DE10062582A1 - Compacted particulate detergent for use in dishwasher or textile washing machines has active substance-containing cavity lined with a polymeric film - Google Patents

Abstract

A compacted body of particulate detergent or cleaning agent has a cavity whose walls are covered with a film. An Independent claim is also included for production of the agents by pressing to give a body with a cavity and covering the cavity surface walls with a film, optionally followed by filling the cavity with a liquid, gel, paste or solid active substance, coating the body with adhesive and covering the cavity opening with a film.

Description

The present invention relates to detergent tablets, processes for their preparation and their use in cleaning procedures for cleaning dishes and a procedure for washing textiles.

Detergent tablets are broadly described and enjoyable in the art the consumer because of the simple dosage of increasing popularity. Tableted Rei detergents have a number of advantages over powdered products: they are one easier to dose and handle and have advantages due to their compact structure storage and transport. There is therefore an extremely wide state of the art Detergents and cleaning agent molded articles, which are also found in a comprehensive patent literature reflected. Early on the developers of tablet-shaped products came up with the idea Men, on different composite areas of the mold certain ingredients release under defined conditions in the washing or cleaning cycle, so the Rei improve their success. Here are in addition to the pharmaceutics be In particular, core / shell tablets and ring / core tablets knew multilayered bodies enforced today for many areas of washing and cleaning or hygiene be offered. The optical differentiation of products is also becoming increasingly important so that single-phase and monochromatic molded body in the field of washing and cleaning far were displaced by multiphase moldings. Currently marketed are two-layered Moldings with one white and one colored phase or with two differently colored ones Layers. In addition, there are point tablets, toroidal tablets, coated tablets, etc., currently have a subordinate meaning.

Polyphase cleaning tablets for the WC are described for example in EP 055 100 (Jeyes Group). This document discloses toilet cleaner blocks that have a molded body Comprising bodies of a slow-dissolving detergent composition into which a Bleaching tablet is embedded. This document simultaneously discloses the most diverse off Design forms of multiphase moldings. The production of the moldings takes place after  Teach this document either by inserting a compressed bleach tablet into a mold and encapsulating this tablet with the detergent composition, or by pouring a portion of the detergent composition into the mold, followed by the onset of ver pressed bleach tablet and possibly subsequent pouring with further Reinigungsmit telzusammensetzung.

EP 481 547 (Unilever) also describes multiphase detergent tablets suitable for the automatic dishwashing should be used. These shaped bodies have the form of Core / shell tablets and are prepared by stepwise compression of the ingredients: First, the compression of a bleaching composition into a shaped body, which in a semi-filled with a polymer composition matrix is inserted, which then with another Polymer composition filled and bleached with a polymer jacket molded telformkörper is pressed. The procedure is then followed with an alkaline cleaning repeated average composition, so that there is a three-phase molded body.

Another way to produce optically differentiated detergent tablets is disclosed in international patent applications WO 99/06522, WO 99/27063 and WO 99/27067 (Procter & Gamble). According to the teaching of these documents, a molded article is provided, which has a cavity which is filled with a solidifying melt. Alternatively, a Pul filled and fixed by means of a coating layer in the cavity. All three registrations is in common that the cavity filling area should not be pressed, since in this way pressure-sensitive ingredients should be spared.

Described in the prior art way to prepare melts, inserted into the tablets be poured or cast into moldings, includes a thermal load of Ingredients in the melts. In addition, the exact dosage requires liquid to pasty Substances and the subsequent cooling a high technical complexity, the dependent from the composition of the melt, in part due to shrinkage on cooling and This conditional detachment of the filling is nullified. The filling of cavities with powdery ingredients and the fixation by means of coating is also expensive and with similar stability problems.

The conventional tabletting of multilayer tablets is in the field of washing and Detergent tablets likewise have their limits when only one layer is used should have on the overall molding. If one falls below a certain layer thickness, then one is Pressing a adhering to the rest of the molding layer increasingly difficult.

Although the injection of particulate compositions in cavities of moldings solves the Problem of temperature loading of these fillings, but on the other hand can lead to a delays  This pressed part lead, which requires the addition of dissolution accelerators makes, if called for a timely release of the ingredients from this region is. The introduction of liquid, gel or pasty substances is neither Eingießverfah It is still possible to use compression if these media are not used in the course of manufacture Solidify solids.

Liquid or pasty substances are usually incorporated in capsules and either in encapsulated form dosed or further processed together with other components. The cape However, they have the disadvantage that the capsule material has relatively high wall thicknesses where lengthens the release time and thus delays the release of the substances. On Another disadvantage of capsules is the limited variety of shapes and sizes. As capsule shells (Molded body) usually prefabricated products are used, which are filled. The disadvantage is that capsules only with flowable, d. H. liquid to gelatinous or powdery, Substances can be filled. Another disadvantage is the high production costs, the The substances are first filled into the capsule and then processed further.

The present invention was based on the object to provide moldings in which both temperature and pressure sensitive and flowable, d. H. liquid to gelatinous or powdery, ingredients can be introduced into delimited regions and those without Great effort can be made industrially without the moldings disadvantages in terms of stability or to fear inaccuracies in the dosage would be. Another object was to provide a possibility of substances, wel with conventional dissolution accelerators, disintegration aids or other ingredients The moldings are incompatible regardless of their state of aggregation in shaped bodies integrate. Furthermore, the incorporated substances should be able to be released in a controlled manner, without the recipe having to be changed.

It has now been found that the disadvantages mentioned are avoided when molding articles, which have a cavity used, and the molding-body boundary wall of the cavity covered with a foil. In this way, different components can be used in shaped bodies Consistency and with different properties, such as temperature and / or pressure sensitive as well as flowable, d. H. liquid to gelatinous or powdery, ingredients in a single To incorporate molded bodies. Also, incompatible with each other substances in a molding be incorporated.

The invention relates to detergent tablets of compacted, part chenförmigen detergents and cleaning agents, wherein the shaped body at least one cavity wherein the molding-body-side boundary wall of the cavity (s) is covered with a film (are).  

The cavity in the shaped body according to the invention can have any desired shape. She can do that Divide molded bodies, d. H. have an opening at the top and bottom of the molding, but it can also be a not going through the entire body molding cavity whose Öff tion is visible only on a molding side.

For reasons of process economy, through holes have their openings Opposing surfaces of the moldings lie, and troughs with an opening a molded body side proven. The shape of a through hole or a hollow can be free can be selected, wherein moldings are preferred in which the through hole or the Trough circular, elliptical, triangular, rectangular, square, pentagonal, hexagonal, has seven-cornered or octagonal horizontal sections. Even completely irregular forms like arrowheads or animal forms, trees, clouds, etc. can be realized. As with the moldings in the case of square holes, those with rounded corners and edges or with rounded edges preferred corners and chamfered edges.

The shaped bodies according to the invention can assume any geometric shape, wherein in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segmented, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, octagonal and octagonal prismatic as well rhombohedral forms are preferred. Also completely irregular bases like arrow or animal shapes, trees, clouds, etc. can be realized. Assign the novel moldings per corners and edges, so these are preferably rounded. As additional optical differences is an embodiment with rounded corners and bevelled ("touched") Edges preferred.

The shaped bodies according to the invention can also be produced in a multiphase manner. Out of green the procedural economy here have proven particularly useful two-layer moldings.

The aforementioned geometric realization forms can be arbitrarily with each other combine. Thus, moldings with rectangular or square base and circle round holes and / or hollows are made as well as round shaped bodies with achtecki Holes and / or hollows, the variety of possible combinations no limits are set. For reasons of process economy and aesthetic consumer sentiment are moldings with hole and / or trough particularly preferred in which the mold base surface and the hole or trough cross section have the same geometric shape, for example Shaped body with square base and centrally incorporated square hole or Trough. Particularly preferred in this case are ring shaped bodies, d. H. circular shaped body with circular the hole. As Muldenformen such are particularly preferred, as in the older German  Patent Application DE 198 22 973.9 (Henkel KGaA) are described, to which expressly is referenced.

The size of the trough or the through hole compared to the entire shaped body depends on the desired use of the shaped body. Depending on whether the Ka should be filled with other active substance and whether a lesser or greater amount of active substance should be included, the size of the cavity may vary. Regardless of the purpose of use washing and cleaning agent tablets are preferred in which the Volumenver ratio of moldings to cavity 2: 1 to 100: 1, preferably 3: 1 to 80: 1, more 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 shaped body with closed cavity and the volume of the cavity. The difference between the two volumes gives the volume of the shaped body with cavity. In other words, if the shaped body has, for example, an orthorhombic shape with the side lengths 2, 3 and 4 cm and has a trough with a volume of 2 cm ³ , then the volume of this "basic shaped body" is 22 cm ³ . The volume used to calculate the ratio be 24 cm ³ , since the trough is closed with foil and thereby outwardly orthorhombi shear molding without trough is present. In this example, therefore, the ratio of the volumes is 12: 1. For volume ratios of moldings: cavity below 2: 1, which, of course, can also be realized according to the invention, the instability of the walls can increase.

Similar statements can be made to the surface portions that make up the molded body with the cavity ("base moldings") or the opening area of the cavity on the overall surface of the molded body. Here, detergent tablets are preferred in which 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 4 to 10% of the total surface of the shaped body accounts. In this case, the total surface of the shaped body again corresponds to the total surface area of the shaped body with closed cavity, ie, regardless of the opening area of the trough 52 cm ² in the above example. The opening (s) of the cavity in such an exemplary shaped body in preferred embodiments of the present invention thus has an area of 0.52 to 13 cm ² , preferably of 1.04 to 10.4 cm ² , particularly preferably 1.56 to 7.8 cm ² and especially 2.08 to 5.2 cm ² .

The shaped bodies according to the invention with a cavity are characterized in that the shaped bodies side boundary wall of the cavity is designed with a foil. The laying out of the cavity has the advantage that the ingredients of the molding and those that are placed in the cavity, do not come into contact with each other and avoid unwanted interactions the.  

The cavity can be designed with the film in any manner known to those skilled in the art. For example, finished films can be placed on the moldings and pressed into the cavity or pressed. It is also possible thermoformed molded parts made of film material, which Shape of the cavity, to put in the cavity, d. H. to stick. In another possible Embodiment, solutions or melts of the polymeric material enter the cavity brought, for. B. by pouring, spraying, etc.

Preferred film materials are the polymers known from the prior art. Insbeson In particular detergent and cleaner tablets are preferred in which the film of a poly mer with a molecular weight between 5000 and 500,000 daltons, preferably between 7500 and 250,000 daltons and in particular between 10,000 and 100,000 daltons. With regard the media in which detergents and cleaners are usually introduced are in particular preferred detergent tablets, in which the film consists of a water-soluble consists of polymer.

Such preferred polymers may be of synthetic or natural origin. Become Polymer used on a native or partnative basis as a film material, so are washing and Rei nigungsmittelformkörper preferred in which the film material is selected from one or several substances from the group carrageenan, guar, pectin, xanthan, cellulose and their deri vate, starch and its derivatives, and gelatin.

Carrageenan is a named after the Irish coastal town of Carragheen, educated and similar to Agar built extract of North Atlantic, to Florideen paying red algae. The precipitated from the hot water extract of the algae carrageenan is a colorless to sand-colored Pul ver with molecular weights of 100000-800000 and a sulfate content of about 25%, which is very soluble in warm water. Carrageenan has three main components: The yellow-forming f-fraction consists of D-galactose-4-sulfate and 3,6-anhydro-α-D-galactose, which are alternately glycosidically linked in the 1,3- and 1,4-positions (Agar, in contrast, contains 3,6-anhydro-α-L-galactose). The non-gelling I 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-α-galactose-2-sulfate in 1,4-bond is both water-soluble and gel-forming. Other types of carrageenan are also denoted by Greek letters α, β, γ, μ, ν, ξ, π, ω, χ. Also, the type of cations present (K, NH ₄ , Na, Mg, Ca) affects the solubility of the carrageenans. Semisynthetic products which 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) eenates.

The guar used in the context of the present invention as a film material, including guar flour called, is a greyish white powder, which by grinding the Endosperms originally in the indi and Pakistani territory endemic, now also in other countries, eg. B. in the south the US, cultivated, belonging to the legume family Guar bean (Cyamopsis tetra gonobolus) is obtained. The main constituent of the guar is up to about 85% by weight of the dry Substance Guaran (guar gum, Cyamopsis gum); Secondary components are proteins, lipids and Cellulose. Guaran itself is a polygalactomannan, d. H. a polysaccharide, its linear chain of unsubstituted (see formula I) and in the C6 position with a galactose radical substitu (see formula (II)) mannose units in β-D (1 → 4) -linkage is constructed.

The ratio of I: II is about 2: 1; the II units are contrary to original assumptions not strictly alternating, but in pairs or triplets in the polygalactomannan molecule is assigned. Data on the molar mass of the guaran vary with values of about 2.2.10 ⁵ -2.2.10 ⁶ g / mol depending on the degree of purity of the polysaccharide - the high value was determined on a high-grade product - significantly and correspond to about 1350-13500 sugars - Units / macromolecule. Guaran is insoluble in most organic solvents.

The pectins which can also be used as film material are high molecular weight glycosidic plants substances that are very common in fruits, roots and leaves. The pectins exist in essence from chains of 1,4-α-glycoside. Connected galacturonic acid units whose Säuregrup are esterified to 20-80% with methanol, taking between highly esterified (<50%) and low-esterified pectins (<50%). The pectins have a leaflet structure and stand in the middle of starch and cellulose molecules. Their macromolecules still contain some glucose, galactose, xylose and arabinose and have weakly acidic properties.  

Fruit pectin contains 95%, beet pectin to 85% galacturonic acid. The molar masses of the different The pectins vary between 10000 and 500000. The structural properties are also strongly affected by Degree of polymerization dependent; so form z. As the fruit pectins in the dried state asbestar tiger fibers, the flax pectins, on the other hand, fine, granular powders.

The pectins become by extraction with diluted acids predominantly from the internal portions made of citrus fruit peel, Obstresten or sugar beet cuttings.

Also xanthan is inventively used as a film material. Xanthan gum is a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and has a molecular mass of 2 to 15 million daltons. Xanthan is formed from a chain of β-1,4-linked 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 gum. Xanthan can be described by the following formula:

The celluloses and their derivatives are also suitable as film materials. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulosic sheet materials which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.

Besides cellulose and cellulose derivatives, (modified) dextrins, starch and starch can also be used be used as a film materials.

Suitable nonionic organic film materials are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes  be performed. Preferably, they are medium molecular weight hydrolysis products in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose Equivalent (DE) in the range of 0.5 to 40, especially from 2 to 30 preferred, wherein DE a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 is. Useful are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range of 2000 to 30,000 g / mol.

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

Starch can also be used as a film material for the detergents and cleaners according to the invention moldings are used. Starch is a homoglycan, where the glucose units are α- are linked glycosidically. Starch is composed of two components of different molecular weight composed of: about 20-30% straight-chain amylose (MW about 50,000-150,000) and 70-80% ver branched-chain amylopectin (M.W., about 300,000-2,000,000), besides small amounts are still Contain lipids, phosphoric acid and cations. While the amylose is due to binding in 1,4- Position long, helical, entangled chains with about 300-1200 glucose molecules forms, the chain branches in amylopectin after an average of 25 glucose building blocks by 1,6-binding to a branch-like structure with about 1500-12000 molecules of glucose. ne pure starch are also known as film materials in the context of the present invention. Derivatives obtainable by polymer analogous reactions of starch are suitable. Such che mixed-modified starches include, for example, products from esterifications or Etherifications in which hydroxy hydrogens have been substituted. But also strengths, in the hydroxy groups against functional groups that do not have an oxygen atom ge are replaced, can be used as starch derivatives. In the group of starch Derivatives include, for example, alkali starches, carboxymethyl starch (CMS), starch esters and ethers as well as amino acids.

Among the proteins and modified proteins, gelatin as a film material has stood out DE meaning. Gelatin is a polypeptide (molecular weight: about 15,000 to 250,000 g / mol), the posh By hydrolysis of the collagen contained in the skin and bones of animals under acidic or  alkaline conditions is obtained. The amino acid composition of the gelatin ent speaks largely of the collagen from which it was obtained, and varies in dependence from its provenance. The use of gelatin as a water-soluble shell material is esp Especially in pharmacy in the form of hard or soft gelatin capsules extremely widespread.

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 "tailored" to the desired film permeability upon storage and dissolution of the film when used. Particularly preferred detergent tablets according to the invention are characterized in that the film material is selected from a polymer or polymer mixture, wherein the polymer or at least 50% by weight of the polymer mixture is selected from

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

Water-soluble polymers in the context of the invention are those polymers which are stable at room temperature Water to more than 2.5 wt .-% are soluble.

The films of the detergent tablets according to the invention can in this case may be made of any of the aforementioned polymers, but it can also be mixtures or multilayered layer structures of the polymers are used. The polymers will be described in more detail below.

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

• - Polyvinylpyrrolidone, as represented, for example, under the name Luviskol® (BASF) ben. Polyvinylpyrrolidones are preferred nonionic polymers in the context of the Er making.

Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinones)], abbreviation PVP, are polymers of the general formula (III)

by free-radical polymerization of 1-vinylpyrrolidone by the method of the solvent or Suspension polymerization using radical formers (peroxides, azo compounds) as Initiators are produced. The ionic polymerization of the monomer provides only products low molecular weights. Commercially available polyvinylpyrrolidones have molar masses in the range of approx. 2500-750000 g / mol, which are characterized by the specification of the K values and - K value depending - have glass transition temperatures of 130-175 °. They are called white, hygrosko powder or as aqueous. Solutions offered. Polyvinylpyrrolidones are well soluble in what and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated coals hydrogens, phenols and the like a.).

• - Vinylpyrrolidone / vinyl ester copolymers, such as those under the trademark Luviskol® (BASF). Luviskol® VA 64 and Luviskol® VA 73, each vinylpyr rolidone / vinyl acetate copolymers are particularly preferred nonionic polymers.

The vinyl ester polymers are vinyl ester-accessible polymers having the grouping of formula (IV)

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

The polymerization of the vinyl ester is carried out free-radically by different methods (solutions polymerization, suspension polymerization, emulsion polymerization, bulk polymerization.). Copolymers of vinyl acetate with vinylpyrrolidone contain monomer units of the formulas (III) and (IV)

• Cellulose ethers such as hydroxypropylcellulose, hydroxyethylcellulose and methylhydroxypro pylcellulose, as for example under the trademarks Culminal® and Benecel® (AQUALON).

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

R is 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. Cellulo seether be technically produced 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 etherifying reagent or how many moles of the etherifying agent have been attached on average to an anhydroglucose unit. Hydroxye thylcellulosen are water soluble from a DS of about 0.6 and a MS of about 1. Commercial hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS), respectively. Hydroxyethyl and propylcelluloses are marketed as yellowish-white, odorless and tasteless powders in widely varying degrees of polymerization. Hydroxyethyl and propylcelluloses are soluble in cold and hot water as well as in some (hydrous) organic solvents but insoluble in most (anhydrous) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition.

Polyvinyl alcohols, referred to as PVAL for short, are polymers of the general structure

[-CH ₂ -CH (OH) -] _n

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, be polyvinyl alcohols via polymer-analogous reactions by hydrolysis, technically in particular dere but by alkaline catalyzed transesterification of polyvinyl acetates with alcohols (preferential methanol) in solution. These technical processes are also PVAL too accessible, which contain a predeterminable residual proportion of acetate groups.

Commercially available PVAL (eg Mowiol® grades from Hoechst) come as white-yellowish powders or granules with degrees of polymerization in the range of about 500-2500 (according to Molma 20,000-100,000 g / mol) and have different degrees of hydrolysis  from 98-99 and 87-89 mole%, respectively. So you are partially hydrolyzed polyvinyl acetates with a residual content Acetyl groups of about 1-2 or 11-13 mol%.

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

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

Suitable zwitterionic polymers are, for example, those in the German patent applications DE 39 29 973, DE 21 50 557, DE 28 17 369 and DE 37 08 451 disclosed polymers. Acryla midopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their Alkali and ammonium salts are preferred zwitterionic polymers. Further suitable zwit terionic polymers are Methacroylethylbetain / methacrylate copolymers, which under the name Amersette® (AMERCHOL) are commercially available.

According to the invention suitable anionic polymers include:

• - Vinyl acetate / crotonic acid copolymers, as described for example under the names Re syn (NATIONAL STARCH), Luviset® (BASF) and Gafset® (GAF).

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

[-CH (CH ₃ ) -CH (COOH) -] _n (VI)

• Vinylpyrrolidone / vinyl acrylate copolymers, available, for example, under the trademark Luviflex® (BASF). A preferred polymer is that referred to as Luviflex® VBM-35 (BASF) available vinylpyrrolidone / acrylate terpolymers.
• - Acryfsäure / ethyl acrylate / N-tert.butylacrylamide terpolymers, for example, under the Be Ultrahold® strong (BASF).
• - Graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid alone or im 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 admixture with other copolymerizable compounds on polyalkylene glycols obtained by polymerization in the heat in homogeneous phase characterized in that the polyalky glycols in the monomers of vinyl esters, esters of acrylic or methacrylic acid, in Gegen Waiting for the radical generator to stir.

Suitable vinyl esters are, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and as esters of acrylic acid or methacrylic acid those containing aliphatic alkoxy low molecular weight, so 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 proven.

As polyalkylene glycols in particular polyethylene glycols and polypropylene glycols in Be costume. Polymers of ethylene glycol which are of general formula VII

H- (O-CH ₂ -CH ₂ ) _n -OH (VII)

satisfy, where n can assume values between 1 (ethylene glycol) and several thousand. For polyethylene glycols there are various nomenclatures that can lead to confusion. Technically common is the indication of the average relative molecular weight following the indication "PEG", so that "PEG 200" characterizes a polyethylene glycol having a relative molecular weight of about 190 to about 210. For cosmetic ingredients, a different nomenclature is used in which the abbreviation PEG is hyphenated and directly followed by the hyphen followed by a number corresponding to the number n in formula V above. After this Nomenkla structure (so-called INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997) are at play, 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 names Carbowax® PEG 200 (Union Carbide), Emkapol® 200 (ICI Americas), Lipoxol® 200 MED (HUBS America), Polyglycol® E-200 (Dow Chemical), Alkapol® PEG 300 ( Rhone-Poulenc), Lutrol® E300 (BASF) and the corresponding trading name with higher numbers.

Polypropylene glycols (abbreviated PPG) are polymers of propylene glycol which are of general formula VIII

satisfy, where n can assume values between 1 (propylene glycol) and several thousand. Of particular technical importance here are di-, tri- and tetra-propylene glycols, d. H. the representatives with n = 2, 3 and 4 in formula VI.

In particular, the grafted on polyethylene glycol vinyl acetate copolymers and on Polyethylene glycol grafted polymers of vinyl acetate and crotonic acid are used.

• - grafted and crosslinked copolymers from the copolymerization of
  • a) at least one nonionic type monomer,
  • b) at least one ionic-type monomer,
  • c) of polyethylene glycol and
  • d) a networked person

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

The nonionic monomers may be of very different types and among these the following are preferred: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allylauro rat, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-hexene.  

The nonionic monomers can equally be of very different types, among these, more preferably crotonic acid, allyloxyacetic acid, vinylacetic acid, mal acid, acrylic acid and methacrylic acid are contained in the graft polyamides.

As crosslinkers are preferably ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallyl sucrose with 2 to 5 allyl groups per mole Cul saccharin.

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

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

Among short-chain carboxylic acids or alcohols are those having 1 to 8 carbon atoms to understand, where appropriate, the carbon chains of these compounds by divalent Hetero groups such as -O-, -NH-, -S_ may be interrupted.

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

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

wherein R ^{3 is} -H or -CH ₃ , R ^{2 is} -CH ₃ or -CH (CH ₃ ) ₂ and R ^{1 is} -CH ₃ or a saturated straight or branched C _1-6 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 abovementioned terpolymers preferably result from the copolymerization of 7 to 12 wt .-% crotonic acid, 65 to 86 wt .-%, preferably 71 to 83 wt .-% vinyl acetate and 8 to 20% by weight, preferably 10 to 17% by weight, of allyl or methallyl ester of the formula IX.

• - Tetra and pentapolymers from
  • a) crotonic acid or allyloxyacetic acid
  • b) vinyl acetate or vinyl propionate
  • c) branched allyl or methallyl esters
  • d) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters
  • e) Crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinyl methyl ether, acrylamide and their water-soluble salts
  • f) terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic α-branched monocarboxylic acid.

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

Useful organic film materials are, for example, in the form of their sodium salts also usable in free form polycarboxylic acids. Polymeric polycarboxylates are for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70000 g / mol.

In the context of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses 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 polymers investigated. These data differ significantly from the molecular weight data in which Polystyrolsulfonsäu ren are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified 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, this group may again, the short-chain polyacrylates, the molecular weights of 2000 to 10,000 g / mol, and especially preferably from 3000 to 5000 g / mol, have to be preferred.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As especially suitable have proven copolymers of acrylic acid with maleic acid, the 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Their molecular weight relative to free acid ren, is generally 2000 to 70000 g / mol, preferably 20,000 to 50,000 g / mol and ins special 30,000 to 40,000 g / mol.

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

Particularly preferred as film materials are also biodegradable polymers from more as two different monomer units, for example those which are salts of the monomers Acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as a mono contain mere salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.

Further preferred copolymeric film materials are those described in German Patentanmel DE-A-43 03 320 and DE-A-44 17 734 are described and as monomers vorzugswei acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Likewise, as further preferred film materials are polymeric aminodicarboxylic acids whose sal to name ze or their precursors. Particularly preferred are polyaspartic acids or their salts and derivatives.

Other suitable film materials are polyacetals, which by reaction of dialdehydes with polyol carboxylic acids having 5 to 7 C atoms and at least 3 hydroxyl groups, can be obtained. Preferred polyacetals are selected from dialdehydes such as glyoxal, glutaral dehyd, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Further, preferably usable as film materials polymers are cationic polymers. Under The cationic polymers are the permanent cationic polymers are preferred. As "per Manent cationic "according to the invention refers to such polymers which are independent of pH value of the agent (ie both the film and the other washing and cleaning agent molding)  have a cationic group. These are usually polymers that are quaternary Nitrogen atom, for example in the form of an ammonium group.

Preferred cationic polymers are, for example

• - Quaternized cellulose derivatives, such as those under the names Celquat® and polymer JR® are commercially available. The compounds Celquat® H 100, Celquat® L 200 and Poly JR® 400 are preferred quaternized cellulose derivatives.
• - Polysiloxanes with quaternary groups, such as the commercially available Pro Q2-7224 (manufacturer: Dow Corning, a stabilized trimethylsilylamodimethicone), Dow Corning® 929 emulsion (containing a hydroxylamino-modified silicone, which also as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (Manufacturer: Wacker) and Abil® Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; di quaternary polydimethylsiloxanes, quaternium-80),
• - Cationic guar derivatives, such as those under the trade names Cosmedia® guar and Jaguar® distributed products,
• Polymers Dimethyldiallylammonium salts and their copolymers with esters and amides of Acrylic acid and methacrylic acid. The under the names Merquat®100 (Po ly (dimethyldiallylammonium chloride)) and Merquat® 550 (dimethyldiallylammonium chloride) Acrylamide copolymer) commercially available products are examples of such cationic polymers.
• - Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino and methacrylates such as vinylpyrrolidone quaternized with diethyl sulfate. Dimethylaminomethacrylate copolymers. Such compounds are among the Be Gafquat®734 and Gafquat®755 are commercially available.
• - Vinylpyrrolidone-Methoimidazoliniumchlorid copolymers, as described by Luvi quat® are offered.
• - Quaternized polyvinyl alcohol

as well as those under the designations

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

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

Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, to which expressly refer Reference is made.

Cationic polymers preferred according to the invention are quaternized cellulose derivatives as well 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, the film preferably has one Such thickness, which is responsible for a separation of the ingredients of the molding and the substances that be placed in the cavity while storage is sufficient. Another criterion for the film thickness is the desired release time of the film in the respective application. Slides with a thickness of 1 to 150 microns, preferably from 2 to 100 microns, more preferably from 5 to 75 microns and especially from 10 to 50 microns, have proved to be particularly suitable. Since the one put foil is usually covered with active substance, are no special aesthetic requirements tions to the film.

In a further embodiment of the present invention, the opening of the cavity with a Closed film. This embodiment has the advantage that also flowable substances in the Cavity can be incorporated. The release takes place after removal of the film, z. B. by Dissolve by contact with water.

In the context of the present invention, sealed means that the film containing the opening the cavity (s) closes, adherent to the molding is connected. A packaging in which the Shaped body is therefore not met the inventive criterion of "closing The material may be used as the film material for closing the cavity. as described above for the covering of the molding body-side boundary wall has been. Depending on the intended use, for covering the boundary wall and for closing the cavity same or different film materials in the same or different thicknesses are used.

The film which closes the opening (s) of the cavity (s) is placed on the surface of the shaped body applied and adherent to this, which, for example, by sticking, partial Auf melt or can be done by chemical reaction. It is possible to mold the foil to any shape apply body surfaces and adherent to connect with these, so that the film has a Be stratification, a "coating" of the entire molding. Preferred washing and cleaning However, molding tablets are characterized in that the film is not the entire Encloses moldings.  

For reasons of process economy and aesthetic impression, it is preferred that the Film is applied only to the mold surfaces where it performs a function, d. H. the Closing of cavities is used. Detergents and cleaning agents in which the film only the surfaces of the molding covered, in which openings of the cavity (s) are located therefore preferred.

The shaped bodies according to the invention are preferably washing and cleaning agent tablets. It is possible according to the invention to leave the cavity unfilled and only the visual appeal the outer shape including the possibly colored foil act. In a preferred Embodiment are detergent tablets but are characterized that the cavity is filled with additional active substance. In a particularly preferred embodiment The filled cavity is closed with a foil.

In this way, a shaped body according to the invention comprises two areas in which unterschiedli containing or different release mechanisms and dissolution kinetics ken can be realized. The active substance contained in the cavity can thereby jedweden State of aggregation or any form of presentation. Preferred washing and cleaning Medium shaped tablets contain the further active substance in liquid, gel, pasty or solid Shape.

This embodiment has the advantage that during the incorporation of liquid, gel or pastö these active substances or active substance mixtures do not mix the composition of the molding the nature of the other active substance must be adjusted, since these are no points of contact respectively. The sealed through the film cavity can completely with further Aktivsub be filled. But it is also possible, the cavity before closing only partially fill, in this way, a movement of the filled particles or liquids within to allow the cavity. Especially when filling with regularly shaped larger Parti You can make sexy optical effects a reality. Here are washing and Reinigungsmit telformkörper preferred in which the volume ratio of the through the film and the mold body-enclosed space to the active substance contained in this room 1: 1 to 100: 1, preferably 1.1: 1 to 50: 1, more preferably 1.2: 1 to 25: 1 and especially 1.3: 1 to 10: 1 is. In this terminology, a 1: 1 volume ratio means that the cavity is complete is filled.

Depending on the size of the cavity, the density of the molding, the density of the active sub in the cavity and the degree of filling of the cavity, the proportion of the further active substance in the cavity make up different proportions of the overall molding. Here are washing and Preferred detergent tablets in which the weight ratio of molded body to the in  the active substance contained in the space enclosed by the film and the molded body 1: 1 to 100: 1, preferably 2: 1 to 80: 1, more preferably 3: 1 to 50: 1 and in particular 4: 1 to 30: 1 is. The weight ratio defined above is the ratio of Mass of the unfilled body ("basic body") to the mass of the filling. The mass of Slide is not included in this calculation.

By suitable packaging of moldings and film material, the time at which the substance contained in the cavity is released, be predetermined. For example, can the film be virtually instantaneously soluble, so that the active substance contained in the cavity equal to Beginning of the washing or cleaning cycle is dosed into the washing or cleaning liquor. age natively, the film may be so poorly soluble that only the molding is dissolved and the active substance contained in the cavity is thereby released.

Depending on this release mechanism, for example, moldings can be realized ren, in which the active substance contained in the cavity is dissolved in the cleaning liquor, before the constituents of the molding are dissolved or after this has been done. So are on the one hand detergent tablets and cleaning agent, which are characterized that the active substance contained in the space enclosed by the film dissolves faster as the basic shaped body.

But also detergent tablets, in which the in the through the film The active substance contained in the enclosed space dissolves more slowly than the base molding is imminent ferred embodiments of the present invention.

The shaped bodies according to the invention consist of a basic shaped body which has one or more Has cavities whose molding-side boundary wall with foil (s) is covered. In a preferred embodiment, the cavity is closed with another film and optionally with Aktivsub punched (s) filled. The film materials and preferred physical parameters of the films were already described above. Below is a description of the ingredients of the basic form body, which at the same time can be active substances contained in the cavity, as well as an enumeration of preferred physical parameters for basic moldings and cavi filling ty. By incorporating certain ingredients, on the one hand, the solubility of the filling of Cavity can be specifically accelerated, on the other hand, the release of certain ingredients lead from this filling to benefits in the washing or cleaning process. Ingredients before are at least partially localized in the cavity, for example, the beschrie below surfactants, enzymes, soil-release polymers, builders, bleaches, bleach activators, Bleach catalysts, optical brighteners, silver protectants, etc.  

The base molding in preferred embodiments of the present invention has a high specific gravity. Detergents and cleaning agent tablets which are characterized in that the base tablet has a density above 1000 kgdm ^-3, preferably above 1025 kgdm ^{-3, more} preferably above 1050 kgdm ^-3 and especially above 1100 kgdm ^-3 , are preferred according to the invention.

Further details on physical parameters of the base molding or the finished Detergents and cleaning product tablets and information on the preparation can be found below. The following is a representation of the preferred ingredients of the base molding.

In the context of the present invention, preferred washing and cleaning agent tablets are characterized in that the basic shaped body builders in amounts of 1 to 100 wt .-%, preferably from 5 to 95 wt .-%, particularly preferably from 10 to 90 wt .-% and in particular from 20 to 85 wt .-%, each based on the weight of the base molding contains.

In the detergent tablets according to the invention, all can usually be used in Be included washing and cleaning agents used builders, especially Zeoli the, silicates, carbonates, organic cobuilders and - where no ecological prejudices against their Use exist - also the phosphates.

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

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ module of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are delay-delayed and have secondary washing properties. The dissolution delay compared to conventional amor phen sodium silicates can be caused in various ways, for example by Oberflächenbe treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as they are typical for crystalline substances, but at best one or more maxima of the scattered X-radiation, which have a width of several degrees of the diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of 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 dissolution delay compared with the 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 overdried X-ray amorphous silicates.

In the context of the present invention, preferred washing and cleaning agent tablets are characterized in that the base molding silicate (s), preferably alkali metal silicates, FEM It prefers crystalline or amorphous Alkalidisilikate, in amounts of 10 to 60 wt .-%, before preferably from 15 to 50 wt .-% and in particular from 20 to 40 wt .-%, each based on the weight of the base molding contains.

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

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

can be described. The zeolite can be used both as a builder in a granular Compound used, as well as to a kind of "powdering" of the entire Mi to be pressed usually both ways for the incorporation of the zeolite in the Pre-mix can be used. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22 wt .-%, in particular 20 to 22 wt .-% of bound water.

Of course, a use of the well-known phosphates as builders possible, unless such use should be avoided for environmental reasons. Among the large number of commercially available phosphates, the alkali metal phosphates have particular preference of pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate) are the most important in the detergents and cleaners industry.  

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

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white, very soluble in water lösli surface powder, which lose the water of crystallization on heating and at 200 ° C in the weak acid diphosphate (disodium hydrogen, Na ₂ H ₂ P ₂ O ₇ , at higher temperature in Natiumtrime taphosphat (Na ₃ Pd ₃ O ₉ ) and Maddrell's salt (see below), NaH ₂ PO _{4 is} acidic and forms when phosphoric acid is adjusted to pH 4.5 with caustic soda and the mash is sprayed Potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt of density 2.33 gcm ^-3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is readily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 What serverlust at 95 °), 7 mol. (Density 1.68 gcm ^-3 melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water (density 1.52 gcm ^-3 melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and goes on stronger heating in the diphosphate Na ₄ P ₂ O ₇ . Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous white set which is readily soluble in water.

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

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

Condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ results in higher mol. Sodium and potassium phosphates in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and ket tenförmige types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: melting or annealing phosphates, Gra harsh salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is a water-free, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] which crystallizes free of water or with 6 H ₂ O. _n -Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the saltwater-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, penta sodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtri phosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (<23% P ₂ O ₅ , 25% K ₂ O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. Furthermore, there are also Natriumkaliumtripolyphos phate, which are also used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:

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

These are according to the invention just like sodium tripolyphosphate, potassium tripolyphosphate or Mi can be used from these two; also mixtures of sodium tripolyphosphate and Natri potassium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate  or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium umtripolyphosphat are used in the invention.

In the context of the present invention, preferred washing and cleaning agent tablets are characterized in that the basic shaped body phosphate (s), preferably Alkalimetallphos phat (e), particularly preferably pentasodium or pentakalium triphosphate (sodium or potassium tripolyphosphate), in amounts of from 20 to 80% by weight, preferably from 25 to 75% by weight, to us particular from 30 to 70 wt .-%, each based on the weight of the base molding containing.

As further constituents alkali carriers may be present. Examples of alkali carriers are Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, said alkali metal silicates, alkali metal silicates, and mixtures of the foregoing th substances, for the purposes of this invention preferably the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate. Especially preferred is a builder system containing a mixture of tripolyphosphate and sodium carbonate nat. Also particularly preferred is a builder system comprising a mixture of tripoly phosphate and sodium carbonate and sodium disilicate.

In particular 99999 00070 552 001000280000000200012000285919988800040 0002010062582 00004 99880s detergent tablets contains the base molding Carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonates, particularly preferred Sodium carbonate, in amounts of 5 to 50 wt .-%, preferably from 7.5 to 40 wt .-% and ins particular from 10 to 30 wt .-%, each based on the weight of the base molding.

As organic cobuilders can in the detergent and cleaner form according to the invention in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, asparagine acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates be set. These classes of substances are described below.

Useful organic builders include, for example, those in the form of their sodium salts settable polycarboxylic acids, understood by polycarboxylic acids such carboxylic acids which carry more than one acidity function. For example, these are citric acid, adipin acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acid ren, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use of ecological Reasons are not objectionable, as well as mixtures of these. Preferred salts are the salts 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. The acids are next to their builders kung also typically the property of an acidifying component and thus also serve for Setting a lower and milder pH of detergents or cleaners. in particular Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and to name any mixtures of these.

Other suitable builders are polymeric polycarboxylates, for example the alkali metals tallsalts of polyacrylic acid or polymethacrylic acid, for example those with a relative Molecular weight of 500 to 70000 g / mol.

For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M _w , the particular acid form, which were fundamentally determined 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 polymers investigated. These data differ significantly from the molecular weight data in which Polystyrolsulfonsäu ren are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified 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, this group may again, the short-chain polyacrylates, the molecular weights of 2000 to 10,000 g / mol, and especially preferably from 3000 to 5000 g / mol, have to be preferred.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As especially suitable have proven copolymers of acrylic acid with maleic acid, the 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Their molecular weight relative to free acid ren, is generally 2000 to 70000 g / mol, preferably 20,000 to 50,000 g / mol and ins special 30,000 to 40,000 g / mol.

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

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

Also particularly preferred are biodegradable polymers of more than two different NEN monomer units, for example those containing as monomers, salts of acrylic acid and the Maleic acid and vinyl alcohol or vinyl alcohol derivatives or the monomers used as salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.

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

Likewise, as further preferred builder substances are polymeric aminodicarboxylic acids, their To name salts or their precursors. Particularly preferred are polyaspartic acids or their salts and derivatives, of which in the German patent application DE-A-195 40 086 it is disclosed that in addition to cobuilder properties, it also has a bleach-stabilizing effect respectively.

Further suitable builder substances are polyacetals, which are prepared by reaction of dialdehydes with polyol carboxylic acids having 5 to 7 C atoms and at least 3 hydroxyl groups, can be obtained. Preferred polyacetals are selected from dialdehydes such as glyoxal, glutaral dehyd, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Further suitable organic builder substances are dextrins, for example oligomers or Polymers of carbohydrates that can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes be performed. Preferably, they are medium molecular weight hydrolysis products in the range from 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose Equivalent (DE) in the range of 0.5 to 40, especially from 2 to 30 preferred, wherein DE a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 is. Useful are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range of 2000 to 30,000 g / mol.

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

Also, oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine succinate, are other suitable co-builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS) be preferably used in the form of its sodium or magnesium salts. Further preferred are in Glycerol disuccinates and glycerol trisuccinates are also linked to this context. Suitable use amounts are in zeolithhaltigen and / or silicate-containing formulations at 3 to 15 wt .-%.

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

Another class of substances with co-builder properties are the phosphonates. Han these are in particular hydroxyalkane or aminoalkanephosphonates. Among the hydroxyal kanphosphonaten is the 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a co-builder. It is preferably used as the sodium salt, wherein the disodium salt neutral and the tetrasodium salt is alkaline (pH 9). As Aminoalkanphosphonate occur preferably ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. They are preferably in shape the neutral reacting sodium salts, eg. B. as hexasodium salt of EDTMP or as hepta- and Octa-sodium salt of DTPMP used. As a builder is from the class of phosphonates preferred to use HEDP. The aminoalkanephosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it may, especially if the funds also lead may be preferred to use Aminoalkanphosphonate, in particular DTPMP, or Use mixtures of the above phosphonates.

In addition, all compounds that are able to form complexes with alkaline earth ions be used as co-builders.

The amount of builder is usually between 10 and 70 wt .-%, preferably between 15 and 60 wt .-% and in particular between 20 and 50 wt .-%, each based on the basic shaped body. Again, the amount of builders used depends on the use purpose, so that bleach tablets can have higher amounts of builders (For example, between 20 and 70 wt .-%, preferably between 25 and 65 wt .-% and ins especially between 30 and 55% by weight), for example detergent tablets (usually  10 to 50% by weight, preferably 12.5 to 45% by weight, in particular between 17.5 and 37.5% by weight).

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

Preferred detergent tablets also contain one or more Ten sid (e). In the washing and cleaning agent tablets according to the invention, anionic, nonionic, cationic and / or amphoteric surfactants or mixtures thereof be used. From an application point of view detergent tablets are preferred Mixtures of anionic and nonionic surfactants and detergent tablets not anionic surfactants. The total surfactant content of the tablets is in the case of detergent tablets at 5 to 60 wt .-%, based on the molding weight, wherein surfactant contents over 15 wt .-% while detergent tablets for automatic dishwashing are preferred Example below 5 wt .-% surfactant (s) included.

As anionic surfactants, for example, those of the type of sulfonates and sulfates are set. Preferred surfactants of the sulfonate type are C _9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained, for example, from C _12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous Sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfo fatty acids (ester sulfonates), z. B. the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or Talgfettsäu ren suitable.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Under fatty acid glyceri nests are to be understood as the mono-, di-, and triesters, as well as their mixtures, as described in Her By esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the Um esterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fat acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid re, palmitic acid, stearic acid or behenic acid.

As alk (en) ylsulfates, the alkali metal salts and, in particular, the sodium salts of the sulfuric acid halides are best of the C ₁₂ -C ₁₈ fatty alcohols, for example of coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or of C ₁₀ -C ₂₀ Oxo alcohols and those half esters secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis, which have an analogous degradation behavior as the adequate connec tions based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. Also, 2,3-alkyl sulfates, which are prepared, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products of the Shell Oil Company under the name DAN®, are suitable anionic surfactants.

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

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

As further anionic surfactants are particularly soaps into consideration. Suitable are saturated Fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hy Dried erucic acid and behenic acid and in particular from natural fatty acids, eg. Coconut, Palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants including the soaps may be in the form of their sodium, potassium or Ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine, available. Preferably, the anionic surfactants are in the form of their sodium or potassium salts, especially in the form of the sodium salts.

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

In addition, other nonionic surfactants and alkyl glycosides of the general formula RO (G) _x are used in which R is a primary straight-chain or methyl-branched, in particular special in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol representing a glycose moiety having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of mono-glycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

Another class of preferred nonionic surfactants used either alone nonionic surfactant or used in combination with other nonionic surfactants who , are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fat acid methyl ester, as described, for example, in Japanese Patent Application JP 58/217598 be are written or preferably according to the in the international patent application WO-A- 90/13533 described methods.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N- dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamide may be suitable. The amount of these nonionic surfactants is preferably no longer than that of the ethoxylated fatty alcohols, especially not more than half of them.

Further suitable surfactants are polyhydroxy fatty acid amides of the formula (X)

wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R ^{1 is} hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 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)

in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or a Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C _1-4 alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or per polyoxylated derivatives of this residue.

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

In the context of the present invention, laundry detergents are used as detergent tablets molded tablets containing anionic (s) and nonionic (s) surfactant (s), wherein apply technical advantages of certain proportions, in which the individual surfactant can be used.

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

From an application point of view, it can have advantages if certain classes of surfactants are used in one phases of the detergent tablets or in the entire tablet, d. H. in all phases, not included. Another important embodiment of the present invention Therefore, provision is made for at least one phase of the shaped bodies to be free of nonionic surfactants is.

Conversely, however, the content of individual phases or of the entire molding, d. H. all phases, on certain surfactants a positive effect can be achieved. The introduction of the Alkylpolyglycosides described above has proved to be advantageous, so that washing and Detergent tablets are preferred in which at least one phase of the moldings Al kylpolyglycoside contains.

Similar to the nonionic surfactants can also be removed from the omission of anionic Surfactants resulting from single or all phases washing and cleaning detergent tablets, the are more suitable for certain applications. It is therefore within the scope of the present Invention and detergent tablets are conceivable in which at least one Pha the shaped body is free of anionic surfactants.

As already mentioned, the use of surfactants in automatic dishwashing detergent tablets is preferably restricted to the use of small amounts of nonionic surfactants. In the context of the present invention preferably detergent tablets as detergent tablets and detergent tablets are preferably characterized in that the basic body has total surfactant contents below 5% by weight. preferably below 4 wt .-%, particularly preferably below 3 wt .-% and in particular below 2 wt .-%, each based on the weight of the base molding having. The surfactants used in machine dishwashing detergents are usually only low-foaming nonionic surfactants. By contrast, representatives from the groups of anionic, cationic or amphoteric surfactants have less importance. With particular preference, the detergents according to the invention contain moldings for machine dishwashing nonionic surfactants, in particular nonionic surfactants from the group of alkoxylated alcohols. As nonionic surfactants are vorzugswei se alkoxylated, preferably 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 used in which the alcohol radical is linear or preferably methyl-branched in the 2-position may contain or linear and methyl-branched radicals in the mixture, as they are usually present in oxo alcohol residues. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for. From coconut, palm, tallow or oleyl alcohol, and on average from 2 to 8 EO per mole of alcohol. Examples of preferred ethoxylated alcohols include C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In particular, in the inventive preparation of detergent tablets or Reini For machine dishwashing detergent tablets, it is preferred that the washing and Detergent tablets contain a nonionic surfactant which has a melting point above Room temperature. Accordingly, contains at least one of the deformable masses in he inventive method preferably a nonionic surfactant having a melting point above half of 20 ° C. Preferably used nonionic surfactants have melting points above from 25 ° C, particularly preferably used nonionic surfactants have melting points between 25 and 60 ° C, in particular between 26.6 and 43.3 ° C.

Suitable nonionic surfactants, the melting or softening points in said temperature Have, for example, low foaming nonionic surfactants, the Room temperature can be solid or highly viscous. Become highly viscous at room temperature Niotensides used, it is preferred that these have a viscosity above 20 Pas, preferably wise above 35 Pas and in particular above 40 Pas. Also Niotenside, the at Room temperature waxy consistency, are preferred.

Preferred nonionic surfactants to be used at room temperature are from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures thereof Surfactants with structurally complicated surfactants such as polyoxypropy len / polyoxyethylene / polyoxypropylene (PQ / EO / PO) surfactants. Such (PO / EO / PO) -nonosides draw Moreover, they are characterized by good foam control.

In a preferred embodiment of the present invention, this is nonionic surfactants with a melting point above room temperature, an ethoxylated nonionic surfactant derived from the reac tion of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, more preferably at least 15 mol, in particular at least 20 mol Ethylene oxide per mole of alcohol or alkylphenol emerged.  

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

The nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the Molecule. Preferably, such PO units make up to 25 wt .-%, more preferably bis to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Surfactants. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally contain polyoxyethylene-polyoxypropylene block copolymer units point. The alcohol or alkylphenol part of such nonionic surfactant molecules is preferably more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight the total molecular weight of such nonionic surfactants.

Further particularly preferred nonionic surfactants having melting points above room temperature 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene Block polymer blends containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block A copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and contained 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

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

A further preferred surfactant can be defined by the formula

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

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

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

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

in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value x ≧ 2, then each R ³ in the above formula may be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. 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 may be different if x ≧ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO ) (PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO ) (PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

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

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

simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x is 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 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

In order to facilitate the disintegration of highly compacted molded articles, it is possible to disintegrate to incorporate medium, so-called tablet disintegrants, into the base moldings in order to reduce their decomposition shorten times. Among disintegrants and disintegrants according to Römpp (9th edition, Bd. 6, p. 4440) and Voigt "textbook of pharmaceutical technology" (6. Edition, 1987, pp. 182-184) understood excipients which are responsible for the rapid disintegration of tablets in Water or gastric juice and provide for the release of the drugs in resorbable form.

These substances, which are also referred to as "explosives" due to their effect, increase their size when water enters their volume, on the one hand increases the intrinsic volume (swelling), on the other hand  also, via the release of gases, a pressure can be generated which the tablet is in smaller particles disintegrate. Well-known disintegration aids are, for example, Carbo nat / citric acid systems, although other organic acids can be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinyl pyrrole lidon (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

Preferred detergent tablets contain from 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 aids, in each case based on the molding body weight. Contains only the base mold Desintegrations auxiliaries, the details given relate only to the weight of the basic tablet.

As preferred disintegrating agents, cellulose-based disintegrating agents are used in the present invention, so that preferred washing and Reinigungsmittelformkör by such disintegration agent based on cellulose in amounts of 0.5 to 10 wt .-%, preferably 3 to 7 wt .-% and in particular 4 to 6 wt .-%. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulosic disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, more preferably below 20% by weight, based on the disintegration agent based on cellulose. It is particularly preferred to use cellulose-based disintegrating agent as pure cellulose which is free of cellulose derivatives.

The cellulose used as disintegration assistant is preferably not in finely divided form but before blending into the pre-mixes to be pressed into a coarser one Form transferred, for example, granulated or compacted. Washing and Reinigungsmittelformkör which contain disintegrants in granular or optionally cogranulated form are incorporated in US Pat the German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel)  and international patent application WO 98/40463 (Henkel). These writings are also details of the production of granulated, compacted or cogranulated cellulosic to remove sesprengmittel. The particle sizes of such disintegrating agents are mostly above 200 microns, preferably at least 90 wt .-% between 300 and 1600 microns and in particular especially at least 90 wt .-% between 400 and 1200 microns. The aforementioned and in The cited documents described in more detail coarser cellulose disintegration aids are preferably used as disintegration aids in the context of the present invention and commercially, for example, under the name Arbocel® TF-30-HG from Retten maier available.

As another disintegrating agent based on cellulose or as a component of this component can microcrystalline cellulose. This microcrystalline cellulose is made by partial Obtained hydrolysis of celluloses under such conditions that only the amorphous regions (ca. 30% of the total cellulose mass) of the celluloses attack and completely dissolve the crystalline ones areas (about 70%) but without damage. A subsequent disaggregation of The microfine celluloses resulting from the hydrolysis provide the microcrystalline celluloses Pri have particle sizes of about 5 microns and, for example, granules with a medium Particle size of 200 microns are compacted.

In the context of the present invention, preferred washing and cleaning agent tablets Ent additionally contain a disintegration aid, preferably a disintegration aid Cellulose base, preferably in granular, cogranulated or compacted form, in quantities from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the molding body weight.

The detergent tablets according to the invention can moreover be both contain a gas-developing effervescent system in the base molding as well as in the cavity. The gas-evolving effervescent system may consist of a single substance which, when in contact with Water releases a gas. Among these compounds, in particular, the magnesium peroxide is too name that releases oxygen on contact with water. Usually, there is gas release de Sprudel system, however, in turn, consists of at least two components that are under each other Gas formation react. While here a variety of systems is thinkable and executable, the For example, release nitrogen, oxygen or hydrogen, which is in the Invention according to washing and cleaning agent moldings used Sprudelsystem both by economic as well as ecological aspects. Favorite brewing Systems consist of alkali metal carbonate and / or bicarbonate and an acidity agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution Zen.  

In the alkali metal carbonates or bicarbonates, the sodium and potassium salts are made Cost reasons over the other salts clearly preferred. Of course you have to not the respective pure alkali metal carbonates or bicarbonates are used; Rather, mixtures of different carbonates and bicarbonates may be preferred.

In preferred detergent tablets, the effervescent system is 2 to 20% by weight. %, preferably 3 to 15 wt .-% and in particular 5 to 10 wt .-% of an alkali metal carbonate or -hydrogencarbonats and 1 to 15, preferably 2 to 12 and especially 3 to 10 wt. % of an Acidifizierungsmittels, in each case based on the entire molding used.

Acidifying agents which release carbon dioxide from the alkali salts in aqueous solution are For example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used. However, preference is given to organic acidification used, wherein the citric acid is a particularly preferred Acidifizierungsmittel. However, it is also possible in particular to use the other solid mono-, oligo- and polycarboxylic acids. Tartaric acid, succinic acid, malonic acid, adipic acid are again preferred from this group maleic acid, fumaric acid, oxalic acid and polyacrylic acid. Organic sulfonic acids like Ami Dosulfonic acid are also used. Commercially available and as Acidifizierungsmittel in Sokalan® DCS (Warenzei BASF), a mixture of succinic acid (max 31 wt .-%), glutaric acid (max. %) and adipic acid (max 33 wt%).

In the context of the present invention, preference is given to washing and cleaning agent tablets, in which as the acidifying agent in the effervescent system a substance from the group of organic di-, Tri- and oligocarboxylic acids or mixtures of these can be used.

Among the compounds serving as bleaching agents in water H ₂ O _2, the sodium perborate tetrahydrate and the sodium perborate monohydrate are of particular importance. Further usable bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrate 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 may also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaching agents are the diacyl peroxides, such as. B. dibenzoyl peroxide. Further typical organic bleaching agents are the peroxyacids, examples being the alkyl peroxy acids and the aryl peroxyacids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, ε-phthalimido peroxycaproic acid [phthaloiminoperoxyhexanoic 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, diperoxysebacic acid, diperoxybrassic acid, diperoxyphthalic acids, Decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronate) can be used.

As a bleaching agent in the inventive detergent tablets for machine Dishwashing can also chlorine or bromine releasing substances are used. Among the suitable chlorine or bromine-releasing materials are, for example, heterocyclic N- Bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or salts thereof with cations such as Potassium and sodium are considered. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

The bleaching agents are usually used in automatic dishwashing detergents in amounts of from 1 to 30% by weight, preferably from 2.5 to 20% by weight and in particular from 5 to 15% by weight, respectively based on the agent used. In the context of the present invention, the mentioned proportions on the weight of the base molding.

Bleach activators which aid in the action of the bleaching agents may also form part of the Be the basic molding. Known bleach activators are compounds which have one or more N- or O-acyl groups such as substances from the class of anhydrides, the ester, the imides and the acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, Tetraa cetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.

As bleach activators, compounds which are aliphatic under perhydrolysis conditions Peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, can be used. Are suitable Substances which contain O- and / or N-acyl groups of said C atom number and / or optionally bear substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5- Diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular Tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso- NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyvalent Alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl Morpholinium acetonitrile methylsulfate (MMA), and those of the German patent applications  DE 196 16 693 and DE 196 16 767 known enol esters and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular Pentaacetylglucose (PAG), Pentaacetylfruktose, Tetraacetylxylose and Octaacetyllactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated Lactams, for example N-benzoyl-caprolactam. Hydrophilic substituted acyl acetals and Acyllactams are also preferably used. Also combinations of conventional Bleach activators can be used. The bleach activators are in mechanical Dishwashing agents usually in amounts of 0.1 to 20 wt .-%, preferably from 0.25 to 15 wt .-% and in particular from 1 to 10 wt .-%, each based on the agent used. in the In the context of the present invention, the stated proportions relate to the weight of the Basic tablet.

In addition to the conventional bleach activators or in their place may also soge called Blleichkatalysatoren be incorporated into the active substance particles. For these substances are bleach-enhancing transition metal salts or transition metal complexes such as for example Mn, Fe, Co, Ru or Mo-salene complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru-amine complexes are useful as bleach catalysts.

Bleach activators from the group of the multiply acylated alkylenediamines, in particular especially tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), preferably in Men to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, especially 2 to 8 wt .-% and be more preferably 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 of manganese and / or cobalt salts ze and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) - Complexes, cobalt (carbonyl) complexes, chlorides of cobalt or manganese, manganese Sulfates are in conventional amounts, preferably in an amount up to 5 wt .-%, in particular from 0.0025% to 1% and more preferably from 0.01% to 0.25% by weight, each based on the total agent used. But in special cases can be more Bleach activator can be used.

Detergent tablets, characterized in that the base tablet bleaching agent from the group of oxygen or halogen bleaches, in particular the Chlorine bleach, with particular preference of sodium perborate and sodium percarbonate, in Amounts of from 2 to 25% by weight, preferably from 5 to 20% by weight and in particular from 10 to 15% by weight  each based on the weight of the base molding mass contains, are an inven According to the preferred embodiment of the present invention.

It is also preferred that the base molding and / or the active substance (s) in the cavity Bleach activators included. Detergent tablets in which the basic tablet by bleach activators from the groups of the polyacylated alkylenediamines, in particular Tetraacetylethylenediamine (TAED), the N-acylimides, in particular N-nonanoylsuccinimide (NOSI), the acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) and n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), in amounts of 0.25 to 15 wt .-%, preferably from 0.5 to 10 wt .-% and in particular from 1 to 5 wt .-%, depending Because based on the weight of the base molding contains, are also preferred.

The detergent tablets according to the invention can be used in particular in the basic tablet to protect the items to be washed or the machine contain corrosion inhibitors, in particular Silver protectants in the field of automatic dishwashing has a special importance ha ben. It is possible to use the known substances of the prior art. Generally, you can all silver protectants selected from the group of triazoles, benzotriazoles, the bisben zotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes are used. Particularly preferred to use are benzotriazole and / or Al kylaminotriazol. In addition, cleaning agent formulations often contain active chlorine-containing agents, which can significantly reduce the corrosion of the silver surface. In chlorine-free cleaners who especially the oxygen- and nitrogen-containing organic redox-active compounds, such as and trihydric phenols, e.g. Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, Phloroglucin, pyrogallol or derivatives of these classes of compounds. Also salt and complex Inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often found in Ver turn. Preference is given here to the transition metal salts which are selected from the group the manganese and / or cobalt salts and / or complexes, more preferably the cobalt (ammin) - Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of the Cobalt or manganese and manganese sulfate. Also, zinc compounds for Verhinde tion of corrosion on the items to be used.

In the context of the present invention, preferred detergent tablets contains the base molding silver protectants from the group of triazoles, benzotriazoles, the Bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes, more preferably benzotriazole and / or alkylaminotriazole, in amounts of from 0.01 to 5% by weight, preferably from 0.05 to 4% by weight and in particular from 0.5 to 3% by weight, respectively based on the weight of the base molding.  

Of course, however, the cavity may also contain silver protection agents, the basic form body either also contains silver protectants or is free of such compounds.

In addition to the ingredients mentioned above, further classes of substances are available for Inkorpo ration in detergents and cleaners. So are washing and cleaning detergent tablets before zugt, in which the base molding further one or more substances from the groups of Enzymes, corrosion inhibitors. Scale inhibitors, cobuilders, dyes and / or fragrances in Ge samtmengen from 6 to 30 wt .-%, preferably from 7.5 to 25 wt .-% and in particular of 10 to 20 wt .-%, each based on the weight of the base molding contains.

In addition to the ingredients mentioned Builder, surfactant, disintegrating aid bleach and Bleach activator can the detergent tablets according to the invention further in Detergents and cleaners conventional ingredients from the group of dyes, fragrances, opti brighteners, enzymes, foam inhibitors, silicone oils, anti redeposition agents, graying agents bitenen, color transfer inhibitors and corrosion inhibitors.

As enzymes are in the base moldings in particular those from the classes of Hydrola sen as the proteases, esterases, lipases or lipolytic enzymes, amylases, glyco sylhydrolases and mixtures of the enzymes mentioned in question. All these hydrolases contribute to Removal of stains such as proteinaceous, fatty or starchy stains. to Bleach can also be used oxidoreductases. Particularly well suited are from Bakte trunks or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Co prinus Cinereus and Humicola insolens and their genetically modified variants recovered enzymatic agents. Preferably, subtilisin type proteases and in particular proteases derived from Bacillus lentus. Here are En zymmischungen, for example from protease and amylase or protease and lipase or lipoly table-acting enzymes or from protease, amylase and lipase or lipolytic En enzymes or protease, lipase or lipolytic enzymes, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of be special interest. Examples of such lipolytic enzymes are the known cuti noses. Peroxidases or oxidases have also proved suitable in some cases. To the suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and Pectinases.

The enzymes may be adsorbed to carriers or embedded in encapsulating substances to them to protect against premature decomposition. The proportion of enzymes, enzyme mixtures or En For example, granules may contain about 0.1 to 5% by weight, preferably 0.5 to about 4.5% by weight.  be in the context of the present invention are preferred detergent tablets characterized in that the base molding contains protease and / or amylase.

Characterized in that the washing and Renigungsmittelformkörper the invention or the En zym (s) in two fundamentally different areas (rm base molding and / or as active substance or substance mixture in the cavity) may contain moldings with very well-defined enzyme release and provide effect. The table below gives an overview of possible enzyme distributions in the washing and cleaning agent tablets according to the invention:

Basic tablet cavity amylase - protease - lipase - Amylase + protease - Amylase + lipase - Protease + lipase - Amylase + protease + lipase - - amylase - protease - lipase - Amylase + protease - Amylase + lipase - Protease + lipase - Amylase + protease + lipase amylase amylase protease amylase Amylase + protease amylase amylase protease protease protease Amylase + protease protease amylase Amylase + protease protease Amylase + protease Amylase + protease Amylase + protease lipase amylase Amylase + lipase amylase Protease + lipase amylase Amylase + protease + lipase amylase lipase protease Amylase + lipase protease Protease + lipase protease Amylase + protease + lipase protease lipase Amylase + protease Amylase + lipase Amylase + protease Protease + lipase Amylase + protease Amylase + protease + lipase Amylase + protease

Dyes and fragrances can the detergent tablets according to the invention added both in the base molding and in the preparations contained in the cavity to improve the aesthetics of the resulting products and enhance the versatility of the product In addition to the performance, we needed a visual and sensory "typical and unmistakable" pro product. As perfume oils or perfumes, individual fragrance compounds gene, z. As the synthetic products of the ester, ether, aldehyde, ketone, alcohol and Hydrocarbons are used. Fragrance compounds of the ester type are e.g. B. Ben cylacetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzene zylcarbinylacetate, phenylethylacetate, linalylbenzoate, benzylformate, ethylmethylphenylglycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example Benzyl ethyl ether, to the aldehydes z. As the linear alkanals with 8-18 C-atoms, citral, citro nellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal the ketones z. As the Jonone, α-Isomethylionon and Methylcedrylketon, to the alcohols anethole, Citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons The main ingredients include terpenes such as limonene and pinene. However, preferred are Mi scents of various fragrances, which together create an appealing scent witness. Such perfume oils may also contain natural perfume mixtures as they come from vegetable sources are available, for. Pine, citrus, jasmine, patchouly, rose or ylang Ylang oil. Also suitable are Muscat, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, Cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanu möl and orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the detergents and cleaners according to the invention However, it may also be advantageous to apply the fragrances on carriers that the adhesion intensify the perfume on the wash and through a slower release of fragrance for a long time keeping the fragrance of the textiles. As such carrier materials, for example, Cy clodextrine proven, the cyclodextrin-perfume complexes additionally with further auxiliary can be coated.  

In order to improve the aesthetic impression of the agents according to the invention, it may (or parts thereof) with suitable dyes. Preferred dyes, the selection of which Professional no difficulty, have a high storage stability and insensitivity the other ingredients of the products and against light, and Substantivity to the substrates to be treated with the agents such as textiles, glass, Ke ramik or plastic crockery so as not to stain it.

The detergent tablets according to the invention may have one or more opti containing brightener (s). These substances, which are also called "whiteners", are used in moder NEN detergent used since even freshly washed and bleached white laundry a having slight solubility. Optical brighteners are organic dyes that form part of the un convert visible UV radiation of sunlight into longer wavelength blue light. The emission This blue light complements the "gap" in the light reflected from the textile, so that one with optical Brightener treated textile appears whiter and brighter to the eye. Because the mechanism of action of brighteners presupposing their attraction to the fibers, a distinction is made according to "to fibers, for example brighteners for cotton, polyamide or polyester fibers The customary whitening agents suitable for incorporation into detergents are included in the substance to five structural groups. The stilbene, the diphenylstilbene, the cumene-quinoline, the diphe nylpyrazoline group and the group of the combination of benzoxazole or benzimidazole with konju greedy systems. An overview of common brighteners is, for example, in G. Jakobi, A. Löhr "Detergents and Textile Washing", VCH Verlag, Weinheim, 1987, pages 94 to 100, can be found. Suitable z. B. Salts of 4,4'-bis [(4-anilino-6-morpholino-s-triazin-2-yl) amino] -stilbene-2,2'- disulfonic acid or compounds of similar construction, which instead of the morpholino group a Diethanolamino group, a methylamino group, an anilino group or a 2- Wear methoxyethylamino group. Furthermore, brighteners of the type of substituted di phenylstyryle be present, for. For example, the alkali salts of 4,4-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4- chloro-3-sulfostyryl) -diphenyls, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls. Also mixtures The aforementioned brightener can be used.

In addition, the detergent tablets may also contain components, wel This has a positive effect on the oil and grease wash-out properties of textiles (so-called repel lents). This effect becomes particularly clear when a textile is soiled before several times with a detergent according to the invention containing this oil and fat dissolving component contains, was washed. Among 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 wt .-% and to hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ether, and from the state known in the art polymers of phthalic acid and / or terephthalic acid or of their  Derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalate or anionic and / or nonionic modified derivatives of these. Especially preferred of these are the sulfonated derivatives of phthalic acid and terephthalic acid Polymers.

As foam inhibitors, which can be used in the inventive compositions come For example, soaps, paraffins or silicone oils, optionally on Trägerermateria lien can be applied.

Grayness inhibitors have the task of removing the dirt removed from the fiber in the fleet to keep it suspended and thus prevent the dirt from being rebuilt. These are water-soluble colloids mostly organic nature suitable, for example, the water-soluble sal ze polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids or the Cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also what Serosoluble, acidic group-containing polyamides are suitable for this purpose. Continue to read use soluble starch preparations and other starch products than those mentioned above, z. Degraded starch, aldehyde levels, etc. Also, polyvinylpyrrolidone is useful. Prefers however, cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyal kylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, Me methylcarboxymethylcellulose and mixtures thereof in amounts of from 0.1 to 5% by weight, based on the means used

As textile fabrics, in particular of rayon, rayon, cotton and their mixtures, to wrinkle own, because the single fibers against sagging, kinking. Presses and quet transverse to the fiber direction are sensitive, the compositions of the invention can be synthetic Contain wrinkling agents. These include, for example, synthetic products on the base of fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, alkylolamides or fatty alcohols len, which are usually reacted with ethylene oxide, or products based on lecithin or modi fied phosphoric acid ester.

For controlling microorganisms, the agents according to the invention may have antimicrobial activity contain substances. Here one differentiates depending upon antimicrobial spectrum and Wirkungsme mechanism between bacteriostats and bactericides, fungiostats and fungicides etc. Important Substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halo genphenols and Phenolmercuriacetat, whereby completely renounced on these compounds can be.

Unwanted changes caused by oxygen and other oxidative processes In order to prevent changes to the preparations and / or treated textiles, the agents may use antioxidants  contain. This class of compounds includes, for example, substituted phenols, Hydroquinones, catechols and aromatic amines as well as organic sulfides, polysulfides, Dithiocarbamates, phosphites and phosphonates.

Increased comfort may result from the additional use of antistatic agents which the agents according to the invention are additionally attached. Antistatic agents increase the surface area chenleitfähigkeit and thus allow an improved drainage of formed charges. Outer Antistatic agents are usually substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. This mostly border Surface-active antistatic agents can be converted into nitrogen-containing (amines, amides, quaternary ammonium ver compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkylsulfonates, alkylsul fate) subdivide antistatics. External antistatics are disclosed, for example, in patent applications FR 1,156,513, GB 873,214 and GB 839,407. The lauryl (or stearyl) disclosed herein Dimethylbenzylammoniumchloride are suitable as antistatic agents for textiles or as an additive to Detergents, with an additional Avivageeffekt is achieved.

To improve the water absorbency, the rewettability of the treated Textiles and to facilitate the ironing of the treated textiles in the fiction, be used according to the means, for example, silicone derivatives. These improve additionally the rinsing out of the agents by their foam-inhibiting properties. Preferred Sili konderivate are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have up to five carbon atoms and are completely or partially fluorinated. Preferred silicones are poly dimethylsiloxanes, which may optionally be derivatized and then amino-functional or have quaternized or Si-OH, Si-H and / or Si-Cl bonds. The viscosities of be preferred silicones are in the range between 100 and 100,000 centistokes at 25 ° C, with the Silicones in amounts between 0.2 and 5 wt .-%, based on the total agent who used you can.

Finally, the compositions of the invention may also contain UV absorbers, which behan on the put on textiles and improve the lightfastness of the fibers. Connections that have these desired properties are, for example, by non-radiation Desak active compounds and derivatives of benzophenone having substituents in 2- and / or 4-position. Furthermore, substituted benzotriazoles, in the 3-position phenyl substituent ized acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, or ganic Ni complexes as well as natural substances such as umbelliferone and the body's own urocanic acid suitable.

The ingredients described above can of course also in the trough filling be incorporated. In the context of the present invention, preferred detergent tablets  are characterized in that in the through the film and the Formkörper enclosed space contained active substance at least one active substance from the Group of enzymes, surfactants, soil-release polymers, disintegration aids, bleach, Bleach activators, bleach catalysts, silver protectants and mixtures thereof.

By dividing the detergent tablets according to the invention in base moldings and active substance (s) or active substance mixtures contained in the cavity or preparation (s) ingredients can be separated from each other, resulting in either a stock stability-improving separation of incompatible ingredients or controlled release tion of certain active substances can be used. In preferred washing and cleaning Medium moldings contains the base molding or in the through the film and the molding active substance contained bleach, while the other area of the Mold contains bleach activators.

Further preferred detergent tablets are characterized in that the Basic shaped body or d in the space enclosed by the film and the molding space contains active ingredient bleach while the other portion of the molded article contains En contains enzymes.

A separation of bleaching agents and corrosion inhibitors or silver protectants can be to reach. Detergent tablets in which the basic tablet or in the active substance contained in the space enclosed by the film and the body bleach contains, while the other portion of the molded body deformable mass corrosion inhibitor contains are also preferred.

Last but not least washing and cleaning agent tablets are preferred in which the base molded body or contained in the space enclosed by the film and the molding space Active ingredient bleach contains, while the other portion of the molded article surfactants preferably nonionic surfactants, with particular preference alkoxylated alcohols with 10 bis 24 carbon atoms and 1 to 5 alkylene oxide units.

In all of the ingredients mentioned above, advantageous properties may result separate them from other ingredients or combine them with certain other ingredients to assemble together. In the case of the moldings according to the invention, the individual Be Rich also have a different content of the same ingredient, which benefits can be achieved. Detergent tablets in which the base tablet and the active sub contained in the space enclosed by the film and the molded body punch containing the same active ingredient in different amounts are preferred. The Be handle "different amount" refers, not to the absolute amount of the ingredient in  the relevant part of the molding, but on the relative amount, based on the phases weight, thus represents a wt .-% statement, based on the individual area, ie the basic form body or the cavity filling, dar.

The optional substance to be incorporated into the cavity is preferably particulate. there the term "active substance" in the context of the present invention is not based on pure substances limited. Rather, it features pure active ingredients, active substance mixtures and diets so that freedom of expression is unlimited. In Ausführungsfor men, in which the cavity is not closed, the particles are preferably of a size, which corresponds approximately to the size of the cavity. If the cavity is closed, for example with a Film as described above, it is preferred if these particular particle size criteria ge so that preferred detergent tablets are characterized in that the active substance contained in the space enclosed by the film has particle sizes between 100 and 5000 microns, preferably between 150 and 2500 microns, more preferably zwi rule 200 and 2000 microns and in particular between 400 and 1600 microns have.

Particulates preferably to be introduced into the cavity (s) of the shaped bodies according to the invention are those which contain surfactants, it being preferred to provide the surfactants for machine dishwashing detergents in dissolution-delayed form in order to release the surfactants from the cavity filling only in the final rinse cycle to reach. In particular rinse aid particles have proven to be suitable for this purpose, as described in the earlier German patent application DE 199 14 364.1 (Henkel KGaA). Such particularly preferably in the cavity introducing particles consist of 0 to 90 wt .-% of one or more carrier materials, 5 to 50 wt .-% of one or more coating substances having a melting point above 30 ° C, 5 to 50 wt .-% of a or more active substances and 0 to 10 wt .-% of other active ingredients and excipients, so that detergent tablets are preferred in which the active substance contained in the space enclosed by the film comprises particles which

• a) 0 to 90 wt .-% of one or more support materials
• b) 5 to 50 wt .-% of one or more shell substances having a melting point above of 30 ° C,
• c) 5 to 50 wt .-% of one or more active ingredients and
• d) 0 to 10 wt .-% further active ingredients and excipients

consist.

The disclosure of this document is expressly incorporated by reference. Nevertheless, the wich most ingredients of these preferably introduced into the cavity "rinse aid particles" below described. Suitable carriers a) are all substances which are solid at room temperature Question. Usually, one will select substances that in the cleaning cycle an additional Have an effect, with builders offer particularly. In preferred particulate  Rinse aids for the filling of the cavity are substances from the group of what are used as carrier materials serlöslichen detergent ingredients, preferably the carbonates, hydrogen carbonates, sulfates, phosphates and the room temperature solid organic Oligocarbonsäu in amounts of 55 to 85 wt .-%, preferably from 60 to 80 wt .-% and in particular of 65 to 75 wt .-%, each based on the particle weight.

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

To the coating substances, which are preferred for those in the present invention as a filling of the cavity used active substance particles are made various requirements On the one hand, the melting or solidification behavior, on the other hand Also, the material properties of the enclosure in the solidified state, d. H. in the active substance particle affect. Since the active substance particles during transport or storage permanently against Protected environment influences, the encasing substance must have a high stability have, for example, occurring during packaging or transport shock loads. The Shell substance should therefore be either at least partially elastic or at least plastic Have properties in order to respond to an occurring impact load by elastic or plastic Deformation to respond and not to break. The enveloping substance should have a melting range (Solidification range) in such a temperature range, in which the to be wrapped Active substances should not be exposed to high thermal stress. On the other hand, the must Melting range, however, be sufficiently high to still at least slightly elevated temperature to provide effective protection for the entrapped active ingredients. According to the invention Enveloping substances have a melting point above 30 ° C.

It has proved to be advantageous if the enveloping substance does not have a sharply defined melting point shows how it usually occurs with pure, crystalline substances, but one under certain circumstances having several degrees Celsius melting range.

The enveloping substance preferably has a melting range of between about 45 ° C and about 75 ° C is. That is, in the present case, that the melting range within the specified Temperature interval occurs and does not denote the width of the melting range. Preferably the width of the melting range is at least 1 ° C, preferably about 2 to about 3 ° C.

The above properties are usually met by so-called waxes. Under "Waxing" is understood to mean a number of natural or artificial substances, usually Melt above 40 ° C without decomposition and behaves just above the melting point are low-viscosity and non-stringy. They have a strong temperature-dependent Consistency and solubility.  

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

Natural waxes include, for example, vegetable waxes such as candelilla wax, Carnauba wax, japan wax, esparto wax, cork wax, guaruma wax, rice germ oil wax, Sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, Shellac wax, spermaceti, lanolin (woolwax), or raffia fat, mineral waxes such as ceresin or Ozokerite (ground wax), or petrochemical waxes such as petrolatum, paraffin waxes or Microcrystalline waxes.

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

Synthetic waxes are generally polyalkylene waxes or polyalkylene glycol waxes Roger that. Can be used as wrapping materials and compounds from other classes that the meet the requirements regarding the softening point. As suitable synthetic Compounds, for example, have higher esters of phthalic acid, in particular Dicyclohexyl phthalate, which is commercially available under the name Unimoll® 66 (Bayer AG), proved. Also suitable are synthetically produced waxes from lower carboxylic acids and Fatty alcohols, for example dimyristyl tartrate, sold under the name Cosmacol® ETLP (Condea) is available. Conversely, synthetic or partially synthetic esters of lower alcohols with Fatty acids can be used from natural sources. For example, the Tegin® 90 falls into this class of substances (Goldschmidt), a glycerol monostearate palmitate. Also shellac, for example shellac KPS- Dreiring-SP (Kalkhoff GmbH) is inventively used as wrapping material.

Likewise to the waxes in the context of the present invention are, for example, the Calculated so-called wax alcohols. Wax alcohols are higher molecular weight, water-insoluble Fatty alcohols with usually about 22 to 40 carbon atoms. The waxy alcohols come for example in the form of wax esters of higher molecular weight fatty acids (wax acids) as Hauptbe part of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1) Tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The envelope of the invention If desired, coated solid particles may also contain wool wax alcohols, among which man Triterpenoid and steroid alcohols, such as lanolin, understands, for example, under the Trade name Argowax® (Pamentier & Co) is available. Also at least proportionately as Component of the envelope can be used in the context of the present invention Fatty acid glycerol esters or fatty acid alkanolamides but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds.  

Particularly preferred coating substances in the active substance particles to be injected into the trough are those from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) Polyethylene glycols having molecular weights between 1500 and 36,000 are preferred, those with Molar masses of 2000 to 6000 are particularly preferred and those having molecular weights of 3000 to 5000 are particularly preferred.

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

satisfy, where n can take values between 10 and 2000. Preferred PPG's have Molma are between 1000 and 10,000, corresponding to values of n between 17 and about 170.

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

H- (O-CH ₂ -CH ₂ ) _n -OH (XIII)

satisfy, where n can take values between 20 and about 1000. The above preferred molecular weight ranges correspond to preferred ranges of the value n in formula IV from about 30 to about 820 (exactly: from 34 to 818), more preferably from about 40 to about 150 (exactly: from 45 to 136) and especially from about 70 to about 120 (exactly: from 68 to 113).

The encapsulating substance contained in the active substance particles according to the invention preferably contains in predominantly paraffin wax. That is, at least 50% by weight of the total contained enveloping substances, preferably more, consist of paraffin wax. Particularly suitable are paraffin wax contents (based on total shell substance) of about 60 wt .-%, about 70 wt .-% or about 80 wt .-%, with even higher levels of, for example, more than 90 wt .-% particularly are preferred. In a particular embodiment of the invention, the total amount of used wrapping substance exclusively from paraffin wax.

Paraffin waxes have, compared to the other mentioned, natural waxes in the context of present invention has the advantage that in an alkaline detergent environment no  Hydrolysis of waxes takes place (as can be expected, for example, in the wax esters), since Paraffin wax contains no hydrolyzable groups.

Paraffin waxes consist mainly of alkanes, as well as low levels of iso and Cycloalkanes. The paraffin to be used according to the invention preferably has essentially no Ingredients having a melting point greater than 70 ° C, more preferably greater than 60 ° C on. Shares of high-melting alkanes in the paraffin can fall below this Melting temperature in the cleaning agent unwanted wax residue on the zu leave cleansing surfaces or the goods to be cleaned. Such wax residues lead usually to an unsightly appearance of the cleaned surface and therefore should be avoided become.

Particulate rinse aids which can be introduced into the cavity and contain as encapsulating substance preferably at least one paraffin wax with a melting range of 50 ° C to 60 ° C.

Preferably, the content of the paraffin wax used is at ambient temperature (in the Usually about 10 to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes as high as possible. The more solid wax components are present in a wax at room temperature, the more useful it is within the scope of the present invention. With increasing proportion of solid wax components increases the load capacity of the active substance particles against impact or friction on others Surfaces on, resulting in a longer-lasting protection of the particles active ingredients. High shares of oils or liquid wax components can lead to a weakening of the particles, whereby pores are opened and the active ingredients the input environment mentioned get abandoned.

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

In any case, however, the coating should have the lowest possible water solubility, even in water with elevated temperature, exhibit a temperature independent release of To avoid active substances as much as possible.

The principle described above serves the delayed release of ingredients to a certain time in the cleaning cycle and can be used particularly advantageous when in Rinsing with lower temperature (for example 55 ° C) is rinsed, so that the  Active substance from the active substance particles only in the rinse cycle at higher temperatures (approx. 70 ° C) is released.

Preferred particulate rinse aids which can be introduced into the cavity according to the invention are characterized characterized in that it contains as shell substance one or more substances with a melting range of 40 ° C to 75 ° C in amounts of 6 to 30 wt .-%, preferably from 7.5 to 25 wt .-% and in particular in particular from 10 to 20 wt .-%, each based on the particle weight. Especially Preference is given to detergent tablets in which the ingredients contained in the cavity Particles as shell substance paraffin (s) or polyalkylene glycols, in particular polyethylene glycols contain.

The contained in the present invention in the cavity to be introduced active substance particles Active substances can be processed at the processing temperature (that is, at the temperature at which the particles prepared) in both solid and liquid form.

The active substances contained in the active substance particles fulfill certain tasks. By the Separation of certain substances or by the time-accelerated or delayed Freiset In this way, the cleaning performance can be improved. Active substances which are preferably incorporated into the active substance particles, are therefore such ingredients of Detergents and cleaning agents that are crucial in the washing and cleaning process.

In preferably in the cavity (s) to be incorporated active substance particles are therefore active as a or several substances from the groups of surfactants, enzymes, bleach, bleach activator, corrosive onsinhibitoren, pad inhibitors, cobuilders and / or fragrances in amounts of 6 to 30 wt .-%, preferably from 7.5 to 25 wt .-% and in particular from 10 to 20 wt .-%, each based on the particle weight. Washing and cleaning agents are particularly preferred shaped tablets in which the cavity is filled with active substance particles which are not active substances anionic surfactant (s) and / or bleaching agents and / or bleach activators and / or enzyme (s) and / or corrosion inhibitors and / or perfumes.

By incorporating surfactants in molten shell material can be a Schmelzsus make pension or emulsion, which in the finished active substance particles or in conffek tioned shaped body according to the invention, at a predetermined time additional Provides detergent substance. For example, can be in this way in the cavity (s) to prepare incorporable active ingredient particles for automatic dishwashing, the addi che surfactant from the molding of the invention only at temperatures release, which Household dishwashers reach only in the final rinse cycle. This way it stands in the Rinse additionally surfactant available, which accelerates the drainage of the water and thus effectively prevents stains on the items to be washed. With a suitable amount of solidified melt suspension  or emulsion in the active substance particles can thus übli on the use übli additional rinse aid can be dispensed with.

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

Another class of active substances that are particularly advantageous in the invention incorporable workable active substance particles are bleaches. This can be particles be prepared and introduced into the cavity (s), the bleach until it reaches be release appropriate temperatures, for example, ready-made cleaning agents that in Clean the rinse cycle enzymatically and release the bleach first in the main rinse cycle. Also detergents for automatic dishwashing are so produced that the rinse cycle to additional bleaching agent are released, causing difficult stains, such as tea stains, Remove more effectively.

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

Another class of compounds which are preferred as active substances in the invention can be used insertable active substance particles are the bleach activators. Also the important representatives from this group of substances have already been described. In the context of the present ing invention preferably pressed into the trough active substance particles contained as active Substance bleach activators, in particular from the groups of polyacylated alkylene diamine, in particular tetraacetylethylenediamine (TAED), of N-acylimides, in particular N- Nonanoylsuccinimide (NOSI), the acylated phenolsulfonates, especially n-nonanoyl or iso nonanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA).

Another important embodiment of the present invention provides for the introduction of enzyme-containing particles into the cavity (s). Such active-substance particles contain enzymes as active substances (e), which have been described in detail above. Particular preference is given here as a particulate, in the cavity (s) to be introduced particles such as 40 to 99.5 wt .-%, preferably 50 to 97.5 wt .-%, particularly preferably 60 to 95 wt .-% and in particular from 70 to 90% by weight of one or more shell substances having a melting point above 30 ° C., from 0.5 to 60% by weight, preferably from 1 to 40% by weight, particularly preferably 2 , 5 to 30 wt .-% and in particular 5 to 25 wt .-% of one or more in the / the shell substance (s) dispersed liquid enzyme preparation (s) and 0 to 20 wt .-%, preferably 0 to 15 wt. %, particularly preferably 0 to 10 wt .-% and in particular 0 to 5 wt .-% and optionally further carrier materials, auxiliaries and / or active ingredients. Accordingly, preferred washing and cleaning agent tablets are characterized in that the active substance contained in the cavity comprises particles which consist of

• a) 40 to 99.5 wt .-%, preferably 50 to 97.5 wt .-%, particularly preferably 60 to 95 wt .-% and in particular 70 to 90 wt .-% of one or more shell substance (s), the has a melting point above 30 ° C / have.
• b) 0.5 to 60% by weight, preferably 1 to 40% by weight, more preferably 2.5 to 30% by weight % and in particular 5 to 25% by weight of one or more in the shell substance (s) dispersed liquid enzyme preparation (s) as well as
• c) 0 to 20 wt .-%, preferably 0 to 15 wt .-%. particularly preferably 0 to 10% by weight and in particular 0 to 5 wt .-% of other carrier materials, excipients and / or active ingredients

consist.

The encasing substances are in this case preferably polyethylene glycols and / or polypropylene glycols, as Active substances have proven themselves liquid enzyme preparations. Such liquid enzyme complexes trate are either based homogeneously on a propylene glycol / water or heterogeneous slurry basis, or they are in a microencapsulated structure. Preferred liquid proteases are, for. Savinase® L, Durazym® L, Esperase® L, and Everlase® from Novo Nordisk, Optimase® L, Purafect® L, Purafect® OX L, Properase® L from Genencor International, and BLAP® L from Biozym Ges. M. b. H .. Preferred amylases are Termamyl® L, Duramyl® L, and BAN® from Novo Nor disk, Maxamyl® WL and Purafect® HPAm L from Genencor International. Preferred lipases are Lipolase® L, Lipolase® ultra L and Lipoprime® L Fa. Novo Nordisk and Lipomax® L the Fa. Genencor International.

As slurries or microencapsulated liquid products z. B. Products like those with SL or LCC designated products of the company. Novo Nordisk be used. The said commercial Liquid enzyme preparations contain, for example, 20 to 90% by weight of propylene glycol or Ge mixed with propylene glycol and water. In the context of the present invention preferred in the Cavity einbringbare enzyme particles are characterized in that they one or more Flüs sig-amylase preparations and / or one or more liquid protease preparations th.

As active substances, fragrances can also be incorporated into the particles to be incorporated. SämT Liche fragrances described in detail above can be used as an active substance become. Incorporation of fragrances into the particles to be incorporated results in cleaning agents which release all or part of the perfume with a time delay. That way are According to the invention, for example, detergents for automatic dishwashing can be produced,  in which the consumer also after completion of the dishes cleaning when opening the machine Perfume note experienced. In this way, the unwanted "Alkaligeruch", the many machine Dishwashing agents attached, be eliminated.

Also corrosion inhibitors can be introduced as an active ingredient in the particles, wherein on the Specialist common substances can be used. As a coating inhibitor has become For example, a combination of enzyme (eg., Lipase) and Kalkseifendispergiermittel proven.

At exceptionally low temperatures, for example at temperatures below 0 ° C, the Active substance particles break under impact load or friction. To the stability with such may improve the low temperatures, the coating substances optionally additives be mixed. Suitable additives must be completely compatible with the molten wax must not significantly change the melting range of the encasing substances improve the elasticity of the coating at low temperatures, the permeability of the Enclosure to water or moisture generally does not increase and allowed to Do not increase the viscosity of the melt of the shell material so far that processing difficult or becomes impossible. Suitable additives containing the brittleness of a substantially paraffin reduce existing envelope at low temperatures are, for example, EVA copolymers, hydrogenated rosin methyl esters, polyethylene or copolymers of ethyl acrylate and 2-ethyl hexyl acrylate.

Another useful additive when using paraffin as a wrapper is the addition of a small amount of a surfactant, for example, a C _12-18 fatty alcohol sulfate. This addition causes a better wetting of the material to be embedded by the enclosure. Advantageously, an addition of the additive in an amount of about <5 wt .-%, preferably <about 2 wt .-%, based on the shell substance. The addition of an additive can in many cases lead to the fact that it is also possible to coat active substances which form a tough, plastic body of paraffin and partially dissolved active substance generally without the addition of additive after the melting of the coating material.

It may also be advantageous to add other additives to the encapsulant, for example to prevent premature discontinuation of the active substances. This is especially true in the production the active substance particles according to the invention without excipients recommend. Dis use this Anti-settling agents, which are also referred to as suspending agents, are known from the prior art Technique, for example, from the paint and printing ink production, known. To the transition from the plastic solidification area to the solid sedimentation phenomena and concentrati Onsgefälle to avoid the substances to be enveloped, for example grenzflä offer chenaktiven substances, solvent-dispersed waxes, montmorillonites, organically modifi Bentonites, (hydrogenated) castor oil derivatives, soya lecithin, ethylcellulose, low molecular weight polyamides,  Metal stearates, calcium soaps or hydrophobized silicic acids. Further Stof 41926 00070 552 001000280000000200012000285914181500040 0002010062582 00004 41807fe, the cause the effects mentioned come from the groups of anti-flooding and the Thixotropic and can chemically as silicone parts (Dimethylpolysiloxane, Methylphenylpolysi loxanes, polyether-modified methylalkylpolysiloxanes), oligomeric titanates and silanes, polyamines, Salts of long-chain polyamines and polycarboxylic acids, amine / amide-functional polyesters or Amine / amide-functional polyacrylates may be referred to.

Additives from the mentioned substance classes are commercially available in an extremely wide variety Lich. Commercial products, which in the context of the method according to the invention advantageously as an additive can be added, for example, Aerosil® 200 (fumed silicic acid, Degussa), Bentone® SD-1, SO-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- Chemistry), Borchigen® ND (sulfo group-free ion exchanger, Borchers), Ser-Ad® FA 601 (Ser vo), Solsperse® (aromatic ethoxylate, ICI), Surfynol® grades (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) as well as the different M-P-A® types X, 60-X, 1078-X, 2000-X and 60-MS (organic compounds, Rheox).

The auxiliaries mentioned can be used in the rinse aid or En zympartikeln depending on the wrapping material and active substance used in varying amounts become. Usual use concentrations for the aforementioned anti-settling, anti-Aus Floating, thioxotropic and dispersing agents are in the range of 0.5 to 8.0 wt .-%, preferably between 1.0 and 5.0 wt .-%, and particularly preferably between 1.5 and 3.0 wt .-%, in each case based on the total amount of coating substance and active substances.

In the context of the present invention, particulate matter to be incorporated into the cavity (s) is preferred Rinse-aid or enzyme particles contain further auxiliaries from the group of the anti-settling agent tel, suspending agents, anti-flooding agents, thixotropic agents and dispersing agents in amounts of 0.5 to 9 wt .-%, preferably between 1 and 7.5 wt .-%, and particularly preferably between 1.5 and 5 wt .-%, each based on the particle weight.

In particular, in the preparation of melt suspensions or emulsions, the active ingredients which are liquid at the processing temperature is the use of special emulsified advantageous. It has been found that in particular emulsifiers from the group of fatty alcohol hole, fatty acids, polyglycerol esters and polyoxyalkylene siloxanes are extremely well suited.  

Fatty alcohols are understood as meaning the alcohols having 6 to 22 carbon atoms obtainable from native fats or oils via the corresponding fatty acids (see below). These alcohols may be substituted in the alkyl chain or partially unsaturated depending on the origin of the coat or oil from which they are derived. As emulsifiers in the active substance particles according to the invention therefore preferably C _6-22 fatty alcohols, preferably C _8-22 fatty alcohols and in particular C _12-16 fatty alcohols with particular preference of C _16-18 fatty alcohols used.

As emulsifiers also all from vegetable or animal oils and fats gewon nenen fatty acids are used. The fatty acids can be independent of their aggregate was saturated or mono- to polyunsaturated. Even with the unsaturated fatty acids are the solid at room temperature species preferred over the liquid or pasty. Of course, not only "pure" fatty acids can be used, but also at the splitting of fats and oils obtained technical fatty acid mixtures, said Ge from an economic point of view are again clearly preferred.

Thus, as emulsifiers in the context of the present invention, for example, individual Use species or mixtures of the following acids: caprylic acid, pelargonic acid, capric acid, Lauric acid, myristic acid, palmitic acid, stearic acid, octadecan-12-ol acid, arachidic acid, Behenic acid, lignoceric acid, cerotic acid, meüssinic acid, 10-undecenoic acid, petrose acid, Petroseiaidic acid, oleic acid, elaidic acid, ricinoleic acid, linolaidic acid, α- and β- Elasteroic acid, gadoleic acid, erucic acid, brassidic acid. Of course, too Fatty acids having an odd number of C atoms can be used, for example undecanoic acid, tride canic acid, pentadecanoic acid, heptadecanoic acid, nonadecanoic acid, heneicosanoic acid, tricosanic acid re, pentacosanoic acid, heptacosanoic acid.

In preferably rinse aid or enzyme particles to be introduced into the cavity, the emulsifier (s) used are C _6-22 -fatty acids, preferably C _{8-22 -fatty} acids and in particular C _{12-18 -fatty} acids, with particular preference given to C _16-18 -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 XIV

in which R ¹ in each glycerol unit is independently H or a fatty acyl radical having 8 to 22 carbon atoms, preferably 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 the degrees of polymerization n = 2, 3, 4, 6 and 10 and are commercially available. Since substances of the type mentioned are also widely used in cosmetic formulations, many of these substances are also classified in the INCI nomenclature (CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 ^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997). This standard cosmetic work includes, for example, information on the following keywords: POLYGLYCERYL-3-BEESWAX, POLYGLYCERYL-3-CETYL ETHER, POLYGLYCERYL-4-COCOATE, POLYGLYCERYL-10-DECALINOLEATE, POLY-GLYCERYL-10-DECAOLEATE, POLYGLYCERYL-10-DECASTEARATE, POLYGLYCERYL-10 GLYCERYL-2-DIISOSTEARATE, POLYGLYCERYL-3-DIISOSTEARATE, POLY-GLYCERYL-10-DIISOSTEARATE, POLYGLYCERYL-2-DI OLEATE, POLY-GLYCERYL-3-DIOLEATE, POLYGLYCERYL-6-DlOLEATE, POLYGLYCERYL-10-DIOLEATE, POLYGLYCERYL 3-DISARTARATE, POLYGLYCERYL-6-DISTEARATE, POLYGLYCERYL-10-DISTEARATE, POLYGLYCERYL-10-HEPTAOLEATE, POLY-GYLCERYL-12-HY DROXYSTEARATE, POLYGLYCERYL-10-HEPTASTEARATE, POLYGLYCERYL-6-HEXA OLEATE, POLYGLYCERYL-2 ISOSTEARATE, POLY-GLYCERYL-4-ISOSTEARATE, POLY-GLY CERYL-6-ISOSTEARATE, POLY-GLYCERYL-10-LAURATE, POLY-LYCERYLMETHACRYLATE, POLYGLYCERYL-10-MYRISTATE, POLYGLYCERYL-2-OLEATE, POLYGLYCERYL-3-OLEATE, POLYGLYCERYL 4-OLEATE, POLYGLYCERYL-6-OLEATE, POLYGLYCERYL-8-OLEATE, POLYGLYCERYL-10-OLEATE, POLYGLYCERYL-6-PENTAOLEATE, POLY GLYCERYL-10- PENTAOLEATE, POLYGLYCERYL-6-PENTA-TAXATE, POLYGLYCERYL-10-PENTA-STEARATE, POLYGLYCERYL-2-SESQUI-IOSOSTEARATE, POLYGLYCERYL-2-SESQUI-OLEATE, POLYGLYCERYL-2-STEARATE, POLYGLYCERYL-3-STEARATE, POLYGLYCERYL-4 - POLYGLYCERYL-10-STEARATE, POLYGLYCERYL-10-STEARATE, POLYGLYCERYL-10-TETRAOLEATE, POLYGLYCERYL-2-TE TRASTEARATE, POLYGLYCERYL-2-TRIISOSTEARATE, POLYGLYCERYL-10-TRIOLEATE, POLYGLYCERYL -6-tristearate. The commercially available products from different manufacturers, which are classified in the cited work under the aforementioned keywords, can be used advantageously in the process step b) according to the invention as emulsifiers.

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 oxide or propylene oxide. Such polyoxyalkylene siloxanes can be described by the general formula XV

wherein each R ^{1 is} independently -OH ₃ or a polyoxyethylene or -propylene group - [CH (R ² ) -CH ₂ -O] _x H group, R ^{2 is} -H or -CH ₃ , x is a number between 1 and 100, preferably between 2 and 20 and in particular below 10, and n indicates the degree of polymerization of the silicone.

Optionally, the mentioned polyoxyalkylene siloxanes can also be attached to the free OH groups of Polyoxyethylene or polyoxypropylene side chains are etherified or esterified. The unethereatened and unesterified polymer of dimethylsiloxane with polyoxyethylene and / or polyoxypropylene is used in The INCI nomenclature is referred to as DIMETHICONE COPOLYOL and is under the trade name Abil® B (Goldschmidt), Alkasil® (Rhône-Poulenc), Silwet® (Union Carbide) or Belsil® DMC 6031 commercially available.

The acetic acid esterified DIMETHICONE COPOLYOL ACETATE (for example Belsil® DMC 6032, 33 and 35, Wacker) and the DIMETHICONE COPOLYOL BUTYL ETHER (eg KF352A, Shin Etsu) can also be used as emulsifiers in the context of the present invention.

In the case of the emulsifiers, the same applies to the wrapping materials and to the ones to be wrapped Substances that they can be used over a wide range. Usually emulsifiers of the type mentioned make 1 to 25 wt .-%, preferably 2 to 20 wt .-% in particular 5 to 10 wt .-% of the weight of the sum of shell materials and Active ingredients. In the context of the present invention, preference is given to the cavity (s) particulate rinse aid or enzyme particles to be incorporated additionally contain emulsifiers from the group of fatty alcohols, fatty acids, polyglycerol esters and / or polyoxyalkylene siloxanes in Amounts from 0.1 to 5 wt .-%, preferably from 0.2 to 3.5 wt .-%, particularly preferably from 0.5 to 2 wt .-% and in particular from 0.75 to 1.25 wt .-%, each based on the Particle weight.

The detergent tablets according to the invention dissolve in the washing or cleaning process completely, and as mentioned above it may have advantages if the different regions have different dissolution rates. Due to the un Different dissolution rates can be in addition to the release of certain ingredients too At certain times, the properties of the washing or cleaning liquor deliberately change be changed. For example, washing and cleaning agent tablets are preferred in which  the pH of a 1 wt .-% - solution of the base molding in water in the range of 8 to 12, preferably from 9 to 11 and in particular from 9.5 to 10, is located.

In addition, washing and cleaning agent tablets are preferred in which the pH a 1 wt .-% - solution of the total molding in water in the range of 7 to 11, before preferably from 7.5 to 10 and in particular from 8 to 9.5, is located.

Another object of the present invention is a process for the preparation of detergent tablets, by the steps

• a) pressing a particulate premix into a compressed part (base moldings) per), which has at least one cavity,
• b) covering the molding-body-side boundary wall of the cavity with film,
• c) optional filling of one or more active substances in liquid, gel, pastö or solid form into the said cavity (s),
• d) optionally applying one or more adhesion promoters to one or more surfaces of the molding
• e) optionally closing the openings of the (filled) cavities with a foil
• f) optional aftertreatment of individual shaped body surfaces or of the entire shaped body

is marked.

With regard to the ingredients of the individual regions of the moldings of the invention or their particulate premixes or compositions, the different areas of the Formed body, applies analogously to the above for the shaped body according to the invention led.

It has proved to be advantageous if the pressed in step a) base moldings Vorge Mixed certain physical criteria is sufficient. Preferred methods are for example there characterized in that the particulate premix in step a) has a bulk density of at least 500 g / l, preferably at least 600 g / l and especially at least 700 g / l has.

Also, the particle size of the compressed in step a) premix preferably satisfies certain Criteria: Processes in which the particulate premix in step a) has particle sizes between 100 and 2000 microns, preferably between 200 and 1800 microns, more preferably zwi 400 and 1600 microns and in particular between 600 and 1400 microns, are fiction, are preferred according to. A further narrowed particle size in the premixes to be compressed can be adjusted to obtain favorable molding properties. In preferred Va For the process according to the invention, the particulate compound compressed in step a) has Premix has a particle size distribution at which less than 10 wt .-%, preferably less  than 7.5 wt .-% and in particular less than 5 wt .-% of the particles greater than 1600 microns or less than 200 microns. Here, narrower particle size distributions are more preferred. Particularly advantageous process variants are characterized in that the in step a) compressed particulate premix has a particle size distribution in which more than 30 wt .-%, preferably more than 40 wt .-% and in particular more than 50 wt .-% of the part chen have a particle size between 600 and 1000 microns.

In carrying out the process step a), the inventive method is not on it limited that only a particulate premix is pressed into a shaped body. Rather, the method step a) can also be extended to the effect that in be Known way manufactures multi-layer moldings by mixing two or more premixes prepares that are pressed together. In this case, the first-filled premix becomes light pre-pressed to bekom a smooth and parallel to the mold bottom running top men, and after filling the second premix to the final molded body endverpreßt. At three or multilayer moldings after each premix addition another Vorver pressing, before the addition of the last premix of the molding is end-pressed. before Preferably, the above-described cavity in the base molding is a trough so that before zugte embodiments of the first method according to the invention characterized are that in step a) multi-layered moldings having a trough, in per se known Be prepared by several different particulate premixes aufeinan to be pressed.

The production of the shaped bodies according to the invention takes place in step a) initially by the troc kene mixing of the ingredients, which may be pre-granulated in whole or in part, and on closing informing, in particular pressing into tablets, whereby conventional Method can be used. For the preparation of the shaped body according to the invention is the premix in a so-called matrix between two punches to a solid Kompri compacted. This process, which is referred to below as tabletting, is divided divided into four sections: metering, compaction (elastic deformation), plastic deformation and Ejecting.

First, the premix is introduced into the die, wherein the filling amount and thus the Weight and the shape of the resulting molded body by the position of the lower punch and the shape of the pressing tool can be determined. The constant dosage even at ho hen molding throughputs is preferably via a volumetric dosing of the Vorge reached. As the tableting progresses, the upper punch touches the pre-mix and continues to lower in the direction of the lower punch. In this compression, the Parti of the premix is pressed closer to each other, wherein the void volume within the Filling between the punches decreases continuously. From a certain position of the upper punch  (and thus from a certain pressure on the premix) begins the plastic Ver Forming, in which the particles flow together and it comes to the formation of the molding. ever according to the physical properties of the premix also part of the Vorgemischparti Pressed and it comes at even higher pressures to sinter the premix. at increasing press speed, so high throughputs, the phase of the elastic Deformation further shortened, so that the resulting moldings more or less large May have cavities. In the last step of tabletting the finished molding pushed out of the die by the lower punch and by subsequent transport directions away. At this time, only the weight of the molded article is final determined because the compacts due to physical processes (re-stretching, crystallographic Effects, cooling etc.) can still change their shape and size.

The tableting is carried out in commercial tablet presses, which in principle with single or Double stamping can be equipped. In the latter case, not only the upper punch to Pressure build-up used, also the lower punch moves during the pressing process on the Upper stamp too, while the upper punch presses down. For small production quantities Eccentric tablet presses are preferably used, in which the one or the stamp on an eccentric disc are fixed, which in turn on an axis with a certain Umlaufge speed is mounted. The movement of these punches is the operation of a übli four-stroke engine comparable. The compression can each with a top and bottom stamp take place, but it can also be attached more stamp on an eccentric disc, wherein the number of die holes is extended accordingly. The throughputs of Exzenterpres Depending on the type, these vary from a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs you can choose rotary tablet presses, where on a so-called Matrizentisch a larger number of matrices is arranged in a circle. The number of matrices varies from 6 to 55 depending on the model, although larger dies are commercially available. Each die on the die table is assigned a top and bottom stamp, again the pressing pressure active only by the upper or lower punch, but also by both stamp on can be built. The die table and the stamps move around a common senk right axis, the stamp using rail-like cam tracks during the Circulated to positions for filling, compaction, plastic deformation and ejection become. At the places where a particularly serious increase or decrease in the Stamp is required (filling, compaction, ejection), these curved paths through additional low-pressure pieces, Nierderzugschienen and Aushebebahnen supported. The filling the die takes place via a rigidly arranged supply device, the so-called filling shoe, the is connected to a reservoir for the premix. The pressing pressure on the premix is individually adjustable via the pressing paths for upper and lower punches, whereby the pressure build-up by passing the stamp shank heads past adjustable pressure rollers.  

Concentric presses can also be equipped with two filling shoes to increase throughput be, with the preparation of a tablet only a semicircle must be run through. to Production of two-layered and multi-layered moldings, several filling shoes in a row arranged without the slightly pressed first layer ejected before further filling becomes. By suitable process control coat and point tablets are forth in this way adjustable, which have a onion-peel-like structure, wherein in the case of the period tablets the Top of the core or the core layers is not covered and thus remains visible. Also Rotary tablet presses can be equipped with single or multiple tools, so that at For example, an outer circle with 50 and an inner circle with 35 holes at the same time Ver be used. The throughputs of modern rotary tablet presses are over one Million moldings per hour.

When tableting with rotary presses, it has proven to be advantageous to carry out the tableting with the lowest possible weight fluctuations of the tablet. In this way, the hardness fluctuations of the tablet can be reduced. Low weight variations 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 of the Füllschuhflügeldrehzahl on the speed of the rotor
• - filling shoe with constant powder height
• - Decoupling of filling shoe and powder feed

To reduce Stempelanbackungen offer all known from the art anti adhesive coatings. Particularly advantageous are plastic coatings, plastic inserts or plastic stamp. Rotary stamps have proved to be advantageous, wherein after Possibility of upper and lower punches should be rotatable. With rotating stamps can be dispensed with a plastic insert usually. Here should the Stempeloberflä be electropolished.

It has also been shown that long pressing times are advantageous. These can be with pressure rails, several pressure rollers or low rotor speeds are set. Since the hardness swank tions of the tablet caused by the fluctuations of the compressive forces, systems should be applied, which limit the pressing force. Here can elastic punches, pneumatic Compensators or resilient elements are used in the force path. Also, the pressure roller be performed resilient.  

Preferred processes in the context of the present invention are characterized in that the compression in step a) takes place at compression 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 .

Tabletting machines suitable for the purposes of the present invention are obtained, for example at the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMA Packaging Systems GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Press AG, Berlin, as well as Roma co GmbH, Worms. Other providers include Dr. med. Herbert Pete, Vienna (AU), Mapag Ma Schinenbau AG, Berne (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Cour toy N.V., Halle (BE / LU) and Mediopharm Kamnik (SI). Particularly suitable is, for example, the Hydraulic double pressure press HPF 630 from LAEIS, D. Tableting tools are included For example, by the company Adams tabletting tools, Dresden, Wilhelm Fett GmbH, black zenbek, Klaus Hammer, Solingen, Herber & Sohne GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Werkzeugbau, Tamm available. Other providers are z. As the Senss AG, Rein oh (CH) and the Medicopharm, Kamnik (51).

In step b), the molding-body-side boundary of the cavity is covered with foil according to the invention. It shoots the optional step c), in which the cavity with active substance (s), active substance mixed or active substance preparations. If the cavity more than one Öff is technically appropriate, the second, third and any further Close openings to make the filling technically easier in this way. Although it is in principle possible to fill a ring molding first, then the upper opening To close the hole to turn over the molding together with filling and the second hole but this requires mechanical devices that allow the filling to fall out prevent. Thus, the cavity of the shaped body produced in step a) has more than one Öff tion, it is preferred that optional step c) - the filling - after (n-1) -maliger Perform the optional steps d) and e) if the number of openings is n. The closing of the last opening then corresponds to the last-time execution of the method step d) and e), to which a step e) can follow.

As already mentioned above, the filling to be optionally introduced into the cavity is preferably two se, with particulate fillings are particularly preferred. Will the cavities of the Moldings filled with particulate compositions, so methods are preferred, in which the particulate composition (s) in step c) have a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l has / have.  

In step d) of the process according to the invention, adhesion promoters are optionally applied to one or more Rere surfaces of the moldings applied. Step d) is particularly necessary if the in the subsequent step to be applied films alone do not have sufficient adhesiveness, to remain on the molding and the mechanical stresses in packaging, Transport and handling without releasing the filling to withstand. The process step d) thus serves in the case of insufficiently adhesive films "sticking" the same.

As a primer substances can be used to the molding surfaces to which they applied give sufficient adhesiveness ("stickiness"), so that the following Ver permanently adhering to the surface. In principle, here are the mentioned in the relevant adhesive literature and in particular in the monographs thereto Substances, wherein in the context of the present invention the application of melts, which have an adhesion-promoting effect at elevated temperature, but no longer sticky after cooling, but are fixed, have a special meaning.

For process step e), the application of the film on some or all surfaces of the molding and the associated closure of the cavity (s) have been detailed above Information referred to here to avoid redundancy.

The moldings produced according to the invention can - as described above - in whole or in part wise be provided with a coating. Procedures in which the post-treatment in step f) consists in the application of a coating layer on the entire shaped body erfindungsge are according to preference.

The detergent tablets according to the invention can be packaged after production, wherein the use of certain packaging systems has been particularly preserved. A further aspect of the present invention is a combination of a detergent tablet (s) according to the invention and a packaging system containing the detergent and cleaner, characterized in that the packaging system has a moisture vapor transmission rate of 0.1 g / l. m ² / day to less than 20 g / m ² / day, when the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%.

The packaging system of the combination of detergent tablets and packaging system according to the invention has a moisture vapor transmission rate of 0.1 g / m ² / day to less than 20 g / m ² / day, when the packaging system at 23 ° C and a relati stored at equilibrium humidity of 85%. The temperature and humidity conditions mentioned are the test conditions specified in DIN standard 53122, whereby according to DIN 53122 minimum deviations are permissible (23 ± 1 ° C, 85 ± 2% relative humidity). The moisture vapor transmission rate of a given packaging system or material can be determined by other standard methods and is also, for example, in the ASTM standard E-96-53T (test for measuring water vapor transmission of material in sheet form) and TAPPI standard T464 m-45 ("Water Vapor Permeability of Sheet Materials at high temperature and Humidity"). The principle of measurement of common methods is based on the Wasseraufnah me of anhydrous calcium chloride, which is stored in a container in the appropriate Atmosphä re, the container is closed at the top with the material to be tested. From the surface of the container, which is closed with the material to be tested (per meationsfläche), the increase in weight of calcium chloride and the exposure time, the moisture vapor transmission rate is after

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

The relative equilibrium moisture, often referred to as "relative humidity", in the measurement of moisture vapor transmission rate in the present invention is 85% at 23 ° C. The absorption capacity of air for water vapor increases with the temperature up to a respective maximum content, the so-called saturation content, and is expressed in g / m ³ . For example, 1 m ^{3 of} air is saturated by 17 ° with 14.4 g of water vapor, at a temperature of 11 ° saturation is already present with 10 g of water vapor. The relative humidity is the percentage expressed ratio of the actually existing water vapor content to the saturation content corresponding to the prevailing temperature. If, for example, air contains 17 ° 12 g / m ^{3 of} water vapor, then the relative humidity is (12 / 14,4) .100 = 83%. If the se air is cooled off, the saturation (100% RH) is reached at the so-called dew point (14 ° in the example), ie, on further cooling, a precipitate forms in the form of fog (dew). Hygrometers and psychrometers are used to quantify moisture.

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

The inventive combinations of detergent tablets and Verpac kungskungssystem can of course in turn in secondary packaging, such as Kar toned or trays, with no secondary requirements on the secondary packaging  have to be asked. The secondary packaging is therefore possible, but not necessary manoeuvrable.

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

The packaging system of the combination according to the invention encloses depending on the execution form of the invention one or more detergent tablets. It is invented According to the invention, it is preferable either to design a shaped body such that it has an application training unit of the washing and cleaning agent comprises, and this shaped body individually ver pack, or pack the number of moldings in a packaging unit, in total an application unit. At a nominal dosage of 80 g washing and cleaning agent is So it is possible according to the invention, a 80 g heavy detergent tablets produce and package individually, but it is also possible according to the invention, two 40 g each to pack heavy detergent tablets in a package to form one to get the combination according to the invention. Of course, this principle can be erwei tern, so that according to the invention combinations also three, four, five or even more washing and Detergent tablets may contain in a packaging unit. Of course you can NEN two or more moldings in a package on different compositions point. In this way it is possible to spatially separate certain components for example to avoid stability problems.

The packaging system of the combination according to the invention can be made of the most diverse Materials exist and assume any external forms. For economic reasons and however, for ease of processing, packaging systems are preferred which the packaging material has a low weight, easy to work and inexpensive is. In inventively preferred combinations, the packaging system consists of a Bag or bag of single-layer or laminated paper and / or plastic film.

In this case, the detergent tablets can be unsorted, d. H. as a loose bed, in a bag of the materials mentioned are filled. It is for aesthetic reasons and preferred for sorting the combinations in secondary packaging, the wash and Rei one or more tablets to be filled into sacks or bags. For one individual application units of detergent tablets, which are in a sack or bag, the term "flow pack" has come to be known in the art. Such "flow Packs "can then - optionally again sorted - optionally packed in outer packaging become what the compact form of the form body underlines.  

The preferably used as a packaging system sacks or bags of monolayer or laminated paper or plastic film can be designed in a variety of ways be, for example, as inflated bag without center seam or bag with center seam, wel heat (heat fusion), adhesives or adhesive tapes. a layered bag or bag materials are the known papers, which may imprä can be fermented, as well as plastic films, which may optionally be coextruded. art fabric foils, which are used in the context of the present invention as a packaging system can, for example, in Hans Domininghaus "The plastics and their properties", 3. Edition, VDI Verlag, Dusseldorf 1988, page 193, indicated. The Fig. 111 shows there at the same time indications of the water vapor permeability of the materials mentioned.

In the context of the present invention, particularly preferred combinations contain as Ver A sack or bag made of single-layered or laminated plastic film with egg ner thickness of 10 to 200 .mu.m, preferably from 20 to 100 .mu.m and in particular from 25 to 50 microns.

Although it is possible, in addition to the films mentioned or papers also wax-coated Pa in the form of cardboard as a packaging system for the washing and cleaning agent form body, it is preferred in the context of the present invention, if the Verpac system does not include boxes of wax-coated paper. The term "Verpackungssy In the context of the present invention, the system always denotes the primary packaging of the Shaped body, d. H. the packaging, which on its inside directly with the molding surface in Contact is. There are no requirements for an optional secondary packaging, so that all common materials and systems can be used here.

As already mentioned above, the detergent tablets contain the inventions combination according to their intended use, further ingredients of washing and detergents in varying amounts. Regardless of the purpose of the form It is inventively preferred that the body or the washing and Reinigungsmittelformkör have / have a relative equilibrium moisture content of less than 30% at 35 ° C.

The relative equilibrium moisture content of the detergent tablets may be are determined by common methods, being used in the present investigations The following procedure was chosen: A water-impermeable 1-liter container with a Lid, which has a closable opening for the introduction of samples, was with a total of 300 g of detergent tablets filled and ge 24 h at a constant 23 ° C ge to ensure a uniform temperature of vessel and substance. The what vapor pressure in the space above the moldings can then be measured with a hygrometer (Hygrotest 6100, Testoterm Ltd., England). The water vapor pressure is now measured every 10 minutes,  until two consecutive values show no deviation (equilibrium humid ness). The o. G. 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 resealable. Also combinations in which the Ver Packing system has a micro perforation can be realisie according to the invention with preference ren.

Another object of the present invention is a washing process for washing Textiles in a household washing machine, characterized in that one or several inventive (n) detergent tablets in the dispenser of the Inserting a washing machine and run a wash program, in the course of which or the Molded bodies are flushed.

However, the molding or bodies need not be metered via the dispensing chamber, but rather can also be put directly into the washing drum. This can be both a dosing, For example, a net meter, are used, but the shaped body can also without Dosing be added directly to the laundry in the drum. A washing process for Wa textiles in a household washing machine, in which one or more inventions The washing and cleaning agent shaped article according to the invention with or without dosing aid into the wash Insert the drum of the washing machine and run a wash program, in the course of the or the moldings are dissolved, is therefore also an object of the present invention dung.

As mentioned above, can also detergent tablets for machine dishes rinse produce by the process according to the invention. Accordingly, a cleaning Method for cleaning dishes in a dishwasher, characterized is that one or more inventive (n) detergent tablets in the dosing chamber of the dishwasher inserts and run a wash program, in the Ver Run the dosing opens and the or the moldings are dissolved, another Ge object of the present invention.

Also in the cleaning process according to the invention can be dispensed with the metering chamber and insert the molding (s) according to the invention into the cutlery basket, for example. Of course, but here is the use of a dosing, for example one Cup, which is mounted in the sink, easily possible. Accordingly, a Rei Cleaning method for cleaning dishes in a dishwasher, in which one or a plurality of detergent tablets according to the invention with or without dosing aid  inserted into the washing compartment of the dishwasher and drain a wash program in the Course of the or the moldings are dissolved, another object of the present invention making.

Claims (52)

1. detergent tablets of compacted, particulate wash and Rei nigungsmittel, wherein the molding has at least one cavity, wherein the formkör Perforated boundary wall of the cavity (s) is covered with a foil (are). 2. detergent tablets according to claim 1, characterized in that the Cavity has the shape of a trough. 3. detergent tablets according to claim 1, characterized in that the Cavity has the shape of a through hole whose openings are connected to two ge located opposite body surfaces. 4. detergent tablets according to one of claims 1 to 3, characterized marked characterized in that the film of a polymer having a molecular weight between 5000 and 500,000 Dalton, preferably between 7500 and 250,000 daltons and especially between 10,000 and 100,000 daltons. 5. detergent tablets according to one of claims 1 to 4, characterized marked records that the film consists of a water-soluble polymer. 6. detergent tablets according to claim 5, characterized in that the Film material is selected from one or more substances from the group carrageenan, Guar, pectin, xanthan, cellulose and its derivatives, starch and its derivatives, and gelati ne. 7. detergent tablets according to claim 5, characterized in that the film material is selected from a polymer or polymer mixture, wherein the polymer or at least 50 wt .-% of the polymer mixture is selected from

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

8. detergent tablets according to one of claims 1 to 7, characterized marked records that the opening of the cavity is closed with a film. 9. detergent tablets according to claim 8, characterized in that the Foil does not surround the entire molded body.   10. detergent tablets according to one of claims 8 or 9, characterized ge indicates that the film covers only the surfaces of the molding in which Opennun gene of the cavity (s) are located. 11. Washing and cleaning product molding according to one of claims 1 to 9, characterized marked records that the cavity contains further active substance. 12. Washing and cleaning product molding according to claim 11, characterized in that the further active substance is contained in liquid, gelatinous, pasty or solid form. 13. detergent tablets according to any one of claims 11 or 12, characterized ge indicates that the further active substance is in particulate form, preferably in pulverulent, granular, extruded, pelleted, prilled, flaky or tableted is. 14 detergent tablets according to one of claims 1 to 13, characterized gekenn characterized in that the volume ratio of molded body to cavity 2: 1 to 100: 1, preferably 3: 1 to 80: 1, more preferably 4: 1 to 50: 1 and in particular 5: 1 to 30: 1, is. 15. Detergent tablets according to one of claims 1 to 14, characterized gekenn records that the volume ratio of the wrapped by the film and the molding senen space to the active substance contained in this room 1: 1 to 100: 1, preferably 1.1: 1 to 50: 1, more preferably 1.2: 1 to 25: 1 and in particular 1.3: 1 to 10: 1. 16. Washing and cleaning product molding according to one of claims 10 to 15, characterized ge indicates that the weight ratio of molding to that in the through the film and The active substance contained in the body enclosed space 1: 1 to 100: 1, preferably 2: 1 to 80: 1, more preferably 3: 1 to 50: 1 and in particular 4: 1 to 30: 1. 17. detergent tablets according to one of claims 1 to 16, characterized marked 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 4 to 10% of the total surface of the Forming body. 18. detergent tablets according to one of claims 8 to 17, characterized marked characterized in that the active substance contained in the space enclosed by the film dissolves faster than the base molding.   19. Detergent tablets according to any one of claims 8 to 18, characterized characterized in that the active substance contained in the space enclosed by the film dissolves more slowly than the base molding. 20. detergent tablets according to one of claims 1 to 19, characterized in that the base molding has a density above 1000 kgdm ^-3 , preferably upper half of 1025 kgdm ^-3 particularly preferably above 1050 kgdm ^-3 and in particular above 1100 kgdm ^-3 . 21. Washing and cleaning product molding according to one of claims 1 to 20, characterized marked characterized in that the basic shaped body builders in amounts of 1 to 100 wt .-%, vorzugswei from 5 to 95% by weight, more preferably from 10 to 90% by weight and in particular from 20% to 85 wt .-%, each based on the weight of the base molding contains. 22. Washing and cleaning product molding according to one of claims 1 to 21, characterized marked characterized in that the basic shaped body phosphate (e), preferably alkali metal phosphate (e), FITS It prefers pentasodium or Pentakaliumtriphosphat (sodium or Kaliumtripolyphos phat), in amounts of 20 to 80 wt .-%, preferably from 25 to T5 wt .-% us in particular re from 30 to 70 wt .-%, each based on the weight of the base molding contains. 23. Washing and cleaning product molding according to one of claims 1 to 22, characterized gekenn characterized in that the base molding carbonate (s) and / or bicarbonate (e), preferably Alkali carbonates, more preferably sodium carbonate, in amounts of 5 to 50 wt .-%, before preferably from 7.5 to 40 wt .-% and in particular from 10 to 30 wt .-%, each based on the weight of the base molding contains. 24. Washing and cleaning product molding according to one of claims 1 to 23, characterized marked records that the base molding silicate (s), preferably alkali silicates, particularly preferred crystalline or amorphous alkali disilicates, in amounts of 10 to 60 wt .-%, preferably from 15 to 50 wt .-% and in particular from 20 to 40 wt .-%, each based on the weight of the basic molding contains. 25. Washing and cleaning product molding according to one of claims 1 to 24, characterized gekenn records that the basic shaped body total surfactant contents below 5 wt .-%, vorzugswei below 4% by weight, more preferably below 3% by weight, and especially below 2 wt .-%, each based on the weight of the base molding having. 26. Washing and cleaning product molding according to one of claims 1 to 25, characterized marked characterized in that the base molding bleach from the group of oxygen or halogen  Bleaching agents, especially chlorine bleaches, with particular preference for sodium Perborate and sodium percarbonate, in amounts of 2 to 25 wt .-%, preferably from 5 to 20 wt .-% and in particular from 10 to 15 wt .-%, each based on the weight of Ba sisformkörper, contains. 27. Washing and cleaning product molding according to one of claims 1 to 26, characterized gekenn characterized in that the base molding bleach activators from the groups of the multiply acylated Alkylenediamines, especially tetraacetylethylenediamine (TAED), the N-acylimides, esp N-nonanoylsuccinimide (NOSI), the acylated phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) and n-methyl-morpholinium-acetonitrile Methyl sulfate (MMA), in amounts of 0.25 to 15 wt .-%, preferably from 0.5 to 10 wt .-% and in particular from 1 to 5 wt .-%, each based on the weight of the Basisformkör pers, contains. 28. detergent tablets according to one of claims 1 to 27, characterized gekenn records that the base molding silver protectants from the group of triazoles, Ben zotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and the over transition metal salts or complexes, more preferably benzotriazole and / or alkylaminotria zol, in amounts of 0.01 to 5 wt .-%, preferably from 0.05 to 4 wt .-% and in particular from 0.5 to 3 wt .-%, each based on the weight of the base molding contains. 29. Washing and cleaning product molding according to one of claims 1 to 28, characterized gekenn characterized in that the base molding further comprises one or more substances from the groups of Enzymes, corrosion inhibitors, scale inhibitors, cobuilders, dyes and / or fragrances in Ge velvet 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 base molding contains. 30. Washing and cleaning product molding according to one of claims 1 to 29, characterized gekenn characterized in that the active substance contained in the cavity at least one active substance from the Group of enzymes, surfactants, is-release polymers, disintegration aids, bleach, Bleach activators, bleach catalysts, silver protectants and mixtures thereof. 31. Washing and cleaning product molding according to one of claims 1 to 30, characterized marked characterized in that the base molding or in which by the film and the molding to contained active substance contains bleach, while the other area of the molding contains bleach activators.   32. Washing and cleaning product molding according to one of claims 1 to 31, characterized gekenn records that the base molding or the active substance contained in the cavity bleach contains while the other portion of the molding contains enzymes. 33. Detergent and cleaning agent molding according to one of claims 1 to 32, characterized gekenn records that the base molding or the active substance contained in the cavity bleach contains, while the other portion of the molding deformable mass corrosion protection contains medium. 34. Detergent and cleaning agent molding according to one of claims 1 to 33, characterized gekenn records that the base molding or the active substance contained in the cavity bleach contains, while the other portion of the molding surfactants, preferably nonionic Surfactants, with particular preference alkoxylated alcohols having 10 to 24 carbon atoms and 1 to 5 alkylene oxide units. 35. Washing and cleaning product molding according to one of claims 1 to 34, characterized gekenn records that the base molding and the active substance contained in the cavity the same Active substance contained in different amounts. 36. Washing and cleaning product molding according to one of claims 1 to 35, characterized marked records that the film covering the molding-body boundary wall of the cavity, a Thickness of 1 to 150 microns, preferably from 2 to 100 microns, more preferably from 5 to 75 microns and in particular from 10 to 50 μm. 37. Washing and cleaning product molding according to one of claims 13 to 36, characterized ge indicates that the active substance contained in the cavity particle sizes between 100 and 5000 microns, preferably between 150 and 2500 microns, more preferably between 200 and 2000 microns, and more preferably between 400 and 1600 microns. 38. Detergent and cleaning agent molding according to one of claims 13 to 37, characterized in that the active substance contained in the cavity comprises particles which consist of

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

consist. 39. Washing and cleaning agent shaped body according to claim 38, characterized in that as Shell substance paraffin (s) or polyalkylene glycols, in particular polyethylene glycols in the par contained in articles. 40. Detergent and cleaning agent molding according to one of claims 38 or 39, characterized ge indicates that the active substance particles contained in the cavity nichtioni as active ingredients surfactant (s) and / or bleaching agents and / or bleach activators and / or enzyme (s) and / or corrosion inhibitors and / or perfumes. 41. Washing and cleaning product molding according to one of claims 13 to 37, characterized in that the active substance contained in the cavity comprises particles which consist of

• a) 40 to 99.5 wt .-%, preferably 50 to 97.5 wt .-%, particularly preferably 60 to 95 wt .-% and in particular 70 to 90 wt .-% of one or more shell substance (s), the has a melting point above 30 ° C,
• b) 0.5 to 60% by weight, preferably 1 to 40% by weight, particularly preferably 2.5 to 30% by weight and in particular 5 to 25% by weight of one or more in the coating substance ( en) dispersed liquid enzyme preparation (s) and
• c) 0 to 20 wt .-%, preferably 0 to 15 wt .-%, more preferably 0 to 10 wt .-% and in particular 0 to 5 wt .-% of other carrier materials, excipients and / or active ingredients.

42. A process for the preparation of detergent tablets characterized by the steps

• a) pressing a particulate premix to a compressed part (Basisformkör per) having at least one cavity,
• b) covering the molding-body-side boundary wall of the cavity with film,
• c) optional filling of one or more active substances in liquid, gel, paste or solid form into the said cavity (s),
• d) optionally applying one or more adhesion promoters to one or more surfaces of the molding
• e) optionally closing the openings of the (filled) cavities with a foil
• f) optional aftertreatment of individual shaped body surfaces or of the entire shaped body.

43. The method according to claim 42, characterized in that the particulate premix in Step a) a bulk density of at least 500 g / l, preferably at least 600 g / l and ins special has at least 700 g / l. 44. The method according to any one of claims 42 or 43, characterized in that the particle shaped premix in step a) particle sizes between 100 and 2000 microns, preferably  between 200 and 1800 microns, more preferably between 400 and 1600 microns and in particular dere between 600 and 1400 microns, has. 45. The method according to any one of claims 42 to 44, characterized in that the teilchenför mige composition (s) in step c) a bulk density of at least 500 g / l, before preferably at least 600 g / l and in particular at least 700 g / l has / have. 46. The method according to any one of claims 42 to 45, characterized in that the Verpres solution in step a) at pressing pressures of 0.01 to 50 kNcm ^-2 , preferably from 0.1 to 40 kNcm ^-2 and in particular from 1 to 25 kNcm ^-2 . 47. The method according to any one of claims 42 to 46, characterized in that the Nachbe act in step f) in the application of a coating layer on the entire molded body be stands. 48. Combination of (a) washing and cleaning agent shaped body (s) according to one of Ansprü che 1 to 41 and a detergent or the detergent tablets containing the packaging system, characterized in that the packaging system a moisture keitsdampfdurchlässigkeitsrate of 0.1 g / m ² / day to less than 20 g / m ² / day, when the packaging system is stored at 23 ° C and a relative equilibrium moisture content of 85% ge. 49. Cleaning method for cleaning dishes in a dishwasher, thereby ge indicates that one or more detergent tablets according to egg nem of claims 1 to 40 inserts into the dosing of the dishwasher and a Spülpro runs off, in the course of which opens the dosing and the or the shape body to be dissolved. 50. Cleaning method for cleaning dishes in a dishwasher, thereby ge indicates that one or more detergent tablets according to egg nem of claims 1 to 41 with or without dosing in the washing compartment of the dishwasher sets and run a wash program, in the course of which dissolved the moldings or become. 51. Washing method for washing textiles in a household washing machine, ge indicates that one or more detergent tablets according to egg nem of claims 1 to 41 inserts in the dispensing compartment of the washing machine and a Run off wash program, in the course of which or the moldings are flushed.   52. Washing method for washing textiles in a household washing machine, ge indicates that one or more detergent tablets according to egg Nem of claims 1 to 41 with or without dosing in the washing drum of Waschma inserting machine and run a wash program, in the course of which or the Formkör be dissolved by.