DE10064635A1 - Detergent tablets with delayed solubility comprise compressed particulate detergents ingredients including builder(s) and surfactant(s) - Google Patents

Abstract

Detergent tablets with delayed solubility on contact with water, comprising compressed particulate detergents ingredients including builder(s) and surfactant(s), comprise a coating that covers less than 100% of the tablet. An Independent claim is also included for a process for producing coated detergent tablets, comprising pressing particulate detergents ingredients and providing the resulting tablet with a coating that covers less than 100% of the tablet.

Description

The present invention relates to detergent tablets made of compression tetem particulate cleaning agent containing builders (e), surfactant (s) and counter if necessary, further detergent or cleaning agent components. In particular, the Invention detergent tablets which are used for washing textiles in used in a household washing machine and briefly referred to as detergent tablets become.

Detergent tablets are widely described in the prior art are becoming increasingly popular with consumers because of the simple dosage. They include, for example, detergent tablets for washing textiles, Rei Detergent tablets fit machine dishwashing or hard cleaning Surfaces, bleach tablets for use in washing machines or dishwashers, Water softening tablets or stain tablets.

Tableted detergents and cleaning agents have a number of powdered detergents Advantages: They are easier to dose and handle and because of their compact structure Advantages in storage and transport. Even in the Patentlite As a result, laundry detergent and cleaning product tablets are comprehensively described. On Problem that always occurs when using washing and cleaning active moldings occurs again, the too slow disintegration and dissolving speed of the shaped body is below Conditions of use. Because sufficiently stable, d. H. shape and break resistant shape body can only be produced by relatively high pressure, it comes  to a strong compression of the molded parts and to a consequent uncontrollable, delayed disintegration of the shaped body in the aqueous liquor and thus too slow a release of the active substances in the washing or cleaning supply operation. Another problem, especially with detergents and cleaning agents Moldings occurs, the friability of the moldings or their often insufficient Stability against abrasion and edge break. So can be sufficiently stable, d. H. hard detergent tablets are produced, but these are often the Strain on packaging, transport and handling, d. H. Fall and rubbing stress not sufficiently grown, so that edge breakage and signs of abrasion Appearance of the molded body or even to a complete destruction lead the molded structure.

To overcome the dichotomy between hardness, i. H. Transport and handling stabilizer lity, and easy disintegration of the moldings are many solutions in the prior art has been developed. A well known from the pharmacy and in the field of Detergent tablets are an extensive approach to incorporation Certain disintegration aids that facilitate the access of water or upon entry swell from water or develop gas or disintegrate in another form. Other proposed solutions from the patent literature describe the pressing of Vor Mixing certain particle sizes, the separation of individual ingredients from be agreed other ingredients as well as the coating of individual ingredients or the entire molded body with binders.

The coating of detergent tablets, also in German Language usage is increasingly referred to as "coating" is the subject of some Pa patent filings.

This is how the European patent applications EP 846 754, EP 846 755 and EP describe EP 846 756 (Procter & Gamble) coated detergent tablets which have a "core" compressed, particulate detergent and cleaning agent and a "coating" sen, dicarboxylic acids, in particular adipic acid, being used as coating materials  be, if necessary, other ingredients, such as disintegration tools included.

Coated detergent tablets are also the subject of European patent applications EP 716 144 (Unilever). According to the information in this document, the hardness of the Reinforce tablets with a "coating" without affecting the disintegration and dissolution times to be pregnant. Film-forming substances, in particular, are used as coating agents re copolymers of acrylic acid and maleic acid or sugar called.

The older German patent application DE 199 20 118.8 (Henkel) describes washing or Detergent tablets that be with certain polymers or polymer mixtures are layered, with the coating materials mentioned thin but stable Coating layers can be achieved that reflect the physical properties of the molded body improve.

There is little information on the application of the coating to all of the documents mentioned remove. Most documents lack information on the thickness of the coating layer Likewise. It is also common to all writings that the entire molded body is provided with the coating. This has the consequence that the resolution or the Zer case the molded body can only be used when the application liquor has applied the coating has at least partially dissolved or eroded. Are from the prior art Shaped bodies without a coating are known, which immediately after being mixed with water in Be have come into contact, disintegrate, and have the disadvantage that they are low Have fracture stability. The coated moldings have the disadvantage that that their rate of decay is unpredictable and it releases the content substances can come at times when these substances are not fully effective can fold.

The present invention was based on the object, coated washing and Rei Provide detergent tablets that have a defined decay and release kinetics gene, the detergent or cleaning agent components released preferably delayed be set. The decay and release kinetics should in particular use the existing ones  Techniques can be set. It is also desirable that the Bruchsta bility, especially the edge breaking stability of the molded body is maintained.

The invention therefore relates to a detergent tablet made of ver dense particulate washing or cleaning agent, containing builders, Ten sid (e) and optionally further detergent or cleaning agent components, the such is made up that it has a delayed solubility in contact with water, because characterized in that the molded body has a coating which is less than 100% of the molded body covered.

The coating applied according to the invention covers less than 100% of the molded article pers. This ensures that, on the one hand, the fracture stability, e.g. B. the edge breakage balance, can be guaranteed and at the same time the decay and release kinetics of the form body can be adjusted.

The coating that covers less than 100% of the molded body, that is a partial coating layering, for example, can have recesses (holes). This Ausspa stanchions can be designed in any way. In one possible embodiment, the Recesses evenly distributed over the molded body, so that the coating the Molded body covered like a net.

In a further embodiment, the coating has only one or a few Recesses arranged on one or more of the surfaces of the molded body are. In one possible embodiment, the coating has on the molded body only one recess, preferably on the top of the molded body. This Ausspa tion can have any geometric round or angular shape, z. B. circular mig, rectangular, square, polygonal or annular. In a wide Ren embodiment, the molded body has chamfered edges on which the Ausspa stanchions. In yet another embodiment, the cutouts are located the side surfaces.  

The coating applied according to the invention, which is less than 100% of the shaped body covered, can also serve for the optical design of the moldings. For example, NEN differently colored coatings are applied to white moldings, whereby by the type of recesses can be obtained with any optical design.

The partial coating of the detergent tablets according to the invention, sometimes referred to below as partial coating, serves to protect mecha nically sensitive areas of the molded body from excessive stress and the resulting following negative phenomena such as edge breakage. It is preferred here the surface of the moldings according to the invention that are not affected by the coating is designed to be as large as possible. Here are detergents or cleaning agents Shaped bodies preferred, in which the coating is at least 50%, preferably at least at least 75% and in particular at least 85% of the total surface of the molded body covered.

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

Regardless of the type and composition of the coating, it is preferred that To keep amounts of coating materials as low as possible. Preferably that is Weight ratio of uncoated molded body to coating greater than 10 to 1, preferably greater than 50 to 1 and in particular greater than 100 to 1.

Depending on the composition of the coating and the type of coating material The thickness of the coating varies depending on the materials used. Certain film-forming polymers  can provide mechanical protection with significantly lower layer thicknesses cause, for example, coating materials such as solidified salt melts, etc. Irrespective of the parameters mentioned are washing or cleaning agents according to the invention preferred moldings, in which the thickness of the coating 0.1 to 3000 microns, preferably 0.5 to 500 microns and in particular 5 to 250 microns.

After the general information about the coating, more specific information follows individual coating materials preferred in the context of the present invention can be used as a partial coating.

Within the scope of the present invention, numerous materials are the ingredients of the Coating suitable. For example, they come from the groups of inorganic Salts, the organic water-soluble compounds, the polymers, the carbohydrates or detergent or cleaning agent ingredients, which list is by no means is complete. Particularly preferred materials for partial coating are next described below.

For example, detergent tablets are preferred in which the Coating one or more solid substances with a water solubility of more than 200 g / l at 20 ° C.

The partial coating applied to the moldings according to the invention can thereby Made entirely from the stated solids with a water solubility of more than 200 g / l exist at 20 ° C, but it can of course also contain other ingredients. The coating materials mentioned have solubilities above 200 by themselves Grams of solubilizer in one liter of deionized water at 20 ° C as such Coating materials are suitable for a whole series in the context of the present invention of compounds consisting both of the group of covalent compounds and can come from the group of salts. As already mentioned, it is preferred if the Coating materials have even higher solubilities. An overview of the solv Peculiarities of ingredients of Par tialcoatings gives the following list. The solubility values given in this table  - unless other temperatures are explicitly mentioned - on solubility at 20 ° C.

In the context of the present invention, it is preferred to use coating materials which in addition to their water solubility and that associated with their use as a coating Improvement of the physical properties of the detergent and cleaning agent form body have other positive effects. This means that in the context of the present Invention of the use of coating materials is preferred, which in addition Washing or cleaning process washing and cleaning active or supportive have shafts. So another property of the coating can be in the setting the pH of the washing or cleaning liquor, but it can also be the primary washability or secondary washability of the detergent tablets per improve.

The following substances which are preferred in the context of the present invention are the following substances:

Carbon or dicarboxylic acids are also preferably used as coating materials, preferably those with an even number of carbon atoms. Particularly preferred carbon or dicarboxylic acids are those with at least 4, preferably with at least 6, particularly preferably with at least 8 and in particular those with 8 to 13 carbon atoms tomen. Particularly preferred dicarboxylic acids are, for example, adipic acid, pimeline acid, suberic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, brassylic acid and their mixtures. But also tetradecanoic acid, pentadecanoic acid and thapsic acid suitable coating materials. Particularly preferred carboxylic acids are those with 12 to 22 carbon atoms, with those having 18 to 22 carbon atoms being particularly preferred.

So are detergent tablets, in which the coating carbonic acid ren includes, those having 12 to 22, preferably 18 to 22 carbon atoms preferred and especially the species with an even number of carbon atoms which are preferred, a further preferred embodiment of the present invention.  Another preferred embodiment are detergents or cleaning agents Shaped bodies, which are characterized in that the coating around dicarboxylic acids summarizes, those with at least 4, preferably with at least 6, particularly preferred with at least 8 and in particular those with 8 to 13 carbon atoms are preferred and among them the species with an even number of carbon atoms is particularly preferred are. Regarding the particularly preferred individual compounds from the group mentioned Pen the carbonic and dicarboxylic acids can refer to the above statements become.

Other suitable coating materials are film-forming substances. Under this again preferred are polyalkylene glycols, especially polyethylene and polypropylene glycol cole, polymers and copolymers of (meth) acrylic acid, in particular copolymers of Acrylic acid and maleic acid, as well as sugar.

Polyalkylene glycols in particular include polyethylene glycols and polypropylene glycols. Particularly preferred coating materials are those from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG), polyethylene glycols with molecular weights between 1500 and 36,000 being preferred, those with molecular weights from 2000 to 6000 being particularly preferred and those with molecular weights of 3000 to 5000 being particularly preferred are. Polyethylene glycols are polymers of ethylene glycol which have the general formula I

H- (O-CH ₂ -CH ₂ ) _n -OH (I)

are sufficient, where n can take values between 1 (ethylene glycol) and several thousand. For preferred PEG, n assumes values between 20 and approximately 1000. The abovementioned preferred molecular weight ranges correspond to preferred ranges of the value n in formula I from approximately 30 to approximately 820 (exactly: from 34 to 818), particularly preferably from approximately 40 to approximately 150 (precisely: from 45 to 136 ) and in particular from approx. 70 to approx. 120 (exactly: from 68 to 113). There are different nouns for polyethylene glycols that can lead to confusion. The specification of the average relative molecular weight following the specification "PEG" is customary in technical terms, so that "PEG 2000" characterizes a polyethylene glycol with a relative molar mass of approximately 2000 gmol ^-1 . A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and a number follows the hyphen directly, which corresponds to the number n in the above formula I. According to this nomenclature (known as INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997), for example, PEG-33 to PEG-136 can be used with preference. Polyethylene glycols are commercially available, for example, under the trade names Carbowax® PEG 2000 (Union Carbide), Emkapol® 2000 (ICI Americas), Lipoxol® 2000 MED (HÜLS America), Polyglycol®E-2000 (Dow Chemical), Alkapol® PEG 3000 ( Rhone-Poulenc), Lutrol® E3000 (BASF) and the corresponding trade names with higher numbers.

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

are sufficient, n taking values between 1 (propylene glycol) and several thousand can. In preferred farms, n takes values between 10 and 2000. Be preferred PPGs have molar masses between 1000 and 10,000, corresponding to bets of n between 17 and about 170.

The polymers of (meth) acrylic acid, especially the copolymers of acrylic acid and Maleic acid are known as cobuilders for detergents or cleaning agents. you will be described below.

The term "sugar" in the context of the present invention denotes simple and Multiple sugar, i.e. monosaccharides and oligosaccharides, in which 2 to 6 monosaccha ride are linked together like acetals. "Sugar" are within the scope of the present  Invention thus monosaccharides, disaccharides, trisaccharides, tetra-, penta- and hexasac charide.

Monosaccharides are linear polyhydroxy aldehydes (aldoses) or polyhydroxy ketones (Ketoses). They usually have a chain length of five (pentoses) or six (Hexoses) carbon atoms. Monosaccharides with more (heptoses, octoses etc.) or fewer (tetroses) carbon atoms are relatively rare. Some monosaccharides have a large number of asymmetric carbon atoms. For a hexose with four asymmetric C- Atoms this gives a number of 24 stereoisomers. The orientation of the OH Group at the highest numbered asymmetr. C atom in the Fischer projection divides the Mo nosaccharides in D- u. L-configured rows. With the naturally occurring mono saccharidem, the D configuration is far more common. Form monosaccharides, if there is intramolecular hemiacetals so that ring-shaped structures (Pyranoses) and furan type (furanoses). Smaller rings are unstable, larger ones Rings resistant only in aqueous solutions. Cyclization creates another asymmetric carbon atom (the so-called anomeric carbon atom), which determines the number of possible stereoi somere doubled again. This is indicated by the prefixes α- u. expressed in β. The Bil Formation of the hemiacetals is a dynamic process that is influenced by various factors such as Temperature, solvent, pH, etc. depends. Mostly there are mixtures of the two anomeric forms, sometimes also as mixtures of the furanose and pyranose forms.

Monosaccharides which can be used as sugar in the context of the present invention include for example the tetroses D (-) - erythrose and D (-) - threose as well as D (-) - erythrulose, the Pentoses D (-) - ribose, D (-) - ribulose, D (-) - arabinose, D (+) - xylose, D (-) - xylulose as well D (-) - Lyxose and the Hexoses D (+) - Allose, D (+) - Altrose, D (+) - Glucose, D (+) - Mannose, D (-) - Gulose, D (-) - Idose, D (+) - Galactvse, D (+) - Talose, D (+) - psicose, D (-) - Fructose, D (+) - Sorbose and D (-) - Tagatose. The most important and most widespread monosacchari de are: D-glucose, D-galactose, D-mannose, D-fructose, L-arabinose, D-xylose, D- Ribose et al. 2-deoxy-D-ribose.

Disaccharides are made up of two simple monos linked by glycosidic bonds saccharide molecules (D-glucose, D-fructose and others). Is the glycosidic bond  between the acetal carbon atoms (1 for aldoses or 2 for ketoses) both monosaccharides, so that the ring shape is fixed in both; that show sugar no mutarotation, do not react with ketone reagents and no longer have a reduced effect rend (Fehling negative: trehalose or sucrose type). Connects the glycoside binding the acetal carbon atom of a monosaccharide to any one the second, this can still take the open-chain form, and the sugar works still reducing (Fehling positive: maltose type).

The main disaccharides are sucrose (cane sugar, sucrose), trehalose, lactose (Milk sugar), lactulose, maltose (malt sugar), cellobiose (breakdown product of cellulo se), gentobiose, melibiosis, turanose and others.

Trisaccharides are carbohydrates that consist of 3 glycosidically linked mono saccharides are built up and for which one occasionally also has the incorrect name Trios meets. Trisaccharides are relatively rare in nature, examples are genes tianose, kestose, maltotriose, melecitose, raffinose, and as an example of aminosugar containing trisaccharides streptomycin and validamycin.

Tetrasaccharides are oligosaccharides with 4 monosaccharide units. Examples of this Compound classes are stachyose, lychnose (galactose-glucose-fructose-galactose) and Secalose (from 4-fructose units).

In the context of the present invention, saccharides from the Group glucose, fructose, sucrose, cellubiosis, maltose, lactose, lactulose, ribose and their mixtures used. Washing or cleaning agents are particularly preferred telformkörper whose coatings contain glucose and / or sucrose.

Preferred detergent or cleaning agent form in the context of the present invention bodies are characterized in that the coating film-forming substances, ins special from the groups of polyethylene and / or polypropylene glycols, the copoly mers of acrylic acid and maleic acid or the sugar.  

Polymers other than those mentioned so far can also be used with particular preference as coating materials. Here, detergent tablets according to the invention are preferred in which the coating comprises a polymer or polymer mixture which is selected from

• a) water-soluble nonionic polymers from the group of
  • 1. polyvinylpyrrolidones,
  • 2. vinyl pyrrolidone / vinyl ester copolymers,
  • 3. Cellulose ether
  • 4. homopolymers of vinyl alcohol, copolymers of vinyl alcohol with monomers which can be copolymerized or hydrolysis products of vinyl ester homopolymers or vinyl ester copolymers with copolymerizable monomers,
• b) water-soluble amphoteric polymers from the group of
  • 1. Alkyl acrylamide / acrylic acid copolymers
  • 2. Alkyl acrylamide / methacrylic acid copolymers
  • 3. Alkyl acrylamide / methyl methacrylic acid copolymers
  • 4. Alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
  • 5. Alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
  • 6. Alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
  • 7. Alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers
  • 8. Copolymers
    • 1. unsaturated carboxylic acids
    • 2. cationically derivatized unsaturated carboxylic acids
    • 3. optionally further ionic or nonionic monomers
• c) water-soluble zwitterionic polymers from the group of
  • 1. Acrylamidoalkyltrialkylammoniumchlorid / acrylic acid copolymers and their alkali and ammonium salts
  • 2. Acrylamidoalkyltrialkylammoniumchlorid / methacrylic acid copolymers and their alkali and ammonium salts
  • 3. Methacroylethyl betaine / methacrylate copolymers
• d) water-soluble anionic polymers from the group of
  • 1. Vinyl acetate / crotonic acid copolymers
  • 2. Vinyl pyrrolidone / vinyl acrylate copolymers
  • 3. Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers
  • 4. Graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols
  • 5. grafted and crosslinked copolymers from the copolymerization of
    • 1. at least one monomer of the non-ionic type,
    • 2. at least one monomer of the ionic type,
    • 3. of polyethylene glycol and
    • 4. a networked person
  • 6. copolymers obtained by copolymerizing at least one monomer of each of the following three groups:
    • 1. esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
    • 2. unsaturated carboxylic acids,
    • 3. Esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group d6ii) with saturated or unsaturated, straight-chain or branched C _8-18 alcohol
  • 7. Graft copolymers obtainable by grafting d7i) polyalkylene oxides with d7ii) vinyl acetate
  • 8. Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ster
  • 9. Tetra and pentapolymers
    • 1. Crotonic acid or allyloxyacetic acid
    • 2. Vinyl acetate or vinyl propionate
    • 3. branched allyl or methallyl esters
    • 4. Vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters
  • 10. Crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinyl methyl ether, acrylamide and their water-soluble salts
  • 11. Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the α-position
• e) water-soluble cationic polymers from the group of
  • 1. quaternized cellulose derivatives
  • 2. Polysiloxanes with quaternary groups
  • 3. cationic guar derivatives
  • 4. polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid
  • 5. Copolymers of vinyl pyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate
  • 6. Vinyl pyrrolidone-methoimidazolinium chloride copolymers
  • 7. Quaternized polyvinyl alcohol
  • 8. Polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27
• f) polyurethanes.

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

These preferred detergent tablets according to the invention are partially coated with a polymer or polymer mixture, the polymer (and accordingly, the entire partial coating) or at least 50% by weight of the polymer mixture (and thus at least 50% of the partial coating) from certain polymers is selected. The partial coating consists entirely or at least 50% of its ge weight of water-soluble polymers from the group of nonionic, amphoteric, zwitterionic, anionic and / or cationic polymers. These polymers will described in more detail below.

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

• - Polyvinylpyrrolidones, such as those under the name Luviskol® (BASF) are sold. Polyvinyl pyrrolidones are preferred nonionic poly mere within the scope of the invention.
• - Polyvinylpyrrolidone [Poly (1-vinyl-2-pyrrolidinone)], abbreviation PVP, are polymers of the general formula (III)
  which are prepared by radical polymerization of 1-vinylpyrrolidone by solution or suspension polymerization using radical formers (peroxides, azo compounds) as initiators. The ionic polymerization of the monomer only provides products with low molecular weights. Commercial polyvinylpyrrolidones have molar masses in the range of approx. 2500-750000 g / mol, which are characterized by the specification of the K values and - depending on the K value - have glass transition temperatures of 130-175 °. They are 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, ice sig, chlorinated hydrocarbons, phenols, etc.).
• - Vinyl pyrrolidone / vinyl ester copolymers, such as those sold under the trademark Luviskol® (BASF). Luviskol® VA 64 and Luviskol® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred non-ionic polymers.
  The vinyl ester polymers are polymers accessible from vinyl esters with the grouping of the formula (N)
  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 polymerisation of the vinyl esters takes place radically according to different processes (solution polymerisation, suspension polymerisation, emulsion polymerisation, bulk polymerisation.). Copolymers of vinyl acetate with vinyl pyrrolidone contain monomer units of the formulas (III) and (IV)
• - Cellulose ethers, such as hydroxypropyl cellulose, hydroxyethyl cellulose and methyl hydroxypropyl cellulose, as are sold, for example, under the trademarks Culminal® and Benecel® (AQUALON).
  Cellulose ethers can be described by the general formula (V)
  in R represents H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products at least one R in formula (V) represents -CH ₂ CH ₂ CH ₂ -OH or -CH ₂ CH ₂ -OH. Cellulose ethers are manufactured industrially by etherification of alkali cellulose (e.g. with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of the cellulose have reacted with the etherification reagent or how many moles of the etherification reagent have been attached to an anhydroglucose unit on average. Hydroxyethyl celluloses are water-soluble from a DS of approx. 0.6 or an MS of approx. 1. Commercial hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS). Hydroxyethyl and propyl celluloses are marketed as yellowish white, odorless and tasteless powders in widely differing degrees of polymerization. Hydroxyethyl and propyl celluloses are soluble in cold and hot water and in some (water-containing) organic solvents, but insoluble in most (anhydrous) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition.
• - Homopolymers of vinyl alcohol, copolymers of vinyl alcohol with copolymerizable monomers or hydrolysis products of vinyl ester homopolymers or vinyl ester copolymers with copolymerizable monomers can also be used.
  Homopolymers or copolymers of vinyl alcohol cannot be obtained by polymerizing vinyl alcohol (H ₂ C = CH-OH), since its concentration in the tau tomeren equilibrium with acetaldehyde (H ₃ C-CHO) is too low. These polymers are therefore mainly from polyvinyl esters, in particular polyvinyl acetates, via polymer-analogous reactions such as hydrolysis, but technically in particular by alkaline-catalyzed transesterification with alcohols (preferably methanol) in solution.
  If the corresponding vinyl ester homopolymers or vinyl ester copolymers are not hydrolyzed, then these are coating materials of the second group mentioned.
  "Polyvinyl alcohols" (abbreviation PVAL, sometimes also PVOH) is the name for polymers of the general structure
  which in small proportions (approx. 2%) also structural units of the type
  contain.

Commercial polyvinyl alcohols, which are used as white-yellowish powder or granules with poly degrees of merization in the range from approx. 100 to 2500 (molar masses from approx. 4000 to 100,000 g / mol) are offered, have degrees of hydrolysis of 98-99 or 87-89 mol%, therefore still contain a residual content of acetyl groups. The Po are characterized Lyvinyl alcohols on the part of the manufacturers by indicating the degree of polymerization of the Starting polymers, the degree of hydrolysis, the saponification number or the solution viscosity ty.

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and few strong polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils fen. Polyvinyl alcohols are classified as toxicologically safe and are organic at least partially biodegradable. The water solubility can be improved by post-treatment treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or reduce by treatment with dichromates, boric acid or borax. The coatings  Polyvinyl alcohol are largely impenetrable for gases such as oxygen, stick substance, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.

Preferably, polyvinyl alcohols of a certain molecular weight range, such as from 10,000 to 100,000 gmol ^-1, preferably from 11,000 to 90,000 gmol ^- is ^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 about 2100, preferably between about 220 to about 1890, especially preferably between about 240 to about 1680 and especially between about 260 to about 1500.

The polyvinyl alcohols described above are widely available commercially at for example under the trademark Mowiol® (Clariant). As part of the present Polyvinyl alcohols particularly suitable according to the invention are, for example, Mowiol® 3-83, Mo. wiol® 4-88, Mowiol® 5-88 and Mowiol® 8-88.

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

Suitable zwitterionic polymers are, for example, those in the German patent applications dungen DE 39 29 973, DE 21 50 557, DE 28 17 369 and DE 37 08 451 disclosed poly merisate. Acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic Acid copolymers and their alkali and ammonium salts are preferred zwitterio African polymers. Other suitable zwitterionic polymers are methacroylethyl betainl methacrylate copolymers sold under the name Amersette® (AMERCHOL) Are available commercially.

Anionic polymers suitable according to the invention include:

• - Vinyl acetate / crotonic acid copolymers, as are commercially available, for example, under the names Resyn® (NATIONAL STARCH), Luviset® (BASF) and Gafset® (GAF).
  In addition to monomer units of the above formula (IV), these polymers also have monomer units of the general formula (VI):
  [-CH (CH ₃ ) -CH (COOH) -] _n (VI)
• - Vinylpyrrolidone / vinyl acrylate copolymers, available for example under the Wa logo Luviflex® (BASF). A preferred polymer is that under the designation Luviflex® VBM-35 (BASF) available vinyl pyrrolidone / acrylate terpolymers.
• - Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers, for example under the name Ultrahold® strong (BASF) are sold.  
• - Graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols
  Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture with other copolymerizable compounds on polyalkylene glycols, are obtained by polymerization in the heat in a homogeneous phase by converting the polyalkylene glycols into the monomers of the vinyl esters, esters of acrylic acid or methacrylic acid, stirred in the presence of radical 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 those which have low molecular weight aliphatic alcohols, in particular ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2- Methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol, are available.
  Polyalkylene glycols in particular include polyethylene glycols and polypropylene glycols. Polymers of ethylene glycol which have the general formula V
  H- (O-CH ₂ -CH ₂ ) _n -OH (VII)
  are sufficient, where n can take values between 1 (ethylene glycol) and several thousand. There are various nomenclatures for polyethylene glycols that can lead to confusion. The specification of the average relative molecular weight following the specification "PEG" is technically customary, so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210. A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and immediately after the hyphen is followed by a number which corresponds to the number n in the formula V mentioned above. According to this nomenclature (known as NCI nomenclature, CTFA International Cosmetic Ingre serves Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997), for example, PEG-4, PEG-6, PEG-8, PEG 9, PEG-10, PEG-12, PEG-14 and PEG-16 can be used. Polyethylene glycols are commercially available, for example, under the trade names Carbowax® PEG 200 (Uni on Carbide), Emkapol® 200 (ICI Americas), Lipoxol® 200 MED (HÜLS America). Polyglycol® E-200 (Dow Chemical), Alkapol® PEG 300 (Rhone-Poulenc), Lutrol® E300 (BASF) and the corresponding trade names with higher numbers.
  Polypropylene glycols (PPG) are polymers of propylene glycol that have the general formula VI
  are sufficient, where n values can be between 1 (propylene glycol) and several thousand. Technically important here are, in particular, di-, tri- and tetra-propylene glycol, ie the representatives with n = 2, 3 and 4 in formula VIII.
  In particular, the vinyl acetate copolymers grafted onto polyethylene glycols and the polymers of vinyl acetate and crotonic acid grafted onto polyethylene glycols can be used.
• - grafted and crosslinked copolymers from the copolymerization of
  • a) at least one monomer of the non-ionic type,
  • b) at least one monomer of the ionic type,
  • c) of polyethylene glycol and
  • d) a networked person
  The polyethylene glycol used has a molecular weight between 200 and several million, preferably between 300 and 30,000.
  The nonionic monomers can be of very different types and the following are preferred: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allyl laurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-hexene.
  The non-ionic monomers can likewise be of very different types, of which crotonic acid, allyloxyacetic acid, vinyl acetic acid, maleic acid, acrylic acid and methacrylic acid are particularly preferably contained in the graft polymers.
  Ethylene glycol dimethacrylate, diallyl phthalate, or tho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallylsucrose with 2 to 5 allyl groups per molecule of saccharin are preferably used as crosslinkers.
  The grafted and crosslinked copolymers described above are preferably formed from:
  • 1. 5 to 85% by weight of at least one non-ionic type monomer,
  • 2. 3 to 80% by weight of at least one monomer of the ionic type,
  • 3. 2 to 50 wt .-%, preferably 5 to 30 wt .-% polyethylene glycol and
  • 4. 0.1 to 8% by weight of a crosslinking agent, the percentage of the crosslinking agent being formed by the ratio of the total weights of i), ii) and iii).
• - Copolymers obtained by copolymerizing at least one monomer of each of the following three groups:
  • 1. esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
  • 2. unsaturated carboxylic acids,
  • 3. Esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group ii) with saturated or unsaturated, straight-chain or branched C _8-18 alcohol
• - Among short-chain carboxylic acids or alcohols are those with 1 to 8 Koh To understand lenstoffatomen, whereby the carbon chains of these compounds against may also be interrupted by double-bonded hetero groups such as -O-, -NH-, -S can.
• - Graft copolymers of polyalkylene oxide on vinyl acetate are described in European patent application EP 219 048 A (BASF). They are obtainable by grafting a polyalkylene oxide with vinyl acetate, it being possible for the acetate groups of the vinyl acetate to be partially saponified. Suitable polyalkylene oxides are, in particular, polymers having ethylene oxide, propylene oxide and butylene oxide units, with polyethylene oxide being preferred.
  The graft copolymers can be prepared, for example, by dissolving the polyalkylene oxides in vinyl acetate and continuous or discontinuous polymerization after addition of a polymerization initiator, or by semi-continuous polymerization, in which part of the polymerization mixture of polyalkylene oxide, vinyl acetate and polymerization initiator is heated to the polymerization temperature, after which the rest is added to the mixture to be polymerized. The graft copolymers can also be obtained by introducing polyalkylene oxide, heating to the polymerization temperature and adding vinyl acetate and polymerization initiator either all at once, batchwise or, preferably, continuously.
  If the graft composites described above are used, the coating contains at least 50% by weight of graft copolymers which can be obtained by grafting (a) polyalkylene oxides with a molecular weight of 1500 to 70,000 gmol-1 with (b) vinyl acetate in the weight ratio of (a) : (b) from 100: 1 to 1: 5, the acetate groups optionally being saponified up to 15%.
  In preferred embodiments of the present invention, the molecular weight of the polyalkylene oxides contained in the graft copolymers is 2,000 to 50,000 gmol-1, preferably 2500 to 40,000 gmol-1, particularly preferably 3,000 to 20,000 gmol-1 and in particular 4,000 to 10,000 gmol-1. Corresponding detergent tablets are preferred according to the invention.
  Depending on the desired properties of the coating, the proportion of the individual monomers can vary. Coatings are preferred in which the vinyl acetate content in the graft copolymers is 1 to 60% by weight, preferably 2 to 50% by weight, particularly preferably 3 to 40% by weight and in particular 5 to 25% by weight, each based on the graft copolymer.
  A graft copolymer which is particularly preferred in the context of the present invention is based on a polyethylene oxide with an average molecular weight of 6000 gmol-1 (corresponding to 136 ethylene oxide units), which contains about 3 parts by weight of vinyl acetate per part by weight of polyethylene oxide. This polymer, which has an average molecular weight of approximately 24000 gmol-1, is sold commercially by BASF under the name Soka lan (r) HP22.
• Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester These terpolymers contain monomer units of the general formulas (II) and (IV) (see above) and monomer units of one or more allyl or methallyesters of the formula IX:
  wherein R ^{3 is} -H or -CH ₃ , R ^{2 is} -CH ₃ or -CH (CH ₃ ) ₂ and R ^{1 is} -CH ₃ or a saturated straight-chain or branched C _1-6 alkyl radical and the sum of the carbon atoms in the radicals R ¹ and R ^{2 is} preferably 7, 6, 5, 4, 3 or 2. The above-mentioned terpolymers preferably result from the copolymerization of 7 to 12% by weight of crotonic acid, 65 to 86% by weight, preferably 71 to 83% by weight of vinyl acetate and 8 to 20% by weight, preferably 10 to 17 % By weight of allyl or methallyl esters of the formula IX.
• - Tetra and pentapolymers
  • 1. Crotonic acid or allyloxyacetic acid
  • 2. Vinyl acetate or vinyl propionate
  • 3. branched allyl or methallyl esters
  • 4. Vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters
• - Crotonic acid copolymers with one or more monomers from the group Ethylene, vinylbenzene, vinyl methyl ether, acrylamide and their water-soluble salts
• - Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphati monocarboxylic acid branched in the α-position.

Other polymers that can preferably be used as part of the coating are cationic Polymers. Among the cationic polymers are the permanently cationic Po polymers preferred. According to the invention, such polymers are termed “permanently cationic” referred to, regardless of the pH of the agent (i.e. both the coating and also of the shaped body) have a cationic group. These are usually polyme re, which contains a quaternary nitrogen atom, for example in the form of an ammonium group hold.

Preferred cationic polymers are, for example

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

as well as those under the designations

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

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

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

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

Other suitable coating materials are polyurethanes, which are usually composed of diisocyanates (X) and diols (XI).

O = C = NR ⁴ -N = C = O (X),

HOR ⁵ -OH (XI),

the diols being selected at least in part from polyethylene glycols (XIa) and / or polypropylene glycols (XIb)

and R ⁴ and R ⁵ independently of one another represent a substituted or unsubstituted, straight-chain or branched alkyl, aryl or alkylaryl radical with 1 to 24 carbon atoms and n each represent numbers from 5 to 2000.

The detergent tablets according to the invention are provided with a loading layering that contains certain polyurethanes. These polymers will follow described in more detail.

Polyurethanes are polyadducts of at least two different types of monomers,

• - A di- or polyisocyanate (A) and
• - A compound (B) with at least 2 active hydrogen atoms per mole kül

The polyurethanes contained in the coating of the moldings according to the invention are obtained from reaction mixtures in which at least one diisocyanate Formula (X) and at least one polyethylene glycol of the formula (XIa) and / or at least a polypropylene glycol of the formula (XIb) are contained.

The reaction mixtures can additionally contain further polyisocyanates. Also a ge hold the reaction mixtures - and thus the polyurethanes - on other diols, triplets, Diamines, triamines, polyetherols and polyesterols are possible. The Compounds with more than 2 active hydrogen atoms usually only in small Amounts in combination with a large excess of 2 active compounds Hydrogen atoms used.

With the addition of other diols, etc., certain proportions to the fiction compulsory polyethylene and / or polypropylene glycol present in the polyurethane col units to be observed. Detergent tablets are preferred here, in which at least 10% by weight, preferably at least 25% by weight, especially before Adds at least 50 wt .-% and in particular at least 75 wt .-% of those in the polyurethane han reacted diols are selected from polyethylene glycols (XIa) and / or Polypro pylene glycols (XIb).  

The polyurethanes contain diisocyanates of the formula (X) as a monomer unit. The diisocyanates used are predominantly hexamethylene diisocyanate, 2,4- and 2,6-toluenediisocyanate, 4,4'-methylene di (phenyl isocyanate) and in particular isophorone diisocyanate. These compounds can be described by the formula I listed above, in which R ^{1 represents} a connecting group of carbon atoms, for example a methylene, ethylene, propylene, butylene, pentylene, hexylene, etc. group. In the above-mentioned, industrially most used hexamethylene diisocyanate (HMDI), R ¹ = (CH ₂ ) ₆ , in 2,4- or 2,6-toluenediisocyanate (TDI) R ^{1 is} C ₆ H ₃ -CH ₃ ), in 4,4'-methylenedi (phenyl isocyanate) (MDI) for C ₆ H ₄ -CH ₂ -C ₆ H ₄ ), and in isophorone diisocyanate R ¹ stands for the isophorone residue (3,5,5-trimethyl-2- cyclohexenone).

The polyurethanes used according to the invention as the coating material further contain diols of the formula (XI) as a monomer unit, these diols at least partly originating from the group of the polyethylene glycols (XIa) and / or the polypropylene glycols (XIb). Polyethylene glycols are polymers of ethylene glycol that have the general formula (XIa)

H- (O-CH ₂ -CH ₂ ) _n -OH (XIa)

are sufficient, where n can have values between 5 and 2000. There are various nomenclatures for polyethylene glycols that can lead to confusion. Technically common is the specification of the average relative molecular weight following the specification "PEG", so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210. A different noun is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and directly after the hyphen is followed by a number which corresponds to the number n in the above formula (IXa). According to this nomenclature (known as INCI nomenclature CTFA Inter national Cosmetic Ingredient Dictionary and Handbook, try 5 ^th Edition, The Cosmetic, Toile and Fragrance Association, Washington, 1997), for example, PEG-6, PEG-8, PEG-9, PEG -10, PEG-12, PEG-14 and PEG-16 can be used as a monomer module. Polyethylene glycols are commercially available, for example, under the trade names Carbowax® PEG (Union Carbide), Emkapol® (ICI Americas), Lipoxol® MED (HÜLS America), Polyglycol®E (Dow Chemical), Alkapol® PEG (Rhone-Poulenc), Lutrol ®E (BASF).

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

are sufficient, where n can have values between 5 and 2000.

Both in the case of compounds of the formula (XIa) and in the case of compounds of the formula mel (XIb) are those representatives preferred monomer units in which the number n for a number between 6 and 1500, preferably between 7 and 1200, particularly preferred between 8 and 1000, more preferably between 9 and 500 and in particular between 10 and 200 stands. For certain applications, polyethylene and polypropylene gly cole of the formulas (XIa) and / or (XIb) may be preferred, in which n is a number between 15 and 150, preferably between 20 and 100, particularly preferably between 25 and 75 and especially between 30 and 60.

Examples of optional further in the reaction mixtures for the production of the polyurethane ne contained compounds are ethylene glycol, 1,2- and 1,3-propylene glycol, butylene glycol kole, ethylenediamine, propylenediamine, 1,4-diaminobutane, hexamethylenediamine and α, ω- Diamines based on long-chain alkanes or polyalkylene oxides. Po are preferred lyurethane, the additional diamines in the coating, preferably hexamethylene dia min and / or hydroxycarboxylic acids, preferably dimethylolpropionic acid.

In summary, those which are composed of diisocyanates (X) and diols (XI) are particularly preferred as polyurethanes

O = C = NR ⁴ -N = C = O (X),

HOR ⁵ -OH (XI),

where R ⁴ for a methylene-ethylene-propylene, butylene, pentylene group or for - (CH ₂ ) ₆ - or for 2,4- or 2,6-C ₆ H ₃ -CH ₃ , or for C ₆ H ₄ -CH ₂ -C ₆ H ₄ or isophore radical (3,5,5-trimethyl-2-cyclohexenone) and R ^{5 is} selected from -CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n - or -CH ₂ -CH ₂ - (O-CH (CH ₃ ) -CH ₂ ) _n - with n = 4 to 1999.

Depending on which reactants are reacted with each other to form the polyurethanes, the result is polymers with different structural units. Preferred structural units are represented by the formula (XII)

- [OC (O) -NH-R ⁴ -NH-C (O) -OR ⁵ ] _k - (XII),

in which R ^{4 stands} for - (CH ₂ ) ₆ - or for 2,4- or 2,6-C ₆ H ₃ -CH ₃ , or for C ₆ H ₄ -CH ₂ -C ₆ H ₄ and R ⁵ is selected from -CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n - or - CH (CH ₃ ) -CH ₂ - (O-CH (CH ₃ ) - CH ₂ ) _n -, where n is a Number from 5 to 199 and k is a number from 1 to 2000.

The diisocyanates described as preferred can be reacted with all the diols described as preferred to give polyurethanes, so that preferably used polyurethanes have one or more of the structural units (XIIa) to (XIIh):

- [OC (O) -NH- (CH ₂ ) ₆ -NH-C (O) -O-CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n ] _k - (XIIa),

- [OC (O) -NH- (2,4-C ₆ H ₃ -CH ₃ ) -NH-C (O) -O-CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n ] _k - (XIIb),

- [OC (O) -NH- (2,6-C ₆ H ₃ -CH ₃ ) -NH-C (O) -O-CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n ] _k - (XIIc),

- [OC (O) -NH- (C ₆ H ₄ -CH ₂ -C ₆ H ₄ ) -NH-C (O) -O-CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n ] _k - (XIId),

- [OC (O) -NH- (CH ₂ ) ₆ -NH-C (O) -O-CH (CH ₃ ) -CH ₂ - (O-CH (CH ₃ ) -CH ₂ ) _n ] _k - ( XIIe)

- [OC (O) -NH- (2,4-C ₆ H ₃ -CH ₃ ) -NH-C (O) -O-CH (CH ₃ ) -CH ₂ - (O-CH (CH ₃ ) - CH ₂ ) _n ] _k - (XIIf),

- [OC (O) -NH- (2,6-C ₆ H ₃ -CH ₃ ) -NH-C (O) -O-CH (CH ₃ ) -CH ₂ - (O-CH (CH ₃ ) - CH ₂ ) _n ] _k - (XIIg),

- [OC (O) -NH- (C ₆ H ₄ -CH ₂ -C ₆ H ₄ ) -NH-C (O) -O-CH (CH ₃ ) -CH ₂ - (O-CH (CH ₃ ) -CH ₂ ) _n ] _k - (XIIh),

where n is a number from 5 to 199 and k is a number from 1 to 2000.

As already mentioned above, the reaction mixtures can be used in addition to diisocyanates (X) and diols (XI) also other compounds from the group of polyisocyanates (ins special triisocyanates and tetraisocyanates) and from the group of polyols and / or Di- or Polymaine included. In particular triols, tetrols, pentols and hexols as well as di- and triamines can be included in the reaction mixtures. A verbin content with more than two "active" H atoms (all classes of substances mentioned above with the exception of diamines) leads to partial crosslinking of the polyurethane Reaction products and can have advantageous properties such as control of the Dissolving behavior, abrasion stability or flexibility of the coating, process advantages effect when applying the coating etc. The content is usually such Compounds with more than two "active" H atoms on the reaction mixture less than 20% by weight of the total reactants used for the diisocyanates preferably less than 15% by weight and in particular less than 5% by weight.

Polyurethanes are particularly incorporated into the coating when it is should be particularly resistant to mechanical stress. The polyurethanes impart elasticity and stability to the coating and can follow the above Given amount of water-soluble polymers up to 50 wt .-% of the coating turn off.

Another group of suitable polymers are the so-called LCST polymers. With the LCST Polymers are substances that dissolve better at low temperatures exhibit higher than at higher temperatures. They are also called substances with un critical critical separation temperature or turbidity temperature.  

The LCST substances are preferably selected from alkylated and / or hydroxyal alkylated polysaccharides, cellulose ethers, acrylamides, such as polyisopropylacrylamide, Copolymers of acrylamides, polyvinylcaprolactam, copolymers of polyvinylca prolactam, especially those with polyvinyl pyrrolidone, polyvinyl methyl ether, copoly mers of polyvinyl methyl ether and blends of these substances.

Examples of alkylated and / or hydroxyalkylated polysaccharides are hydroxypropyl methyl cellulose (HPMC), ethyl (hydroxyethyl) cellulose (EHEC), hydroxypropyl cellulose (HPC), methyl cellulose (MC), propyl cellulose (PC), carboxymethyl methyl cellulose (CMMC), hydroxybutyl cellulose (HBC), hydroxybutyl methyl cellulose (HBMC), Hydrdoxyethylcellulose (HEC), Hydroxyethylcarboxymethylcellulose (HECMC), Hy droxyethylethyl cellulose (HEEC), hydroxypropyl cellulose (HPC), Hy hydroxypropyl carboxymethyl cellulose (HPCMC), hydroxyethyl methyl cellulose (HEMC), Methyl hydroxyethyl cellulose (MHEC), methyl hydroxyethyl propyl cellulose (MHEPC) and their mixtures, wherein methyl cellulose, methyl hydroxyethyl cellulose and methyl hy droxypropycellulose, hydroxypropylcellulose and slightly ethoxylated MC or mixtures the foregoing are preferred.

Other examples of LCST substances are mixtures of cellulose ethers with car boxymethyl cellulose (CMC). Other polymers that have a lower critical segregation temperature in water and which are also suitable are polymers of mono- or di-N-alkylated acrylamides, such as isopropylacrylamide, copolymers of mono- or Di-N-substituted acrylamides with acrylates and / or acrylic acids or mixtures of intertwined networks of the abovementioned (co) polymers, copolymers of isopropylacrylamide and polyvinylcaprolactam. Copolymers are also suitable with polyethylene oxide, such as ethylene oxide / propylene oxide copolymers and graft copolymers of alkylated acrylamides with polyethylene oxide, polymethacrylic acid, polyvinyl alcohol and copolymers thereof, polyvinyl methyl ether, certain proteins such as poly (VATGVV), a repeating unit in the natural protein elastin and certain algina te. Mixtures of these polymers with salts, low molecular weight organic compounds Additions or surfactants can also be used as LCST substances.  

The partial coating can contain other ingredients in addition to the coating materials ten that improve the physical properties of the coating or be give layered moldings advantageous properties. For example possible, so-called small components such as dyes or optical Auf lighter or foam inhibitors to incorporate into the coating. Become coating materials that are only poorly or slowly water-soluble, so Des integration aids are incorporated into the coating. Such according to the invention ß detergent tablets, in which the coating additionally Disintegration aid in amounts from 0.1 to 10% by weight, preferably from 0.2 to 7.5% by weight and in particular from 0.25 to 5% by weight, based in each case on the coating layer, contains are preferred in the context of the present invention.

The use of the disintegration aids described in detail below is particularly important Especially recommended for acid coating layers, with usual use concentrations for the disintegration aids in the coating layers at 0.1 to 5% by weight on the coating layer.

The components of the partial coating of the moldings according to the invention were described above described in more detail. In the following, the components of the moldings themselves, i.e. H. the uncoated molded body. These moldings are subsequently to Part referred to as a "basic molded article" to provide a verbal delimitation against the term “Shaped body” or “tablet” for the washing and cleaning agents coated according to the invention to achieve moldings, but sometimes the general term "Shaped body" used. Since the subject of the present invention with a par tialcoated basic moldings, the following apply to the basic moldings of course, also given for washing and cleaning according to the invention shaped tablets that meet the corresponding conditions, and vice versa.

The basic moldings contain builders (e) and surfactant (e) as essential components. In the base moldings according to the invention, all can usually be found in washing and Builders used in cleaning agents, in particular zeolites,  Silicates, carbonates, organic cobuilders and - where no ecological prejudices against their use persists - including the phosphates.

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

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compaction / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted in such a way that the products have microcrystalline ranges of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a release delay compared to the conventional water glass glasses, are described, for example, in German patent application DE-A-44 00 024. 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 mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X), which was developed by CONDEA Augusta S. p. A. is sold under the brand name VEGOBOND AX® and through the formula

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

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

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

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

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

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

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

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

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

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

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

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

As organic cobuilders, in particular polycarboxylates / Polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and phosphonates can be used. This Substance classes are described below.

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

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

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

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

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

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

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

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

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

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

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

Other suitable builder substances are polyacetals, which are produced by the implementation of Dial dehyden with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups pointing to 86615 00070 552 001000280000000200012000285918650400040 0002010064635 00004 86496. Preferred polyacetals are from Dialde hyden such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from Obtained polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

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

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

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

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

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

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

The amount of builder is usually between 10 and 70 wt .-%, preferably as between 15 and 60 wt .-% and in particular between 20 and 50 wt .-%. The The amount of builders used depends on the intended use, so that bleaching medium tablets and tablets for machine dishwashing May have builders (for example between 20 and 70% by weight, preferably as between 25 and 65 wt .-% and in particular between 30 and 55 wt .-%), as for example detergent tablets (usually 10 to 50% by weight, preferably 12.5 up to 45% by weight and in particular between 17.5 and 37.5% by weight).

Preferred base tablets furthermore contain one or more surfactant (s). In the base Shaped bodies can be anionic, nonionic, cationic and / or amphoteric surfactants or mixtures of these are used. Preferred are from from a nutritional point of view, mixtures of anionic and nonionic surfactants. The  The total surfactant content of the moldings is 5 to 60% by weight. based on the molding by weight, with surfactant contents above 15% by weight being preferred.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In the context of the present invention, preference is given to base moldings which contain anionic (s) and nonionic (s) surfactant (s), with application advantages from be correct proportions in which the individual surfactant classes are used, can result.

For example, base moldings in which the ratio of Anionic surfactant (s) to nonionic surfactant (s) between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2. Washing and washing are also preferred Detergent tablets which contain anionic (s) and / or nonionic (s) surfactant (s) hold and total surfactant contents above 2.5 wt .-%, preferably above 5 wt .-% and in particular above 10% by weight, in each case based on the shaped body weight. Detergent tablets are particularly preferred, the surfactant (s), preferably anionic (s) and / or nonionic (s) surfactant (s), in quantities from 5 to 40% by weight, preferably from 7.5 to 35% by weight, particularly preferably from 10 up to 30 wt .-% and in particular from 12.5 to 25 wt .-%, each based on the shape body weight, included.  

From an application point of view, it can be advantageous if certain classes of surfactants in some phases of the base molding or in the entire molding, d. H. in all phases, are not included. Another important embodiment of the present invention therefore provides that at least one phase of the moldings is free of nonionic tensi that is.

Conversely, the content of individual phases or the entire form can also be used body, d. H. all phases, certain surfactants have a positive effect. The The introduction of the alkyl polyglycosides described above has been found to be advantageous pointed so that base moldings are preferred in which at least one phase of the mold Contains alkyl polyglycosides.

Similar to the nonionic surfactants can also be left out of anioni tensides result from individual or all phases of basic shaped bodies which are suitable for certain areas of application are better suited. It is therefore within the scope of the present Invention detergent tablets also conceivable, in which at least a phase of the moldings is free from anionic surfactants.

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

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

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

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

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

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

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

Other nonionic surfactants to be used with particular preference with melting points above Room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethy len / polyoxypropylene block polymer blends, the 75 wt .-% of an inverted block Co polymers of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles Propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxy propylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles Propylene oxide per mole of trimethylol propane.

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

Another preferred surfactant can be represented by the formula

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

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

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

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

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

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

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

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

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

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

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

Preferred base agent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration aids, each based on the weight of the molded body.

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

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

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

Preferred detergent and cleaning agent form in the context of the present invention Bodies additionally contain a disintegration aid, preferably a disintegration agent cellulose-based auxiliary agents, preferably in granular, cogranulated or compact tated form, in amounts of 0.5 to 10 wt .-%, preferably from 3 to 7 wt .-% and in particular from 4 to 6% by weight, in each case based on the weight of the shaped body, where preferred disintegration aids average particle sizes above 300 microns preferably have above 400 microns and in particular above 500 microns.

The detergent tablets according to the invention can moreover both in the basic molded body [part a)] and in the partial coating a gas-evolving one Shower system included. The gas-developing shower system can consist of a single sub punch exist, which releases a gas on contact with water. Among these connections Magnesium peroxide should be mentioned in particular, which is oxygen when in contact with water releases. Usually, however, the gas-releasing bubble system itself consists of at least two components that react with one another to form gas. While here a variety of systems is conceivable and executable, for example nitrogen, acid Release substance or hydrogen, that will in the washing and Bubble system used detergent tablets based on both economic and also choose based on ecological considerations. Preferred shower systems consist of alkali metal carbonate and / or hydrogen carbonate and an acidification detergent, which is suitable from the alkali metal salts in aqueous solution carbon dioxide release.

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

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

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

In addition to the ingredients mentioned builder, surfactant and disintegration aid, The detergent tablets according to the invention are further used in detergents. and cleaning agents usual ingredients from the group of bleaching agents, bleaching agents gates, dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, Anti-redeposition agents, graying inhibitors, color transfer inhibitors and corro ion inhibitors included.

The detergents and cleaning agents can be used to develop the desired bleaching performance Shaped body of the present invention contain bleach. Here in particular in particular the usual bleaching agents from the group sodium perborate monohydrate, Sodium perborate tetrahydrate and sodium percarbonate have proven their worth.  

"Sodium percarbonate" is a non-specific term for sodium carbonate peroxohydrates which, strictly speaking, are not "percarbonates" (ie salts of percarbonic acid) but hydrogen peroxide adducts with sodium carbonate. The merchandise has the average composition 2 Na ₂ CO ₃ .3 H ₂ O ₂ and is therefore not peroxycarbonate. Sodium percarbonate forms a white, water-soluble powder with a density of 2.14 gcm ^-3 , which easily breaks down into sodium carbonate and bleaching or oxidizing oxygen.

Sodium carbonate peroxohydrate was first made in 1899 by precipitation with ethanol from a Obtained solution of sodium carbonate in hydrogen peroxide, but mistakenly as peroxy viewed carbonate. It was not until 1909 that the compound was Addition compound recognized, nevertheless the historical designation "sodium per carbonate "prevailed in practice.

The industrial production of sodium percarbonate is mainly produced by precipitation from an aqueous solution (so-called wet process). Here, aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium percarbonate is precipitated by salting-out agents (predominantly sodium chloride), crystallization aids (for example polyphosphates, polyacrylates) and stabilizers (for example Mg ²⁺ ions). The precipitated salt, which still contains 5 to 12% by weight of mother liquor, is then trifused and dried at 90 ° C. in fluid bed dryers. The bulk density of the finished product can vary between 800 and 1200 g / l depending on the manufacturing process. As a rule, the percarbonate is stabilized by an additional coating. Coating processes and substances used for coating are widely described in the patent literature. Basically, all commercially available percarbonate types can be used according to the invention, such as those offered by the companies Solvay Interox, Degussa, Kemara or Akzo.

In the bleaching agents used, the content of the moldings in these substances is from Depending on the intended use of the molded body. While common universal detergents in Ta in sheet form between 5 and 30% by weight, preferably between 7.5 and 25% by weight and contain in particular between 12.5 and 22.5% by weight of bleach, the contents are  for bleach or bleach booster tablets between 15 and 50 wt .-%, preferably between 22.5 and 45% by weight and in particular between 30 and 40% by weight.

In addition to the bleaching agents used, the washing and Detergent tablets contain bleach activator (s), which is within the scope of the invention is preferred. Bleach activators are used in detergents and cleaning agents incorporated to improve cleaning when washing at temperatures of 60 ° C and below achieve bleaching effect. As bleach activators, compounds that are under Perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 C- Atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzo result acid, are used. Suitable substances are O- and / or N- Acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl carry groups. Multi-acylated alkylenediamines, in particular tetraa, are preferred cetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4- dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetyl glycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated more term alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5- dihydrofuran.

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

If the moldings according to the invention contain bleach activators, they each contain Weil based on the entire molded body, between 0.5 and 30 wt .-%, preferably between 1 and 20% by weight and in particular between 2 and 15% by weight of one or more other bleach activators or bleach catalysts. Depending on the intended use of the manufactured  Shaped bodies can vary these amounts. So are in typical universal detergent tablets bleach activator contents between 0.5 and 10 wt .-%, preferably between 2 and 8 wt .-% and in particular between 4 and 6 wt .-% usual, while Bleach tablets definitely higher contents, for example between 5 and 30 wt .-%, preferably between 7.5 and 25% by weight and in particular between 10 and 20% by weight can have. The expert is not limited in his freedom of formulation restricts and can make stronger or weaker bleaching detergent tablets , detergent tablets or bleach tablets by changing the contents of bleach activator and bleaching agent varied.

A particularly preferably used bleach activator is the N, N, N ', N'- Tetraacetylethylenediamine, which is widely used in detergents and cleaning agents. Accordingly, preferred detergent tablets are thereby ge indicates that as a bleach activator tetraacetylethylenediamine in the above Amounts are used.

In addition to the ingredients mentioned, bleach, bleach activator, builder, surfactant and Disintegration aids, the washing and cleaning agents according to the invention molded body further ingredients from the group that are common in washing and cleaning agents of dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, Anti-redeposition agents, graying inhibitors, color exhaustion inhibitors and corro ion inhibitors included.

For the aesthetic impression of the detergent and cleaning agent form according to the invention to improve the body, they can be colored with suitable dyes. before drawn dyes, the selection of which is not difficult for the person skilled in the art a high storage stability and insensitivity to the other ingredients of the Medium and against light and no pronounced substantivity towards textile fibers in order not to stain them.

Preferred for use in the detergent and cleaning agent form according to the invention bodies are all colorants that can be oxidatively destroyed in the washing process as well  Mixtures of these with suitable blue dyes, so-called blue tones. It turned out to be proven to use colorants that are in water or at room temperature liquid organic substances are soluble. For example, anionic ones are suitable Colorants, e.g. B. anionic nitroso dyes. A possible colorant is, for example se Naphtholgrün (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020), which as a trade product, for example, available as Basacid® Green 970 from BASF, Ludwigshafen is, and mixtures of these with suitable blue dyes. As another colorant come Pigmosol® Blue 6900 (CI 74160), Pigmosol® Green 8730 (CI 74260), Basonyl® Red S4S FL (CI 45170), Sandolan® Rhodamine EB400 (CI 45 100), Basacid® Yellow 094 (CI 47005), Sicovit® Patent Blue 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), Pigment Blue 15 (CI 74160), Supranol® Blau GLW (CAS 12219-32-8, CI Acidblue 221)), Nylosan® Yellow N-7GL SGR (CAS 61814-57-I, C1 Acidyellow 218) and / or Sandolan® Blue (CI Acid Blue 182, CAS 12219-26-0).

When choosing the colorant, care must be taken to ensure that the colorants do not have too strong an affinity for the textile surfaces and especially for synthetic fibers. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stabilities against oxidation. Generally speaking, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaning agents varies. In the case of readily water-soluble colorants, e.g. B. the above-mentioned Basacid® green or the above-mentioned Sandolan® blue, dyeing medium concentrations are typically selected in the range of a few 10 ^-2 to 10 ^-3 wt .-%. In the preferred because of their brilliance, but less water-soluble pigment dyes, for. B. the above-mentioned Pigmosol® dyes, the suitable concentration of the colorant in washing or cleaning agents, however, is typically a few 10 ^-3 to 10 ^-4 wt .-%.

The moldings can be optical brighteners of the derivative type of the diaminostilbene contain sulfonic acid or its alkali metal salts. Are suitable for. B. salts of 4,4'- Bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or the like  built-up compounds that a diethanolamino instead of the morpholino group group, a methylamino group, an anilino group or a 2-methoxyethylamino wear group. Brighteners of the substituted diphenylstyryl type can also be used be essential, e.g. B. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3- sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures too the aforementioned brighteners can be used. The optical brighteners are in the detergent tablets according to the invention in concentrations between between 0.01 and 1% by weight, preferably between 0.05 and 0.5% by weight and in particular between 0.1 and 0.25% by weight, based in each case on the entire shaped body puts.

Fragrances are added to the agents according to the invention in order to maintain an aesthetic appearance to improve product pressure and consumer in addition to product performance a visually and sensorially "typical and distinctive" product is available put. As perfume oils or fragrances, individual fragrance compounds, e.g. B. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and Koh type Hydrogen oils are used. Fragrance compounds of the ester type are e.g. B. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dime thylbenzylcarbinylacetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethylmethyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. To the Ethers include, for example, benzyl ethyl ether, the aldehydes e.g. B. the linear Alka nale with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. B. the Jonone, OC- Isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, are hydrocarbons mainly the terpenes such as limes and pinene. However, Wed are preferred uses different fragrances, which together make an appealing Generate fragrance. Such perfume oils can also contain natural fragrance mixtures ten, as they are accessible from plant sources, e.g. B. Pine, Citrus, Jasmine, Pat chouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, Ka millen oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil,  Vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil neroliol, Orange peel oil and sandalwood oil.

The content of the detergent and cleaning agent form according to the invention is usually body of fragrances up to 2% by weight of the total formulation. The fragrances can can be incorporated directly into the agents according to the invention, but it can also be advantageous be to apply the fragrances to carriers that will adhere the perfume to the laundry intensify and through a slower fragrance release for long-lasting fragrance of the texti lien worry. Cyclodextrins, for example, have proven to be such carrier materials lasts, the cyclodextrin-perfume complexes additionally with other auxiliary substances fen can be coated.

Enzymes in particular come from the hydrolase classes such as the protea sen, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned in question. All this hy drolasen wear in the laundry to remove stains such as protein, fat or starchy stains and graying. Cellulases and other glycosyl hy drolasen can also be removed by removing pilling and microfibrils Color preservation and increase the softness of the textile. For bleaching or Inhibition of color transfer can also be used oxidoreductases. Beson are particularly suitable from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well their genetically modified variants obtained enzymatic active ingredients. before Proteases of the subtilisin type and in particular proteases derived from Ba cillus lentus are used. There are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytically acting enes zymmen or from protease, amylase and lipase or lipolytic 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 special interest. Examples of such lipolytic enzymes are the well-known cutinases. Peroxidases or oxidases have also been found in some  Cases proved to be suitable. Suitable amylases include in particular alpha- Amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferred as cellobiohydrolases, endoglucanases and glucosidases, which also cellobiases ge are called, or mixtures of these are used. Since different cellulase Distinguishing types by their CMCase and Avicelase activities can by ge targeted mixtures of the cellulases the desired activities can be set.

The enzymes can be adsorbed on carriers or embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5% by weight.

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

The moldings according to the invention are produced in two steps. In the first step are in a known manner detergent tablets by Ver press particulate detergent and cleaning compositions are produced, the second step can be provided with the coating.  

Another object of the present invention is therefore a method of manufacture development of coated detergent tablets by known per se Pressing a particulate detergent or cleaning agent composition because characterized in that the molded body after pressing with a coating are provided, which covers less than 100% of the molded body.

Analogous to the explanations regarding the washing and cleaning agents according to the invention Shaped bodies are also the polymers mentioned in the process according to the invention preferred, so that reference can be made to the above statements.

A description of the two major process steps follows.

The molded articles to be coated later according to the invention are produced next through the dry mixing of the components that are partially or completely pre-granulated can be lated, and then bringing information, in particular pressing to tablet ten, whereby conventional methods can be used. To make the The pre-mix is molded in a so-called die between two stamps compacted into a solid compressed. This process, hereinafter referred to briefly as a tablet is divided into four sections: dosing, compression (elasti deformation), plastic deformation and ejection.

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

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

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

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

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

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

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

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

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

The moldings can ge in a predetermined spatial shape and a predetermined size be manufactured. Practically all sensibly manageable designs come as a spatial form conditions, for example the formation as a board, the shape of a bar or bar, Cubes, cuboids and corresponding room elements with flat side surfaces and esp special cylindrical configurations with circular or oval cross-section. This last embodiment covers the presentation form from the tablet to com Compact cylinder pieces with a ratio of height to diameter above 1.

The portioned compacts can each be separate individual elements be formed, the predetermined dosage of washing and / or cleaning medium corresponds. However, it is also possible to form compacts that have a plurality connect such mass units in a compact, in particular by vorege bene predetermined breaking points the easy separability of portioned smaller units hen is. For the use of textile detergents in machines of the type common in Europe with horizontally arranged mechanics, the formation of the portioned compacts as Tablets, in the shape of a cylinder or cuboid, with a diameter / height Ratio in the range of about 0.5: 2 to 2: 0.5 is preferred. Commercial hydrau Lik presses, eccentric presses or rotary presses are suitable devices in particular especially for the production of such compacts.

The spatial shape of another embodiment of the shaped body is in its dimensions the induction chamber of commercial household washing machines adapted so that the Shaped bodies can be metered directly into the induction chamber without a metering aid, where it dissolves during the induction process. Of course, there is also a stake the detergent tablets are easily possible via a dosing aid and within the present invention preferred.

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

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

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

In addition to the layer structure, multi-phase moldings can also be in the form of a toroidal core Tablets, core coated tablets or so-called "bulleye" tablets are produced. An overview of such embodiments of multi-phase tablets is in EP 055 100 (Jeyes Group). This document discloses blocks of toilet detergent, which composes a molded body from a slowly soluble detergent tion in which a bleach tablet is embedded. This document reveals at the same time the most diverse designs of multiphase molded bodies from from simple multi-phase tablets to complicated multi-layer systems Insoles.

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

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

Preferred manufacturing processes for detergent tablets are based on a surfactant-containing one Granulate from that with other processing components to one to be pressed particulate premix is prepared. Completely analogous to the above stungen about preferred ingredients of the washing and cleaning agent according to the invention The use of further ingredients in their manufacture is also to be transferred to the molded article In preferred processes, the particulate premix additionally contains surfactant containing granulate (s) and has a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l.  

In preferred processes according to the invention, the surfactant-containing granules have particles sizes between 100 and 2000 microns, preferably between 200 and 1800 microns, particularly preferably between 400 and 1600 μm and in particular between 600 and 1400 μm.

The other ingredients of the washing and cleaning agents according to the invention Shaped bodies can be introduced into the process according to the invention, for which purpose the reference is made to the above statements. Preferred processes are characterized thereby records that the particulate premix additionally one or more substances from the Group of bleaching agents, bleach activators, disintegration aids, enzymes, pH Adjusting agents, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, Silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, Contains color transfer inhibitors and corrosion inhibitors.

The second step of the method according to the invention comprises the application of the par tialcoating. This can be based on common methods of coating bodies are gripped, in particular thus the immersion of parts of the molded body in or Spray these parts with a melt, solution or dispersion of the above-mentioned Po mers. Accordingly, preferred methods according to the invention are characterized thereby net that the coating by partial immersion of the molded body in or by Be spray these areas with a melt, solution, emulsion or dispersion of a or several coating materials.

For applying a coating that covers less than 100% of the molded body, preferably has recesses, various methods are available to the person skilled in the art Available. In one possible embodiment, the molded body is only partially loaded layers, d. H. surfaces become on the surface during the coating process of the molded body is not coated.

In another embodiment, the areas where there are recesses should be covered. After applying the coating, the cover is removed again removed. This embodiment offers the possibility of covering any shape use, whereby an optical differentiation can be achieved.  

In a further embodiment, the moldings are completely coated on finally the coating is partially removed. Removing the coating can in any way, by grinding or milling. In a preferred version Staltung this embodiment, a base molding is used, the survey having. The base molding is completely coated. Below is the Erhe Grinded exercise so that a recess in the coating is obtained.

In a further embodiment of the present invention, the coating is in one applied in such a thickness that it does not form a closed layer, but the shape body covered like a net.

Depending on the materials that are used for the partial coating the manufacturing process can be varied. For substances that can be melted without decomposing and form stable, adequately processable melts is the process of melting Layering preferred, since the corresponding coating layer is quickly formed and on the use of additional aids such as solvents etc. can be dispensed with can. In particular inorganic salts, organic compounds such as urea or the Polyalkylene glycols are preferably applied via the melt coating process the mechanically sensitive molded body areas applied. Here are procedures preferred at which a melt at temperatures of 40 to 200 ° C, preferably from 45 to 170 ° C and in particular from 50 to 150 ° C on the edges of the moldings will be carried.

Depending on the geometry of the moldings, the melt can be applied by suitable means Molded nozzles and spraying of the melt take place, but it is also possible to mold body past brushes, fleeces or micro-nozzles, the melt on the ge dosing the desired areas where it solidifies and forms the partial coating. Also ent speaking-shaped chambers in which the melt is present in predetermined areas, which only allow contact to the molded body at certain points and the insertion or rolling the moldings in or through these chambers are applicable Method.  

Substances that cannot be melted or can only be melted at great expense can be the solution. Dispersion or emulsion can be applied. These include in particular the named Polymers. Appropriate processes in which a solution, emulsion or dispersion one or more coating materials with concentrations of 1 to 95% by weight, preferably from 5 to 90% by weight and in particular from 10 to 80%, in each case based on the solution, emulsion or dispersion to which the edges of the moldings are applied, are preferred.

Since the immersion of the mechanically sensitive areas of washing or cleaning medium shaped bodies in melts or solutions or dispersions only under high tech nical effort leads to the desired partial coatings, it is within the scope of In the present invention, solutions or dispersions are preferably applied to the moldings spray, the solvent or dispersant evaporates and a coating leaves on the corresponding parts of the molded body. In preferred fiction The method is an aqueous solution of one or more polymers from the above mentioned groups a) to e) on the mechanically sensitive parts of the moldings sprayed, the aqueous solution, in each case based on the solution, 1 to 20% by weight, preferably 2 to 15 wt .-% and in particular 4 to 10 wt .-% polymer (s) from the Groups a) to e), optionally up to 20% by weight, preferably up to 10% by weight, and in particular in particular less than 5% by weight of one or more water-miscible solvents and the rest contains water.

To shorten the drying time, the aqueous solution or dis persion other water-miscible volatile solvents can be added. These come in particular from the group of alcohols, ethanol, n-propanol and iso-propanol are preferred. Ethanol and ethanol are particularly recommended for cost reasons iso-propanol.

In the context of the invention, aqueous dispersions are to be understood as such dispersions hen whose outer phase consists mainly of water. The outer phase can go over it other water-miscible solvents such as ethanol and iso-  Contain propanol; these further solvents are at most in amounts of up to 20% by weight. %, based on the total, included. The outer phase preferably contains water as the only solvent; contains a further preferred embodiment in the Ren phase, based on the total agent, no more than 5% of other solvents.

The spraying of such aqueous solutions or dispersions can vary Types occur that are familiar to the expert. For example, the solution or Dispersion are fed to a nozzle by means of a pump system, where the solution or Dispersion is atomized by the high shear forces. The resulting spray mist can then be directed to the shaped body to be coated, which follows optionally with the help of suitable measures (for example blowing with he warmed air). However, it is also possible to use a multi-component nozzle turn and the aqueous solutions or dispersions with the help of a gas stream to atomize the nozzle. In the simplest case, a two-substance nozzle is used and as a carrier Gas compressed air used. To the dispersion, if necessary, before oxidation or other To protect their interactions with the carrier gas, other carrier gases can also be used such as nitrogen, noble gases, lower alkanes or ethers can be used.

It is also possible to reduce the water content of the dispersion or solution, which shortens drying times, interactions with moisture-sensitive Ingredients on the molded body surface are minimized and production costs are reduced. The lower alcohols mentioned above are also suitable as solvents here, completely anhydrous solvent mixtures are less preferred because certain Amounts of water favor the formation of an even coating layer. In preferred method according to the invention is a solution or dispersion of a several polymers from groups a) to e) in a solvent or solvent mixture from the group water, ethanol, propanol, iso-propanol, n-heptane and their Mixtures with the aid of inert blowing agents from the group nitrogen, nitrous oxide, Propane, butane, dimethyl ether and mixtures thereof are sprayed onto the moldings.  

In such preferred process variants according to the invention, the solutions or dispersions advantageously have the following composition, the details relating in each case to the dispersion to be sprayed on:

• a) 30 to 99% by weight, preferably 40 to 90% by weight and in particular 50 to 85% by weight Ethanol, propanol, isopropanol, n-heptane or mixtures thereof,
• b) 0 to 20, preferably 1 to 15 and in particular 2 to 10% by weight of water,
• c) 1 to 50, preferably 2 to 25 and in particular 3 to 10% by weight of one or several polymers from groups a) to e).

Other ingredients of the dispersions to be sprayed on can be, for example, color or Fragrances or pigments. Such additives improve the visual, for example or olfactory impression of the molded articles coated according to the invention. Color and Fragrances have been described in detail above. Pigments come for example white pigments such as titanium dioxide or zinc sulfide, pearlescent pigments or colored pigments elements into consideration, the latter in inorganic pigments and organic pigments can be shared. All of the pigments mentioned are preferred if they are used wise finely divided, d. H. with average particle sizes of 100 µm and well below set.

In order to achieve the formation of a uniform and as thin a coating as possible, it is preferred to make the solution or dispersion of the coating materials as fine as possible to be nebulized before it hits the molded body. Process according to the invention, in de NEN the solution and / or dispersion in question is injected onto the moldings is brought, the mean droplet size in the spray less than 100 microns before is preferably less than 50 microns and in particular less than 35 microns, be vorzugt. In this way, the above-mentioned preferred thickness of the loading Realize layering easily.

Of course, what has been said above for solutions and dispersions also applies to Emulsions.  

In preferred processes within the scope of the present invention, the solution contains Emulsion or dispersion as a solvent, emulsion base or dispersant one or more substances from the group water, methanol, ethanol, 1-propanol, 2- Propanol, diethyl ether, n-heptane and their mixtures and is made with the help of inert Blowing agents from the group of air, nitrogen, nitrous oxide, propane, butane and dimethyl ther and their mixtures sprayed onto the moldings.

This inventive use of a partial coating leads to partially coated molded articles pern with advantageous properties, as the examples below show. Regarding preferred embodiments of the use according to the invention (ingredients, zu composition of the premix, preferred coating materials etc.) applies analogously standing for the method according to the invention.

Preferred embodiments of the present invention are shown in the accompanying figures shown. Show it

Fig. 1 shows a section through a fully coated multi-phase molded bodies comprising a collection,

A section through the Formkörpfer from Fig. 1, in which the survey was ent Fig. 2 removed,

Fig. 3 shows a molded body with an annular recess

Fig. 4 is a side view of a molded body with chamfered edges and

Fig. 5 shows a molded body with recesses on the side surface.

In Fig. 1, a shaped body is shown, which consists of three phases, an upper phase 1, a middle stage and a lower 2 Phase 3. Furthermore, the molded body has an elevation 4 . It is completely covered with a coating 5 .

In order to achieve a partial coating, the elevation 4 is removed by grinding, whereby the recess 6 is formed. In the embodiment shown in FIGS. 1 and 2, the recess 6 is held by grinding the elevation 4 flat. In this embodiment, the ingredients of the upper phase 1 first come into contact with water and are released. As soon as phase 1 has completely dissolved or disintegrated, only the ingredients of phase 2 come into contact with water and are released. The ingredients of lower phase 3 are then released .

Another embodiment of the present invention is shown in Fig. 3, in which an annular recess 7 is obtained by appropriate annular removal of the coating 5 Be.

It is obvious to the person skilled in the art that the cutouts can also be located in other areas of the shaped bodies. For example, the edges 8 of the completely coated shaped bodies can be milled off, so that the cutouts are located in the chamfered edges, as shown in FIG. 4.

In a further embodiment of the present invention, as shown in Fig. 5 Darge, the coating on the side surface 9 of the molded body is removed all around, so that the recess (s) are located on the side surfaces. In this embodiment, the water first comes into contact with the middle phase 2 , which is released immediately, while the upper phase 1 and the lower phase 3 only come into contact with water at a later point in time.

LIST OF REFERENCE NUMBERS

1

upper phase

2

middle phase

3

lower phase

4

survey

5

coating

6

recess

7

annular recess

8th

edge

9

faces

Claims (26)

1. Detergent or cleaning product tablets made of compressed particulate washing or cleaning agent, containing builders (e), surfactant (s) and optionally further detergent or cleaning agent components, which is so prepared that it has a delayed solubility in contact with water, thereby characterized in that the shaped body has a coating that covers less than 100% of the shaped body. 2. shaped detergent or cleaning product according to claim 1, characterized in that the coating at least 50%, preferably at least 75% and in particular which covers at least 85% of the total surface of the molded body. 3. shaped detergent or cleaning product according to one of claims 1 or 2, characterized characterized in that the coating on the uncoated molded body is a network forms. 4. Detergent tablets according to one of claims 1 or 2, characterized characterized in that the coating has recesses. 5. Detergent tablets according to claim 4, characterized in that the recess is arranged on the top of the molded body and an arbitrary has a geometric round or square shape, such as a circle, rectangle, square, Polygon, or is annular. 6. shaped detergent or cleaning product according to one of claims 1 or 2, characterized characterized in that the molded body has chamfered edges on which the off savings. 7. Detergent tablets according to one of claims 1 or 2, characterized characterized in that the recesses are on the side surfaces.   8. shaped detergent or cleaning product according to one of claims 1 to 7, characterized characterized in that the weight ratio of uncoated molded body to Be Layering greater than 10 to 1, preferably greater than 50 to 1 and especially larger is greater than 100 to 1. 9. shaped detergent or cleaning product according to one of claims 1 to 8, characterized characterized in that the thickness of the coating 0.1 to 3000 microns, preferably 0.5 up to 500 µm and in particular 5 to 250 µm. 10. shaped detergent or cleaning product according to one of claims 1 to 7, characterized characterized in that the coating one or more solid substances with a What Solubility of more than 200 g / l at 20 ° C includes. 11. shaped detergent or cleaning product according to one of claims 1 to 8, characterized characterized in that the coating comprises carboxylic acids, those with 12 to 22, preferably having 18 to 22 carbon atoms and preferred among them Species with an even number of carbon atoms are particularly preferred. 12. Detergent tablets according to one of claims 1 to 9, characterized characterized in that the coating comprises dicarboxylic acids, those with min at least 4, preferably with at least 6, particularly preferably with at least 8 and especially preferred those with 8 to 13 carbon atoms and among them the Species with an even number of carbon atoms are particularly preferred. 13. Detergent or cleaning product tablet according to one of claims 1 to 10, characterized characterized in that the coating film-forming substances, in particular from the Groups of polyethylene and / or polypropylene glycols, copolymers of acrylic acid and maleic acid or the sugar.   14. Detergent tablets according to one of claims 1 to 11, characterized in that the coating comprises a polymer or polymer mixture which is selected from

• a) water-soluble nonionic polymers from the group of
  • 1. polyvinylpyrrolidones,
  • 2. vinyl pyrrolidone / vinyl ester copolymers,
  • 3. Cellulose ether
  • 4. Homopolymers of vinyl alcohol, copolymers of vinyl alcohol with copolymerizable monomers or hydrolysis products of vinyl ester homopolymers or vinyl ester copolymers with copolymerizable monomers
• b) water-soluble amphoteric polymers from the group of
  • 1. Alkyl acrylamide / acrylic acid copolymers
  • 2. Alkyl acrylamide / methacrylic acid copolymers
  • 3. Alkyl acrylamide / methyl methacrylic acid copolymers
  • 4. Alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
  • 5. Alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
  • 6. Alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
  • 7. Alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers
  • 8. Copolymers
    • 1. unsaturated carboxylic acids
    • 2. cationically derivatized unsaturated carboxylic acids
    • 3. optionally further ionic or nonionic monomers
• c) water-soluble zwitterionic polymers from the group of
  • 1. Acrylamidoalkyltrialkylammoniumchlorid / acrylic acid copolymers and their alkali and ammonium salts
  • 2. Acrylamidoalkyltrialkylammoniumchlorid / methacrylic acid copolymers and their alkali and ammonium salts
  • 3. Methacroylethyl betaine / methacrylate copolymers
• d) water-soluble anionic polymers from the group of
  • 1. Vinyl acetate / crotonic acid copolymers
  • 2. Vinyl pyrrolidone / vinyl acrylate copolymers
  • 3. Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers
  • 4. Graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols
  • 5. grafted and crosslinked copolymers from the copolymerization of
    • 1. at least one monomer of the non-ionic type,
    • 2. at least one monomer of the ionic type,
    • 3. of polyethylene glycol and
    • 4. a networked person
  • 6. copolymers obtained by copolymerizing at least one monomer of each of the following three groups:
    • 1. esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
    • 2. unsaturated carboxylic acids,
    • 3. Esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group d6ii) with saturated or unsaturated, straight-chain or branched C _8-18 alcohol
  • 7. Graft copolymers obtainable by grafting d7i) polyalkylene oxides with d7ii) vinyl acetate
  • 8. Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ster
  • 9. Tetra and pentapolymers
    • 1. Crotonic acid or allyloxyacetic acid
    • 2. Vinyl acetate or vinyl propionate
    • 3. branched allyl or methallyl esters
    • 4. Vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters
  • 10. Crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinyl methyl ether, acrylamide and their water-soluble salts
  • 11. Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the α-position
• e) water-soluble cationic polymers from the group of
  • 1. quaternized cellulose derivatives
  • 2. Polysiloxanes with quaternary groups
  • 3. cationic guar derivatives
  • 4. polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid
  • 5. Copolymers of vinyl pyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate
  • 6. Vinyl pyrrolidone-methoimidazolinium chloride copolymers
  • 7. Quaternized polyvinyl alcohol
  • 8. Polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27
• f) polyurethanes
• g) LCST polymers, preferably selected from alkylated and / or hydroxyalkylated polysaccharides, cellulose ethers, acrylamides, such as polyisopropylacrylamide, copolymers of acrylamides, polyvinylcaprolactam, copolymers of polyvinylcaprolactam, in particular those with polyvinylpyrrolidone, polyvinylmethylether, copolymers of polyvinylendmethyl ether substances.

15. Detergent or cleaning product tablet according to one of claims 1 to 12 characterized in that the coating additionally contains a disintegration aid Amounts from 0.1 to 10 wt .-%, preferably from 0.2 to 7.5 wt .-% and in particular dere from 0.25 to 5 wt .-%, each based on the coating layer. contains. 16. shaped detergent or cleaning product according to one of claims 1 to 13, characterized characterized in that the moldings additionally a disintegration aid preferably a cellulose-based disintegration aid, preferably in granules rer, cogranulated or compacted form, in amounts of 0.5 to 10 wt .-% before preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based to the weight of the shaped body, with preferred disintegration aids average particle sizes above 300 microns, preferably above 400 microns and have in particular above 500 microns. 17. Detergent tablets according to one of claims 1 to 14, characterized characterized in that they contain anionic (s) and / or nonionic (s) surfactant (s) and total surfactant contents above 2.5% by weight, preferably above 5% by weight and in particular above 10% by weight, in each case based on the molding per weight. 18. Process for the production of coated detergent tablets pern by pressing a particulate washing or cleaning agent known per se detergent composition, characterized in that the shaped body after Pressing can be provided with a coating which is less than 100% of the Shaped body covered. 19. The method according to claim 18, characterized in that the surface areas of the pressed molded body, which should not be covered with a coating be covered, the coating applied and then the cover like which is removed.   20. The method according to claim 18, characterized in that the molded body according to the Pressing is first completely coated and then the coating is partially removed. 21. The method according to claim 20, characterized in that the pressed molded body has an elevation that is removed after the application of the coating. 22. The method according to claim 18, characterized in that the coating with a Layer thickness is applied that no closed layer is formed. 23. The method according to any one of claims 18 to 22, characterized in that the loading layer by partially immersing the molded bodies in or by spraying them Areas with a melt, solution, emulsion or dispersion of one or more Coating materials are made. 24. The method according to any one of claims 18 to 21, characterized in that a Melt at temperatures from 40 to 200 ° C, preferably from 45 to 170 ° C and in particular from 50 to 150 ° C is applied to the edges of the moldings. 25. The method according to any one of claims 18 to 24, characterized in that a Lö solution, emulsion or dispersion of one or more coating materials Concentrations from I to 95 wt .-%, preferably from 5 to 90 wt .-% and esp special from 10 to 80%, in each case based on the solution, emulsion or dispersion, is applied to the edges of the moldings. 26. The method according to claim 25, characterized in that the solution, emulsion or Dispersion as a solvent, emulsion base or dispersant one or several substances from the group water, methanol, ethanol, 1-propanol, 2-propanol, Contains diethyl ether, n-heptane and their mixtures and with the help of inert Air, nitrogen, nitrous oxide, propane, butane, dime blowing agents ethyl ether and mixtures thereof is sprayed onto the moldings.