DE19939992A1 - Detergent tablets, useful in domestic washing machine or automatic dishwasher, have pressed part with cavity (partly) enclosing solid part and also (partly) filled with active substance - Google Patents

Abstract

In laundry or other detergent tablets with: (a) a pressed part containing at least one cavity; and, (b) another solid part, (partly) enclosed in the cavity. Part (b) does not completely fill the cavity in part (a) and the rest is (partly) filled with active substance. Independent claims are also included for: (i) the production of multiphase laundry or other detergent tablets; (ii) a combination of the detergent tablets and a packaging system.

Description

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

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

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

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

Another way of producing optically differentiated detergents and cleaning agents Shaped body is in the international patent applications WO99 / 46522, WO99 / 27063 and WO99 / 27067 (Procter & Gamble). According to the teaching of these writings a molded body is provided which has a cavity with a solidifying Melt is filled. Alternatively, a powder is filled in and by means of a coating layer attached in the cavity. All three applications have in common that the cavity  filling area should not be pressed, because in this way "pressure sensitive" In contents should be spared.

The older German patent application DE 199 09 271.0 (Henkel) proposes a method for Production of multi-phase detergent tablets before, in which a part Chen-shaped premix is pressed into shaped bodies, optional on the surfaces Adhesion promoters are applied, after which further active substance, for example in the form Prepressed molded body is applied. This document also describes the contribution pre-tableted active substance (mixtures) in cavities of other moldings.

The present invention was based on the object that in the older German Patent application DE 199 09 271.0 described methods and those disclosed therein Developing molded articles. In particular, the adhesion promoter should be functional become part of the molded articles and specific tasks in the detergent or cleaning agent ben take over. Another object of the present invention was to provide moldings To provide, which also contain temperature-sensitive ingredients in delimited Re gions can be introduced, the delimited region in terms of size should not be subject to any restrictions with regard to the overall molded body. there on the one hand, there should be an optical differentiation from conventional two layered tablets can be achieved, on the other hand, the production of the molded body without great technical effort also work safely in large series without the shape Disadvantages in terms of stability or inaccuracies in the dosage would be feared. The controlled release of certain active substances increases Achieving predetermined times was another object of the present invention.

It has now been found that the disadvantages mentioned are avoided and the desired ones Effects are achieved if "cores" contain pre-compressed molded bodies in cavities which do not completely fill the cavity. In this way lies in the molded body additional space in front of that with further active substance in liquid, gel-like, pasty or solid form can be filled.  

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

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

include, wherein part b) does not completely fill the cavity in part a) and the lead the cavity is at least partially filled with active substance.

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

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

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

The shape of the cavity can also be freely selected within wide limits. Because of Process economics have through holes, the openings of which ge lie opposite surfaces of the moldings, and troughs with an opening on one Molded body proven. In preferred laundry detergent and cleaning product tablets  the cavity in the form of a through hole, the openings of which are located on two ge opposite shaped body surfaces. The shape of such a continuous Holes can be chosen freely, with molded bodies being preferred in which the through hole circular, elliptical, triangular, rectangular, square, pentagonal, has hexagonal, heptagonal or octagonal horizontal sections. Also completely crazy Gular hole shapes such as arrow or animal shapes, trees, clouds, etc. can be realized become. As with the shaped bodies, in the case of angular holes, those are also removed rounded corners and edges or with rounded corners and chamfered edges before moves.

The geometric implementation forms mentioned above can be combined as desired combine other. Shaped bodies with a rectangular or square base can round holes as well as round shaped bodies with achtec holes, with no limit to the variety of possible combinations are. For reasons of process economy and aesthetic consumer perception Shaped articles with a hole are particularly preferred in which the shaped body base area and the hole cross section have the same geometric shape, for example shaped bodies with square base and centrally integrated square hole. Especially ring shaped bodies are preferred, i. H. circular shaped body with a circular hole.

If the above Principle of the hole open on two opposite sides of the molded body is reduced to an opening, mold bodies are obtained. According to the invention Detergent tablets in which the cavity is in the form of a trough has are also preferred. As with the "perforated bodies", they can be invented molded article according to the invention also in this embodiment, any geometric shape assume, in particular concave, convex, biconcave, biconvex, cubic, tetra gonal, orthorhombic, cylindrical, spherical, segment-like, disc-shaped ge, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, five-, you rectangular and octagonal prismatic and rhombohedral shapes are preferred. Also completely irregular base areas such as arrow or animal shapes, trees, clouds, etc. will be realized. If the molded body has corners and edges, these are preferred  rounded. As an additional optical differentiation is an embodiment with abge rounded corners and chamfered ("chamfered") edges preferred.

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

Part b) of the shaped body according to the invention is at least partially in the cavity of the Part a) included, wherein the cavity is not completely filled and a cavity in the Part a) remains. Depending on the design of the cavity in the pressed part a), part b) can Completely close the cavity, but it is also possible that part b) for example only closes one side of a through hole in part a) and the remaining cavity, which then effectively represents a hollow that forms the cavity. Part b) can also can be used as a closure in a cavity open on one side in part a), whereby a cavity is formed which does not contact any outer surfaces of the molded body. Laundry or detergent tablets, in which part b) closes the cavity in part a) and the remaining cavity is thus completely enclosed by a) and b) are invented preferred according to the invention.

Of course, this embodiment is not for closing troughs moldings limited; rather, there can also be a through hole in the pressed part a) with a correspondingly shaped part b) or with two different parts b) be closed so that a cavity forms inside the tablet. In logi The continuation of the principle mentioned can also be cavities with several openings Seal the openings with one or more parts b).  

The size of the trough or through hole compared to the overall shape body depends on the intended use of the molded body. Depending on with how much more active substance the remaining hollow volume is filled should and whether a smaller or larger amount of active substance should be contained the size of the cavity and the size of the part not completely filling the cavity b) vary. Detergent and cleaning agent forms are independent of the intended use body preferred, in which the volume ratio of pressed part a) to part b) 2: 1 to 100: 1, preferably 3: 1 to 80: 1, particularly preferably 4: 1 to 50: 1 and in particular 5: 1 to 30: 1.

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

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

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

Part b) and the base molding [part a)] are preferably optically distinguishable colors. In addition to the optical differentiation, application technology advantages can be achieved by different solubilities of the different shaped body areas can be achieved. Detergent tablets in which part b) dissolves faster than part a), are preferred according to the invention. By incorporating certain components, egg on the one hand, the solubility of part b) can be accelerated in a targeted manner, on the other hand, the Release of certain ingredients from part b) for advantages in washing or cleaning lead process. Ingredients that are preferably at least partially located in part b), are, for example, the disintegration aids, surfactants, Enzymes, soil-release polymers, builders, bleaches, bleach activators, bleach kata analyzers, optical brighteners, silver protection agents, etc. The accelerated release of a or more of the active substances mentioned can be used to increase performance the, for example, by enzymes a washing or cleaning process earlier and thus are available longer. Also the premature release of bleach or sau Ren components are easily possible and often with lei when washing or cleaning advantages.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 140 ° and changes to diphosphate Na ₄ P ₂ O ₇ when heated more strongly. Disodium hydrogen phosphate is produced by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm ^-3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 gcm ^-3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises e.g. B. when He's heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As a special copolymers of acrylic acid with maleic acid, 50 to Contain 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative mole Cooling mass, based on free acids, is generally from 2000 to 70,000 g / mol preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,400 g / mol.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Another class of preferred nonionic surfactants, which are used either as allei some nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and pro poxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as described, for example, in Japanese Pa tentanmeldung JP 58/217598 are described or which preferably according to the in ternational patent application WO-A-90/13533 who produced the.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Another preferred surfactant can be represented by the formula

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

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

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

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

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

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

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

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

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

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

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

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

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

The cellulose used as disintegration aid is preferably not finely divided form, but before mixing into the premixes to be pressed converted into a coarser form, for example granulated or compacted. Washing and Detergent tablets, the disintegrant in granular or optionally cogranu Contained form, are in the German patent applications DE 197 09 991 (Ste fan Herzog) and DE 197 10 254 (Henkel) and the international patent application WO98 / 40463 (Henkel). These writings are also more detailed information on the Her position of granulated, compacted or cogranulated cellulose disintegrants men. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 µm and in particular to at least 90% by weight between 400 and 1200 µm. The above and in the writings cited described coarser disintegration aids on cellulose In the context of the present invention, bases are preferred as disintegration aids used and commercially, for example under the name Arbocel® TF-30-HG by available from Rettenmaier.

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

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

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

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

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

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

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

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

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

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

Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable. The bleaches are usually used in machine dishwashing detergents in amounts of 1 up to 30% by weight, preferably from 2.5 to 20% by weight and in particular from 5 to 15% by weight, each based on the agent used. In the context of the present invention the proportions mentioned on the weight of the base molding [part a)], so that Detergent tablets are preferred in which the base tablet Bleaching agents from the group of oxygen or halogen bleaching agents, in particular the Chlorine bleach, with particular preference for sodium perborate and Sodium percarbonate, in amounts of 2 to 25% by weight, preferably 5 to 20% by weight and in particular from 10 to 15 wt .-%, each based on the weight of the Basic molding, contains.  

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

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

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

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

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

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

The detergent tablets according to the invention can in particular in the basic form contain corrosion inhibitors to protect the dishes or the machine, especially silver protection agents in the field of automatic dishwashing have special meaning. The known substances of the prior art can be used Technology. In general, silver protection agents can be selected from the group of Triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotria zole and the transition metal salts or complexes are used. Especially before benzotriazole and / or alkylaminotriazole are to be used. One finds in cleaners formulation 99999 00070 552 001000280000000200012000285919988800040 0002019939992 00004 99880en in addition often active chlorine-containing agents that corrode the Can significantly reduce the silver surface. Chlorine-free cleaners are special Oxygen and nitrogen-containing organic redox-active compounds, such as two and trihydric phenols, e.g. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid right, phloroglucin, pyrogallol or derivatives of these classes of compounds. Also salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts, the are selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the Cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulphide fats. Zinc compounds can also be used to prevent corrosion on the wash ware be set.

Preferred detergent and cleaning agent form in the context of the present invention bodies contain the basic shaped body of silver protection agent from the group of triazoles, the Benzotriazoles, the Bisbenzotriazole, the Aminotriazole, the Alkylaminotriazole and the  Transition metal salts or complexes, particularly preferably benzotriazole and / or alky laminotriazole, in amounts of 0.01 to 5% by weight, preferably 0.05 to 4% by weight and in particular from 0.5 to 3% by weight, in each case based on the weight of the basic shape body.

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

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

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

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

Because the detergent tablets according to the invention can contain the enzyme (s) in two or even three fundamentally different areas, tablets with a very precisely defined enzyme release and action can be provided. The table below gives an overview of possible enzyme distributions in detergent tablets according to the invention:

Dyes and fragrances can be used in the dishwasher detergents according to the invention both in the base molding and in part b) and / or in the filling of the cavity  can be added to improve the aesthetic impression of the resulting products and to the consumer, in addition to the performance, a visually and sensory "typical and unmatched interchangeable "product. As perfume oils or fragrances can individual fragrance compounds, e.g. B. the synthetic products of the ester type, Ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Smell Compounds of the ester type are e.g. B. benzyl acetate, phenoxyethyl isobutyrate, p- tert-Butylcyclohexylacetate, Linalylacetat, Dimethylbenzylcarbinylacetat, Phenylethylace tat, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, Styrallyl propionate and benzyl salicylate. The ethers include, for example, benzylethyl lether, to the aldehydes z. B. the linear alkanals with 8-18 C atoms, Citral, Citronel lal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeo nal, to the ketones z. B. the Jonone, α-isomethylionone and methylcedryl ketone to the Alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and ter pineol, the hydrocarbons mainly include terpenes such as limonene and Pinene. However, mixtures of different odoriferous substances are preferably used create an appealing fragrance together. Such perfume oils can also be natural che fragrance mixtures contain, as they are accessible from plant sources, for. B. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Are also suitable Muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden flower oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well Orange blossom oil, neroliol, orange peel oil and sandalwood oil.

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

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

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

By dividing the detergent tablets according to the invention into Base moldings [part a)] and "core moldings" [part b)] and "cavity filling" [part c)] ingredients can be separated from each other, which either leads to a storage stability separation of incompatible ingredients or to a controlled release setting certain active substances can be used. In preferred fiction The three different Be richly used in particular to combine the active ingredient bleach / bleach activator, Bleach / enzyme, bleach / silver protectant, bleach / fragrance, bleach tel / optical brightener, bleach / dye, bleach / surfactant, bleaching assets tor / enzyme, bleach activator / silver protection agent, bleach activator / fragrance, bleach activa tor / optical brightener, bleach activator / dye, bleach activator / surfactant or non-ionic separate surfactant / anionic surfactant to achieve performance benefits. It can also be controlled by the controlled release of certain ingredients the individual regions or by specifically varying the solubility of the individual regions performance benefits can be achieved.

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

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

Also a separation of bleach and corrosion inhibitors or silver protection agents can be achieved. Detergent tablets in which the basic tablet by or the core molding inserted into the base molding or the cavity filling Contains bleach, while at least one other part contains anti-corrosion agents, are also preferred.

Last but not least, detergent tablets are preferred, in which the Base molding or the core molding inserted into the base molding or the Cavity filling contains bleach, while at least one other part contains surfactants preferably nonionic surfactants, with particular preference for alkoxylated alcohols having 10 to 24 carbon atoms and 1 to 5 alkylene oxide units.

Not only can a complete separation of the ingredients be beneficial, also through Varying amounts of individual ingredients in the different shaped body areas beneficial effects can be achieved. Detergent tablets, the are characterized in that at least two of the three shaped body regions (base molded body, core molded body, cavity filling) the same active ingredient in different Containing amounts are preferred according to the invention. As examples of ingredients, at who benefit from the division into the different regions are disinte conditioning aids, dyes and fragrances, optical brighteners, polymers, silver protection agents To name surfactants and enzymes. The term "different amounts" denotes the content of the individual molded part of the substance in question on the molded part area, is therefore a% by weight statement that does not refer to the absolute Amounts of the ingredient.  

All of the ingredients described above can be contained in all different areas of the moldings according to the invention. While part a) of the moldings according to the invention can be produced by pressing, with tablet in particular being an important process, parts b) and c) can be produced in different ways. Another object of the present invention is also a method for the production of multi-phase detergent tablets, through the steps

• a) compressing particulate premixes to give moldings which at least have a cavity
• b) Production of moldings which at least partially into the cavity are available
• c) Filling part of the cavity with active substance in solid, liquid, high viscous or plastic form,
• d) inserting the end products of process step b) into the cavity the end products of process step a),
• e) optional aftertreatment of the moldings

is marked.

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

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

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

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

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

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

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

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

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

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

• - Use of plastic inserts with small thickness tolerances
• - Low number of revolutions of the rotor
• - Big filling shoes
• - Matching the filler paddle speed to the speed of the rotor
• - Filling shoe with constant powder height
• - Decoupling of filling shoe and powder feed.

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

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

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

Tableting machines suitable for the purposes of the present invention are, for example available from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMA Verpackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms. Other providers are, for example Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Li verpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy N.V., Halle (BE / LU) and Me diopharm Kamnik (51). The hydraulic double is particularly suitable HPF 630 printing press from LAEIS, D. Tableting tools are, for example, from the company Adams Tablettierwerkzeuge, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Söhne GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharmatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Werkzeugbau, Tamm available. Other providers are e.g. B. the Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).

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

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

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

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

Bleach and bleach activators can also be separated analogously. Also procedure at which are produced in step a) two-layer moldings by two under different particulate premixes are pressed together, one of which is a or more bleaches and the other contains one or more bleach activators preferred embodiments of the present invention.

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

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

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

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

In step b), moldings are produced which at least partially extend into the cavity let the molded body a) be inserted. These can - as explained above - the Ka Seal the vity and form a completely enclosed cavity. But you can also close a cavity open on both sides only on one side, so that one-sided open cavity remains, which is at least partially filled with active substance.

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

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

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

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

Depending on the shape of the pressed part a) and the at least partially in the part b) to be used for the cavity, process steps c) and d) are carried out in below different order. Part b) closes the cavity in part a) completely and forms thus preferred moldings according to the invention, in which the remaining cavity is completely enclosed by parts a) and b), so in step c) there will be more  Active substance filled in before the cavity through step d) - the insertion of part b) - is closed. However, it is also possible, according to the invention, to first convert part b) into the ver pressed part and then insert a remaining cavity at least partially to be filled with further active substance, i.e. to carry out step d) before step c). This The procedure can be implemented, for example, in the case of base moldings [parts a)] which have a cavity in the form of a through hole. You can make holes like that seal on one side with suitable parts b), whereby in this process step d) Part a) forms a trough shaped body "a) + b)". That way The trough formed then represents the remaining cavity, which in process step c) is at least partially filled with active substance. If it is wanted, can this process step c) connect a further process step d), so that ultimately a basic molded body with a through hole is closed by two parts b) where with a cavity remaining inside, at least partially with active substance was filled.

Regardless of whether process step c) or process step d) has been carried out is in process step c) at least part of the later remaining cavity filled with further active substance. This additional active substance can be the remaining one Completely fill the cavity, but it is also possible that part of the cavity un remains filled. In the context of the present invention, it is preferred that at least 50%, preferably at least 60% and in particular at least 70% of the cavity vo lumens can be filled with further active substance. Here are washing or cleaning medium shaped bodies preferred, in which the volume ratio of the unfilled cavity to the active substance contained in this room 1: 1 to 100: 1, preferably 1.1: 1 to 50: 1, particularly preferably 1.2: 1 to 25: 1 and in particular 1.3: 1 to 10: 1. In this Terminology means a volume ratio of 1: 1 that the cavity is completely exhausted is filling.

Depending on the size of the cavity, the density of the molded body, the density of the Active ingredient in the cavity and the degree of filling of the cavity can be the proportion of the other Make up different amounts of active substance in the cavity in the overall molded article. Here, detergent tablets are preferred in which the Ge  weight ratio of molded body to the active substance contained in the cavity 1: 1 to 100: 1, preferably 2: 1 to 80: 1, particularly preferably 3: 1 to 50: 1 and in particular 4: 1 is up to 30: 1. The weight ratio defined above is the Ratio of the mass of the shaped body not filled with further active substance {mass of the "base molding" [part a)] plus the mass of part b)} to the mass of the filling [part c)].

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

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

But also laundry detergent and cleaning product tablets, in which the ent in the cavity active substance [part c)] that dissolves more slowly than the basic tablet [part a)] are preferred embodiments of the present invention.

The filling of the cavity volume (above and below as part c) of the fiction designated shaped body) contains at least one active substance, but can also contain a mixture of several active substances. Just like part b) are as active sub punch for the incorporation in part c) active substances, which contain ingredient fen from part a) enter into undesirable interactions. Particularly preferred ingredient  fe for part c) are those resulting from the tableting of part a) or the manufacturing process ren of part b) would be adversely affected. Such active substances are, for example Surfactants, bleaches, bleach activators, bleach catalysts, enzymes, corrosion inhibitors gates and / or silver protection agents, perfume, alkali carriers or acidifying agents. The individual substances are described in detail above. Procedure in which the cavity in step c) with at least one active substance from the group of bleaches, bleach activators, enzymes, pH adjusters, fragrances, perfume carriers, fluorescent agents, colors substances, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, ver antifouling, color transfer and corrosion inhibitors is filled, are preferred embodiments of the present invention. The cavity filling can take a wide variety of forms, such as particulate (powdery mig or granular), gel-like, liquid or plastic. The cavity filling does not have to be full consist of active substance, for example, active substances Use on carrier materials or in carrier matrices. Last but not least, they are also thinly flowing Active to highly viscous or pasty solutions, suspensions or emulsions Substances in solvents or solvent mixtures can be used as part c).

For carrying out process step c) it is preferred that the cavity filling is introduced into the cavity in a flowable form. With solid active substances or Zu Preparations can be introduced into the cavity and subsequently approved nete measures, such as fixation with a coating layer, are attached. In Cases in which the cavity is closed to the outside can on the attachment can of course also be dispensed with. Analogous versions apply to flowable Cavity fillings in liquid, gel-like, pasty or plastic form, which by Hardening, for example solidification of melts, evaporation of solvents, kri stallisation, polymerisation, pseudoplastic property changes through change can be fixed in the cavity by shear forces or by special binders, if necessary or desired.

The void fill [part c)] may contain particulate solids. These particles can be produced using all of the prior art methods, for example by spray drying, granulation, encapsulation, agglomeration, granulation, pelletizing  tion, extrusion, roller compaction, etc. If desired, the particles can by incorporating binders or by forming a coating over the particles are attached to the cavity.

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

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

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

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

consist.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

H- (O-CH ₂ -CH ₂ ) _n -OH (IV)

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

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

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

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

Particulate rinse aid which can preferably be introduced into the cavity contain as enveloping substance punch at least one paraffin wax with a melting range from 50 ° C to 60 ° C.

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

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

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

The principle described above serves to delay the release of ingredients a certain time in the cleaning cycle and can be particularly advantageous use if in the main wash cycle at a lower temperature (e.g. 55 ° C) is rinsed so that the active substance from the active substance particles only in the rinse cycle is released at higher temperatures (approx. 70 ° C).

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

The active substance particles to be introduced into the cavity according to the invention ent Active ingredients held at processing temperature (i.e. at the temperature at of which the particles are produced) are available in both solid and liquid form.

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

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

By incorporating surfactants into the melted shell material, one can Produce melt suspension or emulsion, which in the finished active substance particle or in the ready-made molded body according to the invention, to a predetermined Provides additional wash-active substance at the appropriate time. For example, in this way, active substance particles that can be incorporated into the cavity (s) for mechanical Manufacture dishwashing, the additional surfactant from the form of the invention Only release the body at normal household dishwashers only reach in the rinse aid. In this way there is additional surfactant in the rinse aid available, which accelerates the drainage of the water and so stains on the rinse well prevented effectively. With a suitable amount of solidified melt suspension or emulsion in the active substance particles can thus be more commonly used today additional rinse aid can be dispensed with.

In active substance particles which can preferably be introduced into the cavity, the or the active substance (s) selected from the group of nonionic surfactants, in particular the alkoxylated alcohols. These substances have already been described in detail.  

Another class of active substances that are particularly advantageous in the inventions Bleaching agents that can be incorporated according to the invention are bleaching agents. Here, particles can be produced and introduced into the cavity (s) that form the Release bleach only when certain temperatures are reached, for example finished made-up cleaning agents that clean enzymatically in the pre-rinse cycle and only in the Release the bleach on the main rinse cycle. There are also cleaning agents for the machine nelle dishwashing can be produced so that additional bleach releases in the rinse cycle and difficult stains, such as tea stains, are removed more effectively nen.

In particulate active substance particles which can preferably be incorporated into the cavity is / are therefore the active substance (s) selected from the group of oxygen or Halogen bleach, especially chlorine bleach. These substances were also already described in detail.

Another class of compounds that are preferred as active substances in the inventions Active substance particles which can be introduced according to the invention are the Bleach activators. The important representatives from this group of substances have already been described. Within the scope of the present invention, preferably inserted into the cavity (s) brought active substance particles contain bleach activators, in particular as active substance from the groups of multiply acylated alkylenediamines, in particular tetraacetylethyl lendiamine (TAED), the N-acylimide, especially N-nonanoylsuccinimide (NOSI), the acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA).

Another important embodiment of the present invention provides for the introduction of enzyme-containing particles into the cavity (s). Such active substance particles contain as active substance (s) enzymes which have been described in detail above. Particular preference is given here to particulate particles to be introduced into the cavity (s) which are 40 to 99.5% by weight, preferably 50 to 97.5% by weight, particularly preferably 60 to 95% by weight and in particular 70 to 90% by weight of one or more coating substance (s) which has / 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. Accordingly, preferred methods are characterized in that the cavity filling [part c)] comprises active substance particles which consist of

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

consist.

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

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

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

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

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

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

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

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

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

Within the scope of the present invention, the part to be worked into the cavity (s) is preferred Chen-like rinse aid or enzyme particles contain other auxiliary substances from the group the anti-settling, floating, anti-floating, thixotropic and dis Pergierhilfsmittel in amounts of 0.5 to 9 wt .-%, preferably between 1 and 7.5 Wt .-%, and particularly preferably between 1.5 and 5 wt .-%, each based on the Particle weight.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The coating layer optionally applied to the part c) introduced into the cavity can applied to the surface of part c) and firmly connected to it, what for example by gluing, partial melting or by chemical reaction can be done.

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

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

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

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

The guar which can be used as a coating material in the context of the present invention, also called guar flour, is an off-white powder which, by grinding the endosperm, was originally endemic in Indian and Pakistani regions, but is now also available in other countries, e.g. B. cultivated in the south of the USA, the guar bean family (Cyamopsis tetragonobolus) is obtained from the legume family. The main constituent of the guar is up to approx. 85% by weight of the dry substance guaran (guar gum, cyamopsis gum); Minor components are proteins, lipids and cellulose. Guaran itself is a polygalactomannan, ie a polysaccharide, whose linear chain of unsubstituted (see formula I) and substituted in the C6 position with a galactose residue (see formula (II) mannose units in β-D- (1 → 4) link is established.

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

The pectins, which can also be used as coating material, are high-molecular glycosidic plant substances that are very common in fruits, roots and leaves. The pectins consist essentially of chains of 1,4-α-glycoside-linked galacturonic acid units, the acid groups of which are 20-80% esterified with methanol, one between high-esterified (<50%) and low-esterified pectins (<50%) differs. The pectins have a sheet structure and are thus in the middle of starch and cellulose molecules. Your macromolecules still contain some glucose, galactose, xylose and arabinose and have weakly acidic properties.

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

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

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

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

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

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

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

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

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

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

• a) water-soluble nonionic polymers from the group of
  • 1. polyvinylpyrrolidones,
  • 2. vinyl pyrrolidone / vinyl ester copolymers,
  • 3. Cellulose ether
• b) water-soluble amphoteric polymers from the group of
  • 1. Alkyl acrylamide / acrylic acid copolymers
  • 2. Alkyl acrylamide / methacrylic acid copolymers
  • 3. Alkyl acrylamide / methyl methacrylic acid copolymers
  • 4. Alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
  • 5. Alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
  • 6. Alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
  • 7. Alkyl acrylamide / alkyl methacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers
  • 8. Copolymers
    • 1. unsaturated carboxylic acids
    • 2. Canonically derivatized unsaturated carboxylic acids
    • 3. optionally further ionic or nonionic monomers
• c) water-soluble zwitterionic polymers from the group of
  • 1. Acrylamidoalkyltrialkylammoniumchlorid / acrylic acid copolymers and their alkali and ammonium salts
  • 2. Acrylamidoalkyltrialkylammoniumchlorid / methacrylic acid copolymers and their alkali and ammonium salts
  • 3. Methacroylethyl betaine / methacrylate copolymers
• d) water-soluble anionic polymers from the group of
  • 1. Vinyl acetate / crotonic acid copolymers
  • 2. Vinyl pyrrolidone / vinyl acrylate copolymers
  • 3. Acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers
  • 4. Graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols
  • 5. grafted and crosslinked copolymers from the copolymerization of
    • 1. at least one monomer of the non-ionic type,
    • 2. at least one monomer of the ionic type,
    • 3. of polyethylene glycol and
    • 4. a networked person
  • 6. copolymers obtained by copolymerizing at least one monomer of each of the following three groups:
    • 1. esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
    • 2. unsaturated carboxylic acids,
    • 3. Esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group d6ii) with saturated or unsaturated, straight-chain or branched C _8-18 alcohols
  • 7. Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester
  • 8. Tetra and pentapolymers
    • 1. Crotonic acid or allyloxyacetic acid
    • 2. Vinyl acetate or vinyl propionate
    • 3. branched allyl or methallyl esters
    • 4. Vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters
  • 9. Crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinymethyl ether, acrylamide and their water-soluble salts
  • 10. Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the α-position
• e) water-soluble cationic polymers from the group of
  • 1. quaternized cellulose derivatives
  • 2. Polysiloxanes with quaternary groups
  • 3. cationic guar derivatives
  • 4. polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid
  • 5. Copolymers of vinyl pyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate
  • 6. Vinyl pyrrolidone-methoimidazolinium chloride copolymers
  • 7. Quaternized polyvinyl alcohol
  • 8. Polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

Water-soluble polymers in the sense of the invention are those polymers which are at room temperature temperature are more than 2.5% by weight soluble in water.

The coating of the detergent tablets according to the invention can there be made from individual of the aforementioned polymers, but it can also Mixtures or multi-layer structures made of the polymers can be used. The Polymers are described in more detail below.

Water-soluble polymers preferred according to the invention are nonionic. Suitable non-ionogenic polymers are, for example:

• - Polyvinylpyrrolidones, such as those under the name Luviskol® (BASF) are sold. Polyvinyl pyrrolidones are preferred nonionic poly mere within the scope of the invention.  
• - Polyvinylpyrrolidone [Poly (1-vinyl-2-pyrrolidinone)], abbreviation PVP, are polymers of the general formula (III)
  which are produced by 40378 00070 552 001000280000000200012000285914026700040 0002019939992 00004 40259 radical polymerization of 1-vinylpyrrolidone by solution or suspension polymerization using radical formers (peroxides, azo compounds) as initiators. The ionic polymerization of the monomer only provides products with low molecular weights. Commercial polyvinylpyrrolidones have molar masses in the range of approx. 2500-750000 g / mol, which are characterized by the specification of the K values and - depending on the K value - have glass transition temperatures of 130-175 °. They are offered as white, hygroscopic powders or as aqueous solutions. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).
• - Vinyl pyrrolidone / vinyl ester copolymers, such as those found under the goods logo Luviskol® (BASF). Luviskol® VA 64 and Luviskol® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred nonionic polymers.

The vinyl ester polymers are polymers accessible from vinyl esters with the grouping of the formula (IV)

as a characteristic basic building block of macromolecules. Of these, the vinyl acetate polymers (R = CH ₃ ) with polyvinyl acetates are by far the most important technical representatives.

The vinyl esters are polymerized by free radicals using different processes (solution polymerization, suspension polymerization, emulsion polymerization, substance polymerization). Copolymers of vinyl acetate with vinyl pyrrolidone contain monomer units of the formulas (III) and (IV):

• - Cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and methyl hy droxypropyl cellulose, as they are for example under the trademark Culminal® and Benecel® (AQUALON) are sold.

Cellulose ethers can be described by the general formula (V)

in R represents H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products, at least one R in formula (III) is -CH ₂ CH ₂ CH ₂ -OH or -CH ₂ CH ₂ -OH. Cellulose ethers are produced industrially by etherification of alkali cellulose (e.g. with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of the cellulose have reacted with the etherification reagent or how many moles of the etherification reagent have been attached to an anhydroglucose unit on average. Hydroxyethyl celluloses are soluble in water from a DS of approx. 0.6 or an MS of approx. 1. Commercial hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS). Hydroxyethyl and propyl celluloses are marketed as yellowish white, odorless and tasteless powders in widely differing degrees of polymerization. Hydroxyethyl and propyl celluloses are soluble in cold droxyethyl and propyl celluloses are soluble in cold and hot water and in some (water-containing) organic solvents, but insoluble in most (anhydrous) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition.

Polyvinyl alcohols, abbreviated as PVAL, are polymers of the general structure

[-CH ₂ -CH (OH) -] _n

which in small proportions also structural units of the type

[-CH ₂ -CH (OH) -CH (OH) -CH ₂ ]

contain. Because the corresponding monomer, vinyl alcohol, does not exist in free form dig is, polyvinyl alcohols via polymer-analogous reactions by hydrolysis, technically in particular, however, by alkaline-catalyzed transesterification of polyvinyl aceta ten with alcohols (preferably methanol) in solution. Through this techni procedures are also accessible to PVAL, which have a predeterminable residual proportion Contain acetate groups.

Commercial PVAL (e.g. Mowiol® grades from Hoechst) come as white yellowish powder or granules with degrees of polymerization in the range of approx. 500-2500 (corresponding to molar masses of approx. 20,000-100,000 g / mol) in the trade and below different degrees of hydrolysis of 98-99 and 87-89 mol%. So you're partially saponified lyvinylacetate with a residual acetyl group content of approx. 1-2 or 11-13 mol%.

The water solubility of PVAL can be improved by post-treatment with aldehydes (acetal tion), by complexing with Ni or Cu salts or by treatment with dichro mate, reduce boric acid, borax and thus adjust to the desired values.

Other polymers suitable according to the invention are water-soluble amphopolymers. The amphoteric polymers are amphoteric polymers, ie polymers which contain both free amino groups and free -COOH or SO ₃ H groups in the molecule and are capable of forming internal salts, zwitterionic polymers which have quaternary ammonium groups and -COO ^- - or -SO ₃ ^- contain groups, and summarized such polymers that contain -COOH or SO ₃ H groups and quaternary ammonium groups. An example of an amphopolymer which can be used according to the invention is the acrylic resin available under the name Amphomer®, which is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) acrylamide and two or more monomers from the group consisting of acrylic acid, Methacrylic acid and its simple esters. Likewise preferred amphopolymers are composed of unsaturated carboxylic acids (e.g. acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (e.g. acrylamidopropyltrimethylammonium chloride) and optionally further ionic or nonionic monomers, such as, for example, in German rule 39 29 973 and the state of the art cited therein. Terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium chloride, as are commercially available under the name Merquat®2001 N, are particularly preferred amphopolymers according to the invention. Other suitable amphoteric polymers are, for example, the octylacrylamide / methyl methacrylate / tert.-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers available under the names Amphomer® and Amphomer® LV-71 (DELFT NATIONAL).

Suitable zwitterionic polymers are, for example, those in the German patent applications dungen DE 39 29 973, DE 21 50 557, DE 28 17 369 and DE 37 08 451 disclosed poly merisate. Acrylamidopropyltrimethylammonium chloride / acrylic acid or -Methacrylic acid copolymers and their alkali and ammonium salts are preferred zwitterionic polymers. Suitable zwitterionic polymers are methacroy Methyl betaine / methacrylate copolymers sold under the name Amersette® (AMERCHOL) are commercially available.

Anionic polymers suitable according to the invention include:

• - Vinyl acetate / crotonic acid copolymers, as described, for example, under the Be drawings Resyn® (NATIONAL STARCH), Luviset® (BASF) and Gafset® (GAF) are on the market.

In addition to monomer units of the above formula (IV), these polymers also have monomer units of the general formula (VI):

(-CH (CH ₃ ) -CH (COOH) -] _n (VI)

• - Vinylpyrrolidone / vinyl acrylate copolymers, available for example under the Wa logo Luviflex® (BASF). A preferred polymer is that under the designation Luviflex® VBM-35 (BASF) available vinyl pyrrolidone / acrylate terpolymers.
• - Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers, for example under the name Ultrahold® strong (BASF) are sold.
• - Graft polymers from vinyl esters, esters of acrylic acid or methacrylic acid alone or in a mixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polykalkylene glycols.

Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid alone or in a mixture with other copolymerizable compounds on polyalky Lenglycols are obtained by polymerization in the heat in a homogeneous phase ten that the polyalkylene glycols in the monomers of the vinyl esters, esters of acrylic acid or methacrylic acid, stirred in the presence of radical formers.

Suitable vinyl esters are, for example, vinyl acetate, vinyl propionate, vinylbu tyrate, vinyl benzoate and as an ester of acrylic acid or methacrylic acid those with low molecular weight aliphatic alcohols, in particular ethanol, Pro panol, isopropanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1- Pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-  Methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol, are available, proven.

Polyalkylene glycols in particular include polyethylene glycols and polypropylene glycols. Polymers of ethylene glycol which have the general formula VII

H- (O-CH ₂ -CH ₂ ) _n -OH (VII)

are sufficient, where n can take values between 1 (ethylene glycol) and several thousand. There are various nomenclatures for polyethylene glycols that can lead to confusion. The specification of the average relative molecular weight following the specification "PEG" is technically customary, so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210. A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and directly after the hyphen is followed by a number which corresponds to the number n in the formula V mentioned above. According to this nomenclature (so-called INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 ^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997), for example, PEG-4, PEG-6, PEG-8, PEG -9, PEG-10, PEG-12, PEG-14 and PEG-16 can be used. Polyethylene glycols are commercially available, for example, under the trade names Carbowax® PEG 200 (Union Carbide), Emkapol® 200 (ICI Americas), Lipoxol® 200 MED (HÜLS America), Polyglycol® E-200 (Dow Chemical), Alkapol® PEG 300 ( Rhône-Poulenc), Lutrol® E300 (BASF) and the corresponding trade names with higher numbers.

Polypropylene glycols (PPG) are polymers of propylene glycol that have the general formula VIII

are sufficient, n taking values between 1 (propylene glycol) and several thousand can. Technically important here are in particular di-, tri- and tetrapropylene glycol, i.e. H. the representatives with n = 2, 3 and 4 in formula VI.

In particular, the vinyl acetate copolymers grafted onto polyethylene glycols and the polymers of vinyl acetate and coton acid grafted onto polyethylene glycols can be used.

• - Grafted and crosslinked copolymers from the copolymerization of
  • a) at least one monomer of the non-ionic type,
  • b) at least one monomer of the ionic type,
  • c) of polyethylene glycol and
  • d) a crosslinker

The polyethylene glycol used has a molecular weight between 200 and more ren million, preferably between 300 and 30,000.

The non-ionic monomers can be of very different types and under the following are preferred: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, Allyl stearate, allyl laurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, Stearyl vinyl ether and 1-hexene.

The non-ionic monomers can equally be of very different types be, among them particularly preferred crotonic acid, allyloxyacetic acid, vinyls Acetic acid, maleic acid, acrylic acid and methacrylic acid contained in the graft polymers are.

Ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallylsucrose with 2 to 5 Allyl groups per molecule of saccharin.  

The grafted and crosslinked copolymers described above are preferably formed from:

• a) 5 to 85% by weight of at least one non-ionic type monomer,
• b) 3 to 80% by weight of at least one monomer of the ionic type,
• c) 2 to 50 wt .-%, preferably 5 to 30 wt .-% polyethylene glycol and
• d) 0.1 to 8% by weight of a crosslinking agent, the percentage of the crosslinking agent being formed by the ratio of the total weights of i), ii) and iii).
  • - Copolymers obtained by copolymerizing at least one monomer of each of the following three groups:
• e) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids ren,
• f) unsaturated carboxylic acids,
• g) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group ii) with saturated or unsaturated, straight-chain or branched C _8-18 alcohol.

Short-chain carboxylic acids or alcohols are understood to mean those with 1 to 8 carbon atoms, where the carbon chains of these compounds may be interrupted by double-bonded hetero groups such as -O-, -NH-, -S-.

• - Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester

These terpolymers contain monomer units of the general formulas (II) and (IV) (see above) and monomer units of one or more allyl or methallyesters of the formula IX:

wherein R ^{3 is} -H or -CH ₃ , R ^{2 is} -CH ₃ or -CH (CH ₃ ) ₂ and R ^{1 is} -CH ₃ or a saturated, straight-chain or branched C _1-6 alkyl radical and the sum of Carbon atoms in the radicals R ¹ and R ^{2 is} preferably 7, 6, 5, 4, 3 or 2.

The above-mentioned terpolymers preferably result from the copolymerization of 7 to 12% by weight of crotonic acid, 65 to 86% by weight, preferably 71 to 83% by weight of vinyl acetate and 8 to 20% by weight, preferably 10 to 17 % By weight of allyl or methally letsre of formula IX.

• - Tetra and pentapolymers
  • a) Crotonic acid or allyloxyacetic acid
  • b) vinyl acetate or vinyl propionate
  • c) branched allyl or methallyl esters
  • d) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters
• - Crotonic acid copolymers with one or more monomers from the group Ethylene, vinylbenzene, vinymethyl ether, acrylamide and their water-soluble salts
• - Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphati monocarboxylic acid branched in the α-position.

The anionic polymers in particular offer polycar as coating materials boxylates / polycarboxylic acids, polymeric polycarboxylates, polyaspartic acid, polyacetals and dextrins, which are described below.  

Usable organic coating materials are, for example, those in the form of their sodium salts but also polycarboxylic acids which can be used in free form. Polymeric polycarboxylates are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70,000 g / mol.

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

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

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

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

Biodegradable polymers are also particularly preferred as coating materials from more than two different monomer units, for example those that are mono mere salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol Derivatives or the monomers as salts of acrylic acid and 2-alkylallylsulfonic acid such as containing sugar derivatives.

Further preferred copolymeric coating materials are those which are described in the German Pa tent applications DE-A-43 03 320 and DE-A-44 17 734 are described and as Mo Nomers are preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyla have acetate.

Likewise, other preferred coating materials are polymeric aminodicarboxylic acids, to name their salts or their precursors. Polyas are particularly preferred Paraginic acids or their salts and derivatives.

Other suitable coating materials are polyacetals, which are obtained by reacting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 Hy have droxyl groups, can be obtained. Preferred polyacetals are made from Dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other polymers which can preferably be used as coating materials are cationic polymers re. The permanent cationic polymers are among the cationic polymers prefers. According to the invention, such polymers are considered to be “permanently cationic” records, regardless of the pH of the agent (i.e. both the coating layer and also of the rest of the detergent tablets) has a cationic group point. These are usually polymers that have a quaternary nitrogen atom, for example in the form of an ammonium group.

Preferred cationic polymers are, for example

• - Quaternized cellulose derivatives, such as those under the names Celquat® and Po lymer JR © are commercially available. The connections Celquat® H 100, Celquat® L 200 and Polymer JR® 400 are preferred quaternized cellulose derivatives.
• - Polysiloxanes with quaternary groups, such as those obtained commercially products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silylamodimethicone), Dow Corning® 929 emulsion (containing a hydroxylamino modified silicone, also called amodimethicone), SM-2059 (Manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80),
• - Cationic guar derivatives, in particular those under the trade names Cosme dia® Guar and Jaguar® products sold,
• - Polymer Dimethyldiallylammoniumsalze and their copolymers with esters and Amides of acrylic acid and methacrylic acid. The under the designations Mer quat® 100 (poly (dimethyldiallylammonium chloride)) and Merquat® 550 (dimethyl diallylammonium chloride-acrylamide copolymer) commercially available products are examples of such cationic polymers.
• - Copolymers of vinyl pyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, such as vinyl quaternized with diethyl sulfate pyrrolidone-dimethylaminomethacrylate copolymers. Such connections are under the names Gafquat® 734 and Gafquat® 755 are commercially available.
• - Vinylpyrrolidone-methoimidazolinium chloride copolymers, as described under the Be drawing Luviquat®.
• - quaternized polyvinyl alcohol

as well as those under the designations

• - polyquaternium 2,
• - Polyquaternium 17,
• - Polyquaternium 18 and
• - Polyquaternium 27

known polymers with quaternary nitrogen atoms in the main polymer chain. The ge polymers are named according to the so-called INCI nomenclature, with detailed information in the CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 ^th

Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, to which express reference is made here.

Cationic polymers preferred according to the invention are quaternized cellulose derivatives as well as polymeric dimethyldiallylammonium salts and their copolymers. Cationic Cel Lulose derivatives, especially the commercial product Polymer®JR 400, are very special preferred cationic polymers.

Carbon or dicarboxylic acids are also preferably used as coating materials, or those with an even number of carbon atoms. Particularly preferred carbon or Di carboxylic acids are those with at least 4, preferably with at least 6, particularly preferably with at least 8 and in particular those with 8 to 13 carbon atoms. Particularly preferred dicarboxylic acids are, for example, adipic acid, pimelic acid, Suberic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, brassylic acid and their mixtures. But also tetradecanoic acid, pentadecanoic acid and thapsic acid suitable coating materials. Particularly preferred carboxylic acids are those with 12 to 22 carbon atoms, with those having 18 to 22 carbon atoms being particularly preferred. The use of the disintegration aids described above is particularly important for Acid coating layers are recommended, with usual use concentrations for the Disintegration aid in the coating layers at 0.1 to 5 wt .-%, based on the Coating layer.

Regardless of the chemical composition of the coating layer are fiction according detergent tablets preferred, which characterized are that the coating layer, which fixes part c) in the cavity, a thickness of 1 to 150 µm, preferably from 2 to 100 µm, particularly preferably from 5 to 75 µm and in particular which has from 10 to 50 microns.  

The cavity filling [part c)] can also be in liquid, gel-like, pasty or plastic be introduced into the cavity. In cases where the cavity is not is closed by step d) of the method according to the invention, but the hollow If the space filling has an external surface, it is preferred that part c) after cures when inserted into the cavity. In addition to cooling highly viscous melt Other hardening mechanisms can also be used to form hard particles. So is it is also possible according to the invention to use suspensions or emulsions of active substance zen to use in curable matrices for step c), the curing example se by radiation (UV light, gamma rays, microwaves) or chemical reaction (Use of hardeners, oxidation, reduction, polymerization, polycondensation, polyaddi tion etc.).

If a melt solidifies due to the lowering of the temperature as a cavity filling is set by heating a composition of active substance (s) and optional carriers as well as meltable matrix materials in a flowable melt transferred. This melt is then filled into the cavity and allowed to cool, whereby solidification occurs. The above are suitable as meltable matrix materials envelope materials described in detail, in particular paraffins, polyethylene and polypro pylene glycols, waxes and mixtures thereof.

In certain cases (see above), the procedure is followed by filling the cavity in step d), in which the molded body manufactured in step b) pressed the cavity Part a) is used. This can be done in preferred embodiments of the present Invention lead to a closing of the cavity, but it is also possible to use openings release to realize certain dissolution and release kinetics.

The moldings produced according to the invention can, as described above, entirely or partially provided with a coating. Procedures in which the Nachbe act in step e) in applying a coating layer on the entire molded body there are preferred according to the invention. The coating materials that can be used for this were already described in detail.  

The laundry detergent and cleaning product tablets according to the invention can be packaged after manufacture, the use of certain packaging systems having proven particularly effective. Another aspect of the present invention is a combination of (a) detergent tablets according to the invention and a packaging system containing the detergent tablets, characterized in that the packaging system has a moisture vapor permeability rate of 0.1 g / m ² / Day to less than 20 g / m ² / day if the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%.

The packaging system of the combination of detergent tablets and packaging system according to the invention has a moisture vapor permeability rate 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 named temperature and humidity conditions are the test conditions that are mentioned in the DIN standard 53122, whereby according to DIN 53122 minimal deviations are permitted (23 ± 1 ° C, 85 ± 2% relative humidity). The moisture vapor permeability rate of a given packaging system or material can be determined by further standard methods and is, for example, also in the ASTM standard E-96-53T ("Test for measuring Water Vapor transmission of Materials in Sheet form") and in the TAPPI standard T464 m- 45 ("Water Vapor Permeability of Sheet Materials at high temperature and Humidity"). The measuring principle of current methods is based on the water absorption of anhydrous calcium chloride, which is stored in a container in the appropriate atmosphere, the container being closed at the top with the material to be tested. From the surface of the container, which is closed with the material to be tested (permeation surface), the increase in weight of calcium chloride and the exposure time, the moisture vapor transmission rate can be determined

calculate, where A is the area of the material to be tested in cm ² , x is the weight gain of calcium chloride in g and y is the exposure time in h.

The relative equilibrium humidity, often referred to as "relative humidity", is 85% at 23 ° C. when measuring the moisture vapor transmission rate within the scope of the present invention. The absorption capacity of air for water vapor increases with temperature up to a respective maximum content, the so-called saturation content, and is given in g / m ³ . For example, 1 m ^{3 of} air at 17 ° is saturated with 14.4 g of water vapor; at a temperature of 11 ° there is already saturation with 10 g of water vapor. The relative humidity is the ratio of the actual water vapor content to the saturation content corresponding to the prevailing temperature. For example, if air contains 17 ° 12 g / m ³ water vapor, then the relative humidity = (12 / 14.4) .100 = 83%. If you cool this air, then the saturation (100% r.L.) is reached at the so-called dew point (in the example: 14 °), ie, if it cools further, a precipitate is formed in the form of mist (dew). Hygrometers and psy chrometers are used for the quantitative determination of moisture.

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

The combinations of detergent tablets and Packaging system can of course in turn in secondary packaging for example, cardboard boxes or trays, are packed, with the secondary packaging no further requirements have to be made. The secondary packaging is that if possible, but not necessary.  

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

The packaging system of the combination according to the invention encloses depending on the design Form of the invention one or more detergent tablets. It is preferred according to the invention either to design a shaped body such that it comprises an application unit of the detergent and cleaning agent, and this form body to be packed individually, or the number of shaped bodies in one packaging unit to pack, which in total comprises an application unit. With a target dosage of According to the invention, 80 g of detergent and cleaning agent is possible to sweat an 80 g to produce and to individually package detergent tablets, it is but also possible according to the invention, two washing and cleaning agents each weighing 40 g Packing the shaped body in a packaging to form a Kombinati according to the invention to get on. This principle can of course be expanded, so that fiction three, four, five or even more detergents and cleaning agents according to combinations can contain molded articles in a packaging unit. Of course, two can or more moldings in one package have different compositions sen. In this way it is possible to spatially separate certain components separate, for example to avoid stability problems.

The packaging system of the combination according to the invention can differ from the materials and take on any external shape. From economic For reasons of and for reasons of easier processability, however, there are packaging systems Steme preferred, in which the packaging material is light in weight, easily process and is inexpensive. In combinations preferred according to the invention the packaging system consists of a sack or pouch made of single-layer or laminated Paper and / or plastic film.

The detergent tablets can be unsorted, i. H. as loose bulk tion, be filled into a bag made of the materials mentioned. But it is from aesthetic table reasons and for sorting the combinations in secondary packaging moves, the detergent tablets individually or in several sorted in  Fill sacks or bags. For individual application units for washing and cleaning molded article, which are in a sack or pouch, has in Tech nik the term "flow pack" naturalized. Such "flow packs" can then - again preferably sorted - optionally packed in outer packaging, what the compact Offer form of the molded body underlines.

The preferably used as a packaging system sacks or bags made of monolayer or laminated paper or plastic film 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 caused by heat (hot fusion), adhesives or adhesive tapes which are locked. Single-layer bag or sack materials are the known papers, which can optionally be impregnated, as well as plastic films, which can optionally be co-extruded. Plastic films that can be used as a packaging system in the context of the present invention are given, for example, in Hans Domininghaus "The plastics and their properties", 3rd edition, VDI Verlag, Düssel dorf, 1988, page 193. Fig. 111 shown there also gives reference points for the water vapor permeability of the materials mentioned.

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

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

As already mentioned above, the detergent tablets contain molded articles the combination according to the invention, depending on its intended use, further content fabrics of washing and cleaning agents in varying amounts. Regardless of the ver application of the shaped body, it is preferred according to the invention that the or Detergent tablets have a relative equilibrium moisture content of less than 30% at 35 ° C.

The relative equilibrium moisture content of the detergent tablets can are determined according to common methods, whereby within the scope of the present The following procedure was chosen for investigations: Liter jar with a lid, which has a closable opening for insertion of samples, was washed with a total of 300 g of detergent tablets filled with pern and kept at a constant 23 ° C for 24 h in order to maintain a constant temperature of Ensure vessel and substance. The water vapor pressure in the room over the form can then use a hygrometer (Hygrotest 6100, Testoterm Ltd., England) be true. The water vapor pressure is now measured every 10 minutes until two successive values show no deviation (equilibrium moisture). The above Hygrometer allows a direct display of the recorded values in% relative humidity action.

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

Another object of the present invention is a washing method for washing of textiles in a household washing machine, which is characterized in that one or more detergent tablets according to the invention in the Insert the washing machine's washing compartment and run a washing program, in the course of which the molded body or bodies are washed in.  

The molded article or articles do not have to be metered through the induction chamber, however can also be put directly into the washing drum. Both one Dosing aid, for example a net metering device, can be used, the shaped bodies can but can also be added directly to the laundry in the drum without metering aid. On Washing process for washing textiles in a household washing machine, in which one or more shaped detergent tablets according to the invention with or without dosing aid in the washing drum of the washing machine and a Letting the washing program run, in the course of which the shaped body or bodies is dissolved is therefore also an object of the present invention.

As mentioned above, detergent tablets can also be used for machines Manufacture dishwashing according to the inventive method. Is accordingly a cleaning method for cleaning dishes in a dishwasher, the characterized in that one or more washing (s) according to the invention and detergent tablets into the dosing chamber of the dishwasher and a Rinsing program can run, in the course of which the dosing chamber opens and the or the moldings are dissolved, another object of the present invention.

Also in the cleaning process according to the invention, one can check the metering chamber spruce and the shaped body or bodies according to the invention, for example, in the cutlery insert basket. Of course, the use of a dosing aid is also here for example, a basket that is attached in the sink, easily possible. Accordingly, a cleaning method for cleaning dishes in a ge dishwasher, in which one or more washing machine (s) according to the invention Detergent tablets with or without dosing aid in the dishwasher's wash cabinet inserted and a rinsing program can run, in the course of which the molded body (s) be resolved, another object of the present invention.

Claims (39)

1. Detergent tablets, comprising

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

characterized in that part b) does not completely fill the cavity in part a) and the remaining cavity is at least partially filled with active substance. 2. shaped detergent or cleaning product according to claim 1, characterized in that part b) closes the cavity in part a) and thus the remaining cavity is completely enclosed by a) and b). 3. shaped detergent or cleaning product according to one of claims 1 or 2, characterized characterized in that the weight ratio of part a) to part b) 1: 1 to 100: 1, before preferably 2: 1 to 80: 1, particularly preferably 3: 1 to 50: 1 and in particular 4: 1 to 30: 1 is. 4. Detergent or cleaning product tablet according to one of claims 1 to 3, characterized characterized in that the outwardly visible surface of part b) from 1 to 25% preferably 2 to 20%, particularly preferably 3 to 15% and in particular 4 to 10% of the Makes up the total surface of the filled molded body. 5. Detergent tablets according to one of claims 2 to 4, characterized characterized in that the volume ratio of that formed by parts a) and b) Cavity to the overall molded body 1: 1 to 50: 1, preferably 2: 1 to 40: 1, particularly is preferably 3: 1 to 30: 1 and in particular 4: 1 to 20: 1. 6. Detergent tablets according to one of claims 1 to 5, characterized characterized in that part b) dissolves faster than part a).   7. Detergent tablets according to one of claims 1 to 5, characterized characterized in that part b) dissolves more slowly than part a). 8. Detergent tablets according to one of claims 1 to 7, characterized in that the base tablet [part a)] has a density above 1000 kgdm ^-3 , preferably above 1025 kgdm ^-3 , particularly preferably above 1050 kgdm ^-3 and in particular above 1100 kgdm ^-3 . 9. shaped detergent or cleaning product according to one of claims 1 to 8, characterized characterized in that the basic shaped body builders in amounts of 1 to 100% by weight %, preferably from 5 to 95% by weight, particularly preferably from 10 to 94% by weight and in particular from 20 to 85% by weight, in each case based on the weight of the base molded body, contains. 10. shaped detergent or cleaning product according to one of claims 1 to 9, characterized characterized in that the base molding phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (natri um- or potassium tripolyphosphate), in amounts of 20 to 80 wt .-%, preferably from 25 to 75% by weight and in particular from 30 to 70% by weight, in each case based on the weight of the base molding. 11. shaped detergent or cleaning product according to one of claims 1 to 10, characterized characterized in that the base molding carbonate (s) and / or hydrogen carbonate (s), preferably alkali carbonates, particularly preferably sodium carbonate, in amounts of 5 to 50% by weight, preferably from 7.5 to 40% by weight and in particular from 10 to 30 % By weight, based in each case on the weight of the base molding. 12. Detergent tablets according to one of claims 1 to 11, characterized characterized in that the base molding silicate (s), preferably alkali silicates, be particularly preferably crystalline or amorphous alkali disilicates, in amounts of 10 to 60 % By weight, preferably from 15 to 50% by weight and in particular from 20 to 40% by weight %, each based on the weight of the base molding.   13. Detergent or cleaning product tablet according to one of claims 1 to 12, characterized characterized in that the base molding total surfactant content below 5 wt .-% %, preferably below 4% by weight, particularly preferably below 3% by weight and in particular below 2 wt .-%, each based on the weight of the Basic molded body. 14. Detergent tablets according to one of claims 1 to 13, characterized characterized in that the base molding bleach from the group of oxygen or halogen bleaching agents, in particular chlorine bleaching agents, with particular reference preference for sodium perborate and sodium percarbonate, in amounts from 2 to 25 % By weight, preferably from 5 to 20% by weight and in particular from 10 to 15% by weight, each based on the weight of the base molding. 15. Detergent tablets according to one of claims 1 to 14, characterized characterized in that the base molding bleach activators from the groups of multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), the N-acylimides, especially N-nonanoylsuccinimide (NOSI), the acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso- NOBS and n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), in amounts of 0.25 to 15% by weight, preferably from 0.5 to 10% by weight and in particular from 1 to 5 wt .-%, each based on the weight of the base molding, contains. 16. Detergent tablets according to one of claims 1 to 15, characterized characterized in that the base molding silver protection agent from the group of the tria zoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotria zoles and the transition metal salts or complexes, particularly preferably benzotriazole and / or alkylaminotriazole, in amounts of 0.01 to 5% by weight, preferably 0.05 up to 4 wt .-% and in particular from 0.5 to 3 wt .-%, each based on the Ge importance of the base molding.   17. Detergent tablets according to one of claims 1 to 16, characterized characterized in that the base molding continues to be one or more substances from the Groups of enzymes, corrosion inhibitors, scale inhibitors, cobuilders, color and / or fragrances in total amounts from 6 to 30% by weight, preferably from 7.5 to 25 wt .-% and in particular from 10 to 20 wt .-%, each based on the weight of the base molding. 18. Detergent tablets according to one of claims 1 to 17, characterized characterized in that the core molding [part b)] at least one active ingredient from the Group of enzymes, surfactants, soil-release polymers, disintegration aids, Bleaching agents, bleach activators, bleaching catalysts, silver preservatives and mixtures out of this, contains. 19. Detergent tablets according to one of claims 1 to 18, characterized characterized in that the base molding or inserted into the base molding Core moldings or the cavity filling contains bleach while at least another contains bleach activators. 20. Detergent tablets according to one of claims 1 to 19, characterized characterized in that the base molding or inserted into the base molding Core moldings or the cavity filling contains bleach while at least another part contains enzymes. 21. Detergent or cleaning product tablet according to one of claims 1 to 20, characterized characterized in that the base molding or inserted into the base molding Core moldings or the cavity filling contains bleach while at least another part contains anti-corrosion agents. 22. Detergent tablets according to one of claims 1 to 21, characterized characterized in that the base molding or inserted into the base molding Core moldings or the cavity filling contains bleach while at least another part of surfactants, preferably nonionic surfactants, with particular preference  addition of alkoxylated alcohols with 10 to 24 carbon atoms and 1 to 5 alkylene contains oxide units. 23. Detergent tablets according to one of claims 1 to 22, characterized characterized in that at least two of the three shaped body regions (basic shaped body, Core moldings, cavity filling) the same active ingredient in different amounts contain. 24. A process for the production of multi-phase detergent tablets, characterized by the steps

• a) pressing particulate premixes into shaped bodies which have at least one cavity,
• b) production of moldings which can be at least partially inserted into the cavity,
• c) filling part of the cavity with active substance in solid, liquid, highly viscous or plastic form,
• d) inserting the end products of process step b) into the cavity of the end products of step a),
• e) optional aftertreatment of the moldings.

25. The method according to claim 24, characterized in that the particulate pre mixtures in step a) a bulk density of at least 500 g / l, preferably at least have at least 600 g / l and in particular at least 700 g / l. 26. The method according to any one of claims 24 or 25, characterized in that the Particulate premixes in step a) particle sizes between 100 and 2000 µm, preferably between 200 and 1800 µm, particularly preferably between 400 and 1600 µm and in particular between 600 and 1400 µm. 27. The method according to any one of claims 24 to 26, characterized in that the pressing in step a) at pressing pressures from 0.01 to 50 kNcm ^-2 , preferably from 0.1 to 40 kNcm ^-2 and in particular from 1 to 25 kNcm ^-2 takes place. 28. The method according to any one of claims 24 to 27, characterized in that in step a) multilayered moldings are produced in a manner known per se by several different particulate premixes are pressed together. 29. The method according to claim 28, characterized in that in step a) two-layer Shaped bodies are made by two different particulate Vorgemi be pressed together, one of which contains one or more bleaches and the other contains one or more enzymes. 30. The method according to any one of claims 28 or 29, characterized in that in Step a) two-layer moldings are produced by using two different ones particulate premixes are pressed together, one of which is one or contains several bleaches and the other one or more bleach activators. 31. The method according to any one of claims 24 to 30, characterized in that the Shaped body in step b) by casting, extrusion, extrusion or sintering getting produced. 32. The method according to any one of claims 24 to 30, characterized in that the Moldings in step b) are produced by tableting. 33. The method according to any one of claims 24 to 32, characterized in that the Ka vity in step c) with a mixture of adhesion promoters) and active substances) be is filled. 34. The method according to any one of claims 24 to 33, characterized in that the Ka vita in step c) with at least one active substance from the group of bleaching agents, Bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescence mit tel, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical Auf brighter, graying inhibitors, color transfer inhibitors and corrosion inhibitors is filled.   35. Combination of (a) detergent tablet (s) according to one of claims 1 to 24 and a packaging system containing the detergent tablet or tablets, characterized in that the packaging system has a moisture vapor permeability rate of 0.1 g / m ² / Day to less than 20 g / m ² / day if the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%. 36. Washing method for washing textiles in a household washing machine, there characterized in that one or more washing or cleaning agents Shaped body according to one of claims 1 to 24 in the washing chamber of the washing machine insert machine and run a washing program, in the course of which the Shaped bodies are washed in. 37. Washing method for washing textiles in a household washing machine, there characterized in that one or more detergents and cleaning agents Shaped body according to one of claims 1 to 24 with or without dosing aid in the Insert the washing drum of the washing machine and run a washing program, in the course of which or the shaped body are dissolved. 38. Cleaning method for cleaning dishes in a dishwasher, because characterized in that one or more detergents and cleaning agents Shaped body according to one of claims 1 to 24 in the dosing chamber of the dishwasher inserted and a rinsing program can run, in the course of which the dosing chamber opens and the molded article (s) are dissolved. 39. Cleaning process for cleaning dishes in a dishwasher, because characterized in that one or more detergents and cleaning agents Shaped body according to one of claims 1 to 24 with or without dosing aid in the rinse insert the dishwasher and run a washing program, in the course of which the shaped body or bodies are dissolved.