WO2003099985A2

WO2003099985A2 - Tablet portions which can be dosed in a rinsing chamber

Info

Publication number: WO2003099985A2
Application number: PCT/EP2003/005082
Authority: WO
Inventors: Peter Schmiedel; Gerard Veldman; Thorsten Bastigkeit; Matthias Reimann; Wolfgang Barthel; Alexander Lambotte
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2002-05-24
Filing date: 2003-05-15
Publication date: 2003-12-04
Also published as: WO2003099985A3; AU2003240647A1; DE10245262A1; DE10223266C1

Abstract

Aesthetically pleasing tablets, which are not provided with a covering made of a water insoluble film, comprise a covering made a of water soluble film which is arranged close to the moulded body. The tablets contain at least one swellable disintegration agent.

Description

"Detergent dosage tablets"

The present invention is in the field of compact moldings, preferably in the field of moldings which have washing and cleaning properties. Such moldings can, for example, base materials, raw materials and / or active substances from the fields of building materials, pharmaceuticals, in particular in the field of animal health, cosmetics, agricultural products, such as feed, crop protection or fertilizers, adhesives, dyes, the food and / or the personal care products contain, but preferred are detergent tablets, for example detergent tablets for washing textiles, detergent tablets for machine dishwashing or cleaning hard surfaces, bleach tablets for use in washing machines or dishwashers, water softening tablets or stain remover tablets; these individual forms of supply are summarized below under the term "detergent or cleaning agent tablets". In particular, the invention relates to detergent tablets which are used for washing textiles in a household washing machine and are briefly referred to as detergent tablets.

Detergent tablets are widely described in the prior art and are becoming increasingly popular with consumers because of the simple dosage. Tableted detergents and cleaning agents have a number of advantages over powdered ones: They are easier to dose and handle and, thanks to their compact structure, have advantages in terms of storage and transport. Detergent tablets are therefore also comprehensively described in the patent literature. A problem that occurs again and again when using shaped articles which are active in washing and cleaning is the insufficient rate of disintegration and dissolution of the shaped articles under conditions of use. Since sufficiently stable, that is to say shape and break-resistant molded articles can only be produced by relatively high compression pressures, there is a strong compression of the molded article components and consequent delayed disintegration of the molded article in the aqueous liquor and thus to a slow release of the active substances in the washing or cleaning process. The delayed disintegration of the moldings has the further disadvantage that many detergent tablets cannot be washed in via the induction chamber of household washing machines, since the tablets do not disintegrate into secondary particles that are small enough to be washed out of the induction chamber into the washing drum to become. Another problem that arises in particular with detergent tablets is the friability of the tablets or their often insufficient stability against abrasion. Sufficiently break-resistant, ie hard, detergent tablets can be produced, but these are often not able to withstand the stresses during packaging, transport and handling, ie falling and rubbing loads, so that edge breaking and abrasion phenomena impair the appearance of the tablet or even lead to a complete destruction of the molded body structure.

To overcome the dichotomy between hardness, i.e. Transport and handling stability, and easy disintegration of the moldings, many solutions have been developed in the prior art. A particularly well-known approach from the pharmaceutical industry and extended to the field of detergent tablets is the incorporation of certain disintegration aids which facilitate the access of water or which swell or develop gas or other forms upon access of water. Other proposed solutions from the patent literature describe the compression of premixes of certain particle sizes, the separation of individual ingredients from certain other ingredients, and the coating of individual ingredients or of the entire shaped body with binders.

The disadvantage of the detergent tablets on the market is that they still have to be provided with an outer packaging which protects the ingredients from environmental influences (in particular moisture). These "flow packs" made of water-insoluble materials must be removed by the consumer before metering, which can be annoying to the consumer and cause waste. Approaches to solving this problem are coating the shaped body with water-soluble polymers or using water-soluble packaging.

A coating provides visually appealing tablets with a smooth, shiny surface and advantageous haptic properties. However, the coating of tablets technically complex and expensive. The use of water-soluble packaging is described in the prior art in the form of bags made of water-soluble film. However, tablets packed in this way can no longer be dosed via the induction chamber, since the water-soluble material prevents the access of water to the tablet and thus the disintegration of the shaped body for too long, so that the induction process is ended and the tablet remains undissolved in the induction chamber or at least larger ones Residues caused.

European patent EP 888 448 B1 discloses a detergent concentrate for the production of ready-to-use aqueous detergent solutions in detergent storage tanks of cleaning machines, in particular high-pressure cleaners, spray extraction devices or the like, which comprises a constituent which releases gas in contact with water, the detergent concentrate being packaged in portions in a water-soluble packaging , in such a way that the covering lies in close contact with the cleaning agent concentrate, the covering, however, being different from a coating applied to the cleaning agent concentrate. The gas-releasing shower system means that as soon as the detergent concentrate inside the casing comes into contact with water, i.e. when the first leak in the casing is formed, gas is released, which inflates and finally blows up the casing and thereby exposes the detergent concentrate entirely to the surrounding water. The increased gas development that occurs leads to a stirring effect, which greatly accelerates the dissolution of the water-soluble coating, but also of the other components of the concentrate. According to the teaching of this document, at least 20% by weight shower system must be used in order to achieve acceptable dissolution times in the minute range. These periods are far too long to be able to be flushed into the detergent dispenser.

The object of the present invention was to provide aesthetically appealing tablets. In particular, aesthetically appealing detergent or cleaning agent tablets should be provided, which do not have to be provided with an outer packaging made of water-insoluble film and nevertheless can be washed in via the detergent dispenser of household washing machines. The tablets should be in the Contrary to tablets in tubular bags made of water-soluble film, it can be washed in without leaving any residue.

It has now been found that a wrapping made of water-soluble film, which lies closely against the shaped body, enables it to be rinsed in via the rinsing chamber if the tablets simultaneously contain a swellable disintegration aid.

In a first embodiment, the present invention relates to a tablet comprising a water-soluble casing which lies in close contact with the tablet, the tablet containing at least one swellable disintegration aid.

In the context of the present application, “tablet” or “shaped body” are referred to as dimensionally stable, solid bodies, irrespective of the type of manufacture. Such bodies can be produced, for example, by crystallization, molding, injection molding, reactive or thermal sintering, (co) extrusion, prilling, pastilling, or compacting processes such as calendering or tableting. The production of the "tablets" or "tablets" by tableting is particularly preferred in the context of the present application. The tablet therefore preferably consists of compressed, particulate material.

Suitable swellable disintegration aids are, for example, bentonites or other swellable silicates. It is also possible to use synthetic polymers, in particular the superabsorbents or cross-linked polyvinylpyrrolidone used in the hygiene sector.

Polymers based on starch and / or cellulose are used with particular advantage as swellable disintegration aids. These basic substances can be processed alone or as a mixture with other natural and / or synthetic polymers to form swellable disintegrants.

In the simplest case, a cellulose-containing material or pure cellulose can be converted into secondary particles by granulation, compaction or other application of pressure, which swell on contact with water and thus as a disintegrant serve. Wood pulp has proven itself as a cellulose-containing material that is accessible by thermal or chemical-thermal processes from wood or wood shavings (sawdust, sawmill waste). This cellulose material from the TMP process (thermo-mechanical pulp) or the CTMP process (chemo-thermo-mechanical pulp) can then be compacted by applying pressure, preferably roller-compiled, and converted into particle form. Of course, pure cellulose can also be used completely analogously, although this is more expensive in terms of raw materials. Both microcrystalline and amorphous, finely divided cellulose and mixtures thereof can be used here.

Another way is to granulate the cellulose-containing material with the addition of granulating aids. Solutions of synthetic polymers or nonionic surfactants, for example, have proven useful as granulating aids.

In order to avoid residues on textiles washed with the agents according to the invention, the primary fiber length of the cellulose used or the cellulose in the cellulose-containing material should be less than 200 μm, primary fiber lengths less than 100 μm, in particular less than 50 μm, being preferred. The secondary particles ideally have a particle size distribution in which more than 90% by weight of the particles have sizes above 200 μm. A certain amount of dust can contribute to an improved storage stability of the tablets produced with it. Fractions of a fine dust fraction of less than 0.1 mm up to 10% by weight, preferably up to 8% by weight, can be present in the disintegrant granules used according to the invention.

The finely divided cellulose preferably has bulk densities from 40 g / l to 300 g / l, very particularly preferably from 65 g / l to 170 g / l. If already granulated types are used, their bulk density is higher and, in an advantageous embodiment, can be from 350 g / l to 550 g / l. The bulk densities of the cellulose derivatives are typically in the range from 50 g / l to 1000 g / l, preferably in the range from 100 g / l and 800 g / l.

As already stated, cellulose-based disintegration aids can also be used which contain other active ingredients or auxiliaries in addition to cellulose. Suitable here are, for example, compressed disintegrant granules composed of 60-99% by weight of non-water-soluble, water-swellable cellulose and, if appropriate, further modified water-swellable polysaccharide derivatives, 1 - 40% by weight of at least one polymeric binder in the form of a polymer or copolymer of (meth) acrylic acid and / or its salts, and 0 - 7% by weight of at least one liquid surfactant that forms water. These disintegrants preferably have a moisture content of 2 to 8% by weight.

The proportion of cellulose in such disintegrant granules is between 60 to 99% by weight, preferably between 60 to 95% by weight. Regenerated celluloses such as viscose can also be used in these explosives. Particularly regenerated celluloses in powder form are characterized by very good water absorption. The viscose powder can be made from cut viscose fiber or by precipitation of the dissolved viscose. Low molecular weight cellulose degraded by electron beam is also suitable, for example, for producing such disintegrant granules. Furthermore, the swellable disintegration aids contained in the tablets according to the invention can contain water-swellable cellulose derivatives, such as cellulose ethers and cellulose esters and starch or starch derivatives, as well as other swellable polysaccharides and polygalactomannans, for example ionically modified celluloses and starches such as carboxymethyl-modified cellulose and starch, nonionically modified starch and alkoxylated celluloses Celluloses and starches such as hydroxypropyl and hydroxyethyl starch or hydroxypropyl and hydroxyethyl cellulose and alkyl etherified products such as methyl cellulose and mixed modified celluloses and starches from the above modifications, optionally combined with a modification which leads to crosslinking. Suitable starches are also cold-swelling starches, which are formed by mechanical or degrading reactions on the starch grain. These primarily include swelling starches from extruder and drum dryer processes as well as enzymatic, oxidizing or acid-degrading modified products. Chemically derivatized starches preferably contain substituents which are linked to the polysaccharide chains in sufficient numbers by ester and ether groups

Starches modified with ionic substituents such as carboxylate, hydroxyalkyl or phosphate groups have proven to be particularly advantageous and are therefore preferred. The use of slightly cross-linked starches has also proven itself to improve the swelling behavior. Also treated with alkaline Starches can be used because of their good cold water swellability. In an advantageous embodiment, the combination of cellulose with cellulose derivatives and / or starch and / or starch derivatives has proven itself. The proportions can vary within wide limits, based on the combination the proportion of cellulose derivatives and / or starch and / or starch derivatives is preferably 0.1 to 85% by weight, particularly preferably 5 to 50% by weight.

Polymers or copolymers of (meth) acrylic acid or mixtures of such polymers or copolymers are used as binders in preferred disintegration aid granules. The polymers are selected from the group of homopolymers of (meth) acrylic acid, from the group of copolymers with the following monomer components of ethylenically unsaturated dicarboxylic acids and / or their anhydrides and / or ethylenically unsaturated sulfonic acids and / or acrylic esters and / or vinyl esters and / or vinyl ethers or their saponification products and / or crosslinking agents and / or graft bases based on polyhydroxy compounds.

Uncrosslinked polymers or copolymers of (meth) acrylic acid with weight average molecular weights of 5,000 to 70,000 have proven to be particularly suitable. The copolymers are preferably copolymers of (meth) acrylic acid and ethylenically unsaturated dicarboxylic acids or their anhydrides, such as maleic acid or maleic anhydride, which contain, for example, 40 to 90% by weight of (meth) acrylic acid and 60 to 10% by weight of maleic acid or Contain maleic anhydride whose relative molar mass, based on free acids, is between 3,000 and 100,000, preferably 3,000 to 70,000 and very particularly preferably 5,000 to 50,000. Also suitable as binders have been ter- and quattropolymeric polycarboxylates, built up from (meth) acrylic acid, maleic acid and optionally fully or partially saponified vinyl alcohol derivatives, or from (meth) acrylic acid, ethylenically unsaturated sulfonic acids and polyhydroxy units, such as sugar derivatives, or from (Meth) acrylic acid, maleic acid, vinyl alcohol derivatives and sulfonic acid group-containing monomers.

The polymeric binders are preferably used in the production in the form of their aqueous solutions, but can also be used in the form of finely divided powders. The binder polymers are preferably in partially or fully neutralized form, the salt formation preferably takes place with cations of alkali metals, ammonia and amines, or mixtures thereof.

The proportion of the polymers / copolymers in preferred disintegrants is between 1 and 40% by weight, preferably between 1 and 20% by weight, particularly preferably between 5 and 15% by weight. Polymer contents above 15% in the disintegrant lead to harder disintegrant granules, while polymer contents below 1% tend to form soft granules which are less resistant to abrasion.

Suitable polymer binders are also crosslinked polymers made from (meth) acrylic acid. They are preferably used as finely divided powders and preferably have average particle sizes of 0.045 mm to 0.150 mm and are preferably used at 0.1 to 10% by weight. Particles with average particle sizes of more than 0.150 mm also result in good disintegrant granules, but after dissolving the tablets produced with the granules, they lead to swelling bodies which are visually visible as particles and, for example in the case of textile washes, are deposited in a clearly visible manner on the textile material in a disruptive manner. A special embodiment of the invention is the combination of soluble poly (meth) acrylate homopolymers and copolymers and the aforementioned finely divided crosslinked polymer particles.

As a further component, preferably used disintegrant granules contain one or more liquid, gel-forming surfactants selected from the group of nonionic, anionic or amphoteric surfactants, which are present in amounts of up to 7% by weight, preferably up to 3.5% by weight can. If the surfactant content in the disintegrant is too high, this results in increased abrasion of the tablets produced with it and poorer swelling properties.

The nonionic surfactants are described in detail below.

Disintegration aids preferably used according to the invention are notable for their particular swelling kinetics, the expansion not changing linearly as a function of time, but already reaching a very high level after a very short time. The swelling behavior in the first 10 seconds after contact with water is of particular interest. The specific water absorption capacity disintegration aids preferably used can be determined gravimetrically and are preferably 500 to 2000%.

The liquid absorption (also referred to as specific porosity) of preferred disintegrants is in a range from over 600 ml / kg, preferably from over 750 ml / kg, in particular in the range from 800 to 1000 ml / kg.

Granulated disintegrant granules are first produced by mixing the granulate components using customary mixing methods. For example, mixers from Vomm, Lödige, Schugi, Eirich, Henschel or Fukae can be used. In this first step of mixing and granulating, pre-compounds are produced by agglomeration processes.

In the next step, these pre-compounds are mechanically compressed. Compression using pressure can be done in several ways. The products can be placed between two pressure surfaces in roller compressors, e.g. B. smooth or profiled. The compactate is ejected as a strand. Compaction methods in matrices with punches or cushion rollers result in compact forms such as tablets or briquettes. Roller compactors, extruders, roller or cube presses, but also pelletizing presses can be used as compaction machines.

Compression with pelleting presses has proven to be particularly suitable, granules which can be dried without further comminution being obtained by suitable process control. Suitable pelleting presses are e.g. manufactured by Amandus Kahl and Fitzpatrick.

The coarse, compacted particles are crushed, whereby, for example, mills, shredders or roller mills are suitable. The shredding can be carried out before or after drying. Preferred water contents of 2-8% by weight, preferably 2.5-7% by weight and particularly preferably 3-5% by weight can be set in the drying process. Conventional dryers such as drum dryers (temperatures eg from 95-120 ° C) or fluid bed dryers (temperatures eg from 70-100 ° C) are suitable for this. Also suitable as swellable disintegration aids are coprocessates which are obtained from polysaccharide material and insoluble disintegrants. The above-mentioned substances from the groups powdered cellulose, microcrystalline cellulose and mixtures thereof are particularly suitable as polysaccharide materials; Insoluble disintegrants that can be used here are, in particular, insoluble polyacrylic acid monopolymer, insoluble polyacrylamide monopolymer, insoluble polyacrylic acid-polyacrylamide copolymer and mixtures thereof.

The content of the individual components in these disintegrants can vary within wide limits, for example from 1 to 60% by weight of insoluble polyacrylic product disintegrant and 40 to 99% by weight of cellulose. A content of 3 to 60% by weight of insoluble polyacrylic product disintegrant and 40 to 97% by weight of cellulose is preferred. A content of 5 to 30% by weight of insoluble polyacrylic product disintegrant and 70 to 95% by weight of cellulose is even more preferred. Optionally, small amounts of other disintegrants, e.g. various starches, effervescent mixtures e.g. from sodium carbonate and sodium hydrogen sulfate, etc., these amounts being offset by corresponding deductions from the amount of cellulose, i.e. be compensated.

This suitable disintegrant can be obtained by coprocessing a cellulose as defined above with an insoluble disintegrant as defined above by wet or dry compression under pressure. The term "coprocessing" is used here to dry compress e.g. between counter-rotating compacting rollers at pressures of 20-60 kN, preferably 30-50 kN, or wet compaction after the addition of water, by kneading or pressing moist plastic masses through a sieve, a perforated disc or via an extruder and then drying.

In summary, a tablet according to the invention is preferred which contains a swellable disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 1 to 8% by weight and in particular 2 to 7 wt .-%, each based on the weight of the molded body contains. The coated tablets according to the invention have a coating made of water-soluble material. This can be a single material or a blend of different materials. In preferred tablets according to the invention, the water-soluble coating comprises one or more materials from the group (optionally acetalized) polyvinyl alcohol (PVAL) and / or PVAL copolymers, polyvinyl pyrrolidone, polyethylene oxide, polyethylene glycol, gelatin, cellulose and their derivatives, in particular MC, HEC, HPC, HPMC and / or CMC, and / or copolymers and mixtures thereof. Possibly. Plasticizers known to the person skilled in the art can be added to the coatings to increase the flexibility of the material.

In the context of the present invention, polyvinyl alcohols are particularly preferred as water-soluble polymers. "Polyvinyl alcohols" (abbreviation PVAL, occasionally also PVOH) is the name for polymers of the general structure

CHo CH CHo CH -

I I

OH OH

which in small proportions (approx. 2%) also structural units of the type

contain.

Commercial polyvinyl alcohols, which are offered as white-yellowish powders or granules with degrees of polymerization in the range from approx. 100 to 2500 (molar masses from approx. 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , therefore still contain a residual content of acetyl groups. The manufacturers characterize the polyvinyl alcohols by stating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number and the solution viscosity. Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few strongly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically safe and are at least partially biodegradable. The water solubility can be reduced by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid or borax. Polyvinyl alcohol is largely impenetrable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allows water vapor to pass through.

Tablets preferred in the context of the present invention are characterized in that the water-soluble coating comprises polyvinyl alcohols and / or PVAL copolymers, the degree of hydrolysis of which is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and is in particular 82 to 88 mol%.

Polyvinyl alcohols of a certain molecular weight range are preferably used, tablets according to the invention being preferred in which the water-soluble coating comprises polyvinyl alcohols and / or PVAL copolymers, the molecular weight of which is in the range from 3,500 to 100,000 gmol ^"1 , preferably from 10,000 to 90,000 gmol ^{" 1} , particularly preferably from 12,000 to 80,000 gmol ^"1 and in particular from 13,000 to 70,000 gmol ^{" 1} .

The degree of polymerization of such preferred polyvinyl alcohols is between approximately 200 to approximately 2100, preferably between approximately 220 to approximately 1890, particularly preferably between approximately 240 to approximately 1680 and in particular between approximately 260 to approximately 1500.

Tablets preferred according to the invention are characterized in that the water-soluble coating comprises polyvinyl alcohols and / or PVAL copolymers whose average degree of polymerization is between 80 and 700, preferably between 150 and 400, particularly preferably between 180 and 300 and / or their molecular weight ratio MG (50% ) to MG (90%) is between 0.3 and 1, preferably between 0.4 and 0.8 and in particular between 0.45 and 0.6. The polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ^® (Clariant). In the present invention, particularly suitable polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88 and Mowiol ^® 8-88.

Further polyvinyl alcohols that are particularly suitable as materials for the water-soluble coating can be found in the table below:

Other polyvinyl alcohols suitable as a material for the water-soluble coating are ELVANOL ^® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX ^® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gohsenol ^® NK-05, A-300, AH-22, C-500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (trademark of Nippon Gohsei KK). ERKOL types from Wacker are also suitable.

Another preferred group of water-soluble polymers that can serve as a coating according to the invention are the polyvinylpyrrolidones. These are sold, for example, under the name Luviskol ^® (BASF). Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinones)], abbreviation PVP, are polymers of the general formula (I)

which are prepared by free-radical polymerization of 1-vinylpyrrolidone by solution or suspension polymerization using free-radical formers (peroxides, azo compounds) as initiators. The ionic polymerization of the monomer only provides products with low molecular weights. Commercial polyvinylpyrrolidones have molar masses in the range from approx. 2500-750000 g / mol, which are characterized by the K values and, depending on the K value, have glass transition temperatures of 130-175 °. They are presented as white, hygroscopic powders or as aqueous ones. Solutions offered. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).

Also suitable are copolymers of vinylpyrrolidone with other monomers, in particular vinylpyrrolidone / Vinylester copolymers, as are marketed, for example under the trademark Luviskol ^® (BASF). Luviskol ^® VA 64 and Luviskol ^® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred nonionic polymers.

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

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, bulk polymerization). Copolymers of vinyl acetate with vinyl pyrrolidone contain monomer units of the formulas (I) and (II)

Other suitable water-soluble polymers are the polyethylene glycols (polyethylene oxides), which are briefly referred to as PEG. PEG are polymers of ethylene glycol which have the general formula (III)

H- (O-CH ₂ -CH ₂ ) _n -OH (III)

are sufficient, where n can have values between 5 and> 100,000.

PEGs are manufactured industrially by anionic ring opening polymerization of ethylene oxide (oxirane), usually in the presence of small amounts of water. Depending on how the reaction is carried out, they have molar masses in the range from approx. 200-5,000,000 g / mol, corresponding to degrees of polymerization from approx.

The products with molar masses <approx. 25,000 g / mol are liquid at room temperature and are referred to as the actual polyethylene glycols, abbreviation PEG. These short chain PEGs can in particular be other water soluble polymers e.g. Polyvinyl alcohols or cellulose ethers can be added as plasticizers. The polyethylene glycols which can be used according to the invention and are solid at room temperature are referred to as polyethylene oxides, abbreviation PEOX. High molecular weight polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and therefore only show weak glycol properties.

According to the invention, gelatin is also suitable as a water-soluble coating material, which is preferably used together with other polymers. Gelatin is a polypeptide (molecular weight: approx. 15,000 to> 250,000 g / mol), which is primarily obtained by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions. The amino acid composition of the gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance. The use of gelatin as Water-soluble casing material is extremely widespread, especially in the pharmaceutical industry in the form of hard or soft gelatin capsules. In the form of films, gelatin is used only to a minor extent because of its high price in comparison to the abovementioned polymers.

Further water-soluble polymers suitable according to the invention as a coating are described below:

Cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and methylhydroxypropyl cellulose, as sold for example under the trademark Culminal® ^® and Benecel ^® (AQUALON). Cellulose ethers can be described by the general formula (IV)

in R represents H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products at least one R in formula (III) is -CH ₂ CH ₂ CH ₂ -OH or -CH ₂ CH ₂ -OH. Cellulose ethers are produced industrially by etherification of alkali cellulose (eg with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of the cellulose have reacted with the etherification reagent or how many moles of the etherification reagent have been attached to an anhydroglucose unit on average. Hydroxyethyl celluloses are soluble in water from a DS of approx. 0.6 or an MS of approx. 1. Commercially available 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 and hot water and in some (water-containing) organic solvents, but insoluble in most (water-free) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition.

Preferred tablets according to the invention are characterized in that the water-soluble coating comprises hydroxypropylmethyl cellulose (HPMC), which has a degree of substitution (average number of methoxy groups per anhydroglucose unit of the cellulose) from 1.0 to 2.0, preferably from 1.4 to 1.9 , and has a molar substitution (average number of hydroxypropoxyl groups per anhydroglucose unit of cellulose) from 0.1 to 0.3, preferably from 0.15 to 0.25.

Other polymers suitable according to the invention are water-soluble amphopolymers. Ampho-polymers include amphoteric polymers, ie polymers that contain free amino groups as well as free -COOH or SO ₃ H groups in the molecule and are capable of forming internal salts, zwitterionic polymers that contain quaternary ammonium groups and - COO ^" - or -SO ₃ ^" groups, and summarized such polymers that contain -COOH or SO ₃ H groups and quaternary ammonium groups. An example of the present invention amphopolymer suitable is that available under the name Amphomer ^® acrylic resin which is a copolymer of tert-butylaminoethyl methacrylate, N- (1, 1, 3,3-tetramethylbutyl) -acrylamide and two or more monomers from the group of acrylic acid, Methacrylic acid and its simple esters. Likewise preferred amphopolymers are composed of unsaturated carboxylic acids (e.g. acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (e.g. acrylamidopropyl-trimethyl-ammonium chloride) and optionally further ionic or non-ionic monomers, as described, for example, in German Offenlegungsschrift 39 29 973 and the one cited therein State of the art can be found. Terpolymers of acrylic acid, methyl acrylate and 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 those available under the names Amphomer ^® and Amphomer ^® LV-71 (DELFT NATIONAL) octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers.

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

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

[-CH (CH ₃ ) -CH (COOH) -] _n (V)

Vinyl pyrrolidone / vinyl acrylate copolymers, available for example under the

Trademark Luviflex ^® (BASF). A preferred polymer is under

Name Luviflex ^® VBM-35 (BASF) available vinyl pyrrolidone / acrylate

Terpolymers.

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

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

Such grafted polymers of vinyl esters, esters of acrylic acid or

Methacrylic acid alone or as a mixture with other copolymerisable

Compounds on polyalkylene glycols are obtained by hot polymerization in a homogeneous phase in that the polyalkylene glycols in the

Monomers of vinyl esters, esters of acrylic acid or methacrylic acid, in

In the presence of radical formers.

Suitable vinyl esters include, for example, vinyl acetate, vinyl propionate,

Vinyl butyrate, vinyl benzoate and, as an ester of acrylic acid or methacrylic acid, those which are associated with low molecular weight aliphatic alcohols, in particular ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-1-

Propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-

Propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-

Butanol, 1-hexanol, are available, proven.

Polypropylene glycols (PPG) are polymers of propylene glycol that have the general formula VI H- (O-CH-CH ₂ ) _π -OH (VI)

I CH ₃

are sufficient, where n can have values between 1 (propylene glycol) and several thousand. Technically important are di-, tri- and

Tetrapropylene glycol, i.e. the representatives with n = 2, 3 and 4 in formula VI.

In particular, those grafted onto polyethylene glycols

Vinyl acetate copolymers and the polymers grafted onto polyethylene glycols

Vinyl acetate and crotonic acid are used. grafted and crosslinked copolymers from the copolymerization of i) at least one monomer of the nonionic type, ii) at least one monomer of the ionic type, iii) of polyethylene glycol and iv) a crosslinker

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

The non-ionic monomers can be of very different types and among these the following are preferred: vinyl acetate, vinyl stearate, vinyl laurate,

Vinyl propionate, allyl stearate, allyl laurate, diethyl maleate, allyl acetate, methyl methacrylate,

Cetyl vinyl ether, stearyl vinyl ether and 1-hexene.

The non-ionic monomers can equally be of very different

Be types, among them particularly preferred crotonic acid,

Allyloxyacetic acid, vinyl acetic acid, maleic acid, acrylic acid and methacrylic acid are contained in the graft polymers.

Preferred crosslinkers are ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallylsucrose with 2 to 5 allyl groups per molecule of saccharin.

The grafted and crosslinked copolymers described above are preferably formed from: i) 5 to 85% by weight of at least one monomer of the nonionic type, ii) 3 to 80% by weight of at least one monomer of the ionic type, iii) 2 to 50 wt .-%, preferably 5 to 30 wt .-% polyethylene glycol and iv) 0.1 to 8% by weight of a crosslinking agent, the percentage of the crosslinking agent being formed by the ratio of the total weights of i), ii) and iii). Copolymers obtained by copolymerizing at least one monomer from each of the following three groups: i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated

Carboxylic acids, ii) unsaturated carboxylic acids, iii) esters of long chain carboxylic acids and unsaturated alcohols and / or esters of the carboxylic acids of group ii) with saturated or unsaturated, linear or branched C ₈ ι ₈ alcohol, short-chain carboxylic acids or alcohols are those to understand with 1 to 8 carbon atoms, where the carbon chains of these compounds may optionally 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 VII:

R ¹ R ³

I I

R ² -CC (O) -O-CH ₂ - C = CH ₂ (VII)

I CH ₃

wherein R ^{3 is} -H or -CH ₃ , R ^{2 is} -CH ₃ or -CH (CH ₃ ) ₂ and R ^{1 is} -CH ₃ or a saturated straight-chain or branched C _1-6 alkyl radical and the sum of the carbon atoms in the radicals R ¹ and R ^{2 is} preferably 7, 6, 5, 4, 3 or 2. The above-mentioned terpolymers preferably result from the copolymerization of 7 to 12% by weight of crotonic acid, 65 to 86% by weight, preferably 71 to 83% by weight of vinyl acetate and 8 to 20% by weight, preferably 10 to 17% by weight .-% Allyl- or Methallyletsre of formula VII. Tetra and pentapolymers i) crotonic acid or allyloxyacetic acid ii) vinyl acetate or vinyl propionate iii) branched allyl or methallyl esters iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters

Crotonic acid copolymers with one or more monomers from the group

Ethylene, vinylbenzene, vinymethyl ether, acrylamide and their water-soluble salts

Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the D position.

Other polymers which can preferably be used according to the invention as a coating are cationic polymers. The permanent cationic polymers are preferred among the cationic polymers. According to the invention, "permanently cationic" means those polymers which have a cationic group irrespective of the pH. These are generally polymers which contain a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic polymers are, for example, quaternized cellulose Derivatives as commercially available under the names Celquat ^® and Polymer JR ^® The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives.

Polysiloxanes with quaternary groups, such as the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silylamodimethicon), Dow Corning ^® 929 Emulsion (containing a hydroxylamino-modified silicone which is also known as 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, such as in particular the products marketed under the trade names Cosmedia ^® Guar and Jaguar ^® ,

Polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) commercially available products are examples of such cationic polymers. Copolymers of vinyl pyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, such as, for example, vinyl pyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat ^® 734 and Gafquat ^® 755.

Vinylpyrrolidone methoimidazolinium chloride copolymers such as those sold under the name Luviquat ^®, quaternized polyvinyl alcohol, as well as those known under the designations Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 polymers having quaternary nitrogen atoms in the polymer main chain. The polymers mentioned 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 becomes.

Cationic polymers preferred according to the invention are quaternized cellulose derivatives and polymeric dimethyldiallylammonium salts and their copolymers. Cationic cellulose derivatives, in particular the commercial product Polymer ^® JR 400, are very particularly preferred cationic polymers.

In addition to the water-soluble polymer or the water-soluble polymers, the coating of the tablets according to the invention can contain further ingredients which in particular improve the processability of the starting materials for the coating. Plasticizers and release agents are particularly worth mentioning here. In addition, dyes and / or fragrances and optical brighteners can be incorporated into the water-soluble coating in order to achieve aesthetic effects there.

According to the invention, in particular hydrophilic, high-boiling liquids can be used as plasticizers, it being possible, if appropriate, to use solids as a solution, dispersion or melt at room temperature. Particularly preferred plasticizers come from the group consisting of glycol, di-, tri-, tetra-, penta-, hexa-, hepta-, Octa-, nona-, deca-, undeca-, dodecaethylene glycol, glycerin, neopentyl glycol, trimethylolpropane, pentaerythritol, mono-, di-, triglycerides, surfactants, especially non-ionic surfactants, and mixtures thereof.

Ethylene glycol (1, 2-ethanediol, "glycol") is a colorless, viscous, sweet-tasting, highly hygroscopic liquid that is miscible with water, alcohols and acetone and has a density of 1, 113. The solidification point of ethylene glycol is - 11.5 ° C, the liquid boils at 198 ° C. Technically, ethylene glycol is obtained from ethylene oxide by heating with water under pressure, and promising manufacturing processes can also be based on the acetoxylation of ethylene and subsequent hydrolysis or on synthesis gas reactions.

Diethylene glycol (2,2'-oxydiethanol, digol), HO- (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -OH, is a colorless, viscous, hygroscopic, sweet-tasting liquid, density 1, 12, which at - 6 ° C melts and boils at 245 ° C. Diglycol is miscible in any ratio with water, alcohols, glycol ether, ketones, esters, chloroform, but not with hydrocarbons and oils. The diethylene glycol, usually called diglycol in practice, is made from ethylene oxide and ethylene glycol (ethoxylation) and is thus practically the starting link for the polyethylene glycols (see above).

Glycerin is a colorless, clear, difficult to move, odorless, sweet-tasting hygroscopic liquid with a density of 1, 261 that solidifies at 18.2 ° C. Glycerin was originally only a by-product of fat saponification, but is now technically synthesized in large quantities. Most technical processes are based on propene, which is processed into glycerol via the intermediate stages allyl chloride, epichlorohydrin. Another technical process is the hydroxylation of allyl alcohol with hydrogen peroxide at the WO ₃ contact via the glycide stage.

Trimethylolpropane [TMP, Et ol, Ettriol, 1, 1, 1-tris (hydroxymethyl) propane] is chemically exactly designated 2-ethyl-2-hydroxymethyl-1, 3-propanediol and comes in the form of colorless, hygroscopic masses with a melting point of 57-59 ° C and a boiling point of 160 ° C (7 hPa) in the trade. It is soluble in water, alcohol, acetone, but insoluble in aliphatic and aromatic hydrocarbons. It is produced by reacting formaldehyde with butyraldehyde in the presence of alkalis. Pentaerythritol [2,2-bis (hydroxymethyl) -1, 3-propanediol, penta, PE] is a white, crystalline powder with a sweet taste that is not hygroscopic and flammable and has a density of 1,399 and a melting point of 262 ° C and a boiling point of 276 ° C (40 hPa). Pentaerythritol is readily soluble in boiling water, slightly soluble in alcohol and insoluble in benzene, carbon tetrachloride, ether, petroleum ether. Technically, pentaerythritol is prepared by reacting formaldehyde with acetaldehyde in an aqueous solution of Ca (OH) ₂ or NaOH at 15-45 ° C. First, a mixed aldol reaction takes place, in which formaldehyde reacts as the carbonyl component and acetaldehyde as the methylene component. Due to the high carbonyl activity of formaldehyde, the reaction of acetaldehyde with itself almost does not occur. Finally, the tris (hydroxymethyl) acetaldehyde thus formed is converted into pentaerythritol and formate in a crossed Cannizzaro reaction with formaldehyde.

Mono-, di- and triglycerides are esters of fatty acids, preferably longer-chain fatty acids with glycerol, one, two or three OH groups of the glycerol being esterified, depending on the type of glyceride. Examples of suitable acid components with which the glycerol can be esterified in mono-, di- or triglycerides which can be used as plasticizers are hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid etc. In the context of the present compound, preference is given to using fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanic acid (behenic acid), tetracosanoic acid (lignoceric acid) Hexacosanoic acid (cerotinic acid), triacotanoic acid (melissic acid) and the unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselaidic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octane acid , 12c-octadecadienoic acid (linoleic acid), 9t, 12t-octadecadienoic acid (Linolaidic acid) and 9c, 12c, 15c-octadecatreic acid (linolenic acid). For cost reasons, the native fatty substances (triglycerides) or the modified native fatty substances (partially hydrolyzed fats and oils) can also be used directly. Alternatively, fatty acid mixtures can also be prepared by cleaving native fats and oils and then separated are, the purified fractions are later converted to mono-, di- or triglycerides. Acids are esterified with the Glacerin here, coconut oil fatty acid (in particular, about 6 wt .-% C _8, 6 wt .-% C ₁₀ 48 wt .-% C ₁₂ 18 wt .-% C _14, 10 percent .-% C _16, 2 wt .-% _C18, 8 wt .-% C ₁₈ - 1 wt .-% C _18), palm kernel oil fatty acid (about 4 wt .-% C _8, 5 wt .-% C _10, 50 wt .-% _C12, 15 wt .-% C _1, 7 wt .-% C _16, 2 wt .-% Cι _8, 15 wt .-% C ₁₈ - 1 wt .-% C ₁₈ ), Tallow fatty acid (approx. 3 wt.% C ₁₄ , 26 wt.% C ₁₆ , 2 wt.% C ₁₆ -, 2 wt.% C ₇ , 17 wt.% C ₁₈ , 44 wt. -% C ₁₈ -, 3% by weight C ₁₈ -, 1% by weight C ₁₈ ), hardened tallow fatty acid (approx. 2% by weight C ₁₄ , 28% by weight C ₁₆ , 2% by weight C _17, 63 wt .-% C _18: 1 wt .-% C _18), technical grade oleic acid (about 1 wt .-% C _12, 3 wt .-% C _14, 5 wt .-% C _16, 6 % C ₁₆ -, 1% C ₁₇ , 2% C ₁₈ , 70% C ₁₈ -, 10% C ₁₈ -, 0.5% C ₁₈ ^•••), technical palmitic / stearic acid (about 1 wt .-% C _12, 2 wt .-% C _1, 45 wt .-% C _16, 2 wt .-% C ₁₇ 47 wt .-% C ₁₈ , 1% by weight C ₁₈ ) and soybean oil oleic acid (approx. 2% by weight C ₁ , 15% by weight C ₁₆ , 5% by weight C ₁₈ , 25% by weight Cι ₈ -, 45% by weight C ₁₈ -, 7% by weight % C ₁₈ -) -

Surfactants, in particular nonionic surfactants, are also suitable as further plasticizers. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. Alcohols with 3 EO or 4 EO, C _9-1 ι alcohol containing 7 EO, C ₁₃ .ι ₅ alcohols containing 3 EO, 5 EO, 7 EO or 8 EO - Preferred ethoxylated alcohols include, for example, C _12- ι , Ci _∑ .iβ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12- ι alcohol with 3 EO and C ₁₂ .ι ₈ alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. It is particularly preferred to use nonionic surfactants which have a melting point above room temperature as plasticizers. Accordingly, preferred coatings are characterized in that non-ionic surfactant (s) with a melting point above 20 ° C., preferably above 25 ° C., particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43, are used as plasticizers , 3 ° C, can be used.

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

Preferred nonionic surfactants to be used at room temperature originate from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols, and mixtures of these surfactants with structurally more complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.

In a preferred embodiment of the present invention, the nonionic surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has resulted.

A particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C _16th ₂₀ alcohol), preferably a C ₁₈ alcohol and at least 12 mole, preferably at least 15 mol and recovered in particular at least 20 moles of ethylene oxide , Among these, the so-called "narrow ranks ethoxylates" (see above) are particularly preferred. Accordingly, is / are particularly preferred in methods of the invention ethoxylated (s) nonionic surfactant (s) employed, the / from C _6-2 o-monohydroxy alkanols or C _6- ₂₀ -alkylphenols or Cι. ₆ ₂ o-fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.

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

Other nonionic surfactants with melting points above room temperature that are particularly preferably used contain 40 to 70% of one

Polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blends containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Further preferred nonionic surfactants satisfy the formula

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

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, if x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which 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 ² and R ^{3 are} as defined above and x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ² Have 9 to 14 carbon atoms, R ³ stands for H and x assumes values from 6 to 15.

Further substances which can preferably be used as plasticizers are glycerol carbonate, propylene glycol and propylene carbonate.

Glycerol carbonate can be obtained by transesterification of ethylene carbonate or dimethyl carbonate with glycerin, ethylene glycol or methanol being obtained as by-products. Another synthetic route starts from glycidol (2,3-epoxy-1-propanol), which is converted under pressure in the presence of catalysts with CO ₂ to form glycerol carbonate. Glycerol carbonate is a clear, easily movable liquid with a density of 1, 398 ^"3 , which boils at 125-130 ° C (0.15 mbar).

There are two isomers of propylene glycol, 1, 3-propanediol and 1, 2-propanediol. 1, 3-propanediol (trimethylene glycol) is a neutral, colorless and odorless, sweet-tasting liquid with a density of 1, 0597 that solidifies at -32 ° C and boils at 214 ° C. 1,3-propanediol can be prepared from acrolein and water with subsequent catalytic hydrogenation.

Technically far more important is 1, 2-propanediol (propylene glycol), which is an oily, colorless, almost odorless liquid, density 1, 0381, which solidifies at -60 ° C and boils at 188 ° C. 1, 2-propanediol is made from propylene oxide by adding water.

Propylene carbonate is a water-bright, easily movable liquid with a density of 1, 21 ^"3 , the melting point is -49 ° C, the boiling point is 242 ° C. Propylene carbonate is also commercially available at 200 ° C due to the reaction of propylene oxide and CO ₂ and 80 bar accessible.

Highly disperse silicas are particularly suitable as additional additives, which are preferably in solid form at room temperature. Pyrogenic silicas such as the commercially available Aerosil ^® or precipitated silicas are available here. Especially Preferred methods according to the invention are characterized in that one or more materials from the group (preferably highly disperse) silica, dispersion powder, high molecular weight polyglycols, stearic acid and / or stearic acid salts, and / or from the group of inorganic salts such as sodium sulfate, calcium chloride and / or or from the group of inclusion formers such as urea, cyclodextrin and / or from the group of superadsorbers such as (preferably crosslinked) polyacrylic acid and / or their salts such as Cabloc 5066 / CTF and mixtures thereof.

The water-soluble coverings can also contain disintegrants which accelerate the disintegration of the film due to their swelling. In addition, these substances can perform a “wicking function” which accelerates penetration of the coating upon contact with water and thus swelling of the swellable disintegrant contained in the tablet.

The water-soluble covering can be obtained from the above-mentioned materials or their mixtures by injection molding or blow molding. The casting can take place both from the melt and from a solution with subsequent drying. Other methods for shaping plastics processing are also suitable. For reasons of process economy, however, it is preferred that the water-soluble coating of the tablets according to the invention is formed from a film material whose thickness is 10 to 100 μm, preferably 20 to 75 μm and in particular 30 to 50 μm.

The cover is in close contact with the tablet, but the cover is different from a coating applied to the tablet. The content of the tablet in swellable disintegration aid means that, as soon as the tablet inside the casing comes into contact with water, ie when the first leak in the casing is formed or when it is merely moistened, the tablet expands, the casing bursting and the tablet is completely exposed to the surrounding water. This effect is so fast that the subsequent flushing in through the flushing chamber is not hindered, which enables residue-free flushing. For the coated tablets according to the invention it is important that the coating lies tightly against the surface of the tablets at every point. Ideally, the casing is even under tension, but this is not absolutely necessary. This tight fit of the covering is conducive to disintegration: the first time it comes into contact with water, the covering will let a small amount of water through at some point, although it does not need to dissolve at first. At this point, the disintegrant contained in the tablet begins to swell. This leads to the casing suddenly tearing open as a result of the increase in volume of the tablet and releasing the tablet. The mechanism described here will not work if the wrapper is not snug because the tablet can swell without the wrapper being blown up. The use of a swellable disintegration agent is superior to a gas-generating system, since its explosive effect in any case leads to the casing being torn open. In a gas-generating system, the explosive effect can "fizzle out" by the gas escaping from a leak in the casing.

Preferred tablets according to the invention are characterized in that the distance between the tablet and the water-soluble coating over the entire surface of the tablet is 0.1 to 1000 μm, preferably 0.5 to 500 μm, particularly preferably 1 to 250 μm and in particular 2.5 to 100 μm , is.

In a preferred embodiment, the film wrapping is first loosely placed around a tablet and welded and then shrunk onto the tablet, so that there is close contact between the film packaging and the detergent concentrate. Accordingly, tablets according to the invention are characterized in that the covering is a film packaging shrunk onto the tablet.

As mentioned at the beginning, the tablets according to the invention can contain raw materials, raw materials and / or active substances from the fields of building materials, pharmaceuticals, in particular in the field of animal health, cosmetics, agricultural products, such as feed, crop protection agents or fertilizers, and adhesives containing dyes, foods and / or personal care products. However, preference is given to those tablets which, in addition to the swellable disintegration aid, contain further customary constituents of washing or cleaning agents, which are briefly described below become. Although it is also possible to incorporate so-called effervescent systems into these washing or cleaning agent tablets preferred according to the invention, it has been shown that these systems have a rather disruptive effect on the ability to be flushed in, in particular of washing or cleaning agent tablets, and are not very effective for the reason described above are, so that preferred tablets according to the invention are free of gas-developing effervescent systems.

The washing or cleaning agent tablets preferred according to the invention preferably contain surfactant (s), it being possible to use anionic, nonionic, cationic and / or amphoteric surfactants. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants for textile detergents, the proportion of anionic surfactants being greater than the proportion of nonionic surfactants. The total surfactant content of the washing or cleaning agent tablets is preferably below 30% by weight, based on the total agent. Nonionic surfactants have already been described above as optional plasticizers for the coating. The same substances can also be used as washing-active substances in the tablets.

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

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester.

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

Other suitable surfactants are polyhydroxy fatty acid amides of the formula VIII below,

R

I R-CO-N- [Z] VIII

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

The group of polyhydroxy fatty acid amides also includes compounds of the formula IX below,

R ¹ -OR ²

I R-CO-N- [Z] IX

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, or phenyl radicals are preferred and [Z] stands for a linear polyhydroxyalkyl radical whose alkyl chain has at least two Hydroxyl groups is substituted, or alkoxylated, preferably ethoxylated or propylated derivatives of this radical.

[Z] is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

The content of non-ionic surfactants in detergent tablets according to the invention which are suitable for laundry washing is 5 to 20% by weight, preferably 7 to 15% by weight and in particular 9 to 14% by weight, in each case based on the total agent.

Low-foaming nonionic surfactants are preferably used in automatic dishwashing detergents.

In connection with the surfactants mentioned, anionic, cationic and / or amphoteric surfactants can also be used, these being of only minor importance because of their foaming behavior in automatic dishwashing detergents and mostly only in amounts below 10% by weight, mostly even below 5% by weight .-%, for example from 0.01 to 2.5 wt .-%, each based on the agent. In contrast, these surfactants are of significantly greater importance in detergents. The detergent or cleaning agent tablets according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as the surfactant component.

The agents according to the invention can contain, for example, cationic compounds of the formulas X, XI or XII as cationic active substances: R ¹

I

R ¹ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (X)

I

(CH ₂ ) _n -TR ²

R ¹

R ¹ -N ^{l +)} - (CH ₂ ) _n -CH-CH ₂ (XI)

R ¹ TT

R ¹

I

R ³ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (XII)

wherein each group R ^{1 is} independently selected from _-6 alkyl, alkenyl or hydroxyalkyl groups; each group R ² is independently selected from C _{_8-28} alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n - TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

The anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C _2-0 ₈ monoolefins with an end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products, in Consideration. Also suitable are alkanesulfonates, which are for example obtained from _2- Cι ι ₈ alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

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

The alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty 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, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₂ -C ₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₄ -C ₁₅ alkyl sulfates are preferred for washing technology reasons. In addition, 2,3-alkyl sulfates, which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ n 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 especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ -β fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

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

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

The content of anionic surfactants in preferred textile detergents according to the invention is 5 to 25% by weight, preferably 7 to 22% by weight and in particular 10 to 20% by weight, in each case based on the total composition.

In the context of the present invention, preferred agents additionally contain one or more substances from the group of builders, bleaching agents, bleach activators, enzymes, electrolytes, non-aqueous solvents, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, graying inhibitors, run-in preventers, Anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, phobing and impregnating agents, swelling and anti-slip agents as well as UV absorbers.

The builders that can be contained in the agents according to the invention include, in particular, phosphates, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.

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

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

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

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gladly ^"3 , water loss at 95 °), 7 mol. (Density 1, 68 gladly ^{" 3} , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1, 52 like ^"3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to diphosphate Na P ₂ O ₇ when heated. Disodium hydrogenphosphate is used by neutralizing phosphoric acid with soda solution produced by 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 like dodecahydrate have a density of 1.62 ^"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 ), a density of 2.536 ^{″ 3} . Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ PO, is a white, deliquescent, granular powder with a density of 2.56 ^"3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It occurs, for example, when heated of Thomas slag with coal and potassium sulfate Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na P ₂ O ₇ , exists in anhydrous form (density 2.534 like ^"3 , melting point 988 °, also given 880 °) and as decahydrate (density 1, 815-1, 836 like ^{" 3} , melting point 94 ° under water loss). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na P ₂ O ₇ is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ^ O _? , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 ^"3 , which is soluble in water, the pH of the 1% solution at 25 ° being 10.4.

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

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O. -Na with n = 3. Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁ 0 (potassium tripolyphosphate), a 50 wt .-% is used for example in the form of solution (> 23% P ₂ O _5, 25% K ₂ O) in the trade. 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 can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of Potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x +} ι H ₂ O, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. 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 ß- and δ-

Sodium disilicates Na ₂ Si ₂ O ₅ yH ₂ O preferred.

Amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more 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 as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates also have a delay in dissolution compared to conventional water glasses. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

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 are also suitable Mixtures of A, X and / or P. Commercially available and preferably used in the context of the present invention is, for example, a co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X), which is available from CONDEA Augusta SpA is sold under the brand name VEGOBOND AX ^® and through the formula

nNa ₂ O ^• (1-n) K ₂ O ^■ AI ₂ O ₃ ^■ (2 - 2.5) SiO ₂ ^• (3.5 - 5.5) H ₂ O

can be described. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups , -C ₂ -C ₁ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Other important builders are in particular the carbonates, citrates and silicates. Trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate builders from the class of disilicates and / or metasilicates are preferably used.

Alkali carriers can be present as further constituents. Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates,

Alkali metal sesquicarbonates, alkali silicates, alkali metasilicates, and mixtures of the abovementioned substances, the alkali metal carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, preferably being used for the purposes of this invention.

A builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred.

A builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred. In addition, other ingredients may be present, washing, rinsing or cleaning agents according to the invention being preferred which additionally contain one or more substances from the group of the acidifying agents, chelate complexing agents or the deposit-inhibiting polymers.

Both inorganic acids and organic acids are suitable as acidifiers, provided they are compatible with the other ingredients. For reasons of consumer protection and handling safety, the solid mono-, oligo- and polycarboxylic acids in particular can be used. From this group, preference is again given to citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. The anhydrides of these acids can also be used as acidifying agents, maleic anhydride and succinic anhydride in particular being commercially available. Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight).

Another possible group of ingredients are the chelating agents. Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination point on a central atom, i. H. is at least "bidentate". In this case, normally elongated compounds are closed to form rings by complex formation via an ion. The number of ligands bound depends on the coordination number of the central ion.

Common chelate complexing agents preferred within the scope of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Complex-forming polymers, that is to say polymers which carry functional groups either in the main chain itself or laterally to it, which can act as ligands and which generally react with suitable metal atoms to form chelate complexes, can be used according to the invention. The polymer-bound ligands of the The resulting metal complexes can originate from just one macromolecule or they can belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.

Complexing groups (ligands) of conventional complex-forming polymers are iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxime, aminophosphoric acid, (cyclic) polyamino, mercapto, 1,3-dicarbonyl - And crown ether residues with z. T. very specific Activities against ions of different metals. The base polymers of many commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinyl pyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided with further ligand functionalities by polymer-analogous conversions.

In the context of the present invention, particular preference is given to detergent tablets which comprise one or more chelating agents from the groups of

(i) polycarboxylic acids in which the sum of the carboxylic and optionally

Hydroxyl groups is at least 5,

(ii) nitrogen-containing mono- or polycarboxylic acids,

(iii) geminal diphosphonic acids,

(iv) aminophosphonic acids,

(v) phosphonopolycarboxylic acids,

(vi) cyclodextrins

in amounts above 0.1% by weight, preferably above 0.5% by weight, particularly preferably above 1% by weight and in particular above 2.5% by weight, in each case based on the weight of the By means of, included. All complexing agents of the prior art can be used within the scope of the present invention. These can belong to different chemical groups. The following are preferably used individually or in a mixture:

a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, such as gluconic acid, b) nitrogen-containing mono- or polycarboxylic acids, such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, isopropynedioic acid, nitrosedioic diacetic acid, nitrosedioic diacetic acid, nitrosedioic diacetic acid, nitro-3-dio-diacetic acid, nitro-3-dio-diacetic acid, 3-nitro-dio-diacetic acid, 3-nitro-dio-diacetic acid, 3-nitro-dio-diacetic acid, and 3-nitro-dio-diacetic acid, and 3-nitro-dio-diacetic acid, and 3-nitro-dio-diacetic acid, and 3-nitro-d-dio-acetic acid, , N, N-di- (β-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid or nitrilotriacetic acid (NTA ), c) geminal diphosphonic acids such as 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), their higher homologues with up to 8 carbon atoms and derivatives thereof containing hydroxyl or amino groups, and 1-aminoethane-1, 1-diphosphonic acid, their higher Homologs with up to 8 carbon atoms as well as derivatives thereof containing hydroxyl or amino groups, d) aminophosphonic acids such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (met ethylene phosphonic acid) or nitrilotri (methylene phosphonic acid), e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1, 2,4-tricarboxylic acid and f) cyclodextrins.

In the context of this patent application, polycarboxylic acids a) are understood to mean carboxylic acids - also monocarboxylic acids - in which the sum of carboxyl and the hydroxyl groups contained in the molecule is at least 5. Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. At the alkaline pH values of the treatment solutions required according to the invention, these complexing agents are at least partially present as anions. It is immaterial whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali metal, ammonium or alkylammonium salts, in particular sodium salts, are preferred. Deposit-inhibiting polymers can also be contained in the agents according to the invention. These substances, which can have different chemical structures, originate, for example, from the groups of low molecular weight polyacrylates with molecular weights between 1000 and 20,000 daltons, polymers with molecular weights below 15,000 daltons being preferred.

Deposit-inhibiting polymers can also have cobuilder properties. Organic cobuilders which can be used in the dishwasher detergents according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.

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

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

Polymeric polycarboxylates are also suitable as builders or scale inhibitors, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol. For the purposes of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. 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 500 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights from 1000 to 10000 g / mol, and particularly preferably from 1000 to 4000 g / mol, can in turn be preferred from this group.

Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionic monomers are particularly preferably used in the agents according to the invention. The copolymers containing sulfonic acid groups are described in detail below.

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

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight. Biodegradable polymers of more than two different monomer units are also particularly preferred, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers , Further preferred copolymers are those which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Polyaspartic acids or their salts and derivatives are particularly preferred which, in addition to cobuilder properties, also have a bleach-stabilizing effect.

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

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used. The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

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

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9). Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned. In addition to the substances from the classes of substances mentioned, the agents according to the invention can contain further usual ingredients of detergents, dishwashing detergents or cleaning agents, bleaching agents, bleach activators, enzymes, silver protection agents, colorants and fragrances being particularly important. These substances are described below.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C. and below, bleach activators can be incorporated into the detergent tablets. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetyloxy and 2,5-diacetyloxy and 2,5-glycodiacetyl, ethylene glycol 2,5-dihydrofuran.

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

Particularly suitable enzymes are those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxireductases can also be used to bleach or inhibit the transfer of color. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but especially protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

The enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, approximately 0.1 to 5% by weight, preferably 0.12 to approximately 2% by weight. Detergent tablets according to the invention for machine dishwashing can contain corrosion inhibitors to protect the items to be washed or the machine, silver protection agents in particular being particularly important in the area of machine dishwashing. The known substances of the prior art can be used. In general, silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. In addition, active chlorine-containing agents are often found in cleaner formulations, which can significantly reduce the corroding of the silver surface. In chlorine-free cleaners, especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preferred here are the transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can also be used to prevent corrosion on the wash ware.

A wide number of different salts can be used as electrolytes from the group of inorganic salts. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing point of view, the use of NaCl or MgCl ₂ in the agents according to the invention is preferred. The proportion of electrolytes in the agents according to the invention is usually 0.5 to 5% by weight.

In order to bring the pH of the agents according to the invention into the desired range, the use of pH adjusting agents can be indicated. All known acids or alkalis can be used here, provided that their use is not for technical or ecological reasons or for reasons of Prohibits consumer protection. The amount of these adjusting agents usually does not exceed 5% by weight of the total formulation.

In order to improve the aesthetic impression of the agents according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity towards textile fibers in order not to dye them.

Foam inhibitors which can be used in the agents according to the invention are, for example, soaps, paraffins or silicone oils, which can optionally be applied to carrier materials. Suitable anti-redeposition agents, which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether as well as the polymers of phthalic acid and / or terephthalic acid or of their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

Optical brighteners (so-called "whiteners") can be added to the agents according to the invention in order to eliminate graying and yellowing of the treated textiles. These substances attach to the fibers and bring about a brightening and simulated bleaching effect by converting invisible ultraviolet radiation into visible longer-wave light, wherein the absorbed from sunlight ultraviolet light is radiated as pale bluish fluorescence and produces the yellow shade of the grayed or yellowed laundry pure white Suitable compounds are derived, for example, ^{^{'2,2-diamino'}} from the substance classes of the 4,4 -. stilbenedisulfonic ( flavonic), ^{4,4'-biphenylene} -Distyryl, Methylumbelliferone, coumarins, dihydroquinolinones, 1, 3-diaryl pyrazolines, naphthalimides, benzoxazole, benzisoxazole and benzimidazole systems, and the substituted heterocycles Pyrene derivatives. The optical brighteners are usually used in amounts between 0.05 and 0.3% by weight, based on the finished composition.

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

The agents according to the invention can also be provided with additional benefits. For example, color transfer inhibiting compositions, agents with an “anti-gray formula”, agents with ironing relief, agents with special fragrance release, agents with improved dirt release or prevention of re-soiling, antibacterial agents, UV protection agents, color-refreshing agents, etc. can be formulated. Some examples are explained below:

Since textile fabrics, in particular rayon, rayon, cotton and their mixtures, can be wrinkled because the individual fibers prevent bending and kinking. If pressing and squeezing across the fiber direction are sensitive, the agents according to the invention can contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters. To combat microorganisms, the agents according to the invention can contain antimicrobial agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarlylsulfonates, halogenophenols and phenol mercuric acetate, although these compounds can be dispensed with entirely in the agents according to the invention.

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

Increased wearing comfort can result from the additional use of antstatics, which are additionally added to the agents according to the invention. Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve. External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Lauryl (or stearyl) dimethylbenzylammonium chlorides are suitable as antistatic agents for textiles or as an additive to detergents, with an additional softening 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 according to the invention due to their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated. Preferred silicones are Polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. The viscosities of the preferred silicones at 25 ° C. are in the range between 100 and 100,000 centistokes, the silicones being used in amounts between 0.2 and 5% by weight, based on the total agent.

Finally, the agents according to the invention can also contain UV absorbers, which absorb onto the treated textiles and improve the light resistance of the fibers. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position. Substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid are also suitable.

The coated detergent or cleaning agent tablets according to the invention are distinguished from conventional detergent or cleaning agent tablets by a number of advantages: they have an aesthetic appearance, they have advantages in terms of handling (convenience), since no waste has to be disposed of during use, they avoid one Contact of the consumer with the active ingredients when touching the tablet, have high mechanical stability and have no abrasion or crumbs.

Another object of the present invention is a method for producing the coated detergent tablets according to the invention. For this purpose, detergent or cleaning agent tablets are first produced in a manner known per se. Crystallization, molding, injection molding, reactive or thermal sintering, (co) extrusion, prilling, pastillation, or compacting processes such as calendering or tableting are suitable as production methods for the tablets, in particular the washing or cleaning agent tablets. The preparation of the tablets by tableting is particularly preferred in the context of the present application. This tablet production is carried out first by dry mixing of the components, which can be wholly or partially pre-granulated, and then providing information, in particular pressing them into tablets, using conventional methods. To produce the tablets, the premix is compressed in a so-called die between two punches to form a solid compressed product. This process, which is briefly referred to below as tabletting, is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection.

First of all, the premix is introduced into the die, the filling quantity and thus the weight and the shape of the molding being formed being determined by the position of the lower punch and the shape of the pressing tool. The constant dosing, even at high molding throughputs, is preferably achieved by volumetric dosing of the premix. As the tableting continues, the upper punch touches the premix and lowers further towards the lower punch. With this compression, the particles of the premix are pressed closer together, the void volume within the filling between the punches continuously decreasing. From a certain position of the upper punch (and thus from a certain pressure on the premix) the plastic deformation begins, in which the particles flow together and the molded body is formed. Depending on the physical properties of the premix, some of the premix particles are also crushed and sintering of the premix occurs at even higher pressures. With increasing pressing speed, that is to say high throughput quantities, the phase of elastic deformation is shortened further and further, so that the resulting shaped bodies can have more or less large cavities. In the last step of tableting, the finished molded body is pressed out of the die by the lower punch and transported away by subsequent transport devices. At this point in time, only the weight of the molded body is finally determined, since the compacts can still change their shape and size due to physical processes (stretching, crystallographic effects, cooling, etc.). Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches. In the latter case, not only is the upper stamp used to build up pressure, the lower stamp also moves towards the upper stamp during the pressing process, while the upper stamp presses down. For small production quantities, eccentric tablet presses are preferably used, in which the stamp or stamps are attached to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed. The movement of these rams is comparable to that of a conventional four-stroke engine. The pressing can take place with one upper and one lower punch, but several punches can also be attached to one eccentric disk, the number of die holes being correspondingly increased. The throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.

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

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

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

- Use of plastic inserts with small thickness tolerances

- Low number of revolutions of the rotor

- Big filling shoes

- Matching the filler paddle speed to the speed of the rotor

- Filling shoe with constant powder height

- Decoupling of filling shoe and powder feed

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

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

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

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

The spatial shape of another embodiment of the shaped bodies is adapted in its dimensions to the induction chamber of commercially available household washing machines, so that the tablets can be dosed directly into the induction chamber without metering aid, where they dissolve during the induction process. However, it is also possible that the various components are not pressed into a uniform tablet, but that shaped bodies are obtained which have several layers, that is to say at least two layers. It is also possible that these different layers have different dissolving speeds. This can result in advantageous performance properties of the molded articles. If, for example, components are contained in the moldings which have a mutually negative effect, it is possible to integrate one component in the more rapidly soluble layer and to incorporate the other component in a more slowly soluble layer, so that the first component has already reacted. when the second goes into solution. The layer structure of the shaped bodies can be stacked, with the inner layer (s) already loosening at the edges of the shaped body when the outer layers have not yet been completely detached, but it is also possible for the inner layer (s) to be completely encased ) can be achieved by the layer (s) lying further outwards, which leads to the premature dissolution of components of the inner layer (s).

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

In addition to the layer structure, multi-phase tablets can also be produced in the form of toroidal core tablets, core-coated tablets or so-called “bulleye” tablets. An overview of such embodiments of multi-phase tablets can be found in EP 055 100 (Jeyes Group). This document discloses toilet block detergents comprising a molded body of a slowly soluble detergent composition in which a bleach tablet is embedded. At the same time, this document discloses the most varied designs of multi-phase tablets, from simple multi-phase tablets to complicated multi-layer systems with inlays.

After compression, the tablets are extremely stable. The breaking strength of cylindrical shaped bodies can be determined via the measured variable of the diametrical breaking load. This can be determined according to

2P σ - ^■ πDt

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

• The wrapping of the tablets according to the invention with a tight-fitting

Sheathing has the further advantage that the pressures can be reduced. The tight wrapping significantly improves the stability of the tablets: tablet breakage and edge breakage are prevented, the friability (abrasion tendency) is reduced to zero. This increased stability enables packaging in bulk in a secondary pack, for example a box. Since the tight wrapping makes the tablet mechanically stable, the hardness of the tablet can be reduced. This can save explosives, making the formula more compact.

Another object of the present invention is thus a process for the production with water-soluble coatings of tightly coated tablets, which by the steps a) placing a water-soluble film on a mold (s); b) inserting tablets (s) into the mold (s); c) placing another water-soluble film on the tablet (s) in the form (s); d) sealing and optional cutting of the foils is marked.

After the tablets have been produced, they are transferred into forms which the tablets can hold. The molding tools can be designed as individual units, but it is also possible and preferred for reasons of process economy to use molding tools which have a large number of shapes. A water-soluble film is placed over these molds, which is subsequently pressed into the mold by inserting the tablet (s) into the mold (s).

Alternatively, the film can be inserted into the mold by heating and / or vacuum before the tablet is inserted. Here, preferred methods are characterized in that the deformation of the water-soluble film is supported by inserting the tablet (s) in step b) by heating the film and / or applying a vacuum.

The height of the shape determines the position of the sealing seam created later. In a second step, the foil-lined or covered form is filled with a tablet. A second sheet of the film is placed over the form filled with the tablet and then stretched with a sealing tool and sealed together with the lower film.

If the tablet inserted into the mold is flush with the top of the mold, the sealing seam is formed as a "brim" on one end face of the tablet. Here, a simple plate can be used for sealing, but this has the disadvantage that the film that covers the top side the tablet covered with heat.

Alternatively, the sealing seam can also be designed so that it runs along the outer surface of the tablet. In this case, the tablet protrudes from the mold and another part of the tablet protrudes from the mold. Sealing cannot now be done with a plate-like sealing tool done, but is done with an annular tool. This method has the advantage that the lowering of the ring-shaped sealing tool additionally tightens the upper film. In addition, the heat effect on the tablet is significantly reduced compared to a "heating plate".

In summary, methods according to the invention are preferred in which the tablet (s) in step b) after insertion into the mold (s) does not end / close flush with the top of the mold, but rather protrudes / protrudes therefrom Sealing is carried out with an annular sealing tool (s) which has / have opening surface (s) through which the tablet fits.

The term “ring-shaped sealing tool” is not limited to circular “rings” in the narrower sense. Rather, this term also includes rectangular or square, oval, triangular or other, even completely irregular, shapes. The annular sealing tool only has to be adapted to the shape of the tablets to be sealed in such a way that it can be put over the tablet. Ideally, it lies close to the outer surface of the tablet.

In this variant of the method, it is aesthetically disadvantageous that the sealing seam protrudes. On the one hand, it is detrimental to the aesthetic appearance of the product, on the other hand, it could suggest to the consumer that the wrapper should be removed before the product can be used. This can be eliminated by a further process step in that it is applied to the outer surface of the tablet and sealed with an annular sealing tool.

Therefore, another embodiment does not contain a protruding sealing seam. This is either placed on the outer surface in such a way that it is not or only barely recognizable, or a method is used for inserting the tablet into the casing which does not reveal any protruding sealing seam.

A further variant of the method according to the invention for producing coverings with a seam that is not or hardly recognizable provides therefore for the sealing seam to be sealed to the outer surface of the tablet during the sealing. This preferred method is characterized in that the tablet (s) in step b) closes / closes flush with the top of the mold after being inserted into the mold (s), the tablet being raised during the sealing step d), as a result of which the sealing seam on the lateral surface of the Tablet is sealed.

Here, the top film, which is on the mold, in which the bottom film and tablet are located, is pressed onto the top of the mold with an annular sealing tool, which has been brought to the sealing temperature on its inside, the tablet is removed from the mold through the sealing tool pushed out, the sealing tool is pressed on the outside of the outer surface of the tablet and welded the top and bottom films together. This creates a barely visible seam.

Another variant of the method provides that the tablets are first packaged in water-soluble films either by the processes disclosed above or by conventional packaging methods of the prior art, and then the film packaging is shrunk onto the molded article. This shrink film is a film that has been stretched and contracts again when heated. It is possible to produce wrappings that lie very close to the surface of the tablet.

Processes which are likewise preferred according to the invention are characterized in that pre-stretched films are used as water-soluble film (s) in steps a) and c) and are shrink-fitted onto the tablet (s) in step d) or thereafter.

In addition to the aforementioned preferred embodiments, this application relates to further preferred refinements of the process according to the invention, in particular to those process variants in which the water-soluble film used is exposed to thermal effects in the course of the process.

Another preferred subject of the present application is therefore a method according to the invention for the production with water-soluble coatings of tightly coated tablets, characterized in that a water-soluble film, before being placed on a mold (s), at temperatures above 50 ° C., preferably above 70 ° C and especially above 90 ° C, is heated. The process according to the invention is facilitated and the process result is improved by heating the film before the shaping process. As an alternative to heating, or in addition to being placed on the mold (s), the film can be heated during the forming process. Another object of the present application is therefore a method according to the invention for the production with water-soluble coatings of tightly coated tablets, characterized in that the deformation of the water-soluble film by inserting the tablet (s) in step b) by heating the film to temperatures of 100 up to 120 ° C is supported.

A combination of the latter two preferred method variants is possible and preferred.

The sealing, which takes place in step d) of the method according to the invention, is preferably carried out at higher temperatures. Processes according to the invention which operate at temperatures above 100 ° C. but below 200 ° C. are preferred here. Another object of the present application is therefore a process for the production with water-soluble coatings of tightly coated tablets, in which the sealing of the film in step d) at temperatures from 140 ° C to 180 ° C, preferably from 150 ° C to 170 ° C and in particular at temperatures of 155 ° C to 165 ° C, is carried out.

It has proven to be advantageous if the film to be deformed in the mold (s) and the film with which sealing is carried out have different material thicknesses. A further preferred embodiment of the method according to the invention is therefore a method in which the water-soluble film which is shaped in the mold (s) is of a thickness from 30 to 80 μm, preferably from 35 to 70 μm and in particular from 40 to 60 μm, having.

The thickness of the sealing film is preferably less. Here, methods are preferred in which the water-soluble film which is applied in step c) has a thickness of 20 to 60 μm, preferably 25 to 50 μm and in particular 30 to 45 μm. Instead of a single-layer film, multi-layer film laminates can also be used according to the invention. Such laminates have the advantage that the individual layers can be adapted to the respective environmental conditions. For example, an inner film can be used which is inert to the composition to be filled and which does not react with the filling. An outer film, which withstands the environmental influences better, can protect the composition against external influences in such a two-film laminate. Of course, three-film laminates, four-film laminates, etc. can also be used according to the invention, wherein the individual films can be assigned different functions (mechanical stabilization, vapor barrier, optics, functionality by incorporating ingredients, etc.).

Another method for tightly wrapping tablets with water-soluble film is to use shaping rollers which have depressions into which the tablets fit. The use of form rollers enables several process variants. On the one hand, tablets can be placed and transported on a band of water-soluble film, covered with a further water-soluble film and sealed at a certain point in the apparatus with a sealing form roller. As an alternative, the second water-soluble film can also be fed in in the vicinity of the sealing molding roll.

A reverse process variant consists in applying a water-soluble film to a molding roll, feeding tablets to the film-covered molds and sealing water-soluble film fed in at another point.

The methods described above use a form roller in conjunction with a plane. Advantageously, however, two counter-rotating form rollers can also be used, the forms ideally being able to hold half a tablet each. A process carried out in this way for the production with water-soluble coatings of tightly coated tablets is characterized in that two foils made of water-soluble material are passed through a pair of opposing shaping rollers which have depressions, with a) the foils being sealed to one another by the shaping rollers at the edge of a depression ; b) a tablet is inserted between the two foils sealed to one another; c) the rollers receive the film-covered tablet in a recess and cover it with the film; d) the film-covered tablet is sealed at the other edge of the depression by the molding roll.

This method enables the production of large numbers of tablets according to the invention.

The tablets used in the processes according to the invention are preferably washing or cleaning agent tablets, that is tablets with at least one detergent or cleaning ingredient, preferably from the group of surfactants, builders, bleaching agents, bleach activators, enzymes, electrolytes, non-aqueous solvents, pH Adjusting agents, fragrances, perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents,

Color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, phobing and impregnating agents, swelling and anti-slip agents and UV absorbers.

Another object of the present invention is the use of detergent tablets according to the invention in

Household washing machines or dishwashers.

The particular advantages of the detergent or cleaning agent tablets according to the invention become apparent in particular when metered through the dispenser of household washing machines. Another object of the present invention is therefore the use of detergent tablets according to the invention as detergent tablets for detergent dispensers for household washing machines.

The mentioned and other advantages are clearly illustrated in the description of exemplary embodiments which are illustrated in the accompanying drawing. In it shows 1 shows a variant of the method according to the invention;

2 shows a variant of the method according to the invention according to claim 15.

1 a) shows a variant of the method according to the invention in a sectional side view. A film 3 was placed over a mold 1 and was pressed into the mold by inserting a tablet 2. The mold 1 filled with the film 3 and the tablet 2 is covered with a further film 3 and the films 3 are welded with the aid of a sealing tool 4 and placed closely on the tablet. The sealing tool 4 is shown in this figure as an annular sealing tool which seals only at the edges, but avoids heating of the film-covered tablet 2.

Fig. 1 b) shows a coated tablet according to the invention, with a close-fitting cover in a sectional side view, which was obtained according to the procedure described above. The sealing seam 5 runs around the outer surface of the tablet 2 and protrudes from it.

2 shows the method variant according to claim 15 in a sectional side view. In FIG. 2 a) a film 3 was placed over a mold 1, which was pressed into the mold by inserting a tablet 2. In this case, the top of the tablet 2 is flush with the shape edge.

In Fig. 2 b) the form 1 filled with the film 3 and the tablet 2 is covered with a further film 3 and the films 3 are welded with the aid of a sealing tool 4 and placed closely on the tablet. The sealing tool 4 is shown in this figure as an annular sealing tool which seals only at the edges, but avoids heating of the film-covered tablet 2.

2 c) shows that the tablet 2 is lifted out of the mold 1 during the sealing process, as a result of which the sealing seam 5 is applied to the tablet, which leads to a smooth outer surface of the tablet 2. This is shown again in a sectional side view in FIG. 2 d). LIST OF REFERENCE NUMBERS

Form tablet foil sealing tool sealing seam

Examples:

A film of hydroxypropyl methyl cellulose was produced in the following way:

• Prepare an 8% solution of MHPC 25 (Hercules) with 30% (based on MHPC) PEG 400 as a plasticizer.

• Squeegee with a 400 Dm squeegee

• Drying at 50 ° C

• Detachment from the substrate

A transparent, glossy film with a thickness of 30 dm was created.

This film was used in the examples below to wrap detergent tablets.

Example 1 :

The film obtained according to the method described above was placed over a mold and pressed with a commercial Persil ^® -Waschmitteltablette into the mold. The form filled with the film and the tablet was covered with another identically composed film and the films were welded and applied tightly to the tablet using an annular sealing tool which seals only at the edges but avoids heating of the film-covered tablet.

Similarly, using the process described above, commercially available Persil ^® tabs were provided with closely fitting films of the following types:

• Synthana PT 40, PT 30

• Hydrolene (Idroplast) LFT 30, LFT 25, LFT 40

In the following the disintegration times of these tablets with and without wrapping were determined. For this purpose, the disintegration times of 2 similar tablets after immersion in water were determined using a stopwatch. The disintegration times when immersed in water were between 10 and 20 s for the uncoated tabs. The Disintegration times of the coated tabs were between 15 s and 30 s. It can be seen that the disintegration times are only extended by the films by 5-10 s.

For comparison: a tablet that is packed in a tubular bag of the same foils requires a time of more than 1 min to disintegrate, which is too long for dosing via the induction chamber.

The tablets described were placed in the dispenser drawer of a commercially available washing machine (Miele W 918) and a normal washing program was started. All tablets washed in without residue.

Furthermore, the diametric fracture hardness of the coated and non-coated tablets was determined using a tablet hardness measuring device from Schleuniger. The hardness of the uncoated tablets was approx. 40 N, and the coating hardness increased the fracture hardness to 120 N.

Example 2:

For the same films as in Example 1 commercial Persil ^® roll-up tabs of claim 15 were wrapped according to the process variant.

The films in question were placed over a mold and pressed into the mold with a commercially available Persil ^® detergent tablet. The form filled with the film and the tablet was covered with another identically composed film and the films were welded and applied tightly to the tablet using an annular sealing tool which seals only at the edges but avoids heating of the film-covered tablet. During the sealing process, the tablet was lifted out of the mold so that the sealing seam was sealed to the outer surface of the tablet.

Claims

claims:

1. tablet, comprising a water-soluble coating which is in close contact with the tablet, characterized in that the tablet contains at least one swellable disintegration aid.

2. Tablet according to claim 1, characterized in that it is a swellable disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 1 to 8% by weight and contains in particular from 2 to 7% by weight, in each case based on the weight of the shaped body.

3. Tablet according to one of claims 1 or 2, characterized in that the water-soluble coating one or more materials from the group (optionally acetalized) polyvinyl alcohol (PVAL) and / or PVAL copolymers, polyvinylpyrrolidone, polyethylene oxide, polyethylene glycol, gelatin, cellulose and their derivatives, in particular MC, HEC, HPC, HPMC and / or CMC, and / or copolymers and mixtures thereof.

4. Tablet according to one of claims 1 to 3, characterized in that the water-soluble coating comprises polyvinyl alcohols and / or PVAL copolymers whose degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol -% and in particular 82 to 88 mol%.

5. Tablet according to one of claims 1 to 4, characterized in that the water-soluble coating comprises polyvinyl alcohols and / or PVAL copolymers, the molecular weight in the range from 3,500 to 100,000 gmol ^'1 , preferably from 10,000 to 90,000 gmol ^"1 , particularly preferred from 12,000 to 80,000 gmol ^'1 and in particular from 13,000 to 70,000 gmol ^{' 1} .

6. Tablet according to one of claims 1 to 5, characterized in that the water-soluble coating comprises polyvinyl alcohols and / or PVAL copolymers whose average degree of polymerization is between 80 and 700, preferably between 150 and 400, particularly preferably between 180 and 300 and / or whose molecular weight ratio MG (50%) to MG (90%) is between 0.3 and 1, preferably between 0.4 and 0.8 and in particular between 0.45 and 0.6.

7. Tablet according to one of claims 1 to 6, characterized in that the water-soluble coating comprises hydroxypropylmethyl cellulose (HPMC) which has a degree of substitution (average number of methoxy groups per anhydroglucose unit of cellulose) from 1.0 to 2.0, preferably from 1, 4 to 1, 9, and a molar substitution (average number of hydroxypropoxyl groups per anhydroglucose unit of the cellulose) from 0.1 to 0.3, preferably from 0.15 to 0.25.

8. Tablet according to one of claims 1 to 7, characterized in that the water-soluble coating is formed from a film material whose thickness is 10 to 100 microns, preferably 20 to 75 microns and in particular 30 to 50 microns.

9. Tablet according to one of claims 1 to 8, characterized in that the distance between the tablet and water-soluble coating over the entire surface of the tablet 0.1 to 1000 microns, preferably 0.5 to 500 microns, particularly preferably 1 to 250 microns and in particular 2.5 to 100 dm.

10. Tablet according to one of claims 1 to 9, characterized in that the covering is a film packaging shrunk onto the tablet.

11. Tablet according to one of claims 1 to 10, characterized in that it is free of gas-developing effervescent systems.

12. A process for the production with water-soluble coatings of tightly coated tablets, characterized by the steps a) placing a water-soluble film on a mold (s); b) inserting the tablet (s) into the mold (s); c) placing another water-soluble film on the tablet (s) in the form (s); d) sealing and optional cutting of the foils.

13. The method according to claim 12, characterized in that the deformation of the water-soluble film is supported by inserting the tablet (s) in step b) by heating the film and / or applying a vacuum.

14. The method according to any one of claims 12 or 13, characterized in that the tablet (s) in step b) after insertion into the mold (s) does not end / close flush with the top of the mold, but protrudes / protrudes from it ,

15. The method according to any one of claims 12 or 13, characterized in that the tablet (s) in step b) after insertion into the mold (s) ends / close flush with the top of the mold, the tablet during the sealing step d) is raised, whereby the sealing seam is sealed to the outer surface of the tablet.

16. The method according to any one of claims 12 to 15, characterized in that the sealing is carried out with (an) annular sealing tool (s) which has / have (an) opening surface (s) through which the tablet fits / - fit.

17. The method according to any one of claims 12 to 16, characterized in that pre-stretched films are used as water-soluble film (s) in steps a) and c), which films are shrunk onto the tablet (s) in step d) or thereafter ,

18. The method according to any one of claims 12 to 17, characterized in that a water-soluble film before placing on a mold (s) tool at temperatures above 50 ° C, preferably above 70 ° C and in particular above 90 ° C, is heated.

19. The method according to any one of claims 12 to 17, characterized in that the deformation of the water-soluble film is supported by inserting the tablet (s) in step b) by heating the film to temperatures of 100 to 120 ° C.

20. The method according to any one of claims 12 to 17, characterized in that the sealing of the film in step d) at temperatures from 140 ° C to 180 ° C, preferably from 150 ° C to 170 ° C and in particular at temperatures from 155 ° C to 165 ° C.

21. The method according to any one of claims 12 to 20, characterized in that the water-soluble film which is formed in the mold (s) tool, a thickness of 30 to 80 microns, preferably from 35 to 70 microns and in particular from 40 to 60 microns , having.

22. The method according to any one of claims 12 to 21, characterized in that the water-soluble film, which is placed in step c), has a thickness of 20 to 60 microns, preferably from 25 to 50 microns and in particular from 30 to 45 microns ,

23. A process for the production with water-soluble wrappings of tightly wrapped tablets, characterized in that two foils of water-soluble material are passed through a pair of opposing shaping rollers which have depressions, wherein a) the foils are sealed to one another by the shaping rollers at the edge of a depression; b) a tablet is placed between the two foils sealed together; c) the rollers take the film-covered tablet in a recess and cover it with the film; d) the film-covered tablet is sealed at the other edge of the depression by the molding roll.

24. Use of tablets according to one of claims 1 to 11 in household washing machines or dishwashers.

25. Use of tablets according to one of claims 1 to 11 as detergent tablets for household washing machines.