DE19957438A1 - Detergent tablets - Google Patents

Abstract

Particle-shaped ingredients are introduced into the cavity of a pre-moulded shaped body, whereby filling adherence is improved, said ingredients are not subjected to the effects of temperature and the apparatus required to produce said bodies is kept to a minimum.

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 tablet and possibly subsequent pouring over with further 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. About enzymes and enzyme performance is in nothing of this writing.

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 poured in and coated 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.

The present invention was based on the object of providing moldings where temperature-sensitive ingredients are also introduced into defined regions can be, the demarcated region in terms of size in relation to the Overall molded body should not be subject to any restrictions. One should also on the one hand, an optical differentiation from conventional two-layer tablets can be achieved that, on the other hand, should be the production of the molded body without great technical effort also work safely in large series without the moldings having disadvantages in terms of Have stability or inaccuracies in the dosage would be feared.

It has now been found that the disadvantages mentioned are avoided if parti cone-shaped ingredients are pressed into a cavity of a pre-compressed molded body. On this improves the adhesion of the filling, the temperature load of the contents substances excluded and the expenditure on equipment minimized.

The invention relates to detergent tablets comprising

• a) a pressed part (base molding) which has at least one trough, and  
• b) at least one further pressed part, which in said trough (s) of the basic shape body pressed in.

The pressed part a) of the detergent tablets according to the invention is described with the term "base molding" and characterizes in the context of Present invention the manufactured by tabletting processes known per se Shaped body that has a trough. In preferred embodiments of the present According to the invention, the base molding is first produced and the further pressed part in a further step onto or into this base molding. The resulting product is hereinafter referred to as "molded article" or "Ta marked ".

The base molding can take any geometric shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylin drical, spherical, segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, pentagonal, octagonal and octagonal prismatic and rhombohedral shapes are preferred. Also completely irregular base areas like Arrow or animal shapes, trees, clouds, etc. can be realized. Point the base molded body corners and edges, they are preferably rounded. As an additional optical differentiation is an embodiment with rounded corners and abge beveled ("chamfered") edges preferred.

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, five, seven 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 basic shaped bodies, troughs with rounded corners or edges are with rounded corners and chamfered edges preferred. Are particularly preferred Trough shapes as described in the older German patent application DE 198 22 973.9 (Hen kel KGaA), to which express reference is made here.  

The size of the trough in comparison to the entire molded body depends on the ge desired use of the molded body. Depending on whether pressed in the second Part of a smaller or larger amount of active substance should be included The size of the trough varies. Washing and cleaning are independent of the intended use preferred moldings, in which the weight ratio of base moldings for trough filling in the range from 1: 1 to 100: 1, preferably from 2: 1 to 80: 1, particularly is preferably from 3: 1 to 50: 1 and in particular from 4: 1 to 30: 1.

Similar statements can be made about the surface proportions that the basic molding per or make out the trough fill on the entire surface of the molded body. Here Detergent tablets are preferred in which the surface of the pressed-in trough filling 1 to 25%, preferably 2 to 20%, particularly preferably 3 up to 15% and in particular 4 to 10% of the total surface of the filled shaped body matters.

For example, if the overall molded body has dimensions of 20 × 20 × 40 mm and thus a total surface area of 40 cm ² , trough fillings are preferred which have a surface area of 0.4 to 10 cm ² , preferably 0.8 to 8 cm ² , particularly preferred have from 1.2 to 6 cm ² and in particular from 1.6 to 4 cm ² .

The trough filling and the base molding are preferably optically distinguishable colored. In addition to the optical differentiation, there can be application-related advantages who achieved by different solubilities of the different shaped body areas the. Detergent tablets in which the pressed trough fill dissolves faster than the base molding, are preferred according to the invention. By In corporation of certain components can reduce the solubility of the well filling targeted acceleration, on the other hand, the release of certain ingredients the trough filling leads to advantages in the washing or cleaning process. Ingredients, which are preferably located at least partially in the trough filling, for example the disintegration aids, surfactants, enzymes, soil-release  Polymers, builders, bleaches, bleach activators, bleach catalysts, optical Brightener silver protection agent etc.

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 has a density above 1000 gdm ^-3 , preferably above 1025 gdm ^-3 , particularly preferably above 1050 gdm ^-3 and in particular above 1100 gdm ^-3 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 x 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 fine 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 Mi are also suitable  combinations of A, X and / or P. Commercially available and within the scope of the present A co-crystallizate of zeolite X can also preferably be used according to the invention and zeolite A (approx. 80% by weight zeolite X), which is available from CONDEA Augusta S.p.A.

is sold under the brand name VEGOBOND AX® and through the formula

n Na 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 (in particular 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 5 H ₂ O) and 12 mol. Water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to diphosphate Na ₄ P ₂ O ₇ when heated more strongly. 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 39-40% P ₂ O ₅ ) have 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 heats of 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] that crystallizes with 6 H ₂ O. _n -Na with n = 3. In 100 g of water about 17 g dissolve at room temperature, at 20 ° approx. 20 g, at 100 ° around 32 g of the salt free of water; 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 + 2 KOH → 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.

In the context 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 duhte with average molecular weights in the range of 400 to 500000 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 able to oxidize 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 especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol esters 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 58/217598 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 having 6 to 22 carbon atoms, R ¹ for hydrogen, 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 aryl radical with 2 to 8 carbon atoms and R ² for a linear, branched or cyclic alkyl radical or is an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] being 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 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 has total surfactant contents 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 _12-18 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 fraction 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 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 hydroxy 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 98/40163 (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 a gas-developing shower set both in the basic molded body and in the recess filling stem included. The gas-developing shower system can be made from a single substance stand, which releases a gas on contact with water. Among these connections is in particular Special mention should be made of magnesium peroxide, which releases oxygen on contact with water puts. Usually, however, the gas-releasing bubble system itself consists of min at least two components that react with one another to form gas. While here one Many systems are conceivable and executable, for example nitrogen, oxygen or release hydrogen, it will in the washing and cleaning according to the invention Fibrous system used bubble system based on both economic and let choose based on ecological considerations. Preferred shower systems best hen from alkali metal carbonate and / or hydrogen carbonate and an acidification  medium, which is suitable to free carbon dioxide from the alkali metal salts in aqueous solution clog.

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.

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 bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing 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 the peroxy acids, examples of which include the alkyl peroxy acids and the 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 are based on the weight of the base molding.

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 (DADHT), 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) - Co-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.

Detergent tablets, which are characterized in that the base molded body bleach from the group of oxygen or halogen bleach, esp special of 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% by weight, in each case based on the weight of the basic shape body mass, are a preferred embodiment of the invention lying invention.

It is also preferred that the base molding and / or the trough fill be bleached activators included. Detergent tablets, in which the basic form body bleach activators from the groups of multiply acylated alkylenediamines, esp special tetraacetylethylenediamine (TAED), the N-acylimides, especially N- Nonanoyl succinimide (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 of 0.5 to 10 wt .-% and in particular from 1 to 5 wt .-%, each based on the Ge weight of the base molding, are also preferred.

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  Organic and redox-active compounds containing oxygen and nitrogen, 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% by weight, in each case based on the weight of the base molded body.

Of course, the trough filling can also contain silver protection agents, whereby the base molding either also contains or is free of silver protection agents Connections is.

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 help remove 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.

Because the detergent tablets according to the invention can contain the enzyme (s) in two fundamentally different areas, tablets with a very precisely defined enzyme release and action can be provided. The table below gives an overview of possible enzyme distributions 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 the region can be added to the aesthetic Improve impression of the emerging products and the consumer besides the lei a visually and sensorially "typical and unmistakable" product supply. As perfume oils or fragrances, individual fragrance compounds, e.g. B. the synthetic products of the type of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons are used. Fragrance compounds of the ester type are z. B. benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate tat, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, Ethyl methylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsa licylate. The ethers include, for example, benzyl ethyl ether, the aldehydes z. B. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cy clamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones z. B. the Jono ne, α-isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, citronellol, Eu genol, geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons mainly include the terpenes like limes and pinene. However, Wed are preferred uses different fragrances, which together make an appealing Generate fragrance. Such perfume oils can also contain natural fragrance mixtures ten, as they are accessible from plant sources, e.g. B. Pine, Citrus, Jasmine, Pat chouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, Ka millen oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, Vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, Orange peel oil and sandalwood oil.  

The fragrances can be incorporated directly into the washing and cleaning agents according to the invention be worked, but it can also be advantageous to apply the fragrances to carriers conditions that increase the adhesion of the perfume to the laundry and a slower rate Fragrance release ensures long-lasting fragrance of the textiles. As such carrier materials Cyclodextrins have proven themselves, for example, the cyclodextrin perfume Complexes can also be coated with other auxiliaries.

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 turn them on to dye.

The ingredients described above can of course also in the troughs filling are incorporated. Preferred laundry detergents within the scope of the present invention and detergent tablets are characterized in that in the basic form part pressed in at least one active ingredient from the group of enzymes, surfactants, soil-release polymers, disintegration aids, bleaches, bleach activators, bleach contains catalysts, silver protective agents and mixtures thereof.

By dividing the detergent tablets according to the invention into Basic molded body and pressed-in trough filling (s) can contain ingredients from each other be separated, which either incompa to a storage stability-improving separation tibler ingredients or for a controlled release of certain active substances can be used. In preferred detergent tablets, the Base molding or the part of the bleach pressed into the base molding, while the other part contains bleach activators.  

Further preferred detergent tablets are characterized in that that the base molding or the part of the bleach pressed into the base molding contains, while the other part contains enzymes.

Also a separation of bleach and corrosion inhibitors or silver protection agents can be achieved. Detergent tablets in which the basic tablet contains or bleached into the base molded part, during the other partially deformable mass containing anti-corrosion agents are also preferred.

Last but not least, detergent tablets are preferred, in which the Contains the base molding or the part of the bleach pressed into the base molding, while the other part surfactants, preferably nonionic surfactants, especially Preference for alkoxylated alcohols with 10 to 24 carbon atoms and 1 to 5 alkyls lenoxide units.

Particle-shaped assemblies to be pressed particularly preferably into the trough shaped body compositions are those which contain surfactants, it being preferred to include these surfactants in provide release-delayed form to release the pressed-in well filling can only be reached in rinse aid. Rinse aid particles in particular have been used for this lasts as it is in the older German patent application DE 199 14.364.1 (Henkel KGaA) to be discribed. Such particles which are particularly preferably to be pressed into the depression consist of 30 to 90% by weight of one or more carrier materials, 5 to 40% by weight one or more coating substances with a melting point above 30 ° C, 5 to 40 % By weight of one or more active substances and 0 to 10% by weight of further active ingredients and auxiliaries fabrics. Reference is expressly made to the disclosure of this document. Yet the most important ingredients of this "Klar" can be pressed into the trough dishwasher particles "described below. All of the carrier substances a) are included Room temperature solid substances in question. Usually you are made of fabrics choose that have an additional effect in the cleaning process, whereby builders special offer. In preferred particulate rinse aid for the bowl filling are carrier materials from the group of water-soluble washing and cleaning agents agent ingredients, preferably the carbonates, hydrogen carbonates, sulfates, Phos  phate and the solid organic oligocarboxylic acids at room temperature in amounts of 55 to 85% by weight, preferably from 60 to 80% by weight 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, which are preferred in the invention as a trough filling rinse aid particles are used, there are 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 rinse aid particles. Since the rinse aid particles last during transport or storage should be properly protected against environmental influences, the coating substance must be high 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 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, such as 70673 00070 552 001000280000000200012000285917056200040 0002019957438 00004 70554rd, 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 enveloping substances in the rinse aid par to be pressed into the trough Articles are those from the group of polyethylene glycols (PEG) and / or polypropy lenglycole (PPG) contains, with polyethylene glycols with molecular weights between 1500 and 36,000 preferred, those with molecular weights from 2000 to 6000 particularly preferred and sol che with molecular weights of 3000 to 5000 are particularly preferred.

Here, rinse aid particles are particularly preferred which contain propylene glycol (DPG) and / or polyethylene glycol (PEG) as the only coating substance. Polypropylene glycols (abbreviation PPG) which can be used according to the invention 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 coating substance contained in the rinse aid particles according to the invention preferably contains predominantly paraffin wax. That is, at least 50% by weight of the total contained enveloping substances, preferably more, consist of paraffin wax. Especially paraffin wax contents (based on the total coating substance) of approximately 60% by weight are suitable, about 70% by weight or about 80% by weight, with even higher proportions of, for example, more than 90% by weight are particularly preferred. In a special embodiment of the Invention consists entirely of the total amount of coating substance used 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 pressed into the trough contain as the coating 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 rinse aid particles to impacts or rubbing against 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 should be such that the rinse aid 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 particularly advantageous  use if in the main wash cycle at a lower temperature (e.g. 55 ° C) is rinsed so that the active substance from the rinse aid particles only in the rinse aid higher temperatures (approx. 70 ° C) is released.

Preferred rinse aid which can be pressed into the trough according to the invention are preferred 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.

Active substance (s)

Contained in the rinse aid particles to be pressed into the trough according to the invention Active ingredients can be processed at the processing temperature (i.e. the temperature at which the Particles are produced) both in solid and in liquid form.

The active substances contained in the rinse aid 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 rinse aid particles are therefore ingredients of detergents and cleaning agents that are decisive on Washing or cleaning process are involved.

In rinse aid particles which are preferably to be incorporated into the trough are therefore active substances one or more substances from the groups of surfactants, enzymes, bleaching agents, bleaching agents vator, corrosion inhibitors, scale inhibitors, cobuilders and / or fragrances in quantities from 6 to 30% by weight, preferably from 7.5 to 25% by weight and in particular from 10 to 20% by weight. each based on the particle weight.

By incorporating surfactants into the melted shell material, one can Prepare melt suspension or emulsion, which in the finished rinse aid particle or in the finished pressed molded body according to the invention, at a predetermined time  provides additional washing-active substance. For example, on this How to prepare injectable rinse aid particles for machine dishwashing, the the additional surfactant from the shaped body according to the invention only at temperatures release which household dishwashers only reach in the final rinse cycle chen. In this way, additional surfactant is available in the rinse cycle the drainage of the water accelerates and effectively prevents stains on the wash ware different. With a suitable amount of solidified enamel suspension or emulsion in the clar Detergent particles can thus be used when using additional rinse aid that is common today to be dispensed with.

The rinse aid particles that can preferably be pressed into the trough are therefore the one or more Active substance (s) selected from the group of nonionic surfactants, in particular the alkoxylated alcohols. These substances have already been described in detail.

Another class of active substances that are particularly advantageous in the inventions Bleaching agents that can be pressed in according to the invention are bleaching agents. Here particles can be produced and pressed into the trough that the bleach first Release when certain temperatures are reached, for example ready-made products Detergents that clean enzymatically in the pre-wash cycle and only in the main wash cycle release the bleach. There are also cleaning agents for automatic dishwashing len can be produced so that additional bleach is released in the rinse cycle and so difficult stains, such as removing tea stains more effectively.

Therefore, it is / are in particulate rinse aid particles which are preferably pressed into the trough the active substance (s) selected from the group of oxygen or halogen Bleach, especially chlorine bleach. These substances have already been described in detail.

Another class of compounds that are preferred as active substances in the inventions bleached particles can be used in accordance with the invention activators. The important representatives from this group of substances have already been described ben. In the context of the present invention, rinse aid preferably pressed into the trough  ler particles contain bleach activators as active substance, especially from the groups the multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), the N-acylimides, especially N-nonanoylsuccinimide (NOSI), the acylated phenolsul fonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso- NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA).

Another important embodiment of the present invention provides the press fit enzyme-containing rinse aid particles into the well. Such rinse aid particles contain as Active ingredient (s) enzymes, which have been described in detail above. Especially preferred as particulate particles to be pressed into the trough are those the 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 has a melting point above 30 ° C., 0.5 to 60% by weight, preferably as 1 to 40 wt .-%, particularly preferably 2.5 to 30 wt .-% and in particular 5 to 25 % By weight of one or more liquid enzyme dispersed in the coating substance (s) preparation (s) and 0 to 20% by weight, preferably 0 to 15% by weight, especially before adds 0 to 10% by weight and in particular 0 to 5% by weight and optionally further carriers contain materials, auxiliaries and / or active ingredients. The coating substances are preferred here Polyethylene glycols and / or polypropylene glycols, as active substances, have become liquid Proven enzyme preparations. Such liquid enzyme concentrates are either homo uen on a propylene glycol / water basis or heterogeneous as a slurry, or they are in microencapsulated structure. Preferred liquid proteases are e.g. B. Savinase® L, Dura zym® L, Esperase L, and Everlase® from Novo Nordisk, Optimase® L, Purafect® L, Purafect® OX L, Properase® L from Genencor International, and BLAP® L from Bio zym Ges.m.b.H. Preferred amylases are Termamyl® L, Duramyl® L, and BAN® Novo Nordisk, Maxamyl® WL 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 International.

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 pressed into the well enzyme particles are ge indicates that they are one or more liquid amylase preparations and / or one or contain several liquid protease preparations.

Fragrances can also be used as active substances in those to be pressed in according to the invention Incorporate rinse aid particles. All fragrances described in detail above can be used as an active substance. When fragrances are incorporated into The rinse aid particles result in detergents that cover all or part of the Release perfumes with a time delay. In this way, according to the invention, for example Detergents for machine dishwashing can be produced, in which the consumption The perfume note even after cleaning the dishes when opening the machine experienced. In this way, the undesirable "alkaline smell", the many machine Dishwashing detergent adhered to, removed.

Corrosion inhibitors can also be incorporated into the rinse aid particles as an active ingredient, the substances familiar to the person skilled in the art can be used. As Base inhibitor has, for example, a combination of enzyme (e.g. lipase) and Lime soap dispersant proven.

Auxiliaries

At exceptionally low temperatures, for example at temperatures below 0 ° C, the rinse aid particles can be exposed to shock or friction or when pressed into the Break the hollow. To improve stability at such low temperatures, you can additives may be added to the coating substances. Suitable additives must can be completely mixed with the melted wax, may The melting range of the coating substances does not change significantly, the elasticity of the Enhancing the sheathing at low temperatures may increase the permeability of the sheathing compared to water or moisture in general and must not increase the viscosity do not increase the melt of the coating material to such an extent that processing is difficult or becomes impossible at all. Suitable additives that are essentially brittle Paraffin existing wrapping at low temperatures are, for example  EVA copolymers, hydrogenated resin acid methyl ester, polyethylene or copolymers 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 manufacture of the rinse aid particles according to the invention without an excipient The anti-settling agents that can be used for this purpose, who are also known as floating agents those are from the prior art, for example from paint and printing inks position, known. To make the transition from plastic solidification to solid Signs of sedimentation and concentration gradient of the substances to be coated To avoid, there are, for example, surface-active substances in solution dispersed waxes, montmorillonites, organically modified bentonites, (hydrogenated) Castor oil derivatives, soy lecithin, ethyl cellulose, low molecular weight polyamides, metal stea rate, calcium soaps or hydrophobicized silicas. Other substances that the called effects, 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 functional amide polyester 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 (Rotem & 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 auxiliaries mentioned can be used in the rinse aid to be pressed in according to the invention particles depending on the coating material and active substance in varying amounts be set. Usual use concentrations for the anti-settling, Anti-floating, thioxotropic and dispersing agents are in the range from 0.5 to 8.0 % By weight, preferably between 1.0 and 5.0% by weight, and particularly preferably between 1.5 and 3.0 wt .-%, each based on the total amount of coating substance and active fabrics.

In the context of the present invention, particles to be pressed into the depression are preferred shaped rinse aid contains other auxiliary substances from the group of anti-settling agents, Suspending agents, anti - floating agents, thixotropic agents and dispersing agents in Amounts from 0.5 to 9% by weight, preferably between 1 and 7.5% by weight, and particularly preferably between 1.5 and 5% by weight, based in each case 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. Further details on the production of the invention Rinse aid particles follow below.

Under fatty alcohols the native fats or oils are converted to the corresponding ones Understand fatty acids (see below) available alcohols with 6 to 22 carbon atoms. These alcohols can vary depending on the origin of the fat or oil from which they are obtained are substituted or unsaturated in places in the alkyl chain.

The emulsifiers used in the rinse aid _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.  

In preferred rinse aid particles, the emulsifier (s) used are C _6-22 fatty acids, preferably C _8-22 fatty acids and in particular C _12-18 fatty acids, with particular preference given to the C _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, POLYGLYLELEATE-POLYGLYCATEL POLYGLYCERYL-8-OLEATE, POLYGLYCERYL-10-OLEATE, POLYGLYCERYL-6-PENTAOLEATE, POLYG LYCERYL-10-PENTAOLEATE, POLYGLYCERYL-6-PENTASTEARATE, POLYGLYCERYL-10-PENTASTEARATE, POLYGLYCERYL-2-SESQUI IOSOSTEARATE, POLYGLYCERYL-2-SESQUIOLEATE, POLYGLYARYATEURY-2-SESQUIOLEATE -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 particles 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 DIMETHICONE COPOLYOL ACETATE esterified with acetic acid (for example BelsiI® DMC 6032, -33 and -35, Wacker) and the DIMETHICONE COPOLYOL BUTYL ETHERS (eg KF352A, Shin Etsu) are also considered within the scope of the present invention Emulsifiers can be used.

The same applies to the emulsifiers as to the wrapping materials and those to be wrapped Substances that can be used over a wide range. 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 envelope materials and active substances.

In the context of the present invention, particles to be pressed into the depression are preferred Black rinse aids 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.

The part to be pressed into the trough of the base molding can be in the form of a particulate composition put into the trough and there by pressing into a compact Part of the molded body are transferred. These can be particulate Compositions both in terms of their particle size and in terms of their Bulk density and its genesis, d. H. of the process used to manufacture them  to get voted. In particular, therefore, dusts, powders, granules, extrudates, and pressag glomerates, compactates, scales, flakes, etc. are pressed into the cavity as particles be where they form the pressed part b) of the molded body according to the invention.

When using fusible substances as ingredients of the compressed part b) Particulate preparations which are pressed into the trough, also by others Processes are produced, which is preferred in the context of the present invention. For this purpose, in particular, prilling, pastilling or shingling are suitable.

The Ver preferably to be used according to the invention for the production of compressible particles driving, which is briefly referred to as prilling, involves the production of granular bodies meltable substances, with the melt from the respective ingredients at the top a tower is sprayed in a defined droplet size, freezes and freezes the prills at the bottom of the tower accumulate as granules.

In general, all gases can be used as the cold gas stream, the Temperature of the gas is below the melting temperature of the melt. Long time To avoid falling stretches, cooled gases are often used, for example with frozen air or even with liquid nitrogen that is injected into the spray towers.

The grain size of the resulting prills can be varied by the choice of droplet size particle sizes in the range from 0.5 to 2 mm, preferably around 1 mm.

An alternative method of twisting is pastilling. Another execution Form of the present invention therefore sees as a substep a method for producing position of pelletized detergent components, in which you melt on dosed chilled pastilles.

Pastilling involves metering the melt from the respective ingredients a (cooled) belt or rotating, inclined plate that is below the temperature Have melting temperature of the melt and preferably below room temperature  be cooled. Here too, process variants can be carried out in which the pastilles are frozen. However, measures must be taken to prevent this condensing be hit by humidity.

The pastillation provides larger particles, the sizes between technically common processes rule 2 and 10 mm, preferably between 3 and 6 mm.

As an even more economical variant for the production of particulate cleaning agents components of the above-mentioned composition from melts can be used Cooling rollers. Another sub-step of the present invention is therefore a method for the production of particulate detergent components, in which one Applying or spraying the melt onto a chill roll, scraping off the solidified melt and crushed if necessary. The use of chill rolls enables a problem-free Setting the desired particle size range, which is also un can be below 1 mm, for example 200 to 700 µm.

Of course, it is also possible according to the invention to combine the particulates before being pressed into the trough to form a separate "core molding" squeeze. This "core molding" can then be "large, single particle" in the Insert trough and press in. The core molding can be produced so that it can be inserted directly into the trough, but its geometry can also be selected so that the final positive connection with the trough only takes place through the press-in process. In particular when using meltable substances in the molded part b), the manufacturer is development of the shaped bodies according to the invention by separate production (pressing) of a Base molding a) and a core molding b), which is preferably pressed from prills is the joining and the final compression of both parts, preferred. In preferred Embodiments of this process variant are more of the pressed-in molded body phase.

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 and in the base molding injected part contain the same active ingredient in different amounts, are invented preferred according to the invention. As examples of ingredients where the division into Different regions have advantages are disintegration aids, color and Perfumes, optical brighteners, polymers, silver preservatives, tensides and enzymes nen. The term "different amounts" denotes the salary of the individual Shaped body area on the substance in question, based on the shaped body area thus a% by weight statement that does not relate to the absolute amounts of the ingredient pulls.

Preferred detergent and cleaning agent form in the context of the present invention Bodies are characterized in that the moldings are less than 2% by weight, preferably as less than 1.5 wt .-%, particularly preferably less than 1 wt .-% and in particular which contain less than 0.5% by weight of free water. The term "free water" knows records the water content of the agent, which is not in the form of water of hydration and / or Kon tap water is bound. This is in preferred washing and cleaning agents Moldings below 2% by weight, preferably below 1.5% by weight, particularly preferably below 1 wt .-% and in particular even less than 0.5 wt .-%, each based on the combination settlement. Accordingly, water can essentially only in chemical and / or physical Kalisch bound form or as part of the raw materials present as a solid or compounds, but not as a liquid, solution or dispersion in the Invention moderate detergent tablets are included. Advantageously white sen the detergent tablets according to the invention a total of one Water content of not more than 15 wt .-%, so this water is not in liquid ger free form, but is chemically and / or physically bound, and it esp it is particularly preferred that the content of carbonates and / or silicates is not bound whose water in the compositions according to the invention not more than 10% by weight and in particular not more than 7% by weight. In the manufacture of the fiction According to compositions, water-containing liquids can be used, provided that by adding an "internal desiccant", for example a hydratable one  Substance in non-hydrated form, the content of free water under the above Limit is maintained.

The part pressed into the base molding is already through the use of the press pressure bonded in the manufacturing process with the surface of the base molding the. For further stabilization for extreme loads or protection of the Mul to effect the filling against atmospheric influences, a coating on the Trough filling or molded body sides, which carry the trough filling, are applied. Detergent tablets, in which the in the base tablet pressed part is coated with a coating layer are preferred according to the invention. Of course, the entire molded body can also be coated with a coating layer become.

The detergent tablets according to the invention dissolve in the detergent or cleaning cycle completely, whereby - as mentioned above - it can have advantages, if the different regions have different dissolving speeds. Due to the different dissolution rates, in addition to the release certain ingredients at certain times also the properties of the washing or cleaning liquor can be specifically changed. So are for example washing and cleaning Preferred shaped tablets, in which the pH of a 1 wt .-% solution of the base molding in water in the range from 8 to 12, preferably from 9 to 11 and in particular from 9.5 to 10.

In addition to this, detergent tablets are preferred in which the pH of a 1% by weight solution of the entire molded body in water in the range from 7 to 11, preferably from 7.5 to 10 and in particular from 8 to 9.5.

Another object of the present invention is a method for producing detergent tablets characterized by the steps

• a) pressing a particulate premix into a pressed part (base molded body) which has at least one trough,  
• b) filling one or more particulate composition (s) into the be said hollow (s),
• c) Compressing the composition (s) filled in step b) to a width ren pressed part (s), which / in the said trough (s) of the base molding presses present / present and
• d) optional post-treatment of individual molded body surfaces or the entire mold body.

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

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 premix in step a) Bulk density of at least 500 g / l, preferably at least 600 g / l and in particular has 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 premix 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, are preferred according to the invention. Another narrowed particle size In the pre-mixes to be pressed four can be used to obtain advantageous moldings properties can be discontinued. In preferred variants for the Ver driving, the particulate premix pressed in step a) has 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 are. Narrower particle size distributions are further preferred here. Especially Advantageous process variants are characterized in that the step a) pressed particulate premix has a particle size distribution in which  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 hend described cavity in the base molding a trough, so that preferred Ausfüh tion forms of the first method according to the invention are characterized in that in step a) multilayered shaped bodies which have a depression, in a manner known per se Be prepared by making several different particulate premixes be 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 compacted to a solid grain size. 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 the. 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.

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).

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), the mold bodies are made with a powdery composition filled, which is pressed into the molded body in step c). Analogous to the information for Process step a) can also be carried out for the particulate composition (s) specify preferred physical parameters in process step b): processes in which the particulate composition (s) in step b) has a bulk density of at least at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l has / have and methods in which the particulate composition (s) in Step b) particle sizes between 100 and 2000 microns, preferably between 200 and 1800 µm, particularly preferably between 400 and 1600 µm and in particular between 600 and 1400 μm, has / have preferred embodiments of the present the invention.

The pressing force, which acts on the base molding or the trough filling during the pressing in steps a) and b), preferably leads to different surface loads, that is to say pressing pressures. Processes which are characterized in that 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 and process, at to which the pressing in step c) takes place at press pressures of 1 to 100 kNcm ^-2 , preferably 2.5 to 50 kNcm ^-2 and in particular 5 to 25 kNcm ^-2 , are preferred according to the invention.

The compression of the particulate composition into the trough can be carried out analogously to The base moldings are produced on tablet presses. A method is preferred way, in which the basic molded body is first produced with a trough, then filled and then on  then be pressed again. This can be done by ejecting the basic molded body from egg ner first tablet press, filling and transport in a second tablet press hen in which the final pressing takes place. Alternatively, the final compression can also be carried out Pressure rollers that roll over the molded articles on a conveyor belt are successful But it is also possible to use a rotary tablet press with a different stem to provide fur sets, so that a first stamp set indentations in the moldings presses and the second set of stamps after filling by re-pressing for a tarpaulin Molded surface ensures.

The moldings produced according to the invention can, as described above, entirely or partially provided with a coating. Procedures in which the Nachbe act in step d) in the application of a coating layer on the molded body surface (s), in of whom the filled trough (s) are located, or in the application of a coating layer insists on the entire molded body are preferred according to the invention.

The laundry detergent and cleaning product tablets according to the invention can be packaged after manufacture, the use of certain packaging systems having proven particularly useful, since these packaging systems on the one hand increase the storage stability of the contents, but on the other hand surprisingly also significantly improve the long-term liability of the mullet filling. Another object of the present invention is therefore a combination of (a) detergent tablets according to the invention and one or more detergent tablets contain the packaging system, the packaging system having 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 of 0.1 g / m / day to less than 20 g / m ² / day when the packaging system is at 23 ° C. and a relative Equilibrium moisture of 85% is stored. 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 an 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", is 85% at 23 ° C. when measuring the moisture vapor transmission rate within the scope of the present invention. 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 fog (dew). Hygrometers and psy chrometers are used for the quantitative determination of moisture.

The relative equilibrium humidity of 85% at 23 ° C can be found, for example, in La Borehouses with humidity control depending on the device type to ± 2% r. Adjust L. exactly. Even over saturated solutions of certain salts form in closed systems constant and well-defined relative humidity at a given temperature, that on the phase equilibrium between partial pressure of water, saturated solution and soil body are based.

The combinations of detergent tablets and Packaging system can of course in turn in secondary packaging for example, cardboard boxes or trays, are packed, with the secondary packaging no further requirements have to be made. The secondary packaging is that if 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 encloses depending on the design Form of the invention one or more detergent tablets. It is preferred according to the invention either to design a shaped body such that it comprises an application unit of the detergent and cleaning agent, and this form body to be packed individually, or the number of shaped bodies in one packaging unit to pack, which in total comprises an application unit. With a target dosage of According to the invention, 80 g of detergent and cleaning agent is possible to sweat an 80 g to produce and to individually package detergent tablets, it is but also possible according to the invention, two washing and cleaning agents each weighing 40 g Packing the shaped body in a packaging to form a Kombinati according to the invention to get on. This principle can of course be expanded, so that fiction three, four, five or even more detergents and cleaning agents according to combinations can contain molded articles in a packaging unit. Of course, two can  or more moldings in one package have different compositions sen. In this way it is possible to spatially separate certain components separate, for example to avoid stability problems.

The packaging system of the combination according to the invention can differ from the materials and take on any external shape. From economic For reasons of and for reasons of easier processability, however, there are packaging systems Steme preferred, in which the packaging material is light in weight, easily process and is 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, i. H. as loose bulk tion, be filled into a bag made of the materials mentioned. But it is from aesthetic table reasons and for sorting the combinations in secondary packaging moves, the detergent tablets individually or in several sorted in Fill sacks or bags. For individual application units for washing and cleaning molded article, which are in a sack or pouch, has in Tech nik the term "flow pack" naturalized. Such "flow packs" can then - again preferably sorted - optionally packed in outer packaging, what the compact Offer form of the molded body underlines.

The sacks or bags made of one layer, which are preferably to be used as a packaging system Mixed or laminated paper or plastic film can be used in many different ways and be designed, for example as an inflated bag without a central seam or as Bags with central seam, which are caused by heat (hot fusion), adhesives or adhesive tapes which are locked. Single-layer bag or sack materials are the known Papers, which may or may not be impregnated, as well as plastic films, which are opposed can also be co-extruded. Plastic films that are within the scope of the present Er can be used as a packaging system are, for example, in Hans Domininghaus "The plastics and their properties", 3rd edition, VDI Verlag, Düssel  dorf, 1988, page 193. Fig. 111 shown there indicates at the same time breakpoints on the water vapor permeability of the materials mentioned.

Combinations particularly preferred within the scope of the present invention as a packaging system, a sack or bag made of single-layer or laminated art material film with a thickness of 10 to 200 microns, preferably from 20 to 100 microns and esp special from 25 to 50 µm.

Although it is possible, wax-coated in addition to the films or papers mentioned Papers in the form of cardboard boxes as a packaging system for washing and cleaning to use medium shaped bodies, it is preferred in the context of the present invention if the packaging system does not include boxes made of wax-coated paper. The The term “packaging system” in the context of the present invention always the primary packaging of the moldings, d. H. the packaging that is on the inside is in direct contact with the molded body surface. To an optional secondary pack No requirements are made, so that all common materials and Systems can be used.

As already mentioned above, the detergent tablets contain molded articles the combination according to the invention, depending on its intended use, further content fabrics of washing and cleaning agents in varying amounts. Regardless of the ver application of the shaped body, it is preferred according to the invention that the or 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 are determined according to common methods, whereby within the scope of the present The following procedure was chosen for investigations: Liter jar with a lid, which has a closable opening for insertion of samples, was washed with a total of 300 g of detergent tablets pem filled and kept at a constant 23 ° C for 24 h in order to maintain a constant temperature of Ensure vessel and substance. The water vapor pressure in the room over the form  can then use a hygrometer (Hygrotest 6100, Testoterm Ltd., England) be true. The water vapor pressure is now measured every 10 minutes until two successive values show no deviation (equilibrium moisture). The above Hygrometer allows a direct display of the recorded values in% relative humidity action.

Embodiments of the combination according to the invention are also preferred which the packaging system is designed to be resealable. Also combinations, where the packaging system has a microperforation, can be fiction according to implement with preference.

Claims (46)

1. Detergent tablets, comprising

• a) a pressed part (base molding) which has at least one trough, and
• b) at least one further pressed part, which is pressed into said troughs) of the base body.

2. Detergent tablets according to claim 1, characterized in that the weight ratio of the base molding to the trough filling is in the range of 1: 1 to 100: 1, preferably from 2: 1 to 80: 1, particularly preferably from 3: 1 to 50: 1 and is in particular from 4: 1 to 30: 1. 3. Detergent tablets according to one of claims 1 or 2, characterized characterized in that the surface of the pressed-in well filling 1 to 25%, before 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. 4. Detergent tablets according to one of claims 1 to 3, characterized characterized in that the pressed-in trough filling dissolves faster than the base molded body. 5. Detergent tablets according to one of claims 1 to 3, characterized characterized in that the pressed-in trough filling dissolves more slowly than the base molded body. 6. Detergent tablets according to one of claims 1 to 5, characterized in that the base tablet has a density above 1000 gdm ^-3 , preferably above 1025 gdm ^-3 , particularly preferably above 1050 gdm ^-3 and in particular above 1100 gdm ^-3 . 7. Detergent tablets according to one of claims 1 to 6, 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. 8. Detergent tablets according to one of claims 1 to 7, 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. 9. Detergent tablets according to one of claims 1 to 8, 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. 10. Detergent tablets according to one of claims 1 to 9, 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. 11. Detergent tablets according to one of claims 1 to 10, 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. 12. Detergent tablets according to one of claims 1 to 11, 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. 13. Detergent tablets according to one of claims 1 to 12, 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. 14. Detergent tablets according to one of claims 1 to 13, 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. 15. Detergent tablets according to one of claims 1 to 14, 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. 16. Detergent tablets according to one of claims 1 to 15, characterized characterized in that the part pressed into the base molding has at least one Active ingredient from the group of enzymes, surfactants, soil-release polymers, disintegrati  auxiliary agents, bleaching agents, bleach activators, bleaching catalysts, silver protection agents and mixtures thereof. 17. Detergent tablets according to one of claims 1 to 16, characterized characterized in that the base molding or the one pressed into the base molding Part contains bleach, while the other part contains bleach activators. 18. Detergent tablets according to one of claims 1 to 17, characterized characterized in that the base molding or the one pressed into the base molding Part contains bleach, while the other part contains enzymes. 19. Detergent tablets according to one of claims 1 to 18, characterized characterized in that the base molding or the one pressed into the base molding Part contains bleach, while the other part deformable mass contains corrosion contains protective agents. 20. Detergent tablets according to one of claims 1 to 19, characterized characterized in that the base molding or the one pressed into the base molding Part contains bleach, while the other part contains surfactants, preferably nonionic Surfactants, with particular preference for alkoxylated alcohols with 10 to 24 carbons contains atoms and 1 to 5 alkylene oxide units. 21. Detergent tablets according to one of claims 1 to 20, characterized characterized in that the base molding and the one pressed into the base molding Part of the same active ingredient in different amounts. 22. Detergent tablets according to one of claims 1 to 21, characterized in that the particles pressed into the base tablets from

• a) 30 to 90% by weight of one or more carrier materials,
• b) 5 to 40% by weight of one or more coating substances with a melting point above 30 ° C.,
• c) 5 to 40 wt .-% of one or more active substances and
• d) there are 0 to 10% by weight of further active ingredients and auxiliaries.

23. Detergent tablets according to claim 22, characterized in that that as the coating substance paraffin (s) or polyalkylene glycols, especially polyethylene lenglycole are contained in the particles. 24. Detergent tablets according to one of claims 22 or 23, there characterized in that the particles pressed into the base molding as active substances non-ionic surfactant (s) and / or bleaching agents and / or bleach activators and / or contain enzyme (s) and / or corrosion inhibitors and / or fragrances. 25. Detergent tablets according to one of claims 1 to 21, characterized in that the particles pressed into the base tablets from

• 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 coating substance (s), which have 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 substances in the shell / s (en) dispersed liquid enzyme preparation (s) and
• 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, auxiliaries and / or active substances

contain. 26. Detergent tablets according to one of claims 1 to 25, characterized characterized in that the moldings less than 2 wt .-%, preferably less than 1.5% by weight, particularly preferably less than 1% by weight and in particular less than Contain 0.5% by weight of free water.   27. Detergent tablets according to one of claims 1 to 26, characterized characterized in that the part pressed into the base molding with a coating layer is covered. 28. Detergent tablets according to one of claims 1 to 27, characterized characterized in that the pH of a 1 wt .-% solution of the base molding in water in the range from 8 to 12, preferably from 9 to 11 and in particular from 9.5 to 10. 29. Detergent tablets according to one of claims 1 to 28, characterized characterized in that the pH of a 1 wt .-% solution of the entire form body in water in the range of 7 to 11, preferably from 7.5 to 10 and in particular which is from 8 to 9.5. 30. Process for the production of detergent tablets characterized by the steps

• a) pressing a particulate premix into a pressed part (base molding) which has at least one depression,
• b) filling one or more particulate composition (s) into the said well (s),
• c) pressing the composition (s) filled in step b) into (a) further pressed part (s) which is / are present pressed into said depression (s) of the base molding and
• d) optional post-treatment of individual molded body surfaces or the entire molded body.

31. The method according to claim 30, characterized in that the particulate pre mixture in step a) a bulk density of at least 500 g / l, preferably at least 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 premix 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 part Chen-shaped (n) compositions) 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 points / have. 34. The method according to any one of claims 30 to 33, characterized in that the part Chen-shaped (n) compositions) in step b) 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. 35. The method according to any one of claims 30 to 34, characterized in that the pressing in step a) at pressing pressures from 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. 36. The method according to any one of claims 30 to 35, characterized in that the pressing in step c) at pressing pressures from 1 to 100 kNcm ^-2 , preferably from 2.5 to 50 kNcm ^-2 and in particular from 5 to 25 kNcm ^{- 2} is done. 37. The method according to any one of claims 30 to 36, characterized in that the Aftertreatment in step d) in the application of a coating layer to the moldings area (s) in which the filled trough (s) are located. 38. The method according to any one of claims 30 to 37, characterized in that the Post-treatment in step d) in the application of a coating layer on the entire Shaped body consists. 39. 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%. 40. Combination according to claim 39, characterized in that the packaging system has a moisture vapor permeability rate of 0.5 g / m ² / day to less than 15 g / m ² / day. 41. Combination according to one of claims 39 or 40, characterized in that the or the detergent tablets have a relative equilibrium moisture content less than 30% at 35 ° C. 42. Combination according to one of claims 39 to 41, characterized in that the Packing system consisting of a sack or pouch made of single-layer or laminated There is paper and / or plastic film. 43. Combination according to claim 42, characterized in that the packaging system from a sack or bag made of single-layer or laminated plastic film with a Thickness from 10 to 200 μm, preferably from 20 to 100 μm and in particular from 25 up to 50 µm. 44. Combination according to one of claims 39 to 43, characterized in that the Packaging system does not include boxes made of wax-coated paper. 45. Combination according to one of claims 39 to 44, characterized in that the Packaging system is designed to be resealable. 46. Combination according to one of claims 39 to 45, characterized in that the Packaging system has a microperforation.