EP1261686B1 - Multiphase moulded detergent bodies with non-pressed parts - Google Patents

Description

The present invention relates to detergent tablets having a plurality of non-compressed portions.

Detergent or detergent tablets are widely described in the art and have prevailed because of their advantages in commerce and the consumer.

The customary production of detergent tablets comprises the preparation of particulate premixes which are compressed into tablets by tabletting methods known to those skilled in the art. However, this method of preparation has significant disadvantages, since pressure-sensitive ingredients can be damaged during manufacture. So far, these ingredients such as e.g. encapsulated enzymes, etc. can not be incorporated into tablets without loss of activity. In some cases, even instability or total inactivity could be expected.

In addition, the supply form of the compressed tablet implies that the ingredients are in direct physical proximity to each other, resulting in undesirable reactions, instabilities, inactivities or loss of active ingredient in incompatible substances.

To solve the above-mentioned problems, it has been proposed in the prior art to provide multi-phase tablets in which several layers are pressed on each other. However, this has the disadvantage that the lower layers are subjected to a multiple pressure load, resulting in deteriorated solubility. In addition, the problems mentioned were not completely solved because more than three-layer tablets can not be produced with reasonable technical effort.

Another approach is the international patent applications WO99 / 06522 . WO99 / 27063 and WO99 / 27067 refer to. Here it is proposed to provide tablets of compressed and non-compressed portions and to incorporate pressure-sensitive substances into the non-compressed portions. However, the problem with simultaneous incorporation and separation of several pressure-sensitive ingredients is not solved here.

WO99 / 27064 describes mono- or multi-phase gel-like molded articles which are produced from a liquid mixture containing a thickening system. The liquid mixture is poured into a mold and thickened or hardened there. Thereafter, another gelling mixture may be added to the mold. The molded body rests in this form until the second gel is hardened.

The European patent application EP0055100 has multi-phase tablets for toilet cleaning to the contents, wherein the first portion can be pressed or extruded or poured, while the second portion is obtained by casting or extrusion. The first portion is slowly soluble, the second faster.

1. (a) einen ersten nicht-verpreßten Teil, der Aktivsubstanz enthält
2. (b) einen weiteren nicht-verpreßten Teil, der Aktivsubstanz enthält

umfassen, wobei der Formkörper Enzyme enthält und der nicht-verpresste Teil (a) durch Sintern hergestellt wurde. WO 96/06156 discloses rapidly soluble single phase detergent tablets obtained by sintering by microwave technique. There was therefore still a need to provide improved detergent tablets which combine the highest degree of mechanical stability with good solubility and also allow the economical production and the incorporation of pressure-sensitive ingredients in embodiments with more than three phases. According to a first embodiment, therefore, the present invention relates to detergent tablets, the

1. (a) a first non-compressed part containing active substance
2. (b) another non-compressed part containing active substance

wherein the shaped body contains enzymes and the non-compressed part (a) was produced by sintering.

The present invention is not limited in the design of the individual non-compressed portions. Nevertheless, it has proved to be advantageous for application reasons when the second non-compressed part (b) does not completely enclose the first non-compressed part (a).

Of course, the present invention is not limited to biphasic moldings. Detergent tablets containing a first non-compressed portion (a), a second non-compressed portion (b) and, in addition, other non-compressed portions are preferred embodiments of the present invention. Explicit to call here are three, four, five and six-phase moldings from the corresponding number of non-compressed parts.

Of course, according to the invention consisting of at least two non-compressed parts moldings can also be designed so that they contain other compressed parts, if this is desired for certain reasons. A combination of a two-part tablet according to the invention of two non-compressed portions with a single-phase or multi-phase, for example two-layer, conventionally compressed tablet is therefore also possible. In this way, the advantages of the present invention, for example by adhering inventive moldings to non-inventive moldings can also be used.

In the case of multiphase moldings, embodiments are particularly preferred in which the first non-compressed portion (a) has a plurality of cavities and each further non-compressed part is at least partially contained in a cavity.

The non-compressed part (a) may assume any geometric shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, five-, seven- and octagonal-prismatic and rhombohedral forms are preferred. Even completely irregular surfaces such as arrow or animal shapes, trees, clouds, etc. can be realized. If the base molding has corners and edges, these are preferably rounded off. As additional optical differentiation, an embodiment with rounded corners and chamfered edges is preferred.

The shape of the cavity (s) can also be chosen freely, wherein moldings are preferred in which at least one cavity is a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, hexagonal, octagonal, prismatic and rhombohedral shapes. Completely irregular cavity forms such as arrow or animal forms, trees, clouds etc. can also be realized. As with the non-compressed portions (a), cavities with rounded corners and edges or with rounded corners and chamfered edges are preferred.

The size of the cavity compared to the entire molded body depends on the intended use of the molded body. Depending on whether a lower or greater amount of active substance is to be contained in the second measured amount, the size of the cavity may vary. Regardless of the intended use, detergent tablets are preferred in which the weight ratio of non-compressed part (a) to non-compressed part (b) ranges from 1: 1 to 100: 1, preferably from 2: 1 to 80: 1 , more preferably from 3: 1 to 50: 1 and in particular from 4: 1 to 30: 1.

Similar statements can be made to the surface portions that make up the first or second non-compressed portions of the total surface of the moldings. Here, washing and cleaning agent portions are preferred in which the surface of the second non-compressed part constitutes 1 to 25%, preferably 2 to 20%, particularly preferably 3 to 15% and in particular 4 to 10% of the total surface of the shaped body.

If, for example, the overall shaped article has dimensions of 20 × 20 × 40 mm and thus a total surface area of 40 cm ² , then second non-compressed parts (b) are preferred which have a surface area of from 0.4 to 10 cm ² , preferably from 0.8 to 8 cm ² , more preferably from 1.2 to 6 cm ² and in particular from 1.6 to 4 cm ² .

The second non-compressed part (b) and the "base molded article" (a) are preferably dyed optically distinguishable. In addition to the optical differentiation, application advantages can result from this.

The different phaseity of the shaped body can be used for drug separation. Particularly preferred detergent tablets according to the invention are those in which the first non-compressed part (a) and the second non-compressed part (b) contain at least one different active substance.

In particular, both laundry detergent or detergent tablets in which the first non-compressed part (a) or the second non-compressed part (b) contains bleach, while the other part contains bleach activators, as well as detergent tablets, in which the first non-compressed part (a) or the second non-compressed part (b) contains bleaching agent, while the other part contains enzymes, and detergent tablets in which the first non-compressed part (a) or the second one does not - compressed part (b) Bleach contains, while the other part contains corrosion inhibitors, preferred embodiments of the present invention.

Preference is also given to detergent tablets which are characterized in that the first non-compressed part (a) or the second non-compressed part (b) contains bleach, while the other part alkoxylated surfactants, preferably nonionic surfactants, with particular preference Alcohols having 10 to 24 carbon atoms and 1 to 5 alkylene oxide units.

Detergent and cleaning product according to one of Claims 1 to 13, characterized in that the first non-compressed part (a) and the second non-compressed part (b) contain the same active substance in different amounts. Examples of ingredients in which the division into the different regions has advantages are disintegration aids, dyes and perfumes, optical brighteners, polymers, silver protectants To name surfactants and enzymes. The term "different amounts" here denotes the content of the individual shaped body area on the relevant substance, based on the shaped body area, is therefore a percentage by weight which does not relate to the absolute amounts of the ingredient.

In the context of the present invention, particular preference is given to detergent tablets in which at least one non-compressed part, preferably the non-compressed part (b), is coated with a coating layer.

This coating layer can be used to control the dissolution kinetics of the other non-compressed part, but it can also serve to attach the other non-compressed part to another non-compressed part, in which one, for example, a non-compressed part (b) one or in the cavity of a non-compressed part (a) sets and fixed by applying a coating layer.

Corresponding detergent tablets in which the non-compressed part (b) is fastened by the coating layer on or in the non-compressed part (a) are also preferred.

If the entire shaped bodies according to the invention or individual non-compressed parts are coated, preference is given to washing or cleaning agent shaped bodies in which the coating layer contains one or more substances from the groups of the fatty acids, fatty alcohols, diols, esters, ethers, carboxylic acids, dicarboxylic acids, polyvinyl acetate ( PVA), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVAl), polyethylene glycol (PEG), polypropylene glycol (PPG) and mixtures thereof.

genügen, wobei n Werte zwischen 10 und 2000 annehmen kann. Bevorzugte PPG weisen Molmassen zwischen 1000 und 10.000, entsprechend Werten von n zwischen 17 und ca. 170, auf.Polypropylene glycols which can be used according to the invention (abbreviated PPG) are polymers of propylene glycol which correspond to the general formula I

satisfy, where n can take values between 10 and 2000. Preferred PPG have molecular weights between 1000 and 10,000, corresponding to values of n between 17 and about 170.

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

H- (O-CH ₂ -CH ₂ ) _n -OH (II)

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

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

Thus, detergent tablets wherein the coating comprises carboxylic acids, with those having from 12 to 22, preferably from 18 to 22, carbon atoms being preferred and among which the even-numbered carbon species are particularly preferred, another preferred embodiment of the present invention. A likewise preferred embodiment are detergent tablets or detergent tablets, which are characterized in that the coating comprises dicarboxylic acids, 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 even number of carbon atoms are particularly preferred. With regard to the particularly preferred individual compounds from the said groups of carboxylic and dicarboxylic acids, reference may be made to the above statements.

Further suitable coating materials are film-forming substances. Preferred among these are polyalkylene glycols, especially polyethylene and polypropylene glycols, polymers and copolymers of (meth) acrylic acid, in particular copolymers of acrylic acid and maleic acid, and also sugars.

Polyethylene and propylene glycols are described below. The polymers of (meth) acrylic acid, in particular the copolymers of acrylic acid and maleic acid, are known as co-builders for detergents or cleaners. They are described below.

The term "sugar" in the context of the present invention denotes single and multiple sugars, ie monosaccharides and oligosaccharides, in which 2 to 6 monosaccharides are connected to one another in an acetal fashion. In the context of the present invention, "sugars" are therefore monosaccharides, disaccharides, trisaccharides, tetra-, penta- and hexasaccharides.

Monosaccharides which can be used as sugar in the context of the present invention are, for example, the tetroses D (-) - erythrose and D (-) - threose and also D (-) - erythrulose, the pentoses D (-) - ribose, D (-) - ribulose, D (-) - arabinose, D (+) - xylose, D (-) - xylulose and D (-) - lyxose and the hexoses D (+) - allose, D (+) - altrose, D (+) - glucose , D (+) - mannose, D (-) - gulose, D (-) - idose, D (+) - galactose, D (+) - talose, D (+) - psicose, D (-) - fructose, D (+) - sorbose and D (-) - tagatose. The most important and widely used monosaccharides are: D-glucose, D-galactose, D-mannose, D-fructose, L-arabinose, D-xylose, D-ribose and the like. 2-deoxy-D-ribose.

The most important disaccharides are sucrose (cane sugar, sucrose), trehalose, lactose (milk sugar), lactulose, maltose (malt sugar), cellobiose (degradation product of cellulose), gentobiose, melibiose, turanose and others.

Trisaccharides are carbohydrates, which are composed of 3 glycosidically linked monosaccharides and for which one occasionally encounters the incorrect name of trioses. Trisaccharides are relatively rare in nature, examples are gentianose, kestose, maltotriose, melecitose, raffinose, and as an example of amino sugar-containing trisaccharides streptomycin and validamycin.

Tetrasaccharides are oligosaccharides with 4 monosaccharide units. Examples of this class of compounds are stachyose, lychnose (galactose-glucose-fructose-galactose) and secalose (from 4-fructose units).

In the context of the present invention, preferred sugars are saccharides from the group consisting of glucose, fructose, sucrose, cellulose, maltose, lactose, lactulose, ribose and mixtures thereof. Particular preference is given to washing or cleaning agent tablets whose coatings contain glucose and / or sucrose.

In the context of the present invention preferred detergent tablets are characterized in that the coating film-forming substances, in particular from the groups of polyethylene and / or polypropylene glycols, the copolymers of acrylic acid and maleic acid or the sugar contains.

• a) wasserlöslichen nichtionischen Polymeren aus der Gruppe der
  • a1) Polyvinylpyrrolidone,
  • a2) Vinylpyrrolidon/Vinylester-Copolymere,
  • a3) Celluloseether
• b) wasserlöslichen amphoteren Polymeren aus der Gruppe der
  • b1) Alkylacrylamid/Acrylsäure-Copolymere
  • b2) Alkylacrylamid/Methacrylsäure-Copolymere
  • b3) Alkylacrylamid/Methylmethacrylsäure-Copolymere
  • b4) Alkylacrylamid/Acrylsäure/Alkylaminoalkyl(meth)acrylsäure -Copolymere
  • b5) Alkylacrylamid/Methacrylsäure/Alkylaminoalkyl(meth)acrylsäure - Copolymere
  • b6) Alkylacrylamid/Methylmethacrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymere
  • b7) Alkylacrylamid/Alkymethacrylat/Alkylaminoethylmethacrylat/Alkylmethacrylat-Copolymere
  • b8) Copolymere aus
    • b8i) ungesättigten Carbonsäuren
    • b8ii) kationisch derivatisierten ungesättigten Carbonsäuren
    • b8iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren
• c) wasserlöslichen zwitterionischen Polymeren aus der Gruppe der
  • c1) Acrylamidoalkyltrialkylammoniumchlorid/Acrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze
  • c2) Acrylamidoalkyltrialkylammoniumchlorid/Methacrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze
  • c3) Methacroylethylbetain/Methacrylat-Copolymere
• d) wasserlöslichen anionischen Polymeren aus der Gruppe der
  • d1) Vinylacetat/Crotonsäure-Copolymere
  • d2) Vinylpyrrolidon/Vinylacrylat-Copolymere
  • d3) Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere
  • d4) Pfropfpolymere aus Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure, Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglycolen
  • d5) gepropften und vernetzten Copolymere aus der Copolymerisation von
    • d5i) mindesten einem Monomeren vom nicht-ionischen Typ,
    • d5ii) mindestens einem Monomeren vom ionischen Typ,
    • d5iii) von Polyethylenglycol und
    • d5iv) einem Vernetzter
  • d6) durch Copolymerisation mindestens eines Monomeren jeder der drei folgenden Gruppen erhaltenen Copolymere:
    • d6i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesättigter Alkohole und ungesättigter Carbonsäuren,
    • d6ii) ungesättigte Carbonsäuren,
    • d6iii) Ester langkettiger Carbonsäuren und ungesättigter Alkohole und/oder Ester aus den Carbonsäuren der Gruppe d6ii) mit gesättigten oder ungesättigten, geradkettigen oder verzweigten C₈-₁₈-Alkohols
  • d7) Terpolymere aus Crotonsäure, Vinylacetat und einem Allyl- oder Methallylester
  • d8) Tetra- und Pentapolymere aus
    • d8i) Crotonsäure oder Allyloxyessigsäure
    • d8ii) Vinylacetat oder Vinylpropionat
    • d8iii) verzweigten Allyl- oder Methallylestern
    • d8iv) Vinylethern, Vinylesterrn oder geradkettigen Allyl- oder Methallylestern
  • d9) Crotonsäure-Copolymere mit einem oder mehreren Monomeren aus der Gruppe Ethylen, Vinylbenzol, Vinymethylether, Acrylamid und deren wasserlöslicher Salze
  • d10) Terpolymere aus Vinylacetat, Crotonsäure und Vinylestern einer gesättigten aliphatischen in α-Stellung verzweigten Monocarbonsäure
• e) wasserlöslichen kationischen Polymeren aus der Gruppe der
  • e1) quaternierten Cellulose-Derivate
  • e2) Polysiloxane mit quaternären Gruppen
  • e3) kationischen Guar-Derivate
  • e4) polymeren Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure
  • e5) Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats und -methacrylats
  • e6) Vinylpyrrolidon-Methoimidazoliniumchlorid-Copolymere
  • e7) quaternierter Polyvinylalkohol
  • e8) unter den INCI-Bezeichnungen Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 und Polyquaternium 27 angegeben Polymere.

Other polymers than those mentioned above can be used with particular preference as coating materials. In this case, detergent tablets or 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
  • a1) polyvinylpyrrolidones,
  • a2) vinylpyrrolidone / vinyl ester copolymers,
  • a3) cellulose ethers
• b) water-soluble amphoteric polymers from the group of
  • b1) alkylacrylamide / acrylic acid copolymers
  • b2) alkylacrylamide / methacrylic acid copolymers
  • b3) alkylacrylamide / methylmethacrylic acid copolymers
  • b4) Alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
  • b5) Alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
  • b6) Alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
  • b7) Alkylacrylamide / Alkymethacrylate / Alkylaminoethylmethacrylate / Alkylmethacrylate Copolymers
  • b8) copolymers
    • b8i) unsaturated carboxylic acids
    • b8ii) cationically derivatized unsaturated carboxylic acids
    • b8iii) optionally further ionic or nonionic monomers
• c) water-soluble zwitterionic polymers from the group of
  • c1) acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts
  • c2) acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts
  • c3) Methacroylethylbetaine / methacrylate copolymers
• d) water-soluble anionic polymers from the group of
  • d1) vinyl acetate / crotonic acid copolymers
  • d2) vinylpyrrolidone / vinyl acrylate copolymers
  • d3) acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers
  • d4) graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in admixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols
  • d5) grafted and crosslinked copolymers from the copolymerization of
    • d5i) at least one nonionic type monomer,
    • d5ii) at least one ionic-type monomer,
    • d5iii) of polyethylene glycol and
    • d5iv) a networked one
  • d6) copolymers obtained by copolymerization of at least one monomer of each of the following three groups:
    • d6i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
    • d6ii) unsaturated carboxylic acids,
    • d6iii) esters of long chain carboxylic acids and unsaturated alcohols and / or esters of the carboxylic acids of group d6ii) with saturated or unsaturated, linear or branched C _8-18 alcohol
  • d7) terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester
  • d8) tetra- and pentapolymers from
    • d8i) crotonic acid or allyloxyacetic acid
    • d8ii) vinyl acetate or vinyl propionate
    • d8iii) branched allyl or methallyl esters
    • d8iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters
  • d9) Crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinyl methyl ether, acrylamide and their water-soluble salts
  • d10) terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic α-branched monocarboxylic acid
• e) water-soluble cationic polymers from the group of
  • e1) quaternized cellulose derivatives
  • e2) polysiloxanes with quaternary groups
  • e3) cationic guar derivatives
  • e4) polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid
  • e5) Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate
  • e6) vinylpyrrolidone-methoimidazolinium chloride copolymers
  • e7) quaternized polyvinyl alcohol
  • e8) polymers listed under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

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

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

• Polyvinylpyrrolidone, wie sie beispielsweise unter der Bezeichnung Luviskol^® (BASF) vertrieben werden. Polyvinylpyrrolidone sind bevorzugte nichtionische Polymere im Rahmen der Erfindung.
  Polyvinylpyrrolidone [Poly(1-vinyl-2-pyrrolidinone)], Kurzzeichen PVP, sind Polymere der nachstehenden allgemeinen Formel
  
  die durch radikalische Polymerisation von 1-Vinylpyrrolidon nach Verfahren der Lösungs- oder Suspensionspolymerisation unter Einsatz von Radikalbildnern (Peroxide, Azo-Verbindungen) als Initiatoren hergestellt werden. Die ionische Polymerisation des Monomeren liefert nur Produkte mit niedrigen Molmassen.
• Vinylpyrrolidon/Vinylester-Copolymere, wie sie beispielsweise unter dem Warenzeichen Luviskol^® (BASF) vertrieben werden. Luviskol^® VA 64 und Luviskol^® VA 73, jeweils Vinylpyrrolidon/Vinylacetat-Copolymere, sind besonders bevorzugte nichtionische Polymere.
  Die Vinylester-Polymere sind aus Vinylestern zugängliche Polymere mit der Gruppierung der Formel
  
  als charakteristischem Grundbaustein der Makromoleküle. Von diesen haben die Vinylacetat-Polymere (R = CH₃) mit Polyvinylacetaten als mit Abstand wichtigsten Vertretern die größte technische Bedeutung.
• Celluloseether, wie Hydroxypropylcellulose, Hydroxyethylcellulose und Methylhydroxypropylcellulose, wie sie beispielsweise unter den Warenzeichen Culminal^® und Benecel^® (AQUALON) vertrieben werden.
  Celluloseether lassen sich durch die folgende allgemeine Formel beschreiben,
  
  in R für H oder einen Alkyl-, Alkenyl-, Alkinyl-, Aryl- oder Alkylarylrest steht. In bevorzugten Produkten steht mindestens ein R in der vorstehenden Formel für -CH₂CH₂CH₂-OH oder -CH₂CH₂-OH.

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

• Polyvinylpyrrolidones, as sold for example under the name Luviskol ^® (BASF). Polyvinylpyrrolidones are preferred nonionic polymers in the invention.
  Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinones)], abbreviation PVP, are polymers of the general formula below
  
  which are prepared by free-radical polymerization of 1-vinylpyrrolidone by the method of solution or suspension polymerization using free-radical initiators (peroxides, azo compounds) as initiators. The ionic polymerization of the monomer provides only low molecular weight products.
• Vinylpyrrolidone / vinyl ester copolymers, as sold, for example, 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 vinyl ester-accessible polymers having the moiety of the formula
  
  as a characteristic building block of the macromolecules. Of these, the vinyl acetate polymers (R = CH ₃ ) with polyvinyl acetates as by far the most important representatives of the greatest technical importance.
• Cellulose ethers, such as hydroxypropylcellulose, hydroxyethylcellulose and methylhydroxypropylcellulose, as sold, for example, under the trademarks Culminal ^® and Benecel ^® (AQUALON).
  Cellulose ethers can be described by the following general formula
  
  R is H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products, at least one R in the above formula is -CH ₂ CH ₂ CH ₂ -OH or -CH ₂ CH ₂ -OH.

Further polymers which are suitable according to the invention are water-soluble amphopolymers. 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, are zwitterionic polymers which contain quaternary ammonium groups in the molecule. COO ^- - or -SO ₃ ^- groups, and summarized those polymers containing -COOH or SO ₃ H groups and quaternary ammonium groups. An example of the present invention amphopolymer suitable is the acrylic resin commercially available as Amphomer ^® is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) -acrylamide and two or more monomers from the group of acrylic acid, Represents methacrylic acid and its simple esters. Likewise preferred amphopolymers are composed of unsaturated carboxylic acids (for example acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (for example acrylamidopropyltrimethylammonium chloride) and optionally further ionic or nonionic monomers. Terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium as they are commercially available under the name Merquat ^® 2001 N, are inventively particularly preferred amphopolymers. Other suitable amphoteric polymers are available for example under the names Amphomer ^® and Amphomer ^® LV-71 (DELFT NATIONAL) 2-hydroxypropyl-pylmethacrylat copolymers octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate /.

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

• Vinylacetat/Crotonsäure-Copolymere, wie sie beispielsweise unter den Bezeichnungen Resyn^® (NATIONAL STARCH), Luviset^® (BASF) und Gafset^® (GAF) im Handel sind.

According to the invention suitable anionic polymers include:

• Vinyl acetate / crotonic acid copolymers, such as those sold under the names Resyn ^® (National Starch), Luviset ^® (BASF) and Gafset ^® (GAF) are commercially available.

• Vinylpyrrolidon/Vinylacrylat-Copolymere, erhältlich beispielsweise unter dem Warenzeichen Luviflex^® (BASF). Ein bevorzugtes Polymer ist das unter der Bezeichnung Luviflex^® VBM-35 (BASF) erhältliche Vinylpyrrolidon/Acrylat-Terpolymere.
• Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere, die beispielsweise unter der Bezeichnung Ultrahold^® strong (BASF) vertrieben werden.
• Pfropfpolymere aus Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure, Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglycolen Solche gepfropften Polymere von Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch mit anderen copolymerisierbaren Verbindungen auf Polyalkylenglycolen werden durch Polymerisation in der Hitze in homogener Phase dadurch erhalten, daß man die Polyalkylenglycole in die Monomeren der Vinylester, Ester von Acrylsäure oder Methacrylsäure, in Gegenwart von Radikalbildner einrührt. Als geeignete Vinylester haben sich beispielsweise Vinylacetat, Vinylpropionat, Vinylbutyrat, Vinylbenzoat und als Ester von Acrylsäure oder Methacrylsäure diejenigen, die mit aliphatischen Alkoholen mit niedrigem Molekulargewicht, also insbesondere Ethanol, Propanol, Isopropanol, 1-Butanol, 2-Butanol, 2-Methy-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, erhältlich sind, bewährt.

In addition to monomer units of the abovementioned formula, these polymers also have monomer units of the general formula given below:

[-CH (CH ₃ ) -CH (COOH) -] _n

• Vinylpyrrolidone / vinyl acrylate copolymers, obtainable for example under the trade name Luviflex ^® (BASF). A preferred polymer is the VBM-35 (BASF) under the name Luviflex ^® available vinylpyrrolidone / acrylate terpolymers.
• Acrylic acid / ethyl acrylate / N-tert.butyl acrylamide terpolymers, for example, under the name Ultrahold ^® strong (BASF).
• Graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in admixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols. Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in admixture with other copolymerizable compounds Polyalkylene glycols are obtained by homogeneous heat polymerization by stirring the polyalkylene glycols into the monomers of the vinyl esters, esters of acrylic acid or methacrylic acid in the presence of free radical generator. Suitable vinyl esters are, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and esters of acrylic acid or methacrylic acid, those with aliphatic alcohols of low molecular weight, ie in particular ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl 1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol, are proven.

• gepropfte und vernetzte Copolymere aus der Copolymerisation von
  1. i) mindesten einem Monomeren vom nicht-ionischen Typ,
  2. ii) mindestens einem Monomeren vom ionischen Typ,
  3. iii) von Polyethylenglycol und
  4. iv) einem Vernetzter

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
  1. i) at least one nonionic type monomer,
  2. ii) at least one ionic-type monomer,
  3. iii) of polyethylene glycol and
  4. iv) 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 may be of very different types and of these preferred are: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allylaurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-hexene.

The non-ionic monomers may equally be of very different types, among which particularly preferably crotonic acid, allyloxyacetic acid, vinylacetic acid, maleic acid, acrylic acid and methacrylic acid are contained in the grafting polymers.

The crosslinking agents used are preferably ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallyl sucrose having 2 to 5 allyl groups per molecule of saccharin.

1. i) 5 bis 85 Gew.-% mindesten eine Monomeren vom nicht-ionischen Typ,
2. ii) 3 bis 80 Gew.-% mindestens eines Monomeren vom ionischen Typ,
3. iii) 2 bis 50 Gew.-%, vorzugsweise 5 bis 30 Gew.-% Polyethylenglycol und
4. iv) 0,1 bis 8 Gew.-% eines Vernetzers, wobei der Prozentsatz des Vernetzers durch das Verhältnis der Gesamtgewichte von i), ii) und iii) ausgebildet ist.
   • durch Copolymerisation mindestens eines Monomeren jeder der drei folgenden Gruppen erhaltene Copolymere:
     1. i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesättigter Alkohole und ungesättigter Carbonsäuren,
     2. ii) ungesättigte Carbonsäuren,
     3. iii) Ester langkettiger Carbonsäuren und ungesättigter Alkohole und/oder Ester aus den Carbonsäuren der Gruppe ii) mit gesättigten oder ungesättigten, geradkettigen oder verzweigten C₈-₁₈-Alkohols
     
     Unter kurzkettigen Carbonsäuren bzw. Alkoholen sind dabei solche mit 1 bis 8 Kohlenstoffatomen zu verstehen, wobei die Kohlenstoffketten dieser Verbindungen gegebenenfalls durch zweibindige Heterogruppen wie -O-, -NH-, -S- unterbrochen sein können.
   • Terpolymere aus Crotonsäure, Vinylacetat und einem Allyl- oder Methallylester Diese Terpolymere enthalten Monomereinheiten der vorstehend genannten allgemeinen Formeln für Crotonsäure- bzw. Vinylacetat (siehe oben) sowie Monomereinheiten aus einem oder mehreren Allyl- oder Methallyestern der Formel
     
     worin R³ für -H oder -CH₃, R² für -CH₃ oder -CH(CH₃)₂ und R¹ für -CH₃ oder einen gesättigten geradkettigen oder verzweigten C₁-₆-Alkylrest steht und die Summe der Kohlenstoffatome in den Resten R¹ und R² vorzugsweise 7, 6, 5, 4, 3 oder 2 ist.

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

1. i) from 5 to 85% by weight of at least one nonionic type monomer,
2. ii) from 3 to 80% by weight of at least one ionic-type monomer,
3. iii) 2 to 50 wt .-%, preferably 5 to 30 wt .-% polyethylene glycol and
4. iv) 0.1 to 8 wt% of a crosslinker, wherein the percentage of crosslinker is formed by the ratio of the total weights of i), ii) and iii).
   • Copolymers obtained by copolymerization of at least one monomer of each of the following three groups:
     1. i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
     2. ii) unsaturated carboxylic acids,
     3. iii) esters of long chain carboxylic acids and unsaturated alcohols and / or esters of the carboxylic acids of group ii) with saturated or unsaturated, linear or branched C _8-18 alcohol
     
     Short-chain carboxylic acids or alcohols are to be understood as meaning those having 1 to 8 carbon atoms, it being possible for the carbon chains of these compounds to be interrupted, if appropriate, by divalent hetero groups such as -O-, -NH-, -S-.
   • Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester These terpolymers contain monomer units of the abovementioned general formulas for crotonic acid or vinyl acetate (see above) and monomer units of one or more allyl or methallyl esters of the formula
     
     wherein R ³ is -H or -CH _3, R ² is -CH ₃ or -CH (CH _{3) 2} and R ¹ is -CH ₃ or a saturated straight or branched C _1-6 -alkyl radical and the sum of the carbon atoms in the radicals R ¹ and R ^{2 is} preferably 7, 6, 5, 4, 3 or 2.

• Tetra- und Pentapolymere aus
  1. i) Crotonsäure oder Allyloxyessigsäure
  2. ii) Vinylacetat oder Vinylpropionat
  3. iii) verzweigten Allyl- oder Methallylestern
  4. iv) Vinylethern, Vinylesterrn oder geradkettigen Allyl- oder Methallylestern
• Crotonsäure-Copolymere mit einem oder mehreren Monomeren aus der Gruppe Ethylen, Vinylbenzol, Vinymethylether, Acrylamid und deren wasserlöslicher Salze
• Terpolymere aus Vinylacetat, Crotonsäure und Vinylestern einer gesättigten aliphatischen in α-Stellung verzweigten Monocarbonsäure.

The abovementioned terpolymers preferably result from the copolymerization of 7 to 12% by weight of crotonic acid, 65 to 86% by weight, preferably 71 to 83% by weight of vinyl acetate and 8 to 20% by weight, preferably 10 to 17% by weight .-% allyl or Methallyletsre the above formula.

• Tetra and pentapolymers from
  1. i) crotonic acid or allyloxyacetic acid
  2. ii) vinyl acetate or vinyl propionate
  3. iii) branched allyl or methallyl esters
  4. iv) vinyl ethers, Vinylesterrn or straight-chain allyl or methallyl esters
• Crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinyl methyl ether, acrylamide and their water-soluble salts
• Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic α-branched monocarboxylic acid.

Further, preferably used as part of the coating polymers are cationic polymers. Among the cationic polymers, the permanent cationic polymers are preferred. According to the invention, "permanently cationic" refers to polymers which have a cationic group, irrespective of the pH of the agent (ie both the coating and the shaped body). These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group.

• quaternisierte Cellulose-Derivate, wie sie unter den Bezeichnungen Celquat^® und Polymer JR^® im Handel erhältlich sind. Die Verbindungen Celquat^® H 100, Celquat^® L 200 und Polymer JR^®400 sind bevorzugte quaternierte Cellulose-Derivate.
• Polysiloxane mit quaternären Gruppen, wie beispielsweise die im Handel erhältlichen Produkte Q2-7224 (Hersteller: Dow Corning; ein stabilisiertes Trimethylsilylamodimethicon), Dow Corning^® 929 Emulsion (enthaltend ein hydroxyl-amino-modifiziertes Silicon, das auch als Amodimethicone bezeichnet wird), SM-2059 (Hersteller: General Electric), SLM-55067 (Hersteller: Wacker) sowie Abil^®-Quat 3270 und 3272 (Hersteller: Th. Goldschmidt; diquaternäre Polydimethylsiloxane, Quaternium-80),
• Kationische Guar-Derivate, wie insbesondere die unter den Handelsnamen Cosmedia^®Guar und Jaguar^® vertiebenen Produkte,
• Polymere Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure. Die unter den Bezeichnungen Merquat^®100 (Poly(dimethyldiallylammoniumchlorid)) und Merquat^®550 (Dimethyldiallylammoniumchlorid-Acrylamid-Copolymer) im Handel erhältlichen Produkte sind Beispiele für solche kationischen Polymere.
• Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats und -methacrylats, wie beispielsweise mit Diethylsulfat quaternierte Vinylpyrrolidon-Dimethylaminomethacrylat-Copolymere. Solche Verbindungen sind unter den Bezeichnungen Gafquat^®734 und Gafquat^®755 im Handel erhältlich.
• Vinylpyrrolidon-Methoimidazoliniumchlorid-Copolymere, wie sie unter der Bezeichnung Luviquat^® angeboten werden.
• quaternierter Polyvinylalkohol

sowie die unter den Bezeichnungen

• Polyquaternium 2,
• Polyquaternium 17,
• Polyquaternium 18 und
• Polyquaternium 27

bekannten Polymeren mit quartären Stickstoffatomen in der Polymerhauptkette. Die genannten Polymere sind dabei nach der sogenannten INCI-Nomenklatur bezeichnet, wobei sich detaillierte Angaben im CTFA International Cosmetic Ingredient Dictionary and Handbook, 5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997 , finden, auf die hier ausdrücklich Bezug genommen wird.Preferred cationic polymers are, for example

• quaternized cellulose derivatives, such as are available under the names of Celquat ^® and Polymer JR ^® commercially. The compounds Celquat ^® H 100, Celquat L 200 and Polymer JR ^{® ®} 400 are preferred quaternized cellulose derivatives.
• Polysiloxanes having quaternary groups, such as the commercially available products Q2-7224 (manufactured by Dow Corning, a stabilized trimethylsilylamodimethicone), Dow ^Corning® 929 emulsion (containing a hydroxylamino-modified Also referred to as amodimethicone silicone), 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 the vertiebenen under the trade names Cosmedia® ^® Guar and Jaguar ^® products,
• Polymers Dimethyldiallylammoniumsalze and their copolymers with esters and amides of acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) are examples of such cationic polymers.
• Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, such as diethyl sulfate quaternized vinylpyrrolidone-dimethylaminomethacrylate copolymers. Such compounds are sold under the names Gafquat ^® 734 and Gafquat ^® 755 commercially.
• Vinylpyrrolidone methoimidazolinium chloride copolymers, as offered under the name Luviquat.RTM ^®.
• quaternized polyvinyl alcohol

as well as those under the designations

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

known polymers with quaternary nitrogen atoms in the polymer main chain. The polymers mentioned are designated according to the so-called INCI nomenclature, with detailed See CTFA International Cosmetic Ingredient Dictionary and Handbook, 5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997 , which are expressly incorporated herein by reference.

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

In order to make the coating even more resistant to mechanical stress, polyurethanes can be incorporated into the coating. These impart elasticity and stability to the coating and can account for up to 50% by weight of the coating, according to the amount of water-soluble polymers indicated above.

Polyurethanes are water-insoluble in the sense of the invention when they are soluble in water at room temperature to less than 2.5 wt .-%.

• einer Verbindung (A) mit mindestens 2 aktiven Wasserstoffatomen pro Molekül und
• einem Di- oder Polyisocyanat (B).

The polyurethanes consist of at least two different monomer types,

• a compound (A) having at least 2 active hydrogen atoms per molecule and
• a di- or polyisocyanate (B).

The compounds (A) may be, for example, diols, triols, diamines, triamines, polyetherols and polyesterols. The compounds having more than 2 active hydrogen atoms are usually used only in small amounts in combination with a large excess of compounds having 2 active hydrogen atoms.

Examples of compounds (A) are ethylene glycol, 1,2- and 1,3-propylene glycol, butylene glycols, di-, tri-, tetra- and poly-ethylene and -Propylenglykole, copolymers of lower alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide, Ethylenediamine, propylenediamine, 1,4-diaminobutane, hexamethylenediamine and α, ω-diamines based on long-chain alkanes or polyalkylene oxides.

Polyurethanes in which the compounds (A) are diols, triols and polyetherols may be preferred according to the invention. In particular, polyethylene glycols and polypropylene glycols having molecular weights between 200 and 3000, in particular between 1600 and 2500, have proven to be particularly suitable in individual cases. Polyesterols are usually obtained by modifying the compound (A) with dicarboxylic acids such as phthalic acid, isophthalic acid and adipic acid.

As compounds (B) predominantly hexamethylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 4,4'-methylene di (phenyl isocyanate) and in particular isophorone diisocyanate are used. These compounds can be described by the following general formula:

O = C = NR ⁴ -N = C = O,

wherein R ^{4 is} a linking moiety of carbon atoms, for example, a methylene-ethylene-propylene, butylene, pentylene, hexylene, etc. group. In the abovementioned, technically most widely used hexamethylene diisocyanate (HMDI), R ⁴ = (CH ₂ ) ₆ , in 2,4- or 2,6-toluene diisocyanate (TDI) R ^{4 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 ^{4 is} the isophorone radical (3,5,5-trimethyl-2-cyclohexenone) ,

Furthermore, the polyurethanes used in the invention may contain other building blocks such as diamines as chain extenders and hydroxycarboxylic acids. Dialkylolcarboxylic acids such as dimethylolpropionic acid are particularly suitable hydroxycarboxylic acids. With regard to the further building blocks, there is no fundamental restriction as to whether they are nonionic, anionic or cationic building blocks.

For further information on the construction and production of polyurethanes, reference is expressly made to the articles in the relevant reviews such as Römpps Chemie-Lexikon and Ullmanns Enzyklopädie der technischen Chemie.

• ausschließlich aliphatische Gruppen im Molekül
• keine freien Isocyanatgruppen im Molekül
• Polyether- und Polyesterpolyurethane
• anionische Gruppen im Molekül.

Polyurethanes which have proved to be particularly suitable according to the invention in many cases have been able to be characterized as follows:

• exclusively aliphatic groups in the molecule
• no free isocyanate groups in the molecule
• Polyether and polyester polyurethanes
• anionic groups in the molecule.

Furthermore, it has proved to be advantageous for the preparation of the coated detergent tablets according to the invention if the polyurethanes are not mixed directly with the other components of the partial coating but are introduced in the form of aqueous dispersions. Such dispersions usually have a solids content of about 20-50%, in particular about 35-45%, and are also commercially available.

In addition to the coating materials, the coating may contain further ingredients which improve the physical properties of the coating or impart advantageous properties to the coated molding. For example, it is possible to incorporate so-called small components such as dyes or optical brighteners or foam inhibitors in the coating. If coating materials are used which are poorly or slowly soluble in water, disintegration aids can be incorporated into the coating. Such laundry detergent or cleaning product tablets according to the invention in which the coating additionally contains a disintegration aid in amounts of 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. %, in each case based on the coating layer, are preferred in the context of the present invention.

The use of the disintegration assistant described in detail below is particularly recommended in the case of acid coating layers, with typical use concentrations for the disintegration aids in the coating layers being 0.1 to 5% by weight, based on the coating layer.

It is additionally preferred in the context of the present invention to provide the second non-compressed part with a coating in order to protect it from dissolution during a washing or cleaning cycle which takes place earlier in time. Here, the pH-dependent solubility of the coating is a particularly preferred control mechanism.

The principle of pH-dependent water solubility is generally based on protonation or deprotonation of functional side groups of the polymer molecules, as a result of which their charge state changes accordingly. The polymer must now be such that it dissolves in the stable charged state at a certain pH in water, in the uncharged state at another pH, however, precipitates. In the context of the present invention, it is preferred that the polymers used according to the invention have a lower water solubility at a higher pH than at lower pH values or even become insoluble in water at relatively high pH values.

Polymers with pH-dependent solubility are known in particular from pharmacy. Here, e.g. acid-insoluble polymers are used to give tablets an enteric-coated, but colonic-soluble, coating. Such acid-insoluble polymers are usually based on derivatives of polyacrylic acid, which is present in the acidic region in undissoziierter and thus insoluble form, in the alkaline range, but typically neutralized at pH 8 and goes as a polyanion in solution.

Also in the opposite case - soluble in the acidic range, insoluble in the alkaline range - examples are known in the art. These substances, in which the polymer molecules mostly carry amino-substituted side chains, are e.g. used for the preparation of gastric juice-soluble tablet coatings. They usually dissolve at pH values below 5. Polymers in which the solubility change from soluble to insoluble at higher pHs are not known in the pharmaceutical arts because these pHs are physiologically meaningless.

Particularly preferred suitable substances are basic (co) polymers which have amino groups or aminoalkyl groups. Comonomers may be, for example, conventional acrylates, methacrylates, maleinates or derivatives of these compounds. A particularly suitable aminoalkyl methacrylate copolymer marketed by Rohm (Eudragit ^®).

Particularly preferred detergent tablets or detergent tablets are characterized in that the second non-compressed part (b) with an amino group-containing polymer, preferably a copolymer of basic monomers such as dialkylaminoalkyl (meth) acrylates with acrylic acid esters, coated.

Also, detergent tablets in which the second non-compressed part (b) is coated with an ampholytic polymer, preferably a copolymer of basic monomers such as dialkylaminoalkyl (meth) acrylates with substituted or unsubstituted acrylic acids and / or (meth) acrylic acids. , are used and preferred according to the invention.

In addition to the thermodynamic solubility, the dissolution kinetics of a filmed substance or the decrease in its mechanical stability may be important for the application. The solution kinetics of the switch substances used according to the invention is pH-dependent at room temperature down to the alkaline range, ie the films are significantly longer stable at pH 10 than at a pH of 8.5, although they are thermodynamically soluble at both pH values are.

In a further embodiment of the present invention, therefore, polymers are used whose water solubility varies between pH 6 to 7 and which are less soluble at higher pH than at lower pH. Suitable polymers contain, as already described above, basic groups, for example primary, secondary or tertiary amino groups, imino groups, amido groups or pyridine groups, generally those which have a quaternizable nitrogen atom. These are protonated at lower pHs, whereby the polymer is soluble. At higher pH, the molecule becomes uncharged and becomes insoluble. As a rule, the transition takes place - referred to below as the "switching point", depending on the pK _B value of the basic groups and their density along the polymer chain, in the range of acidic pH values. The present invention therefore furthermore relates to a polymer in which the switching point lies in a range between pH 6 and 7.

• Abhängig vom pK_B-Wert erfolgt im Bereich höherer pH-Werte nur noch eine sehr geringe pH-abhängige Änderung des Ladungszustandes des Polymers in Lösung. Daher muß es gelingen, durch diese geringe Änderung des Ladungszustandes die Löslichkeit entscheidend zu beeinflussen. Das Polymer muß also genau eine solche Hydrophilie aufweisen, dass es in völlig ungeladenem Zustand unlöslich, jedoch bei einer bereits geringen Aufladung löslich wird.

This shift of the switching point succeeds in principle in the following way:

• Depending on the pK _B value, only a very small pH-dependent change in the charge state of the polymer in solution takes place in the region of higher pH values. Therefore it must succeed in decisively influencing the solubility through this slight change in the state of charge. The polymer must therefore have precisely such a hydrophilicity that it becomes insoluble in a completely uncharged state, but becomes soluble when already slightly charged.

• Copolymerisation eines Monomers mit basischer Funktion mit einem hydrophileren Monomer. Durch das Einbauverhältnis der jeweiligen Comonomeren wird der Schaltpunkt beeinflußt.
• Hydrophilierung des basische Gruppen tragenden Polymers durch eine polymeranaloge Umsetzung. Durch den Modifikationsgrad wird der Schaltpunkt beeinflusst.

To adjust the hydrophilicity, the following methods can be used:

• Copolymerization of a monomer with a basic function with a more hydrophilic monomer. Due to the incorporation ratio of the respective comonomers, the switching point is influenced.
• Hydrophilization of the basic group-bearing polymer by a polymer-analogous reaction. The degree of modification influences the switching point.

In addition to simple hydrophilization, it is also possible to introduce basic functions of different pK _B values. Due to the ratio of both groups and the resulting hydrophilicity of the molecule, the switching point can be influenced.

A particularly preferred polymer of this class of substances is an N-oxidized polyvinylpyridine.

The pH-shift-sensitive switches according to the invention and used according to the invention can be used for all applications, in particular in the washing, rinsing or cleaning agent sector, in which an active ingredient is to be released from the alkaline to the neutral when the pH is lowered. This may be the case both in the washing machine washing and in the automatic dishwashing. In particular, the application is claimed to formulate parts of a detergent formulation for automatic dishwashing, (eg surfactants, perfume, Soil Repellant, acid, complexing agents, builders, etc., or preparations containing these agents) with the polymer according to the invention, so that these are not released in the main rinse at high pH, but are released in the subsequent rinse cycle with lower pH.

The polymer according to the invention can be used both as a coating material and as a matrix material, binder or disintegrant. It does not require that yourself completely dissolves the polymer at the appropriate pH conditions to release the drug. Rather, it is sufficient if, for example, the permeability of a polymer film changes and, for example, the penetration of water into the drug formulation is made possible. As a result, a secondary effect, for example the activation of an effervescent system or the swelling of a water-swellable disintegrants, which are known in particular from the pharmaceutical industry, ensure the complete release of the active substance.

In a further preferred embodiment of the invention, so-called pH-shift boosters are used in addition to the above-mentioned switches. As a result, it can be prevented, at least to a large extent, that after the rinse cycle residues, which in particular consist of the pH-dependent, soluble substance itself, are found. For the purposes of this invention, suitable pH-shift boosters are all substances and formulations which are capable of controlling the extent of the pH shift either locally, i. in the immediate vicinity of the particular pH-shift-sensitive substance used, or also generalized, i. in the entire rinsing, to enlarge. These include all organic and / or inorganic water-soluble acids or acid-reacting salts, in particular at least one substance from the group of alkylbenzenesulfonic acids, alkylsulfuric acids, citric acid, oxalic acid and / or alkali metal hydrogensulfates.

The pH-Shift booster can be incorporated into the washing, rinsing or cleaning agent. In a further embodiment of the invention, however, it is also possible to supply the pH-shift booster externally to the machine either after the end of the cleaning cycle or at the beginning of the rinse cycle or by a special delivery system (by coating with a slowly dissolving coating agent). or by diffusion from a matrix material.

The coated second measured amount may have a further coating, e.g. to enable a release only in the last wash or cleaning cycle. In this way, for example, the first coating with pH-dependent solubility can be protected from environmental influences.

Detergent tablets in which the coated second non-compressed part (b) has a further coating which is preferably selected is made of polyvinyl acetate and / or polyvinyl alcohol and at> 50 ° C melting substances, preferably paraffins and / or polyethylene glycols, are preferred.

Polyvinylpyrrolidone (PVP) can also be used.

Polyvinyl alcohols (abbreviated PVAL) are polymers of the general structure

[-CH ₂ -CH (OH) -] _n

in small quantities also structural units of the type

[-CH ₂ -CH (OH) -CH (OH) -CH ₂ -]

contain. Since the corresponding monomer (vinyl alcohol) is not stable in free form, polyvinyl alcohols are obtained via polymer-analogous reactions by hydrolysis, in particular by alkali-catalyzed transesterification of polyvinyl acetates with alcohols, preferably with methanol. By these technical methods, PVAL are also available which contain a predetermined residual amount of acetate groups.

Commercially available PVOH (eg Mowiol ^® grades from Hoechst) are supplied as white-yellowish powders or granules with degrees of polymerization in the range of about 500 to 2500 (corresponding to molecular weights of about 20,000 to 100,000 g / mol) in trade and have different degrees of hydrolysis from 98 to 99 and 87 to 89 mol%, respectively. So they are partially hydrolyzed polyvinyl acetates with a residual content of acetyl groups of about 1 to 2 or 11 to 13 mol%.

The water solubility of PVAL can be reduced by aftertreatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set specifically to desired values. Films made of PVAL are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.

Examples of suitable water PVAL films under the name "SOLUBLON® ^®" from Syntana Handelsgesellschaft E. Harke GmbH & Co. available PVAL films. Their temperature-dependent solubility in water can be adjusted precisely, and films of this product series are available which are soluble in all relevant for the application temperature ranges in the aqueous phase.

Polyvinylpyrrolidones, referred to as PVP for short, can be described by the following general formula:

PVP are prepared by radical polymerization of 1-vinylpyrrolidone. Commercially available PVP have molecular weights in the range of about 2500 to 750,000 g / mol and are available as white, hygroscopic powders or as aqueous solutions.

In adjusting the solubility kinetics of the second non-compressed part (b), detergent tablets are preferred in which at least the second non-compressed part (b) of one at a pH below the pH of the former Cleaning course is comprised of water-soluble material.

Particular preference is given to washing or cleaning agent shaped articles in which the second non-compressed part (b) is coated with a material which contains the non-compressed part (b) at pH values above 11, preferably above 10 and in particular above 9 protects against dissolution in the time running earlier washing or cleaning cycle, with particularly preferred detergent tablets are characterized in that the coating the second non-compressed part (b) at pH values below 6, preferably below 7 and especially below 8 does not protect against dissolution.

The non-compressed part (a) is produced by sintering.

The other non-compressed molded body parts are prepared by methods familiar to those skilled in the art, which does not have to resort to the application of high pressures. "Not compressed" means in the context of the present invention in particular "not produced by tabletting". According to the invention, pressure exertions of more than 5 kN / cm ² , preferably of more than 2.5 kN / cm ² , more preferably of more than 1 kN / cm ² and especially of more than 0.1 kN / cm ² , are to be avoided. End products of processes in which particulate premixes are compressed by the use of pressures above 5 kN / cm ² by reducing the intra- and inter-particulate spaces to moldings, according to the invention should not be referred to as "non-compressed part". The application of lower pressures, for example, for shaping deformable masses or particle heaps, without the achievement of an adhering composite (a tablet) may be in individual cases, however, be beneficial.

Particularly preferred production variants for non-compressed shaped-body parts are the sintering, the casting, the hardening of deformable masses and the production of particles, e.g. by granulation, pelleting, extrusion, agglomeration etc ..

The sintering represents the provision of an optionally preformed particulate matter which is converted under the influence of external conditions (temperature, radiation, reactive gases, liquids, etc.) into a compact molded body part. Examples of sintering processes are known from the prior art production of moldings by microwaves or radiation curing.

Another preferred sintering process for producing non-compressed molded body parts is reactive sintering. Herein, the starting components are shaped and then solidified by reacting a component A and a component B with each other, whereby the components A and B are mixed with the starting components, applied thereto or added after the information. In carrying out this process, the components A and B react to solidify the individual ingredients together. The formed reaction product of the components A and B connects the individual starting components in such a way that a solid, relatively break-resistant shaped body is obtained.

With this method, moldings are obtained with a good decay. Since the binding of the individual ingredients is carried out by a reactive sintering and is not due to the "stickiness" of the granules of the premix, it is not necessary to adapt the recipe to the binding properties of the individual ingredients. These can be arbitrarily adapted depending on their effectiveness.

In order to react the components A and B together, it has been found to be advantageous if the starting components are mixed with the component A or before they are brought into shape with it. Examples of compounds of component A are the alkali metal hydroxides, in particular NaOH and KOH, alkaline earth hydroxides, in particular Ca (OH) ₂ , alkali metal silicates organic or inorganic acids such as citric acid, or acidic salts such as hydrogen sulfate, anhydrous hydratable salts or hydrated water-containing salts such as soda , Acetates, sulfates, alkali metal, wherein the aforementioned compounds, if possible, can also be used in the form of their aqueous solutions.

The component B is selected such that it reacts with the component A without exerting higher pressures or substantial increase in temperature to form a solid to solidify the other existing starting components. Examples of compounds of component B are CO ₂ , NH ₃ , water vapor or spray, hydrated water-containing salts, which optionally react with the present as component A anhydrous salts by hydrate migration, hydrates forming anhydrous salts with the hydrate water-containing salts of the component A react under hydrate migration, SO ₂ , SO ₃ , HCl, HBr, silicon halides such as SiCl ₄ or silicic acid ester S (OR) _x R ' _4-x .

The above-mentioned components A and B are interchangeable, provided that two components are used which react with each other under sintering.

In a preferred embodiment of this preparation route, the starting components are mixed or coated with compounds of component A and then admixed with the compounds of component B. It has proven to be particularly suitable if the compounds of component B are gaseous. The shaped starting components (hereinafter referred to as preforms) can then either be gassed in a simple manner or introduced into a gas atmosphere. A particularly preferred combination of the components A and B are concentrated solutions of the alkali metal hydroxides, in particular NaOH and KOH, and alkaline earth hydroxides, such as Ca (OH) ₂ , or alkali metal silicates as component A and CO ₂ as component B.

To carry out the process of the invention, the starting components are first brought into shape, ie they are usually in a die, which has the outer shape of the molded article to be precipitated. The starting components are preferably in powdery to granular form. First, they are mixed or coated with the component A. After filling into the matrix or tablet form, it has proved to be preferable to slightly press the starting components in the matrix, for example by hand or with a stamp at a pressure below that mentioned above Values, in particular below 100 N / cm ² . It is also possible to compress the premix by vibration (knock compaction).

Subsequently, unless component A is already present in a mixture with the starting components, they are coated therewith and mixed with component B. After the reaction has ended, a break-resistant shaped body is obtained without the action of pressure or temperature.

If one of the components A or B is a gas, then a preform can be mixed with it, for example, so that the gas flows through it. This process allows a uniform hardening of the molding within a short time.

In a further variant of the method, a preform is introduced into an atmosphere of the reactive gas. This variant is easy to perform. It is possible to produce moldings having a hardness gradient, i. Shaped bodies which have only a harder surface up to moldings which are completely cured.

A preform or the premix can also be reacted under pressure with the reactive gas. This process variant has the advantage that the surface cures quickly to form a hard shell, wherein the curing process can be stopped here already or as described above on increasing curing stages and fully cured moldings can be produced.

The foregoing process variants could also be combined by first allowing reactive gas to flow through the preform to displace air. Then set the preform of a gas atmosphere at atmospheric pressure. By the reaction between the gas and the second component gas is automatically sucked into the molding.

In one possible embodiment of the present invention, not the starting mixture but a preform which has already been shaped is coated with component A and subsequently reacted with component B. It cures the layer located on the surface of the preform while maintaining the loose or slightly compacted structure in the core. Such moldings are characterized by a particularly good decay behavior.

The single further non-compressed molded body part can also be produced by casting. This can be influenced either by choice of starting materials or by suspending the desired ingredients in a fusible matrix.

Also, the solidification of solutions which have ambient temperature is one way to make other non-compressed parts. Aqueous solutions can be prepared according to the methods known in the art by the addition of thickeners to cut-resistant Thickened molding body areas. Examples of such thickeners that form solid jellies are alginates, pectins, gelatin, etc.

Suitable for the preparation of other gelatinous, dimensionally stable non-compressed portions of aqueous or non-aqueous solutions are preferably polymeric thickeners. These high molecular weight substances, which are also called swelling agents and absorb liquids, swell up and finally pass into viscous true or colloidal solutions, originate from the groups of natural polymers, the modified natural polymers and the fully synthetic polymers.

Naturally derived polymers which are used as thickening agents are, for example, agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein. Modified natural products come mainly from the group of modified starches and celluloses, examples which may be mentioned here carboxymethylcellulose and other cellulose ethers, hydroxyethyl and propylcellulose and core flour ethers.

A large group of thickeners, which find wide use in a variety of applications, are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes.

Thickeners from said substance classes are widely available commercially and are sold for example under the trade name Acusol ^® -820 (methacrylic acid (stearyl alcohol 20 EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral ^® -GT- 282-S (alkyl polyglycol ethers, Akzo), DEUTEROL ^® polymer-11 (dicarboxylic acid copolymer, Schoner GmbH) deuteron ^® -xg (anionic heteropolysaccharide based on β-D-glucose, D-mannose, D-glucuronic acid, Schoner GmbH ) deuteron ^® -XN (nonionic polysaccharide Schoner GmbH), DICRYLAN ^® -Verdicker-O (ethylene oxide adduct, 50% solution in water / isopropanol, Pfersse Chemie), EMA ^® -81 and EMA ^® -91 (ethylene-maleic anhydride Copolymer, Monsanto), thickener-QR-1001 (polyurethane emulsion, 19-21% in water / diglycol ether, Rohm & Haas), Mirox ^® -AM (anionic acrylic acid-acrylate copolymer dispersion, 25% in water, Stockhausen), SER-AD FX 1100 (hydrophobic urethane polymer, Servo Delden), Shellflo ^® -S (high molecular weight polysaccharide with formaldehyde stabilized, Shell), and Shellflo XA ^® (xanthan biopolymer, stabilized with formaldehyde, Shell).

Preferred non-compressed parts (a) contain as thickeners 0.2 to 4 wt .-%, preferably 0.3 to 3 wt .-% and in particular 0.4 to 1.5 wt .-%, of a polysaccharide.

A preferred polymeric thickener is xanthan gum, a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and having a molecular weight of from 2 to 15 million daltons. Xanthan is formed from a chain of β-1,4-linked glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan gum.

Preferred non-compressed proportions (a) contain as thickening agent in each case based on the total agent 0.2 to 4 wt .-%, preferably 0.3 to 3 wt .-% and in particular 0.4 to 1.5 wt .-% , Xanthan gum.

Further suitable thickeners are polyurethanes or modified polyacrylates, which are usually used in amounts of from 0.2 to 5% by weight, based on the total non-compressed portion.

in der R¹ für einen niedermolekularen oder polymeren Diol-Rest, R² für eine aliphatische oder aromatische Gruppe und n für eine natürliche Zahl steht. R¹ ist dabei vorzugsweise eine lineare oder verzweigte C₂-₁₂-Alk(en)ylgruppe, kann aber auch ein Rest eines höherwertigen Alkohols sein, wodurch quervernetzte Polyurethane gebildet werden, die sich von der oben angegebenen Formel III dadurch unterscheiden, daß an den Rest R¹ weitere -O-CO-NH-Gruppen gebunden sind.Polyurethanes (PUR) are prepared by polyaddition from dihydric and higher alcohols and isocyanates and can be described by the general formula III

in which R ^{1 is} a low molecular weight or polymeric diol radical, R ^{2 is} an aliphatic or aromatic group and n is a natural number. R ¹ is preferably a linear or branched C ₂ - ₁₂ -alk (en) yl group, but also a residue of a higher alcohol may be thereby crosslinked polyurethanes are formed which differ from the above formula III characterized in that at the Rest R ¹ further -O-CO-NH groups are bonded.

Technically important PU are from polyester and / or polyether diols and, for example, from 2,4- and 2,6-toluene diisocyanate (TDI, R ² = C ₆ H ₃ -CH ₃ ), 4,4'-methylenedi (phenyl isocyanate ) (MDI, R ² = C ₆ H ₄ -CH ₂ -C ₆ H ₄ ) or hexamethylene diisocyanate [HMDI, R ² = (CH ₂ ) ₆ ].

Commercially available thickener based on polyurethane are, for example, under the names Acrysol ^® PM 12 V (mixture of 3-5% modified starch and 14-16% polyurethane resin in water, Rohm & Haas), Borchigel ^® L75-N (non-ionic polyurethane dispersion, 50% in water, Borchers), Coatex ^® BR-100-P (PUR-dispersion, 50% in water / butyl glycol, Dimed), Nopco ^® DSX-1514 (polyurethane dispersion, 40% in water / Butyltrigylcol, Henkel-Nopco), thickener QR 1001 (20% polyurethane emulsion in water / Digylcolether, Rohm & Haas) and Rilanit ^® VPW-3116 (polyurethane dispersion, 43% in water, Henkel) available.

Preferred non-compressed parts (a) contain from 0.2 to 4 wt .-%, preferably 0.3 to 3 wt .-% and in particular 0.5 to 1.5 wt .-% of a polyurethane.

in der R³ für H oder einen verzweigten oder unverzweigten C_1-4-Alk(en)ylrest, X für N-R⁵ oder O, R⁴ für einen gegebenenfalls alkoxylierten verzweigten oder unverzweigten, evtl. substituierten C_8-22-Alk(en)ylrest, R⁵ für H oder R⁴ und n für eine natürliche Zahl steht. Allgemein sind solche modifizierten Polyacrylate Ester oder Amide von Acrylsäure bzw. einer α-substituierten Acrylsäure. Unter diesen Polymeren bevorzugt sind solche, bei denen R³ für H oder eine Methylgruppe steht. Bei den Polyacrylamiden (X = N-R⁵) sind sowohl einfach (R⁵ = H) als auch zweifach (R⁵ = R⁴) N-substituierte Amidstrukturen möglich, wobei die beiden Kohlenwasserstoffreste, die an das N-Atom gebunden sind, unabhängig voneinander aus gegebenenfalls alkoxylierten verzweigten oder unverzweigten C₈-₂₂-Alk(en)ylresten ausgewählt werden können. Unter den Polyacrylestern (X = O) sind solche bevorzugt, in denen der Alkohol aus natürlichen oder synthetischen Fetten bzw. Ölen gewonnen wurde und zusätzlich alkoxyliert, vorzugsweise ethoxliert ist. Bevorzugte Alkoxlierungsgrade liegen zwischen 2 und 30, wobei Alkoxylierungsgrade zwischen 10 und 15 besonders bevorzugt sind.Modified polyacrylates which can be used in the context of the present invention are derived, for example, from acrylic acid or methacrylic acid and can be described by the general formula IV

in the R ^{3 is} H or a branched or unbranched C _1-4 -alk (en) yl radical, X is NR ⁵ or O, R ^{4 is} an optionally alkoxylated branched or unbranched, possibly substituted C _8-22 -alk (s ) ylrest, R ^{5 is} H or R ⁴ and n is a natural number. In general, such modified polyacrylates are esters or amides of acrylic acid or of an α-substituted acrylic acid. Preferred among these polymers are those in which R ^{3 is} H or a methyl group. In the polyacrylamides (X = NR ⁵ ), both simple (R ⁵ = H) and also doubly (R ⁵ = R ⁴ ) N-substituted amide structures are possible, the two hydrocarbon radicals which are bonded to the N atom being independent of one another of optionally alkoxylated, branched or unbranched C _8-22 -alk (en) can be selected ylresten. Among the polyacrylic esters (X = O), preference is given to those in which the alcohol was obtained from natural or synthetic fats or oils and additionally alkoxylated, preferably ethoxylated. Preferred alkoxylation levels are between 2 and 30, with degrees of alkoxylation between 10 and 15 being particularly preferred.

Since the polymers which can be used are technical compounds, the designation of the radicals bound to X represents a statistical mean value which, in individual cases, can vary with regard to chain length or degree of alkoxylation. Formula II merely indicates formulas for idealized homopolymers. In the context of the present invention, however, it is also possible to use copolymers in which the proportion of monomer units which satisfy the formula II is at least 30% by weight. For example, it is also possible to use copolymers of modified polyacrylates and acrylic acid or salts thereof which still have acidic H atoms or basic -COO ^- groups.

in der R⁴ für einen vorzugsweise unverzweigten, gesättigten oder ungesättigten C_8-22-Alk(en)ylrest, R⁶ und R⁷ unabhängig voneinander für H oder CH₃ stehen, der Polymerisationsgrad n eine natürliche Zahl und der Alkoxylierungsgrad a eine natürliche Zahl zwischen 2 und 30, vorzugsweise zwischen 10 und 20 ist. R⁴ ist dabei vorzugsweise ein Fettalkoholrest, der aus natürlichen oder synthetischen Quellen gewonnen wurde, wobei der Fettalkohol wiederum bevorzugt ethoxyliert (R⁶=H)ist.In the context of the present invention preferably used modified polyacrylates are polyacrylate-polymethacrylate copolymers which satisfy the formula IVa

yl radical in which R ⁴ _8-22 -alk is a preferably unbranched, saturated or unsaturated C (s), R ⁶ and R ⁷ are independently H or CH _3, the degree of polymerization n is a natural number and the degree of alkoxylation a is a natural number between 2 and 30, preferably between 10 and 20. R ⁴ is preferably a fatty alcohol radical which has been obtained from natural or synthetic sources, the fatty alcohol in turn preferably ethoxylated (R ⁶ = H).

Products of the formula IVa are commercially available for example under the name Acusol ^® 820 (Rohm & Haas) in the form of 30 wt .-% strength dispersion in water available. In the said commercial product R ^{4 is} a stearyl radical, R ⁶ is a hydrogen atom, R ⁷ is H or CH ₃ and the degree of ethoxylation a is 20.

Preferred non-compressed proportions (a) contain from 0.2 to 4% by weight, preferably from 0.3 to 3% by weight and in particular from 0.5 to 1.5% by weight of a modified polyacrylate, based on the total agent of formula IV.

In a further preferred embodiment of the present invention, the non-compressed molded article (a) is prepared by curing reformable materials previously formed into the desired shape by molding processes. Detergent tablets in which non-compressed part (a) has been prepared by curing are accordingly also preferred.

The hardening of the deformable mass (s) can be effected by different mechanisms, the time-delayed water binding, the cooling below the melting point, the evaporation of solvents, the crystallization, by chemical reaction (s), in particular polymerization and the change of rheological properties, e.g. by altered shearing of the mass (s) as the most important curing mechanisms in addition to the already mentioned radiation curing by UV, alpha-beta or gamma rays or microwaves are mentioned.

In this preferred embodiment, a deformable, preferably plastic, mass is produced, which can be processed shaping without high pressures. After the shaping processing, curing then takes place by suitable initiation or waiting of a certain period of time. If masses are processed which have self-hardening properties without further initiation, this must be taken into account during processing in order to avoid hardening during shaping processing and thus blockages and process disruptions.

The time-delayed water binding in the masses can be realized in turn in different ways. For example, masses that contain hydratable, anhydrous raw materials or low hydration grade raw materials that can convert into stable higher hydrates, as well as water, are suitable. The formation of the hydrates, which does not occur spontaneously, then leads to the binding of free water, which in turn leads to a hardening of the masses. A shaping processing with low pressures is then no longer possible, and there are handling stable shaped body, which can optionally be further treated and / or packaged.

The staggered water binding can also be effected, for example, by incorporating hydrated water-containing salts, which dissolve in their own water of crystallization when the temperature increases, into the masses. If the temperature decreases later, the water of crystallization is bound again, which leads to a loss of shaping processability with simple means and to a solidification of the masses.

The swelling of natural or synthetic polymers as a time-delayed water binding mechanism can also be used within the scope of the process according to the invention. Here, blends of unswollen polymer and suitable swelling agent, e.g. Water, diols, glycerol, etc., are incorporated into the masses, wherein a swelling and curing takes place after shaping.

The most important mechanism of curing by time-delayed water binding is the use of a combination of water and anhydrous or low-raw materials that hydrate slowly. For this purpose, in particular offer substances that contribute to the cleaning performance in the washing or cleaning process. In the context of the process according to the invention preferred ingredients of the deformable masses are, for example, phosphates, carbonates, silicates and zeolites.

It is particularly preferred if the resulting hydrate forms have low melting points, since in this way a combination of the curing mechanisms is achieved by internal drying and cooling. Preferred processes are characterized in that the deformable mass (s) 10 to 95 wt .-%, preferably 15 to 90 wt .-%, particularly preferably 20 to 85 wt .-% and in particular 25 to 80 wt. % anhydrous substances which pass through hydration in a hydrate form having a melting point below 120 ° C, preferably below 100 ° C and in particular below 80 ° C.

The deformable properties of the compositions can be influenced by the addition of plasticizing aids such as polyethylene glycols, polypropylene glycols, waxes, paraffins, nonionic surfactants, etc. Further information on the mentioned classes of substances can be found below.

Another mechanism for curing the processed in the process according to the invention masses is the cooling in the processing of the masses above their softening point. Methods in which the hardening of the deformable mass (s) by cooling below the melting point are therefore preferred.

Under the influence of temperature softenable masses can be easily assembled by mixing the desired other ingredients with a meltable or softenable material and the mixture is heated to temperatures in the softening of this substance and processed molding at these temperatures. In this case, waxes, paraffins, polyalkylene glycols, etc. are particularly preferably used as meltable or softenable substances. These are described below.

The meltable or softenable substances should have a melting range (solidification range) in such a temperature range in which the remaining ingredients of the masses to be processed are not exposed to excessive thermal stress. On the other hand, however, the melting range must be sufficiently high in order to still provide a handleable molding at at least slightly elevated temperature. In preferred compositions according to the invention, the meltable or softenable substances have a melting point above 30 ° C.

It has proved to be advantageous if the meltable or softenable substances do not show a sharply defined melting point, as usually occurs in the case of pure, crystalline substances, but instead have a melting range which may be several degrees Celsius. The meltable or softenable substances preferably have a melting range of between about 45 ° C and about 75 ° C. That is, in the present case, the melting range occurs within the specified temperature interval and does not denote the width of the melting range. Preferably, the width of the melting range is at least 1 ° C, preferably from about 2 to about 3 ° C.

The above properties are usually met by so-called waxes. "Waxing" is understood to mean a series of naturally or artificially produced substances which generally melt above 40 ° C. without decomposition and are already relatively low-viscosity and non-stringy just above the melting point. They have a strong temperature-dependent consistency and solubility.

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

The natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, Japan wax, Espartograswachs, cork wax, guaruma wax, rice germ oil wax, sugarcane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, spermaceti, lanolin (wool wax), or crepe fat, mineral waxes such as ceresin or ozokerite (groundwax), or petrochemical waxes such as petrolatum, paraffin waxes or microwaxes.

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

Synthetic waxes are generally understood as meaning polyalkylene waxes or polyalkylene glycol waxes. It is also possible to use as meltable or softenable substances for the compositions which cure by cooling, and compounds from other substance classes which meet the stated requirements with regard to the softening point. As suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl phthalate, commercially available under the name Unimoll 66 ^® (Bayer AG) is available, proven. Also suitable are synthetic waxes made of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ^® ETLP (Condea) is available. Conversely, synthetic or partially synthetic esters of lower alcohols can be used with fatty acids from natural sources. This class of substances includes, for example, ^Tegin® 90 (Goldschmidt), a glycerol monostearate palmitate. Shellac, for example shellac KPS three-ring SP (Kalkhoff GmbH) can also be used according to the invention as meltable or softenable substances.

Likewise to the waxes in the context of the present invention, for example, the so-called wax alcohols are calculated. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols having generally about 22 to 40 carbon atoms. The wax alcohols are, for example, in the form of wax esters of higher molecular weight fatty acids (wax acids) as the main constituent of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The envelope of the solid particles coated according to the invention can optionally also containing wool wax alcohols, which are understood Triterpenoid- and steroid alcohols, such as lanolin, which is available for example under the trade name Argowax ^® (Pamentier & Co). In the context of the present invention, fatty acid glycerol esters or fatty acid alkanolamides but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds may likewise be used as part of the meltable or softenable substances.

Particularly preferred meltable or softenable substances in the masses to be processed include those from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG), with polyethylene glycols having molecular weights of between 1500 and 36,000 being preferred, and those having molecular weights of from 2000 to 6000 being particularly preferred and those having molecular weights of 3,000 to 5,000 are particularly preferred. Also, corresponding processes, which are characterized in that the plastically deformable mass (s) at least one substance from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) contains / are preferred. Here, according to the invention, masses to be processed are particularly preferred, which contain propylene glycols (PPG) and / or polyethylene glycols (PEG) as sole meltable or softenable substances. These substances have been described in detail above.

In a further preferred embodiment, the masses to be processed according to the invention contain in the predominant proportion paraffin wax. That is, at least 50% by weight of the total contained meltable or softenable substances, preferably more, consist of paraffin wax. Particularly suitable are paraffin wax contents (based on the total amount of meltable or softenable substances) of about 60% by weight, about 70% by weight or about 80% by weight, with even higher proportions of, for example, more than 90% by weight. are particularly preferred. In a particular embodiment of the invention, the total amount of the meltable or softenable substances used of at least one mass consists exclusively of paraffin wax.

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

Paraffin waxes consist mainly of alkanes, as well as low levels of iso- and cycloalkanes. The paraffin to be used according to the invention preferably has substantially no constituents with a melting point of more than 70 ° C., more preferably of more than 60 ° C. Shares of high-melting alkanes in the paraffin can fall below this melting temperature in the detergent leaving unwanted wax residue on the surfaces to be cleaned or the property to be cleaned. Such wax residues usually lead to an unsightly appearance of the cleaned surface and should therefore be avoided.

Preferably to be processed compositions contain as meltable or softenable substances at least one paraffin wax having a melting range of 50 ° C to 60 ° C, wherein preferred methods are characterized in that the deformable mass (s) a paraffin wax having a melting range of 50 ° C to 55 ° C contains / contain.

Preferably, the content of the paraffin wax used at ambient temperature (usually about 10 to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes as high as possible. The more solid wax constituents in a wax at room temperature, the more useful it is within the scope of the present invention. As the proportion of solid wax constituents increases, the end-of-processability of the process end products increases against impacts or friction on other surfaces, resulting in longer-lasting protection. High levels of oils or liquid wax components can lead to a weakening of the moldings or moldings areas, whereby pores are opened and the active ingredients are exposed to the aforementioned environmental influences.

The meltable or softenable substances may contain, in addition to paraffin as the main constituent, one or more of the abovementioned waxes or waxy substances. In a further preferred embodiment of the present invention that should be the Melting or softenable substances forming mixture be such that the mass and the molded body or molded body component formed therefrom are at least substantially water-insoluble. The solubility in water should not exceed about 10 mg / l at a temperature of about 30 ° C and preferably be below 5 mg / l.

In such cases, however, the meltable or softenable substances should have the lowest possible water solubility, even in water at elevated temperature, in order to avoid as much as possible a temperature-independent release of the active substances.

The principle described above is the delayed release of ingredients at a certain time in the cleaning cycle and can be particularly advantageous when rinsing in the main rinse at a lower temperature (for example 55 ° C), so that the active substance from the rinse aid particles only in the rinse cycle at higher Temperatures (about 70 ° C) is released.

Preferred compositions to be processed according to the invention are characterized in that they comprise, as meltable or softenable substances, one or more substances having a melting range from 40 ° C. to 75 ° C. in amounts of from 6 to 30% by weight, preferably from 7.5 to 25 Wt .-% and in particular from 10 to 20 wt .-%, each based on the weight of the mass.

Another mechanism by which the curing of the masses can take place is the evaporation of solvents. For this purpose, solutions or dispersions of the desired ingredients can be prepared in one or more suitable, volatile solvents which, after the shaping processing step, release and harden the solvent (s). Suitable solvents are, for example, lower alkanols, aldehydes, ethers, esters, etc., the selection of which is carried out depending on the further composition of the masses to be processed. Particularly suitable solvents for such processes in which the hardening of the deformable mass (s) takes place by evaporation of solvents are 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 and the acetic acid esters of the abovementioned alcohols, in particular ethyl acetate.

The evaporation of said solvents can be accelerated by the subsequent heating shaping, or by air movement. Combinations of the measures mentioned are suitable for this purpose, for example, the blowing of the cut moldings with hot or hot air.

Another mechanism that may underlie the hardening of the molding materials used to form parts of the molding (a) is crystallization. Methods in which the hardening of the deformable mass (s) occurs by crystallization are also preferred.

The crystallization as a mechanism underlying the curing can be used, for example, by melting of crystalline substances as the basis of one or more molding masses. After processing such systems go into a higher order state, which in turn leads to the curing of the entire formed body. The crystallization can also be carried out by crystallization from supersaturated solution. In the context of the present invention, supersaturation is the term for a metastable state in which, in a closed system, more of a substance is present than is required for saturation. A supersaturated solution obtained, for example, by supercooling thus contains more solute than it is likely to contain in thermal equilibrium. The excess of dissolved matter may be made by seeding with germs or dust particles or by shaking the system for instant crystallization. In the context of the present invention, the term "supersaturated" always refers to a temperature of 20 ° C. Dissolve in a particular solvent at a temperature of 20 ° C of a substance x grams in liters, the solution in the context of the present invention is to be described as "supersaturated" if it contains (x + y) grams of the substance in liters where y> 0. Thus, in the context of the present invention, solutions which are used at an elevated temperature as the basis of a mass to be processed and which are processed at this temperature are also to be termed "supersaturated" is more solute in the solution than would dissolve at 20 ° C in the same amount of solvent.

By the term "solubility", the present invention means the maximum amount of a substance that can hold the solvent at a certain temperature, i. the proportion of the solute in a solution saturated at the temperature in question. If a solution contains more solute than it is likely to contain at thermodynamic equilibrium (for example, supercooling) at a given temperature, it is called supersaturated. By seeding with germs can cause the excess precipitates as a bottom body of the now only saturated solution. However, a solution that is saturated with respect to a substance is capable of dissolving other substances (for example, it is still possible to dissolve sugar in a saturated saline solution).

The state of supersaturation can, as described above, be achieved by slow cooling or by supercooling of a solution, as long as the solute is more soluble in the solvent at higher temperatures. Other ways to achieve supersaturated solutions, for example, include the combination of two solutions whose ingredients react to another substance, which does not precipitate immediately (prevented or delayed precipitation reactions). The latter mechanism is particularly suitable as a basis for the formation of compositions to be processed according to the invention.

In principle, the state of supersaturation can be achieved with any type of solution, although the application of the principle described in the present application, as already mentioned, is used in the production of detergents and cleaners. Accordingly, some systems that tend in principle to form supersaturated solutions, according to the invention are less well used, since the underlying material systems ecologically, toxicologically or for economic reasons can not be used. In addition to nonionic surfactants or common nonaqueous solvents, therefore, processes according to the invention with the last-mentioned curing mechanism are particularly preferred in which a supersaturated aqueous solution is used as the basis for at least one mass to be processed.

As already mentioned above, the state of supersaturation in the context of the present invention refers to the saturated solution at 20 ° C. By using solutions that have a temperature above 20 ° C, the state of supersaturation can be easily reached. Processes according to the invention in which the composition which sets by crystallization has a temperature between 35 and 120 ° C., preferably between 40 and 110 ° C., more preferably between 45 and 90 ° C. and in particular between 50 and 80 ° C., during processing in the context of the present invention.

Since the prepared detergent tablets are usually neither stored at elevated temperatures nor later applied at these elevated temperatures, the cooling of the mixture results in the precipitation of the solute content from the supersaturated solution exceeding the saturation limit at 20 ° C contained in the solution. The supersaturated solution can thus be divided on cooling into a saturated solution and a bottom body. But it is also possible that by recrystallization and hydration phenomena the supersaturated solution solidifies on cooling to a solid. This is the case, for example, when certain hydrazine-containing salts dissolve on heating in their water of crystallization. On cooling, supersaturated solutions are often formed here, which solidify by mechanical action or addition of seed to give a solid-the salt containing water of crystallization as the thermodynamically stable state at room temperature. This phenomenon is known, for example, from sodium thiosulfate pentahydrate and sodium acetate trihydrate, it being possible in particular for the latter hydrazine-containing salt in the form of the supersaturated solution to be used advantageously in the process according to the invention. Special detergent ingredients, such as phosphonates, also show this phenomenon and are outstandingly suitable as granulation aids in the form of the solutions. For this purpose, the corresponding phosphonic acids (see below) are neutralized with concentrated alkali metal hydroxide solution, the solution heating up by the heat of neutralization. Upon cooling, these solutions form solids of the corresponding alkali phosphonates. By incorporating further detergent ingredients in the still warm solutions can be prepared according to the invention processable masses of different composition. Particularly preferred methods according to the invention are characterized in that the supersaturated solution used as the basis of the hardening composition in Room temperature solidified to a solid. It is preferred here that the previously supersaturated solution can not be reconverted into a supersaturated solution after solidification to a solid by heating to the temperature at which the supersaturated solution was formed. This is the case, for example, with the phosphonates mentioned.

The supersaturated solution serving as the basis of the hardening composition can - as mentioned above - be obtained in several ways and then be processed according to the invention after optional addition of further ingredients. A simple way, for example, is that the supersaturated solution used as the basis of the hardening mass is prepared by dissolving the solute in heated solvent. Are dissolved in this way in the heated solvent, higher amounts of the solute than would dissolve at 20 ° C, so there is a supersaturated in the context of the present invention solution that either hot (see above) or cooled and in the metastable state in the Mixer can be given.

It is also possible to dehydrate salts containing water of hydration by "dry" heating and dissolve in its own water of crystallization (see above). This, too, is a method for producing supersaturated solutions which can be used in the context of the present invention.

Another way is to add a non-supersaturated solution with a gas or other liquid or solution so that the solute in the solution reacts to a less soluble substance or dissolves more poorly in the mixture of solvents. The combination of two solutions, each containing two substances which react with each other to a poorly soluble substance, is also a method for producing supersaturated solutions, as long as the less soluble material fails instantaneously. Processes which are likewise preferred in the context of the present invention are characterized in that the supersaturated solution which serves as the basis of the hardening composition is prepared by combining two or more solutions. Examples of such ways of producing supersaturated solutions are discussed below.

Preferred processes according to the invention are characterized in that the supersaturated aqueous solution is obtained by combining an aqueous solution of one or more acidic ones Ingredients of detergents and cleaners, preferably from the group of surfactant acids, the builder acids and the complexing acids, and an aqueous alkali solution, preferably an aqueous alkali metal hydroxide solution, in particular an aqueous sodium hydroxide solution is obtained.

Among the representatives of the aforementioned classes of compounds already mentioned above, in particular the phosphonates occupy an outstanding position in the context of the present invention. In preferred processes according to the invention, therefore, the supersaturated aqueous solution is obtained by combining an aqueous phosphonic acid solution with concentrations above 45% by weight, preferably above 50% by weight and in particular above 55% by weight, based in each case on the phosphonic acid solution and an aqueous sodium hydroxide solution Concentrations above 35 wt .-%, preferably above 40 wt .-% and in particular above 45 wt .-%, each based on the sodium hydroxide solution.

The hardening of the deformable mass (s) can also take place according to the invention by chemical reaction (s), in particular polymerization. In principle, all chemical reactions are suitable which, starting from one or more liquid to pasty substances, lead to solids by reaction with (another) substance (s). In particular, chemical reactions that do not abruptly lead to the mentioned state change, are suitable. From the variety of chemical reactions that lead to the solidification phenomenon, particularly reactions are suitable in which the construction of larger molecules is made of smaller molecules. These, in turn, preferably include reactions in which many small molecules react to (a) larger molecule (s). These are so-called polyreactions (polymerization, polyaddition, polycondensation) and polymer-analogous reactions. The corresponding polymers, polyadducts (polyaddition products) or polycondensates (polycondensation products) then give the finished cut molded article its strength.

With regard to the intended use of the products according to the invention, it is preferred to use as a hardening mechanism the formation of such solid substances from liquid or pasty starting materials which are present in the washing and cleaning agent anyway as ingredients, such as co-builders, soil repellents or soil-release polymers are to be used. Such co-builders may be derived, for example, from the groups of polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, etc. These classes of substances are described below.

Another mechanism by which the hardening of the deformable mass (s) can take place in the context of the method according to the invention is curing by changing the rheological properties.

It makes use of the property that certain substances under the influence of shear forces change their rheological properties in some cases drastically. Examples of such systems which are familiar to the person skilled in the art are, for example, sheet silicates which, when sheared in suitable matrices, have a strong thickening effect and can lead to sliceable masses.

Of course, in a mass and two or more curing mechanisms are connected or used simultaneously. Here, for example, the crystallization with simultaneous solvent evaporation, the cooling with simultaneous crystallization, the water binding ("internal drying") with simultaneous external drying, etc. offer.

Analogously to the preparation of the non-compressed part (a), the non-compressed part (b) can be produced. Thus, preference is here given to washing or cleaning agent shaped bodies in which the non-compressed part (b) was produced by sintering, just as washing or cleaning agent shaped bodies are preferred in which the non-compressed part (b) was produced by casting.

Also, detergent tablets characterized in that the non-compressed part (b) was prepared by solidifying solutions ("gelatinizing") or detergent tablets in which the non-compressed part (b) was hardened were prepared, are preferred embodiments of the present invention.

Last but not least, it is also possible to produce detergent tablets in which the non-compressed part (b) is particulate. Details can be found below.

For biphasic moldings, there are thus many possibilities according to the invention, depending on whether parts (a) and (b) are produced in different or the same way. An overview of the genesis of the non-compressed molded body parts (a) and (b) for a molded article according to the invention from two areas / constituents is shown in the following table, which can be expanded analogously to three-phase, four-phase, five-phase, etc. moldings. non-compressed part (a) non-compressed part (b) sintered sintered sintered thermally sintered sintered sintered by irradiation sintered sintered by chemical reaction sintered cast sintered gelatinous sintered hardened sintered cured by delayed water binding sintered cured by cooling below the melting point sintered cured by evaporation of solvents sintered cured by crystallization sintered cured by chemical reaction (s), in particular polymerization sintered cured by changing the rheological properties sintered particulate sintered particulate, attached with adhesion promoter thermally sintered sintered thermally sintered thermally sintered thermally sintered sintered by irradiation thermally sintered sintered by chemical reaction thermally sintered cast thermally sintered gelatinous thermally sintered hardened thermally sintered cured by delayed water binding thermally sintered cured by cooling below the melting point thermally sintered cured by evaporation of solvents thermally sintered cured by crystallization thermally sintered cured by chemical reaction (s), in particular polymerization thermally sintered cured by changing the rheological properties thermally sintered particulate thermally sintered particulate, attached with adhesion promoter sintered by irradiation sintered sintered by irradiation thermally sintered sintered by irradiation sintered by irradiation sintered by irradiation sintered by chemical reaction sintered by irradiation cast sintered by irradiation gelatinous sintered by irradiation hardened sintered by irradiation cured by delayed water binding sintered by irradiation cured by cooling below the melting point sintered by irradiation cured by evaporation of solvents sintered by irradiation cured by crystallization sintered by irradiation cured by chemical reaction (s), in particular polymerization sintered by irradiation cured by changing the rheological properties sintered by irradiation particulate sintered by irradiation particulate, attached with adhesion promoter sintered by chemical reaction sintered sintered by chemical reaction thermally sintered sintered by chemical reaction sintered by irradiation sintered by chemical reaction sintered by chemical reaction sintered by chemical reaction cast sintered by chemical reaction gelatinous sintered by chemical reaction hardened sintered by chemical reaction cured by delayed water binding sintered by chemical reaction cured by cooling below the melting point sintered by chemical reaction cured by evaporation of solvents sintered by chemical reaction cured by crystallization sintered by chemical reaction cured by chemical reaction (s), in particular polymerization sintered by chemical reaction cured by changing the rheological properties sintered by chemical reaction particulate sintered by chemical reaction particulate, attached with adhesion promoter

The following is a description of the main ingredients of the detergent tablets according to the invention, wherein after a general description of the ingredients on the distribution of these substances on individual areas of the shaped body according to the invention is discussed.

Preferred detergent tablets according to the invention contain one or more surfactants. Accordingly, it is preferred that at least one of the non-compressed parts contains surfactant (s) as the active substance. In the detergent tablets according to the invention anionic, nonionic, cationic and / or amphoteric surfactants or mixtures thereof may be used. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants. The total surfactant content of the tablets in the case of detergent tablets is 5 to 60% by weight, based on the tablet weight, with surfactant contents above 15% by weight being preferred, whereas automatic dishwashing detergent tablets preferably contain less than 5% by weight of surfactant (e ) contain.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. Suitable surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred.

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

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.

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

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

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl branched radicals in the mixture may contain, as they are usually present in Oxoalkoholresten.

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

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

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht.Further suitable surfactants are polyhydroxy fatty acid amides of the formula V

in the RCO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.

In the context of the present invention, detergent tablets or detergent tablets which contain anionic (s) and nonionic surfactant (s) are preferred, technical advantages resulting from certain ratios in which the individual classes of surfactants are used.

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

It may be advantageous from an application point of view if certain classes of surfactant are present in some phases of the detergent tablets or in the entire tablet, i. in all phases, not included. Another important embodiment of the present invention therefore provides that at least one phase of the moldings is free of nonionic surfactants.

Conversely, however, the content of individual phases or of the entire molding, i. all phases, on certain surfactants a positive effect can be achieved. The incorporation of the above-described alkylpolyglycosides has proved to be advantageous, so that detergent tablets are preferred in which at least one phase of the tablets contains alkylpolyglycosides.

Similar to the nonionic surfactants, the omission of anionic surfactants from individual or all phases may result in washing and cleaning agent tablets which are more suitable for certain fields of application. It is therefore in Also conceivable within the scope of the present invention are detergent tablets and detergent tablets in which at least one phase of the tablets is free of anionic surfactants.

As already mentioned, the use of surfactants in automatic dishwashing detergent tablets is preferably restricted to the use of small amounts of nonionic surfactants. Detergent tablets preferably to be used as detergent tablets are characterized in that they contain total surfactant contents below 5% by weight, preferably below 4% by weight, more preferably below 3% by weight and in particular below 2 wt .-%, each based on their total weight, have. As surfactants, only weakly foaming nonionic surfactants are usually used in automatic dishwashing detergents. Representatives from the groups of anionic, cationic or amphoteric surfactants, however, have less importance. With particular preference, inventive detergent tablets for automatic dishwashing 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 on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. In the case of detergent tablets according to the invention or dishwashing detergent tablets, it is preferred for the detergent tablets to comprise a nonionic surfactant which has a melting point above room temperature. Accordingly, at least one of the deformable masses in the process according to the invention preferably contains a nonionic surfactant having a melting point above 20 ° C. Preferably used nonionic surfactants have melting points above 25 ° C, particularly preferably used nonionic surfactants have melting points between 25 and 60 ° C, in particular between 26.6 and 43.3 ° C.

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

Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols, and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also distinguished by good foam control.

In a preferred embodiment of the present invention, the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.

A particularly preferred room temperature solid nonionic surfactant is obtained 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 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide , Of these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

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

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

Nonionic surfactants that may be used with particular Vorzu, are obtainable for example under the name Poly Tergent ^® SLF-18 from Olin Chemicals.

A further preferred surfactant can be defined by the formula

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

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

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

R ¹ O [CH ₂ CH (R ³ ) O] _{x [} CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

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

As described above, each R ³ in the above formula may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. Is for example, x 3, the radical R may be selected ³ 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 selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

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

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

simplified. In the latter formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

The above statements relate in part to the entire moldings, which - as mentioned above - can also be designed in three or four phases. Based on the individual non-compressed portion containing surfactant (s), automatic dishwashing detergent tablets are preferred, the total surfactant contents below 5% by weight, preferably below 4% by weight, more preferably below 3% by weight. -% and in particular below 2 wt .-%, each based on the non-compressed part and in particular based on the weight of the non-compressed part (a) having.

The detergent tablets according to the invention preferably comprise builders, which in turn preferably originate from the groups of zeolites, silicates, carbonates, bicarbonates, phosphates and polymers. In particular, in the non-compressed shaped body parts produced by curing, preferred ingredients are selected from the group of phosphates, with alkali metal phosphates being particularly preferred. These substances are used in the preparation of the masses in anhydrous or low-form and set the desired plastic properties of the masses with water and optional Platisizierhilfsmitteln. After the shaping processing, the hardening of the shaped and cut strands is then carried out by hydration of the phosphates. Of course, however, phosphates may also be included in non-compressed parts prepared by other routes, e.g. by sintering.

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

In preferred detergent tablets, at least one non-compressed portion, in particular the non-compressed portion, contains (a) phosphate (s), preferably alkali metal phosphate (s), more preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in quantities from 20 to 80 wt .-%, preferably from 25 to 75 wt .-% and in particular from 30 to 70 wt .-%, each based on the non-compressed portion.

If phosphates are used as sole hydratable substances in hardening masses, then the amount of added water should not exceed their water binding capacity in order to keep the content of the shaped bodies to a minimum in free water. Overall, in order to comply with the abovementioned limit values, methods have been found to be preferred in which the weight ratio of phosphate (s) to water in the deformable mass is less than 1: 0.3, preferably less than 1: 0.25 and in particular less than 1: 0, 2 is.

Further ingredients which may be present in the detergent tablets instead of or in addition to phosphates are carbonates and / or bicarbonates, preference being given to the alkali metal salts and, in particular, the potassium and / or sodium salts. Preferred detergent tablets contain carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonates, more preferably sodium carbonate, in amounts of from 5 to 50% by weight, preferably from 7.5 to 40% by weight and in particular of 10 to 30 wt .-%, each based on a non-compressed portion and in particular based on the weight of the non-compressed part (a).

Here, too, in the case of production by curing with respect to the water content of the masses, the above applies. In particular, methods have been found to be preferred in which the weight ratio of carbonate (s) and / or bicarbonate (s) to water in the deformable mass is less than 1: 0.2, preferably less than 1: 0.15 and in particular less than 1: 0.1.

Further ingredients which may be present instead of or in addition to the said phosphates and / or carbonates / bicarbonates in the detergent tablets according to the invention are silicates, the alkali metal silicates and especially the amorphous and / or crystalline potassium and / or sodium disilicates are preferred.

Suitable crystalline layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

Other useful builders are amorphous sodium silicates with an Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and more preferably 1: 2 to 1: 2.6, which Delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous".

In the context of the present invention, preferred detergent tablets contain silicate (s), preferably alkali metal silicates, more preferably crystalline or amorphous alkali disilicates, in amounts of 10 to 60% by weight, preferably 15 to 50% by weight and in particular 20 to 40 wt .-%, each based on the total molding or based on the weight of the non-compressed part (a).

Here, too, the above applies to the preparation of curing with respect to the water content of the masses. In particular, methods have been preferred in which the weight ratio of silicate (s) to water in the deformable mass is less than 1: 0.25, preferably less than 1: 0.2 and in particular less than 1: 0.15.

Also suitable as an important component in the washing or cleaning agent tablets according to the invention are substances from the group of zeolites. Especially with detergent tablets, these substances are preferred builders. Zeolites have the general formula

M _{2 / n} O · Al ₂ O ₃ · xSiO ₂ · yH ₂ O

in which M is a cation of valency n, x stands for values which are greater than or equal to 2 and y can assume values between 0 and 20.

Preferred detergent tablets are characterized in that they contain zeolite (s), preferably zeolite A, zeolite P, zeolite X and mixtures thereof, in amounts of from 10 to 60% by weight, preferably from 15 to 50% by weight. and especially from 20 to 40% by weight.

The particle sizes of the preferably used faujasite-type zeolites are preferably in the range from 0.1 to 100 .mu.m, preferably between 0.5 and 50 .mu.m and in particular between 1 and 30 .mu.m, in each case measured using standard particle size determination methods.

It is generally preferred to use finely divided solids, regardless of whether these are the zeolites mentioned or other builders or bleaches, bleach activators or other Feststsoffe. In general, in the case of processing by curing, process variants are preferred in which the average particle size of the solids used is below 400 μm, preferably below 300 μm and in particular below 200 μm.

The mean particle size represents the arithmetic mean of the individual particle sizes, which may still vary. Particularly preferred processes are characterized in that less than 10% by weight, preferably less than 5% by weight and in particular less than 1% by weight of the solids used in the deformable mass (s) have particle sizes above 1000 μm , The upper particle size range can be narrowed even further, so that particularly preferred processes are characterized in that less than 15 wt .-%, preferably less than 10 wt .-% and in particular less than 5 wt .-% of the deformable Mass (s) of solids used have particle sizes above 800 microns.

In general, however, even narrower particle size distributions are preferred in which the fluctuation range around the average particle size is at most 50%, preferably at most 40% and in particular at most 30% of the average particle size, ie the particle sizes are minimally 0.7 and, at most, 1.3. times the mean particle size.

Above, the weight ratio of water to certain ingredients in the invention preferably to be processed masses was given for the preparation of the other non-compressed parts via curing. After processing, this water is preferably bound in the form of water of hydration, so that the Verfahrensendprodukte preferably have a significantly lower free water content. Preferred end products of the process according to the invention are substantially anhydrous, ie in a state in which the content of liquid, ie not present in the form of water of hydration and / or water of constitution below 2 wt .-%, preferably below 1 wt .-% and especially even below 0.5 wt .-%, each based on the moldings, is. Accordingly, detergent tablets or detergent tablets according to the invention which contain less than 10% by weight, preferably less than 5% by weight, particularly preferably less than 1% by weight and in particular less than 0.5% by weight, of free water are preferred , Accordingly, water can essentially only be present in chemically and / or physically bound form or as a constituent of the raw materials or compounds present as solid, but not as a liquid, solution or dispersion in the end products. Advantageously, the shaped bodies at the end of the manufacturing process a total water content of not more than 15 wt .-%, which water is thus not present in liquid free form, but chemically and / or physically bound, and it is particularly preferred that the content of zeolite and / or to Silicates bound water in solid premix not more than 10 wt .-% and in particular not more than 7 wt .-% is.

In the context of the present invention, particularly preferred detergent tablets or detergent tablets not only have an extremely low proportion of free water, but are preferably themselves still able to bind further free water. In preferred detergent tablets, the water content of the tablets is 50 to 100% of the calculated water binding capacity.

wobei n die Zahl der Wassermoleküle im entsprechenden Hydrat der Substanz und M die Molmasse der nicht hydratisierten Substanz ist. Damit ergibt sich beispielsweise für das Wasserbindevermögen von wasserfreiem Natriumcarbonat (Bildung von Natriumcarbonat-Monohydrat) ein Wert von $$\mathit{WBV}=\frac{1\cdot 18}{2\cdot 23+12+3\cdot 16}=0,17$$

The water binding capacity is the ability of a substance (here: the washing or cleaning agent shaped body) to absorb water in chemically stable form and ultimately indicates how much water in the form of stable hydrates of a substance or a shaped body can be bound. The dimensionless value of the water-binding capacity (WBV) is calculated from: $$\mathit{WBV}=\frac{n\cdot 18}{M}.$$

where n is the number of water molecules in the corresponding hydrate of the substance and M is the molecular weight of the non-hydrated substance. This results in a value of, for example, the water binding capacity of anhydrous sodium carbonate (formation of sodium carbonate monohydrate) $$\mathit{WBV}=\frac{1\cdot 18}{2\cdot 23+12+3\cdot 16}=0.17$$

The value WBV can be calculated for all hydrate-forming substances which are used in the compositions to be processed according to the invention. About the percentage of these substances then gives the total water binding capacity of the recipe. In preferred Verfahrensendprodukten the water content is then between 50 and 100% of this calculated value.

In addition to the water content of the washing or cleaning agent tablets and the ratio of water to certain raw materials in the case of the preparation of the other non-compressed molded article by curing and information about the absolute water content of the invention to be processed masses are made. In particularly preferred processes, the deformable mass (s) during processing have a water content of from 2.5 to 30% by weight, preferably from 5 to 25% by weight and in particular from 7.5 to 20% by weight .-%, in each case based on the mass, on.

In addition to the constituents builder and surfactant, the detergent tablets according to the invention may contain further ingredients customary in detergents and cleaners from the group of bleaches, bleach activators, disintegration aids, dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, anti redeposition agents, grayness inhibitors, Color transfer inhibitors and corrosion inhibitors.

Preferred detergent tablets contain from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, of one or more disintegration aids, in each case based on the weight of the tablet. If only one non-compressed portion of disintegration aid is included, the information given is based solely on the weight of this non-compressed portion.

In the context of the present invention, preferred detergent tablets also contain a disintegration aid, preferably a cellulose-based disintegration assistant, preferably in granular, cogranulated or compacted form, in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight. -% and in particular from 4 to 6 wt .-%, each based on the molding weight.

The detergent tablets according to the invention may moreover contain a gas-evolving effervescent system which is incorporated in one or more of the masses to be processed. The gas-evolving effervescent system may consist of a single substance that releases a gas upon contact with water. Among these compounds In particular, mention should be made of magnesium peroxide, which liberates oxygen on contact with water. Usually, however, the gas-releasing effervescent system in turn consists of at least two constituents which react with one another to form gas. While here a variety of systems is thinkable and executable that release, for example, nitrogen, oxygen or hydrogen, the bubble system used in the detergent tablets according to the invention can be selected both on the basis of economic as well as ecological aspects. Preferred effervescent systems consist of alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution.

In preferred detergent tablets, the effervescent system is 2 to 20% by weight, preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or bicarbonate and 1 to 15, preferably 2 to 12 and in particular 3 to 10 wt .-% of an Acidifizierungsmittels, in each case based on the entire molded body used. The content of individual masses of the substances mentioned may well be higher.

Acidifying agents which release carbon dioxide from the alkali metal salts in aqueous solution include, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts. However, preference is given to using organic acidifying agents, the citric acid being a particularly preferred acidifying agent. However, it is also possible in particular to use the other solid mono-, oligo- and polycarboxylic acids. Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are again preferred from this group. Organic sulfonic acids such as sulfamic acid are also usable. A commercially available as an acidifier in the context of the present invention is also preferably usable Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) (and adipic acid at most 33% by weight).

In the context of the present invention, preference is given to detergent tablets and cleansing agent tablets in which a substance from the group of organic di-, tri- and oligocarboxylic acids or mixtures thereof is used as the acidifying agent in the effervescent system.

Among the compounds which serve as bleaches and deliver H ₂ O ₂ in water, sodium percarbonate has particular significance. Here, "sodium percarbonate" is a non-specific term used for sodium carbonate peroxohydrates, which strictly speaking are not "percarbonates" (ie salts of percarbonate) but hydrogen peroxide adducts of sodium carbonate. The commercial product has the average composition 2 Na ₂ CO ₃ · 3 H ₂ O ₂ and is therefore no peroxycarbonate. Sodium percarbonate forms a white, water-soluble powder with a density of 2.14 gcm ^-3 , which readily decomposes into sodium carbonate and bleaching or oxidizing oxygen.

Further useful bleaching agents are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and peroxygenic salts or peracids which yield H ₂ O ₂ , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced. If such bleach tablets are to be used for textile washing, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, regardless of which other ingredients are contained in the tablets. When cleaning or bleaching tablets for automatic dishwashing are prepared, it is also possible to use bleaching agents from the group of organic bleaching agents. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.

Chlorinating or bromine-releasing substances can also be used as bleaching agents in machine dishwashing moldings. Examples of suitable chlorine or bromine-releasing materials are heterocyclic N-bromo and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or salts thereof Cations such as potassium and sodium into consideration. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

In order to achieve an improved bleaching effect when washing or cleaning at temperatures of 60 ° C and below, bleach activators can be incorporated. Bleach activators which support the action of the bleaching agents are, for example, compounds which contain one or more N- or O-acyl groups, such as substances from the class of the anhydrides, the esters, the imides and the acylated imidazoles or oximes. Examples are tetraacetylethylenediamine (TAED), tetraacetylmethylenediamine (TAMD) and tetraacetylhexylenediamine (TAHD), but also pentaacetylglucose (PAG), 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine (DADHT) and isatoic anhydride (ISA).

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

Preference is given to bleach activators from the group of the polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n -Methyl-morpholinium acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, particularly 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-% based on the total agent used.

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

Further preferred detergent tablets are characterized in that at least one of the non-compressed portions contains silver protectants from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes, more preferably benzotriazole and / or alkylaminotriazole , in amounts of 0.01 to 5 wt .-%, preferably from 0.05 to 4 wt .-% and in particular from 0.5 to 3 wt .-%, each based on the mass.

The said corrosion inhibitors can also be incorporated into the masses to be processed in order to protect the items to be washed or the machine, with silver protectants being of particular importance in the field of automatic dishwashing.

If corrosion inhibitors are used in multiphase moldings, it is preferable to separate them from the bleaching agents. Detergent tablets in which one of the non-compressed parts contains bleach while another contains anticorrosion agent are therefore preferred.

Also, the separation of the bleach from other ingredients may be advantageous. Detergent tablets according to the invention in which one non-compressed portion contains bleach while another contains enzyme are also preferred. Suitable enzymes include in particular those from the classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other Glykosylhydrolasen and mixtures of said enzymes in question. It is also possible to use oxidoreductases for bleaching or inhibiting color transfer.

The enzymes may be adsorbed to carriers or embedded in encapsulants to protect against premature degradation. The proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-%, each based on the non-compressed part.

Other ingredients that may be part of one or more non-compressed portion (s) within the scope of the process of the present invention are, for example, co-builders, dyes, optical brighteners, fragrances, soil-release compounds, soil repellents, antioxidants, fluorescers, foam inhibitors, silicone surfactants. and / or paraffin oils, dye transfer inhibitors, graying inhibitors, detergency boosters, etc. These materials are described below.

In order to improve the aesthetic impression of the detergent tablets according to the invention, they can be wholly or partially dyed with suitable dyes. Special optical effects can be achieved if in the case of the production of moldings from several masses, the masses to be processed are colored differently. Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to the treated substrates such as textile fibers or dishes so as not to stain them.

Preferred for use in detergent tablets according to the invention are all colorants which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners. It has proved to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances.

The detergent tablets according to the invention may contain one or more optical brighteners. These fabrics, also called "whiteners", are used in modern laundry detergents because even freshly washed and bleached white laundry has a slight yellow tinge.

Fragrances are added to the compositions according to the invention in order to improve the aesthetic impression of the products and to provide the consumer, in addition to the performance of the product, a visually and sensory "typical and unmistakable" product. As perfume oils or fragrances, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used.

Usually, the content of perfume in the washing and cleaning agent tablets produced according to the invention is up to 2% by weight of the total formulation.

In addition, the detergent tablets may also contain components which positively influence the oil and grease washability from textiles (so-called soil repellents). Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.

Suitable foam inhibitors which can be used in the compositions according to the invention are, for example, soaps, paraffins or silicone oils, which may optionally be applied to support materials.

Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, soluble starch preparations and other than the above starch products can be used, eg degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. However, preference is given to using cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof in amounts of from 0.1 to 5% by weight, based on the compositions

Since textile fabrics, in particular of rayon, rayon, cotton and their mixtures, can crumple because the individual fibers against bending, kinking. Pressing and squeezing transverse to the fiber direction are sensitive, the compositions according to the invention may contain synthetic crease inhibitors. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.

For controlling microorganisms, the compositions prepared according to the invention may contain antimicrobial agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungiostats and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate, although it is entirely possible to do without these compounds.

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

An increased wearing comfort can result from the additional use of antistatic agents, which are additionally added to the compositions according to the invention. Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges.

To improve the water absorption capacity, the rewettability of the treated textiles and to facilitate the ironing of the treated textiles, for example, silicone derivatives can be used in the compositions according to the invention. These additionally improve the rinsing behavior of the agents by their foam-inhibiting properties.

Finally, the compositions according to the invention may also contain UV absorbers which are absorbed by the treated textiles and improve the light resistance of the fibers. Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position.

In all of the above-mentioned ingredients, advantageous properties may result from separating them from other ingredients, or assembling them together with certain other ingredients. In the case of multiphase moldings, the individual phases can also have a different content of the same ingredient, whereby advantages can be achieved.

In particular, washing or cleaning agent shaped bodies according to the invention are preferred in which the non-compressed part (a) builders in amounts of 1 to 100 wt .-%, preferably from 5 to 95 wt .-%, particularly preferably from 10 to 90 wt. -% and in particular from 20 to 85 wt .-%, each based on the weight of the non-compressed part (a) contains.

Also preferred are detergent tablets in which the non-compressed part comprises (a) phosphate (s), preferably alkali metal phosphate (s), more preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of from 20 to 80 wt .-%, preferably from 25 to 75 wt .-%, in particular from 30 to 70 wt .-%, each based on the weight of the non-compressed part (a) contains.

Also preferred are detergent tablets or detergent tablets which are characterized in that the non-compressed part comprises (a) carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonates, more preferably sodium carbonate, in amounts of from 5 to 50% by weight. %, preferably from 7.5 to 40 wt .-% and in particular from 10 to 30 wt .-%, each based on the weight of the non-compressed part (a) contains.

Also detergent tablets or detergent tablets in which the non-compressed part comprises (a) silicate (s), preferably alkali metal silicates, particularly preferably crystalline or amorphous alkali disilicates, in amounts of from 10 to 60% by weight, preferably from 15 to 50% by weight. % and in particular from 20 to 40 wt .-%, each based on the weight of the non-compressed part (a) contains, are preferred embodiments of the present invention.

Likewise, detergent tablets are characterized in that the non-compressed part (a) total surfactant contents below 5 wt .-%, preferably below 4 wt .-%, more preferably below 3 wt .-% and in particular below 2 wt .-%, each based on the weight of the non-compressed part (a), preferably.

Further preferred laundry detergent or cleaning product tablets are characterized in that the non-compressed component comprises (a) bleaching agents selected from the group consisting of oxygen or halogen bleaches, in particular chlorine bleaches, with particular preference to sodium perborate and sodium percarbonate in amounts of from 2 to 25% by weight .-%, preferably from 5 to 20 wt .-% and in particular from 10 to 15 wt .-%, each based on the weight of the non-compressed part (a).

In addition, laundry detergent or detergent tablets are preferred in which the non-compressed part comprises (a) bleach activators from the groups of the polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), the acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) and n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), in amounts of from 0.25 to 15% by weight, preferably from 0.5 to 10 Wt .-% and in particular from 1 to 5 wt .-%, each based on the weight of the non-compressed part (a) contains.

Also washing or cleaning tablets, in which the non-compressed part (a) silver protectants from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes, more preferably benzotriazole and / or alkylaminotriazole, in Amounts of 0.01 to 5 wt .-%, preferably from 0.05 to 4 wt .-% and in particular from 0.5 to 3 wt .-%, each based on the weight of the non-compressed part (a), contains, represent preferred embodiments of the present invention.

Another preferred embodiment of the present invention are detergent tablets which are characterized in that the non-compressed component (a) further contains one or more substances from the groups of enzymes, corrosion inhibitors, coating inhibitors, cobuilders, dyes and / or fragrances in total amounts of 6 to 30 wt .-%, preferably from 7.5 to 25 wt .-% and in particular from 10 to 20 wt .-%, each based on the weight of the non-compressed part (a).

Last but not least, detergent tablets or detergent tablets are particularly preferred in which the second non-compressed part (b) is a coated, preferably multi-layered shaped article which is glued into the cavity of the non-compressed part (a).

The detergent tablets according to the invention completely dissolve in the washing or cleaning cycle, wherein - as mentioned above - it can have advantages if the different regions have different dissolution rates. Due to the different dissolution rates, the properties of the washing or cleaning liquor can be selectively changed in addition to the release of certain ingredients at certain times. For example, detergent tablets are preferred in which the pH of a 1% strength by weight solution of the basic tablet in water is in the range from 8 to 12, preferably from 9 to 11 and in particular from 9.5 to 10 ,

In addition to this detergent and cleaner tablets are preferred in which the pH of a 1 wt .-% - solution of the total molding in water in the range of 7 to 11, preferably from 7.5 to 10 and in particular from 8 to 9, 5, lies.

The detergent tablets according to the invention can be provided in a wide variety of geometric shapes. For example, they can be manufactured in a predetermined spatial form and a predetermined size, as a spatial form come practically all sensible designs come into consideration, for example, the training as a blackboard, the bar or bar form, cubes, blocks and corresponding space elements with flat side surfaces and in particular cylindrical embodiments with a circular or oval cross-section. This last embodiment covers the presentation form of the tablet up to compact cylinder pieces with a ratio of height to diameter above 1.

The detergent tablets according to the invention may in each case be in the form of individual elements which are separate from each other and which corresponds to the predetermined metered quantity of the washing and / or cleaning agents. Likewise, it is possible to form the individual non-compressed portions so that a plurality of such mass units is connected in a compact, wherein in particular by predetermined breaking points the easy separability portioned smaller units is provided. For the use of laundry detergents in machines of the type commonly used in Europe with horizontally arranged mechanism, the formation as tablets, in cylindrical or parallelepiped form may be expedient, with a diameter / height ratio in the range of about 0.5: 2 to 2: 0 5 is preferred.

The spatial form of another embodiment of the moldings is adapted in their dimensions of the dispenser of commercial household washing machines, so that the moldings can be metered without dosing directly into the dispenser, where it dissolves during the dispensing process. Of course, however, a use of the detergent tablets via a dosing is easily possible and preferred in the context of the present invention.

Another preferred molded article which can be produced has a plate-like or tabular structure with alternately thick long and thin short segments, so that individual segments of this "bar" at the predetermined breaking points, which are the short thin segments, broken and in the Machine can be entered. This The principle of the "bar-shaped" shaped body wash can also be realized in other geometric shapes, for example vertical triangles, which are joined together only on one of their sides.

Such "bar-shaped" strand sections can be produced by a post-cutting post-treatment step, which consists in pressing a second knife or a second set of knives into the cut strand sections without dividing them. Even a superficial shaping or production of positive or negative lettering can be carried out according to the invention. Accordingly, preferred processes are characterized in that the cut-to-size moldings are subjected to a post-treatment step.

The aftertreatment step may include impressions of patterns, shapes, etc., in addition to memorizing lettering. In this way, for example, universal detergents prepared according to the invention can be identified by symbols such as glasses, plates, pots, pans, etc., by a T-shirt symbol, color detergents prepared according to the invention by a wool symbol, machine dishwashing detergent tablets produced according to the invention. There are no limits to the creativity of product managers. Preferred methods according to the invention therefore comprise, as post-treatment step, an additional shaping step, in particular embossing.

A subsequent coating of the cut moldings is also possible, if the application of an additional coating should be desired. Here, methods are preferred in which the post-treatment step comprises coating the shaped bodies with a pourable material, preferably a pourable material having a viscosity of <5000 mPas.

Irrespective of the number of phases and the type of after-treatment, preference is generally given to detergent tablets which are characterized in that they have a density above 800 kgdm ^-3 , preferably above 900 kgdm ^-3 , particularly preferably above 1000 kgdm ^{. 3} and in particular above 1100 kgdm ^-3 exhibit. In such moldings, the advantages of the offer form of a compact washing or cleaning agent are particularly evident.

1. (a) Herstellung eines ersten nicht-verpreßten Teils (a), der Aktivsubstanz enthält,
2. (b) Herstellung eines zweiten nicht-verpreßten Teils (b), der Aktivsubstanz enthält,
3. (c) Verbinden der beiden Formkörperteile durch An- oder Ineinanderfügen zum Formkörper, wobei der Verfahrensschritt (a) das Sintern umfasst.

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

1. (a) Preparation of a first non-compressed part (a) containing active substance
2. (b) preparing a second non-compressed part (b) containing active substance,
3. (c) joining the two molded body parts by joining or joining them to the shaped body, wherein the method step (a) comprises the sintering.

The joining may be a "sticking" known to those skilled in the art, but it is also possible that the molded body parts merely stick together due to their geometry. Processes according to the invention in which the adhesion between the molded article parts (a) and (b) is assisted by adhesion promoters are preferred.

As adhesion promoters, it is possible to use substances which impart sufficient adhesiveness ("stickiness") to the shaped body surfaces to which they are applied so that the non-compressed parts applied in the subsequent process step adhere permanently to the surface. In principle, the substances mentioned in the relevant adhesives literature and in particular in the monographs are suitable for this purpose, whereby in the context of the present invention the application of melts, which act as adhesion promoters at elevated temperatures but are no longer tacky after cooling, but a special one Meaning.

Processes according to the invention in which, as adhesion promoter, melting of one or more substances having a melting range from 40 ° C. to 75 ° C. is applied to one or more surfaces of the molded article (a), after which the molded article (e) (b) is adhered / are therefore preferred.

At the adhesion promoters, which are optionally applied, various requirements are made, on the one hand affect the melting or solidification behavior, on the other hand, but also the material properties of the "glue point" in the solidified region at ambient temperature. Since the applied to the molding layer of the Adhesive should permanently hold the "glued" non-compressed parts during transport or storage, it must have a high stability against, for example, occurring during packaging or transport shock loads. The adhesion promoters should therefore either have at least partially elastic or at least plastic properties in order to react to an occurring impact load by elastic or plastic deformation and not to break. The adhesion promoters should have a melting range in such a temperature range in which the unpressurized parts to be applied are not exposed to excessive thermal stress. On the other hand, however, the melting range must be sufficiently high to still provide effective adhesion of the applied non-compressed parts at at least slightly elevated temperature. According to the invention, the coating substances preferably have a melting point above 30 ° C. The width of the melting range of the adhesion promoter also has direct effects on the process performance: The molded body provided with primer must be brought in the subsequent process step in contact with the applied non-compressed parts - in the meantime, the adhesion must not be lost. After incorporation of the active ingredients, the adhesion should be reduced as quickly as possible in order to avoid unnecessary loss of time or to prevent caking and stagnation in subsequent process steps or handling and packaging. In the case of using melts, the reduction in adhesiveness can be promoted by cooling (for example, blowing with cold air).

It has proved to be advantageous if the adhesion promoters do not show a sharply defined melting point, as is usually the case with pure, crystalline substances, but instead have a melting range possibly encompassing several degrees Celsius.

The adhesion promoters preferably have a melting range of between about 45 ° C and about 75 ° C. That is, in the present case, the melting range occurs within the specified temperature interval and does not denote the width of the melting range. Preferably, the width of the melting range is at least 1 ° C, preferably from about 2 to about 3 ° C.

The above properties are usually met by so-called waxes, which have already been described in detail above.

The adhesion promoters to be applied can be pure substances or substance mixtures. In the latter case, the melt may contain varying amounts of primer and excipients.

The principle described above serves the delayed detachment of the "glued" non-compressed portions at a certain time, for example in the cleaning cycle of a dishwasher and can be particularly advantageous when rinsing in the main wash at a lower temperature (for example 55 ° C), so that the active substance is released from the adhesive layer only in the rinse cycle at higher temperatures (about 70 ° C).

However, the said principle can also be reversed to the effect that the non-compressed part (s) are not delayed by the adhesive layer but are released at an accelerated rate. This can be achieved in the process according to the invention in a simple manner that are not used as adhesion promoter Löseverzögerer, but dissolution accelerator, so that the glued non-compressed parts do not dissolve slower from the molding, but faster. In contrast to the poorly water-soluble adhesion promoters described above, preferred adhesion promoters are readily soluble in water for rapid release. The water solubility of the primer can be significantly increased by certain additives, for example by incorporation of slightly soluble salts or effervescent systems. Such dissolution-accelerated adhesion promoters (with or without additions of further solubility improvers) lead to a rapid detachment and release of the active substances at the beginning of the cleaning cycle.

The release acceleration can also be achieved or supported by certain geometric factors. Detailed comments can be found below.

In addition to melting, other substances than adhesion promoters can be applied in the process according to the invention. For this purpose, for example, concentrated salt solutions are suitable, which are converted after application of the active ingredients by crystallization or evaporation / evaporation in an adhesion-promoting salt crust. Of course, it is also possible to use supersaturated solutions or solutions of salts in solvent mixtures.

Also suitable as adhesion promoters are solutions or suspensions of water-soluble or -dispersible polymers, preferably polycarboxylates. These substances have already been described above because of their co-builder properties.

Other particularly suitable adhesion promoters are solutions of water-soluble substances from the group (acetalized) polyvinyl alcohol, polyvinylpyrrolidone, gelatin and mixtures thereof. These substances have already been described in detail.

Preferred adhesion promoters which can be used as aqueous solution in the process according to the invention consist of a polymer having a molecular weight between 5000 and 500,000 daltons, preferably between 7500 and 250,000 daltons and in particular between 10,000 and 100,000 daltons. The layer of the adhesion promoter present between the individual shaped body regions after drying of the adhesion promoter preferably has a thickness of from 1 to 150 μm, preferably from 2 to 100 μm, particularly preferably from 5 to 75 μm and in particular from 10 to 50 μm.

1. (a) Herstellung eines ersten nicht-verpreßten Teils (a), der Aktivsubstanz enthält und mindestens eine Kavität aufweist,
2. (b) Herstellung eines zweiten nicht-verpreßten Teils (b), der Aktivsubstanz enthält,
3. (c) Verbinden der beiden Formkörperteile durch mindestens anteilsweises Einfügen des Formkörperteils (b) in die Kavität des Formkörperteils (a)

umfaßt, als auch ein Verfahren zur Herstellung von Wasch- oder Reinigungsmittelformkörpern, welches durch die Schritte

1. (a) Herstellung eines ersten nicht-verpreßten Teils (a), der Aktivsubstanz enthält und mindestens eine Kavität aufweist,
2. (b) Einfügen von Aktivsubstanz in die Kavität(en) des Formkörperteils (a) unter Bildung eines Formkörperteils (b),
3. (c) Fixieren des Formkörperteils (b) in der Kavität des Formkörperteils (a).

gekennzeichnet ist, wobei der Verfahrensschritt (a) jeweils das Sintern umfasst.Another object of the present invention are both a process for the preparation of detergent tablets, comprising the steps

1. (a) preparing a first non-compressed part (a) containing active substance and having at least one cavity,
2. (b) preparing a second non-compressed part (b) containing active substance,
3. (c) connecting the two molded body parts by inserting the molded body part (b) into the cavity of the molded body part at least in part (a)

as well as a process for the preparation of detergent tablets, which by the steps

1. (a) preparing a first non-compressed part (a) containing active substance and having at least one cavity,
2. (b) inserting active substance into the cavity (s) of the molded body part (a) to form a shaped body part (b),
3. (c) fixing the molded body part (b) in the cavity of the molded body part (a).

wherein the method step (a) in each case comprises the sintering.

For non-compressed parts with one or more cavities, reference may be made to the above statements (see above). Preferred processes are characterized in that the active substance in step (b) is carried out by pouring in liquid to pasty media, by sprinkling in particulate media or by inserting preformed non-compressed molded body parts.

As already described in detail above, methods are preferred in which the fixation in step (c) takes place by coating the overall shaped body or the shaped body surfaces in which cavities are located.

Also, processes which are characterized in that the fixation in step (c) by curing, spraying with adhesion promoters, sintering, gelatinization or sticking of other molding constituents are preferred according to the invention.

In particular, these are steps that have already been described in detail above, which is why reference is made to the above statements.

Also preferred are processes which are either characterized in that process step (b) comprises sintering or characterized in that process step (b) comprises casting or in that process step (b) comprises solidifying solutions (" Gelatinizing ").

Last but not least, methods are also preferred in which process step (b) comprises the curing.

A special feature is possible if the non-compressed part (a) has one or more cavities, since then methods are possible in which the non-compressed part (b) is particulate.

These particles may then be e.g. be introduced into the cavity (s) and there fixed by means of a coating layer or by spraying with adhesion promoters in the manner described above.

The detergent tablets according to the invention can be packaged after production, wherein the use of certain packaging systems has proven particularly useful, since these packaging systems increase the storage stability of the ingredients on the one hand, but surprisingly also significantly improve the long-term adhesion of the tray filling. Another object of the present invention is therefore a combination of (a) inventive detergent tablets and a packaging system containing the detergent tablets or detergent tablets, wherein the packaging system has a moisture vapor transmission rate of from 0.1 g / m ² / day to less than 20 g / m ² / day when the packaging system is stored at 23 ° C and a relative equilibrium moisture content of 85%.

berechnen, wobei A die Fläche des zu testenden Materials in cm², x die Gewichtszunahme des Calciumchlorids in g und y die Expositionszeit in h bedeutet.The packaging system of the combination of detergent tablets and packaging system according to the invention has a moisture vapor transmission rate of 0.1 g / m ² / day to less than 20 g / m ² / day when the packaging system at 23 ° C and a relative Equilibrium moisture content of 85% is stored. The temperature and humidity conditions mentioned are the test conditions specified in DIN standard 53122, with minimum deviations permissible according to DIN 53122 (23 ± 1 ° C, 85 ± 2% relative humidity). The moisture vapor transmission rate of a given packaging system or material can be determined by other standard methods and is also, for example, in the ASTM standard E-96-53T (test for measuring water vapor transmission of material in sheet form) and TAPPI standard T464 m-45 ("Water Vapor Permeability of Sheet Materials at High Temperature Humidity"). The measuring principle of common methods is based on the water absorption of anhydrous calcium chloride, which is stored in a container in the appropriate atmosphere, the container is sealed at the top with the material to be tested. From the surface of the container, which is closed with the material to be tested (permeation surface), the increase in weight of the calcium chloride and the exposure time, the moisture vapor transmission rate decreases $$\mathit{FDDR}=\frac{24\cdot 10000}{A}\cdot \frac{x}{y}\left[G/m^2/24H\right]$$

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

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

For example, the relative equilibrium moisture content of 85% at 23 ° C can be precisely adjusted to +/- 2% RH in laboratory chambers with humidity control, depending on the device type. Even saturated solutions of certain salts form constant and well-defined relative humidities in closed systems at a given temperature, based on the phase equilibrium between partial pressure of the water, saturated solution and soil body.

The inventive combinations of detergent tablets and packaging system can of course in turn be packaged in secondary packaging, such as cardboard or trays, with no secondary requirements for the secondary packaging. The secondary packaging is therefore possible, but not necessary.

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

Depending on the embodiment of the invention, the packaging system of the combination according to the invention encloses one or more washing and cleaning agent tablets. It is inventively preferred either to make a shaped body such that it comprises an application unit of the detergent and cleaning agent, and to pack this shaped body individually, or to pack the number of moldings in a packaging unit, which in total comprises an application unit. With a target dosage of 80 g detergent and cleaning agent, it is thus possible according to the invention to produce a 80 g heavy detergent tablets and pack individually, but it is also possible according to the invention to pack two 40 g each heavy detergent tablets in a package to arrive at a combination according to the invention. Of course, this principle can be extended so that combinations according to the invention can also contain three, four, five or even more detergent tablets in one packaging unit. Of course, two or more moldings in a package may have different compositions. In this way, it is possible to spatially separate certain components, for example to avoid stability problems.

The packaging system of the combination according to the invention may consist of a wide variety of materials and take on any external forms. However, for economic reasons and for ease of processability, packaging systems are preferred in which the packaging material has a low weight, easy to work with and is inexpensive. In inventively preferred combinations, the packaging system consists of a bag or sack of single-layer or laminated paper and / or plastic film.

The detergent tablets may be unsorted, i. as a loose filling, be filled in a bag of the materials mentioned. However, for aesthetic reasons and for sorting the combinations in secondary packaging, it is preferable to fill the washing and cleaning agent tablets individually or in a plurality of different sizes into sacks or bags. For individual application units of the detergent tablets, which are located in a bag or bag, the term "flow pack" has become common in the art. Such "flow packs" can then - again preferably sorted - optionally be packaged in outer packaging, which emphasizes the compact form of the molded article.

The preferably used as packaging system bags or bags of single-layer or laminated paper or plastic film can be designed in a variety of ways, such as inflated bag without center seam or bags with center seam, which closed by heat (heat fusion), adhesives or adhesive tapes become. Single-layer bag or bag materials are the known papers, which may optionally be impregnated, as well as plastic films, which may optionally be coextruded. Plastic films that can be used in the context of the present invention as a packaging system are, for example, in Hans Domininghaus "The plastics and their properties", 3rd edition, VDI Verlag, Dusseldorf 1988, page 193 , stated. The figure 111 shown there also provides clues to the water vapor permeability of the materials mentioned.

In the context of the present invention particularly preferred combinations contain as packaging system a bag or bag of single-layer or laminated plastic film having a thickness of 10 to 200 .mu.m, preferably from 20 to 100 .mu.m and in particular from 25 to 50 microns.

Although it is possible to use wax-coated papers in the form of cardboard as a packaging system for the detergent tablets in addition to the foils or papers mentioned above, it is preferred for the present invention if the packaging system does not comprise cardboard boxes of wax-coated paper. In the context of the present invention, the term "packaging system always characterizes the primary packaging of the shaped bodies, ie the packaging which is in direct contact with the molded body surface on its inner side can be used.

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

The relative equilibrium moisture content of the washing and cleaning agent tablets can be determined by conventional methods, the following procedure being selected in the context of the present investigations: A water-impermeable 1-liter vessel with a lid which has a closable opening for the introduction of samples filled with a total of 300 g detergent tablets and held for 24 h at a constant 23 ° C to ensure a uniform temperature of the vessel and substance. The water vapor pressure in the space above the moldings can then be determined with a hygrometer (Hygrotest 6100, Testoterm Ltd., England). The water vapor pressure is now measured every 10 minutes until two consecutive values show no deviation (equilibrium humidity). The o.g. Hygrometer allows a direct display of the recorded values in% relative humidity.

Also preferred are embodiments of the combination according to the invention, in which the packaging system is reclosable. Also combinations, where the packaging system has a micro perforation can be realized according to the invention with preference.

Claims (55)

1. A washing agent shaped body or cleaning agent shaped body, comprising

   (a) a first uncompressed part which contains active substance,

   (b) a further uncompressed part which contains active substance,

   wherein the shaped body contains enzymes and the uncompressed part (a) was produced by sintering.
2. The washing agent shaped body or cleaning agent shaped body according to claim 1, characterized in that the second uncompressed part (b) does not completely encase the first uncompressed part (a).
3. The washing agent shaped body or cleaning agent shaped body according to one of the preceding claims, characterized in that said body contains a first uncompressed component (a), a second uncompressed component (b) and, in addition, further uncompressed components.
4. The washing agent shaped body or cleaning agent shaped body according to claim 3, characterized in that the first uncompressed component (a) comprises a plurality of cavities and each further uncompressed part is contained in a cavity at least in part.
5. The washing agent shaped body or cleaning agent shaped body according to one of the preceding claims, characterized in that the first uncompressed part (a) and the second uncompressed part (b) contain at least one different active substance.
6. The washing agent shaped body or cleaning agent shaped body according to one of the preceding claims, characterized in that the first uncompressed part (a) or the second uncompressed part (b) contains bleaching agent, whilst the other part contains bleach activators.
7. The washing agent shaped body and cleaning agent shaped body according to one of the preceding claims, characterized in that the first uncompressed part (a) or the second uncompressed part (b) contains bleaching agent, whilst the other part contains enzymes.
8. The washing agent shaped body and cleaning agent shaped body according to one of the preceding claims, characterized in that the first uncompressed part (a) or the second uncompressed part (b) contains bleaching agent, whilst the other part contains corrosion protection agent.
9. The washing agent shaped body and cleaning agent shaped body according to one of the preceding claims, characterized in that the first uncompressed part (a) or the second uncompressed part (b) contains bleaching agent, whilst the other part contains surfactants, preferably non-ionic surfactants, particularly preferably alkoxylated alcohols having 10 to 24 carbon atoms and 1 to 5 alkylene oxide units.
10. The washing agent shaped body and cleaning agent shaped body according to one of the preceding claims, characterized in that the first uncompressed part (a) and the second uncompressed part (b) contain the same active ingredient in different quantities.
11. The washing agent shaped body or cleaning agent shaped body according to one of the preceding claims, characterized in that at least one uncompressed part, preferably the uncompressed part (b), is encased by a coating layer.
12. The washing agent shaped body or cleaning agent shaped body according to claim 11, characterized in that the uncompressed part (b) is attached to or in the uncompressed part (a) by means of the coating layer.
13. The washing agent shaped body or cleaning agent shaped body according to one of claims 11 or 12, characterized in that the coating layer contains one or more substances from the group consisting of the fatty acids, fatty alcohols, diols, esters, ethers, carboxylic acids, dicarboxylic acids, polyvinyl acetate (PVA), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVAI), polyethylene glycol (PEG), polypropylene glycol (PPG) and mixtures thereof.
14. The washing agent shaped body or cleaning agent shaped body according to one of claims 11 to 13, characterized in that the second uncompressed part (b) is coated with a polymer which contains an amino group, preferably with a copolymer of basic monomers such as (dialkylamino) alkyl methacrylates with acrylic acid esters.
15. The washing agent shaped body or cleaning agent shaped body according to one of claims 11 to 13, characterized in that the second uncompressed part (b) is coated with an ampholytic polymer, preferably a copolymer of basic monomers such as (dialkylamino) alkyl methacrylates with substituted or non-substituted acrylic acids and/or (meth)acrylic acids.
16. The washing agent shaped body or cleaning agent shaped body according to one of claims 14 or 15, characterized in that the coated second uncompressed part (b) comprises a further coating which is preferably selected from polyvinyl acetate and/or polyvinyl alcohol and from the substances which melt at > 50 °C, preferably paraffins and/or polyethylene glycols.
17. The washing agent shaped body or cleaning agent shaped body according to one of the preceding claims, characterized in that at least the second uncompressed part (b) is encased by a material that is water-soluble at a pH value below the pH value of the preceding washing or cleaning operation.
18. A washing agent shaped body or cleaning agent shaped body according to one of the preceding claims, characterized in that the second uncompressed part (b) is coated with a material which protects the uncompressed part (b) at pH values greater than 11, preferably greater than 10 and in particular greater than 9, against dissolution in the earlier washing or cleaning operation.
19. The washing agent shaped body or cleaning agent shaped body according to claim 18, characterized in that the coating does not protect the second uncompressed part (b) against dissolution at pH values less than 6, preferably less than 7 and in particular less than 8.
20. The washing agent shaped body or cleaning agent shaped body according to one of the preceding claims, characterized in that the uncompressed part (b) was produced by sintering.
21. The washing agent shaped body or cleaning agent shaped body according to one of the preceding claims, characterized in that the uncompressed part (b) was produced by casting.
22. The washing agent shaped body or cleaning agent shaped body according to one of the preceding claims, characterized in that the uncompressed part (b) was produced by setting solutions ("gelatinating").
23. The washing agent shaped body or cleaning agent shaped body according to one of the preceding claims, characterized in that the uncompressed part (b) was produced by curing.
24. The washing agent shaped body or cleaning agent shaped body according to one of the preceding claims, characterized in that the uncompressed part (b) is particulate.
25. The washing agent shaped body or cleaning agent shaped body according to one of the preceding claims, characterized in that the uncompressed part (a) contains builders in quantities of 1 to 100 wt.%, preferably of 5 to 95 wt.%, particularly preferably of 10 to 90 wt.% and in particular of 20 to 85 wt.%, based on the weight of the uncompressed part (a) in each case.
26. The washing agent shaped body or cleaning agent shaped body according to one of the preceding claims, characterized in that the uncompressed part (a) contains phosphate(s), preferably alkali metal phosphate(s), particularly preferably pentasodium phosphate or pentapotassium phosphate (sodium or potassium tripolyphosphate), in quantities of 20 to 80 wt.%, preferably of 25 to 75 wt.%, in particular of 30 to 70 wt.%, based on the weight of the uncompressed part (a) in each case.
27. The washing agent shaped body or cleaning agent shaped body according to one of the preceding claims, characterized in that the uncompressed part (a) contains carbonate(s) and/or hydrogen carbonate(s), preferably alkali carbonates, particularly preferably sodium carbonate, in quantities of 5 to 50 wt.%, preferably of 7.5 to 40 wt.% and in particular of 10 to 30 wt.%, based on the weight of the uncompressed part (a) in each case.
28. The washing agent shaped body or cleaning agent shaped body according to one of the preceding claims, characterized in that the uncompressed part (a) contains silicate(s), preferably alkali silicates, particularly preferably crystalline or amorphous alkali disilicate, in quantities of 10 to 60 wt.%, preferably of 15 to 50 wt.% and in particular of 20 to 40 wt.%, based on the weight of the uncompressed part (a) in each case.
29. The washing agent shaped body or cleaning agent shaped body according to one of the preceding claims, characterized in that the uncompressed part (a) has a total surfactant content of less than 5 wt.%, preferably less than 4 wt.%, particularly preferably less than 3 wt.% and in particular less than 2 wt.%, based on the weight of the uncompressed part (a) in each case.
30. The washing agent shaped body or cleaning agent shaped body according to one of the preceding claims, characterized in that the uncompressed part (a) contains bleaching agent from the group consisting of oxygen bleaching agent or halogen bleaching agent, in particular chlorine bleaching agent, particularly preferably sodium perborate and sodium percarbonate, in quantities of 2 to 25 wt.%, preferably of 5 to 20 wt.% and in particular of 10 to 15 wt.%, based on the weight of the uncompressed part (a) in each case.
31. The washing agent shaped body or cleaning agent shaped body according to one of the preceding claims, characterized in that the uncompressed part (a) contains bleach activators from the groups consisting of polyacylated alkylene diamines, in particular tetraacetylethylenediamine (TAED), N-acyl amides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or iso-nonanoyl oxybenzene sulfonate (n- or iso-NOBS) and N-methyl morpholinium acetonitrile methylsulfate (MMA), in quantities of 0.25 to 15 wt.%, preferably of 0.5 to 10 wt.% and in particular of 1 to 5 wt.%, based on the weight of the uncompressed part (a) in each case.
32. The washing agent shaped body or cleaning agent shaped body according to one of the preceding claims, characterized in that the uncompressed part (a) contains silver-protecting agent from the group consisting of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkyl aminotriazoles and transition metal salts or transition metal complexes, particularly preferably benzotriazole and/or alkyl aminotriazole, in quantities of 0.01 to 5 wt.%, preferably of 0.05 to 4 wt.% and in particular of 0.5 to 3 wt.%, based on the weight of the uncompressed part (a) in each case.
33. The washing agent shaped body or cleaning agent shaped body according to one of the preceding claims, characterized in that the uncompressed part (a) in addition contains one or more substances from the groups consisting of enzymes, corrosion inhibitors, surface inhibitors, cobuilders, dyes or fragrances in total quantities of 6 to 30 wt.%, preferably of 7.5 to 25 wt.% and in particular of 10 to 20 wt.%, based on the weight of the uncompressed part (a) in each case.
34. The washing agent shaped body or cleaning agent shaped body according to one of the preceding claims, characterized in that the second uncompressed part (b) is a coated, preferably multilayer-coated shaped body, which is cemented in place in the cavity in the uncompressed part (a).
35. A method for producing washing agent shaped bodies or cleaning agent shaped bodies, comprising the steps of:

    (a) producing a first uncompressed part (a) which contains active substance,

    (b) producing a second uncompressed part (b) which contains active substance,

    (c) connecting the two shaped body parts by attaching to or interlocking with the shaped body,

    characterized in that the method step (a) comprises sintering.
36. The method according to claim 35, characterized in that the adhesion between the shaped body parts (a) and (b) is supported by adhesion promoters.
37. The method according to claim 36, characterized in that, in step (c), melts of one or more substances having a melting range of 40°C to 75°C are applied as adhesion promoters to one or more surfaces of the shaped body part (a), after which (the) shaped body part(s) (b) is/are adhered on.
38. The method according to claim 36, characterized in that, in step (c), one or more substances from the group consisting of paraffin waxes, preferably having a melting range of 50°C to 55°C, and/or consisting of polyethylene glycols (PEG) and/or polypropylene glycols (PPG) and/or consisting of natural waxes and/or fatty alcohols, are applied as adhesion promoters.
39. The method according to claim 36, characterized in that, in step (c), concentrated salt solutions are applied as adhesion promoters to one or more surfaces of the shaped body part (a).
40. The method according to claim 36, characterized in that, in step (c), solutions or suspensions of water-soluble or water-dispersible polymers, preferably polycarboxylates, are applied as adhesion promoters to one or more surfaces of the shaped body part (a).
41. A method for producing washing agent shaped bodies or cleaning agent shaped bodies, comprising the steps of:

    (a) producing a first uncompressed part (a) which contains active substance and has at least one cavity,

    (b) producing a second uncompressed part (b) which contains active substance,

    (c) connecting the two shaped body parts by inserting the shaped body (b) into the cavity in the shaped body (a) at least in part,

    characterized in that the method step (a) comprises sintering.
42. A method for producing washing agent shaped bodies or cleaning agent shaped bodies, comprising the steps of:

    (a) producing a first uncompressed part (a) which contains active substance and has at least one cavity,

    (b) inserting active substance into the cavity or cavities in the shaped body part (a) to form a shaped body part (b),

    (c) fixing the shaped body part (b) in the cavity in the shaped body part (a),

    characterized in that method step (a) comprises sintering.
43. The method according to claim 42, characterized in that the active substance in step (b) results by pouring liquid to pasty media, by spreading particulate media or by inserting previously produced, uncompressed shaped body parts.
44. The method according to one of claims 42 or 43, characterized in that the fixing in step (c) takes place by coating the entire shaped body or the shaped body surfaces in which there are cavities.
45. The method according to one of claims 42 or 43, characterized in that the fixing in step (c) takes place by curing, spraying with adhesion promoters, sintering, gelatinating or adhering on further shaped body components.
46. The method according to one of the preceding claims, characterized in that method step (b) comprises sintering.
47. The method according to one of claims 35 to 45, characterized in that method step (b) comprises casting.
48. The method according to one of claims 35 to 45, characterized in that method step (b) comprises setting solutions ("gelatinating").
49. The method according to one of claims 35 to 45, characterized in that method step (b) comprises curing.
50. The method according to one of claims 35 to 49, characterized in that the uncompressed part (b) is particulate.
51. A combination of a washing agent shaped body or cleaning agent shaped body according to one of claims 1 to 34 and a packaging system containing the washing agent shaped body or cleaning agent shaped body, characterized in that the packaging system has a moisture vapor transmission rate of 0.1 g/m²/day to less than 20 g/m²/day, if the packaging system is stored at 23°C and an equilibrium relative humidity of 85%.
52. The combination according to claim 51, characterized in that the packaging system has a moisture vapor transmission rate of 0.5 g/m²/day to less than 15 g/m²/day.
53. The combination according to one of claims 51 or 52, characterized in that the packaging system consists of a bag or pouch made of single-layer or laminated paper and/or plastics film.
54. The combination according to claim 53, characterized in that the packaging system consists of a bag or pouch made of single-layer or laminated plastics film having a thickness of 10 to 200 µm, preferably of 20 to 100 µm and in particular of 25 to 50 µm.
55. The combination according to one of claims 51 to 54, characterized in that the packaging system does not comprise cardboard made of wax-coated paper.