DE19932765A1 - Filled detergent tablets - Google Patents

Abstract

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

Description

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

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

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

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

Another way of producing optically differentiated detergents and cleaning agents Shaped body is in the international patent applications WO 99/06522, WO 99/27063 and WO 99/27067 (Procter & Gamble). According to the teaching of these writings a molded body is provided which has a cavity with a solidifying Melt is filled. Alternatively, a powder is filled in and by means of a coating layer attached in the cavity. All three registrations have in common that the Kavi area to be filled should not be pressed, since pressure sensitive In contents should be spared.  

The way in the prior art to prepare melts into the tablets inserted or which are poured into molded bodies includes a thermal Contamination of the ingredients in the melts. In addition, the exact dosage requires liquid to pasty media and the subsequent cooling a high technical Effort that depends in part on the composition of the melt Shrinkage when cooling and the resulting detachment of the filling is made. The filling of cavities with powdery ingredients and the fixie Coating is also complex and has similar stability problems is liable.

The conventional tableting of multilayer tablets takes place in the field of Detergent tablets also have their limits if only one layer should have a small proportion of the total molded body. If you fall below a be if the layer thickness was correct, then there is pressing of one adhering to the rest of the molded body Layer increasingly difficult.

The pressing of particulate compositions into cavities of moldings solves the problem of the temperature load of these fillings, but on the other hand can a release delay of this pressed part cause an addition of release attachment nigern required if there is an accelerated release of the ingredients from this region. The introduction of liquid, gel-like or pasty media en is neither possible via pouring processes nor via pressing if these medi s do not solidify in the course of production.

The present invention was based on the object of providing moldings in which both temperature and pressure sensitive ingredients in limited Re gions can be introduced, the delimited region in terms of size should not be subject to any restrictions with regard to the overall molded body. there on the one hand, there should be an optical differentiation from conventional two layered tablets can be achieved, on the other hand, the production of the molded body without great technical effort also work safely in large series without the shape Disadvantages in terms of stability or inaccuracies in the dosage  would be feared. In addition, an accelerated release of the ingredient Fe from the delimited region may be possible without admitting certain recipe-related Modifications to be bound. A form of induction should be provided which are independent of the physical state of the active substances to be introduced into the region or active substance mixtures, such active substances also being included in the region should be portable and releasable from the region in an accelerated manner Chen accelerators or disintegration aids are incompatible. Not least liquids, gels or pastes should also be able to be permanently incorporated without that a change in this condition is necessary until use.

It has now been found that the disadvantages mentioned are avoided if one liquid ge, gel-like, pasty or solid ingredients in a cavity of a pre-compressed form body and seals the cavity with a film. In this way the tem temperature or pressure load of the ingredients excluded and the above task solving complex.

The invention relates to detergent tablets made of compressed, Particulate detergents and cleaning agents in which the shaped body has at least one Has cavity, the opening (s) is / are closed with a film.

The cavity in the molded body produced in step a) can have any shape. You can cut through the molded body, d. H. an opening on the top and bottom of the Have molded body, but it can not through the entire molded body going cavity, the opening of which is visible only on one side of the molded body.

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

Of course, the moldings according to the invention can also be multiphase be put. For reasons of process economy, there are two layers Shaped body especially proven.

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

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

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

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

The size of the trough or the through hole compared to the entire molded body depends on the intended use of the molded body. The size of the cavity can vary depending on whether the cavity is to be filled with further active substance and whether a smaller or larger amount of active substance is to be contained. Regardless of the intended use, detergent tablets are preferred in which the volume ratio of molded article to cavity is 2: 1 to 100: 1, preferably 3: 1 to 80: 1, particularly preferably 4: 1 to 50: 1 and in particular 5: 1 to 30: 1. The volume ratio is calculated from the volume of the finished molding according to the invention, ie the molding which has the cavity, which is closed with the film, and the volume of the cavity. The difference between the two volumes gives the volume of the molded body with a cavity in which the cavity is not closed with foil. In other words: if the shaped body has an orthorhombic shape with the side lengths 2, 3 and 4 cm and has a trough with a volume of 2 cm ³ , the volume of this “basic shaped body” is 22 cm ³ . The volume used to calculate the ratio is 24 cm ³ , since the trough is closed with foil and thus there is an orthorhombic molded body without a trough to the outside. In this example, the ratio of the volumes is thus 12: 1. In the case of volume ratios of molded bodies: cavities below 2: 1, which according to the invention can of course also be implemented, the instability of the walls can increase.

Similar statements can be made about the surface proportions that the shaped body with the cavity (“basic shaped body”) or the opening area of the cavity make up on the total surface of the shaped body. Here, detergent tablets are preferred in which the area of the opening (s) in the cavity (s) is 1 to 25%, preferably 2 to 20%, particularly preferably 3 to 15% and in particular 4 to 10% of the total surface area of the tablet matters. The total surface of the molded body corresponds here again to the total surface of the molded body with a closed cavity, in the example above, regardless of the opening area of the trough, 52 cm ² . In such an exemplary shaped body in preferred embodiments of the present invention, the opening (s) of the cavity thus have 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 in particular 2.08 to 5.2 cm ² .

The moldings with cavity according to the invention are characterized in that the Opening (s) of the cavity (s) are closed with foil. It is part of the present ing invention under the term "closed" to understand that the film that the Closes the opening of the cavity (s), is firmly connected to the molded body. A Packaging, in which the molded body is inserted, therefore does not meet the requirements of the invention moderate criterion of "closing".  

The film that closes the opening (s) of the cavity (s) is applied to the surface of the Shaped body applied and bonded to this, for example, by An stick, partial melting or by chemical reaction. It is possible to apply the film to all molded body surfaces and to adhere firmly to them connect so that the film is a coating, a "coating" of the entire molded body matters. Preferred detergent tablets are, however, thereby characterized in that the film does not enclose the entire molded body.

For reasons of process economy and aesthetic impression, it is preferred that the film is only applied to the surfaces of the moldings where it has a function fulfilled, d. H. serves to close cavities. Detergent tablets per, in which the film only covers the surfaces of the molding in which there are openings of the cavity (s) are therefore preferred.

The cavity sealing film can of course also be a laminate of several differently composed foils, about different compositions The opening of the cavity can at certain times in the individual film layers Washing and cleaning cycle are released, which is particularly advantageous if the closed cavity contains further active substance.

Preferred film materials are the polymers known from the prior art. In particular, detergent tablets are preferred in which the film from a polymer with a molecular weight between 5000 and 500,000 daltons, preferably between 7,500 and 250,000 daltons and in particular between 10,000 and 100,000 dal tone, exists. With regard to the media, in the washing and cleaning agents usually se are introduced, in particular detergent tablets are before moves, in which the film consists of a water-soluble polymer.

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

Carrageenan is an extract from North Atlantic red algae, which is one of the florid plants, and is named after the Irish coastal town of Carragheen. The carrageenan precipitated from the hot water extract of the algae is a colorless to sand-colored powder with molar masses of 100,000-800,000 and a sulfate content of approx. 25%, which is very easily soluble in warm water. There are three main components in carrageenan: The yellow-forming f fraction consists of D-galactose-4-sulfate and 3,6-anhydro-α-D-galactose, which are alternately glycosidically linked in the 1,3- and 1,4-positions are (in contrast, agar contains 3,6-anhydro-α-L-galactose). The non-gelling 1 fraction is composed of 1,3-glycosidically linked D-galactose-2-sulfate and 1,4-linked D-galactose-2,6-disulfate residues and is easily soluble in cold water. The i-carrageenan composed of D-galactose-4-sulfate in 1,3-bond and 3,6-anhydro-α-D-galactose-2-sulfate in 1,4-bond is both water-soluble and gel-forming. Other types of carrageenan are also designated with Greek letters: α, β, γ, µ, ν, ξ, π, ω, χ. The type of cations present (K, NH ₄ , Na, Mg, Ca) also influences the solubility of the carrageenans. Semi-synthetic products that contain only one type of ion and can also be used as film materials in the context of the present invention are also called carrag (h) eenate.

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

The ratio of I: II is approximately 2: 1; contrary to the original assumptions, the II units are not strictly alternating, but are arranged in pairs or triplets in the polygalactomannan molecule. Information on the molar mass of guaran varies significantly with values of approx. 2.2.10 ⁵ -2.2.10 ⁶ g / mol depending on the degree of purity of the polysaccharide - the high value was determined on a highly purified product - and corresponds to approx. 1350-13,500 sugar- Units / macromolecule. Guaran is insoluble in most organic solvents.

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

Fruit pectin contains 95%, beet pectin up to 85% galacturonic acid. The molecular weights of the ver Different pectins vary between 10,000 and 50,000. Also the structural properties are strongly dependent on the degree of polymerization; so form z. B. the fruit pectins in dry Asbestos-like fibers, while the flax pectins, on the other hand, are fine, granular powders.

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

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

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

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

Dextrins, for example oli, are suitable as nonionic organic film materials gomers or polymers of carbohydrates by partial hydrolysis of starches can be obtained. The hydrolysis can be carried out according to conventional methods, for example acid or enzyme-catalyzed processes are carried out. It is preferably Hy Drolysis products with average molecular weights in the range from 400 to 50,000 g / mol. It is a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular special from 2 to 30 preferred, DE being a customary measure of the reducing Effect of a polysaccharide compared to dextrose, which has a DE of 100, is. Both maltodextrins with a DE between 3 and 20 and dry can be used glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and White dextrins with higher molar masses in the range from 2000 to 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 are known. An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Starch can also be used as a film material for the washing and cleaning according to the invention middle moldings are used. Starch is a homoglycan, with the glucose Units are linked α-glycosidically. Starch is made up of two components Chen molecular weight built: From approx. 20-30% straight-chain amylose (MW. approx. 50,000-150,000) and 70-80% branched chain amylopectin (MW approx. 300,000-2,000,000), there are also small amounts of lipids, phosphoric acid and cations contain. While the amylose is long due to the 1,4-position binding,  helical, ver forms looped chains with about 300-1200 glucose molecules, the chain branches for amylopectin after an average of 25 glucose units through 1,6-binding a knot-like structure with about 1500-12,000 molecules of glucose. In addition to pure starch ke as film materials in the context of the present invention are also starch Derivatives obtainable from starch by polymer-analogous reactions are suitable. Sol chemically modified starches include, for example, products from vereste stungen or etherifications in which hydroxy hydrogen atoms have been substituted. But also strengths in which the hydroxy groups against functional groups that are not are bound via an oxygen atom, can be replaced as starch derivatives deploy. The group of starch derivatives includes, for example, alkali starches, car boxymethyl starch (CMS), starch esters and ethers and amino starches.

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

Other polymers which can be used as film materials are synthetic polymers which are preferably water-swellable and / or water-soluble. Such synthetic-based polymers can be "tailored" for the desired film permeability during 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, the polymer or at least 50% by weight of the polymer mixture being selected from

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

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

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

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

• - Polyvinylpyrrolidones, such as those under the name Luviskol® (BASF) are sold. Polyvinyl pyrrolidones are preferred nonionic poly mere within the scope of the invention.

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

by radical polymerization of 1-vinylpyrrolidone by the process of or suspension polymerization using radical formers (peroxides, azo Compounds) are prepared as initiators. The ionic polymerization of the mono meren only supplies products with low molecular weights. Commercial polyvinylpyrrolidones have molar masses in the range of approx. 2500-750,000 g / mol, which can be Values are characterized and - depending on the K value - glass transition temperatures of Own 130-175 °. They are presented as white, hygroscopic powders or as aqueous ones. Solution gene offered. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, Phe nole u. a.).

• - Vinyl pyrrolidone / vinyl ester copolymers, such as those found under the goods logo Luviskol® (BASF). Luviskol® VA 64 and Luviskol® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred nonionic polymers.

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

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

The vinyl esters are polymerized by free radicals using various processes (Solution polymerization, suspension polymerization, emulsion polymerization, substance polymerization). Copolymers of vinyl acetate with vinyl pyrrolidone contain mono units of formulas (III) and (IV)

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

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

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

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

[-CH ₂ -CH (OH) -] _n

which in small proportions also structural units of the type

[-CH ₂ -CH (OH) -CH (OH) -CH ₂ ]

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

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

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

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

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

Anionic polymers suitable according to the invention include:

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

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

[-CH (CH ₃ ) -CH (COOH) -) _n (VI)

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

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

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

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

H- (O-CH ₂ -CH ₂ ) _n -OH (VII)

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

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

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

In particular, the vinyl acetate copolymers and the polymers of vinyl acetate and crotonic acid grafted onto polyethylene glycols be set.

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

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

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

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

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

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

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

Short-chain carboxylic acids or alcohols include those with 1 to 8 carbons To understand atoms of matter, given the carbon chains of these compounds if can be interrupted by double-bonded hetero groups such as -O-, -NH-, -S_.

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

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

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

The terpolymers mentioned above preferably result from the copolymerization on from 7 to 12% by weight crotonic acid, 65 to 86% by weight, preferably 71 to 83% by weight Vinyl acetate and 8 to 20 wt .-%, preferably 10 to 17 wt .-% allyl or methallyl ster of formula IX.

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

In the case of anionic polymers, polycar is particularly suitable as film material boxylates / polycarboxylic acids, polymeric polycarboxylates, polyaspartic acid, polyacetals and dextrins, which are described below.

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

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

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2000 to 20,000 g / mol. Because of their superior solubility, the This group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10,000 g / mol, and particularly preferably from 3000 to 5000 g / mol, are preferred his.

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

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

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

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

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

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

Other polymers that can preferably be used as film materials are cationic polymers. The permanent cationic polymers are among the cationic polymers moves. According to the invention, such polymers are termed “permanently cationic” if which are independent of the pH of the agent (i.e. both the film and the rest Detergent tablets) have a cationic group. these are usually polymers that have a quaternary nitrogen atom, for example in the form of a Ammonium group.

Preferred cationic polymers are, for example

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

as well as those under the designations

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

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

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

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

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

Together with the molded body, which has at least one cavity, that forms with the Shaped adhesive bonded film the washing and cleaning according to the invention medium shaped body. In the case of closed mold bodies, the structure is reminiscent the molded body of the invention to a "drum" in which a cavity through a Foil is closed. It is possible according to the invention to leave the cavity empty and to use only the visual appeal of such molded articles, preferred washing and cleaning agents Means shaped body are characterized in that in the through the film and the active body enclosed space is contained.

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

When incorporating liquid, gel-like or pasty active substances or active substances Punch mixtures must be the composition of the molded body and the film on the filling be adjusted to prevent premature destruction of the film or a loss of activity avoid substance through the molded body. This is firmer when it is incorporated Substances in the cavity only to a minor extent (chemical incompatibilities)  required so that preferred detergent tablets further active substance in particle form, preferably in powder, granular, extruded, pelle tied, prilled, flaked or tableted form.

The cavity closed by the film can completely with additional Aktivsub be filled with punch. However, it is also possible to only close the cavity before closing partially fill to move the filled particles or rivers to allow liquids within the cavity. Especially when filling with regular Larger shaped larger particles can create attractive optical effects. Here, detergent tablets are preferred, in which the volume ratio of the space enclosed by the film and the molded body to that in active substance contained in this space 1: 1 to 100: 1, preferably 1.1: 1 to 50: 1, be is particularly preferably 1.2: 1 to 25: 1 and in particular 1.3: 1 to 10: 1. In this term Technology means a volume ratio of 1: 1 that the cavity is completely filled.

Depending on the size of the cavity, the density of the molded body, the density of the Active ingredient in the cavity and the degree of filling of the cavity can be the proportion of the other Make up different amounts of active substance in the cavity in the overall molded article. Here, detergent tablets are preferred in which the weight ratio of molded body to that in which is enclosed by the film and the molded body NEN containing active substance 1: 1 to 100: 1, preferably 2: 1 to 80: 1, particularly is preferably 3: 1 to 50: 1 and in particular 4: 1 to 30: 1. With the above defi weighted ratio is the ratio of the mass of the unfilled Shaped body ("basic shaped body") to the mass of the filling. The mass of the film is at this calculation is not taken into account.

The time can be reduced by suitable assembly of the shaped body and the film material The point at which the substance contained in the cavity is released determines who the. For example, the film can be instantly soluble, so that the in the cavity Active substance contained in the at the beginning of the washing or cleaning cycle Washing or cleaning liquor is dosed. Alternatively, the film can be so bad  be soluble, that only the molded body is dissolved and the Ak contained in the cavity active substance is thereby released.

Depending on this release mechanism, moldings can be made, for example Realize in which the active substance contained in the cavity in the cleaning liquor is dissolved before the constituents of the shaped body are dissolved or after this happened. On the one hand, detergent tablets are preferred which are characterized in that in the through the film and the molded body enclosed active substance dissolves faster than the basic molded body.

But also laundry detergent and cleaning product tablets, in which the in the by Active substance contained in the film and the space enclosed in the molded body dissolves more slowly as the base molding, are preferred embodiments of the present invention.

The shaped bodies according to the invention consist of a basic shaped body, the one or has several cavities, film (s) that seal (s) these cavity (s) as well as optional active substance (s) contained in the cavity (s). The foil materials and preferred physical parameters of the films have already been described above. It Now follows a description of the ingredients of the base molding, which are active at the same time substances that are contained in the cavity, as well as an enumeration preferred physical parameter for basic molded body and cavity filling. By Incorporation of certain components can on the one hand increase the solubility of the filling of the Ka targeted acceleration, on the other hand, the release of certain ingredients Fe from this filling lead to advantages in the washing or cleaning process. Ingredients, which are preferably located at least partially in the cavity are, for example surfactants, enzymes, soil-release polymers, builders, described below Bleaching agents, bleach activators, bleaching catalysts, optical brighteners, silver protection medium etc.

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

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

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

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

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

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

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

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

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

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

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

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

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

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to the diphosphate Na ₄ P ₂ O ₇ when heated to a greater extent. Disodium hydrogen phosphate is produced by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

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

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

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

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

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

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

Preferred detergent and cleaning agent form in the context of the present invention Bodies are characterized in that the basic shaped body phosphate (s), preferably 99999 00070 552 001000280000000200012000285919988800040 0002019932765 00004 99880g Alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (Sodium or potassium tripolyphosphate), in amounts of 20 to 80 wt .-%, preferably from 25 to 75% by weight and in particular from 30 to 70% by weight, in each case based on the Weight of the base molding.

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

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

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

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

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

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

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

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2000 to 20,000 g / mol. Because of their superior solubility, the This group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10,000 g / mol, and particularly preferably from 3000 to 5000 g / mol, are preferred his.

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

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

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

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

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

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

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

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be. The hydrolysis can be carried out according to conventional methods, for example acid or enzyme lysed procedures are carried out. It is preferably hydrolysis pro Products with average molecular weights in the range of 400 to 50,000 g / mol. There is a poly saccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30 preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and dry glu can be used cosesirupe with a DE between 20 and 37 as well as so-called yellow dextrins and White dextrins with higher molar masses in the range from 2000 to 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 are known. An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

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

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

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

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

The amount of builder is usually between 10 and 70 wt .-%, preferably as between 15 and 60 wt .-% and in particular between 20 and 50 wt .-%, each Weil based on the base molding. Again, the amount of buil used depend on the intended use, so that bleach tablets in higher amounts May have builders (for example between 20 and 70% by weight, preferably as between 25 and 65 wt .-% and in particular between 30 and 55 wt .-%), as for example detergent tablets (usually 10 to 50% by weight, preferably 12.5 up to 45% by weight and in particular between 17.5 and 37.5% by weight).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In particular in the production of detergent tablets according to the invention or Detergent tablets for automatic dishwashing, it is preferred that the Detergent tablets contain a nonionic surfactant, the one Has melting point above room temperature. Accordingly, contains at least one the deformable masses in the process according to the invention are preferably nonionic Surfactant with a melting point above 20 ° C. Nonionics to be used preferably cal surfactants have melting points above 25 ° C., particularly preferably one setting 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 the above Temperature range are, for example, low-foaming nonionic ten side, which can be solid or highly viscous at room temperature. Will be at room temperature used highly viscous nonionic surfactants, it is preferred that these have a viscosity above half of 20 Pas, preferably above 35 Pas and in particular above 40 Pas exhibit. Also non-ionic surfactants, which have a waxy consistency at room temperature, are preferred.

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

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

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

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

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

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

Another preferred surfactant can be represented by the formula

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

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

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

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

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

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

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

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

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

In order to facilitate the disintegration of highly compressed moldings, it is possible to disintegrate to incorporate auxiliary agents, so-called tablet disintegrants, into the base tablets, to shorten disintegration times. Under tablet disintegrants or disintegration accelerators according to Römpp (9th edition, Vol. 6, p. 4440) and Voigt "Textbook of pharma zeutischen Technologie "(6th edition, 1987, pp. 182-184) understood auxiliary substances for the rapid disintegration of tablets in water or gastric juice and for the release of the phar provide maka in an absorbable form.

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

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

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

The cellulose used as disintegration aid is preferably not finely divided form, but before mixing into the premixes to be pressed converted into a coarser form, for example granulated or compacted. Washing and Detergent tablets, the disintegrant in granular or optionally cogranu Contained form, are in the German patent applications DE 197 09 991 (Ste fan Herzog) and DE 197 10 254 (Henkel) and the international patent application WO 98/40463 (Henkel). These writings are also more detailed information on the Her position of granulated, compacted or cogranulated cellulose disintegrants men. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 µm and in particular to at least 90% by weight between 400 and 1200 µm. The above and in the writings cited described coarser disintegration aids on cellulose In the context of the present invention, bases are preferred as disintegration aids used and commercially, for example under the name Arbocel® TF-30-HG by available from Rettenmaier.

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

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

The detergent tablets according to the invention can moreover a gas-developing shower system both in the base molding and in the cavity contain. The gas-developing shower system can consist of a single substance, which releases a gas on contact with water. Among these connections is particular to name the magnesium peroxide, which releases oxygen when in contact with water. Usual However, the gas-releasing bubble system in turn consists of at least two components that react with each other to form gas. While here a lot Number of systems is conceivable and executable, for example nitrogen, oxygen or Release hydrogen, that will in the washing and cleaning according to the invention medium shaped bodies used bubble system based on both economic and let hand choose ecological aspects. Preferred shower systems exist from alkali metal carbonate and / or hydrogen carbonate and an acidifying agent, which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.

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

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

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

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

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other usable bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -supplying peracidic salts or peracids, such as per benzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Cleaning agents according to the invention can also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaches are the diacyl peroxides, such as. B. dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimido phanoacidaprooxyaproic acid (poxycaproperaproic acid) , nonenylamidopersuccinates)], o- Carboxybenzamidoperoxycapronsäure N-nonenylamidoperadipic acid and N, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, Diperocysebacinsäure, Diper oxybrassylsäure, phthalic diperoxy-die, 2-decyldiperoxybutane -1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

As a bleach in the detergent tablets according to the invention for the machine Dishwashing can also use chlorine or bromine-releasing substances. Suitable chlorine or bromine releasing materials include, for example heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, Tribromo isocyanuric acid, dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

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

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

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

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

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

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

Detergent tablets, which are characterized in that the base molded body bleach from the group of oxygen or halogen bleach, esp special of the chlorine bleach, with particular preference for sodium perborate and Sodium percarbonate, in amounts of 2 to 25% by weight, preferably 5 to 20% by weight and in particular from 10 to 15% by weight, in each case based on the weight of the basic shape body mass, are a preferred embodiment of the invention lying invention.

It is also preferred that the base molding and / or the active substance (s) in the Cavity bleach activators included. Detergent tablets in which the base molding bleach activators from the groups of polyacylated alkylene diamines, especially tetraacetylethylenediamine (TAED), the N-acylimides, in particular N-nonanoylsuccinimide (NOSI), the acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) and n-methyl-morpholinium Acetonitrile methyl sulfate (MMA), in amounts of 0.25 to 15% by weight, preferably of 0.5 to 10 wt .-% and in particular from 1 to 5 wt .-%, each based on the Ge weight of the base molding, are also preferred.

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

In detergents and cleaning agents preferred within the scope of the present invention The basic molded body contains silver protection agents from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes, particularly preferably benzotriazole and / or Alkylaminotriazole, in amounts of 0.01 to 5% by weight, preferably 0.05 to 4% by weight and in particular from 0.5 to 3% by weight, in each case based on the weight of the base molded body.

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

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

In addition to the ingredients mentioned builder, surfactant, disintegration aid bleach The detergents and cleaning agents according to the invention can be agents and bleach activators molded body further ingredients from the group that are common in washing and cleaning agents of dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, Anti-redeposition agents, graying inhibitors, color transfer inhibitors and corro ion inhibitors included.

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

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

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

Dyes and fragrances can be the detergent and cleaning agent form according to the invention form both in the base molding and in the preparation contained in the cavity can be added to improve the aesthetic impression of the resulting products sern and the consumer in addition to the performance a visually and sensory "typical and to provide a distinctive "product. As perfume oils or fragrances individual fragrance compounds, e.g. B. the synthetic products of the type Esters, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are e.g. B. benzyl acetate, phenoxyethyl isobuty rat, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenyl ethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example Benzyl ethyl ether, to the aldehydes z. B. the linear alkanals with 8-18 C atoms, citral, Citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. B. the Jonone, α-isomethylionon and methylcedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include terpenes such as soda nen and pinen. However, mixtures of different fragrances are preferably used det, which together create an appealing fragrance. Such parflime oils can also contain natural fragrance mixtures as they are accessible from plant sources, e.g. B. pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lin flower oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil such as orange blossom oil, neroliol, orange peel oil and sandalwood oil.  

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

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

The detergent tablets according to the invention can have one or more Other optical brighteners included. These substances, which are also called "whiteners", are used in modern detergents, since they are even freshly washed and bleached white laundry has a slight yellow tinge. Optical brighteners are organic colors substances that contain part of the invisible UV radiation from sunlight in longer waves convert blue light. The emission of this blue light complements the "gap" in the from Textile reflected light, so that a textile treated with optical brighteners the eye appears whiter and lighter. Because the mechanism of action of brighteners hen presupposes the fibers, a distinction is made depending on the "dyed" fibers for example brighteners for cotton, polyamide or polyester fibers. The Handelsübli Brighteners suitable for incorporation in detergents essentially belong here five structural groups on the stilbene, the diphenylstilbene, the coumarin-quinoline, the diphenylpyrazoline group and the group of the combination of benzoxazole or Ben zimidazole with conjugated systems. An overview of common brighteners is an example in G. Jakobi, A. Löhr "Detergents and Textile Washing", VCH Verlag, Weinheim, 1987, pages 94 to 100. Are suitable for. B. Salts of 4,4-bis [(4-anilino-6-  morpholino-s-triazin-2-yl) amino] -stilbene-2,2'-disulfonic acid or of a similar structure Compounds which, instead of the morpholino group, a diethanolamino group, a Me wear thylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, e.g. B. 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. Mixtures of the pre named brighteners can be used.

In addition, the detergent tablets can also ent components hold, which positively influence the oil and fat washability from textiles (so-called called soil repellents). This effect is particularly evident when a textile is dirty is already several times with a detergent according to the invention, this Contains oil and fat-dissolving component, was washed. Among the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methylhydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and of hydroxypropoxyl groups from 1 to 15 wt .-%, each bezo gene on the nonionic cellulose ether, as well as those known from the prior art Polymers of phthalic acid and / or terephthalic acid or their derivatives, in particular special polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Especially be of these, the sulfonated derivatives of phthalic and terephthalic acids are preferred re-polymers.

As foam inhibitors that can be used in the agents according to the invention, For example, soaps, paraffins or silicone oils come into consideration, which if necessary can be applied to carrier materials.

Graying inhibitors have the task of removing the dirt detached from the fiber in the Keep the liquor suspended and thus prevent the dirt from re-opening. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acid Ren starch or cellulose or salts of acidic sulfuric acid esters of cellulose  or strength. Water-soluble polyamides containing acidic groups are also suitable for the suitable purpose. Soluble starch preparations and others other than that can also be used Use the above starch products, e.g. B. degraded starch, aldehyde starches, etc. Polyvinyl pyrrolidone can also be used. However, cellulose ethers such as Carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixtures ther such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxy methyl cellulose and mixtures thereof in amounts of 0.1 to 5 wt .-%, based on the Means used.

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

To combat microorganisms, the agents according to the invention can be antimicro bielle contain active ingredients. A distinction is made here depending on the antimicrobial spectrum and mechanism of action between bacteriostatics and bactericides, fungiostatics and Fungicides, etc. Important substances from these groups are, for example, benzalkonium chloride, alkylarlyl sulfonates, halophenols and phenol mercuric acetate, whereby also complete Lich these connections can be dispensed with.

To unwanted, caused by oxygen and other oxidative processes Prevent changes to the agents and / or the treated textiles which contain antioxidants. This connection class includes, for example substituted phenols, hydroquinones, pyrocatechols and aromatic amines and or ganic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

Increased comfort can result from the additional use of antistatic agents ren, which are additionally added to the agents according to the invention. Enlarge antistatic agents  ß improve the surface conductivity and thus enable an improved drainage det charges. External antistatic agents are usually substances with at least one hydrophilic molecular ligands and give a more or less hy on the surfaces wholesale copy film. These mostly surface-active antistatic agents can be put in stick containing substances (amines, amides, quaternary ammonium compounds), containing phosphorus (Phos divide phosphoric acid ester) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. External antistatic agents are, for example, in patent applications FR 1,156,513, GB 873 214 and GB 839 407. The lauryl (or stearyl) dimethyl disclosed here Benzylammonium chlorides are suitable as antistatic agents for textiles or as additives Detergents, with an additional finishing effect.

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

Finally, the agents according to the invention can also contain UV absorbers which act on the treated textiles and improve the lightfastness of the fibers. Connect Applications which have these desired properties are, for example, those by radiation-free deactivation of active compounds and derivatives of benzophenone with substituents in the 2- and / or 4-position. Substituted benzotria are also available zole, in the 3-position phenyl-substituted acrylates (cinnamic acid derivatives), optionally with Cyano groups in the 2-position, salicylates, organic Ni complexes and natural products such as Umbelliferon and the body's own urocanoic acid are suitable.  

The ingredients described above can of course also in the troughs filling are incorporated. Preferred laundry detergents within the scope of the present invention and detergent tablets are characterized in that the in the by Foil and the enclosed space containing active substance at least one egg Active ingredient from the group of enzymes, surfactants, soil release polymers, disintegration on aids, bleaches, bleach activators, bleach catalysts, silver preservatives and Mixtures thereof.

By dividing the detergent tablets according to the invention into Basic molded body and active substance (s) or active substance contained in the cavity Mix or preparation (s) ingredients can be separated from each other, what either to separate incompatible ingredients to improve storage stability or can be used for a controlled release of certain active substances. In preferred detergent tablets contain the base tablet or the active substance contained in the space enclosed by the film and the molded body punch bleach, while the other area of the molded body contains bleach activators.

Further preferred detergent tablets are characterized in that that the base molding or in which the foil and the molding enclose active area contains bleach, while the other area of the molded body contains enzymes.

Also a separation of bleach and corrosion inhibitors or silver protection agents can be achieved. Detergent tablets in which the basic tablet per or contained in the space enclosed by the film and the molded body Active substance contains bleach, while the other area of the molding deforms Bare mass contains anti-corrosion agents are also preferred.

Last but not least, detergent tablets are preferred, in which the Basic molded body or in the one enclosed by the film and the molded body Room contains active substance containing bleach, while the other area of the  Shaped body surfactants, preferably nonionic surfactants, with particular preference alkoxylated alcohols with 10 to 24 carbon atoms and 1 to 5 alkylene oxide units, contains.

All of the ingredients mentioned above can have advantageous properties result in separating them from other ingredients or combining them with certain others To assemble ingredients together. In the molded articles according to the invention the individual areas can also have a different content of the same content Have fabric, whereby advantages can be achieved. Detergents and cleaning agents Shaped body, in which the basic shaped body and in the through the film and the mold Active substance contained in the body-enclosed space contains the same active substance in below contain different amounts are preferred. The term "different men ge "does not refer to the absolute amount of the ingredient in the subject Part of the molded body, but on the relative amount, based on the phase weight, therefore represents a percentage by weight based on the individual area, ie the basic form body or the cavity filling.

The active substance optionally to be incorporated into the cavity is preferably particulate mig. The term "active substance" is not within the scope of the present invention limited to pure substances. Rather, it characterizes pure active substances, active substance mixtures and preparation forms, so that the freedom of formulation no limits zen are set. If particulate matter is enclosed in the cavity (s), it is preferred if these certain particle size criteria meet, so preferred Detergent tablets are characterized in that in the Parti active substance contained by the film and the molded body kel sizes between 100 and 5000 microns, preferably between 150 and 2500 microns, esp preferably between 200 and 2000 µm and in particular between 400 and 1600 µm, having.

Particularly preferred to introduce into the cavity (s) of the moldings according to the invention are particulate compositions which contain surfactants, it being preferred to provide these surfactants for machine dishwashing detergents in a solution-delayed form in order to release the surfactants from the cavity filling only in rinse aid to reach gear. Rinse aid particles such as are described in the older German patent application DE 199 14.364.1 (Henkel KGaA) have proven particularly useful for this purpose. Such particles, which are particularly preferably introduced into the cavity, consist of 0 to 90% by weight of one or more carrier materials, 5 to 50% by weight of one or more coating substances with a melting point above 30 ° C., 5 to 50% by weight. one or more active substances and 0 to 10% by weight of further active substances and auxiliaries, so that detergent tablets are preferred, in which the active substance contained in the space enclosed by the film and the molded article comprises particles which consist of

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

consist.

Reference is expressly made to the disclosure of this document. Still be the most important ingredients of this "rinse aid par described below. Carriers a) all come at room temperature solid substances in question. Usually you will select substances that are in the Cleaning cycle develop an additional effect, with builders in particular to offer. In preferred particulate rinse aids for filling the cavity are as Carrier materials Fabrics from the group of water-soluble washing and cleaning agents tel ingredients, preferably the carbonates, hydrogen carbonates, sulfates, phosphates and the organic oligocarboxylic acids which are solid at room temperature in amounts of 55 to 85% by weight, preferably from 60 to 80% by weight and in particular from 65 to 75% by weight, each based on the particle weight.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

H- (O-CH ₂ -CH ₂ ) _n -OH (XIII)

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Another class of compounds that are preferred as active substances in the inventions Active substance particles which can be introduced according to the invention are the Bleach activators. The important representatives from this group of substances have already been described. In the context of the present invention preferably pressed into the trough Active substance particles contain bleach activators as active substance, in particular from the Groups of polyacylated alkylenediamines, especially tetraacetylethylenediamine  (TAED), the N-acylimides, especially N-nonanoylsuccinimide (NOSI), the acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA).

Another important embodiment of the present invention provides for the introduction of enzyme-containing particles into the cavity (s). Such active substance particles contain as active substance (s) enzymes which have been described in detail above. Particular preference is given here to particulate particles to be introduced into the cavity (s) which are 40 to 99.5% by weight, preferably 50 to 97.5% by weight, particularly preferably 60 to 95% by weight and in particular 70 to 90% by weight of one or more coating substance (s) which has / have a melting point above 30 ° C., 0.5 to 60% by weight, preferably 1 to 40% by weight, particularly preferably 2.5 to 30% by weight and in particular 5 to 25% by weight of one or more liquid enzyme preparation (s) dispersed in the coating substance (s) and 0 to 20% by weight, preferably 0 to 15% by weight. -%, particularly preferably 0 to 10 wt .-% and in particular 0 to 5 wt .-% and optionally contain other carrier materials, auxiliaries and / or active ingredients. Preferred detergent and cleaning agent shaped bodies are accordingly characterized in that the active substance contained in the space enclosed by the film and the shaped body comprises particles which consist of

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

consist.

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

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

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

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

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

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

It can also be advantageous to add further additives to the coating substance in order to to prevent early withdrawal of the active substances. This is particularly so in the production of the active substance particles according to the invention without carriers guess. The anti-settling agents that can be used for this purpose, also known as floating agents are from the prior art, for example from the lacquer and printing inks manufacturing, known. To make the transition from the plastic solidification area to the festival Sedimentation phenomena and concentration gradient of the sub to be encased To avoid punching, there are, for example, surface-active substances in Lö dispersed waxes, montmorillonites, organically modified bentonites, (hy  third) castor oil derivatives, soy lecithin, ethyl cellulose, low molecular weight polyamides, Me tall stearates, calcium soaps or hydrophobized silicas. Other substances that the effects mentioned come from the groups of anti-floating agents and Thixotropic agents and can be used chemically as silicone oils (D 44015 00070 552 001000280000000200012000285914390400040 0002019932765 00004 43896imethylpolysiloxane, methyl phenylpolysiloxanes, polyether-modified methylalkylpolysiloxanes), oligomeric titanates and silanes, polyamines, salts from long-chain polyamines and polycarboxylic acids, Amine / amide-functional polyesters or amine / amide-functional polyacrylates become.

Additives from the classes of substances mentioned are commercially extremely diverse available. Commercial products that are advantageous in the context of the method according to the invention Aerosil® 200 (pyrogenic pebbles acid, Degussa), Bentone® SD-1, SD-2, 34, 52 and 57 (Bentonite, Rheox), Bentone® SD-3, 27 and 38 (hectorite, Rheox), Tixogel® EZ 100 or VP-A (organically modified Smec tit, Südchemie), Tixogel® VG, VP and VZ (montmorillonite loaded with QAV, Südche mie), Disperbyk® 161 (block copolymer, Byk-Chemie), Borchigen® ND (sulfo-free er ion exchanger, Borchers), Ser-Ad® FA 601 (servo), Solsperse® (aromatic Ethoxylate, ICI), Surfynol® types (Air Products), Tamol® and Triton® types (Rohm & Haas), Texaphor®963, 3241 and 3250 (polymers, Henkel), Rilanit® types (Hen kel), Thixcin® E and R (castor oil derivatives, Rheox), Thixatrol® ST and GST (castor oil Derivatives, Rheox), Thixatrol® SR, SR 100, TSR and TSR 100 (polyamide polymers, Rheox), Thixatrol® 289 (polyester polymer, Rheox) and the various M-P-A® Types X, 60-X, 1078-X, 2000-X and 60-MS (organic compounds, Rheox).

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

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

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

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

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

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

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

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

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

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

Another group of emulsifiers which can be used in the rinse aid or enzyme particles to be incorporated into the cavity (s) according to the invention are substituted silicones which carry side chains which have not been reacted with ethylene or propylene oxide. Such polyoxyalkylene siloxanes can be described by the general formula XV

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

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

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

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

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

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

Another object of the present invention is a method for producing detergent tablets, which comprises the steps

• a) pressing a particulate premix into a pressed part (base molded body) which has at least one cavity,
• b) optional filling of one or more active substances in liquid, gel-like, pasty or solid form in said cavity (s),
• c) optional application of one or more adhesion promoters to one or more Surfaces of the molded body,
• d) sealing the openings of the (filled) cavities with a film,
• e) optional post-treatment of individual molded body surfaces or the entire mold body

is marked.

With regard to the ingredients of the individual areas of the shaped bodies according to the invention or their particulate premixes or compositions which differ  Lichen areas of the molded body result, applies analogously to the invention above according to the molded body.

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

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

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

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

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

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

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

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

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

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

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

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

Processes preferred in the context of the present invention are characterized in that the pressing 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} is done.

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

In step b), the cavity is optionally mixed with active substance (s), active substance mixtures or filled with active substance preparations. Unless the cavity has more than one opening points out, it is expedient from a procedural point of view, the second, third and any further Closing openings to make filling technically easier design. In principle, it is also possible to fill a shaped ring body first, then to close the upper opening of the hole, to turn the molded body and its filling over and also to close the second hole, but this requires mechanical devices conditions that prevent the filling from falling out. If the cavity of the in step a) manufactured molded body on more than one opening, it is preferred to the optional Step b) - filling - only after steps (c) and (d) have been carried out (n-1) to be carried out when the number of openings is n. Closing the last opening corresponds to the last time the process steps c) and d) were carried out a step e) can connect.

As already mentioned above, the filling that can optionally be introduced into the cavity is preferably solid, with particulate fillings being particularly preferred. Will the Cavities of the moldings filled with particulate compositions, so Ver preferably drive in which the particulate composition (s) in step b) Bulk density of at least 500 g / l, preferably at least 600 g / l and in particular has / have at least 700 g / l.

In step c) of the method according to the invention, adhesion promoters are optionally applied to a or applied several surfaces of the shaped body. Step c) is then particularly necessary This is particularly the case if the foils to be applied in the subsequent step are not sufficient have proper adhesion to remain on the molded body and the mechani strain on packaging, transport and handling without releasing the fill resisting. Process step c) is therefore not sufficiently adherent capable foils "sticking" to them.

Substances can be used as adhesion promoters on the surfaces of the molded bodies on which they are applied be worn, give sufficient adhesion ("stickiness"), so that the in  subsequent process step, films adhering permanently to the surface. In principle, here are those in the relevant adhesive literature and especially in the monographs mentioned for this purpose, whereby within the scope of the present Invention of the application of melts, which adheres at an elevated temperature have a telephoning effect, but after cooling down they are no longer sticky, but solid, a special one Importance.

Regarding process step d), the application of the film to some or all surfaces of the mold body and the associated closing of the cavity (s) have already been further detailed information given above, to which reference is made here in order to avoid redundancies avoid.

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

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

The packaging system of the combination of detergent tablets (s) and packaging system has, according to the invention, a moisture vapor permeability rate of 0.1 g / m ² / day to less than 20 gm ² / day when the packaging system is at 23 ° C. and a relative equilibrium humidity of 85% is stored. The named temperature and humidity conditions are the test conditions that are mentioned in the DIN standard 53122, whereby according to DIN 53122 minimal deviations are permitted (23 ± 1 ° C, 85 ± 2% relative humidity). The moisture vapor permeability rate of a given packaging system or material can be determined according to further standard methods and is, for example, also in the ASTM standard E-96-53T ("Test for measuring Water Vapor transmission of Materials in Sheet form") and in the TAPPI standard T464 m-45 ("Water Vapor Permeability of Sheet Materials at high temperature and Humidity"). The measuring principle of current methods is based on the water absorption of anhydrous calcium chloride, which is stored in a container in the corresponding atmosphere, the container being closed at the top with the material to be tested. From the surface of the container, which is closed with the material to be tested (permeation surface), the increase in weight of calcium chloride and the exposure time, the moisture vapor transmission rate can be determined

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

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

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

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

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

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

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

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

The preferably used as a packaging system sacks or bags made of monolayer or laminated paper or plastic film can be designed in a wide variety of ways, for example as a blown-up bag without a central seam or as a bag with a central seam, which is caused by heat (hot fusion), adhesives or adhesive tapes which are locked. Single-layer bag or sack materials are the known papers, which can optionally be impregnated, as well as plastic films, which can optionally be co-extruded. Plastic films that can be used as a packaging system in the context of the present invention are given, for example, in Hans Domininghaus "The plastics and their properties", 3rd edition, VDI Verlag, Düssel dorf 1988, page 193. Fig. 111 shown there also gives reference points for the water vapor permeability of the materials mentioned.

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

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

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

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

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

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

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

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

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

Examples Manufacture of detergent tablets for automatic dishwashing Process step a) Manufacture of molded bodies

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

The weight of the base tablets was 20 g.

Process step b) Filled with active substance

As a particulate active substance for filling the cavity, commercially available par particulate enzyme preparations (Protease BLAP® S 260, company Biozym GmbH) with  a bulk density of 800 g / l and an average particle size of 400 microns in the Filled in hollow. The filling quantity was 1 g, the volume of the cavity being 80% was filled.

Process step c) Applying adhesion promoter to the surface

The mold bodies filled in step b) were on the top, on which Publ cavity with 100 mg of a 20% solution of polyvinyl alcohol (Mo wiol® 10-98, from Hoechst).

Process step d) Apply the film

The filled moldings, on the upper side of which the adhesive bond medium, were covered with a polyvinyl alcohol film (type M8630, Greensol) locked.

Process step e) Aftercare

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

The moldings according to the invention were characterized by a firm bond between Foil and base molding from, so that no loss of active substance could occur. If a tablet is placed in water (20 ° C, 16 ° dH), an inflation is observed hen the polyvinyl alcohol film, which directly bursts open and releases the enzyme particle follows. The contents of the well filling become full within 5 seconds constantly released.

Claims (51)

1. Detergent tablets made of compressed, particulate detergent, characterized in that the tablet has at least one cavity, the opening (s) of which is / are closed with a film. 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, the openings of which located on two opposite surfaces of the molded body. 4. Detergent tablets according to one of claims 1 to 3, characterized characterized in that the film made of a polymer with a molecular weight between 5000 and 500,000 daltons, preferably between 7,500 and 250,000 daltons, and in particular between 10,000 and 100,000 Daltons. 5. Detergent tablets according to one of claims 1 to 4, characterized characterized in 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 their derivatives, starch and their Derivatives and gelatin. 7. Detergent tablets according to claim 5, characterized in that the film material is selected from a polymer or polymer mixture, the polymer or at least 50% by weight of the polymer mixture being selected from

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

8. Detergent tablets according to one of claims 1 to 7, characterized characterized in that the film does not enclose the entire molded body. 9. Detergent tablets according to one of claims 1 to 8, characterized characterized in that the film only covers the surfaces of the shaped body in which There are openings in the cavity (s). 10. Detergent tablets according to one of claims 1 to 9, characterized characterized in that in the space enclosed by the film and the molded body further active substance is contained. 11. Detergent tablets according to claim 10, characterized in that the further active substance ent in liquid, gel, pasty or solid form hold is.   12. Detergent tablets according to one of claims 10 or 11, there characterized in that the further active substance in particle form, preferably in powder, granular, extruded, pelleted, prilled, flaked or ta bletted form, is included. 13. Detergent tablets according to one of claims 1 to 12, characterized characterized in that the volume ratio of molded body to cavity is 2: 1 to 100: 1, preferably 3: 1 to 80: 1, particularly preferably 4: 1 to 50: 1 and in particular 5: 1 to 30: 1. 14. Detergent tablets according to one of claims 1 to 13, characterized characterized in that the volume ratio of that through the film and the shape body-enclosed space to the active substance contained in this space 1: 1 to 100: 1, preferably 1.1: 1 to 50: 1, particularly preferably 1.2: 1 to 25: 1 and in particular which is 1.3: 1 to 10: 1. 15. Detergent tablets according to one of claims 10 to 14, characterized characterized in that the weight ratio of molded body to that in the by the Foil and the molded body enclosed space containing active substance 1: 1 to 100: 1, preferably 2: 1 to 80: 1, particularly preferably 3: 1 to 50: 1 and in particular 4: 1 to 30: 1. 16. Detergent tablets according to one of claims 1 to 15, characterized characterized in that the area of the opening (s) of the cavity (s) 1 to 25%, preferably example 2 to 20%, particularly preferably 3 to 15% and in particular 4 to 10% of the Ge makes up the entire surface of the molded body. 17. Detergent tablets according to one of claims 10 to 16, characterized characterized in that the enclosed by the film and the molded body Active substance contained in a room dissolves faster than the basic molded body.   18. Detergent tablets according to one of claims 10 to 17, characterized characterized in that the enclosed by the film and the molded body Active substance contained in the room dissolves more slowly than the basic molded body. 19. Detergent tablets according to one of claims 1 to 18, characterized in that the base tablet has a density above 1000 kgdm ^-3 , preferably above 1025 kgdm ^-3 , particularly preferably above 1050 kgdm ^-3 and in particular above 1100 kgdm ^-3 . 20. Detergent tablets according to one of claims 1 to 19, characterized characterized in that the basic shaped body builders in amounts of 1 to 100 wt .-%, preferably from 5 to 95% by weight, particularly preferably from 10 to 90% by weight and in particular from 20 to 85% by weight, in each case based on the weight of the base molded body, contains. 21. Detergent tablets according to one of claims 1 to 20, characterized characterized in that the base molding phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (natri um- or potassium tripolyphosphate), in amounts of 20 to 80 wt .-%, preferably from 25 to 75% by weight and in particular from 30 to 70% by weight, in each case based on the weight of the base molding. 22. Detergent tablets according to one of claims 1 to 21, characterized characterized in that the base molding carbonate (s) and / or hydrogen carbonate (s), preferably alkali carbonates, particularly preferably sodium carbonate, in amounts of 5 to 50% by weight, preferably 7.5 to 40% by weight and in particular 10 to 30% by weight, each based on the weight of the base molding. 23. Detergent tablets according to one of claims 1 to 22, characterized characterized in that the base molding silicate (s), preferably alkali silicates, be particularly preferably crystalline or amorphous alkali disilicates, in amounts of 10 to 60% by weight,  preferably from 15 to 50% by weight and in particular from 20 to 40% by weight, each based on the weight of the base molding. 24. Detergent tablets according to one of claims 1 to 23, characterized characterized in that the base molding total surfactant contents below 5 wt .-%, preferably below 4% by weight, particularly preferably below 3% by weight and in particular below 2 wt .-%, each based on the weight of the Basic molded body. 25. Detergent tablets according to one of claims 1 to 24, characterized characterized in that the base molding bleach from the group of oxygen or halogen bleaching agents, in particular chlorine bleaching agents, with particular reference preference for sodium perborate and sodium percarbonate, in amounts of 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. 26. Detergent tablets according to one of claims 1 to 25, characterized characterized in that the base molding bleach activators from the groups of multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), the N-acylimides, especially N-nonanoylsuccinimide (NOSI), the acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso- NOBS) and n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), in amounts of 0.25 to 15% by weight, preferably from 0.5 to 10% by weight and in particular from 1 to 5 wt .-%, each based on the weight of the base molding, contains. 27. Detergent tablets according to one of claims 1 to 26, characterized characterized in that the base molding silver protection agent from the group of the tria zoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotria zoles and the transition metal salts or complexes, particularly preferably benzotriazole and / or alkylaminotriazole, in amounts of 0.01 to 5% by weight, preferably 0.05 up to 4 wt .-% and in particular from 0.5 to 3 wt .-%, each based on the Ge importance of the base molding.   28. Detergent tablets according to one of claims 1 to 27, characterized characterized in that the base molding continues to be one or more substances from the Groups of enzymes, corrosion inhibitors, scale inhibitors, cobuilders, color and / or fragrances in total amounts from 6 to 30% by weight, preferably from 7.5 to 25 wt .-% and in particular from 10 to 20 wt .-%, each based on the weight of the base molding. 29. Detergent tablets according to one of claims 1 to 28, characterized characterized in that the enclosed by the film and the molded body Active substance containing space at least one active substance from the group of En zymes, surfactants, soil-release polymers, disintegration aids, bleach, bleach activators, bleaching catalysts, silver preservatives and mixtures thereof. 30. Detergent tablets according to one of claims 1 to 29, characterized characterized in that the base molding or in the through the film and the Molded enclosed space containing active substance contains bleach, wäh rend the other area of the molded body contains bleach activators. 31. Detergent tablets according to one of claims 1 to 30, characterized characterized in that the base molding or in the through the film and the Molded enclosed space containing active substance contains bleach, wäh rend the other area of the molded body contains enzymes. 32. Detergent tablets according to one of claims 1 to 31, characterized characterized in that the base molding or in the through the film and the Molded enclosed space containing active substance contains bleach, wäh rend the other area of the molded body deformable mass anti-corrosion agent contains. 33. Detergent tablets according to one of claims 1 to 32, characterized characterized in that the base molding or in the through the film and the  Molded enclosed space containing active substance contains bleach, wäh rend the other area of the molded body surfactants, preferably nonionic tensi de, with particular preference for alkoxylated alcohols with 10 to 24 carbon atoms toms and 1 to 5 alkylene oxide units. 34. Detergent tablets according to one of claims 1 to 33, characterized characterized in that the base molding and in the through the film and Shaped body enclosed active substance contained the same active ingredient in contain different amounts. 35. Detergent tablets according to one of claims 1 to 34, characterized characterized in that the film which closes the cavity has a thickness of 1 to 150 µm, preferably from 2 to 100 µm, particularly preferably from 5 to 75 µm, and in particular special from 10 to 50 microns. 36. Detergent tablets according to one of claims 12 to 35, characterized characterized in that the enclosed by the film and the molded body Active substance contained in the room Particle sizes between 100 and 5000 µm, preferred as between 150 and 2500 microns, particularly preferably between 200 and 2000 microns and in particular between 400 and 1600 microns. 37. Detergent tablets according to one of claims 12 to 36, characterized in that the active substance contained in the space enclosed by the film and the molded article comprises particles which consist of

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

consist. 38. Detergent tablets according to claim 37, characterized in that as the coating substance paraffin (s) or polyalkylene glycols, especially polyethylene lenglycole are contained in the particles. 39. Detergent tablets according to one of claims 37 or 38, there characterized in that the enclosed in the film and the molded body Active substance particles contained in its space as active substances non-ionic ten sid (s) and / or bleaching agents and / or bleach activators and / or enzyme (s) and / or Contain corrosion inhibitors and / or fragrances. 40. Shaped detergent and cleaning product according to one of claims 12 to 36, characterized in that the active substance contained in the space enclosed by the film and the shaped body comprises particles consisting of

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

consist. 41. Process for the production of detergent tablets characterized by the steps

• a) pressing a particulate premix into a pressed part (base molding) which has at least one cavity,
• b) optional filling of one or more active substances in liquid, gel, paste or solid form into the cavity (s) in question,
• c) optional application of one or more adhesion promoters to one or more surfaces of the shaped body
• d) sealing the openings of the (filled) cavities with a film
• e) optional post-treatment of individual molded body surfaces or the entire molded body.

42. The method according to claim 41, characterized in that the particulate pre mixture in step a) a bulk density of at least 500 g / l, preferably at least at least 600 g / l and in particular at least 700 g / l. 43. The method according to any one of claims 41 or 42, characterized in that the particulate premix in step a) particle sizes between 100 and 2000 μm, preferably between 200 and 1800 μm, particularly preferably between 400 and 1600 µm and in particular between 600 and 1400 µm. 44. The method according to any one of claims 41 to 43, characterized in that the part Chen-like composition (s) in step b) a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l points / have. 45. The method according to any one of claims 41 to 44, characterized in that the pressing in step a) at pressing pressures from 0.01 to 50 kNcm ^-2 , preferably from 0.1 to 40 kNcm ^-2 and in particular from 1 to 25 kNcm ^-2 takes place. 46. The method according to any one of claims 41 to 45, characterized in that the Post-treatment in step e) in the application of a coating layer on the entire Shaped body consists. 47. Combination of (a) detergent tablet (s) according to one of claims 1 to 40 and a packaging system containing the detergent tablet or tablets, characterized in that the packaging system has a moisture vapor permeability rate of 0.1 g / m ² / Day to less than 20 g / m ² / day if the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%. 48. Cleaning process for cleaning dishes in a dishwasher, because characterized in that one or more detergents and cleaning agents Shaped body according to one of claims 1 to 40 in the dosing chamber of the dishwasher inserted and a rinsing program can run, in the course of which the dosing chamber opens and the molded article (s) are dissolved. 49. Cleaning method for cleaning dishes in a dishwasher, because characterized in that one or more detergents and cleaning agents Shaped body according to one of claims 1 to 40 with or without dosing aid in the rinse insert the dishwasher and run a washing program, in the course of which the shaped body or bodies are dissolved. 50. Washing method for washing textiles in a household washing machine, there characterized in that one or more detergents and cleaning agents Shaped body according to one of claims 1 to 40 in the washing chamber of the washing machine insert machine and run a washing program, in the course of which the Shaped bodies are washed in. 51. Washing method for washing textiles in a household washing machine, there characterized in that one or more detergents and cleaning agents Shaped body according to one of claims 1 to 40 with or without dosing aid in the Insert the washing drum of the washing machine and run a washing program, in the course of which or the shaped body are dissolved.