WO2001005929A1

WO2001005929A1 - Detergent moulded bodies and lined cleansing agents

Info

Publication number: WO2001005929A1
Application number: PCT/EP2000/006321
Authority: WO
Inventors: Thomas Holderbaum
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1999-07-14
Filing date: 2000-07-05
Publication date: 2001-01-25
Also published as: AU5536300A; CA2313875A1; DE19932765A1

Abstract

The invention concerns a method which consists in inserting liquid, gel, pasty or particulate ingredients in the cavity of a compacted moulded body, then in closing the cavity with a film to prevent the ingredients for being temperature- and pressure-stressed so as to increase the number of possible formulations, even in cases where there is incompatibility of use between the different ingredients.

Description

, Filled detergent tablets "

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

Detergent tablets are widely described in the prior art and are becoming increasingly popular with consumers because of the simple dosage. Tableted cleaning agents have a number of advantages over powdered products: They are easier to dose and handle and, thanks to their compact structure, have advantages in terms of storage and transport. There is therefore an extremely broad state of the art for detergent tablets, which is also reflected in an extensive patent literature. At an early stage, the developers of tablet-shaped products came up with the idea of releasing certain ingredients through differently composed areas of the molded articles only under defined conditions in the washing or cleaning cycle, in order to improve cleaning success. In addition to the core / shell tablets and ring / core tablets which are well known from pharmacy, multi-layered shaped articles have become established, which are now offered for many areas of washing and cleaning or hygiene. The optical differentiation of the products is also becoming increasingly important, so that single-phase and single-color moldings in the field of washing and cleaning have largely been replaced by multi-phase moldings. Two-layer moldings with a white and a colored phase or with two differently colored layers are currently customary on the market. In addition, there are point tablets, toroidal tablets, coated tablets, etc., which currently have a rather minor meaning.

Multi-phase cleaning tablets for the toilet are described for example in EP 055 100 (Jeyes Group). This document discloses blocks of toilet cleaners that comprise a molded body of a slowly soluble detergent composition in which a bleach tablet is embedded. At the same time, this document discloses the most varied forms of configuration of multiphase shaped bodies. According to the teaching of this document, the moldings are produced either by inserting a compressed bleach tablet into a mold and pouring this tablet with the detergent composition, or by pouring part of the detergent composition into the mold, followed by inserting the compressed bleach tablet and possibly subsequently pouring over it with another Detergent composition.

EP 481 547 (Unilever) also describes multi-phase detergent tablets which are to be used for automatic dishwashing. These shaped bodies are in the form of core / shell tablets and are produced by gradually compressing the constituents: first, a bleaching agent composition is pressed into a shaped body, which is placed in a matrix half-filled with a polymer composition, which is then filled with another polymer composition and into one provided with a polymer jacket molded bleach is pressed. The process is then repeated with an alkaline detergent composition, so that a three-phase shaped body results.

Another way of producing optically differentiated detergent tablets is described in international patent applications WO99 / 06522, WO99 / 27063 and WO99 / 27067 (Procter & Gamble). According to the teaching of these documents, a shaped body is provided which has a cavity which is filled with a solidifying melt. Alternatively, a powder is filled in and fixed in the cavity by means of a coating layer. All three applications have in common that the area filling the cavity should not be pressed, since pressure-sensitive ingredients are to be protected in this way.

The way described in the prior art to prepare melts into which tablets are placed or which are poured into moldings involves thermal stressing of the ingredients in the melts. In addition, the exact dosage requires liquid to pasty media and the subsequent cooling, a high technical outlay which, depending on the composition of the melt, is partially offset by shrinkage during cooling and the resulting detachment of the filling. The filling of cavities with powdery ingredients and the fixation by means of coating is also complex and has similar stability problems.

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

Pressing in particulate compositions into cavities of moldings solves the problem of the thermal stress on these fillings, but on the other hand can lead to a delay in the release of this pressed part, which requires the addition of dissolving accelerators if an accelerated release of the ingredients from this region is required. The introduction of liquid, yellow or pasty media is not possible using the pouring process or pressing, if these media do not solidify during production.

The present invention was based on the object of providing moldings in which both temperature and pressure-sensitive ingredients can be introduced into delimited regions, the size of the delimited region being subject to no restrictions with respect to the overall shaped body. On the one hand, an optical differentiation from conventional two-layer tablets should be achieved, on the other hand, the production of the molded articles should work safely without large technical effort, even in large series, without the molded articles having disadvantages in terms of stability or inaccuracies in the dosage. In addition, an accelerated release of the ingredients from the delimited region should be possible without being tied to certain recipe modifications. A form of induction should be provided which is independent of the state of matter of the active substances or mixtures of active substances to be introduced into the region, whereby those active substances which are incompatible with conventional dissolving accelerators or disintegration aids should also be able to be incorporated into the region and released from the region in an accelerated manner. Last but not least, liquids, gels or pastes should also be able to be permanently incorporated without changing this state until use.

It has now been found that the disadvantages mentioned are avoided if liquid, gel-like, pasty or solid ingredients are introduced into a cavity of a pre-compressed molded body and the cavity is sealed with a film. In this way, the temperature or pressure load of the ingredients is excluded and the mentioned task complex is solved.

The invention relates to detergent tablets made of compressed, particulate detergent and detergent in which the tablet has at least one cavity, the opening (s) of which is / are closed with a film.

The cavity in the molded body produced in step a) can have any shape. It can cut through the molded part, i.e. have an opening on the top and bottom of the molded body, but it can also be a cavity that does not extend through the entire molded body, the opening of which is only visible on one side of the molded body.

The shaped bodies according to the invention can take on any geometric shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, five, ellipsoid hexagonal and octagonal prismatic and rhombohedral shapes are preferred. Completely irregular base areas such as arrow or animal shapes, trees, clouds, etc. can also be realized. If the shaped bodies according to the invention have corners and edges, they are preferably rounded. As an additional optical differentiation, an embodiment with rounded corners and beveled (“gripped”) edges is preferred. Of course, the molded bodies according to the invention can also be produced in multiple phases. For reasons of process economy, two-layer molded bodies have proven particularly useful here.

The shape of the cavity can also be freely selected within wide limits. For reasons of process economy, through holes, the openings of which lie on opposite surfaces of the molded body, and troughs with an opening on one side of the molded body have proven successful. In preferred washing and cleaning agent shaped bodies, the cavity has the shape of a through hole, the openings of which are located on two opposing shaped body surfaces. The shape of such a through hole can be chosen freely, with shaped bodies being preferred in which the through hole has circular, elliptical, triangular, rectangular, square, pentagonal, hexagonal, seven-sided or octagonal horizontal sections. Completely irregular hole shapes such as arrow or animal shapes, trees, clouds etc. can also be realized. As with the molded bodies, in the case of square holes, those with rounded corners and edges or with rounded corners and chamfered edges are preferred.

The geometric implementation forms mentioned above can be combined with one another as desired. Shaped bodies with a rectangular or square base and circular holes can be produced as well as round shaped bodies with octagonal holes, whereby there are no limits to the variety of possible combinations. For reasons of process economy and aesthetic consumer perception, molded bodies with a hole are particularly preferred in which the molded body base and the hole cross-section have the same geometric shape, for example molded bodies with a square base and a centrally incorporated square hole. Ring-shaped bodies are particularly preferred, i.e. circular shaped body with a circular hole.

If the above-mentioned principle of the hole open on two opposite sides of the shaped body is reduced to one opening, trough shaped bodies are obtained. Detergent shaped articles according to the invention, in which the cavity has the shape of a depression, are likewise preferred. As with the "perforated bodies", the invented The inventive shaped body also assume any geometrical shape in this embodiment, in particular concave, convex, biconcave, biconvex, cubic, tetrahedral, orthorhombic, cylindrical, spherical, cylinder segment-like, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, elliptical, pyramidal -, Hexagonal and octagonal-prismatic and rhombohedral shapes are preferred. Completely irregular base areas such as arrow or animal shapes, trees, clouds, etc. can also be realized. If the molded body has corners and edges, these are preferably rounded. As an additional optical differentiation, an embodiment with rounded corners and beveled (“chamfered”) edges is preferred.

The shape of the trough can also be chosen freely, preference being given to shaped bodies in which at least one trough has a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid , five, seven and octagonal prismatic and rhombohedral shape can take. Completely irregular trough shapes such as arrow or animal shapes, trees, clouds, etc. can also be realized. As with the molded bodies, troughs with rounded corners and edges or with rounded corners and chamfered edges are preferred. Trough shapes as described in the older German patent application DE 198 22 973.9 (Henkel KGaA), to which express reference is made here, are particularly preferred.

The size of the trough or the through hole in comparison to the entire molded body depends on the intended use of the molded body. The size of the cavity can vary depending on whether the cavity is to be filled with further active substance and whether a smaller or larger amount of active substance is to be contained. Regardless of the intended use, detergent tablets are preferred in which the volume ratio of molded article to cavity is 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. The volume ratio is calculated from the volume of the finished molded body according to the invention, ie the molded body which has the cavity which is closed with the film and the volume of the cavity. The difference between the two volumes gives the volume of the molded body with cavity, in which the cavity is not sealed with foil. is closed. In other words: if the molded body has, for example, an orthorhombic shape with side lengths of 2, 3 and 4 cm and has a trough with a volume of 2 cm, the volume of this “basic molded body” is 22 cm of the ratio used volume is 24 cm ³ , since the trough is closed with film and thus an orthorhombic molded body without a trough is present on the outside, in this example the ratio of the volumes is therefore 12: 1. In the case of volume ratios molded body: cavity below 2: 1, which can of course also be implemented according to the invention, the instability of the walls can increase.

Similar statements can be made regarding the surface proportions that the molded body with the cavity (“basic body”) or the opening area of the cavity make up on the entire surface of the molded body. Here, detergent molded article bodies are preferred in which the area of the opening (s ) of the cavity (s) constitutes 1 to 25%, preferably 2 to 20%, particularly preferably 3 to 15% and in particular 4 to 10% of the total surface of the molded body. The total surface of the molded body again corresponds to the total surface of the molded body with the cavity closed, in the above example, regardless of the opening area of the trough, 52 cm ^2. The opening (s) of the cavity in such an exemplary molded body in preferred embodiments of the present invention thus have an area of 0.52 to 13 cm, preferably 1 , 04 to 10.4 cm ² , particularly preferably 1.56 to 7.8 cm ² and in particular 2.08 to 5.2 cm ² .

The molded body according to the invention with a cavity are characterized in that the opening (s) of the cavity (s) are closed with film. In the context of the present invention, the term “closed” is to be understood to mean that the film which closes the opening of the cavity (s) is adhesively bonded to the molded body. Packaging in which the molded body is inserted is therefore unsatisfactory the criterion of "closing" according to the invention.

The film, which closes the opening (s) of the cavity (s), is applied to the surface of the molded body and bonded firmly to it, which can be done, for example, by gluing, partial melting or by chemical reaction. It is It is possible to apply the film to all surfaces of the molded body and to bond them firmly, so that the film forms a coating, a "coating" of the entire molded body. Preferred detergent and cleaning molded bodies are characterized in that the film does not enclose the entire molded body.

For reasons of process economy and aesthetic impression, it is preferred that the film is only applied to the molded body surfaces where it fulfills a function, i.e. serves to close cavities. Detergent tablets in which the film only covers the surfaces of the molded article in which there are openings in the cavity (s) are therefore preferred.

The cavity-closing film can of course also be a laminate of several differently composed films, the opening of the cavity can be released at certain times in the washing and cleaning cycle via different compositions of individual film layers, which is particularly advantageous if the closed cavity contains further active substance ,

Preferred film materials are the polymers known from the prior art. In particular, detergent tablets are preferred in which the film consists of a polymer with a molecular weight of 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 into which detergents and cleaning agents are usually introduced, detergent tablets are particularly preferred in which the film consists of a water-soluble polymer.

Such preferred polymers can be synthetic or natural in origin. If polymers on a native or partial basis are used as film material, then detergent tablets are preferred, in which the film material is selected from one or more substances from the group consisting of carrageenan, guar, pectin, xanthan, cellulose and their derivatives, starch and their derivatives as well as 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 molecular weights of 100000-800000 and a sulfate content of approx. 25%, which is very easily soluble in warm water. There are three main components in carrageenan: The yellow-forming / fraction consists of D-galactose-4-sulfate and 3,6-anhydro-α-D-galactose, which are alternately glycosidically linked in the 1,3- and 1,4-positions (In contrast, agar contains 3,6-anhydro-α-L-galactose). The non-gelling 1 fraction is composed of 1,3-glycosidically linked D-galactose-2-sulfate and 1,4-linked D-galactose-2,6-disulfate residues and is readily soluble in cold water. The i-carrageenan composed of D-galactose-4-sulfate in 1,3-bond and 3,6-anhydro-aD-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, ß, γ, μ, v, 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 film materials in the context of the present invention are also called carrag (h) eenate.

The guar, also known as guar flour, which can be used as a film material in the context of the present invention, is an off-white powder which, by grinding the endosperm, is endemic to Indian and Pakistani regions and is now also available in other countries, for example in the south of the USA. cultivated guar bean (Cyamopsis tetragonobolus) belonging to 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, the linear chain of which is unsubstituted (see formula I) and substituted in the C6 position with a galactose residue (see formula (II)) mannose units in β-D- (l -> 4) - Link is established. galactose

Manno

II

The ratio of 1:11 is approximately 2: 1; contrary to 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. 2.2T0 ⁵ -2.2T0 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 that can also be used as film 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. connected galacturonic acid units, the acid groups of which are 20-80% esterified with methanol, a distinction being made between highly esterified (> 50%) and low-esterified pectins (<50%). 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 molar masses of the various pectins vary between 10,000 and 500,000. The structural properties are also strongly dependent on the degree of polymerization; so form e.g. the fruit pectins in the dried state asbestos-like fibers, the flax pectins, on the other hand, fine, granular powder.

The pectins are produced by extraction with dilute acids, mainly from the inner parts of citrus fruit peel, leftovers or sugar beet pulp.

Xanthan can also be used as a film 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 ß-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:

Basic unit of xanthan

The celluloses and their derivatives are also suitable as film materials. Pure cellulose has the formal gross composition (C ₆ H] ₀ O ₅ ) _n and, viewed formally, is a ß-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 derivatives which can be obtained from cellulose by polymer-analogous reactions can also be used as cellulose-based film material in the context of the present invention. 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 amino celluloses. In addition to cellulose and cellulose derivatives, (modified) dextrins, starch and starch derivatives can also be used as film materials.

Dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches, are suitable as nonionic organic film materials. The hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as international patent applications WO 92 / 18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608. An oxidized oligosaccharide according to German patent application DE-A-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 film material for the detergent tablets according to the invention. Starch is a homoglycan, with the glucose units linked α-glycosidically. Starch is made up of two components of different molecular weights: 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), in addition there are only a few Contain quantities of lipids, phosphoric acid and cations. While the amylose is long due to the 1,4-position binding, While the amylose forms long, helical, intertwined chains with about 300-1200 glucose molecules as a result of the binding in the 1,4-position, the chain in the amylopectin branches to an knot-like structure after an average of 25 glucose units through 1,6-binding with about 1500-12000 molecules of glucose. In addition to pure starch, starch derivatives which can be obtained from starch by polymer-analogous reactions are also suitable as film materials in the context of the present invention. Such chemically modified starches include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Starches in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as starch derivatives. The group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and starches and amino starches.

Among the proteins and modified proteins, gelatin is of outstanding importance as a film material. Gelatin is a polypeptide (molecular weight: approx. 15,000-> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions. The amino acid composition of the gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance. The use of gelatin as a water-soluble coating material is extremely widespread, especially in the pharmaceutical industry in the form of hard or soft gelatin capsules.

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

a) water-soluble nonionic polymers from the group of al) polyvinylpyrrolidones, a2) vinylpyrrolidone / vinyl ester copolymers, a3) cellulose ethers

b) water-soluble amphoteric polymers from the group of

b 1) alkyl acrylamide / acrylic acid copolymers b2) alkyl acrylamide / methacrylic acid copolymers b3) alkyl acrylamide / methyl methacrylic acid copolymers b4) alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b5) alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid -

Copolymers b6) alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid

Copolymers b7) alkyl acrylamide / alkyl methacrylate alkylaminoethyl methacrylate / alkyl methacrylate copolymers b8) copolymers from b8i) unsaturated carboxylic acids b8ii) cationically derivatized unsaturated carboxylic acids bδiii) optionally further ionic or nonionic monomers

c) water-soluble zwitterionic polymers from the group of

cl) acrylamidoalkyltialkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts c2) acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali and ammonium salts c3) methacroylethylbetaine / methacrylate copolymers

d) water-soluble anionic polymers from the group of

dl) vinyl acetate / crotonic acid copolymers d2) vinylpyrrolidone-vinyl acrylate copolymers d3) acrylic acid / ethyl acrylate / N-tert-butyl acrylamide particles d4) 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 glycol and / or polyalkylene glycol and / or polyalkylene glycol grafted and crosslinked copolymers from the copolymerization of d5i) at least one monomer of the nonionic type, d5ii) at least one monomer of the ionic type, d5iii) of polyethylene glycol and d5iv) a crosslinked d6) obtained by copolymerization of at least one monomer from each of the following three groups Copolymers: d6i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, dόii) unsaturated carboxylic acids, d6iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group dόii) with g esättigten or unsaturated, linear or branched C ₈ _8- ι - alcohol d7) terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester d8) tetra- and pentapolymers of D8i) crotonic acid or allyloxyacetic d8ii) vinyl acetate or vinyl propionate dδiii) branched allyl - or methallyl esters d8iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters d9) crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinylmethylether, acrylamide and their water-soluble salts dlO) Teφolymers 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

el) quaternized cellulose derivatives e2) polysiloxanes with quaternary groups e3) cationic guar derivatives e4) polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid e5) copolymers of vinylpyrrolidone with quaternized derivatives of dialkylmethacrylate6) Vinylpyrrolidone-methoimidazolinium chloride copolymers e7) quaternized polyvinyl alcohol e8) polymers given the INCI names Polyquaternium 2, Polyquatemium 17, Polyquaternium 18 and Polyquatemium 27.

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

The films of the detergent tablets according to the invention can be produced from individual polymers mentioned above, but it is also possible to use mixtures or multilayered layers composed of the polymers. The polymers are described in more detail below.

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

Polyvinylpyrrolidones, such as those sold under the name Luviskol (BASF). Polyvinylpyrrolidones are preferred nonionic polymers in the context of the invention. Polyvinylpyrrolidones [poly (l-vinyl-2-pyrrolidinone)], abbreviation PVP, are polymers of the general formula (III)

which are prepared by free-radical polymerization of 1-vinylpyrrolidone by solution or suspension polymerization using free-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 from 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 presented as white, hygroscopic powders or as aqueous ones. Solutions offered. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).

Vinylpyrrolidone / Vinylester copolymers, as are marketed, for example under the trademark Luviskol ^® (BASF). Luviskol ^® VA 64 and Luviskol ^® VA 73, each vinylpyrrolidone-vinyl acetate copolymers, are particularly preferred nonionic polymers.

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

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

The vinyl esters are polymerized by free radicals using various processes (solution polymerization, suspension polymerization, emulsion polymerization, bulk 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 hydroxypropylcellulose Methylhy- as they are for example sold under the trademark Culminal® ^® and Benecel ^® (AQUALON).

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 (eg 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 in cold Hydroxyethyl and propyl celluloses are soluble in cold and hot water and in some (water-containing) organic solvents, but insoluble in most (water-free) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or 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. Since the corresponding monomer, the vinyl alcohol, is not stable in free form, polyvinyl alcohols are produced in solution via polymer-analogous reactions by hydrolysis, but technically in particular by alkaline-catalyzed transesterification of polyvinyl acetates with alcohols (preferably methanol). These technical processes also make PVAL accessible which contain a predeterminable residual proportion of acetate groups.

Commercial PVAL (e.g. Mowiol ^® types from Hoechst) are commercially available as white-yellow powders or granules with degrees of polymerization in the range of approx. 500-2500 (corresponding to molar masses of approx. 20,000-100,000 g / mol) and have different degrees of hydrolysis of 98 -99 or 87-89 mol%. They are therefore partially saponified polyvinyl acetates with a residual acetyl group content of approx. 1-2 or 11-13 mol%.

The water solubility of PVAL can be reduced by post-treatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus adjust to the desired values.

Other polymers suitable according to the invention are water-soluble amphopolymers. The generic term amphopolymers are amphoteric polymers, ie polymers that are kül contain both free amino groups and free -COOH or SO ₃ H groups and are capable of forming internal salts, zwitterionic polymers which contain quaternary ammonium groups and -COO ^" or -SO ₃ ^" groups in the molecule, and such polymers summarized, which contain -COOH- or SO ₃ H groups and quaternary ammonium groups. An example of the present invention amphopolymer suitable is that available under the name Amphomer ^® acrylic resin which is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) -acrylamide and two or more monomers from the group 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. acrylamidopropyl-trimethyl-ammonium chloride) and optionally further ionic or non-ionic monomers, as described, for example, in German Offenlegungsschrift 39 29 973 and the one cited therein State of the art can be found. Terpolymers of acrylic acid, methyl acrylate and Methacrylamidopropyltrimoni- monium chloride, such as those sold under the name Merquat ^® 2001 N in the trade, are particularly preferred erfmdungsgemäß amphopolymers. Other suitable amphoteric polymers are, for example, / 2-hydroxypropyl methacrylate copolymers of the octylacrylamide / methyl tert-butylaminoethyl methacrylate available under the names Amphomer ^® and Amphomer ^® LV-71 (DELFT NATIONAL).

Suitable zwitterionic polymers are, for example, the polymers disclosed in German patent applications DE 39 29 973, DE 21 50 557, DE 28 17 369 and DE 37 08 451. AcrylamidopropyltrimethylammoniumchloriαVA acrylic acid or methacrylic acid copolymers and their alkali and ammonium salts are preferred zwitterionic polymers. Further suitable zwitterionic polymers are Methacroy- lethylbetain / methacrylate copolymers, which are available under the name Amersette® ^® (AMERCHOL).

Anionic polymers suitable according to the invention include: Vinyl acetate / crotonic acid copolymers, such as are commercially available for example under the names Resyn ^® (National Starch), Luviset ^® (BASF) and Gafset ^® (GAF).

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, obtainable for example under the trade name Luviflex ^® (BASF). A preferred polymer is that available under the name Luviflex VBM-35 ^® (BASF) vinylpyrrolidone / acrylate terpolymers.

Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide tepolymers, which are sold, for example, under the name Ultrahold ^® strict (BASF).

Graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols

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

Suitable vinyl esters are, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and as esters of acrylic acid or methacrylic acid, those which are used with low molecular weight aliphatic alcohols, in particular ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3 Methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol, are available.

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 customary in technical terms, 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 immediately 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- th

Nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997) include PEG-4, PEG-6, PEG-8, PEG-9, PEG-10, PEG-12 , PEG-14 and PEG-16 can be used. Commercially available polyethylene glycols are, for example, under the trade name Carbowax ^® PEG 200 (Union Carbide), Emkapol ^® 200 (ICI Americas), Lipoxol ^® 200 MED (Huls America), polyglycol ^® E-200 (Dow Chemical), Alkapol ^® PEG 300 (Rhone -Poulenc), Lutrol ^® E300 (BASF) and the corresponding trade names with higher numbers.

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

H- (O-CH-CH ₂ ) _n -OH (VIII)

CH ₃ are sufficient, where n can have values between 1 (propylene glycol) and several thousand. Of particular technical importance here are di-, tri- and tetrapropylene glycol, ie 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 crotonic acid grafted onto polyethylene glycols can be used.

grafted and crosslinked copolymers from the copolymerization of i) at least one monomer of the nonionic type, ii) at least one monomer of the ionic type, iii) of polyethylene glycol and iv) a crosslinker

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

The non-ionic monomers can be of very different types and 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-witch.

The non-ionic monomers can likewise be of very different types, of which crotonic acid, allyloxyacetic acid, vinyl acetic acid, maleic acid, acrylic acid and methacrylic acid are particularly preferably contained in the graft olamers.

Preferred crosslinkers 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: i) 5 to 85% by weight of at least one monomer of the nonionic type, ii) 3 to 80% by weight of at least one monomer of the ionic type, iii) 2 to 50% by weight, preferably 5 to 30% by weight, of polyethylene glycol and iv) 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) is.

Copolymers obtained by copolymerizing at least one monomer of each of the following three groups: i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, ii) unsaturated carboxylic acids, iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group ii) with saturated or unsaturated, linear or branched C ₈ _8- ι - alcohol

Short-chain carboxylic acids or alcohols are to be understood as meaning those having 1 to 8 carbon atoms, the carbon chains of these compounds optionally being interrupted by double-bonded hetero groups such as -O-, -NH-, -S_.

Teφolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester

These polymers 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:

R ¹ R ³

R ² -CC (O) -O-CH ₂ - C = CH ₂ (IX)

CH ₃ 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 Cι _-6 alkyl radical and the sum of the carbon atoms in the radicals R ¹ and R ^{2 is} preferably 7, 6, 5, 4, 3 or 2.

The above-mentioned polymers 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 .-% allyl or methallyl esters of the formula IX.

Tetra- and penta-polymers of i) crotonic acid or allyloxyacetic acid ii) vinyl acetate or vinyl propionate iii) branched allyl or methallyl esters iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters

Crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinymethyl ether, acrylamide and their water-soluble salts

Tepolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the α-position.

In the case of anionic polymers, film materials in particular are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, polyaspartic acid, polyacetals and dextrins, which are described below.

Usable organic film materials are, for example, the polycarboxylic acids which can be used in the form of their sodium salts but also in free form. Polymeric polycarboxylates are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol. In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the investigated polymers. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

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

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

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

Also particularly preferred as film materials are biodegradable polymers composed of more than two different monomer units, for example those which, as monomers, salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives, or which, as monomers, salts of acrylic acid and 2-alkylallylsulfonic acid and Contain sugar derivatives. Further preferred copolymeric film materials are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Also to be mentioned as further preferred film materials are polymeric aminodicarboxylic acids, their salts or their precursors. Polyaspartic acids or their salts and derivatives are particularly preferred.

Other suitable film materials are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other polymers that can preferably be used as film materials are cationic polymers. The permanent cationic polymers are preferred among the cationic polymers. According to the invention, polymers which have a cationic group irrespective of the pH of the composition (ie both the film and the rest of the detergent and cleaning product body) are referred to as “permanently cationic”. These are generally polymers which have a quaternary nitrogen atom, for example in the form of an ammonium group.

Preferred cationic polymers are, for example

quaternized cellulose derivatives, as are commercially available under the names Celquat ^® and Polymer JR ^® . The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives. Polysiloxanes with quaternary groups, such as the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silylamodimethicon), Dow Coming ^® 929 Emulsion (containing a hydroxylamino- modified silicone, which is also called amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quatemium-80 )

Cationic guar derivatives, such as, in particular, the products sold under the trade names Cosmedia ^® Guar and Jaguar ^® ,

Polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium 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, for example, vinyl pyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat ^® 734 and Gafquat ^® 755. Vinylpyrrolidone methoimidazolinium chloride copolymers, as offered under the name Luviquat.RTM ^®, quaternized polyvinyl alcohol

as well as those under the designations

Polyquatemium 2, Polyquatemium 17, Polyquatemium 18 and Polyquatemium 27

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

Handbook, 5 Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, which is incorporated herein by reference. Cationic polymers preferred according to the invention are quaternized cellulose derivatives and polymeric dimethyldiallylammonium salts and their copolymers. Cationic cellulose derivatives, in particular the commercial product Polymer ^® JR 400, are very particularly preferred cationic polymers.

Regardless of the chemical composition of the film, detergent tablets according to the invention are preferred, which are characterized in that the film that closes the cavity has a thickness of 1 to 150 μm, preferably 2 to 100 μm, particularly preferably 5 to 75 μm and in particular from 10 to 50 μm.

Together with the molded body, which has at least one cavity, the film bonded to the molded body forms the detergent molded body according to the invention. In the case of closed mold bodies, the structure of the mold bodies according to the invention is reminiscent of a “drum” in which a cavity is closed by a film. According to the invention, it is possible to leave the cavity empty and to use only the optical attraction of such mold bodies, preferred washing and form of detergent are characterized in that the active substance contains the active substance in the space enclosed by the film and the molded body.

In this way, a molded body according to the invention comprises two areas in which different ingredients are contained or different release mechanisms and release kinetics can be realized. The active substance contained in the cavity can take on any physical state or any form of presentation. Preferred detergent tablets contain the further active substance in liquid, gel-like, pasty or solid form.

When incorporating liquid, gel-like or pasty active substances or active substance mixtures, the composition of the molded article and the film must be matched to the filling in order to avoid premature destruction of the film or loss of active substance through the molded article. This is only of minor importance when incorporating solid substances into the cavity (chemical incompatibilities) required so that preferred washing and cleaning agent shaped bodies contain further active substance in particle form, preferably in powdered, granular, extruded, pelleted, tested, flaky or tableted form.

The cavity closed by the film can be completely filled with further active substance. However, it is also possible to fill the cavity only partially before closing, in order in this way to enable the filled particles or liquids to move within the cavity. Particularly when filling with regularly shaped larger particles, attractive optical effects can be achieved. In this case, detergent tablets are preferred, in which the volume ratio of the space enclosed by the film and the tablet to the active substance contained in this room is particularly preferably 1: 1 to 100: 1, preferably 1.1: 1 to 50: 1 1.2: 1 to 25: 1 and in particular 1.3: 1 to 10: 1. In this terminology, a volume ratio of 1: 1 means that the cavity is completely filled.

Depending on the size of the cavity, the density of the molded body, the density of the active substance in the cavity and the degree of filling of the cavity, the proportion of the further active substance in the cavity can make up different proportions of the overall molded body. Here, detergent tablets are preferred in which the weight ratio of molded body to the active substance contained in the space enclosed by the film and the molded body is 1: 1 to 100: 1, preferably 2: 1 to 80: 1, particularly preferably 3: 1 to 50: 1 and in particular 4: 1 to 30: 1. The weight ratio defined above is the ratio of the mass of the unfilled molded article (“basic molded article”) to the mass of the filling. The mass of the film is not taken into account in this calculation.

The time at which the substance contained in the cavity is released can be predetermined by suitable packaging of the molded body and film material. For example, the film can be instantly soluble, so that the active substance contained in the cavity is dosed into the washing or cleaning liquor right at the beginning of the washing or cleaning cycle. Alternatively, the film can be so bad be soluble that only the molded body is dissolved and the active substance contained in the cavity is thereby released.

Depending on this release mechanism, molded bodies can be realized, for example, in which the active substance contained in the cavity is present in the cleaning liquor before the components of the molded body are dissolved or after this has happened. Thus, on the one hand, detergent tablets are preferred, which are characterized in that the active substance contained in the space enclosed by the film and the tablet dissolves faster than the basic tablet.

However, detergent molded articles in which the active substance contained in the space enclosed by the film and the molded article dissolves more slowly than the basic molded article are preferred embodiments of the present invention.

The molded bodies according to the invention consist of a basic molded body which has one or more cavities, film (s) which close these cavities (s) and, optionally, active substance (s) contained in the cavity (s). The film materials and preferred physical parameters of the films have already been described above. There now follows a description of the constituents of the basic molded body, which can at the same time be active substances which are contained in the cavity, and an enumeration of preferred physical parameters for the basic molded body and filling of the cavity. Incooration of certain constituents on the one hand can specifically accelerate the solubility of the filling of the cavity, and on the other hand the release of certain ingredients from this filling can lead to advantages in the washing or cleaning process. Ingredients that are preferably at least partially located in the cavity are, for example, the surfactants, enzymes, soil-release polymers, builders, bleaching agents, bleach activators, bleaching catalysts, optical brighteners, silver preservatives, etc., described below.

In preferred embodiments of the present invention, the basic molded body has a high specific weight. Detergent shaped bodies, which are characterized in that the basic shaped body has a density above 1000 kgdm ^" , preferably above 1025 kgdm ^" , particularly preferably above 1050 kgdm ^" ³ and in particular above 1100 kgdm ^"3 , are preferred according to the invention.

Further details on the physical parameters of the basic molded article or the finished detergent molded article and information on the production can be found below. The preferred ingredients of the basic molded body are shown below.

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

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

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

Amorphous sodium silicates with a module Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The dissolving delay compared to conventional amorphous sodium silicates can be done in different ways, for example be caused by surface treatment, compounding, compacting / compaction or overdrying. In the context of this invention, the term "amoφh" is also understood to mean "roentgenamoφh". 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 integrated in such a way that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray silicates.

Preferred detergent tablets in the context of the present invention are characterized in that the base tablet (s), preferably alkali silicates, particularly preferably crystalline or amorphous alkali disilicates, in amounts of 10 to 60% by weight, preferably 15 to 50% by weight. -% and in particular from 20 to 40 wt .-%, each based on the weight of the basic molded body, 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 of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula

nNa ₂ O ^• (ln) K ₂ O ^• Al ₂ O ₃ ^• (2 - 2.5) SiO ₂ ^• (3.5 - 5.5) H ₂ O can be described. The zeolite can be used both as a builder in a granular compound and can also be used for a kind of "powdering" of the entire mixture to be used, usually both ways of incohering the zeolite into the premix. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

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

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

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 like ^"3 , melting point 60 °) and as a monohydrate (density 2.04 like ^{" 3} ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P Og) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; it occurs when phosphoric acid is adjusted to pH 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt with a density of 2.33 ^"3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 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 gladly ^"3 , water loss at 95 °), 7 mol. (Density 1.68 gladly ^{" 3} , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 like ^"3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to diphosphate Na ₄ P ₂ O when heated more. Disodium hydrogen phosphate is used by neutralizing phosphoric acid with soda solution Made from phenolphthalein as an indicator Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

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

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 like ^"3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 like ^{" 3} , melting point 94 ° with loss of water) , 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 dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 ^"3 , which is soluble in water, the pH of the 1% solution at 25 ° being 10.4.

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

The technically important pentasodium triphosphate, Na ₅ P ₃ θι ₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O. -Na with n = 3. Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength 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 Oιo + H ₂ O

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

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

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

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

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

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

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

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

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

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

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

Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 owns. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0472 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- is also suitable. 196 00 018. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

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

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

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

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

The substances mentioned from the group of builders and cobuilders can of course be part of the compositions contained in the cavity.

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

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Suitable surfactants of the sulfonate type are preferably C i-π- alkyl benzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from _2- Cι ι ₈ -Monoolefmen with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates, which consist of C ₂ - ₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization be won. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerin esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become. Preferred sulfated fatty acid glycerol esters are the sulfate products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

As alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C ₂ -C ₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₀ -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, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₂ -C ₆ alkyl sulfates and C ₂ -C 8 alkyl sulfates and Cj ₄ -C ₁₅ alkyl sulfates are preferred for reasons of washing technology. In addition, 2,3-alkyl sulfates, which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7- ι alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ . ₁₁ alcohols containing on average 3.5 mol ethylene oxide (EO) or C] _2- ι ₈ fatty alcohols containing 1 to 4 EO, are also suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight. Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8- ι ₈ 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 whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

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

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

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical has a methyl or linear branching in the 2-position may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. Preferred ethoxylated alcohols include, for example C _{_12-1} 4 alcohols containing 3 EO or 4 EO, C ₉ n-alcohol with 7 EO, C _13- ι ₅ alcohols containing 3 EO, 5 EO, 7 EO or 8 EO , Cj ₂ . 1 ₈ - alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Cι _2- ι ₄ alcohol with 3 EO and Cι _2- ιg alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.

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

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (X), R ^]

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

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

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

R! -OR ²

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

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R represents a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C - 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 thereof residue.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fractose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example, after the teaching of international application WO-A-95/07331 can be converted into the desired polyhydroxyfatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

In the context of the present invention, detergent tablets which contain anionic (s) and nonionic (s) surfactant (s) are preferred as detergent tablets, application-specific advantages being able to result from certain quantitative ratios in which the individual surfactant classes are used.

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

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

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

Similar to the nonionic surfactants, the omission of anionic surfactants from individual or all phases can result in detergent tablets which are more suitable for certain areas of application. It is therefore in Within the scope of the present invention, detergent tablets are also conceivable in which at least one phase of the tablet is free from anionic surfactants.

As already mentioned, the use of surfactants in detergent tablets for machine dishwashing is preferably limited to the use of nonionic surfactants in small amounts. In the context of the present invention, detergent tablets preferably to be used as detergent tablets are characterized in that the base tablet has total surfactant contents below 5% by weight, preferably below 4% by weight, particularly preferably below 3% by weight and in particular below of 2 wt .-%, based in each case on the weight of the basic molded body. Only weakly foaming nonionic surfactants are usually used as surfactants in automatic dishwashing detergents. By contrast, representatives from the groups of anionic, cationic or amphoteric surfactants are of lesser importance. The detergent tablets according to the invention for machine dishwashing particularly preferably contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C1 ₂ - ₁ 4 alcohols with 3 EO or 4 EO, Cg.n alcohol with 7 EO, Cι _3- i ₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Cι _2- ι ₄ alcohol with 3 EO and Cι _2- ι ₈ alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow ranks ethoxylates, NRE). In addition to these nonionic surfactants, too Fatty alcohols with more than 12 EO can be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In particular in the production of detergent tablets or detergent tablets for machine dishwashing according to the invention, it is preferred that the detergent tablets contain a nonionic surfactant which has a melting point above room temperature. Accordingly, at least one of the deformable masses in the process according to the invention preferably contains a nonionic surfactant with a melting point above 20 ° C. Nonionic surfactants to be used preferably have melting points above 25 ° C., particularly preferred nonionic surfactants have melting points between 25 and 60 ° C., in particular between 26.6 and 43.3 ° C.

Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If highly viscous nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.

Preferred nonionic surfactants to be used at room temperature originate from the groups of alkoxy-etherified nonionic surfactants, in particular ethoxylated primary alcohols, and mixtures of these surfactants with structurally more complex surfactants such as polyoxypropylene / 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, the nonionic surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon 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 resulted.

A particularly preferred nonionic surfactant which is solid at room temperature is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _6-20 alcohol), preferably a C ₈ alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol, of ethylene oxide , Among these, the so-called "narrow ranks ethoxylates" (see above) are particularly preferred.

The nonionic surfactant, which is solid at room temperature, preferably has additional propylene oxide units in the molecule. Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol portion of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.

Further nonionic surfactants with melting points above room temperature which are to be used with particular preference contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which comprises 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol of propylene oxide and 25 % By weight of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Nonionic surfactants that can be used with particular preference are available, for example, from the company Olin Chemicals under the name Poly Tergent® SLF-18. Another preferred surfactant can be represented by the formula

R ^I 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 having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x denotes values between 0.5 and 1, 5 and y represents 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 and R 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 and R 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 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, if x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH) 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 is has been chosen as an example here and can certainly be larger, the range of variation increasing with increasing x values and for example including 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, R and R 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. Particularly preferred are surfactants in which the radicals R ¹ and R ² 9 have up to 14 carbon 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 incorporate disintegration aids, so-called tablet disintegrants, into the basic moldings in order to shorten the disintegration times. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, p. 182-184), tablet disintegrants or accelerators of decay are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in an absorbable form.

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

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred washing and cleaning agent shaped bodies such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 contain up to 6 wt .-%. Pure cellulose has the formal gross composition (C ₆ HιoO ₅ ) _n and, formally speaking, is a ß-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 not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free from cellulose derivatives is particularly preferably used as the disintegrant based on cellulose. The cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be treated. Detergent tablets, which contain disintegrants in granular or optionally granulated form, are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO98 / 40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 μm and in particular at least 90% by weight between 400 and 1200 μm. The above and described in more detail in the documents cited coarser disintegration aids, are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ^® TF-30-HG from Rettenmaier available in the present invention.

Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged. A subsequent disaggregation of the microfine celluloses resulting from the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 μm and can be compacted, for example, to granules with an average particle size of 200 μm.

Detergent tablets preferred in the context of the present invention additionally contain a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight. -% and in particular from 4 to 6 wt .-%, each based on the molded body weight. The detergent tablets according to the invention can also contain a gas-developing shower system both in the base tablet and in the cavity. The gas-developing shower system can consist of a single substance that releases a gas when it comes into contact with water. Among these compounds, magnesium peroxide should be mentioned in particular, which releases oxygen on contact with water. Usually, however, the gas-releasing bubble system itself consists of at least two components that react with one another to form gas. While a large number of systems are conceivable and executable here, which release nitrogen, oxygen or hydrogen, for example, the bubbling system used in the detergent tablets according to the invention can be selected on the basis of both economic and ecological considerations. Preferred effervescent systems consist of alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.

In the case of the alkali metal carbonates or bicarbonates, the sodium and potassium salts are clearly preferred over the other salts for reasons of cost. Of course, the pure alkali metal carbonates or bicarbonates in question do not have to be used; rather, mixtures of different carbonates and hydrogen carbonates may be preferred.

In preferred detergent tablets, the shower system is 2 to 20% by weight, preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or bicarbonate and 1 to 15, preferably 2 to 12 and in particular 3 to 10% by weight of an acidifying agent, based in each case on the entire molded body.

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

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

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Cleaning agents according to the invention can also contain bleaching agents from the category of organic bleaching agents. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxyacids, examples of which include alkylperoxyacids and arylperoxyacids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monophosphate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimoxyhexoxyperoxanoic peroximethanoic acid (PAP)], o-

Carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1, 9-diperoxyazelaic acid, diperocysebacic acid, diperoxydalsyliperoxybutyldoxybutyldoxybutyldiacid, 4-diperoxydiacid, 4-diperoxydiacid, 4-diperoxyacid, -diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used. Chlorine or bromine-releasing substances can also be used as bleaching agents in the detergent tablets according to the invention for machine dishwashing. Suitable chlorine or bromine-releasing materials include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

The bleaching agents are usually used in machine dishwashing detergents in amounts of 1 to 30% by weight, preferably 2.5 to 20% by weight and in particular 5 to 15% by weight, based in each case on the detergent. In the context of the present invention, the proportions mentioned relate to the weight of the basic molded body.

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

Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable are substances which carry O- and / or N-acyl groups of the stated number of carbon atoms and / or optionally substituted benzoyl groups. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso-NOBS), Carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-Moφholinium-Acetonitril-Methylsulfat (MMA), and those from the German patent applications DE 196 16 693 and DE 196 16 767, and also acetylated sorbitol and mannitol and the mixtures thereof (SORMAN), acylated sugar derivatives, especially pentaacetylglucose (PAG), pentaacetyl fructose, tetraacetyl xylose and octaacetyl lactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams , for example N-benzoylcaprolactam. Hydrophilically substituted acylacetals and acyllactams are also preferably used. Combinations of conventional bleach activators can also be used. The bleach activators are usually used in machine dishwashing detergents in amounts of 0.1 to 20% by weight, preferably 0.25 to 15% by weight and in particular 1 to 10% by weight, based in each case on the detergent. In the context of the present invention, the proportions mentioned relate to the weight of the basic molded body.

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

Bleach activators from the grappa of multiply acylated alkylenediamines, in particular tetraacetylethylene diamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (N-) or iso , n-Methyl-Moφholinium-Acetonitril-Methylsulfat (MMA), preferably in amounts up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, particularly 2 to 8 wt .-% and particularly preferred 2 to 6 wt .-% based on the total agent used. Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably cobalt (ammin) - Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate are used in conventional amounts, preferably in an amount of up to 5% by weight, in particular 0.0025% by weight .-% to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total agent used. But in special cases, more bleach activator can be used.

Washing and cleaning agent shaped bodies, which are characterized in that the basic shaped body bleach from the grape of oxygen or halogen bleaches, in particular chlorine bleaches, with particular preference for sodium perborate and sodium percarbonate, in amounts of 2 to 25% by weight, preferably of 5 to 20 wt .-% and in particular from 10 to 15 wt .-% each based on the weight of the Basisformköφers mass, are a preferred embodiment of the present invention.

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

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

In preferred detergent tablets in the context of the present invention, the base tablet contains silver protective agents from the grappa of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes, particularly preferably benzotriazole and / or alkylaminotriazole, in Amounts from 0.01 to 5 wt .-%, preferably from 0.05 to 4 wt .-% and in particular from 0.5 to 3 wt .-%, each based on the weight of the basic molded body.

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

In addition to the ingredients mentioned above, there are other classes of substances for incohering in detergents and cleaning agents. Thus, detergent tablets are preferred, in which the base tablet also contains one or more substances from the groups of enzymes, corrosion inhibitors, scale inhibitors, cobuilders, coloring agents. and / or fragrances in total 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 weight of the basic molded body.

In addition to the constituents mentioned, builder, surfactant, disintegration aid, bleach and bleach activator, the detergent tablets according to the invention can contain further ingredients common in detergents and cleaners from the grape of dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, anti-redeposition agents, graying inhibitors and color transfer inhibitors Corrosion inhibitors included.

Suitable enzymes in the basic form are in particular those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as stains containing protein, fat or starch. Oxidoreductases can also be used for bleaching. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Here are enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytically active enzymes or of protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes, but especially protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases. The enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.5 to about 4.5% by weight. Preferred detergent tablets in the context of the present invention are characterized in that the basic tablet contains protease and / or amylase.

Because the detergent tablets according to the invention can contain the enzyme (s) in two fundamentally different areas (in the base tablet and / or as an active substance or mixture of active substances in the cavity), molded articles with a very precisely defined enzyme release and action can be contained provide. The table below gives an overview of possible enzyme distributions in detergent shaped bodies according to the invention:

Dyes and fragrances can be added to the detergent shaped bodies according to the invention both in the basic shaped body and in the preparations contained in the cavity, in order to improve the aesthetic impression of the resulting products and to provide the consumer with a visually and sensorially "typical and to provide distinctive "product. Individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutylate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl benzyl propylate and styl. The ethers include, for example, benzylethyl ether, the aldehydes include, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones include, for example, the jonones, α-isomethylionone and methylcedryl ketone the alcohols anethol, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and teφineol, the hydrocarbons mainly include tephenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citras, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lentil flower oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil. The fragrances can be incorporated directly into the detergents and cleaning agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.

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

The detergent tablets according to the invention can contain one or more optical brighteners. These fabrics, which are also called "whiteners", are used in modern laundry detergents because even freshly washed and bleached white laundry has a slight yellow tinge. Optical brighteners are organic dyes that convert part of the invisible UV radiation from sunlight into longer-wave blue light. The emission of this blue light complements the "gap" in the light reflected by the textile, so that a textile treated with an optical brightener appears whiter and brighter to the eye. Since the action mechanism of brighteners presupposes that they are drawn onto the fibers, a distinction is made depending on the "dyed" fibers, for example brighteners for cotton, polyamide or polyester fibers. The commercially available brighteners suitable for incoφoration in detergents essentially comprise five structural groups of the stilbene, the diphenylstilbene, the coumarin-quinoline, the diphenylpyrazoline group and the group of the combination of benzoxazole or benzimidazole with conjugated systems. An overview of common brighteners can be found, for example, in G. Jakobi, A. Löhr "Detergents and Textile Washing", VCH-Verlag, Weinheim, 1987, pages 94 to 100. Salts of 4,4'-bis [(4-anilino-6- moφholino-s-triazin-2-yl) amino] -stilbene-2,2'-disulfonic acid or compounds of the same structure which instead of the Moφholino group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brighteners can also be used.

In addition, the detergent tablets can also contain components that positively influence the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component. The preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, based in each case the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

Foam inhibitors that can be used in the agents according to the invention are, for example, soaps, paraffins or silicone oils, which can optionally be applied to carrier materials.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or strength. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof are preferably used in amounts of 0.1 to 5% by weight, based on the detergent

Since textile fabrics, in particular rayon, rayon, cotton and their mixtures, can be wrinkled because the individual fibers prevent bending and kinking. If pressing and squeezing across the fiber direction are sensitive, the agents according to the invention can contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

To combat microorganisms, the agents according to the invention can contain antimicrobial active ingredients. Depending on the antimicrobial spectrum and the mechanism of action, a distinction is made between bacteriostatics and bactericides, fungiostatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarlylsulfonates, halophenols and phenol mercuriacetate, although these compounds can be dispensed with entirely.

In order to prevent undesirable changes in the agents and / or the treated textiles caused by the action of oxygen and other oxidative processes, the agents can contain antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

Increased wearing comfort can result from the additional use of antistatic agents, which are additionally added to the agents according to the invention. Antistatic agents ßem the surface conductivity and thus allow an improved flow of charges. External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. External antistatic agents are described, for example, in patent applications FR 1,156,513, GB 873 214 and GB 839 407. The lauryl (or stearyl) dimethylbenzylammonium chlorides disclosed here are suitable as antistatic agents for textiles or as an additive to detergents, an additional finishing effect being achieved.

To improve the water absorption capacity, the rewettability of the treated textiles and to facilitate the ironing of the treated textiles, for example silicone derivatives can be used in the agents according to the invention. These additionally improve the rinsing behavior of the agents due to their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylsiloxanes, in which the alkyl groups have one to five carbon atoms and are partially or completely fluorinated. Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. The viscosities of the preferred silicones at 25 ° C. are in the range between 100 and 100,000 centistokes, the silicones being used in amounts between 0.2 and 5% by weight, based on the total agent.

Finally, the agents according to the invention can also contain UV absorbers, which absorb onto the treated textiles and improve the light resistance of the fibers. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone with substituents in the 2- and / or 4-position which are effective through radiationless deactivation. Substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural products such as umbelliferone and the body's own urocanoic acid are also suitable. The ingredients described above can of course also be incorporated into the cavity filling. Preferred detergent tablets in the context of the present invention are characterized in that the active substance contained in the space enclosed by the film and the molded article contains at least one active ingredient from the grappa of enzymes, surfactants, soil-release polymers, disintegration aids, bleaching agents, bleach activators , Bleaching catalysts, silver preservatives and mixtures thereof.

By dividing the detergent tablets according to the invention into basic tablets and the active substance (s) or active substance mixtures or preparation (s) contained in the cavity, ingredients can be separated from one another, which either improves the storage stability-improving separation of incompatible ingredients or leads to a controlled release of certain active substances can be used. In preferred detergent tablets, the base tablet or the active substance contained in the space enclosed by the film and the tablet contains bleaching agents, while the other area of the tablet contains bleach activators.

Further preferred washing and cleaning agent molded articles are characterized in that the basic molded article or d contains the bleach contained in the active substance contained in the space enclosed by the film and the molded article, while the other area of the molded article contains enzymes.

A separation of bleach and corrosion inhibitors or silver protection agents can also be achieved. Detergent tablets, in which the base tablet or the active substance contained in the space enclosed by the film and the tablet contains bleach, while the other area of the tablet contains deformable masses of anti-corrosion agents, are also preferred.

Last but not least, detergent tablets are also preferred, in which the base tablet or the active substance contained in the space enclosed by the film and the tablet contains bleach, while the other area of the Formköφers surfactants, preferably nonionic surfactants, with particular preference for alkoxylated alcohols having 10 to 24 carbon atoms and 1 to 5 alkylene oxide units.

With all of the above-mentioned ingredients, advantageous properties can result from separating them from other ingredients or assembling them together with certain other ingredients. In the molded articles according to the invention, the individual areas can also have a different content of the same ingredient, as a result of which advantages can be achieved. Detergent molded articles in which the basic molded article and the active substance contained in the space enclosed by the film and the molded article contain the same active ingredient in different amounts are preferred. The term “different amount” refers not to the absolute amount of the ingredient in the relevant part of the molded body, but to the relative amount, based on the phase weight, ie represents a% by weight based on the individual area, thus the basic molded body or the cavity filling.

The active substance optionally to be incorporated into the cavity is preferably particulate. The term “active substance” in the context of the present invention is not restricted to pure substances. Rather, it denotes pure active substances, active substance mixtures and preparation forms, so that there are no limits to the freedom of formulation. If particulate substances are included in the cavity (s), it is preferred if these specific particle size criteria meet, so that preferred detergent and shaped articles are characterized in that the active substance contained in the space enclosed by the film and the shaped article has particle sizes between 100 and 5000 μm, preferably between 150 and 2500 μm, particularly preferably between 200 and 2000 μm and in particular between 400 and 1600 μm.

Particularly preferred particulate compositions to be introduced into the cavity (s) of the moldings according to the invention are those which contain surfactants, it being preferred to use these surfactants in machine-dishwashing detergents in a solution-delayed form. in order to achieve a release of the surfactants from the cavity filling only in the rinse cycle. Rinse aid articles such as are described in the older German patent application DE 199 14.364.1 (Henkel KGaA) have proven particularly useful for this purpose. Such 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 of one or more active substances and 0 to 10% by weight of further active substances and auxiliaries, so that detergent tablets are preferred in which the active substance contained in the space enclosed by the film and the tablet comprises particles which from 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% by weight of one or more active substances, and d) 0 to 10% by weight of other active ingredients and auxiliaries exist.

Reference is expressly made to the disclosure of this document. Nevertheless, the most important ingredients of these "rinse aid articles" which can preferably be introduced into the cavity are described below. Carriers a) are all substances which are solid at room temperature. Usually, substances will be selected which have an additional effect in the cleaning cycle, with builders being particularly suitable Preferred particulate rinse aids for filling the cavity include, as carrier materials, substances from the category of water-soluble detergent and cleaning agent ingredients, preferably carbonates, hydrogen carbonates, sulfates, phosphates and organic oligocarboxylic acids which are solid at room temperature in amounts of 55 to 85% by weight. -%, preferably from 60 to 80 wt .-% and in particular from 65 to 75 wt .-%, each based on the particle weight.

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

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

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

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

Natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walnut, lanolin (wool wax), or broom wax, mineral wax or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes.

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

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

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

Particularly preferred coating substances in the active substance particles to be pressed into the well are those from the grappa of polyethylene glycols (PEG) and / or polypropylene glycols (PPG), polyethylene glycols with molecular weights between 1500 and 36,000 being preferred, those with molecular weights from 2000 to 6000 being particularly preferred and those with molecular weights of 3000 to 5000 are particularly preferred.

Active substance particles which contain propylene glycols (PPG) and / or polyethylene glycols (PEG) as the sole coating substance are particularly preferred. Polypropylene glycols (abbreviation PPG) which can be used according to the invention are polymers of propylene glycol which have the general formula XII

H- (O-CH-CH ₂ ) _n -OH (XII)

I CH ₃

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

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

H- (O-CH ₂ -CH ₂ ) _n -OH (XIII) are sufficient, where n can have values between 20 and approx. 1000. The preferred molecular weight ranges mentioned above correspond to preferred ranges of the value n in formula IV from approximately 30 to approximately 820 (exactly: from 34 to 818), particularly preferably from approximately 40 to approximately 150 (precisely: from 45 to 136) and in particular from about 70 to about 120 (exactly: from 68 to 113).

The coating substance contained in the active substance particles according to the invention preferably contains 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 60% by weight, approximately 70% by weight or approximately 80% by weight are particularly suitable, with even higher proportions of, for example, more than 90% by weight being particularly preferred. In a special embodiment of the invention, the total amount of the coating substance used consists exclusively of paraffin wax.

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

Paraffin waxes consist mainly of alkanes and low levels of iso- and cycloalkanes. The paraffin to be used according to the invention preferably has essentially no constituents with a melting point of more than 70 ° C., particularly preferably of more than 60 ° C. Portions of high-melting alkanes in the paraffin can leave undesired wax residues on the surfaces to be cleaned or the goods to be cleaned if the melting temperature in the detergent solution drops below this. Such wax residues usually lead to an unsightly appearance on the cleaned surface and should therefore be avoided. Particulate rinse aid which can preferably be introduced into the cavity contain at least one paraffin wax with a melting range of 50 ° C. to 60 ° C. as the coating substance.

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

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

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

The principle described above is used to delay the release of ingredients at a certain point in the cleaning cycle and can be used particularly advantageously when washing in the main wash cycle at a lower temperature (for example 55 ° C.), so that the active substance from the active substance particles only rinses at higher rinses Temperatures (approx. 70 ° C) is released.

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 of 40 ° C to 75 ° C in amounts of 6 to 30% by weight, preferably of, as the coating substance 7.5 to 25 wt .-% and in particular from 10 to 20 wt .-%, each based on the particle weight. Shaped and detergent tablets are particularly preferred in which the particles contained in the cavity contain paraffin (s) or polyalkylene glycols, in particular polyethylene glycols, as the coating substance.

The active substances contained in the active substance particles to be introduced into the cavity according to the invention can be in solid as well as liquid form at the processing temperature (i.e. at the temperature at which the particles are produced).

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

One or more substances from the groups of surfactants, enzymes, bleaching agents, bleach activators, corrosion inhibitors, scale inhibitors, cobuilders and / or fragrances in amounts of 6 to 30% by weight are therefore present as active substances in the active substance particles which are preferably incorporated into the cavity (s). preferably from 7.5 to 25 wt .-% and in particular from 10 to 20 wt .-%, each based on the particle weight. Particularly preferred are detergent tablets, in which the active substance particles contained in the space enclosed by the film and the tablet as active substances are nonionic surfactant (s) and / or bleaching agents and / or bleach activators and / or enzyme (s) and / or contain corrosion inhibitors and / or fragrances.

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

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

Another class of active substances that can be incorporated particularly advantageously into the active substance particles that can be incorporated according to the invention are bleaching agents. Particles can be produced and introduced into the cavity (s) that release the bleaching agent only when certain temperatures are reached, for example ready-made cleaning agents that clean enzymatically in the pre-rinse cycle and only release the bleaching agent in the main rinse cycle. Detergents for automatic dishwashing can also be produced in such a way that additional bleaching agent is released in the rinse cycle and is more effective in removing difficult stains, for example tea stains.

In particulate active substance particles which can preferably be incorporated into the cavity, the active substance (s) is / are selected from the group of oxygen or halogen bleaches, in particular chlorine bleaches. These substances have also been described in detail.

Another class of compounds which can preferably be used as active substances in the active substance particles which can be introduced according to the invention are the bleach activators. The important representatives from this group of fabrics have already been described. In the context of the present invention, active substance particles which are preferably pressed into the well contain bleach activators as active substance, in particular from the grappa 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), n-methyl-morpholium 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. Particularly preferred here as particulate particles to be introduced into the cavity (s) are those 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 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 detergent tablets are characterized in that the active substance contained in the space enclosed by the film and the tablet comprises particles consisting 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 coating substance (s) which have a melting point above 30 ° C., b) 0.5 to 60% by weight. %, preferably 1 to 40% by weight, particularly preferably 2.5 to 30% by weight and in particular 5 to 25% by weight of one or more liquid enzyme preparation (s) dispersed in the coating substance (s) ) and c) 0 to 20% by weight, preferably 0 to 15% by weight, particularly preferably 0 to 10% by weight and in particular 0 to 5% by weight of further carrier materials, auxiliaries and / or active substances.

The coating substances are preferably polyethylene glycols and / or polypropylene glycols, and liquid enzyme preparations have proven themselves as active substances. Such rivers sigenzyme concentrates are either based homogeneously on a propylene glycol / water basis or heterogeneously as a slurry, or they are in a microencapsulated structure. Preferred liquid proteases are Savinase ^® L, Durazym ^® L, Esperase ^® L, and Everlase® ^® from. Novo Nordisk, Optimase.RTM ^® L, Purafect ^® L, Purafect ^® OX L, Properase.RTM ^® L from. Genencor International, and BLAP ^® L from Biozym Ges.mbH. Preferred amylases are ter- mamyl ^® L, Duramyl ^® L, and BAN ^® from. Novo Nordisk, Maxamyl ^® WL and Purafect ^® HP On L from. Genencor International. Preferred lipases are Lipolase ^® L, Lipolase ^® ultra L and Lipoprime ^® L from. Novo Nordisk and Lipomax® ^® L from. Genencor International.

As slurries or microencapsulated liquid products e.g. Products such as the Novo Nordisk products labeled SL or LCC are used. The commercial liquid enzyme preparations mentioned contain, for example, 20 to 90% by weight of propylene glycol or mixtures of propylene glycol and water. In the context of the present invention, enzyme particles which can preferably be introduced into the cavity are characterized in that they contain one or more liquid amylase preparations and / or one or more liquid protease preparations.

Fragrances can also be incorporated into the particles to be introduced as active substances. All fragrances described in detail above can be used as an active substance. When fragrances are incorporated into the particles to be introduced, cleaning agents result that release all or part of the perfume with a time delay. In this way, for example, cleaning agents for machine dishwashing can be produced according to the invention, in which the consumer experiences the perfume note even after the dishes have been cleaned when the machine is opened. In this way, the undesirable "alkali residue" that adheres to many automatic dishwashing detergents can be eliminated.

Corrosion inhibitors can also be incorporated into the particles as active substances, it being possible to use the substances familiar to the person skilled in the art. For example, a combination of enzyme (eg lipase) and lime soap dispersant has proven successful as a scale inhibitor. At exceptionally low temperatures, for example at temperatures below 0 ° C, the active substance particle can break under impact or friction. In order to improve the stability at such low temperatures, additives can optionally be added to the coating substances. Suitable additives must be able to be mixed completely with the molten wax, must not significantly change the melting range of the coating substances, must improve the elasticity of the coating at low temperatures, must not generally increase the permeability of the coating to water or moisture and must not increase the viscosity of the melt Do not increase the wrapping material to such an extent that processing becomes difficult or even impossible. Suitable additives which reduce the brittleness of a sheath consisting essentially of paraffin 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 Cι _2- ι ₈ fatty alcohol sulfate. This addition results in a better wetting of the material to be embedded through the covering. It is advantageous to add the additive in an amount of about <5% by weight, preferably <about 2% by weight, based on the coating substance. The addition of an additive can in many cases lead to the fact that active substances can also be encased which, without the addition of an additive, generally form a tough, plastic body made of paraffin and partially dissolved active substance after the encapsulation material has melted.

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

Additives from the substance classes mentioned are commercially available in a wide variety. Commercial products, which are advantageously in the method of the invention can be added as an additive, for example, Aerosil ^® (acid fumed Kisel-, Degussa) 200, 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 smectite, Südchemie), Tixogel ^® VG, VP and VZ (montmorillonite loaded with QAV, Südchemie), Disperbyk ^® 161 (block copolymer, Byk-Chemie), Borchigen ^® ND (sulfo-free ion exchanger, Borchers), Ser-Ad ^® FA 601 (servo), Solsperse ^® (aromatic ethoxylate, ICI), Surfynol ^® types (Air Products), Tamol ^® and Triton ^® types (Rohm & Haas), Texaphor ^® 963, 3241 and 3250 (polymers, Henkel), Rilanit ^® types (Henkel), Thixcin ^® E and R (castor oil derivatives, Rheox), Thixatrol ^® ST and GST (castor oil derivatives, Rheox), Thixatrol ^® SR, SR 100, TSR and TSR 100 (polyamide polymers, Rheox), Thixatrol ^® 289 (Polyetsre polymer, Rheox) see above like the different MPA types X, 60-X, 1078-X, 2000-X and 60-MS (organic compounds, Rheox).

The auxiliaries mentioned can be used in varying amounts in the rinse aid or enzyme particles to be incorporated according to the invention, depending on the coating material and active substance. Usual use concentrations for the anti-settling, anti-floating, thioxotropic and dispersing agents mentioned above are in the range from 0.5 to 8.0% by weight, preferably between 1.0 and 5.0% by weight, and particularly preferably between 1.5 and 3.0% by weight, based in each case on the total amount of coating substance and active substances. In the context of the present invention, particulate rinse aid or enzyme particles to be incorporated into the cavity (s) preferably contain further auxiliaries from the category of anti-settling agents, floating agents, anti-floating agents, thixotropic agents and dispersing agents in amounts of 0.5 to 9% by weight between 1 and 7.5% by weight, and particularly preferably between 1.5 and 5% by weight, in each case based on the particle weight.

The use of special emulsifiers is particularly advantageous in the production of melt suspensions or emulsions which contain active substances which are liquid at the processing temperature. It has been shown that emulsifiers from the group of fatty alcohols, fatty acids, polyglycerol esters and polyoxyalkylene siloxanes are particularly 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. As emulsifiers in the inventive active ingredient particles is therefore preferably C _6-22 - fatty alcohols, preferably C _8-22 fatty alcohols and in particular Cι ι _2- ₈ fatty alcohols, with particular preference of Ci _ό -iβ fatty alcohols, are used.

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

For example, individual species or mixtures of the following acids can be used as emulsifiers in the context of the present invention: caprylic acid, pelargonic acid, Capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, octadecan-12-ol acid, arachic acid, behenic acid, lignoceric acid, cerotinic acid, melissic acid, 10-undecenoic acid, petroselinic acid, petroselaidic acid, oleic acid, elaidic acid, ricinoleic acid, aelolaidic acid, linoleic acid, linoleic acid , Gadoleic acid Eπicasäure, Brassidinsäure. Of course, it is also possible to use the fatty acids with an odd number of carbon atoms, for example undecanoic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, nonadecanoic acid, heneicosanoic acid, tricosanoic acid, pentacosanoic acid, heptacosanoic acid.

In preferred to be introduced into the cavity rinse aid or enzyme particles are used as emulsifier (s) C _6-22 fatty acids, preferably C _8-22 fatty acids and, in particular Cι ι _2- ₈ - fatty acids, with particular preference of _6- Cι ι ₈ fatty acids , used.

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

R ¹

HO- [CH ₂ -CH-CH ₂ -O] _n -H (XTV),

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-DECAOLEATE, POL YGLYCERYL-10-DEC ASTE ARATE, POLY- GLYCERYL-2-DIISOSTEARATE, POLYGLYCERYL-3-DIISOSTEARATE, POLY- GLYCERYL-10-DIISOSTEARATE, POLYGLYCERYL-2-DIOLEATE , POLYGLYCERYL-6-DIOLEATE, POLYGLYCERYL- 10- DIOLEATE, POLYGLYCERYL-3-DISTEARATE, POLYGLYCERYL-6-

DISTE ARATE, POLYGLYCERYL-10-DISTEARATE, POLYGLYCERYL- 10-

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

LYCERYLMETHACRYLATE, POLYGLYCERYL- 10-MYRISTATE,

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

POLYGLYCERYL- 10-OLEATE, POLYGL YCERYL-6-PENT AOLEATE,

POLYGLYCERYL- 10-PENTAOLE ATE, POLYGLYCERYL-6-PENTASTE ARATE, POLYGLYCERYL- 10-PENTASTEARATE, POLYGLYCERYL-2-SESQUI-

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

POLYGLYCERYL-2-TETRASTEARATE, POLYGLYCERYL-2-TRIISOSTEARATE, POLYGLYCERYL-10-TRIOLEATE, POLYGL YCERYL-6-TRISTEARATE. The commercially available products from different manufacturers, which are classified under the abovementioned keywords in the work mentioned, can advantageously be used as emulsifiers in process step b) according to the invention.

Another group of emulsifiers which can be used in the rinse aid 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 XV R ¹ R ¹ R ¹

I

H ₃ C-Si-O- [Si-O] _n -Si-CH ₃ (XV),

R ¹ R ¹ R ¹

in which each radical R ¹ independently of one another for -CH ₃ or a polyoxyethylene or propylene group - [CH (R ² ) -CH ₂ -O] _x H group, R ² for -H or -CH ₃ , x for a number 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 etherified or esterified on the free OH groups of the polyoxyethylene or polyoxypropylene side chains. The unetherified and unesterified polymer made from dimethylsiloxane with polyoxyethylene and / or polyoxypropylene is referred to in the INCI nomenclature as DIMETHICONE COPOLYOL and is known under the trade names Abil ^® B (Goldschmidt), Alkasil ^® (Rhönen-Poulenc), Silwet ^® (Union Carbide) or Belsil ^® DMC 6031 commercially available.

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

As with the coating materials and the substances to be coated, the same applies to the emulsifiers that they can be used over a wide range. Usually, emulsifiers of the type mentioned make up 1 to 25% by weight, preferably 2 to 20% by weight and in particular 5 to 10% by weight of the weight of the sum of shell materials and active substances. In the context of the present invention, particulate rinse aid or enzyme particles to be introduced preferably into the cavity (s) additionally contain emulsifiers from the grappa of fatty alcohols, fatty acids, polyglycerol esters and / or polyoxyalkylene siloxanes in amounts of 0.1 to 5 % By weight, preferably from 0.2 to 3.5% by weight, particularly preferably from 0.5 to 2% by weight and in particular from 0.75 to 1.25% by weight, in each case based on the particle weight.

The detergent form according to the invention dissolve in the washing or Cleaning cycle completely, whereby - as mentioned above - it can be advantageous if the different regions have different dissolving speeds. Due to the different dissolution rates, in addition to the release of certain ingredients, the properties of the washing or cleaning liquor can also be changed in a targeted manner. For example, detergent tablets are preferred in which the pH of a 1% by weight solution of the base tablet in water is in the range from 8 to 12, preferably from 9 to 11 and in particular from 9.5 to 10 ,

In addition to this, detergent tablets are preferred in which the pH of a 1% by weight solution of the entire tablet in water is in the range from 7 to 11, preferably from 7.5 to 10 and in particular from 8 to 9, 5, lies.

Another object of the present invention is a process for the production of detergent tablets which, through the steps a) pressing a particulate premix to a pressed part (base tablet) which has at least one cavity, b) optionally filling one or more active substances into liquid, gel-like, pasty or solid form in said cavity (s), c) optional application of one or more adhesion promoters on one or more surfaces of the molded body d) sealing of the openings of the (filled) cavities with a foil e) optional Aftertreatment of individual molded body surfaces or the entire molded body is marked.

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

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

The particle size of the premix pressed in step a) preferably also satisfies certain criteria: Methods in which the particulate premix in step a) has particle sizes between 100 and 2000 μm, preferably between 200 and 1800 μm, particularly preferably between 400 and 1600 μm and in particular between 600 and 1400 μm, are preferred according to the invention. A further narrowed particle size in the premixes to be pressed can be adjusted to obtain advantageous molded body properties. In preferred variants for the method according to the invention, the particulate premix pressed in step a) has a particle size distribution in which less than 10% by weight, preferably less than 7.5% by weight and in particular less than 5% by weight of the Particles are larger than 1600 μm or smaller than 200 μm. Narrower particle size distributions are further preferred here. Particularly advantageous process variants are characterized in that the particulate premix pressed in step a) has a particle size distribution in which more than 30% by weight, preferably more than 40% by weight and in particular more than 50% by weight of the particles have a particle size between 600 and 1000 μm.

When carrying out process step a), the process according to the invention is not restricted to the fact that only a particulate premix is pressed into a molded body. Rather, process step a) can also be expanded to the effect that multilayer molded articles are produced in a manner known per se by preparing two or more premixes which are pressed onto one another. In this case, the premix which has been filled in first is slightly pre-pressed in order to obtain a smooth upper surface which runs parallel to the mold body bottom, and after filling in the second premix. mixes to the finished molded article. In the case of three-layer or multi-layer molded articles, a further preliminary treatment is carried out after each premix addition, before the molded article is finally pressed after adding the last premix. The above-described cavity in the basic molded body is preferably a trough, so that preferred embodiments of the first method according to the invention are characterized in that in step a) multilayer molded bodies which have a trough are produced in a manner known per se by using several different particulate Premixes are pressed together.

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

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

Tableting is carried out in commercially available tablet presses, which can in principle be equipped with single or double punches. In the latter case, not only is the upper stamp used to build up pressure, the lower stamp also moves towards the upper stamp during the pressing process, while the upper stamp presses down. For small production quantities, eccentric tablet presses are preferably used, in which the stamp or stamps are attached to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed. The movement of these rams is comparable to that of a conventional four-stroke engine. The pressing can take place with one upper and one lower punch, but several punches can also be attached to one eccentric disc, the number of die bores being correspondingly increased. The throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs, rotary tablet presses are selected in which a larger number of dies is arranged in a circle on a so-called die table. The number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available. Each die on the die table is assigned an upper and lower punch, and again the pressure can be built up actively only by the upper or lower punch, but also by both stamps. The die table and the stamps move about a common vertical axis, the stamps being brought into the positions for filling, compaction, plastic deformation and ejection by means of rail-like cam tracks during the rotation. At locations where a particularly serious lifting or lowering of the punches is required (filling, compacting, ejecting), these cam tracks are before low-pressure pieces, low-tension rails and lifting tracks are supported. The die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix. The pressure on the premix can be individually adjusted via the pressure paths for the upper and lower punches, the pressure build-up being achieved by rolling the punch shaft heads past adjustable pressure rollers.

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

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

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

Processes preferred in the context of the present invention are characterized in that the pressing in step a) is carried out at pressures of from 0.01 to 50 kNcm ^"2 , preferably from 0.1 to 40 kNcm ^{" 2} and in particular from 1 to 25 kNcm ^"2 ,

Tableting machines suitable within the scope of the present invention are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Hom & Noack Pharmatechnik GmbH, Worms, IMA Veφackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms. Other providers include Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Liveeool (GB), I. Holand Ltd., Nottingham (GB), Courtoy NV, Halle (BE / LU) and Me- diopharm Kamnik (SI). For example, the hydraulic double pressure press HPF 630 from LAEIS is particularly suitable. D. Tableting tools are, for example, from Adams Tablettierwerkzeuge, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Söhne GmbH, Hamburg, Hofer GmbH, Weil, Hom & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Werkzeugbau, Tamm available. Other providers include Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI). In step b), the cavity is optionally filled with active substance (s), active substance mixtures or active substance preparations. If the cavity has more than one opening, it is expedient from a procedural point of view to close the second, third and any further openings in order to make filling technically easier in this way. In principle, it is also possible to fill a ring mold first, then to close the upper opening of the hole, to turn the mold together with the filling, and also to close the second hole, but this requires mechanical devices that prevent the filling from falling out. So if the cavity of the molded body produced in step a) has more than one opening, it is preferred to carry out the optional step b) - the filling - only after (nl) the steps c) and d) have been carried out, if the number of the openings is n. Closing the last opening then corresponds to carrying out process steps c) and d) for the last time, which can be followed by step e).

As already mentioned above, the filling that is optionally to be introduced into the cavity is preferably solid, with particulate fillings being particularly preferred. If the cavities of the molded bodies are filled with particulate compositions, methods are preferred in which the particulate composition (s) in step b) has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g / 1 has / have.

In step c) of the method according to the invention, adhesion promoters are optionally applied to one or more surfaces of the molded body. Step c) is particularly necessary if the foils to be applied in the subsequent step alone do not have sufficient adhesion to remain on the molded body and to withstand the mechanical loads during packaging, transport and handling without releasing the filling. Process step c) is thus used in the case of insufficiently adhesive films to "stick" them.

As an adhesion promoter, substances can be used which give the molded body surfaces to which they are applied sufficient adhesion ("stickiness") so that the subsequent process step, films adhering permanently to the surface. In principle, the substances mentioned in the relevant adhesive literature and in particular in the monographs lend themselves to this, but in the context of the present invention the application of melts, which act as adhesives at elevated temperature, are no longer sticky after cooling but are solid Importance.

For process step d), the application of the film to some or all surfaces of the molded body and the associated closing of the cavity (s), detailed information has already been given above, which is referred to here in order to avoid redundancies.

The moldings produced according to the invention can, as described above, be provided with a coating in whole or in part. Methods in which the aftertreatment in step e) consists in applying a coating layer to the entire molded body are preferred according to the invention.

The detergent tablets according to the invention can be packed after manufacture, the use of certain packaging systems having proven particularly useful. Another aspect of the present invention is a combination of (a) washing and cleaning agent shaped body (s) according to the invention and a packaging system containing the washing and cleaning agent shaped body (s), characterized in that the packaging system has a moisture vapor transmission

9 9 fluidity rate from 0.1 g / m / day to less than 20 g / m / day if the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%.

The packaging system of the combination of washing and cleaning agent body (s) and packaging system according to the invention has a moisture vapor permeability

9 9 from 0.1 g / m / day to less than 20 g / m / day if the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%. The specified temperature and humidity conditions are the test conditions that are specified in the DIN Standard 53122 are mentioned, whereby according to DIN 53122 minimal deviations are permitted (23 ± 1 ° C, 85 ± 2% relative humidity). The moisture vapor permeability rate of a given packaging system or material can be determined by further standard methods and is, for example, also in the ASTM standard E-96-53T ("Test for measuring Water Vapor transmission of Materials in Sheet form") and in the TAPPI standard T464 m- 45 ("Water Vapor Permeability of Sheet Materials at high temperature 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. The moisture vapor permeability rate can be determined from the surface of the container which is sealed with the material to be tested (permeation surface), the weight increase in calcium chloride and the exposure time

FDDR = ^{24 in} ° ^ l _{g / m} ^> , Uk]

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

The relative equilibrium humidity, often referred to as “relative air humidity”, is 85% at 23 ° C. when measuring the moisture vapor permeability rate within the scope of the present invention. The 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 Percentage expressed ratio of the actually present water vapor content to the saturation content corresponding to the prevailing temperature. For example, if air contains 17 ° 12 g / m ³ water vapor, then the relative air humidity = (12 / 14.4) T00 = 83%. If you cool this air, then the saturation (100% RH) is reached at the so-called dew point (in the example: 14 °), that is, at white After cooling, a precipitate is formed in the form of fog (Dew). Hygrometers and psychometers are used for the quantitative determination of moisture.

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

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

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

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

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

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

The sacks or bags made of single-layer or laminated paper or plastic film, which are preferably to be used as a packaging system, can be designed in a wide variety of ways, for example as a blown-up bag without a central seam or as a bag with a central seam, which is sealed by heat (hot fusion), adhesives or adhesive tapes become. Single-layer bag or sack materials are the known papers, which may or may not be impregnated, and plastic films, which may or may not be co-extruded. Plastic films that can be used as a packaging system in the context of the present invention are described, for example, in Hans Domininghaus "The plastics and their properties", 3rd edition, VDI Verlag, Dussel- dorf, 1988, page 193. Figure 111 shown there also provides information on the water vapor permeability of the materials mentioned.

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

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

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

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

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

Another object of the present invention is a washing method for washing textiles in a household washing machine, which is characterized in that one or more detergent shaped articles according to the invention are placed in the washing-up chamber of the washing machine and a washing program is run, in the course of which the molded body (s) are washed in.

However, the molded body or bodies do not have to be dosed via the dispenser, but can also be added directly to the washing drum. Both a metering aid, for example a net metering device, can be used here, but the molded bodies can also be added directly to the laundry into the drum without a metering aid. A washing process for washing textiles in a household washing machine, in which one or more detergent shaped articles according to the invention are inserted into the washing drum of the washing machine with or without metering aid and a washing program is run, in the course of which the shaped article (s) are dissolved is therefore also an object of the present invention.

As mentioned above, detergent tablets for automatic dishwashing can also be produced by the method according to the invention. Accordingly, there is a cleaning method for cleaning dishes in a dishwasher, which is characterized in that one or more detergent and cleaning agent tablets according to the invention are inserted into and inserted into the dosing chamber of the dishwasher Rinsing program can run, in the course of which the metering chamber opens and the molded body (s) are dissolved, another object of the present invention.

In the cleaning process according to the invention, too, the metering chamber can be dispensed with and the molded article (s) according to the invention can be inserted, for example, into the cutlery basket. Of course, the use of a dosing aid, for example a basket, which is attached to the wash cabinet, is also possible without any problems. Accordingly, there is a cleaning method for cleaning dishes in a dishwasher, in which one or more detergent and cleaning agent shaped articles according to the invention are inserted into the washing compartment of the dishwasher with or without dosing aid and a washing program is run, in the course of which the shaped article or articles are run be resolved, another object of the present invention.

Examples:

Manufacture of detergent tablets for automatic dishwashing

Process step a): Production of mold bodies:

By pressing two different premixes, two-layer rectangular shaped bodies were produced which had a hollow in the form of a semi-ellipse. The molded bodies consisted of 75% by weight of lower and 25% by weight of upper phase. The following table shows the composition (in% by weight, based on the respective premix) of the two premixes and thus of the two different phases of the mold body:

The weight of the basic molded body is 20 g.

Process step b): Filling with active substance:

Commercially available particulate enzyme preparations (Protease BLAP ^® S 260, from Biozym GmbH) were also used as the particulate active substance for filling the cavity filled with a bulk density of 800 g / 1 and an average particle size of 400 microns in the well. The filling quantity was 1 g, the volume of the cavity being filled to 80%.

Process step c): Applying adhesion promoter to the surface:

In step b) were filled Muldenformköφer on the upper side, on which opening of the cavity was mixed with 100 mg of a 20% solution of polyvinyl alcohol (Mo wiol ^® 10-98, Hoechst) coated.

Process step d): application of the film:

The filled mold bodies, on the top of which there was adhesion promoter on the edges of the mold, were sealed with a polyvinyl alcohol film (type M8630, Greensol).

Process step e): aftertreatment:

The molded articles according to the invention were dried at 40 ° C. for 4 minutes.

The shaped bodies according to the invention were distinguished by a firm bond between the film and the basic shaped body, so that no loss of active substance could occur. If a tablet is placed in water (20 ° C, 16 ° dH), the polyvinyl alcohol film is seen to expand, which is immediately followed by cracking and the release of the enzyme particles. The contents of the well filling are released completely within 5 seconds.

Claims

claims:

1. Washing and cleaning agent molded body made of compressed, particulate washing and cleaning agent, characterized in that the molded body has at least one cavity, the opening (s) of which is / are closed with a film.

2. Detergent and shaped body according to spoke 1, characterized in that the cavity has the shape of a trough.

3. Detergent and shaped body according to spoke 1, characterized in that the cavity has the shape of a through hole, the openings of which are located on two opposing surfaces of the shaped body.

4. Detergent and shaped body according to one of claims 1 to 3, characterized in that the film consists 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.

5. Detergent and cleaning agent according to one of claims 1 to 4, characterized in that the film consists of a water-soluble polymer.

6. Detergent and shaped article according to spoke 5, characterized in that the film material is selected from one or more substances from the grappe carrageenan, guar, pectin, xanthan, cellulose and their derivatives, starch and their derivatives and gelatin.

7. Detergent and molded article according to spoke 5, characterized in that the film 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 Grappe of al) polyvinylpyrrolidones, a2) vinylpyrrolidone / vinyl ester copolymers, a3) cellulose ethers

b) water-soluble amphoteric polymers from the Grappe

b 1) alkyl acrylamide / acrylic acid copolymers b2) alkyl acrylamide / methacrylic acid copolymers b3) alkyl acrylamide / methyl methacrylic acid copolymers b4) alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b5) alkyl acrylamide methacrylic acid / alkylaminoalkyl (meth) acrylic acid -

Copolymers b7) alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers b8) copolymers from b8i) unsaturated carboxylic acids b8ii) cationically derivatized unsaturated carboxylic acids bδiii) optionally further ionic or nonionic monomers

c) water-soluble zwitterionic polymers from the group of

cl) acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts c2) acrylamidoalkyltrialkylammmonium chloride / methacrylic acid copolymers and their alkali and ammonium salts c3) methacroylethylbetaine methacrylate copolymers

d) water-soluble anionic polymers from the Grappe group

dl) vinyl acetate / crotonic acid copolymers d2) vinylpyrrolidone / vinyl acrylate copolymers d3) acrylic acid / ethyl acrylate N-tert-butyl acrylamide particles d4) 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 glycol and / or polyalkylene glycol grafted and crosslinked copolymers obtained from the copolymerization of d5i) at least one monomer of the nonionic type, d5ii) at least one monomer of the ionic type, d5iii) of polyethylene glycol and d5iv) a crosslinker d6) by copolymerization of at least one monomer of each of the three following grapples Copolymers: d6i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, dόii) unsaturated carboxylic acids, döiii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group dόii) with ge saturated or unsaturated, straight-chain or branched C _8- ι ₈ alcohol d7) polymers of crotonic acid, vinyl acetate and an allyl or methallyl ester d8) tetra- and pentapolymers of d8i) crotonic acid or allyloxyacetic acid d8ii) vinyl acetate or vinyl propionate dδii - or methallyl esters d8iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters d9) crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinymethylether, acrylamide and their water-soluble salts dlO) Teφolymers 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 Grappe

el) quaternized cellulose derivatives e2) polysiloxanes with quaternary grapple e3) cationic guar derivatives e4) polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid e5) copolymers of vinylpyrrolidone with quaternized derivatives of dialkyl-methacrylate e) Vinylpyrrolidone-methoimidazolinium chloride copolymers e7) quaternized polyvinyl alcohol e8) polymers given the INCI names Polyquatemium 2, Polyquatemium 17, Polyquatemium 18 and Polyquatemium 27.

8. Detergent and molded article according to one of claims 1 to 7, characterized in that the film does not enclose the entire molded article.

9. Detergent and molded article according to one of claims 1 to 8, characterized in that the film only covers the surfaces of the molded article in which there are openings in the cavity (s).

10. Detergent and molded article according to one of claims 1 to 9, characterized in that further active substance is contained in the space enclosed by the film and the molded article.

11. Detergent and shaped body according to spoke 10, characterized in that the further active substance is contained in liquid, gel-like, pasty or solid form.

12. Detergent form according to one of claims 10 or 11, characterized in that the further active substance is contained in particle form, preferably in powdered, granular, extruded, pelletized, tested, flaky or tableted form.

13. Detergent and molded article according to one of claims 1 to 12, characterized in that the volume ratio of molded article to cavity 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.

14. Detergent and molded article according to one of claims 1 to 13, characterized in that the volume ratio of the space enclosed by the film and the molded article to the active substance contained in this room is 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.

15. Detergent and molded article according to one of claims 10 to 14, characterized in that the weight ratio of molded article to the active substance contained in the space enclosed by the film and the molded article 1: 1 to 100: 1, preferably 2: 1 to 80 : 1, particularly preferably 3: 1 to 50: 1 and in particular 4: 1 to 30: 1.

16. Detergent and molded article according to one of claims 1 to 15, characterized in that the area of the opening (s) of the cavity (s) 1 to 25%, preferably 2 to 20%, particularly preferably 3 to 15% and in particular 4th accounts for up to 10% of the total surface of the molded body.

17. Detergent and molded article according to one of claims 10 to 16, characterized in that the active substance contained in the space enclosed by the film and the molded article dissolves faster than the basic molded article.

18. Detergent and molded article according to one of claims 10 to 17, characterized in that the active substance contained in the space enclosed by the film and the molded article dissolves more slowly than the basic molded article.

19. Washing and cleaning agent molded article according to one of claims 1 to 18, characterized in that the basic molded article has a density above 1000 kgdm ^"3 , preferably above 1025 kgdm ^" , particularly preferably above 1050 kgdm ^" and in particular above 1100 kgdm ^" .

20. Washing and cleaning agent molded article according to one of claims 1 to 19, characterized in that the basic molded article builders in amounts of 1 to 100% by weight, preferably 5 to 95% by weight, particularly preferably 10 to 90% by weight. -% and in particular from 20 to 85 wt .-%, each based on the weight of the basic molded body, contains.

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

22. Washing and cleaning agent molded article according to one of claims 1 to 21, characterized in that the basic molded article carbonate (s) and / or hydrogen carbonate (s), preferably alkah carbonates, particularly preferably sodium carbonate, in amounts of 5 to 50% by weight, preferably from 7.5 to 40% by weight and in particular from 10 to 30% by weight, in each case based on the weight of the basic molded body.

23. Washing and cleaning agent shaped body according to one of claims 1 to 22, characterized in that the basic shaped body silicate (s), preferably alkali silicates, particularly preferably crystalline or amorphous alkali disilicates, in amounts of 10 to 60 % By weight, preferably from 15 to 50% by weight and in particular from 20 to 40% by weight, in each case based on the weight of the basic molded body.

24. Washing and cleaning agent molded article according to one of claims 1 to 23, characterized in that the basic molded article total surfactant contents are below 5% by weight, preferably below 4% by weight, particularly preferably below 3% by weight and in particular below of 2 wt .-%, based in each case on the weight of the basic molded body.

25. Washing and cleaning agent shaped body according to one of claims 1 to 24, characterized in that the basic shaped body bleach from the grape of oxygen or halogen bleaching agents, in particular chlorine bleaching agents, with particular preference for sodium perborate and sodium percarbonate, in amounts of 2 to 25% by weight. -%, preferably from 5 to 20 wt .-% and in particular from 10 to 15 wt .-%, each based on the weight of the basic molded body, contains.

26. Washing and cleaning agent shaped body according to one of claims 1 to 25, characterized in that the basic shaped body bleach activators from the grappa of the multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), the N-acylimides, in particular N-nonanoylsuccinimide (NOSI), the acylated Phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS) and n-methyl-Moφholinium-acetonitrile-methylsulfate (MMA), in amounts of 0.25 to 15 wt .-%, preferably 0.5 up to 10 wt .-% and in particular from 1 to 5 wt .-% each based on the weight of the basic molded body.

27. Washing and cleaning agent form according to one of claims 1 to 26, characterized in that the basic form silver protection agent from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes, particularly preferably benzotriazole and / or alkylaminotriazole, in amounts of 0.01 to 5% by weight, preferably 0.05 to 4% by weight and in particular 0.5 to 3% by weight, in each case based on the weight of the basic molded article, contains.

28. Washing and cleaning agent shaped body according to one of claims 1 to 27, characterized in that the basic shaped body further comprises one or more substances from the grapples of the enzymes, corrosion inhibitors, scale inhibitors, cobuilders, colors and / or fragrances in total amounts of 6 to 30% by weight .-%, preferably from 7.5 to 25 wt .-% and in particular from 10 to 20 wt .-%, each based on the weight of the basic molded body, contains.

29. Detergent and molded article according to one of claims 1 to 28, characterized in that the active substance contained in the space enclosed by the film and the molded article contains at least one active substance from the grape group of enzymes, surfactants, soil-release polymers, disintegration aids, Bleaches, bleach activators, bleach catalysts, silver preservatives and mixtures thereof.

30. Washing and cleaning agent shaped body according to one of claims 1 to 29, characterized in that the basic shaped body or the active substance contained in the space enclosed by the film and the shaped body contains bleaching agents, while the other area of the shaped body contains bleach activators.

31. Detergent and molded article according to one of claims 1 to 30, characterized in that the basic molded article or d contains the active substance contained in the active substance contained in the film and the molded article bleach, while the other area of the molded article contains enzymes.

32. Detergent and molded article according to one of claims 1 to 31, characterized in that the basic molded article or the active substance contained in the space enclosed by the film and the molded article contains bleaching agents, while the other area of the molded article contains deformable mass of corrosion protection agent.

33. Detergent and molded article according to one of claims 1 to 32, characterized in that the basic molded article or in the through the film and Form body enclosed space contains active substance bleach, while the other area of the body contains surfactants, preferably nonionic surfactants, with particular preference for alkoxylated alcohols having 10 to 24 carbon atoms and 1 to 5 alkylene oxide units.

34. Detergent and molded article according to one of claims 1 to 33, characterized in that the basic molded article and the active substance contained in the space enclosed by the film and the molded article contain the same active ingredient in different amounts.

35. Detergent and molded article according to one of claims 1 to 34, characterized in that the film which closes the cavity has a thickness of 1 to 150 µm, preferably 2 to 100 µm, particularly preferably 5 to 75 µm and in particular from 10 to 50 μm.

36. Detergent and molded article according to one of claims 12 to 35, characterized in that the active substance contained in the space enclosed by the film and the molded article has particle sizes between 100 and 5000 μm, preferably between 150 and 2500 μm, particularly preferably between 200 and 2000 μm and in particular between 400 and 1600 μm.

37. Detergent and molded article according to one of claims 12 to 36, characterized in that the active substance contained in the space enclosed by the film and the molded article comprises particles consisting of e) 0 to 90% by weight of one or more carrier materials, f) 5 to 50% by weight of one or more coating substances with a melting point above 30 ° C., g) 5 to 50% by weight of one or more active substances and h) 0 to 10% by weight of further active substances and auxiliaries consist.

38. Detergent and molded articles according to spoke 37, characterized in that paraffin (s) or polyalkylene glycols, in particular polyethylene glycols, are contained in the particles as the coating substance.

39. Detergent and molded article according to one of claims 37 or 38, characterized in that the active substance particles contained in the space enclosed by the film and the molded article as active substances are nonionic surfactant (s) and / or bleach and / or Contain bleach activators and / or enzyme (s) and / or corrosion inhibitors and / or fragrances.

40. Detergent and molded article according to one of claims 12 to 36, characterized in that the active substance contained in the space enclosed by the film and the molded article comprises particles consisting of d) 40 to 99.5% by weight, preferably 50 up to 97.5% by weight, particularly preferably 60 to 95% by weight and in particular 70 to 90% by weight of one or more coating substance (s) which have a melting point above 30 ° C., e) 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 shell substance (s) ( en) dispersed liquid enzyme preparation (s) and f) 0 to 20% by weight, preferably 0 to 15% by weight, particularly preferably 0 to 10% by weight and in particular 0 to 5% by weight of further carrier materials, auxiliaries and / or active ingredients.

41. Process for the production of detergent tablets characterized by the steps f) pressing a particulate premix to a pressed part (base tablet) which has at least one cavity, g) optionally filling one or more active substances into liquid, gel-like, pasty or solid Mold in said cavity (s), h) optional application of one or more adhesion promoters to one or more surfaces of the molded body i) sealing the openings of the (filled) cavities with a film j) optional post-treatment of individual molded body surfaces or the entire molded body.

42. The method according spoke 41, characterized in that the particulate premix in step a) has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g / 1.

43. The method according to any one of claims 41 or 42, characterized in that the particulate premix in step a) 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, having.

44. The method according to any one of claims 41 to 43, characterized in that the particulate ^) composition (s) in step b) has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g / 1 /exhibit.

45. The method according to any one of claims 41 to 44, 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.

46. The method according to any one of claims 41 to 45, characterized in that the after-treatment in step e) consists in applying a coating layer on the entire molded body.

47. Combination of (a) washing and cleaning agent shaped body (s) according to one of claims 1 to 40 and a packaging system containing the washing and cleaning agent shaped body, 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 / day if the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%.

48. Cleaning method for cleaning dishes in a dishwasher, characterized in that one or more detergent and shaped articles according to one of claims 1 to 40 are placed in the dosing chamber of the dishwasher and a washing program can be run, in the course of which the dosing chamber opens and the shaped body or bodies are dissolved.

49. Cleaning method for cleaning dishes in a dishwasher, characterized in that one or more washing and cleaning agent shaped bodies according to one of claims 1 to 40 are inserted with or without metering aid into the washing area of the dishwasher and a washing program is run, in the course of which or the shaped bodies are dissolved.

50. washing method for washing textiles in a household washing machine, characterized in that one or more detergent and shaped articles according to one of claims 1 to 40 are placed in the washing-up chamber of the washing machine and a washing program is run, in the course of which the shaped body or bodies be washed in.

51. Washing method for washing textiles in a household washing machine, characterized in that one or more washing and cleaning agent shaped articles according to one of claims 1 to 40, with or without dosing aid, are placed in the washing drum of the washing machine and a washing program is run, in the course of which or the shaped bodies are dissolved.