WO2000077151A1 - Detergent and cleaning agent shaped bodies - 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

 "Detergent tablets"

The present invention relates to detergent tablets, processes for their production and their use.

Detergent tablets are widely described in the prior art and are becoming increasingly popular with consumers because of the simple dosage. Tableted cleaning agents have a number of advantages over powdered products: They are easier to dose and handle and, thanks to their compact structure, have advantages in terms of storage and transport. There is therefore an extremely broad state of the art for detergent tablets, which is also reflected in an extensive patent literature. At an early stage, the developers of tablet-shaped products came up with the idea of releasing certain ingredients through differently composed areas of the molded bodies only under defined conditions in the washing or cleaning cycle, in order to improve cleaning success. In addition to the core / shell tablets and ring / core tablets which are well known from pharmacy, multi-layered shaped articles have become established, which are now offered for many areas of washing and cleaning or hygiene. The optical differentiation of the products is also becoming increasingly important, so that single-phase and single-color moldings in the field of washing and cleaning have largely been replaced by multi-phase moldings. Two-layer moldings with a white and a colored phase or with two differently colored layers are currently customary on the market. In addition, there are point tablets, toroidal 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 toilet block detergents which comprise a molded body of a slowly soluble detergent composition in which a bleach tablet is embedded. At the same time, this document discloses the most varied forms of configuration of multiphase shaped bodies. According to the teaching of this document, the moldings are produced either by inserting a compressed bleach tablet into a mold and pouring the detergent composition into this tablet, or by pouring part of the detergent composition into the mold, followed by inserting the compressed bleach tablet and possibly subsequently pouring over it with another Detergent composition.

EP 481 547 (Unilever) also describes multiphase detergent tablets which are to be used for automatic dishwashing. These shaped bodies are in the form of core / shell tablets and are produced by gradually compressing the constituents: first, a bleaching agent composition is pressed into a shaped body, which is placed in a matrix half-filled with a polymer composition, which is then filled with another polymer composition and into one provided with a polymer jacket is molded lead clime molded body. The process is then repeated with an alkaline detergent composition, so that a three-phase shaped body results. Nothing is said in this document about enzymes and enzyme performance.

Another way of producing optically differentiated detergent tablets is described in international patent applications WO99 / 06522, WO99 / 27063 and WO99 / 27067 (Procter & Gamble). According to the teaching of these documents, a shaped body is provided which has a cavity which is filled with a solidifying melt. Alternatively, a powder is filled in and fixed in the cavity by means of a coating layer. All three applications have in common that the area filling the cavity should not be pressed, since "pressure-sensitive" ingredients are to be protected in this way. The way described in the prior art to prepare melts into which tablets are inserted or which are poured into molded articles involves thermal stressing of the ingredients in the melts. In addition, the exact dosing of liquid to pasty media and the subsequent cooling require a high level of technical effort, which, depending on the composition of the melt, is partially offset by shrinkage during cooling and the resulting detachment of the filling. The filling of cavities with powdered ingredients and the fixation by means of coating is also complex and has similar stability problems.

The conventional tableting of multi-layer tablets also finds its limits in the field of detergent tablets if a layer should only have a small proportion of the total tablet. If the thickness falls below a certain level, pressing a layer adhering to the rest of the molded body is increasingly difficult.

The present invention was based on the object of providing moldings in which temperature-sensitive ingredients can also be introduced into delimited regions, the size of the delimited region being subject to no restrictions with respect to the overall shaped body. On the one hand, an optical differentiation from conventional two-layer tablets should be achieved, on the other hand, the production of the molded articles should work safely without large technical effort, even in large series, without the molded articles having disadvantages in terms of stability or inaccuracies in the dosage.

It has now been found that the disadvantages mentioned are avoided if particulate ingredients are pressed into a cavity of a pre-compressed molded body. In this way, the adhesion of the filling is improved, the temperature load of the ingredients is excluded and the expenditure on equipment is minimized.

The invention relates to detergent tablets, comprising a) a pressed part (base tablet) which has at least one depression, and b) at least one further pressed part, which is pressed into said depression (s) of the base molding.

The pressed part a) of the detergent tablets according to the invention is described by the term “base tablet” and, in the context of the present invention, characterizes the tablet which has a depression and is produced by known tabletting processes. In preferred embodiments of the present invention, the base tablet is first is produced and the further compressed part is applied to or introduced into this basic shaped body in a further working step. The resulting product is referred to below with the generic term “shaped body” or “tablet”.

The base molding can assume any geometric shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, five, seven, and seven octagonal-prismatic and rhombohedral shapes are preferred. Completely irregular base areas such as arrow or animal shapes, trees, clouds, etc. can also be realized. If the base molding has corners and edges, these are preferably rounded. As an additional optical differentiation, an embodiment with rounded corners and beveled (“chamfered”) edges is preferred.

The shape of the trough can also be chosen freely, preference being given to moldings in which at least one trough has a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal , five, seven and octagonal prismatic and rhombohedral shape can take. Completely irregular trough shapes such as arrow or animal shapes, trees, clouds, etc. can also be realized. As with the basic shaped bodies, troughs with rounded corners and edges or with rounded corners and chamfered edges are preferred. Trough shapes as described in the older German patent application DE 198 22 973.9 (Henkel KGaA), to which express reference is made here, are particularly preferred. The size of the trough in comparison to the entire shaped body depends on the intended use of the shaped body. The size of the trough can vary depending on whether a smaller or larger amount of active substance is to be contained in the second pressed part. Regardless of the intended use, detergent tablets are preferred in which the weight ratio of base tablet to trough filling is in the range from 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.

Similar statements can be made about the surface proportions that the basic molded body or the trough filling make up on the overall surface of the molded body. Here, detergent tablets are preferred, in which the surface of the pressed-in trough filling constitutes 1 to 25%, preferably 2 to 20%, particularly preferably 3 to 15% and in particular 4 to 10% of the total surface of the filled mold.

If, for example, the overall shaped body has dimensions of 20 x 20 x 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 preferably of Have 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 colored to be optically distinguishable. In addition to the optical differentiation, application technology advantages can be achieved through different solubilities of the different shaped body regions. Detergent tablets in which the pressed-in trough filling dissolves faster than the base tablet are preferred according to the invention. By incorporating certain constituents, on the one hand the solubility of the trough filling can be accelerated in a targeted manner, on the other hand the release of certain ingredients from the trough filling can lead to advantages in the washing or cleaning process. Ingredients that are preferably at least partially located in the well filling are, for example, the disintegration aids described below, surfactants, enzymes, soil-release polymers, builders, bleaching agents, bleach activators, bleaching catalysts, optical brighteners, silver protection agents, 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 ^" , particularly preferably above 1050 gdm ^" and in particular above 1100 gdm ^" are preferred according to the invention.

Further details on the physical parameters of the base tablet or the finished detergent tablets as well as information on the production can be found below. The preferred ingredients of the base tablet are shown below.

Preferred detergent tablets in the context of the present invention are characterized in that the base tablet in amounts of 1 to 100% by weight, preferably 5 to 95% by weight, particularly preferably 10 to 90% by weight, and contains in particular from 20 to 85% by weight, based in each case on the weight of the base molding.

All of the builders usually used in detergents and cleaning agents can be present in the detergent tablets according to the invention, in particular thus zeolites, silicates, carbonates, organic cobuilders and — where there are no ecological prejudices against their use — also the phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x θ ₂ χ ₊ ι '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 is 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 disilicate Na ₂ Si ₂ θ ₅ 'yH ₂ O are preferred, with β-sodium disilicate being able to be obtained, for example, by the method described in 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 in dissolving 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, compacting / 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 maxi a 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 provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas 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 delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

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

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

nNa ₂ O ^• (ln) 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 granular compound and can also be used for a type of "powdering" of the entire mixture to be compressed, usually using both ways of incorporating the zeolite into the premix. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It is of course also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the detergent and cleaning agent industry.

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

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 like ^"3 , melting point 60 °) and as a monohydrate (density 2.04 like ^{" 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 sodium hydroxide solution 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 ^"3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO) _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 like ^"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 ^"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. Disodium hydrogenphosphate is lost 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 that like a dodecahydrate a density of 1.62 ^"3 and a melting point of 73-76 ° C (decomposition), as a 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 ), a density of 2.536 ^{″ 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 ^"3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction Heating 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), N ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 like ^"3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 like ^{" 3} , melting point 94 ° with loss of water) . When substances are colorless crystals 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 dewatering 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), KP ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^" , which is soluble in water, the pH of the 1% solution being 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 differentiate 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 Oιo (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O - Well with n = 3. Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and 32 g at 100 °; 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 Oιo (potassium tripolyphosphate), for example in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) on the market. 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 hydrolysing sodium trirnetaphosphate with KOH: (NaPO ₃ ) ₃ + 2 KOH - »Na ₃ K ₂ P ₃ O, ₀ + H ₂ O

According to the invention, these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.

Preferred detergent tablets in the context of the present invention are characterized in that the base tablet phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of 20 to 80% by weight .-%, preferably from 25 to 75 wt .-% and in particular from 30 to 70 wt .-%, each based on the weight of the base molding.

Alkali carriers can be present as further constituents. Examples of alkali carriers include alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, the alkali silicates mentioned, alkali metal silicates, and mixtures of the abovementioned substances, the alkali metal carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, preferably being used for the purposes of this invention. A builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred. A builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred.

In particularly preferred detergent tablets, the base tablet contains carbonate (s) and / or hydrogen carbonate (s), preferably alkali metal carbonates, particularly preferably sodium carbonate, in amounts of 5 to 50% by weight, preferably 7.5 to 40% by weight. % and in particular from 10 to 30 wt .-%, each based on the weight of the base molding. Organic cobuilders which can be used in the detergent tablets according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.

Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

The acids themselves can also be used. In addition to their builder effect, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

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

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), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the investigated polymers. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 2,000 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 used either as a powder or as an aqueous solution. The content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

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

Also particularly preferred are biodegradable polymers composed of more than two different monomer units, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers .

Further preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers. Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A-195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from 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, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 owns. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used.

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

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediaminisisuccinate, are further suitable cobuilders. Ethylene diamine N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are 3 to 15% by weight in formulations containing zeolite and / or silicate.

Further usable organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such cobuilders are described, for example, in international patent application WO 95/20029.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, l-hydroxyethane-l, l-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9). Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. 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. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition, all compounds that are able to form complexes with alkaline earth metal ions can be used as cobuilders. The amount of builder is usually between 10 and 70% by weight, preferably between 15 and 60% by weight and in particular between 20 and 50% by weight. Again, the amount of builders used depends on the intended use, so that bleach tablets can have higher amounts of builders (for example between 20 and 70% by weight, preferably between 25 and 65% by weight and in particular between 30 and 55% by weight) ), for example detergent tablets (usually 10 to 50% by weight, preferably 12.5 to 45% by weight and in particular between 17.5 and 37.5% by weight).

Preferred detergent tablets further contain one or more surfactant (s). Anionic, nonionic, cationic and / or amphoteric surfactants or mixtures of these can be used in the detergent and cleaning agent bodies according to the invention. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants for detergent tablets and nonionic surfactants for detergent tablets. The total surfactant content of the tablets in the case of detergent tablets is 5 to 60% by weight, based on the tablet weight, with surfactant contents above 15% by weight being preferred, while detergent tablets for automatic dishwashing are preferably below 5% by weight surfactant (e ) contain.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C9-1 ₃ -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C ₂ -C ₈ monoolefins with an end or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates which are obtained from C ₁ -C ₈ -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable. Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

As alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid semiesters of the Ci ₂ -C ₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁ -C ₂ o-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, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. For reasons of washing technology, the C ₂ -C ₆ alkyl sulfates and C ₂ -C ₅ alkyl sulfates and C ₄ -C ₅ alkyl sulfates are preferred. In addition, 2,3-alkyl sulfates, which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C ethoxylated with 1 to 6 mol of ethylene oxide. ₂ -Alcohols, such as 2 -methyl-branched C _n -alcohols with an average of 3.5 moles of ethylene oxide (EO) or -C ₂ -ι ₈ fatty alcohols with 1 to 4 EO, are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _{8-0 8} fatty alcohol residues or mixtures thereof. Particularly preferred Sul- fosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which are non-ionic surfactants in themselves (see description below). Again, sulfosuccinates whose fatty alcohol residues 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. Saturated fatty acid soaps are suitable, 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. 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 also 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, in particular in the form of the sodium salts.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue is linear or preferably in 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. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₂ to ₄ alcohols with 3 EO or 4 EO, C _{9 to} 4 alcohols with 7 EO, C ₃ to ₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Cι ₂ - 1 ₈ - alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₁₂ - ₁₄ - alcohol with 3 EO and Cι ₂ -ι ₈ 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 can also use fatty alcohols with more than 12 EO. Examples of this are 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, C 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 preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

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

R ^J

R-CO-N- [Z] (I) in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R 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)

R ^ OR ²

R-CO-N- [Z] (II)

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

[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, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst. In the context of the present invention, detergent tablets which contain anionic (s) and nonionic (s) surfactant (s) are preferred as detergent tablets, application-technical advantages being able to result from certain quantitative ratios in which the individual classes of surfactants are used.

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

From an application point of view, it can be advantageous if certain classes of surfactant are present in some phases of the detergent tablets or in the entire tablet, i.e. in all phases, are not included. A further important embodiment of the present invention therefore provides that at least one phase of the shaped body is free from nonionic surfactants.

Conversely, the content of individual phases or the entire molded body, i.e. all phases, certain surfactants have a positive effect. The introduction of the alkyl polyglycosides described above has proven to be advantageous, so that detergent tablets are preferred in which at least one phase of the tablets contains alkyl polyglycosides.

Similar to the non-ionic surfactants, the omission of anionic surfactants from individual or all phases can result in detergent and cleaning agent bodies that are more suitable for certain areas of application. It is therefore also conceivable within the scope of the present invention for detergent tablets in which at least one phase of the tablets is free from anionic surfactants. As already mentioned, the use of surfactants in detergent tablets 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 of 2% by weight, based in each case on the weight of the base molding. Only weakly foaming nonionic surfactants are usually used as surfactants in automatic dishwashing detergents. By contrast, representatives from the groups of anionic, cationic or amphoteric surfactants 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, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, Ci ₂ -ι ₄ alcohols with 3 EO or 4 EO, C ₉ _n alcohol with 7 EO, Cι ₃ .ι ₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Cι ₂ -ι ₈ alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₂ -ι ₄ alcohol containing 3 EO and C for 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 of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. In order to facilitate the disintegration of highly compressed moldings, disintegration aids, so-called tablet disintegrants, can be incorporated into them in order to shorten the disintegration times. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, p. 182-184), tablet disintegrants or accelerators of decay are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in absorbable form.

These substances, which are also referred to as "explosives" due to their effect, increase their volume when water enters, whereby on the one hand the intrinsic volume increases (swelling) and on the other hand a pressure can be generated by the release of gases, which breaks the tablet into smaller particles disintegrates. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural products 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 disintegration auxiliaries, in each case based on the weight of the tablet. If only the basic tablet contains disintegration aids, the information given relates only to the weight of the basic tablet.

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets have such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 contain up to 6 wt .-%. Pure cellulose has the formal empirical composition (C _E H _{S IO} O) ,, and, formally, is a beta-l, 4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approx. 500 to 5000 glucose units and consequently have an average molecular weight of 50,000 up to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used 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 of cellulose derivatives is particularly preferably used as the disintegrant based on cellulose.

The cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be pressed. Detergent tablets which contain disintegrants in granular or optionally cogranulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO98 / 40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants. 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 at least 90% by weight between 400 and 1200 μm. The coarser disintegration aids based on cellulose that are mentioned above and described in more detail in the cited documents are preferably to be used as disintegration aids in the context of the present invention and are commercially available, for example, under the name Arbocel TF-30-HG from the company Rettenmaier. Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged. A subsequent disaggregation of the microfine celluloses resulting from the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 μm and can be compacted, for example, to granules with an average particle size of 200 μm.

Detergent tablets preferred in the context of the present invention additionally contain a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 to 7 % By weight and in particular from 4 to 6% by weight, in each case based on the body weight.

The detergent tablets according to the invention can moreover contain a gas-developing shower system both in the base tablet and in the trough filling. The gas-developing shower system can consist of a single substance that releases a gas when it comes into contact with water. Among these compounds, magnesium peroxide should be mentioned in particular, which releases oxygen on contact with water. Usually, however, the gas-releasing bubble system itself consists of at least two components that react with one another to form gas. While a large number of systems are conceivable and executable here, which release nitrogen, oxygen or hydrogen, for example, the bubble system used in the detergent tablets according to the invention can be selected on the basis of both economic and ecological aspects. Preferred effervescent systems consist of alkali metal carbonate and / or hydrogen carbonate and an acidifying agent which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution. In the case of the alkali metal carbonates or bicarbonates, the sodium and potassium salts are clearly preferred over the other salts for reasons of cost. Of course, the pure alkali metal carbonates or bicarbonates in question do not have to be used; rather, mixtures of different carbonates and bicarbonates may be preferred for reasons of washing technology.

Preferred detergent tablets are 2 to 20% 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, as the effervescent system and in particular 3 to 10% by weight of an acidifying agent, based in each case on the entire molded body.

Acidifying agents which release carbon dioxide from the alkali salts in aqueous solution are, for example, boric acid and alkali metal bisulfates, alkali metal dihydrogen phosphates and other inorganic salts. However, organic acidifying agents are preferably used, citric acid being a particularly preferred acidifying agent. However, the other solid mono-, oligo- and polycarboxylic acids can also be used in particular. Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are preferred from this group. Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight).

In the context of the present invention, preference is given to shaped tablets and detergents in which a substance from the group of the organic di-, tri- and oligocarboxylic acids or mixtures thereof are used as acidifying agents in the effervescent system.

In addition to the constituents mentioned, builder, surfactant and disintegration aid, the detergent tablets according to the invention can be used in detergents. and cleaning agents contain usual ingredients from the group of bleaching agents, bleach activators, dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, anti-redeposition agents, graying inhibitors, color transfer inhibitors and corrosion inhibitors.

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. Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, 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 bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxyacids, examples of which include alkylperoxyacids and arylperoxyacids. Preferred representatives are (a) the 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-phthalimoxy acid phthalimidoxanoic oxoacid (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, diperocyseboxyacidoxy acid, diperoxic acid, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Substances which release chlorine or bromine can also be used as bleaching agents in the detergent tablets according to the invention for machine dishwashing. Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric 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 bleaching agents are usually used in machine dishwashing detergents in amounts of 1 to 30% by weight, preferably 2.5 to 20% by weight and in particular 5 to 15% by weight, based in each case on the detergent. In the context of the present invention, the proportions mentioned relate to the weight of the base molding.

Bleach activators that support the action of the bleaching agents can also be part of the base molding. Known bleach activators are compounds which contain one or more N- or O-acyl groups, such as substances from the class of anhydrides, esters, imides and acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, l, 5-diacetyl-2,2-dioxo-hexa- hydro-l, 3,5-triazine DADHT and isatoic anhydride ISA.

Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetyloxy, 2,5-acetiacetyl, ethylene glycol 2,5-dihydrofuran, n-methyl-Moφholinium acetonitrile-methyl sulfate (MMA), and the enol esters known from German patent applications DE 196 16 693 and DE 196 16 767 as well as acetylated sorbitol and mannitol or their mixtures (SORMAN), acylated sugar derivatives , in particular pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose as well as acetylated, optionally N-alkylated glu camin and gluconolactone, and / or N-acylated lactams, for example N- Benzoylcaprolactam. Hydrophilically substituted acylacetals and acyllactams are also preferably used. Combinations of conventional bleach activators can also be used. The bleach activators are usually used in machine dishwashing detergents in amounts of 0.1 to 20% by weight, preferably 0.25 to 15% by weight and in particular 1 to 10% by weight, based in each case on the detergent. In the context of the present invention, the proportions mentioned relate to the weight of the base molding.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be incorporated into the rinse aid articles. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.

Bleach activators from the group of multiply acylated alkylenediamines, in particular tetraacetylethylene diamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (N-) or iso-NOBs iso , n-Methyl-Moφholinium-Acetonitril-Methylsulfat (MMA), preferably in amounts up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, particularly 2 to 8 wt .-% and particularly preferred 2 to 6 wt .-% based on the total agent used.

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

Detergent tablets, which are characterized in that the base molding bleach from the group of oxygen or halogen bleaches, in particular chlorine bleaches, with particular preference for sodium perborate and sodium percarbonate, in amounts of 2 to 25% by weight, preferably from 5 to 20% by weight and in particular from 10 to 15% by weight, based in each case on the weight of the basic molded article, are an embodiment of the present invention which is preferred according to the invention.

It is also preferred that the basic molded body and / or the trough fill contain bleach activators. Detergent and shaped body, in which the basic shaped body bleach activators from the groups of polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoloyloxy or isononoloyloxy (isobenzene) - or iso-NOBS) and n-methyl-Moφholinium-acetonitrile-methyl sulfate (MMA), in amounts of 0.25 to 15 wt .-%, preferably from 0.5 to 10 wt .-% and in particular from 1 to 5 wt .-%, each based on the weight of the Basisformköφers, are also preferred.

The detergent tablets according to the invention can contain corrosion inhibitors, in particular in the base tablet to protect the items to be washed or the machine, silver protection agents in particular being particularly important in the area of automatic dishwashing. The known substances of the prior art can be used. In general, silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Benzotriazole and or alkylaminotriazole are particularly preferably to be used. In addition, active chlorine-containing agents are often found in cleaner formulations, which can significantly reduce the corroding of the silver surface. In chlorine-free cleaners, especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, 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 selected from the group consisting of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can also be used to prevent corrosion on the wash ware.

In preferred detergent tablets in the context of the present invention, the base tablet contains silver protective 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 wt .-%, preferably from 0.05 to 4 wt .-% and in particular from 0.5 to 3 wt .-%, each based on the weight of the basic molded body.

Of course, the trough filling can also contain silver protection agents, the basic molded body either also containing silver protection agents or being free of such compounds.

In addition to the ingredients mentioned above, there are other classes of substances for incohering in detergents and cleaning agents. Thus, detergent tablets are preferred, in which the base tablet further comprises one or more substances from the groups of enzymes, corrosion inhibitors, scale inhibitors, cobuilders, dyes and / or fragrances in total amounts of 6 to 30% by weight, preferably 7 5 to 25 wt .-% and in particular from 10 to 20 wt .-%, each based on the weight of the basic molded body, contains.

Enzymes in the basic shaped bodies are in particular those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases help remove stains such as protein, fat or starch. stains. Oxidoreductases can also be used for bleaching. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Sfreptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Here are enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytically active enzymes or of protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes, but especially protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases.

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

Because the detergent tablets according to the invention can contain the enzyme (s) in two fundamentally different areas, tablets with 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 added to the machine dishwashing detergents according to the invention both in the basic molded article and in the region in order to improve the aesthetic impression of the resulting products and to provide the consumer with a visually and sensorially "typical and distinctive" product. Individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl benzylatepylpropionate, stylate propylate, stylate propionate. The ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, and the ketones include, for example, the ionone, α-isomethyl ionone and methyl cedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and teφineol, the hydrocarbons mainly include teφenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil. The fragrances can be incorporated directly into the detergents and cleaning agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.

In order to improve the aesthetic impression of the agents according to the invention, it (or parts thereof) can be colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity to the substrates to be treated with the compositions, such as textiles, glass, ceramics or plastic tableware, not to mention these stain.

The ingredients described above can of course also be incorporated into the cavity filling. Preferred detergent tablets in the context of the present invention are characterized in that the part pressed into the base tablet comprises at least one active ingredient from the group of enzymes, surfactants, soil-release polymers, disintegration aids, bleaching agents, bleach activators, bleaching catalysts, silver preservatives and mixtures thereof , contains.

By dividing the detergent tablets according to the invention into basic tablets and pressed-in trough filling (s), ingredients can be separated from one another, which can either be used to separate incompatible ingredients to improve storage stability or to control the release of certain active substances. In preferred detergent tablets, the base tablet or the part pressed into the base tablet contains bleach, while the other part contains bleach activators. Further preferred washing and cleaning agent shaped bodies are characterized in that the basic shaped body or the part pressed into the basic shaped body contains bleach, while the other part contains enzymes.

A separation of bleach and corrosion inhibitors or silver protection agents can also be achieved. Detergent moldings, in which the base molding or the part pressed into the base molding contains bleach, while the other part contains deformable masses of anti-corrosion agents, are also preferred.

Last but not least, detergent tablets are also preferred, in which the base tablet or the part pressed into the base tablet contains bleach, while the other part contains surfactants, preferably nonionic surfactants, with particular preference to alkoxylated alcohols with 10 to 24 carbon atoms and 1 to 5 alkyl lenoxide units.

Particulate compositions to be pressed into the mold body are particularly preferably those which contain surfactants, it being preferred to provide these surfactants in a solution-delayed form in order to release the pressed-in mold filling only in the rinse cycle. Rinse aid articles such as are described in the older German patent application DE 199 14.364.1 (Henkel KGaA) have proven particularly useful for this purpose. Such particularly preferred particles to be pressed into the trough consist of 30 to 90% by weight of one or more carrier materials, 5 to 40% by weight of one or more coating substances with a melting point above 30 ° C., 5 to 40% by weight of one or several active substances and 0 to 10% by weight of further active substances and auxiliaries. Reference is expressly made to the disclosure of this document. Nevertheless, the most important ingredients of these "rinse aid articles", which can preferably be pressed into the trough, are described below. Carriers a) are all substances which are solid at room temperature. Usually, substances will be selected which have an additional effect in the cleaning cycle, with builders developing In preferred particulate rinse aids for the trough filling, substances from the group of water-soluble detergent and cleaning agent ingredients, preferably carbonates, bicarbonates, sulfates, phosphates, are used as carrier materials. phate and the solid at room temperature organic oligocarboxylic acids in amounts of 55 to 85 wt .-%, preferably from 60 to 80 wt .-% and in particular from 65 to 75 wt .-%, each based on the particle weight.

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

Various requirements are imposed on the coating substances that are used in the rinse aid particles preferably used according to the invention as a bowl filling, on the one hand the melting or solidification behavior, on the other hand also the material properties of the coating in the solidified state, i.e. in the rinse aid article. Since the rinse aid articles are to be permanently protected against environmental influences during transport or storage, the coating substance must have a high stability against, for example, shock loads occurring during packaging or transport. The coating substance should therefore either have at least partially elastic or at least plastic properties in order to react to an impact load caused by elastic or plastic deformation and not to break. The coating substance should have a melting range (solidification range) in such a temperature range in which the active substances to be coated are not exposed to excessive thermal stress. On the other hand, however, the melting range must be sufficiently high to still provide effective protection for the enclosed active substances at at least a slightly elevated temperature. According to the invention, the coating substances have a melting point above 30 ° C.

It has proven to be advantageous if the coating substance does not have a sharply defined melting point, as usually occurs with pure, crystalline substances, but instead has a melting range that may include several degrees Celsius.

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

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

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

Natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, japan 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, walnut, lanolin (wool wax), or broom wax, mineral wax or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes.

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

Synthetic waxes are generally understood to mean polyalkylene waxes or polyalkylene glycol waxes. Compounds from other fabric classes that meet the requirements regarding the softening point can also be used as covering materials. As suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl, which is commercially available under the name Unimoll 66 ^® (Bayer AG), proved. Are also suitable Synthetic waxes of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ^® ETLP (Condea). Conversely, synthetic or partially synthetic esters from lower alcohols with fatty acids from native sources can also be used. Tegin ^® 90 (Goldschmidt), for example, falls into this class of substances Glycerol monostearate palmitate. Shellac, for example Shellac-KPS-Dreiring-SP (Kalkhoff GmbH), can also be used as a coating material according to the invention.

The so-called wax alcohols are also included in the waxes in the context of the present invention, for example. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols with usually about 22 to 40 carbon atoms. The wax alcohols occur, for example, in the form of wax esters of higher molecular fatty acids (wax acids) as the main component of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The coating of the present invention the solid particles coated can optionally also contain wool wax alcohols which are understood to Triteφenoid- and steroid alcohols, for example lanolin understood, which is obtainable for example under the trade name Argowax ^® (Pamentier & Co). In the context of the present invention, fatty acid glycerol esters or fatty acid alkanolamides can also be used, at least in part, as a constituent of the casing, but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds.

Particularly preferred enveloping substances in the rinse aid articles to be pressed into the well are those from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG), polyethylene glycols with molecular weights between 1500 and 36,000 being preferred, those with molecular weights from 2000 to 6000 particularly preferred and those with molecular weights of 3000 to 5000 are particularly preferred.

Here, rinse aid articles are particularly preferred which contain propylene glycols (PPG) and / or polyethylene glycols (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

CH ₃ are sufficient, where n can take values between 10 and 2000. Preferred PPGs have molar masses between 1000 and 10,000, corresponding to values of n between 17 and approximately 170.

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 preferred molecular weight ranges mentioned above correspond to preferred ranges of the value n in formula IV from approximately 30 to approximately 820 (exactly: from 34 to 818), particularly preferably from approximately 40 to approximately 150 (precisely: from 45 to 136) and in particular from about 70 to about 120 (exactly: from 68 to 113).

Preferably, the coating substance contained in the rinse aid articles according to the invention contains paraffin wax in the majority. This means that at least 50% by weight of the total contained substances, preferably more, consist of paraffin wax. Paraffin wax contents (based on the total coating substance) of approximately 60% by weight, approximately 70% by weight or approximately 80% by weight are particularly suitable, with even higher proportions of, for example, more than 90% by weight being particularly preferred. In a special embodiment of the invention, the total amount of the coating substance used consists exclusively of paraffin wax.

Paraffin waxes have the advantage over the other natural waxes mentioned in the context of the present invention that there is no hydrolysis of the waxes in an alkaline detergent environment (as is to be expected, for example, from the wax esters), since paraffin wax contains no hydrolyzable groups.

Paraffin waxes consist mainly of alkanes and 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. Portions of high-melting alkanes in the paraffin can leave undesired wax residues on the surfaces to be cleaned or the goods to be cleaned if the melting temperature in the detergent solution drops below this. Such wax residues usually lead to an unsightly appearance on the cleaned surface and should therefore be avoided.

Particulate rinse aid which can preferably be pressed into the trough contain at least one paraffin wax with a melting range of 50 ° C. to 60 ° C. as the coating substance.

Preferably, the paraffin wax content of alkanes, isoalkanes and cycloalkanes which are solid at ambient temperature (generally about 10 to about 30 ° C.) is as high as possible. The more solid wax components present in a wax at room temperature, the more useful it is within the scope of the present invention. With an increasing proportion of solid wax components, the resilience of the rinse aid articles to impacts or friction on other surfaces increases, which leads to a longer-lasting protection of the particles of active substances. High levels of oils or liquid wax components can weaken the particles, opening pores and exposing the active substances to the environmental influences mentioned at the beginning.

In addition to paraffin, the coating substance can also contain one or more of the above-mentioned waxes or wax-like substances as the main constituent. In principle, the mixture forming the coating substance should be such that the rinse aid articles are at least largely water-insoluble. The solubility in water should not exceed about 10 mg / 1 at a temperature of about 30 ° C. and should preferably be below 5 mg / 1.

In any case, however, the coating should have the lowest possible solubility in water, even in water at an elevated temperature, in order to avoid as far as possible a temperature-independent release of the active substances.

The principle described above serves to delay the release of ingredients at a certain point in the cleaning cycle and can be used particularly advantageously Use when rinsing in the main rinse cycle at a lower temperature (e.g. 55 ° C) so that the active substance from the rinse aid particles is only released in the rinse cycle at higher temperatures (approx. 70 ° C).

Preferred particulate rinse aid which can be pressed into the trough according to the invention are characterized in that they contain one or more substances with a melting range of 40 ° C to 75 ° C in amounts of 6 to 30% by weight, preferably 7.5 to 25% by weight .-% and in particular from 10 to 20 wt .-%, each based on the particle weight.

Active substance (s):

The active substances contained in the rinse aid particles to be pressed into the trough according to the invention can be present both in solid and in liquid form at the processing temperature (i.e. at the temperature at which the particles are produced).

The active substances contained in the rinse aid articles fulfill certain tasks. The cleaning performance can be improved by separating certain substances or by accelerating or delaying the release of additional substances. Active ingredients, which are preferably incorporated into the rinse aid articles, are therefore those ingredients of detergents and cleaning agents that are crucially involved in the washing or cleaning process.

One or more substances from the groups of surfactants, enzymes, bleaching agents, bleach activators, corrosion inhibitors, scale inhibitors, cobuilders and / or fragrances in amounts of 6 to 30% by weight, preferably 7, are therefore present as active substances in the rinse aid articles to be preferably incorporated in the bowl , 5 to 25 wt .-% and in particular from 10 to 20 wt .-%, each based on the particle weight.

By incorporating surfactants into the melted shell material, a melt suspension or emulsion can be produced, which can be produced in the finished rinse aid article or in the molded body according to the invention at a predetermined time. provides additional washing-active substance. For example, press-in rinse aid articles for machine dishwashing can be produced in this way, which release the additional surfactant from the molded article according to the invention only at temperatures which household dishwashers only reach in the rinse cycle. In this way, additional surfactant is available in the rinse cycle, which accelerates the drainage of the water and thus effectively prevents stains on the wash ware. With a suitable amount of solidified melt suspension or emulsion in the rinse aid articles, the use of additional rinse aid customary today can be dispensed with.

In rinse aid articles which can preferably be pressed into the trough, the active substance (s) is / are selected from the group of nonionic surfactants, in particular alkoxylated alcohols. These substances have already been described in detail.

Another class of active substances which can be incorporated with particular advantage into the rinse aid articles which can be pressed in according to the invention are bleaching agents. Particles can be produced and pressed into the trough, which only release the bleaching agent when certain temperatures are reached, for example ready-made cleaning agents that clean enzymatically in the pre-rinse cycle and only release the bleaching agent in the main rinse cycle. Cleaning agents for automatic dishwashing can also be produced in such a way that additional bleaching agents are released in the rinse cycle and are more effective in removing difficult stains, for example tea stains.

In particle-shaped rinse aid articles which are preferably pressed into the trough, the active substance (s) is / are selected from the group of oxygen or halogen bleaching agents, in particular chlorine bleaching agents. These substances have also been described in detail.

Another class of compounds which can preferably be used as active substances in the rinse aid particles pressed in according to the invention are the bleach activators. The important representatives from this group of substances have already been described. In the context of the present invention, rinse aid preferably pressed into the trough Leφartikel contain bleach activators as active substance, especially from the groups of polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxy-n-benzolsulfon iso-NOBS), n-methyl-Moφholinium acetonitrile-methyl sulfate (MMA).

Another important embodiment of the present invention provides for the pressing of enzyme-containing rinse aid articles into the trough. Such rinse aid articles contain as active substance (s) enzymes, which have been described in detail above. Particularly preferred as particulate particles to be pressed into the trough are those which contain 40 to 99.5% by weight, preferably 50 to 97.5% by weight, particularly preferably 60 to 95% by weight and in particular 70 to 90 % By weight of one or more coating substance (s) which have a melting point above 30 ° C., 0.5 to 60% by weight, preferably 1 to 40% by weight, particularly preferably 2.5 to 30 % By weight and in particular 5 to 25% by weight of one or more liquid enzyme preparation (s) dispersed in the coating substance (s) and 0 to 20% by weight, preferably 0 to 15% by weight, particularly preferably 0 to 10 wt .-% and in particular 0 to 5 wt .-% and optionally contain other carrier materials, auxiliaries and / or active ingredients. The coating substances are preferably polyethylene glycols and / or polypropylene glycols, and liquid enzyme preparations have proven themselves as active substances. Such liquid enzyme concentrates are either based homogeneously on a propylene glycol / water basis or heterogeneously as a slurry, or are present in a microencapsulated structure. Preferred liquid proteases are Savinase ^® L, Dura-zyme ^® L, Esperase ^® L, and Everlase® ^® from. Novo Nordisk, Optimase.RTM L, Purafect L, Purafect ^® OX L, Properase.RTM ^® L from. Genencor International, and BLAP ^® L from Biozym Ges.mbH. Preferred amylases are Termamyl ^® L, Duramyl ^® L, and BAN ^® from. Novo Nordisk, Maxamyl ^® WL and Purafect ^® HP On 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, products such as the products from Novo Nordisk labeled SL or LCC can be used, for example. The commercial liquid enzyme preparations mentioned contain, for example, 20 to 90% by weight. Propylene glycol or mixtures of propylene glycol and water. In the context of the present invention, enzyme particles which can preferably be pressed into the well are characterized in that they contain one or more liquid amylase preparations and / or one or more liquid protease preparations.

As active substances, fragrances can also be incorporated into the rinse aid articles to be pressed in according to the invention. All fragrances described in detail above can be used as an active substance. The incorporation of fragrances into the rinse aid articles results in cleaning agents which release all or part of the perfume with a time delay. In this way, for example, cleaning agents for machine dishwashing can be produced according to the invention, in which the consumer experiences the perfume note even after the dishes have been cleaned when the machine is opened. In this way, the undesirable "alkaline smell" that is inherent in many automatic dishwashing detergents can be eliminated.

Corrosion inhibitors can also be introduced into the rinse aid as an active substance, it being possible to use the substances familiar to the person skilled in the art. A combination of an enzyme (e.g. lipase) and lime soap dispersant has proven itself as a coating inhibitor.

Excipients:

At exceptionally low temperatures, for example at temperatures below 0 ° C, the rinse aid article can break under impact or friction or when pressed into the bowl. In order to improve the stability at such low temperatures, additives can optionally be added to the coating substances. Suitable additives must be able to be mixed completely with the molten wax, must not significantly change the melting range of the coating substances, must improve the elasticity of the coating at low temperatures, must not generally increase the permeability of the coating to water or moisture and must not increase the viscosity of the melt Do not increase the wrapping material to such an extent that processing becomes difficult or even impossible. Examples of suitable additives are those which reduce the brittleness of an envelope consisting essentially of paraffin at low temperatures EVA copolymers, hydrogenated resin acid methyl ester, polyethylene or copolymers of ethyl acrylate and 2-ethylhexyl acrylate.

Another useful additive when using paraffin as a coating is the addition of a small amount of a surfactant, for example a Cπ-is 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 may also be advantageous to add further additives to the coating substance, for example to prevent the active substances from settling prematurely. This is particularly advisable when producing the rinse aid articles according to the invention without carriers. The anti-settling agents that can be used for this purpose, which are also referred to as floating agents, are known from the prior art, for example from the manufacture of lacquers and printing inks. In order to avoid sedimentation phenomena and concentration gradients of the substances to be coated during the transition from the plastic solidification area to the solid, there are, for example, surface-active substances, waxes dispersed in solvents, montmorillonites, organically modified bentonites, (hydrogenated) castor oil derivatives, soy lecithin, ethyl cellulose, low molecular weight polyamides, metal steal , Calcium soaps or hydrophobized silicas. Other substances which bring about the effects mentioned come from the groups of anti-floating agents and thixotropic agents and can be chemically used as silicone oils (dimethylpolysiloxanes, methylphenylpolysiloxanes, polyether-modified methylalkylpolysiloxanes), oligomeric titanates and silanes, polyamines, salts from long-chain polyamines and polycarboxylic acids, Amine / amide functional polyesters or amine / amide functional polyacrylates.

Additives from the substance classes mentioned are commercially available in a wide variety. Commercial products that are advantageous in the context of the method according to the invention Aerosil ^® 200 (pyrogenic silicic acid, Degussa), Bentone ^® SD-1, SD-2, 34, 52 and 57 (bentonite, Rheox), Bentone ^® SD-3, 27 and 38 are examples of additives that can be added (Hectorite, Rheox), Tixogel ^® EZ 100 or VP-A (organically modified smectite, Südchemie), Tixogel ^® VG, VP and VZ (montmorillonite, Südchemie loaded with QAV), Disperbyk ^® 161 (block copolymer, Byk-Chemie) , Borchigen ^® ND (sulfo group-free ion exchanger, Borchers), Ser-Ad ^® FA 601 (servo), Solsperse ^® (aromatic ethoxylate, ICI), Surfynol ^® types (Air Products), Tamol ^® and Triton ^® types ( Rohm & Haas), Texaphor ^® 963, 3241 and 3250 (polymers, Henkel), Rilanit ^® types (Henkel), Thixcin ^® 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 MPA ^® types X, 60-X, 1078-X, 2000-X and 60-MS (or ganic compounds, Rheox).

The auxiliaries mentioned can be used in varying amounts in the rinse aid particles to be pressed in according to the invention, depending on the coating material and active substance. Usual use concentrations for the abovementioned 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% by weight, based in each case on the total amount of coating substance and active substances.

In the context of the present invention, particulate rinse aid preferably to be pressed into the well contain further auxiliaries from the group of anti-settling agents, floating agents, anti-floating agents, thixotropic agents and dispersing agents in amounts of 0.5 to 9% by weight, preferably between 1 and 7.5% by weight. -%, and particularly preferably between 1.5 and 5 wt .-%, each based on the particle weight.

The use of special emulsifiers is particularly advantageous in the production of melt suspensions or emulsions which contain active substances which are liquid at the processing temperature. 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 manufacture of the rinse aid articles according to the invention follow below.

Fatty alcohols are understood to mean the alcohols with 6 to 22 carbon atoms obtainable from native fats or oils via the corresponding fatty acids (see below). Depending on the origin of the fat or oil from which they are obtained, these alcohols can be substituted in the alkyl chain or partially unsaturated.

C _{6 are} therefore preferred as emulsifiers in the rinse aid articles according to the invention. ₂₂ fatty alcohols, preferably C _8-22 fatty alcohols and especially C ₂ -ι ₈ fatty alcohols, with particular preference for the C] ₆ .i ₈ fatty alcohols, are used.

All fatty acids obtained from vegetable or animal oils and fats can also be used as emulsifiers. The fatty acids can be saturated or mono- to polyunsaturated regardless of their physical state. In the case of unsaturated fatty acids too, the species which are solid at room temperature are preferred over the liquid or pasty ones. Of course, not only "pure" fatty acids can be used, but also the technical fatty acid mixtures obtained from the cleavage of fats and oils, these mixtures again being clearly preferred from an economic point of view.

For example, individual species or mixtures of the following acids can be used as emulsifiers in the context of the present invention: caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, octadecan-12-oleic acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid , 10- undecenoic acid, petroselinic acid, petroselaidic acid, oleic acid, elaidic acid, ricinoleic acid, linolaidic acid, α- and ß-eläosterainic acid, gadoleic acid, erucic acid, brassidic acid. Of course, it is also possible to use the fatty acids with an odd number of carbon atoms, for example undecanoic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, nonadecanoic acid, heneicosanoic acid, tricosanoic acid, pentacosanoic acid, heptacosanoic acid. In preferred Klarspüleφartikeln be as emulsifier (s) - ₂₂ fatty acids, preferably C ₈ - ₂₂ fatty acids and, in particular Ci2-ι ₈ fatty acids, with particular preference for the C ₁₆ - ₁₈ - fatty acids, are used.

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.

R ¹

HO- [CH ₂ -CH-CH ₂ -O] _n -H (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-DECAOLEERYL ARYGLYE POLY- GLYCERYL-2-DIISOSTEARATE, POLYGLYCERYL-3-DIISOSTEARATE, POLY- GLYCERYL-10-DIISOSTEARATE, POLYGLYCERYL-2-DIOLEATE, POLY-

GLYCERYL-3-DIOLEATE, POLYGLYCERYL-6-DIOLEATE, POLYGLYCERYL-10- DIOLEATE, POLYGLYCERYL-3-DISTEARATE, POLYGLYCERYL-6-

DISTEARATE, POLYGLYCERYL-10-DISTEARATE, POLYGLYCERYL-10-

HEPTAOLEATE, POLY-GYLCERYL-12-HYDROXYSTEARATE, POLYGLYCERYL- 10-HEPTASTEARATE, POLYGLYCERYL-6-HEXAOLEATE, POLYGLYCERYL-2- ISOSTEARATE, POLY-GLYCERYL-4-ISOSTEARATE, POLY-GLYCERYL-6 ISOSTEARATE, POLY-GLYCERYL-10-LAURATE, POLY-

LYCERYLMETHACRYLATE, POLYGLYCERYL- 10-MYRISTATE,

POLYGLYCERYL-2-OLEATE, POLYGLYCERYL-3-OLEATE, POLYGL YCERYL-4-OLEATE, POLYGLYCERYL-6-OLEATE, POLYGLYCERYL-8-OLEATE,

POLYGLYCERYL- 10-OLE ATE, POL YGL YCERYL-6-PENTAOLEATE,

POLYGLYCERYL- 10-PENTAOLE ATE, POLYGL YCERYL-6-PENT ASTE ARATE, POLYGLYCERYL- 10-PENTASTEARATE, POLYGLYCERYL-2-SESQUI-

IOSOSTEARATE, POLYGLYCERYL-2-SESQUIOLEATE, POLYGLYCERYL-2 STEARATE, POLYGLYCERYL-3-STEARATE, POLYGLYCERYL-4-STEARATE, POLYGLYCERYL-8-STEARATE, POLYGLYCERYL- 10-STEARATE, POLYGLY- TETRAOLEATE,

POLYGLYCERYL-2-TETRASTEARATE, POLYGLYCERYL-2-TRIISOSTEARATE, POLYGLYCERYL-10-TRIOLEATE, POLYGL YCERYL-6-TRISTEARATE. 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 articles 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

R ¹ R ¹ R ¹

H ₃ C-Si-O- [Si-O] _n -Si-CH ₃ (VI),

R ¹ R ¹ R ¹

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 is between 1 and 100, preferably between 2 and 20 and in particular below 10, and n indicates the degree of polymerization of the silicone.

Optionally, the polyoxyalkylenesiloxanes mentioned can also be etherified or esterified on the free OH groups of the polyoxyethylene or polyoxypropylene side chains. The unetherified and unesterified polymer made from dimethylsiloxane with polyoxyethylene and / or polyoxypropylene is referred to in the INCI nomenclature as DIMETHICONE COPOLYOL and is known under the trade names Abil ^® B (Goldschmidt), Alkasil ^® (Rhönen-Poulenc), Silwet ^® (Union Carbide) or Belsil ^® DMC 6031 commercially available.

The esterified with acetic acid DIMETHICONE COPOLYOL ACETATE (for example Belsil DMC 6032 ^®, -33 and -35, Wacker) and the Dimethicone Copolyol Butyl Ether (bsp KF352A, Shin Etsu) are usable in the context of the present invention also as emulsifiers.

As with the coating materials and the substances to be coated, the same applies to the emulsifiers that they 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 shell materials and active substances.

In the context of the present invention, particulate rinse aids preferably to be pressed into the well additionally 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 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 basic molded body can be put into the trough as a particulate composition and can be transferred there by pressing into a compact component of the molded body. Such particulate compositions can be free both in terms of their particle size and in terms of their bulk density and their genesis, that is to say the process used for their preparation to get voted. In particular, dusts, powders, granules, extrudates, press agglomerates, compactates, flakes, flakes, etc. can thus be pressed into the depression as particles, where they form the compressed part b) of the molded article according to the invention.

If fusible substances are used as the ingredient of the pressed part b), particulate preparations which are pressed into the cavity can also be produced by other processes, which is preferred in the context of the present invention. For this purpose, in particular, grouting, pastilling or shingling are possible.

The method according to the invention, which is preferably used for the production of vessible particles, which is briefly referred to as prilling, comprises the production of granular bodies from meltable substances, the melt being sprayed from the respective ingredients at the top of a tower in a defined droplet size, freezing and solidifying Prills accumulate at the bottom of the tower as granules.

In general, all gases can be used as the cold gas stream, the temperature of the gas being below the melting temperature of the melt. In order to avoid long falling distances, 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 prills produced can be varied by the choice of the droplet size, particle sizes which are technically simple to implement being in the range from 0.5 to 2 mm, preferably around 1 mm.

An alternative method for grouting is pastilling. A further embodiment of the present invention therefore provides, as a sub-step, a process for the production of pasted detergent components, in which a melt is metered onto cooled pasting plates.

Pastilling comprises metering the melt from the respective ingredients onto a (cooled) belt or rotating, inclined plates, which have a temperature below the 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 the condensation of air humidity.

The pastillation provides larger particles which have sizes between 2 and 10 mm, preferably between 3 and 6 mm, in technically customary processes.

As an even more cost-effective variant for the production of particulate detergent components of the above-mentioned composition from melts, the use of cooling rollers is appropriate. A further sub-step of the present invention is therefore a process for the production of particulate detergent components, in which a melt is applied or sprayed onto a chill roll, the solidified melt is scraped off and, if necessary, comminuted. The use of cooling rollers enables the desired particle size range to be set without problems, which in this method can also be below 1 mm, for example 200 to 700 μm.

Of course, it is also possible according to the invention to address the particulate compositions into a separate “core shaped body” before being pressed into the cavity. This “core shaped body” can then be inserted and pressed into the cavity as a “large, individual particle” be made 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 is only achieved by the press-in process.

Particularly when using fusible substances in the molded body part b), the manufacture of the molded body according to the invention by separate production (molding) of a basic molded body a) and a core molded body b), which is preferably pressed from prills, the joining and the final capping of both parts is preferred. In preferred embodiments of this variant of the method, the pressed-in molded body is multiphase.

Not only a complete separation of the ingredients can be advantageous, but also by varying the amounts of individual ingredients in the different molded body areas beneficial effects can be achieved. Detergent shaped bodies, which are characterized in that the basic shaped body and the part pressed into the basic shaped body contain the same active ingredient in different amounts, are preferred according to the invention. Examples of ingredients in which the division into the different regions have advantages include disintegration aids, colorants and fragrances, optical brighteners, polymers, silver preservatives, surfactants and enzymes. The term “different amounts” characterizes the content of the individual molded article area in the substance in question, based on the molded article area, is therefore a% by weight statement which does not relate to the absolute amounts of the ingredient.

Preferred detergent tablets in the context of the present invention are characterized in that the tablets contain less than 2% by weight, preferably less than 1.5% by weight, particularly preferably less than 1% by weight and in particular less than 0 , 5 wt .-% free water. The term “free water” denotes the water content of the detergent, which is not bound in the form of water of hydration and / or constitutional water. In preferred detergent tablets, this is less than 2% by weight, preferably less than 1.5% by weight. %, particularly preferably less than 1% by weight and in particular even less than 0.5% by weight, in each case based on the composition Accordingly, water can essentially only be in chemically and or physically bound form or as a constituent of those present as a solid Raw materials or compounds, but not as a liquid, solution or dispersion, can be contained in the detergent tablets according to the invention. Advantageously, the detergent tablets according to the invention advantageously have a total water content of not more than 15% by weight, which means that this water does not is in liquid free form, but is chemically and / or physically bound, and it is particularly preferred that the content of water not bound to carbonates and / or to silicates in the compositions according to the invention is not more than 10% by weight and in particular not more than 7% by weight. Water-containing liquids can be used in the preparation of the compositions according to the invention, provided that the addition of an “internal drying agent”, for example a hydratable one Substance in non-hydrated form, the free water content is kept below the limit.

The part pressed into the basic molded body is already firmly bonded to the surface of the basic molded body by the application of the pressure in the manufacturing process. In order to achieve further stabilization for extreme loads or to protect the trough filling against atmospheric influences, a coating can be applied to the trough filling or molded body sides that carry the trough filling. Detergent molded articles in which the part pressed into the basic molded article 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.

The detergent form according to the invention dissolve in the washing or Cleaning cycle completely, whereby - as mentioned above - it can be advantageous if the different regions have different dissolving speeds. Due to the different dissolution rates, in addition to the release of certain ingredients, the properties of the washing or cleaning liquor can also be changed in a targeted manner. For example, detergent tablets are preferred in which the pH of a 1% by weight solution of the base tablet in water is 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 tablet in water is in the range from 7 to 11, preferably from 7.5 to 10 and in particular from 8 to 9, 5, lies.

Another object of the present invention is a process for the production of detergent tablets characterized by the steps a) pressing a particulate premix to a pressed part (base tablet) which has at least one trough, b) pouring one or more particulate composition (s) into said well (s), c) compressing the composition (s) filled in step b) into (a) further compressed part (s) which said in the said Trough (s) of the basic molded body pressed in is / are present and d) optional aftertreatment of individual molded body surfaces or the entire molded body.

With regard to the ingredients of the individual particulate premixes or compositions which result in the different areas of the molded body, the same applies above for the molded body according to the invention.

It has proven to be advantageous if the premix pressed into basic shaped bodies in step a) meets certain physical criteria. Preferred processes are characterized, for example, in that the particulate premix in step a) has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g / 1.

The particle size of the premix pressed in step a) preferably also satisfies certain criteria: Methods in which the particulate premix in step a) has 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. A further narrowed particle size in the premixes to be pressed can be adjusted to obtain advantageous molded body properties. In preferred variants for the method according to the invention, 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 are larger than 1600 μm or smaller than 200 μm. Narrower particle size distributions are further preferred here. Particularly advantageous process variants are characterized in that the particulate premix pressed in step a) 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 restricted to the fact that only a particulate premix is pressed into a molded body. Rather, process step a) can also be expanded to the effect that multilayer molded articles are produced in a manner known per se by preparing two or more premixes which are pressed onto one another. In this case, the premix which has been filled in first is lightly pre-pressed in order to obtain a smooth upper surface which runs parallel to the mold body bottom, and after the second premix is filled in the finished mold body is finally pressed. In the case of three-layer or multi-layer molded bodies, a further preliminary treatment is carried out after each premix addition, before the molded body is finally pressed after addition of the last premix. The above-described cavity in the basic molded body is preferably a trough, so that preferred embodiments of the first method according to the invention are characterized in that in step a) multilayered molded bodies which have a trough are produced in a manner known per se by a plurality of different particulate premixes on top of one another be pressed.

In step a), the molded articles according to the invention are first produced by dry mixing the constituents, which can be wholly or partly pregranulated, and then providing information, in particular compresses to tablets, using conventional methods. To produce the shaped bodies according to the invention, the premix is compacted in a so-called die between two punches to form a solid compact. This process, which is briefly referred to as tableting in the following, is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection.

First, the premix is introduced into the die, the filling quantity and thus the weight and the shape of the molded body being formed being determined by the position of the lower punch and the shape of the pressing tool. The constant dosing, even with high mold throughputs, is preferably via a volumetric Dosage of the premix reached. As the tableting continues, the upper punch touches the premix and lowers further in the direction of the lower punch. During this compression, the particles of the premix are pressed closer together, the void volume within the filling between the punches continuously decreasing. From a certain position of the upper punch (and thus from a certain pressure on the premix), the plastic deformation begins, in which the particles flow together and the molded body is formed. Depending on the physical properties of the premix, some of the premix particles are also crushed and sintering of the premix occurs at even higher pressures. With increasing pressing speed, that is to say high throughput quantities, the phase of elastic deformation is shortened further and further, so that the resulting shaped bodies can have more or less large cavities. In the last step of tableting, the finished molded body is pressed out of the die by the lower punch and transported away by subsequent transport devices. At this point in time, only the weight of the molded body is finally determined, since the compacts can still change their shape and size due to physical processes (stretching, crystallographic effects, cooling, etc.).

Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches. In the latter case, not only is the upper stamp used to build up pressure, the lower stamp also moves towards the upper stamp during the pressing process, while the upper stamp presses down. For small production quantities, eccentric tablet presses are preferably used, in which the punch or stamps are fastened to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed. The movement of these rams is comparable to that of a conventional four-stroke engine. The pressing can take place with one upper and one lower punch, but several punches can also be attached to one eccentric disk, the number of die holes being increased 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 a larger number of dies is arranged in a circle on a so-called die table. The number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available. Each die on the die table is assigned an upper and lower punch, and again the pressure can be built up actively only by the upper or lower punch, but also by both stamps. The die table and the stamps move about a common vertical axis, the stamps being brought into the positions for filling, compaction, plastic deformation and ejection by means of rail-like cam tracks during the rotation. Wherever a particularly serious lifting or lowering of the punches is required (filling, compacting, ejecting), these cam tracks are supported by additional low-pressure pieces, low-tension rails and lifting tracks. The die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix. The pressing pressure on the premix can be individually adjusted via the pressing paths for the upper and lower punches, the pressure being built up by rolling the punch shaft heads past adjustable pressure rollers.

Rotary presses can also be provided with two filling shoes to increase the throughput, with only a semicircle having to be run through to produce a tablet. For the production of two-layer and multi-layer molded bodies, several filling shoes are arranged one behind the other without the slightly pressed first layer being ejected before further filling. With suitable process control, jacket and dot tablets can also be produced in this way, which have an onion-shell-like structure, the top side of the core or the core layers not being covered in the case of the dot tablets and thus remaining visible. Rotary tablet presses can also be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used simultaneously for pressing. The throughputs of modern rotary tablet presses are over one million molded articles per hour. When tableting with concentricity presses, it has proven to be advantageous to carry out the tabletting 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

All non-stick coatings known from the art are suitable for reducing stamp caking. Plastic coatings, plastic inserts or plastic stamps are particularly advantageous. Rotating punches have also proven to be advantageous, with the upper and lower punches being designed to be rotatable if possible. In the case of rotating stamps, a plastic insert can generally be dispensed with. The stamp surfaces should be electropolished here.

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

Tableting machines suitable in the context of the present invention are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Hörn & Noack Pharmatechnik GmbH, Worms, IMA Veφackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms. Other providers include Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Li veφool (GB), I. Holand Ltd., Nottingham (GB), Courtoy NV, Halle (BE / LU) and Mediopharm Kamnik (SI). For example, the hydraulic double pressure press HPF 630 from LAEIS, D. Tablettierwerkzeuge are, for example, from the companies Adams Tablettierwerkzeuge, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Söhne GmbH, Hamburg, Hofer GmbH, Weil, Hörn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Werkzeugbau, Tamm available. Other providers include Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).

As already mentioned above, the molded bodies can be manufactured in a predetermined spatial shape and size. Practically all practical configurations can be considered as the spatial shape, for example, the design as a board, the bar or bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross section. This last embodiment covers the presentation form from the tablet to compact cylinder pieces with a ratio of height to diameter above 1.

Another preferred molded body that can be produced has a plate-like or plate-like structure with alternating thick long and thin short segments, so that individual segments of this "bolt" at the predetermined breaking points, which represent the short thin segments, broken off and into the Machine can be entered. This principle of the "bar-shaped" shaped body detergent can also be realized in other geometric shapes, for example vertically standing triangles, which are connected to one another only on one of their sides along the side.

However, it is also possible that the various components are not pressed into a uniform tablet, but that shaped bodies are obtained which have several layers, that is to say at least two layers. It is also possible that these different layers have different dissolving speeds. This can result in advantageous application properties of the molded body. If, for example, components are contained in the molded body that are mutually nega- tiv influence, it is possible to integrate one component in the more rapidly soluble layer and to incorporate the other component in a slower soluble layer, so that the first component has already reacted when the second goes into solution. The layer structure of the molded body can take place in a stack-like manner, with the inner layer (s) already loosening at the edges of the molded body when the outer layers have not yet been completely removed, but it is also possible for the inner layer (s) to be completely encased ) can be achieved by the layer (s) lying further outwards, which leads to the premature dissolution of components of the inner layer (s).

In a further preferred embodiment of the invention, a molded body consists of at least three layers, i.e. two outer and at least one inner layer, at least one of the inner layers containing a peroxy bleaching agent, while in the case of the stacked molded body the two cover layers and in the case of the shell-shaped molded body the outermost layers, however, are free of peroxy bleach. Furthermore, it is also possible to spatially separate peroxy bleaching agents and any bleach activators and / or enzymes that may be present in a molded body. Such multilayer molded bodies have the advantage that they can be used not only via a dispensing chamber or via a metering device which is added to the washing liquor; rather, in such cases it is also possible to put the molded body into direct contact with the textiles in the machine without the risk of bleaching from bleaching agents and the like.

Similar effects can also be achieved by coating individual constituents of the detergent and cleaning agent composition to be treated or the entire molded article. For this purpose, the bodies to be coated can, for example, be sprayed with aqueous solutions or emulsions, or else they can be coated using the melt coating method.

After pressing, the detergent tablets have a high 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 2E σ = ^■ πDt

Herein σ stands for diametral fracture stress (DFS) in Pa, P is the force in N that leads to the pressure exerted on the molded body that causes the molded body to break, D is the molded body diameter in meters and t the height of the molded body.

The Muldenfor köφer are filled in step b) with a powdery composition, which is pressed into the molded body in step c). Analogous to the information for process step a), preferred physical parameters can also be given for the particulate composition (s) in process step b): Processes in which the particulate composition (s) in step b) has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g / 1, and processes in which the particulate composition (s) in step b) have 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 embodiments of the present invention.

The pressing force, which acts on the basic molded body 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 compression 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 in to which the pressing in step c) takes place at pressures from 1 to 100 kNcm ^"2 , preferably from 2.5 to 50 kNcm ^{" 2} and in particular from 5 to 25 kNcm ^" , are preferred according to the invention.

The particulate composition can be pressed into the trough analogously to the production of the basic shaped body on tablet presses. A method of operation is preferred in which the basic molded body is first produced with a depression, then filled and finally be pressed again. This can be done by ejecting the basic molded body from a first tablet press, infesting it and transporting it to a second tablet press, in which the final treatment takes place. Alternatively, the endveφressung can also be done by pressure rollers that roll over the molded body located on a conveyor belt. However, it is also possible to provide a rotary tablet press with different stamp sets, so that a first stamp set presses depressions into the molded body and the second set of stamps ensures a flat molded body surface after being filled by post-checking.

The moldings produced according to the invention can, as described above, be provided with a coating in whole or in part. Methods in which the aftertreatment in step d) consists in applying a coating layer to the molded body surface (s) in which the filled trough (s) are located, or in applying a coating layer to the entire molded body, are in accordance with the invention prefers.

The detergent tablets according to the invention can be packed 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 ingredients, and on the other hand surprisingly also significantly improve the long-term adhesion of the trough filling. Another object of the present invention is therefore a combination of (a) detergent shaped body (s) according to the invention and a packaging system containing the washing and cleaning agent shaped body (s), 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%.

According to the invention, the packaging system of the combination of detergent and molded article (s) and packaging system has a moisture vapor permeability rate of 0.1 g / m ² / day to less than 20 g / m ² / day when the packaging system is at 23 ° C. and a relative equilibrium humidity of 85% is stored. The specified temperature and humidity conditions are the test conditions that are specified in the DIN Standard 53122 are mentioned, 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. The moisture vapor permeability rate can be determined from the surface of the container which is sealed with the material to be tested (permeation surface), the weight increase in calcium chloride and the exposure time

___, __._- 24 - 10000 xr,,, _Λ _, ι

FDDR = g / m ² / 24b

A y ^J

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 air humidity”, is 85% at 23 ° C. when measuring the moisture vapor permeability rate within the scope of the present invention. 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 Percentage expressed 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 air humidity = (12 / 14.4) - 100 = 83% If one cools this air, then the saturation (100%> RH) is reached at the so-called dew point (in the example: 14 °), ie at further cooling, a precipitate is formed in the form of fog (Dew). Hygrometers and psychometers are used for the quantitative determination of moisture.

The relative equilibrium humidity of 85% at 23 ° C can be adjusted to +/- 2% r.L. in laboratory chambers with humidity control, for example, depending on the device type. adjust exactly. Even over saturated solutions of certain salts, constant and well-defined relative air humidities form in closed systems at a given temperature, which are based on the phase equilibrium between the partial pressure of the water, the saturated solution and the soil.

The combinations of detergent shaped body and packaging system according to the invention can of course in turn be packed in secondary packaging, for example cardboard boxes or trays, with no further requirements being placed on the secondary packaging. The secondary packaging is therefore possible, but not necessary.

Packaging systems preferred in the context of the present invention have a moisture vapor permeability rate of 0.5 g / m ² / day to less than 15 g / m ² / day.

Depending on the embodiment of the invention, the packaging system of the combination according to the invention encompasses one or more detergent tablets. It is preferred according to the invention either to design a shaped body in such a way that it comprises an application unit of the detergent and cleaning agent, and to individually package this shaped body, or to pack the number of shaped bodies in a packaging unit, which in total comprises one application unit. With a nominal dosage of 80 g of detergent and cleaning agent, it is therefore possible according to the invention to produce and individually pack an 80 g heavy detergent and cleaning agent shaped article, but it is also possible according to the invention to pack two 40 g heavy detergent and cleaning agent shaped articles in one packaging to arrive at a combination according to the invention. This principle can of course be expanded so that, according to the invention, combinations can also contain three, four, five or even more detergent tablets in one packaging unit. Of course, two can or more shaped bodies in a packaging have different compositions. In this way it is possible to spatially separate certain components from one another, for example in order to avoid stability problems.

The packaging system of the combination according to the invention can consist of a wide variety of materials and can take on any external shape. For economic reasons and for reasons of easier processing, packaging systems are preferred in which the packaging material is light in weight, easy to process and inexpensive. In combinations preferred according to the invention, the packaging system consists of a sack or pouch made of single-layer or laminated paper and / or plastic film.

The detergent tablets can be unsorted, i.e. as a loose fill, be filled into a bag made of the materials mentioned. However, for aesthetic reasons and for sorting the combinations in secondary packaging, it is preferable to fill the detergent and cleaning agent shaped articles individually or in groups in sacks or bags. The term "flow pack" has become common in the art for individual application units of the detergent tablets that are in a sack or bag. Such "flow packs" can then - again preferably sorted - optionally be packed in re-packaging , which underlines the compact offer form of the molded body.

The sacks or bags made of single-layer or laminated paper or plastic film, which are preferably to be used as a packaging system, can be designed in a wide variety of ways, for example as a blown-up bag without a central seam or as a bag with a central seam which is heated (hot melt), adhesives or adhesive tapes be closed. Single-layer bag or sack materials are the known papers, which can optionally be impregnated, and plastic films, which can optionally be co-extruded. Plastic films that can be used as a packaging system in the context of the present invention are described, for example, in Hans Domininghaus "The plastics and their properties", 3rd edition, VDI Verlag, Dussel- Dorfl 1988, page 193. Figure 111 shown there also provides information on the water vapor permeability of the materials mentioned.

Combinations which are particularly preferred in the context of the present invention contain, as packaging system, a sack or bag made of single-layer or laminated plastic film with a thickness of 10 to 200 μm, preferably 20 to 100 μm and in particular 25 to 50 μm.

Although it is possible to use wax-coated papers in the form of cardboard boxes as packaging systems for the detergent tablets, in addition to the films or papers mentioned, it is preferred in the context of the present invention if the packaging system does not include boxes made of wax-coated paper. In the context of the present invention, the term “packaging system” always denotes the primary packaging of the shaped bodies, i.e. the packaging, which is in direct contact with the inside of the molded body surface. No requirements are placed on an optional secondary vacuum, so that all common materials and systems can be used here.

As already mentioned above, the detergent tablets of the combination according to the invention contain further ingredients of detergents in varying amounts, depending on their intended use. Regardless of the intended use of the molded article, it is preferred according to the invention that the washing and cleaning agent molded article or articles has a relative equilibrium moisture content of less than 30% at 35 ° C.

The relative equilibrium moisture content of the detergent tablets can be determined using standard methods, with the following procedure being chosen within the scope of the present investigations: A water-impermeable 1-liter container with a lid, which has a closable opening for introducing samples, was used filled with a total of 300 g detergent tablets and kept at a constant 23 ° C for 24 hours to ensure a uniform temperature of the container and substance. The water vapor pressure in the room above the form cores can then be determined with a hygrometer (Hygrotest 6100, Testoterm Ltd., England). The water vapor pressure is now measured every 10 minutes until two successive values show no deviation (equilibrium moisture). The above-mentioned hygrometer allows a direct display of the recorded values in% relative humidity.

Also preferred are embodiments of the combination according to the invention in which the packaging system is designed to be resealable. Combinations in which the packaging system has a microperforation can also be preferably implemented according to the invention.

Claims

Claims:

1. Detergent and molded article, comprising a) a pressed part (basic molded article) which has at least one trough, and b) at least one further pressed part which is pressed into said recess (s) of the basic molded article.

2. Detergent and molded article according to claim 1, characterized in that the weight ratio of the basic molded article to the cavity filling is in the range from 1: 1 to 100: 1, preferably from 2: 1 to 80: 1, particularly preferably from 3: 1 to 50: 1 and in particular from 4: 1 to 30: 1.

3. Detergent and shaped body according to one of claims 1 or 2, characterized in that the surface of the pressed-in trough filling 1 to 25%, preferably 2 to 20%, particularly preferably 3 to 15% and in particular 4 to 10% of the total surface of the filled Form bodies makes up.

4. Detergent and molded article according to one of claims 1 to 3, characterized in that the pressed-in mold filling dissolves faster than the basic molded article.

5. Detergent and molded article according to one of claims 1 to 3, characterized in that the pressed-in mold filling dissolves more slowly than the basic molded article.

6. Detergent and molded article according to one of claims 1 to 5, characterized in that the basic molded article has a density above 1000 gdm ^" , preferably above 1025 gdm ^" , particularly preferably above 1050 gdm ^" and in particular above 1100 gdm ^"3 has.

7. Detergent and molded article according to one of claims 1 to 6, characterized in that the basic molded article 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 molded body.

8. washing and cleaning agent shaped body according to one of claims 1 to 7, characterized in that the basic shaped body phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in quantities from 20 to 80% by weight, preferably from 25 to 75% by weight and in particular from 30 to 70% by weight, based in each case on the weight of the basic molded body.

9. washing and cleaning agent molded article according to one of claims 1 to 8, characterized in that the basic molded article carbonate (s) and / or hydrogen carbonate (s), preferably alkali metal carbonates, particularly preferably sodium carbonate, in amounts of 5 to 50% by weight, preferably from 7.5 to 40% by weight and in particular from 10 to 30% by weight, in each case based on the weight of the basic molded body.

10. Washing and cleaning agent shaped body according to one of claims 1 to 9, characterized in that the basic shaped body silicate (s), preferably alkali silicates, particularly preferably crystalline or amorphous alkali disilicates, in amounts of 10 to 60% by weight, preferably 15 to Contains 50 wt .-% and in particular from 20 to 40 wt .-%, each based on the weight of the basic molded body.

11. washing and cleaning agent molded article according to one of claims 1 to 10, characterized in that the basic molded article total surfactant contents below 5% by weight, preferably below 4% by weight, particularly preferably below 3% by weight and in particular below of 2 wt .-%, each based on the weight of the basic molded body.

12. Washing and cleaning agent shaped body according to one of claims 1 to 11, characterized in that the basic shaped body bleaching agent from the group of oxygen or halogen bleaching agents, in particular chlorine bleaching agents, with particular loading. preference of sodium perborate and sodium percarbonate, in amounts of 2 to 25 wt .-%, preferably from 5 to 20 wt .-% and in particular from 10 to 15 wt .-%>, each based on the weight of the basic molded body mass.

13. washing and cleaning agent form according to one of claims 1 to 12, characterized in that the basic form bleach activators from the groups of polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, especially N-nonanoylsuccinimide (NOSI), the acylated Phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS) and n-methyl-Moφholinium-acetonitrile-methylsulfate (MMA), in amounts of 0.25 to 15 wt .-%, preferably of 0.5 to 10 wt .-% and in particular from 1 to 5 wt .-%, each based on the weight of the basic molded body, contains.

14. Washing and cleaning agent shaped body according to one of claims 1 to 13, characterized in that the basic shaped body silver protection agent from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes, especially preferably benzotriazole and / or alkylaminotriazole, in amounts of 0.01 to 5% by weight, preferably 0.05 to 4% by weight and in particular 0.5 to 3% by weight, in each case based on the weight of the Basisformköφers, contains.

15. Washing and cleaning agent shaped body according to one of claims 1 to 14, characterized in that the basic shaped body further comprises one or more substances from the groups of enzymes, corrosion inhibitors, scale inhibitors, cobuilders, colors and / or fragrances in total amounts of 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 basic molded body, contains.

16. Washing and cleaning agent shaped body according to one of claims 1 to 15, characterized in that the part pressed into the basic shaped body comprises at least one active ingredient from the group of enzymes, surfactants, soil-release polymers, disintegrati- on aids, bleaches, bleach activators, bleach catalysts, silver preservatives and mixtures thereof.

17. Washing and cleaning agent shaped body according to one of claims 1 to 16, characterized in that the basic shaped body or the part pressed into the basic shaped body contains bleach, while the other part contains bleach activators.

18. Washing and cleaning agent shaped body according to one of claims 1 to 17, characterized in that the basic shaped body or the part pressed into the basic shaped body contains bleach, while the other part contains enzymes.

19. Washing and cleaning agent shaped body according to one of claims 1 to 18, characterized in that the basic shaped body or the part pressed into the basic shaped body contains bleaching agent, while the other part contains deformable mass anti-corrosion agent.

20. Washing and cleaning agent shaped body according to one of claims 1 to 19, characterized in that the basic shaped body or the part pressed into the basic shaped body contains bleaching agents, while the other part contains surfactants, preferably nonionic surfactants, with particular preference to alkoxylated alcohols having 10 to 24 carbon atoms and 1 to 5 alkylene oxide units.

21. Washing and cleaning agent shaped body according to one of claims 1 to 20, characterized in that the basic shaped body and the part pressed into the basic shaped body contain the same active ingredient in different amounts.

22. Detergent and molded article according to one of claims 1 to 21, characterized in that the particles pressed into the basic molded article from a) 30 to 90% by weight of one or more carrier materials, b) 5 to 40% by weight of one or several 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 form according to claim 22, characterized in that paraffin (s) or polyalkylene glycols, in particular polyethylene glycols, are contained in the particles as the coating substance.

24. Washing and cleaning agent shaped body according to one of claims 22 or 23, characterized in that the particles pressed into the basic shaped body as active ingredients are nonionic surfactant (s) and / or bleaching agents and / or bleach activators and / or enzyme (s) and / or contain corrosion inhibitors and / or fragrances.

25. Washing and cleaning agent shaped body according to one of claims 1 to 21, characterized in that the particles pressed into the basic shaped body 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 liquid enzyme preparation (s) dispersed in the shell substance (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 ingredients.

26. Detergent and molded article according to one of claims 1 to 25, characterized in that the molded article is less than 2% by weight, preferably less than 1.5% by weight, particularly preferably less than 1% by weight and in particular contain less than 0.5% by weight of free water.

27. Washing and cleaning agent molded article according to one of claims 1 to 26, characterized in that the part pressed into the basic molded article is coated with a coating layer.

28. Washing and cleaning agent shaped body according to one of claims 1 to 27, characterized in that the pH of a 1% by weight solution of the basic shaped body in water in the range from 8 to 12, preferably from 9 to 11 and in particular from 9.5 to 10.

29. Detergent and molded article according to one of claims 1 to 28, characterized in that the pH of a 1% by weight solution of the entire molded article in water in the range from 7 to 11, preferably from 7.5 to 10 and in particular from 8 to 9.5.

30. A process for the production of detergent tablets characterized by the steps a) pressing a particulate premix to a pressed part (base tablet) which has at least one depression, b) filling one or more particulate composition (s) into said ^) Trough (s), c) pressing the composition (s) filled in step b) into (a) further pressed part (s) which is / are pressed into said trough (s) of the basic molded body and d) optional aftertreatment of individual Molded body surfaces or the entire molded body.

31. The method according to claim 30, characterized in that the particulate premix in step a) has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g / 1.

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 microns, 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 particulate ^) composition (s) in step b) has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g / 1 /exhibit.

34. The method according to any one of claims 30 to 33, characterized in that the particulate ^) composition (s) in step b) particle sizes between 100 and 2000 microns, preferably between 200 and 1800 microns, particularly preferably between 400 and 1600 microns and in particular between 600 and 1400μm.

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 9 to 40 kNcm ^" and in particular from 1 to 25 kNcm ^" .

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

9 7

50 kNcm ^" and in particular from 5 to 25 kNcm ^" .

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 on the molded body surface (s) in which the filled (n) trough (s) are located, consists.

38. The method according to any one of claims 30 to 37, characterized in that the post-treatment in step d) consists in applying a coating layer on the entire molded body.

39. Combination of (a) washing and cleaning agent shaped body (s) according to one of claims 1 to 28 and a packaging system containing the washing and cleaning agent shaped body, characterized in that the packaging system stem has a moisture vapor transmission rate of 0.1 g / m ² / day to less than 20 g / m ² / day when 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 washing or cleaning agent shaped body has / have a relative equilibrium moisture content of less than 30% at 35 ° C.

42. Combination according to one of claims 39 to 41, characterized in that the packaging system consists of a sack or pouch made of single-layer or laminated paper and / or plastic film.

43. Combination according to claim 42, characterized in that the packaging system consists of a sack or bag made of single-layer or laminated plastic film with a thickness of 10 to 200 μm, preferably 20 to 100 μm and in particular 25 to 50 μm.

44. Combination according to one of claims 39 to 43, characterized in that the packaging system does not comprise 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.