DE 196 16 693 and DE 196 16 767 known enol esters as well acetylated sorbitol and mannitol or their mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetyl glucose (PAG), pentaacetyl fructose, Tetraacetylxylose and Octaacetyllactose as well as acetylated, optionally N-alkylated Glucamine and gluconolactone, and / or N-acylated lactams, for example N- Benzoylcaprolactam. Hydrophilically substituted acylacetals and acyllactams also preferably used. Combinations of conventional bleach activators can be used. The bleach activators are made in machine Dishwashing agents usually in amounts of 0.1 to 20 wt .-%, preferably 0.25 up to 15% by weight and in particular from 1 to 10% by weight, in each case based on the composition, used. In the context of the present invention, the aforementioned relate Quantities based on the weight of the base molding.  

In addition to the conventional bleach activators or in their place, too so-called bleaching catalysts are incorporated into the rinse aid particles. With these Fabrics are bleach-enhancing transition metal salts or transition metals tall complexes such as Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N- containing tripod ligands and Co, Fe, Cu and Ru amine complexes are bleached catalysts can be used.

Bleach activators from the group of multi-acylated alkylene are preferred diamines, especially tetraacetylethylenediamine (TAED), N-acylimides, especially N- Nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile- Methyl sulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0.1% by weight up to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight on the entire medium.

Bleach-enhancing transition metal complexes, especially with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably cobalt (ammin) - Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate in usual amounts, preferably in an amount up to 5 wt .-%, in particular from 0.0025 wt .-% to 1 wt .-% and be particularly preferably from 0.01% by weight to 0.25% by weight, in each case based on the total Means used. But in special cases, more bleach activator can be used the.

It is also preferred that the base molding and / or part b) and / or the filling of the cavity contain bleach activators. Preferred washing or cleaning agents Shaped bodies are characterized in that the basic shaped body consists of bleach activators the groups of polyacylated alkylenediamines, especially tetraacetylethylene diamine (TAED), the N-acylimide, especially N-nonanoylsuccinimide (NOSI), the acy lated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n-  or iso-NOBS) and n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), in men gen from 0.25 to 15 wt .-%, preferably from 0.5 to 10 wt .-% and in particular from 1 up to 5 wt .-%, based in each case on the weight of the base molding.

The detergent tablets according to the invention can in particular in the basic form contain corrosion inhibitors to protect the dishes or the machine, especially silver protection agents in the field of automatic dishwashing have special meaning. The known substances of the prior art can be used Technology. In general, silver protection agents can be selected from the group of Triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotria zole and the transition metal salts or complexes are used. Especially before benzotriazole and / or alkylaminotriazole are to be used. One finds in cleaners In addition, formulations often contain active chlorine, which corrode the Can significantly reduce the silver surface. Chlorine-free cleaners are special Oxygen and nitrogen-containing organic redox-active compounds, such as two and trihydric phenols, e.g. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid right, phloroglucin, pyrogallol or derivatives of these classes of compounds. Also salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts, the are selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the Cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulphide fats. Zinc compounds can also be used to prevent corrosion on the wash ware be set.

In detergents and cleaning agents preferred within the scope of the present invention The basic molded body contains silver protection agents from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes, particularly preferably benzotriazole and / or Alkylaminotriazole, in amounts of 0.01 to 5% by weight, preferably 0.05 to 4% by weight % and in particular from 0.5 to 3 wt .-%, each based on the weight of the base molded body.  

Of course, part b) and / or the filling of the cavity can also be silver contain protective agents, the base molding either also silver protective agents contains or is free of such compounds.

In addition to the ingredients mentioned above, there are other substance classes Incorporation in detergents and cleaning agents. So are detergents and cleaning agents Shaped bodies preferred, in which the base shaped body furthermore one or more substances from the groups of enzymes, corrosion inhibitors, deposit inhibitors, cobuilders, color and / or fragrances in total amounts from 6 to 30% by weight, preferably from 7.5 to 25 % By weight and in particular from 10 to 20% by weight, in each case based on the weight of the Basic molding, contains.

Enzymes in the base tablets come in particular from the classes of Hydrolases such as proteases, esterases, lipases or lipolytic enzymes, Amylases, glycosyl hydrolases and mixtures of the enzymes mentioned in question. All these Hydrolases ask about removing stains such as protein, fat or starch stains. Oxidoreductases can also be used for bleaching. Bacterial strains or fungi such as Bacillus subtilis, Ba cillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants fe. Proteases of the subtilisin type and in particular proteases which are preferred are obtained from Bacillus lentus. There are enzyme mixtures, at act from protease and amylase or protease and lipase or lipolytic the enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytic enzymes, but especially protease and / or lipase-containing mixtures or mixtures with lipolytically active enzyme men of particular interest. Examples of such lipolytic enzymes are the well-known cutinases. Peroxidases or oxidases have also been found in some cases proven suitable. Suitable amylases include in particular alpha-amylases, iso- Amylases, pullulanases and pectinases.

The enzymes can be adsorbed on carriers or embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures  or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5% by weight. Reini preferred in the context of the present invention shaped tablets are characterized in that the base tablet protease and / or contains amylase.

Characterized in that the detergent tablets according to the invention the or which can contain the enzyme (s) in two or even three fundamentally different areas molded articles with a very precisely defined enzyme release and effect provide. The table below gives an overview of possible enzyme distributions lungs in detergent tablets according to the invention:  

Dyes and fragrances can be used in the dishwasher detergents according to the invention both in the base molding and in part b) and / or in the optionally contained fill  tion of the cavity can be added to the aesthetic impression of the resulting Improve products and give consumers a visual and senso in addition to performance to provide a "typical and distinctive" product. As perfume oils or fragrances, individual fragrance compounds, e.g. B. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type become. Fragrance compounds of the ester type are e.g. B. benzyl acetate, phenoxyethy lisobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allylcyclo hexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example as benzyl ethyl ether, to the aldehydes z. B. the linear alkanals with 8-18 C atoms, Citral, Citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lili al and bourgeonal, to the ketones z. B. the Jonone, α-isomethylionon and methylcedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethylal alcohol and terpineol, the hydrocarbons mainly include terpenes such as Lime and pinene. However, mixtures of different fragrances are preferred used, which together create an appealing fragrance. Such perfume oils can NEN also contain natural fragrance mixtures, such as those from plant sources are common; e.g. B. pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Exactly if appropriate, muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and rennet danum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be used directly in the washing and cleaning agents according to the invention Molded body can be incorporated, but it can also be advantageous to the fragrances Apply carriers that increase and adhere the perfume to the laundry a slower fragrance release ensures a long-lasting fragrance of the textiles. As such Carrier materials have proven themselves, for example, cyclodextrins, the Cyclodex trin-perfume complexes can also be coated with other auxiliaries nen.

To improve the aesthetic impression of the agents according to the invention, it can (or Parts of it) can be colored with suitable dyes. Preferred dyes whose  Selection presents no difficulty for the expert, has a high storage stability and insensitivity to the other ingredients of the agent and to Light as well as no pronounced substantivity towards those treated with the means the substrates such as textiles, glass, ceramics or plastic tableware so as not to start them to dye.

The ingredients described above can - as already mentioned - in the basic form be included, but of course also in part b) and / or the filling of the Cavity are incorporated. Preferred in the context of the present invention Detergent tablets are characterized in that the core shape body [part b)] at least one active ingredient from the group of enzymes, surfactants, should release polymers, disintegration aids, bleaching agents, bleach activators, bleaching kata contains analyzers, silver protection agents and mixtures thereof.

By dividing the detergent tablets according to the invention into Basic molded body [part a)] with conical cavity and "core molded body" [part b)] as well optional a "cavity filling" [part c)] ingredients can be separated from each other which either leads to a storage stability-improving separation of incompatible content substances or for the controlled release of certain active substances can. In preferred laundry detergent or cleaning product tablets according to the invention which the three different areas use in particular to combine the active ingredients bleach / bleach activator, bleach / enzyme, bleach / silver protectant, Bleach / perfume, bleach / optical brightener, bleach / dye, bleach medium / surfactant, bleach activator / enzyme, bleach activator / silver protection agent, bleach activa tor / fragrance, bleach activator / optical brightener, bleach activator / dye, bleach acti vator / surfactant or nonionic surfactant / anionic surfactant to separate Achieve performance benefits. In addition, controlled release certain ingredients from the individual regions or by targeted variation of the Solubility of individual regions performance benefits can be achieved.  

In preferred detergent tablets, the base tablet contains or the core molding inserted into the base molding or the cavity filling Bleach, while at least one other part contains bleach activators.

Further preferred detergent tablets are characterized in that that the base molding or the core molding inserted into the base molding or the cavity fill contains bleach, while at least another portion contains enzymes contains.

Also a separation of bleach and corrosion inhibitors or silver protection agents can be achieved. Detergent tablets in which the basic tablet or contains the core molding inserted into the base molding, bleach rend containing at least one other part of anti-corrosion agents are also preferred. Last but not least, detergent tablets are preferred, in which the Base molding or the core molding bleach inserted into the base molding contains, while at least another part contains surfactants, preferably non-ionic surfactants, with particular preference for alkoxylated alcohols having 10 to 24 carbon atoms and 1 to 5 alkylene oxide units.

Not only can a complete separation of the ingredients be beneficial, also through Varying amounts of individual ingredients in the different shaped body areas beneficial effects can be achieved. Detergent tablets, the are characterized in that the base molding or in the base molding inserted core moldings contain the same active ingredient in different amounts, are preferred according to the invention. As examples of ingredients where the breakdown advantages in different regions are disintegration aids, Dyes and fragrances, optical brighteners, polymers, silver preservatives, surfactants and enzymes to call me. The term "different amounts" characterizes the content of individual shaped body area on the substance in question, based on the shaped body rich is therefore a% by weight statement that does not refer to the absolute amounts of the content fabric related.  

Since part b) does not completely fill the cavity in part a) according to the invention, it is possible to bring more active substance into the remaining cavity. This can also - how already described above - can be used for further separation of active substances.

All of the ingredients described above can be contained in all different areas of the moldings according to the invention. While part a) of the shaped articles according to the invention can be produced by pressing, tablet processing being an important method in particular, part b) (and also an optional cavity filling which is referred to as part c) can be produced in different ways. Another object of the present invention is also a method for producing multiphase detergent tablets, which comprises the steps

• a) compressing particulate premixes to give moldings which at least have a conically shaped cavity,
• b) Production of moldings which at least partially into the cavity are available
• c) inserting the process end products of process step b) into the coni cal cavity of the end products of process step a),
• d) optional aftertreatment of the shaped bodies

is marked.

Regarding the ingredients of the individual particulate premixes or together Settlements that result in the different areas of the molded body apply analogously Executed above for the moldings according to the invention.

Optionally, a further process step can be carried out before or after step c), by introducing further active substance into the part of the cavity, part b) not fills out. Here, this part (referred to above and below as "cavity") can be full are constantly filled, only partially filled or remain empty.

It has proven to be advantageous if this is pressed into basic shaped bodies in step a) Premixed certain physical criteria are sufficient. Preferred methods are at  for example characterized in that the particulate premixes in step a) a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular which have at least 700 g / l.

The particle size of the premix pressed in step a) is also preferably sufficient agreed criteria: processes in which the particulate premixes in step a) Particle sizes between 100 and 2000 μm, preferably between 200 and 1800 μm, particularly preferably between 400 and 1600 μm and in particular between 600 and 1400 microns, are preferred according to the invention. A further restricted particle size ß in the premixes to be pressed can be used to obtain advantageous molded bodies properties can be discontinued. In preferred variants for the Ver The particulate premixes pressed in step a) have a particle size distribution in which less than 10% by weight, preferably less than 7.5% by weight % and in particular less than 5% by weight of the particles larger than 1600 μm or smaller than 200 µm. Narrower particle size distributions are further preferred here. Be Particularly advantageous process variants are characterized in that in step a) pressed particulate premixes have a particle size distribution, at of more than 30% by weight, preferably more than 40% by weight and in particular more than 50% % By weight of the particles have a particle size between 600 and 1000 μm.

When carrying out process step a), the process according to the invention is not limited to the fact that only a particulate premix to form a shaped body is pressed. Rather, method step a) can also be expanded to the extent that one produces multilayered shaped bodies in a manner known per se by two or preparing several premixes which are pressed together. Here is the first pre-filled slightly pre-compressed to a smooth and parallel to the shape to get the bottom of the body, and after filling the second bottle mixes to the finished molded body. With three- or multi-layer molded articles After each premix addition, a further pre-compression takes place before after addition of the last premix, the molded body is finally pressed. Preferably the first one described conical cavity in the base molding a trough, so that preferred Embodiments of the first method according to the invention characterized  are that in step a) multilayered molded body which has a conically shaped trough have, are produced in a manner known per se by several different particulate premixes are pressed together.

The molded articles according to the invention are first produced in step a) by dry mixing of the ingredients, which may be partially or fully pre-granulated NEN, and then bringing information, in particular pressing to tablets, whereby conventional methods can be used. To manufacture the Invention According to the shaped body, the premix in a so-called matrix between two Stamping compressed to a solid compressed. This process, briefly below called tableting is divided into four sections: dosage, compression (elastic deformation), plastic deformation and ejection.

First, the premix is introduced into the die, the filling quantity and thus the weight and shape of the resulting molded body through the position of the lower one Stamp and the shape of the press tool can be determined. The constant dose tion even at high molding throughputs is preferably a volumetric Dosage of the premix reached. In the further course of tabletting, the Upper stamp the premix and continues to lower towards the lower stamp. At this compression, the particles of the premix are pressed closer together where at the void volume within the filling between the punches continuously decreases. From a certain position of the upper stamp (and thus from a certain pressure on the premix) begins the plastic deformation, in which the particles flow together and the molded body is formed. Depending on the physi properties of the premix, some of the premix particles are also broken down presses and the premix is sintered at even higher pressures. At increasing press speed, i.e. high throughput, the phase of elasti 's deformation is continuously shortened, so that the resulting molded body more or may have smaller cavities. In the last step of tableting the Finished molded articles are pressed out of the die by the lower punch and through subsequent transport devices transported away. At this point, it's just that Weight of the molded body finally determined, because the compacts due to physical  Processes (stretching, crystallographic effects, cooling etc.) their shape and size can still change.

Tableting takes place in commercially available tablet presses, which are basically or double stamps can be equipped. In the latter case, not only the waiter stamp used to build up pressure, also the lower stamp moves during the Pressing process towards the upper punch, while the upper punch presses down. For Small production quantities are preferably used with eccentric tablet presses which the one or more stamps are attached to an eccentric, which in turn on one Axis is mounted with a certain rotational speed. The movement of this Press ram is comparable to the way a conventional four-stroke engine works. The Ver pressing can be done with one upper and one lower stamp, but several can also be used re stamp on an eccentric disk, the number of die holes gen is expanded accordingly. The throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs, rotary tablet presses are selected, in which on a so-called called matrix table a larger number of matrices is arranged in a circle. The The number of matrices varies between 6 and 55, depending on the model, with larger matrices also are commercially available. Each die on the die table is a top and bottom stamp assigned, again the pressing pressure active only by the upper or lower stamp, but can also be built up by both stamps. The matrix table and the Stamps move around a common vertical axis, the stamp with the help of rail-like cam tracks during the circulation in the positions for Be filling, compression, plastic deformation and discharge. On the stel len, where a particularly serious raising or lowering the stamp is necessary (filling, compacting, ejecting), these cam tracks are replaced by additional che low-pressure pieces, Nierderzugschienen and lifting tracks supported. The filling The matrix is developed via a rigidly arranged feed device, the so-called Filling shoe, which is connected to a reservoir for the premix. The press pressure on the premix is individual via the press paths for upper and lower punches  adjustable, the pressure build-up by rolling the stamp shaft heads past ver adjustable pressure rollers happens.

Rotary presses can also use two filling shoes to increase throughput hen be, with only one semicircle to manufacture a tablet that must. Several fillers are used to produce two- and multi-layer moldings shoes arranged one behind the other without the slightly pressed first layer in front of the further filling is ejected. Appropriate litigation leads to this se also coated and dot tablets can be produced, which have an onion-shell-like structure have, whereby in the case of the point tablets the top of the core or the core layers is not covered and therefore remains visible. Rotary tablet presses are also included Single or multiple tools can be equipped, so that, for example, an outer circle with 50 and an inner circle with 35 holes simultaneously used for pressing the. The throughputs of modern rotary tablet presses are over a million forms body per hour.

When tableting with rotary presses, it has proven to be advantageous to carry out tableting with the smallest possible fluctuations in the weight of the tablet. The fluctuations in hardness of the tablet can also be reduced in this way. Small fluctuations 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 the filler paddle speed to the speed of the rotor
• - Filling shoe with constant powder height
• - Decoupling of filling shoe and powder feed

To reduce the build-up of stamps, all of them can be used in technology known non-stick coatings. Plastic coatings are particularly advantageous, Plastic inlays or plastic stamps. Rotating stamps also have an advantage proven, whereby the upper and lower stamps are rotatable if possible  should. In the case of rotating stamps, a plastic insert is generally not required become. The stamp surfaces should be electropolished here.

It was also shown that long pressing times are advantageous. These can be printed rails, several pressure rollers or low rotor speeds. Since the Fluctuations in the hardness of the tablet are caused by the fluctuations in the pressing forces systems should be used that limit the pressing force. Here elasti cal stamps, pneumatic compensators or resilient elements in the force path be set. The pressure roller can also be designed to be resilient.

Methods according to the invention, in which the pressing in step a) is carried out at pressures of from 0.01 to 50 kNcm ^-2 , preferably from 0.1 to 40 kNcm ^-2 and in particular from 1 to 25 kNcm ^-2 , are particularly preferred.

Tableting machines suitable for the purposes of the present invention are, for example available from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMA Verpackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms. Other providers are, for example Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Li verpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy N.V., Halle (BE / LU) and Me diopharm Kamnik (SI). The hydraulic double is particularly suitable HPF 630 printing press from LAEIS, D. Tableting tools are, for example, from the company Adams Tablettierwerkzeuge, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Söhne GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Werkzeugbau, Tamm available. Other providers are e.g. B. the Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).

The moldings can - as already mentioned above - in a predetermined space shape and predetermined size are manufactured. Practically everyone comes as a spatial form reasonably manageable configurations, for example the training as  Blackboard, the shape of bars or bars, cubes, cuboids and corresponding room elements flat side surfaces and in particular cylindrical configurations with a circle shaped or oval cross section. This last embodiment covers the darbie form from tablets to compact cylinder pieces with a ratio of Height to diameter above 1.

Another preferred shaped body that can be produced has a plate or panel-like structure with alternating thick long and thin short segments, so that individual segments of this "bar" at the predetermined breaking points, the short thin Display segments, can be canceled and entered into the machine. This Principle of the "bar-shaped" shaped detergent can also in other geometri forms, for example vertical triangles that only on one of their Sides are connected alongside one another, can be realized.

But it is also possible that the various components do not become one Tablet are pressed, but that molded bodies are obtained that have several layers ten, i.e. at least two layers. It is also possible that these ver different layers have different dissolving speeds. From this you can advantageous application properties of the molded articles result. If at for example, components are contained in the moldings, which are mutually nega tiv influence, so it is possible to find a component in the more rapidly soluble layer to integrate and incorporate the other component in a slower soluble layer ten, so that the first component has already reacted when the second goes into solution. The layer structure of the moldings can be stacked, with one solder process of the inner layer (s) at the edges of the molded body already takes place, if the outer layers are not yet completely detached, it can also be one complete coating of the inner layer (s) by the outer layer (s) Layer (s) can be reached, which prevents the premature dissolution of Be components of the inner layer (s). Such methods according to the invention, in which in step a) multilayered moldings are produced in a manner known per se, by pressing several different particulate premixes together are preferred embodiments of the present invention.  

As also described above, incompatible ingredients can be identified by the Incor Poration in the different parts a), b) or c) of the moldings according to the invention separate from each other. Such a separation is of course also possible if that part a) is made up of several separate sub-areas. So methods are preferred which are characterized in that in step a) two layers Ge molded body can be produced by two different particulate Vorgemi be pressed together, one of which contains one or more bleaches and the like another contains one or more enzymes and / or bleach activators.

In a further preferred embodiment of the invention, a molded body consists of at least three layers, ie two outer and at least one inner layer, wherein at least one of the inner layers contains a peroxy bleach, while in the case of the stacked shaped body, the two outer layers and in the case of the shell-shaped one Shaped bodies, however, the outermost layers are free of peroxy bleach. Farther it is also possible to use peroxy bleach and any bleach activators present and / or to separate enzymes spatially from one another in a shaped body. Such more Layered moldings have the advantage that they do not have only one induction chamber or via a metering device which is added to the wash liquor can be; rather, it is also possible in such cases to direct the molded body into the machine without causing stains Bleach and the like would be feared.

Similar effects can also be achieved by coating individual components of the detergent and cleaning agent composition to be pressed, or all of them Reach shaped body. For this purpose, the bodies to be coated can be coated with, for example aqueous solutions or emulsions are sprayed, or via the process of Get a coating on the melt coating.

After pressing, the detergent tablets have a high level of stability. The breaking strength of cylindrical shaped bodies can be determined via the measured variable of the diametrical breaking load. This can be determined according to

Here σ stands for diametral fracture stress (DFS) in Pa, P is the force in N which leads to the pressure exerted on the molded body, which is the Breakage of the shaped body causes, D is the shaped body diameter in meters and t is the Height of the molded body.

In step b), moldings are produced which are at least partially conical Have the molded cavity of the molded body a) inserted. These can - as outlined above guided - close the cavity and form a completely enclosed cavity. But you can also close a cavity open on both sides only on one side, so that a cavity open on one side remains, which can optionally be filled with active substance can.

The molding in step b) can be produced by different methods gene, for example by the tabletting already described for step a). Erfin Process according to the invention, in which the shaped bodies in step b) are produced by tableting are preferred. Analog to the information for process step a) read sen in the event that part b) is also produced by tableting, also for the Particulate composition (s) in process step b) preferred physi Specify parameters: procedures in which the particulate composition (s) tongue (s) in step b) a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l has / have and processes in which the particulate composition (s) in step b) particle sizes between 100 and 2000 microns, preferably between 200 and 1800 microns, particularly preferably between 400 and 1600 microns and in particular between 600 and 1400 microns, has / have preferred embodiments of the present invention.

As an alternative to tableting, other manufacturing processes are also suitable for part b). Preferred processes are characterized in that the shaped bodies in step b) be produced by casting, extrusion, extrusion or sintering.  

Depending on the ingredients in part b) of the form produced according to the invention body to be incorporated, there are different manufacturing methods of part b). For example, the pressure load that occurs during tableting can be avoided to protect ingredients, melts can be produced in solidify suitable shapes. In addition to lowering the temperature, such casting processes melting also use other hardening mechanisms, for example time delayed hydration, chemical reaction, radiation curing, etc.. Completely analogously, masses can also be produced which are shaped can and then solidify or harden. Unlike liquids such masses are dimensionally stable even in the processable state, d. H. they keep one once given shape, and no shapes are needed that the body "Force" the outer shape until it hardens. While such masses with low ver shaping forces can be brought into the desired shape and the term strand pressing "is misleading because of the low pressures during processing Extrude particulate or plastic masses even at higher pressures. The ex trusion is another preferred manufacturing process for part b). Last but not least it is also possible to fill particle piles of suitable composition in molds and over temperature increases or by radiation, preferably with microwaves, a To bring about sintering and formation of shaped bodies.

The composition of the moldings produced in step b) can be within wide limits can be varied. In principle, all of the ingredients mentioned above can also or can only be incorporated in part b). Used as the preferred manufacturing process for part b) Casting process chosen, so can further auxiliaries and active ingredients from the groups of Waxes, paraffins, polyalkylene glycols, emulsifiers and stabilizers as "matrix" for the ingredients of part b) are selected. These substances are described below ben, since the melt suspensions or emulsions from which part b) can be formed, are also suitable as a further active substance for the cavity filling.

Depending on the shape of the pressed part a) and the at least partially in the conical cavity part b) is an optional filling step for the cavity before or after process step c). Seals part b) in the conical cavity  Part a) completely and thus forms moldings preferred according to the invention, in which the remaining cavity is completely enclosed by parts a) and b), so can the active substance optionally to be introduced into the cavity is only introduced before step c) because the cavity is closed after inserting part b).

However, it is also possible according to the invention to first insert part b) into the pressed part gene and then a remaining cavity at least partially with further active fill up substance, i.e. the optional filling of the cavity with further active substance punch after step c). This procedure can be used, for example Realize shaped bodies [parts a)] that have a conical cavity in the form of a continuous hole. Such holes can be ver one-sided by suitable parts b) close, whereby in this process step c) part a) quasi a trough shape body "a) + b)" is formed. The trough formed in this way then represents the ver permanent cavity, which can optionally be filled with further active substance. If desired, a further process step can follow process step c) c) connect so that ultimately a basic molded body with a continuous conical hole is closed by two parts b), the inside because of the conical shape of the Cavity remain a cavity, which is before the final occlusion with active substance can be filled.

As already mentioned, the free space due to the special shape of the cavity remains between the basic molded body a) and the "core molded body" b), optionally with another Active substance to be filled. This additional active substance can make up the remaining void Fill the space completely, but it is also possible that part of the cavity is unfilled remains. In the context of the present invention, it is preferred that at least 50% preferably at least 60% and in particular at least 70% of the cavity volume additional active substance to be filled. Here are detergents or cleaning agents body preferred, in which the volume ratio of the unfilled cavity to that in active substance contained in this space 1: 1 to 100: 1, preferably 1, 1: 1 to 50: 1, be is particularly preferably 1.2: 1 to 25: 1 and in particular 1.3: 1 to 10: 1. In this term Technology means a volume ratio of 1: 1 that the cavity is completely filled is.  

Depending on the size of the hollow remaining between parts a) and b) space, the density of the molded body, the density of the active substance in the cavity and the Degree of filling of the cavity can be the proportion of the other active substance in the cavity make up different proportions of the overall molded body. Here are washing or cleaning preferred moldings, in which the weight ratio of moldings to the active substance contained in the cavity 1: 1 to 100: 1, preferably 2: 1 to 80: 1, be is particularly preferably 3: 1 to 50: 1 and in particular 4: 1 to 30: 1. In the above defined weight ratio is the ratio of the mass of the not with further shaped substance filled with active substance {mass of the "basic shaped body" [part a)] plus mass of part b)} to the mass of the cavity filling.

By suitable packaging of the shaped body and active substance, the time, to which the substance contained in the cavity is released can be predetermined. At for example, the active substance can have direct contact with the application liquor (ie not completely enclosed by parts a) and b)) and almost instantly soluble be so that the active substance contained in the cavity right at the beginning of the washing or Cleaning course is dosed into the washing or cleaning liquor. Alternatively, you can the substance is enclosed by parts a) and b) or is so poorly soluble, that only the molded body is dissolved and the active substance contained in the cavity is released by this or only after a delay.

Depending on this release mechanism, moldings can be made, for example realize in which the active substance contained in the cavity in the cleaning liquor is dissolved before the constituents of the shaped body are dissolved or after this happened. On the one hand, detergent tablets are preferred which are characterized in that the active substance contained in the cavity quickly ler solves than the base molding [part a)].

But also detergent tablets, in which the ent in the cavity holding active substance dissolves more slowly than the basic tablet [part a)], are preferred Embodiments of the present invention.  

The optional filling of the cavity volume preferably contains at least At least one active substance, but can also be a mixture of several active substances hold. Just like part b) are active substances for incorporation into the cavity Filling active substances suitable, which contain ingredients from part a) undesired In enter into interactions. In particular, preferred ingredients for cavity filling are those that are caused by the tabletting of part a) or the manufacturing process of part b) ne would be influenced negatively. Such active substances are, for example, surfactants, bleaching agents tel, bleach activators, bleach catalysts, enzymes, corrosion inhibitors and / or Sil Protective agents, perfume, alkali carriers or acidifying agents. The individual substances are described in detail above. Procedures where the cavity is before or after Step c) with at least one active substance from the group of bleaching agents, bleaching agents vators, enzymes, pH adjusting agents, fragrances, perfume carriers, fluorescent agents, dyes, Foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying ungsinhibitors, color transfer inhibitors and corrosion inhibitors are filled preferred embodiments of the present invention.

The cavity filling can take on a wide variety of forms, for example partially Chen-like (powdery or granular), gel-like, liquid or plastic. The cavity Filling does not have to consist entirely of active substance, for example also use active substances on carrier materials or in carrier matrices. Not too lastly, there are also thin to highly viscous or pasty solutions, suspensions or Emulsions of active substances in solvents or solvent mixtures as Cavity filling can be used.

It is imminent for filling the remaining cavity with further active substance moves that the cavity filling is introduced into the cavity in a flowable form. At Solid active substances or preparations can introduce the particles into the cavity and subsequently by suitable measures, for example fixation with a coating layer to be attached. In cases where the cavity is closed to the outside, the attachment can of course also be dispensed with. Analog execution conditions apply to flowable cavity fillings in liquid, gel-like, pasty or plati form, which is caused by hardening, for example solidification of melts, evaporation of  Solvents, crystallization, polymerization, pseudo-plastic property changes fixed in the cavity by changing shear forces or by special binders can, if this is necessary or desired.

The void fill may contain particulate solids. These particles can with all processes of the prior art can be produced, for example by spraying drying, granulation, encapsulation, agglomeration, granulation, pelleting, extrusi on, roller compaction, etc. If desired, the particles can be inco ration of binders or by forming a coating over the particles attached to the cavity.

If different particle mixtures are used as cavity filling, then the different particulate cavity fillings have different particle sizes have, for example, in such a way that the first cavity filling an average particle size has 5%, preferably 10%, particularly preferably 15% and in particular 20% is above the average particle size of the second filling. The term "medium particle size "or" average particle size "refers to the mesh size an imagi granular sieve through which 50% by weight of the particles would fall through. This value can be by sieve analysis with several sieves of different mesh sizes (for example 5, 6 or 7 sieves).

The bulk density of the different particulate cavity fillings can also be un be different. Here, too, it is preferred if the first cavity filling is a bulk has weight that 5%, preferably 10%, particularly preferably 15% and in particular 20% above the bulk density of the second filling.

Particularly preferred particulate compositions (cavity fillings) to be introduced into the cavity (s) of the moldings according to the invention are those which contain surfactants, it being preferred to provide these surfactants for automatic dishwashing agents in a solution-delayed form in order to release the surfactants from the cavity filling can only be reached in rinse aid. Rinse aid particles such as are described in the older German patent application DE 199 14 364.1 (Henkel KGaA) have proven particularly useful for this purpose. Such particles which are particularly preferably introduced into the cavity consist of 0 to 90% by weight of one or more carrier materials, 5 to 50% by weight of one or more coating substances with a melting point above 30 ° C., 5 to 50% by weight one or more active substances and 0 to 10% by weight of further active substances and auxiliaries, so that processes are preferred in which the cavity is filled with particles which consist of

• a) 0 to 90% by weight of one or more carrier materials,
• b) 5 to 50% by weight of one or more coating substances with a melting point above 30 ° C,
• c) 5 to 50 wt .-% of one or more active substances and
• d) 0 to 10% by weight of further active ingredients and auxiliaries

consist.

Reference is expressly made to the disclosure of the aforementioned document men. Nevertheless, the most important ingredients of these are preferred in the cavity bringable "rinse aid particles" described below. Coming as carriers a) all substances that are solid at room temperature are possible. Usually you will be there Select fabrics that have an additional effect in the cleaning process, whereby Offer builders in particular. In preferred particulate rinse aids for The cavity is filled with substances from the group of water-soluble materials Chen detergent and detergent ingredients, preferably the carbonates, hydrogen carbonates, sulfates, phosphates and the organic oligocar solid at room temperature bonic acids in amounts of 55 to 85 wt .-%, preferably from 60 to 80 wt .-% and in particular from 65 to 75% by weight, based in each case on the particle weight.

The preferred carriers mentioned have already been described in detail above ben.

To the coating substances b), which are preferred according to the invention as the filling of the cavity used active substance particles are used, different requirements on the one hand the melting or solidification behavior, on the other however also the material properties of the casing in the solidified state, i. H. in the  Affect active substance particles. Because the active substance particles during transport or storage To be permanently protected against environmental influences, the coating substance must have a high level Stability against, for example, shock loads occurring during packaging or transport gene. The coating substance should either be at least partially elastic or too have at least plastic properties in order to avoid an impact load to react elastic or plastic deformation and not to break. The shell substance should have a melting range (solidification range) in such a temperature range have, in which the active substances to be coated do not have too high a thermal load get abandoned. On the other hand, however, the melting range must be sufficiently high in order to still effective protection for the at least slightly elevated temperature to offer included active substances. According to the invention, the coating substances have one Melting point above 30 ° C.

It has proven to be advantageous if the coating substance does not have a sharply defined one Melting point shows how it usually occurs with pure, crystalline substances, but may have a melting range spanning several degrees Celsius.

The coating substance preferably has a melting range which is between approximately 45 ° C. and is about 75 ° C. In the present case, this means that the melting range within the specified temperature interval occurs and does not denote the width of the Melting range. The width of the melting range is preferably at least 1 ° C. preferably about 2 to about 3 ° C.

The properties mentioned above are usually fulfilled by so-called waxes. "Waxing" is understood to mean a number of natural or artificially obtained substances, which usually melt above 40 ° C without decomposition and a little above the Melting point are relatively low viscosity and not stringy. You assign one strongly temperature-dependent consistency and solubility.

According to their origin, the waxes are divided into three groups, the natural waxes, chemically modified waxes and synthetic waxes.  

Natural waxes include, for example, vegetable waxes such as candelilla wax, Carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, Rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walrus, lanolin (wool wax), or pretzel fat, Mineral waxes such as ceresin or ozokerite (earth wax), or petrochemical waxes such as Petrolatum, paraffin waxes or micro waxes.

The chemically modified waxes include hard waxes such as Montanester waxes, Sassol waxes or hydrogenated jojoba waxes.

Synthetic waxes generally include polyalkylene waxes or Understand polyalkylene glycol waxes. Connections can also be used as covering materials from other classes of substances that meet the stated softening point requirements fulfill. Suitable synthetic compounds have, for example, higher esters of Phthalic acid, especially dicyclohexyl phthalate, commercially available under the name Unimoll® 66 (Bayer AG) is available. Synthetic ones are also suitable Waxes from lower carboxylic acids and fatty alcohols, for example dimyristyl tartrate, the is available under the name Cosmacol® ETLP (Condea). Are reversed too synthetic or semi-synthetic esters from lower alcohols with fatty acids from native Sources can be used. Tegin® 90 (Goldschmidt), for example, falls into this class of substances Glycerol monostearate palmitate. Also shellac, for example Shellac-KPS-Dreiring-SP (Kalkhoff GmbH) can be used according to the invention as a covering material.

The waxes, for example, are also included in the scope of the present invention so-called wax alcohols. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols usually with about 22 to 40 carbon atoms. The Wax alcohols, for example, come in the form of wax esters of higher molecular weight Fatty acids (wax acids) as the main component of many natural waxes. examples for Wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or Melissyl alcohol. The coating of the solid particles coated according to the invention can optionally also contain wool wax alcohols, including triterpenoid and Steroidal alcohols, for example lanolin, means that, for example, under the  Trade name Argowax® (Pamentier & Co) is available. Also at least in part can be used as part of the envelope within the scope of the present invention Fatty acid glycerol esters or fatty acid alkanolamides, but optionally also water-insoluble ones or only slightly water-soluble polyalkylene glycol compounds.

Particularly preferred coating substances in the active substance which can be introduced into the cavity Punch particles are those from the group of polyethylene glycols (PEG) and / or poly propylene glycols (PPG) contains, with polyethylene glycols with molecular weights between 1500 and 36,000 preferred, those with molecular weights from 2000 to 6000 are particularly preferred and those with molecular weights of 3000 to 5000 are particularly preferred.

Here, active substance particles are particularly preferred which contain propylene glycols (PPG) and / or polyethylene glycols (PEG) as the only coating substance. According to the invention, a settable polypropylene glycol (PPG) are polymers of propylene glycol which have the general formula III

are sufficient, where n can take values between 10 and 2000. Preferred PPG show Molar masses between 1000 and 10,000, corresponding to values of n between 17 and approx. 170, on.

Polyethylene glycols (abbreviation PEG) which can preferably be used according to the invention are polymers of ethylene glycol which have the general formula IV

H- (O-CH ₂ -CH ₂ ) _n -OH (IV)

are sufficient, where n can have values between 20 and approx. 1000. The above ge Preferred molecular weight ranges mentioned correspond to preferred ranges chen of the value n in formula IV from approx. 30 to approx. 820 (exactly: from 34 to 818), particularly  preferably from about 40 to about 150 (exactly: from 45 to 136) and in particular from about 70 to approx. 120 (exactly: from 68 to 113).

The hull contained in the active substance particles according to the invention preferably contains Oil substance in the majority of paraffin wax. This means that at least 50% by weight of the total contained substances, preferably more, consist of paraffin wax. Paraffin wax contents (based on the total coating substance) of approximately are particularly suitable 60 wt .-%, about 70 wt .-% or about 80 wt .-%, with even higher proportions of for example, more than 90% by weight are particularly preferred. In a special one Embodiment of the invention consists of the total amount of the coating substance used made exclusively from paraffin wax.

Paraffin waxes have a frame compared to the other natural waxes mentioned The present invention has the advantage that in an alkaline Detergent environment no hydrolysis of the waxes takes place (as for example is to be expected in the wax esters), since paraffin wax has no hydrolyzable groups contains.

Paraffin waxes consist mainly of alkanes, as well as low levels of iso- and Cycloalkanes. The paraffin to be used according to the invention preferably has essentially no constituents with a melting point of more than 70 ° C., particularly preferably of more than 60 ° C. Shares of high-melting alkanes in the paraffin can fall below this melting temperature in the detergent fleet undesirable wax residues on the surfaces to be cleaned or the goods to be cleaned. Such Wax residues usually lead to an unsightly appearance of the cleaned Surface and should therefore be avoided.

Particulate rinse aid which can preferably be introduced into the cavity contain as an envelope Substance at least one paraffin wax with a melting range of 50 ° C to 60 ° C.

The content of the paraffin wax used is preferably at ambient temperature (usually about 10 to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes if possible  high. The more solid wax components in a wax at room temperature, the more useful it is within the scope of the present invention. With increasing share of Solid wax components increase the resilience of the active substance particles Impacts or friction on other surfaces, resulting in longer-lasting protection of the Particle leads to active substances. High levels of oils or liquid wax components can lead to a weakening of the particles, which opens pores and the active substances be exposed to the environmental influences mentioned at the beginning.

In addition to paraffin as the main constituent, the coating substance can also have one or more of the above mentioned waxes or wax-like substances. Basically, that should be the Envelope forming mixture must be such that the active substance particles at least are largely insoluble in water. The solubility in water should be at a temperature of about 30 ° C do not exceed about 10 mg / l and are preferably below 5 mg / l.

In any case, however, the coating should have the lowest possible water solubility, also in Water with elevated temperature, have a temperature-independent release of the Avoid active substances as much as possible.

The principle described above serves to delay the release of ingredients a certain time in the cleaning cycle and can be Use dishwashing particularly advantageously if the main wash cycle is lower Temperature (for example 55 ° C) is rinsed so that the active ingredient from the Active substance particles are only released in the rinse cycle at higher temperatures (approx. 70 ° C) becomes.

Preferred particulate rinse aid that can be introduced into the cavity according to the invention are characterized in that they contain one or more substances with a Melting range from 40 ° C to 75 ° C in amounts of 6 to 30 wt .-%, preferably from 7.5 to 25 wt .-% and in particular from 10 to 20 wt .-%, each based on the part weight, included. Detergent tablets are particularly preferred per, in which the particles contained in the cavity as paraffin (e) or Contain polyalkylene glycols, especially polyethylene glycols.  

The active substance particles to be introduced into the cavity according to the invention Active substances contained can be processed at the processing temperature (i.e. at the temperature, in which the particles are produced) both in solid and in liquid form gene.

The active substances contained in the active substance particles fulfill certain tasks. Through the separation of certain substances or through the accelerated or Delayed release of additional substances can reduce cleaning performance be improved. Active substances that are preferably incorporated into the active substance particles That is why such ingredients of detergents and cleaning agents are decisive are involved in the washing or cleaning process.

In active substance particles to be incorporated preferably into the cavity (s) therefore one or more substances from the groups of surfactants, enzymes, Bleach, bleach activator, corrosion inhibitors, scale inhibitors, cobuilders and / or fragrances in amounts of 6 to 30% by weight, preferably 7.5 to 25% by weight and in particular from 10 to 20% by weight, in each case based on the particle weight hold. Methods in which those contained in the cavity are particularly preferred Active substance particles as active substances non-ionic surfactant (s) and / or bleach and / or bleach activators and / or enzyme (s) and / or corrosion inhibitors and / or Contain fragrances.

By incorporating surfactants into the melted shell material, one can Produce melt suspension or emulsion, which in the finished active substance particle or in the ready-made molded body according to the invention, to a predetermined Provides additional wash-active substance at the appropriate time. For example, active substance particles which can be incorporated into the cavity (s) in this way produce machine dishwashing, the additional surfactant from the fiction, ge Only release moldings that are common household dishes at temperatures Only reach the dishwasher in the final rinse cycle. This way it is in the rinse aid cycle additional surfactant available, which accelerates the drainage of the water and so  Stains on dishes are effectively prevented. With a suitable amount of solidified enamel suspension or emulsion in the active substance particles can thus on the use additional rinse aid, which is common today.

Is / are in active substance particles which can preferably be introduced into the cavity (s) therefore the active ingredient (s) selected from the group of nonionic surfactants, especially the alkoxylated alcohols. These substances have already been discussed in detail described.

Another class of active substances that are particularly advantageous in the inventions Bleaching agents that can be incorporated according to the invention are bleaching agents. Particles can be produced and introduced into the cavity (s), which only release the bleach when certain temperatures are reached, for example wise ready-made cleaning agents that clean enzymatically in the pre-rinse cycle and only release the bleach in the main wash cycle. Also are detergents for that machine dishwashing can be produced so that additional bleach in the rinse cycle are released and so difficult stains, such as tea stains, more effectively remove.

In particulate active substance which can preferably be incorporated into the cavity (s) Particles is / are therefore the active substance (s) selected from the group of the Sauer fabric or halogen bleach, especially chlorine bleach. This substance too zen have already been described in detail.

Another class of compounds that are preferred as active substances in the inventions Active substance particles which can be introduced according to the invention are the Bleach activators. The important representatives from this group of substances have already been described. In the context of the present invention preferably in the / the cavity / Particles introduced into the active substance contain bleach activators as the active substance, especially from the groups of polyacylated alkylenediamines, in particular Tetraacetylethylenediamine (TAED), the N-acylimide, especially N-nonanoylsuccinimide (NOSI), the acylated phenol sulfonates, especially n-nonanoyl- or isononanoyloxy  benzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA).

Another important embodiment of the present invention provides for the introduction of enzyme-containing particles into the cavity (s). Such active substance particles contain as active substance (s) enzymes which have been described in detail above. Be particularly preferred here as particulate particles to be introduced into the cavity (s) are those containing 40 to 99.5% by weight, preferably 50 to 97.5% by weight, particularly preferably 60 to 95% by weight % and in particular 70 to 90% by weight of one or more coating substance (s) which have a melting point above 30 ° C., 0.5 to 60% by weight, preferably 1 to 40% by weight , particularly preferably 2.5 to 30% by weight and in particular 5 to 25% by weight of one or more liquid enzyme preparation (s) dispersed in the coating substance (s) and 0 to 20% by weight, preferably 0 up to 15% by weight, particularly preferably 0 to 10% by weight and in particular 0 to 5% by weight and optionally further carrier materials, auxiliaries and / or active ingredients. Preferred processes are accordingly characterized in that the cavity filling contains ne active substance comprising particles which

• a) 40 to 99.5% by weight, preferably 50 to 97.5% by weight, particularly preferably 60 to 95% by weight and in particular 70 to 90% by weight of one or more enveloping substances punch (s) with a melting point above 30 ° C,
• b) 0.5 to 60% by weight, preferably 1 to 40% by weight, particularly preferably 2.5 to 30 % By weight and in particular 5 to 25% by weight of one or more in the envelope (s) substance (s) dispersed liquid enzyme preparation (s) as well
• c) 0 to 20% by weight, preferably 0 to 15% by weight, particularly preferably 0 to 10 % By weight and in particular 0 to 5% by weight of further carrier materials, auxiliary and / or active substances

consist.

The coating substances are preferably polyethylene glycols and / or polypropylene glycol cole, liquid enzyme preparations have proven themselves as active substances. Such rivers sigenzyme concentrates are either homogeneously based on propylene glycol / water or heterogeneous as a slurry, or they are in a microencapsulated structure. Preferred  Liquid proteases are e.g. B. Savinase® L, Durazym® L, Esperase® L, and Everlase® from Fa. Novo Nordisk, Optimase® L, Purafect® L, Purafect® OX L, Properase® L from Genencor International, and BLAP® L from Biozym Ges. M. b. H .. Preferred amylases are Ter mamyl® L, Duramyl® L, and BAN® from Novo Nordisk, Maxamyl® MTL and Purafect® HPAm L from Genencor International. Preferred lipases are Lipolase® L, Lipolase® ultra L and Lipoprime® L from Novo Nordisk and Lipomax® L from Genencor Inter national.

As slurries or microencapsulated liquid products such. B. Products like those with SL or LCC designated products from Novo Nordisk are used. The above commercially available liquid enzyme preparations contain, for example, 20 to 90% by weight Propylene glycol or mixtures of propylene glycol and water. As part of the present The present invention preferably insertable into the cavity are thus ge indicates that they are one or more liquid amylase preparations and / or one or contain several liquid protease preparations.

Fragrances can also be incorporated into the particles to be introduced as active substances All of the fragrances described in detail above can be active substance can be used. When fragrances are incorporated into the par Particles result in cleaning agents that delay all or part of the perfume release device. In this way, for example, cleaning agents for machine dishwashing can be produced, in which the consumer is also after Digter dishwashing experienced the perfume note when the machine was opened. In this way can cause the undesirable "alkaline smell" of many automatic dishwashing detergents is liable to be eliminated.

Corrosion inhibitors can also be incorporated into the particles as an active ingredient, with the substances familiar to the expert can be used. As a base inhi For example, bitor has a combination of enzyme (e.g. lipase) and lime soaps proven dispersant.  

At exceptionally low temperatures, for example at temperatures below 0 ° C, the active substance particle can break under impact or friction. To stability at such low temperatures can improve the coating substances if necessary Additives are added. Suitable additives must be completely with the Allow melted wax to mix, the melting range of the coating substances Do not change significantly, the elasticity of the sheathing at low temperatures improve the permeability of the casing to water or moisture generally do not increase and must not increase the viscosity of the melt of the shell material increase to the extent that processing becomes difficult or even impossible. Suitable Additives that reduce the brittleness of an envelope consisting essentially of paraffin Lowering at low temperatures are, for example, EVA copolymers, hydrogenated resin Acid methyl ester, polyethylene or copolymers of ethyl acrylate and 2-ethylhexyl acrylate.

Another useful additive when using paraffin as a coating is the addition of a small amount of a surfactant, for example a C _12-18 fatty alcohol sulfate. This addition results in a better wetting of the material to be embedded through the covering. It is advantageous to add the additive in an amount of about <5% by weight, preferably <about 2% by weight, based on the coating substance. The addition of an additive can in many cases lead to the fact that active substances can also be encased which, without the addition of an additive, generally form a tough, plastic body made of paraffin and partially dissolved active substance after the encapsulation material has melted.

It can also be advantageous to add further additives to the coating substance in order to to prevent early withdrawal of the active substances. This is particularly so in the production of the active substance particles according to the invention without carriers guess. The anti-settling agents that can be used for this purpose, also known as floating agents are from the prior art, for example from the lacquer and printing inks manufacturing, known. To make the transition from the plastic solidification area to the festival Sedimentation phenomena and concentration gradient of the sub to be encased To avoid punching, there are, for example, surface-active substances in Lö dispersed waxes, montmorillonites, organically modified bentonites, (hy third) castor oil derivatives, soy lecithin, ethyl cellulose, low molecular weight polyamides, Me  tall stearates, calcium soaps or hydrophobized silicas. Other substances that the effects mentioned come from the groups of anti-floating agents and Thixotropic agents and can be used chemically as silicone oils (dimethylpolysiloxanes, methyl phenylpolysiloxanes, polyether-modified methylalkylpolysiloxanes), oligomeric titanates and silanes, polyamines, salts from long-chain polyamines and polycarboxylic acids, Amine / amide-functional polyesters or amine / amide-functional polyacrylates become.

Additives from the classes of substances mentioned are commercially extremely diverse available. Commercial products that are advantageous in the context of the method according to the invention Aerosil® 200 (pyrogenic pebbles acid, Degussa), Bentone® SD-1, SD-2, 34, 52 and 57 (Bentonite, Rheox), Bentone® SD-3, 27 and 38 (hectorite, Rheox), Tixogel® EZ 100 or VP-A (organically modified Smec tit, Südchemie), Tixogel® VG, VP and VZ (montmorillonite loaded with QAV, Südche mie), Disperbyk® 161 (block copolymer, Byk-Chemie), Borchigen® ND (sulfo-free er ion exchanger, Borchers), Ser-Ad® FA 601 (servo), Solsperse® (aromatic Ethoxylate, ICI), Surfynol® types (Air Products), Tamol® and Triton® types (Rohm & Haas), Texaphor 963, 3241 and 3250 (polymers, Henkel), Rilanit® types (Hen kel), Thixciri E and R (castor oil derivatives, Rheox), Thixatrol® ST and GST (castor oil Derivatives, Rheox), Thixatrol® SR, SR 100, TSR and TSR 100 (polyamide polymers, Rheox), Thixatrol® 289 (Polyetsre polymer, Rheox) and the different M-P-A® Types X, 60-X, 1078-X, 2000-X and 60-MS (organic compounds, Rheox).

The aids mentioned can be used in the rinse aid to be incorporated according to the invention. or enzyme particles depending on the coating material and active substance in varying menus gene can be used. Usual use concentrations for the above mentioned An Anti-settling, anti-floating, thioxotropic and dispersing agents are in the range of 0.5 to 8.0% by weight, preferably between 1.0 and 5.0% by weight, and particularly preferred between 1.5 and 3.0% by weight, based in each case on the total amount of coating substance and Active substances.  

Within the scope of the present invention, preference is given to entering the cavity (s) Particulate rinse aid or enzyme particles contain additional auxiliaries the group of anti-settling agents, suspended agents, anti-floating agents, thixotropic agents and dispersing agents in amounts of 0.5 to 9% by weight, preferably between 1 and 7.5% by weight, and particularly preferably between 1.5 and 5% by weight, in each case based on the particle weight.

Especially in the production of melt suspensions or emulsions that are active Containing substances that are liquid at the processing temperature, the use is speci eller emulsifiers advantageous. It has been shown that in particular emulsifiers from the Group of fatty alcohols, fatty acids, polyglycerol esters and polyoxyalkylene siloxanes are extremely suitable.

Fatty alcohols are understood to mean the alcohols with 6 to 22 carbon atoms obtainable from native fats or oils via the corresponding fatty acids (see below). Depending on the origin of the fat or oil from which they are obtained, these alcohols can be substituted in the alkyl chain or partially unsaturated. The emulsifiers used in the active substance particles according to the invention are therefore preferably C _6-22 fatty alcohols, preferably C _8-22 fatty alcohols and in particular C _12-18 fatty alcohols, with particular preference given to the C _16-18 fatty alcohols.

All of vegetable or animal oils and fats can also be used as emulsifiers obtained fatty acids are used. The fatty acids can be independent of theirs Physical state saturated or mono- to polyunsaturated. Even with the unsown saturated fatty acids are the solid at room temperature compared to the liquid or pasty preferred. Of course, not only "pure" fatty acids can be used but also the technical fat obtained from the splitting of fats and oils acid mixtures, these mixtures again clearly ahead from an economic point of view are moving.

For example, as emulsifiers in the context of the present invention use individual species or mixtures of the following acids: caprylic acid, pelargonic acid,  Capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, octadecan-12-ol acid, arachidic acid, behenic acid, lignoceric acid, cerotinic acid, melissic acid, 10- Undecenoic acid, petroselinic acid, petroselaidic acid, oleic acid, elaidic acid, ricinoleic acid, Linolaidic acid, α- and β-eläosterainic acid, gadoleic acid, erucic acid, brassidic acid. Of course, the fatty acids with an odd number of carbon atoms are also used bar, for example undecanoic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, no nadecanoic acid, heneicosanoic acid, tricosanoic acid, pentacosanoic acid, heptacosanoic acid.

C _6-22 fatty acids, preferably C _8-22 fatty acids and in particular C _12-18 fatty acids, with particular preference for C, are used as emulsifier (s) in the rinse aid or enzyme particles to be preferably introduced into the cavity (s) _16-18 fatty acids.

Particularly preferred emulsifiers in the context of the present invention are polyglycerol esters, in particular esters of fatty acids with polyglycerols. These preferred polyglycerol esters can be described by the general formula V.

in which R ¹ in each glycerol unit is independently H or a fatty acyl radical having 8 to 22 carbon atoms, preferably having 12 to 18 carbon atoms, and n is a number between 2 and 15, preferably between 3 and 10.

These polyglycerol esters are known in particular with degrees of polymerization n = 2, 3, 4, 6 and 10 and are commercially available. As materials of the type mentioned can also be found in cosmetic formulations widespread, some of these substances are classified in the INCI nomenclature (CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997). This standard cosmetic work contains, for example, information on the keywords POLYGLYCERYL-3-BEESWAX, POLYGLYCERYL-3-CETYL ETHER, POLYGLYCERYL-4-COCOATE, POLYGLYCERYL-10-DECALINOLEATE, POLY GLYCERYL-10-DECAOLEYAR, POLYGLYCAR 2-DIISOSTEARATE, POLYGLYCERYL-3-DIISOSTEARATE, POLY GLYCERYL-10-DIISOSTEARATE, POLYGLYCERYL-2-DIOLEATE, POLY GLYCERYL-3-DIOLEATE, POLYGLYCERYL-6-DIOLEATE, POLYGLYCERYLYL-10- 6- DISTEARATE, POLYGLYCERYL-10-DISTEARATE, POLYGLYCERYL-10- HEPTAOLEATE, POLY-GYLCERYL-12-HYDROXYSTEARATE, POLYGLYCERYL- 10-HEPTASTEARATE, POLYGLYCERYL-6-HEXAOLEARATE-POLYGLYLATE-POLYGLYLATE POLY-GLYCERYL-6- ISOSTEARATE, POLY-GLYCERYL-10-LAURATE, POLY LYCERYLMETHACRYLATE, POLYGLYCERYL-10-MYRISTATE, POLYGLYCERYL-2-OLEATE, POLYGLYCERYL-3-OLEATE, POLYGLYCERYL-POLYGLYCERYL-POLYGLYCERYL -8-OLEATE, POLYGLYCERYL-10-OLEATE, POLYGLYCERYL-6-PENTAOLEATE, POLYGL YCERYL-10-PENTAOLEATE, POLYGLYCERYL-6-PENTASTEARATE, POLYGLYCERYL-10-PENTASTEARATE, POLYGLYCERYL-2-SESQUI IOSOSTEARATE, POLYGLYCERYL-2-SESQUIOLEATE, POLYGLYARYATEURLERY-2 -8-STEARATE, POLYGLYCERYL-10-STEARATE, POLY GLYCERYL-2-TETRAISOSTEARATE, POLYGLYCERYL-10-TETRAOLEATE, POLYGLYCERYL-2-TETRASTEARATE, POLYGLYCERYL-2-TRIISOSTEARATE-POLYGLYL-TRY The commercially available products from different manufacturers, which are classified under the abovementioned keywords in the work mentioned, can advantageously be used as emulsifiers in process step b) according to the invention.

Another group of emulsifiers which can be used in the rinse aid or enzyme particles to be incorporated into the cavity (s) according to the invention are substituted silicones which carry side chains reacted with ethylene or propylene oxide. Such polyoxyalkylene siloxanes can be described by the general formula VI

in which each radical R ¹ independently of one another for -CH ₃ or a polyoxyethylene or propylene group - [CH (R ² ) -CH ₂ -O] _x H group, R ² for -H or -CH ₃ , x for a number between 1 and 100, preferably between 2 and 20 and in particular less than 10, and n indicates the degree of polymerization of the silicone.

Optionally, the polyoxyalkylenesiloxanes mentioned can also be attached to the free OH groups of the Polyoxyethylene or polyoxypropylene side chains are etherified or esterified. The Unetherified and unesterified polymer from dimethylsiloxane with polyoxyethylene and / or In the INCI nomenclature, polyoxypropylene is called DIMETHICONE COPOLYOL designated and is under the trade names Abil® B (Goldschmidt), Alkasil® (Rhône- Poulenc), Silwet® (Union Carbide) or Belsil® DMC 6031 commercially available.

The DIMIETHICONE COPOLYOL ACETATE esterified with acetic acid (for example Belsil® DMC 6032, -33 and -35, Wacker) and the DIMETHICONE COPOLYOL BUTYL ETHERS (for example KF352A, Shin Etsu) are within the scope of the present invention can also be used as emulsifiers.

The same applies to the emulsifiers as to the wrapping materials and enveloping substances that they are used over a wide range can. Usually, emulsifiers of the type mentioned make up 1 to 25% by weight, preferably 2 to 20% by weight and in particular 5 to 10% by weight of the weight of the Sum of wrapping materials and active substances. Within the scope of the present invention preferably particulate rinse aid to be introduced into the cavity (s) or Enzyme particles also contain emulsifiers from the group of fatty alcohols, Fatty acids, polyglycerol esters and / or polyoxyalkylene siloxanes in amounts of 0.1 to 5  % By weight, preferably from 0.2 to 3.5% by weight, particularly preferably from 0.5 to 2% by weight and in particular from 0.75 to 1.25% by weight, in each case based on the particle weight.

Regardless of how the particles in a preferred embodiment of the present ing invention can serve as a cavity filling, are composed, can these are attached to the molded body. This is particularly necessary if the cavity to be filled is not closed by (another) part b).

This fixation can be done by applying coating layers or spraying Lö solutions of binding materials, but it is also possible to use particles that are already dematerialien contain to soften superficially by heating, whereby adhesion comparable to sintering on the molded body is achieved. Of course it is also possible, before filling the cavity (s) with further active substance Punch or active substance preparation form adhesion promoter on the surfaces of the cavity to apply. Appropriate procedures in which the cavity is made with a mixture of Adhesion promoter (s) and active substance (s) are filled are preferred.

The coating layer optionally applied to the filling introduced into the cavity can applied to the surface of the cavity filling and adhesively bonded to it be what, for example by gluing, partial melting or by chemi reaction can take place.

The coating layer can of course also be a laminate of several different ones composite coating materials, over different compositions Individual coating layers can fill the cavity at certain times in the Washing and cleaning cycle are released.

Preferred coating materials are the polymers known from the prior art. In particular, detergent tablets are preferred in which the Coa ting layer made of a polymer with a molecular weight between 5000 and 500,000 daltons, preferably between 7500 and 250,000 daltons and in particular between 10,000 and 100,000 daltons. With regard to the media, in the detergents and cleaning agents  Detergent and cleaning agent form are usually introduced body preferred, in which the coating layer be made of a water-soluble polymer stands.

Such preferred polymers can be synthetic or natural in origin. If polymers on a native or part-native basis are used as coating material, then Detergent tablets are preferred, in which the coating material is made of is selected from one or more substances from the group carrageenan, guar, pectin, Xanthan, cellulose and its derivatives, starch and its derivatives and gelatin.

Carrageenan is an extract from North Atlantic red algae, which is one of the florid plants, and is named after the Irish coastal town of Carragheen. The carrageenan filled from the hot water extract of the algae is a colorless to sand-colored powder with molar masses of 100000-800000 and a sulfate content of approx. 25%, which is very easily soluble in warm water. There are three main components in carrageenan: The yellow-forming fraction consists of D-galactose-4-sulfate and 3,6-anhydro-α-D-galactose, which are alternately glycosidically linked in the 1,3- and 1,4-positions (In contrast, agar contains 3,6-anhydro-α-L-galactose). The non-gelling 1 fraction is composed of 1,3-glycosidically linked D-galactose-2-sulfate and 1,4-linked D-galactose-2,6-disulfate residues and is easily soluble in cold water. The i-carrageenan composed of D-galactose-4-sulfate in 1,3-bond and 3,6-anhydro-α-D-galactose-2-sulfate in 1,4-bond is both water-soluble and gel-forming. Other types of carrageenan are also designated with Greek letters: α, β, γ, µ, ν, ξ, π, ω, χ. The type of cations present (K, NH ₄ , Na, Mg, Ca) also influences the solubility of the carrageenans. Semi-synthetic products that contain only one type of ion and can also be used as coating materials in the context of the present invention are also called carrag (h) eenate.

The guar which can be used as coating material in the context of the present invention, too Called guar flour, is an off-white powder that is obtained by grinding the endosperm of the ur originally endemic in the Indian and Pakistani regions, now also in others ren countries, e.g. B. cultivated in the south of the USA, belong to the legume family  guar bean (Cyamopsis tetragonobolus) is obtained. The main ingredient of the guar is with up to approx. 85% by weight of the dry substance guaran (guar gum, cyamopsis Rubber); Minor components are proteins, lipids and cellulose. Guaran itself is a bum lygalactomannan, d. H. a polysaccharide, the linear chain of which is unsubstituted (see Formula VII) and substituted in the C6 position with a galactose residue (see formula (VIII) Mannose units in β-D (1 → 4) linkage is built.

The ratio of VII: VIII is approximately 2: 1; Contrary to original assumptions, the VIII units are not strictly alternating, but are arranged in pairs or triplets in the polygalac tomannan molecule. Information on the molar mass of guaran varies significantly with values of approx. 2.2.10 ⁵ -2.2.10 ⁶ g / mol depending on the degree of purity of the polysaccharide - the high value was determined on a highly purified product - and corresponds to approx. 1350-13500 sugar Units / macromolecule. Guaran is insoluble in most organic solvents.

The pectins, which can also be used as coating material, are high molecular weight glycosidic Plant substances that are very common in fruits, roots and leaves. The pectins consist essentially of chains of 1,4-α-glycoside. associated galacturonic acid Units whose acid groups are esterified to 20-80% with methanol, one between high-esterified (<50%) and low-esterified pectins (<50%). The Pectins have a sheet structure and are therefore in the middle of starch and cellulose  Molecules. Your macromolecules still contain some glucose. Galactose, xylose and Arabinose and have slightly acidic properties.

Fruit pectin contains 95%, beet pectin up to 85% galacturonic acid. The molecular weights of the ver Different pectins vary between 10,000 and 500,000. The structural properties also are strongly dependent on the degree of polymerization; so form z. B. the fruit pectins in dry Asbestos-like fibers, while the flax pectins, on the other hand, are fine, granular powders.

The pectins are mainly extracted from the inside by extraction with dilute acids Portions of citrus fruit peel, leftovers or beet pulp.

Xanthan can also be used as a coating material according to the invention. Xanthan is a microbial anionic heteropolysaccharide that is produced by Xanthomonas campestris and some other species under aerobic conditions and has a molecular weight of 2 to 15 million Daltons. Xanthan is formed from a chain with β-1,4-bound glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan. Xanthan can be described by the following formula:

The celluloses and their derivatives are also suitable as coating materials. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, formally considered, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. As a coating material based on cellulose can be used in the context of the present invention, cellulose derivatives, which are obtainable by polymer-analogous reactions from cellulose. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound by an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.

In addition to cellulose and cellulose derivatives, (modified) dextrins, starch and Starch derivatives are used as coating materials.  

Dextrins, for example, are suitable as nonionic organic coating materials Oligomers or polymers of carbohydrates by partial hydrolysis of starches can be obtained. The hydrolysis can be carried out according to conventional methods, for example acid or enzyme-catalyzed processes are carried out. It is preferably Hy Drolysis products with average molecular weights in the range of 400 to 500000 g / mol. It is a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular special from 2 to 30 preferred, DE being a customary measure of the reducing Effect of a polysaccharide compared to dextrose, which has a DE of 100, is. Both maltodextrins with a DE between 3 and 20 and dry can be used glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and White dextrins with higher molar masses in the range from 2000 to 30000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Starch can also be used as a coating material for the washing and cleaning agents according to the invention moldings are used. Starch is a homoglycan, with the glucose Units are linked α-glycosidically. Starch is made up of two components Chen molecular weight built: From approx. 20-30% straight-chain amylose (MW. approx. 50,000-150,000) and 70-80% branched chain amylopectin (MW. Approx. 300,000- 2,000,000), as well as small amounts of lipids, phosphoric acid and cations contain. While the amylose is long due to the 1,4-position binding, forms helical, intertwined chains with about 300-1200 glucose molecules, In the case of amylopectin, the chain branches out after an average of 25 glucose units by 1,6-binding to a knot-like structure with about 1500-12000 molecules Glucose. In addition to pure starch, coating materials are within the scope of the present Invention also uses starch derivatives derived from starch by polymer-analogous reactions are available. Such chemically modified starches include for example products from esterifications or etherifications in which hydroxy Hydrogen atoms have been substituted. But also strengths in which the hydroxy groups  but also strengths in which the hydroxy groups versus functional groups that are not are bound via an oxygen atom, can be replaced as starch derivatives deploy. The group of starch derivatives includes, for example, alkali starches, car boxymethyl starch (CMS), starch esters and ethers and amino starches.

Gelatin has one of the proteins and modified proteins as a coating material outstanding importance. Gelatin is a polypeptide (molecular weight: approx.15,000- <250,000 g / mol), mainly by hydrolysis of the skin and bones of animals contained collagen is obtained under acidic or alkaline conditions. The Amino acid composition of gelatin largely corresponds to that of collagen, from which it was obtained and varies depending on its provenance. The Use of gelatin as a water-soluble coating material is particularly in the Pharmaceuticals in the form of hard or soft gelatin capsules are extremely widespread.

Other polymers which can be used as coating materials are synthetic polymers which are preferably water-swellable and / or water-soluble. Such synthetic-based polymers can be "tailor-made" for the desired coating permeability during storage and dissolution of the coating layer when used. Particularly preferred detergent tablets according to the invention are characterized in that the coating material is selected from a polymer or polymer mixture, the polymer or at least 50% by weight of the polymer mixture being selected from

• a) water-soluble nonionic polymers from the group of
  • 1. polyvinylpyrrolidones,
  • 2. vinyl pyrrolidone / vinyl ester copolymers,
  • 3. Cellulose ether 4902 00070 552 001000280000000200012000285914479100040 0002019941266 00004 44783S <
  • b) water-soluble amphoteric polymers from the group of
    • 1. Alkyl acrylamide / acrylic acid copolymers
    • 2. Alkyl acrylamide / methacrylic acid copolymers
    • 3. Alkyl acrylamide / methyl methacrylic acid copolymers
    • 4. Alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
    • 5. Alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
    • 6. Alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
    • 7. Alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers
    • 8. Copolymers
      • 1. unsaturated carboxylic acids
      • 2. cationically derivatized unsaturated carboxylic acids
      • 3. optionally further ionic or nonionic monomers
  • c) water-soluble zwitterionic polymers from the group of
    • 1. Acrylamidoalkyltrialkylammoniumchlorid / acrylic acid copolymers and their alkali and ammonium salts
    • 2. Acrylamidoalkyltrialkylammoniumchlorid / methacrylic acid copolymers and their alkali and ammonium salts
    • 3. Methacroylethyl betaine / methacrylate copolymers
  • d) water-soluble anionic polymers from the group of
    • 1. Vinyl acetate / crotonic acid copolymers
    • 2. Vinyl pyrrolidone / vinyl acrylate copolymers
    • 3. Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers
    • 4. Graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols
    • 5. grafted and crosslinked copolymers from the copolymerization of
      • 1. at least one monomer of the non-ionic type,
      • 2. at least one monomer of the ionic type,
      • 3. of polyethylene glycol and
      • 4. a networked person
    • 6. copolymers obtained by copolymerizing at least one monomer of each of the following three groups:
      • 1. esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
      • 2. unsaturated carboxylic acids,
      • 3. Esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group d6ii) with saturated or unsaturated, straight-chain or branched C _8-18 alcohol
    • 7. Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester
    • 8. Tetra and pentapolymers
      • 1. Crotonic acid or allyloxyacetic acid
      • 2. Vinyl acetate or vinyl propionate
      • 3. branched allyl or methallyl esters
      • 4. Vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters
    • 9. Crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinymethyl ether, acrylamide and their water-soluble salts
    • 10. Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the α-position
  • e) water-soluble cationic polymers from the group of
    • 1. quaternized cellulose derivatives
    • 2. Polysiloxanes with quaternary groups
    • 3. cationic guar derivatives
    • 4. polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid
    • 5. Copolymers of vinyl pyrrolidone with quaternized derivatives of dialkyl aminoacrylate and methacrylate
    • 6. Vinyl pyrrolidone-methoimidazolinium chloride copolymers
    • 7. Quaternized polyvinyl alcohol
    • 8. Polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.
  Water-soluble polymers for the purposes of the invention are those polymers which are more than 2.5% by weight soluble in water at room temperature. The coatings of the detergent tablets according to the invention can be produced from individual polymers mentioned above, and may be but also mixtures or multi-layer structures made of the polymers who used the. The polymers are described in more detail below. Water-soluble polymers preferred according to the invention are nonionic. Suitable non-ionogenic polymers are, for example:
  
  • - Polyvinylpyrrolidones, such as those sold under the name Luviskol® (BASF). Polyvinylpyrrolidones are preferred nonionic poly mers in the context of the invention.
  Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinone)], abbreviation PVP, are polymers of the general formula (IX)
  which are prepared by radical polymerization of 1-vinylpyrrolidone by solution or suspension polymerization using radical formers (peroxides, azo compounds) as initiators. The ionic polymerization of the monomer only provides products with low molecular weights. Commercial polyvinylpyrrolidones have molar masses in the range of approx. 2500-750000 g / mol, which are characterized by the specification of the K values and - depending on the K value - have glass transition temperatures of 130-175 °. They are as white, hygroscopic powder or as aqueous. Solutions offered. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).
  • - Vinyl pyrrolidone / vinyl ester copolymers, such as those sold under the trademark Luviskol® (BASF). Luviskol® VA 64 and Luviskol® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred nonionic polymers.
  The vinyl ester polymers are polymers accessible from vinyl esters with the grouping of the formula (X)
  as a characteristic basic building block of macromolecules. Of these, the vinyl acetate polymers (R = CH ₃ ) with polyvinyl acetates are by far the most important technical representatives.The polymerization of the vinyl esters is carried out radically according to different processes (solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization). Copolymers of vinyl acetate with vinyl pyrrolidone contain monomer units of the formulas (IX) and (X).
  • - Cellulose ethers, such as hydroxypropyl cellulose, hydroxyethyl cellulose and methyl hydroxypropyl cellulose, as are sold, for example, under the trademarks Culminal® and Benecel® (AQUALON).
  Cellulose ethers can be described by the general formula (XI)
  in R represents H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products, at least one R in formula (XI) is -CH ₂ CH ₂ CH ₂ -OH or -CH ₂ CH ₂ -OH. Cellulose ethers are produced industrially by etherification of alkali cellulose (e.g. with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups in an anhydroglucose unit of cellulose have reacted with the etherification reagent or how many moles of etherification reagent have been attached to an anhydroglucose unit on average . Hydroxyethyl celluloses are soluble in water from a DS of approx. 0.6 or an MS of approx. 1. Commercial hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS). Hydroxyethyl and propyl celluloses are marketed as yellowish white, odorless and tasteless powders in widely differing degrees of polymerization. Hydroxyethyl and propyl celluloses are soluble in cold and hot water and in some (water-containing) organic solvents, but insoluble in most (water-free) organic solvents; Their aqueous solutions are relatively insensitive to changes in pH or the addition of electrolytes. Polyvinyl alcohols, abbreviated as PVAL, are polymers of the general structure
  [-CH ₂ -CH (OH) -] _n
  which in small proportions also structural units of the type
  [-CH ₂ -CH (OH) -CH (OH) -CH ₂ ]
  contain. Since the corresponding monomer, the vinyl alcohol, is not resistant in its free form, polyvinyl alcohols are prepared via polymer-analogous reactions by hydrolysis, but technically in particular by alkali-catalyzed transesterification of polyvinyl acetates with alcohols (preferably methanol) in solution. These technical processes also make PVAL accessible, which contain a predeterminable residual proportion of acetate groups. Commercial PVAL (e.g. Mowiol® grades from Hoechst) come as white-yellowish powders or granules with degrees of polymerization in the range of approx. 500- 2500 (corresponding to molar masses of approx. 20,000-100,000 g / mol) in the trade and have different degrees of hydrolysis of 98-99 and 87-89 mol%. They are therefore partially saponified polyvinyl acetates with a residual acetyl group content of approx. 1-2 or 11-13 mol%. The water solubility of PVAL can be increased by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, reduce boric acid, borax and thus adjust them to the desired values in a targeted manner. Other polymers suitable according to the invention are water-soluble amphopolymers. The amphoteric polymers are amphoteric polymers, ie polymers which contain both free amino groups and free -COOH or SO ₃ H groups in the molecule and are capable of forming internal salts, zwitterionic polymers which have quaternary ammonium groups and -COO ^- - or -SO ₃ ^- contain groups, and summarized such polymers that contain -COOH or SO ₃ H groups and quaternary ammonium groups. An example of an amphopolymer which can be used according to the invention is the acrylic resin available under the name Amphomer®, which is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) acrylamide and two or more monomers from the group consisting of acrylic acid, Methacrylic acid and its simple esters. Also preferred amphopolymers are composed of unsaturated carboxylic acids (e.g. acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (e.g. acrylic amidopropyl trimethyl ammonium chloride) and optionally other ionic or nonionic monomers, such as, for example, in German rule 39 29 973 and the state of the art cited therein. Terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium chloride, as are commercially available under the name Merquat®2001 N, are particularly preferred amphopolymers according to the invention. Other suitable amphoteric polymers are, for example, the octylacrylamide / methyl methacrylate / tert.-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers available under the names Amphomer® and Amphomer® LV-71 (DELFT NATIONAL). Suitable zwitterionic polymers are, for example, those in the German patent applications DE 39 29 973, DE 21 50 557, DE 28 17 369 and DE 37 08 451 disclosed poly merisate. Acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali and ammonium salts are preferred zwitterionic polymers. Other suitable zwitterionic polymers are methacrylic ethyl betaine / methacrylate copolymers, which are commercially available under the name Amersette® (AMERCHOL). Anionic polymers suitable according to the invention include:
  
  • - Vinyl acetate / crotonic acid copolymers, as are commercially available, for example, under the names Resyn® (NATIONAL STARCH), Luviset® (BASF) and Gafset® (GAF).
  In addition to monomer units of the abovementioned formula (X), these polymers also have monomer units of the general formula (XI):
  [-CH (CH ₃ ) -CH (COOH) -] _n (XI)
  
  • - Vinylpyrrolidone / vinyl acrylate copolymers, available, for example, under the trademark Luviflex® (BASF). A preferred polymer is the vinylpyrrolidone / acrylate terpolymer available under the name Luviflex® VBM-35 (BASF).
  • - Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers, which are sold, for example, under the name Ultrahold® strong (BASF).
  • - Graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols.
  Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture with other copolymerizable compounds on polyalkylene glycols, are obtained by polymerization in the heat in a homogeneous phase by adding the polyalkylene glycols to the monomers of the vinyl esters, esters of acrylic acid or Methacrylic acid, in the presence of radical formers. Suitable vinyl esters include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and, as esters of acrylic acid or methacrylic acid, those which are used with low molecular weight aliphatic alcohols, in particular ethanol, propanol, isopropanol, 1- Butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1- butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol, are available. The polyalkylene glycols in particular include polyethylene glycols and polypropylene glycols. Polymers of ethylene glycol which have the general formula XII
  H- (O-CH ₂ -CH ₂ ) _n -OH (XII)
  are sufficient, where n can take values between 1 (ethylene glycol) and several thousand. There are various nomenclatures for polyethylene glycols that can lead to confusion. The specification of the average relative molecular weight following the specification "PEG" is technically customary, so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210. A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and directly after the hyphen is followed by a number which corresponds to the number n in the formula V mentioned above. According to this nomenclature (so-called INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 ^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997), for example, PEG-4, PEG-6, PEG-8, PEG -9, PEG-10, PEG-12, PEG-14 and PEG-16 can be used. Polyethylene glycols are commercially available, for example, under the trade names Carbowax® PEG 200 (Union Carbide), Emkapol® 200 (ICI Americas), Lipoxol® 200 MED (HÜLS America), Polyglycol® E-200 (Dow Chemical), Alkapol® PEG 300 ( Rhone-Poulenc), Lutrol® E300 (BASF) and the corresponding trade names with higher numbers.Polypropylene glycols (PPG) are polymers of propylene glycol that have the general formula XIII
  are sufficient, where n can have values between 1 (propylene glycol) and several thousand. Technically important here are in particular di-, tri- and tetrapropylene glycol, ie the representatives with n = 2, 3 and 4 in formula XIII. In particular, the vinyl acetate copolymers grafted onto polyethylene glycols and the polymers of vinyl acetate and crotonic acid grafted onto polyethylene glycols can be used.
  • - Grafted and crosslinked copolymers from the copolymerization of
    • a) at least one monomer of the non-ionic type,
    • b) at least one monomer of the ionic type,
    • c) of polyethylene glycol and
    • d) a networked person
  The polyethylene glycol used has a molecular weight between 200 and several million, preferably between 300 and 30,000. The non-ionic monomers can be of very different types and among these the following are preferred: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allyl laurate , Diethylinaleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-hexene. The non-ionic monomers can likewise be of very different types, of which crotonic acid, allyloxyacetic acid, vinyl acetic acid, maleic acid, acrylic acid and methacrylic acid are particularly preferably contained in the graft polymers As crosslinkers are preferably ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallylsucrose with 2 to 5 allyl groups per molecule of saccharin. The grafted and crosslinked copolymers described above are preferred made up from:
  
  • a) 5 to 85% by weight of at least one monomer of the non-ionic type,
  • b) 3 to 80% by weight of at least one monomer of the ionic type,
  • c) 2 to 50 wt .-%, preferably 5 to 30 wt .-% polyethylene glycol and
  • d) 0.1 to 8% by weight of a crosslinking agent, the percentage of the crosslinking agent being formed by the ratio of the total weights of i), ii) and iii).
    • - Copolymers obtained by copolymerizing at least one monomer of each of the following three groups:
  • e) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
  • f) unsaturated carboxylic acids,
  • g) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group ii) with saturated or unsaturated, straight-chain or branched C _8-18 alcohol
  Short-chain carboxylic acids or alcohols are to be understood as meaning those with 1 to 8 carbon atoms, where the carbon chains of these compounds can, if appropriate, be interrupted by double-bonded hetero groups such as -O-, -NH-, -S.
  • - Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester
  These terpolymers contain monomer units of the general formulas (II) and (IV) (see above) and monomer units of one or more allyl or methallyesters of the formula XIV:
  wherein R ^{3 is} -H or -CH ₃ , R ^{2 is} -CH ₃ or -CH (CH ₃ ) ₂ and R ^{1 is} -CH ₃ or a saturated, straight-chain or branched C _1-6 alkyl radical and the sum of Carbon atoms in the radicals R ¹ and R ^{2 is} preferably 7, 6, 5, 4, 3 or 2. The abovementioned terpolymers preferably result from the copolymerization of 7 to 12% by weight of crotonic acid, 65 to 86% by weight. %, preferably 71 to 83% by weight of vinyl acetate and 8 to 20% by weight, preferably 10 to 17% by weight of allyl or methally letsre of the formula IX.
  • - Tetra and pentapolymers
    • a) Crotonic acid or allyloxyacetic acid
    • b) vinyl acetate or vinyl propionate
    • c) branched allyl or methallyl esters
    • d) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters
    • e) Crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinymethyl ether, acrylamide and their water-soluble salts
    • f) Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the α-position.
  The anionic polymers used are in particular polycarbonate / polycarboxylic acids, polymeric polycarboxylates, polyaspartic acid, polyacetals and dextrins, which are described below. Useful organic coating materials are, for example, the polycarboxylic acids which can be used in the form of their sodium salts but also in free form. Polymeric polycarboxylates are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol. For the purposes of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{W of} the particular acid form, which were basically determined by means of gel permeation chromatography (GPC), using a UV detector. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the investigated polymers. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document. 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, the short-chain polyacrylates with molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group. Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 70,000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol. To improve water solubility, the polymers can also use allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer. Particularly preferred as coating materials are also biodegradable polymers of more than two different monomer units, for example those which are monomeric salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or which are monomeric salts of Acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives. Further preferred copolymeric coating materials are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and preferably monomers acrolein and Acrylic acid / acrylic acid salts or acrolein and vinyl acetate Other preferred coating materials include polymeric aminodicarboxylic acids, their salts or their precursors. Polyaspartic acids or their salts and derivatives are particularly preferred. Other suitable coating materials are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid. Other polymers which can preferably be used as coating materials are cationic polymers. The permanent cationic polymers are preferred among the cationic polymers. According to the invention, "permanently cationic" refers to those polymers which have a cationic group regardless of the pH of the composition (ie both the coating layer and the rest of the detergent tablets). These are usually polymers that contain a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic polymers are, for example
  
  • - Quaternized cellulose derivatives, as are commercially available under the names Celquat® and Polymer JR®. The compounds Celquat® H 100, Celquat® L 200 and Polymer JR®400 are preferred quaternized cellulose derivatives.
  • - Polysiloxanes with quaternary groups, such as the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning® 929 emulsion (containing a hydroxylamino-modified silicone, also known as amodimethicone) will), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wak ker) and Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; di quaternary polydimethylsiloxanes, Quaternium-80),
  • - Cationic guar derivatives, such as in particular the products marketed under the trade names Cosmedia®Guar and Jaguar®,
  • - Polymers dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. The products available under the names Merquat®100 (poly (dimethyldiallylammonium chloride)) and Merquat®550 (dimethyldiallylammonium chloride-acrylamide copolymer) in trade are examples of such cationic polymers.
  • - Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as, for example, vinylpyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat®734 and Gafquat®755.
  • - Vinylpyrrolidone-methoimidazolinium chloride copolymers, such as those offered under the name Luviquat®.
  • - quaternized polyvinyl alcohol
  as well as those under the designations
  
  • - polyquaternium 2,
  • - Polyquaternium 17,
  • - Polyquaternium 18 and
  • - Polyquaternium 27
  known polymers with quaternary nitrogen atoms in the main polymer chain. The polymers mentioned are designated according to the so-called INCI nomenclature, with detailed information in the CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 ^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, to which express reference is made here is taken. Cationic polymers preferred according to the invention are quaternized cellulose derivatives and polymeric dimethyldiallylammonium salts and their copolymers. Cationic cellulose derivatives, in particular the commercial product Polymer®JR 400, are very particularly preferred cationic polymers. Carbon or dicarboxylic acids or those with an even number of carbon atoms are also preferably used as coating materials. Particularly preferred carboxylic or dicarboxylic acids are those with at least 4, preferably with at least 6, particularly preferably with at least 8 and in particular those with 8 to 13 carbon atoms. Particularly preferred dicarboxylic acids are, for example, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, brassylic acid and mixtures thereof. However, tetradecanoic acid, pentadecanoic acid and thapsic acid are also suitable coating materials. Particularly preferred carboxylic acids are those with 12 to 22 carbon atoms, those with 18 to 22 carbon atoms being particularly preferred. The use of the disintegration auxiliaries described above is particularly recommended in the case of acid coating layers, the usual use concentrations for the disintegration auxiliaries in the coating layers being 0.1 to 5% by weight, based on the coating layer Detergent tablets are preferred, which are characterized in that the coating layer which fixes part c) in the cavity has a thickness of 1 to 150 µm, preferably 2 to 100 µm, particularly preferably 5 to 75 µm and in particular of 10 to 50 µm. The cavity filling [part c)] can also be introduced into the cavity in liquid, gel-like, pasty or plastic form. In the cases in which the cavity is not closed by step d) of the method according to the invention, but the cavity filling has an external surface, it is preferred that part c) hardens after being introduced into the cavity. In addition to cooling highly viscous melts to hard particles, other hardening mechanisms can also be used. Thus, it is also possible according to the invention to use suspensions or emulsions of active substances in curable matrices for step c), the curing, for example, by radiation (UV light, gamma rays, microwaves) or chemical reaction (use of hardeners, oxidation, Reduction, polymerization, polycondensation, polyaddition, etc.). If a melt that solidifies due to the lowering of the temperature is used as the cavity filling, this is converted into a flowable melt by heating a composition composed of active substance (s) and optional carrier substances and meltable matrix substances. This melt is then filled into the cavity and allowed to cool, whereupon solidification occurs. Suitable meltable matrix materials are the above-described envelope materials, in particular paraffins, polyethylene and polypropylene glycols, waxes and their mixtures. The optional filling of the cavity and the insertion of the core molding b) into the basic molding a) with a conical cavity includes In certain cases (see above), process step d), in which the shaped body is optionally post-treated. The moldings produced according to the invention can, as described above, be provided with a coating in whole or in part. Methods in which the after-treatment in step d) consists in applying a coating layer to the entire molded body are preferred according to the invention. The coating materials that can be used for this purpose have already been described in detail. The detergent tablets according to the invention can be packaged after manufacture, the use of certain packaging systems having proven particularly useful. Another aspect of the present invention is a combination of (a) detergent tablets according to the invention and a packaging system containing the detergent tablets, characterized in that the packaging system has a moisture vapor permeability rate of 0.1 g / m ² / Day to less than 20 g / m ² / day if the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%. The packaging system of the combination of detergent tablets and packaging system according to the invention has a moisture vapor permeability rate from 0.1 g / m ² / day to less than 20 g / m ² / day if the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%. The named temperature and humidity conditions are the test conditions that are mentioned in the DIN standard 53122, whereby according to DIN 53122 minimal deviations are permitted (23 ± 1 ° C, 85 ± 2% relative humidity). The moisture vapor permeability rate of a given packaging system or material can be determined by further standard methods and is, for example, also in the ASTM standard E-96-53T ("Test for measuring Water Vapor transmission of Materials in Sheet form") and in the TAPPI standard T464 m- 45 ("Water Vapor Permeability of Sheet Materials at high temperature and Humidity"). The measuring principle of current methods is based on the water absorption of anhydrous calcium chloride, which is stored in a container in the appropriate atmosphere, the container being closed at the top with the material to be tested. From the surface of the container, which is closed with the material to be tested (permeation surface), the increase in weight of calcium chloride and the exposure time, the moisture vapor transmission rate can be determined
  calculate, where A is the area of the material to be tested in cm ² , x is the weight gain of calcium chloride in g and y is the exposure time in h. The relative equilibrium humidity, often referred to as "relative humidity", contributes to the measurement of the moisture vapor transmission rate the vorlie invention 85% at 23 ° C. The absorption capacity of air for water vapor increases with temperature up to a respective maximum content, the so-called saturation content, and is given in g / m ³ . For example, 1 m ^{3 of} air at 17 ° is saturated with 14.4 g of water vapor; at a temperature of 11 ° there is already saturation with 10 g of water vapor. The relative humidity is the ratio of the actual water vapor content to the saturation content corresponding to the prevailing temperature. For example, if air contains 17 ° 12 g / m ³ water vapor, then the relative humidity = (12 / 14.4) .100 = 83%. If you cool this air, then the saturation (100% r.L.) is reached at the so-called dew point (in the example: 14 °), ie, if it cools further, a precipitate is formed in the form of mist (dew). Hygrometers and psy chrometers are used for the quantitative determination of moisture. The relative equilibrium humidity of 85% at 23 ° C can be adjusted to +/- 2% r. Adjust L. exactly. Constant and well-defined relative air humidities are also formed in closed systems at given temperatures over saturated solutions of certain salts, which are based on the phase equilibrium between partial pressure of water, saturated solution and soil body. The combinations of detergent tablets and packaging system according to the invention can of course be used are in turn packaged in secondary packaging, for example cardboard boxes or trays, with no further requirements being placed on the secondary packaging. The secondary packaging is therefore possible, but not necessary. Packaging systems preferred in the context of the present invention have a moisture vapor permeability rate of 0.5 g / m ² / day to less than 15 g / m ² / day. The packaging system of the combination according to the invention includes each after Ausfüh approximate shape of the invention one or more detergent tablets. It is preferred according to the invention either to design a shaped body in such a way that it comprises an application unit of the detergent and cleaning agent, and to pack this molded body individually, or to pack the number of shaped bodies in a packaging unit, which in total comprises one application unit. With a nominal dosage of 80 g of detergent and cleaning agent, it is therefore possible according to the invention to produce and individually pack an 80 g heavy detergent and cleaning agent tablet, but it is also possible according to the invention to form two 40 g washing and cleaning agent tablets in one Packing packaging to arrive at a combination according to the invention. This principle can of course be expanded, so that fiction, according to combinations can also contain three, four, five or even more detergents and cleaning products in one package. Of course, two or more molded articles can have different compositions in one package. In this way it is possible to spatially separate certain components from one another, for example in order to avoid stability problems. The packaging system of the combination according to the invention can consist of a wide variety of materials and can take on any external shape. For economic reasons and for reasons of easier processability, however, packaging systems are preferred in which the packaging material is light in weight, easy to process and inexpensive. In combinations preferred according to the invention, the packaging system consists of a sack or pouch made of single-layer or laminated paper and / or plastic film. The detergent tablets can be unsorted, ie as a loose fill, filled into a pouch made of the materials mentioned. However, for aesthetic reasons and for sorting the combinations in secondary packaging, it is preferable to fill the detergent tablets individually or in groups in sacks or bags. For individual application units of the detergent tablets that are in a sack or bag, the term "flow pack" has become established in technology. Such "flow packs" can then - again preferably sorted - optionally be packaged in outer packaging, which underlines the compact form of the molded article. The sacks or bags made of monolayer or laminated paper or plastic film, which are preferably used as a packaging system, can be made in a wide variety of ways and Are designed, for example, as a blown bag without a central seam or as a bag with a central seam, which are closed by heat (hot melting), adhesives or adhesive tapes. Single-layer bag or sack materials are the known papers, which can optionally be impregnated, as well as plastic films, which can optionally be co-extruded. Plastic films that can be used as a packaging system in the context of the present invention are given, for example, in Hans Domininghaus "The plastics and their properties", 3rd edition, VDI Verlag, Düssel dorf 1988, page 193. The Fig. 111 shown there also gives reference points to the water vapor permeability of the materials mentioned. In the context of the present invention, particularly preferred combinations contain as a packaging system a sack or bag made of single-layer or laminated plastic film with a thickness of 10 to 200 μm, preferably from 20 to 100 μm and in particular from 25 to 50 μm. Although it is possible to use wax-coated papers in the form of cardboard boxes as packaging systems for the detergent tablets in addition to the foils or papers mentioned, it is preferred in the context of the present invention if the packaging system does not include boxes made of wax-coated paper. In the context of the present invention, the term “packaging system” always characterizes the primary packaging of the shaped bodies, ie the packaging which is in direct contact with the surface of the shaped body on the inside. No requirements are placed on an optional secondary packaging, so that all the usual materials and Systems can be used.As already mentioned above, the detergent tablets of the combination according to the invention contain, depending on their intended use, further ingredients of detergents and cleaning agents in varying amounts. Regardless of the intended use of the tablets, it is preferred according to the invention that the or the detergent tablets have a relative equilibrium moisture content of less than 30% at 35 ° C. The relative equilibrium moisture content of the detergent tablets can be determined using customary methods, in which Ra Based on the present investigations, the following procedure was chosen: A water-impermeable 1-liter vessel with a lid, which has a closable opening for the introduction of samples, was filled with a total of 300 g of detergent tablets and 24 hours at a constant 23 ° C held to ensure a constant temperature of the vessel and substance. The water vapor pressure in the room above the mold can then be determined using a hygrometer (Hygrotest 6100, Testoterm Ltd., England). The water vapor pressure is now measured every 10 minutes until two consecutive values show no deviation (equilibrium moisture). The above-mentioned hygrometer allows the recorded values to be displayed directly in% relative humidity. Also preferred are embodiments of the combination according to the invention in which the packaging system is designed to be reclosable. Combinations in which the packaging system has a microperforation can also be realized according to the invention. Another object of the present invention is a washing method for washing textiles in a household washing machine, which is characterized in that one or more according to the invention Insert the detergent tablets into the washing-up chamber of the washing machine and run a washing program in the course of which the molding (s) are rinsed in. However, the molding (s) do not have to be metered via the washing-in chamber, but can also be added directly to the washing drum become. A metering aid, for example a net metering device, can be used here, but the shaped bodies can also be added directly to the laundry in the drum without a metering aid. A washing process for washing textiles in a household washing machine, in which one or more detergent tablets according to the invention are inserted into the washing drum of the washing machine with or without metering aid and a washing program is run, in the course of which the tablet or tablets are dissolved is therefore also an object of the present invention. As mentioned above, detergent tablets for machine dishwashing can also be produced by the method according to the invention. Accordingly, there is a cleaning method for cleaning dishes in a dishwasher, which is characterized in that one or more detergent tablets according to the invention are placed in the dosing chamber of the dishwasher and a washing program can be run, in the course of which the dosing chamber opens and the molded article (s) are dissolved, a further object of the present invention. Also in the cleaning process according to the invention, one can dispense with the metering chamber and insert the molded article (s) according to the invention, for example, into the cutlery basket. Of course, the use of a dosing aid, for example a basket that is attached to the wash cabinet, is also possible without any problems. Accordingly, a cleaning method for cleaning dishes in a Ge dishwasher, in which one or more inventive detergent tablets are inserted with or without metering aid into the dishwasher's washing compartment and a washing program is run, in the course of which the or the Moldings are dissolved, another object of the present invention.

Claims (42)

1. Detergent tablets, comprising

• a) a pressed part which has at least one cavity,
• b) a further solid part which is present at least partially enclosed in the cavity,

characterized in that the cavity in part a) is conical. 2. shaped detergent or cleaning product according to claim 1, characterized in that part b) does not completely fill this cavity. 3. Detergent tablets according to claim 2, characterized in that part b) closes the cavity and thus the remaining cavity completely is enclosed by a) and b). 4. Detergent tablets according to one of claims 1 or 2, characterized characterized in that the cavity in part a) has the shape of a conical open on one side Has holes. 5. shaped detergent or cleaning product according to one of claims 1 to 4, characterized characterized in that the cavity has a circular cross section. 6. Detergent tablets according to one of claims 1 to 5, characterized characterized in that the smallest diameter of the conical cavity in part a) maxi times 3 mm, preferably a maximum of 2.5 mm and in particular a maximum of 2 mm smaller than its largest diameter. 7. Detergent tablets according to one of claims 4 to 6, characterized characterized in that the conical trough one or more elevations and / or ver wells, preferably having protruding and / or protruding from their bottom.   8. shaped detergent or cleaning product according to claim 7, characterized in that the part that can be inserted into the trough corresponds to one of the elevation / deepening in part a) appropriate deepening / elevation. 9. shaped detergent or cleaning product according to one of claims 1 to 8, characterized characterized in that the weight ratio of part a) to part (s) b) 1: 1 to 100: 1, preferably 2: 1 to 80: 1, particularly preferably 3: 1 to 50: 1 and in particular 4: 1 to 30: 1. 10. shaped detergent or cleaning product according to one of claims 1 to 9, characterized characterized in that the outwardly visible surface of part b) from 1 to 25% preferably 2 to 20%, particularly preferably 3 to 15% and in particular 4 to 10% of the Makes up the total surface of the filled molded body. 11. shaped detergent or cleaning product according to one of claims 2 to 10, characterized characterized in that the volume ratio of that formed by parts a) and b) Cavity to the overall molded body 1: 1 to 50: 1, preferably 2: 1 to 40: 1, particularly is preferably 3: 1 to 30: 1 and in particular 4: 1 to 20: 1. 12. Detergent tablets according to one of claims 1 to 11, characterized characterized in that part b) dissolves faster than part a). 13. Detergent or cleaning product tablet according to one of claims 1 to I 1, characterized characterized in that part b) dissolves more slowly than part a). 14. Detergent tablets according to one of claims 1 to 13, characterized in that the base tablet [part a)] has a density above 1000 kgdm ^-3 , preferably above 1025 kgdm ^-3 , particularly preferably above 1050 kgdm ^-3 and especially above 1100 kgdm ^-3 . 15. Detergent tablets according to one of claims 1 to 14, characterized characterized in that the basic shaped body builders in amounts of 1 to 100 wt.%,  preferably from 5 to 95% by weight, particularly preferably from 10 to 90% by weight and in particular from 20 to 85% by weight, in each case based on the weight of the base molded body, contains. 16. Detergent tablets according to one of claims 1 to 15, characterized characterized in that the base molding phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (natri um- or potassium tripolyphosphate), in amounts of 20 to 80 wt .-%, preferably from 25 to 75% by weight and in particular from 30 to 70% by weight, in each case based on the weight of the base molding. 17. Detergent tablets according to one of claims 1 to 16, characterized characterized in that the base molding carbonate (s) and / or hydrogen carbonate (s), preferably alkali carbonates, particularly preferably sodium carbonate, in amounts of 5 to 50% by weight, preferably 7.5 to 40% by weight and in particular 10 to 30 % By weight, based in each case on the weight of the base molding. 18. Detergent tablets according to one of claims 1 to 17, characterized characterized in that the base molding silicate (s), preferably alkali silicates, be particularly preferably crystalline or amorphous alkali disilicates, in amounts of 10 to 60 % By weight, preferably from 15 to 50% by weight and in particular from 20 to 40% by weight, each based on the weight of the base molding. 19. Detergent tablets according to one of claims 1 to 18, characterized characterized in that the base molding total surfactant contents below 5 wt.%, preferably below 4% by weight, particularly preferably below 3% by weight and in particular below 2 wt .-%, each based on the weight of the Basic molded body. 20. Detergent tablets according to one of claims 1 to 19, characterized characterized in that the base molding bleach from the group of oxygen or halogen bleaching agents, in particular chlorine bleaching agents, with particular reference  preference for sodium perborate and sodium percarbonate, in amounts from 2 to 25 % By weight, preferably from 5 to 20% by weight and in particular from 10 to 15% by weight, each contains mass based on the weight of the base molding. 21. Detergent or cleaning product tablet according to one of claims 1 to 20, characterized characterized in that the base molding bleach activators from the groups of multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), the N-acylimides, especially N-nonanoylsuccinimide (NOSI), the acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso- NOBS) and n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), in amounts of 0.25 to 15% by weight, preferably from 0.5 to 10% by weight and in particular from 1 to 5 wt .-%, each based on the weight of the base molding, contains. 22. Detergent tablets according to one of claims 1 to 21, characterized characterized in that the base molding silver protection agent from the group of the tria zoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotria zoles and the transition metal salts or complexes, particularly preferably benzotriazole and / or alkylaminotriazole, in amounts of 0.01 to 5% by weight, preferably 0.05 up to 4 wt .-% and in particular from 0.5 to 3 wt .-%, each based on the Ge importance of the base molding. 23. Detergent tablets according to one of claims 1 to 22, characterized characterized in that the base molding continues to be one or more substances from the Groups of enzymes, corrosion inhibitors, scale inhibitors, cobuilders, color and / or fragrances in total amounts from 6 to 30% by weight, preferably from 7.5 to 25 wt .-% and in particular from 10 to 20 wt .-%, each based on the weight of the base molding. 24. Detergent tablets according to one of claims 1 to 23, characterized characterized in that the core molding [part b)] at least one active ingredient from the Group of enzymes, surfactants, soil-release polymers, disintegration aids,  Bleaching agents, bleach activators, bleaching catalysts, silver preservatives and mixtures out of this, contains. 25. Detergent tablets according to one of claims 1 to 24, characterized characterized in that the base molding or inserted into the base molding Core moldings contain bleach, while at least one other part contains bleaching stock vatoren contains. 26. Detergent or cleaning product tablet according to one of claims 1 to 25, characterized characterized in that the base molding or inserted into the base molding Core moldings contain bleach, while at least one other part contains enzymes contains. 27. Detergent tablets according to one of claims 1 to 26, characterized characterized in that the base molding or inserted into the base molding Core moldings contain bleach while at least one other part contains corrosion contains protective agents. 28. Detergent tablets according to one of claims 1 to 27, characterized characterized in that the base molding or inserted into the base molding Core moldings contain bleach, while at least one other part contains surfactants, preferably nonionic surfactants, with particular preference for alkoxylated Al contains alcohols with 10 to 24 carbon atoms and 1 to 5 alkylene oxide units. 29. Detergent tablets according to one of claims 1 to 28, characterized characterized in that the base molding and / or the core molding same Active ingredient contained in different amounts. 30. A process for producing multiphase detergent tablets, characterized by the steps

• a) pressing particulate premixes into shaped articles which have at least one conically shaped cavity,
• b) production of moldings which can be at least partially inserted into the cavity,
• c) inserting the process end products of process step b) into the conical cavity of the process end products of process step a),
• d) optional aftertreatment of the shaped bodies.

31. The method according to claim 30, characterized in that the particulate pre mixtures in step a) a bulk density of at least 500 g / l, preferably at least have at least 600 g / l and in particular at least 700 g / l. 32. The method according to any one of claims 30 or 31, characterized in that the Particulate premixes in step a) particle sizes between 100 and 2000 µm, preferably between 200 and 1800 µm, particularly preferably between 400 and 1600 µm and in particular between 600 and 1400 µm. 33. The method according to any one of claims 30 to 32, characterized in that the pressing in step a) at pressing pressures of 0.01 to 50 kNcm ^-2 , preferably from 0.1 to 40 kNcm ^-2 and in particular from 1 to 25 kNcm ^-2 takes place. 34. The method according to any one of claims 30 to 33, characterized in that in step a) multilayered moldings are produced in a manner known per se by several different particulate premixes are pressed together. 35. The method according to claim 34, characterized in that in step a) two-layer Shaped bodies are made by two different particulate Vorgemi be pressed together, one of which contains one or more bleaches and the other contains one or more enzymes and / or bleach activators. 36. The method according to any one of claims 30 to 35, characterized in that the Shaped body in step b) by casting, extrusion, extrusion or sintering getting produced.   37. The method according to any one of claims 30 to 35, characterized in that the Moldings in step b) are produced by tableting. 38. Combination of (a) detergent tablet (s) according to one of claims 1 to 28 and a packaging system containing the detergent tablet or tablets, characterized in that the packaging system has a moisture vapor permeability rate of 0.1 g / m ² / Day to less than 20 g / m ² / day if the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%. 39. Washing method for washing textiles in a household washing machine, there characterized in that one or more washing or cleaning agents Shaped body according to one of claims 1 to 28 in the washing chamber of the washing machine insert machine and run a washing program, in the course of which the Shaped bodies are washed in. 40. Washing process for washing textiles in a household washing machine, there characterized in that one or more detergents and cleaning agents Shaped body according to one of claims 1 to 28 with or without dosing aid in the Insert the washing drum of the washing machine and run a washing program, in the course of which or the shaped body are dissolved. 41. Cleaning process for cleaning dishes in a dishwasher, because characterized in that one or more detergents and cleaning agents Shaped body according to one of claims 1 to 28 in the dosing chamber of the dishwasher inserted and a rinsing program can run, in the course of which the dosing chamber opens and the molded article (s) are dissolved. 42. Cleaning process for cleaning dishes in a dishwasher, because characterized in that one or more detergents and cleaning agents Shaped body according to one of claims 1 to 28 with or without dosing aid in the rinse  insert the dishwasher and run a washing program, in the course of which the shaped body or bodies are dissolved.