DE10061421A1 - Process for the production of glued molded articles - Google Patents

Abstract

The present invention describes a method for producing multiphase detergent tablets, in which, in a first step, base tablets are produced which have at least one cavity, into which adhesion promoters are / are metered in in a second step before the cavity ( en) is filled with (a) core (s), solutions, dispersions, emulsions or melts which have a viscosity below 3000 mPas being used as adhesion promoters in the second step.

Description

The present invention relates to a method for producing multiphase molded articles per, with the individual phases having a different composition can. The method presented is particularly suitable for the production of washing and detergent tablets such as bleach tablets, stain remover tablets, detergent tablets for machine dishwashing, detergents Abletten or water softening tablets.

From German patent applications DE 199 09 271.0 and DE 199 32 568.5 is a Process for the production of multi-phase detergent tablets knows, in which a particulate premix is pressed into moldings, optional one or more adhesion promoters are applied to one or more surfaces of the moldings gene, after which further active substance in solid, highly viscous or plastic form is applied to the moldings. These writings serve as adhesion promoters for example substances from the groups of polyethylene glycols (PEG) and / or poly propylene glycols (PPG), the concentrated salt solutions and the solutions or suspensions Sions of water-soluble or -dispersible polymers disclosed.

Certain embodiments of that described in the aforementioned publications NEN process provide that the shaped body produced by tableting a Ka vity which, for example, a hole through the molded body, or represents a hollow. Adhesion promoter can be filled into this cavity before a separate dosing unit (e.g. a smaller tablet) is placed in the cavity  and is stuck there. Alternatively, the bonding agent can also be applied to the cavity individual dosing unit to be inserted.

While the above-mentioned published documents generally the gluing of shaped bodies reveal to each other certain problems in making "Mul dentabletten "(i.e. tablets with cavities or through holes) not mentioned. So it is necessary in large series production that the adhesion promoter quickly and have it dosed exactly into the cavity. For this purpose, those used as adhesion promoters Substances, for example, are not stringy and must be long enough Maintain adherence in order to firmly bind the "core" used later into the cavity.

The object of the present invention was that from the German Pa Tent applications DE 199 09 271.0 and DE 199 32 568.5 known processes for the Her Position of filled tray tablets to adapt, the procedure to be provided variant should be feasible as a high-speed process.

It has now been found that certain adhesives for high speed ver glue particularly suitable.

The present invention relates to a method in a first embodiment for the production of multi-phase detergent tablets, in which in one first step, base moldings are produced which have at least one cavity have, into which adhesion promoter is / are metered in a second step before in egg In a third step, the cavity (s) are filled with (one) core (s) middle, in a second step, solutions, dispersions, emulsions or melts are used which have a viscosity below 3000 mPas.

In the context of the present invention, the viscosity values relate to viscose measurements at a sample temperature which corresponds to the processing temperature of the Adhesion promoter (s) corresponds (see below), with a Carrimed-plate-plate rheometer, at a shear force of 50 N per square meter, a plate diameter of 5 cm and a measuring system gap of 250 µm, the value reading after 10 seconds of measurement was.  

Preferred methods according to the invention are characterized in that the Adhesion promoter during processing a viscosity below 2500 mPas, preferably two se below 2000 mPas and in particular below 1000 mPas.

The processing temperature of the adhesion promoter (s) depends on the material Nature of the adhesion promoter used and the desired time within which the detention intermediary should develop its liability. Here temperatures are of room temperature temperature (which can be up to 10 to 15 ° C in the winter months) up to high Temperatures above the boiling point of water can be achieved. At the preferred methods of the present invention, the adhesion promoter at a tem temperature between 10 and 130 ° C, preferably between 20 and 110 ° C and in particular metered into the cavity between 20 and 90 ° C.

The adhesion promoter (s) can be metered into the cavity as a melt, what usually temperatures above 30 ° C, preferably above 40 ° C and may require above 50 ° C in particular.

In the context of the present invention, particularly preferred meltable adhesion promoters are substances from the group of polyethylene and polypropylene glycols. Also Mixtures of substances containing these substances are preferred. Method according to the invention ren, in which one or more substances from the groups of Polyethylene glycols (PEG) and / or polypropylene glycols (PPG) are used accordingly preferred embodiments of the present invention.

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

H- (O-CH ₂ -CH ₂ ) _n -OH (IIa)

are sufficient, where n can have values between 1 (ethylene glycol) and over 100,000. Decisive in evaluating whether a polyethylene glycol can be used according to the invention is the viscosity of the PEG at the processing temperature. Because in preferred Processes above 20 ° C and below 90 ° C are the polyethylene lenglycols of the above formula, in which n values between approx. 15 to about 150. The higher molecular weight polyethylene glycols are polymolecular,  d. H. they consist of groups of macromolecules with different moles measure. There are various nomenclatures for polyethylene glycols that lead to confusion can lead. The specification of the average relative is technically common Molecular weight following the indication "PEG", so that "PEG 200" is a polyethylene glycol characterized with a relative molar mass of approx. 190 to approx. 210. According to this noun within the scope of the present invention are the technically customary polyes ethylene glycols PEG 1550, PEG 3000, PEG 4000 and PEG 6000 are preferably used.

A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and a number follows the hyphen directly, which corresponds to the number n in the above formula. According to this nomenclature (known as INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997) according to the invention, for example, PEG-32, PEG-40, PEG-55, PEG 60, PEG-75 and PEG-100 can preferably be used according to the invention.

Polyethylene glycols are commercially available, for example, under the trade names Carbowax® PEG 540 (Union Carbide), Emkapol® 2000 (ICI Americas), Lipoxol® 2000 MED (HÜLS America), Polyglycol® E-1550 (Dow Chemical), Lutrol® E2000 (BASF) and the corresponding trade names with higher numbers.

Polypropylene glycols (abbreviation PPG) which can be used according to the invention are polymers of propylene glycol which have the general formula IIb

are sufficient, where n values can be between 1 (propylene glycol) and approx. 1000. similarity Lich, as with the PEG described above, it comes to the assessment whether a Po lypropylene glycol can be used according to the invention, on the viscosity of the PPG when ver working temperature. Within the scope of the present invention, the technically ge Common polypropylene glycols PPG 1550, PPG 3000, PPG 4000 and PPG 6000 be preferably applicable.  

Because temperature control can be critical when dosing melts, it is preferably, solutions or dispersions of adhesion promoters which are solid at room temperature or Emulsions of adhesion promoters liquid at room temperature according to the invention use. In this case, the emulsions have later ones because of the possible occurrence Problems with core liability are only of minor importance. Also the Because of the settling problem during processing, dispersions are compared to the particularly preferred solutions less suitable.

Particularly preferred adhesion promoters are solutions of certain nonionic substances. Here Methods according to the invention are preferred in which solutions of polyhydric alcohols and / or sugars solid at room temperature are used, preference is given to solutions which, based on the solution, are at least 30% by weight, preferably at least 40% by weight and in particular at least 50% by weight of solid contain substance (s).

Polyhydric alcohols in the context of the present invention are compounds which have at least two hydroxyl groups. The state of matter of these compounds at room temperature (20 ° C) is solid. Particularly suitable polyhydric alcohols are there for example trimethylolpropane, pentaerythritol and the "sugar alcohols", d. H. the polyhydroxy formed from monosaccharides by reduction of the carbonyl group Links. One differentiates between these according to the number of those contained in the molecule Hydroxy groups tetrite, pentite, hexite, etc. In the context of the present invention Particularly suitable sugar alcohols are e.g. B. Threit u. Erythritol, adonite (ribitol), arabitol (formerly: Lyxit) and Xylit, Dulcit (Galactit), Mannit and Sorbit (Glucit), the latter also is called sorbitol.

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

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

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

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

The main disaccharides are sucrose (cane sugar, sucrose), trehalose, lactose (Milk sugar), lactulose, maltose (malt sugar), cellobiose (cellulose breakdown product), Gentobiose, Melibiosis, Turanose and others.

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

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

In the context of the present invention, saccharides from the Group glucose, fructose, sucrose, cellubiosis, maltose, lactose, lactulose, ribose and their mixtures used. Washing and cleaning are particularly preferred medium shaped bodies containing glucose and / or sucrose.

A preferred adhesion promoter that can be used in the form of a solution is sorbitol. Here Methods according to the invention are preferred in which solutions of Sorbitol are used, which, based on the solution, are at least 50% by weight preferably at least 60% by weight and in particular at least 70% by weight of sorbitol contain.

Another preferred class of substances that can be used as an adhesion promoter in the form of their solution are water-soluble polyurethanes. Among them, certain representatives are particularly preferred. Processes according to the invention are preferred here in which solutions or suspensions of polyurethanes composed of diisocyanates (I) and diols (II) are used as adhesion promoters.

O = C = NR ¹ -N = C = O (I),

HOR ² -OH (II),

are used, the diols being selected at least in part from polyethylene glycols (IIa) and / or polypropylene glycols (IIb)

H- (O-CH ₂ -CH ₂ ) _n -OH (IIa),

and R ¹ and R ² independently of one another represent a substituted or unsubstituted, straight-chain or branched alkyl, aryl or alkylaryl radical having 1 to 24 carbon atoms and n each number from 5 to 2000.

These preferred polymers are described in more detail below.

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

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

The polyurethanes used as a solution or suspension or dispersion are there obtained from reaction mixtures in which at least one diisocyanate of the formula (I) and at least one polyethylene glycol of the formula (IIa) and / or at least one Polypro pylene glycol of formula (IIb) are included.

The reaction mixtures can additionally contain further polyisocyanates. Also a Content of the reaction mixtures - and thus the polyurethanes - in other diols, trio len, diamines, triamines, polyetherols and polyesterols is possible. The Compounds with more than 2 active hydrogen atoms usually only in small Amounts in combination with a large excess of 2 active compounds Hydrogen atoms used.

With the addition of other diols, etc., certain proportions to the fiction compulsory polyethylene and / or polypropylene glycol present in the polyurethane col units to be observed. Here are methods in which at least 10% by weight is preferred  at least 25 wt .-%, particularly preferably at least 50 wt .-% ins particularly selected at least 75% by weight of the diols reacted in the polyurethane are made of polyethylene glycols (IIa) and / or polypropylene glycols (IIb).

The solution or dispersion or suspension of the adhesion promoter can besides the special len polyurethanes other ingredients such as ingredients of washing and cleaning agents agents, especially dyes and / or fragrances.

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

The polyurethanes further contain diols of the formula (II) as a monomer unit, these diols at least partly originating from the group of the polyethylene glycols (IIa) and / or the polypropylene glycols (IIb). Polyethylene glycols are polymers of ethylene glycol which have the general formula (IIa)

H- (O-CH ₂ -CH ₂ ) -OH (IIa)

are sufficient (see above).

Polypropylene glycols (abbreviation PPG) are polymers of propylene glycol which have the general formula (IIb)

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

Both in the case of compounds of the formula (IIa) and in the case of compounds of the formula mel (IIb) are such representatives preferred monomer units in which the number n for a number between 6 and 1500, preferably between 7 and 1200, especially before moves between 8 and 1000, more preferably between 9 and 500 and in particular between between 10 and 200. For certain applications, polyethylene and polypro pylene glycols of the formulas (IIa) and / or (IIb) may be preferred, in which n is a number between 15 and 150, preferably between 20 and 100, particularly preferably between 25 and 75 and in particular between 30 and 60.

Examples of optional further in the reaction mixtures for the production of the polyurethane ne contained compounds are ethylene glycol, 1,2- and 1,3-propylene glycol, butylene glycol kole, ethylenediamine, propylenediamine, 1,4-diaminobutane, hexamethylenediamine and α, ω- Diamines based on long-chain alkanes or polyalkylene oxides. invention Detergent tablets in which the polyurethanes in the coating tion additional diamines, preferably hexamethylene diamine and / or hydroxycar bonic acids, preferably dimethylolpropionic acid, are preferred.

In summary, these statements are particularly preferred methods in the context of the present invention, characterized in that solutions or suspensions of polyurethanes from diisocyanates (I) and diols (II) are used

O = C = NR ¹ -N = C = O (I),

HOR ² -OH (II),

where R ¹ for a methylene-ethylene-propylene, butylene, pentylene group or for - (CH ₂ ) ₆ - or for 2,4- or 2,6-C ₆ H ₃ -CH ₃ , or for C ₆ H ₄ -CH ₂ -C ₆ H ₄ or for an isopho ronrest (3,5,5-trimethyl-2-cyclohexenone) and R ^{2 is} selected from -CH ₂ -CH ₂ - (O- CH ₂ -CH ₂ ) _n - or -CH ₂ -CH ₂ - (O-CH (CH ₃ ) -CH ₂ ) _n - with n = 4 to 1999.

Depending on which reactants are reacted with each other to form the polyurethanes, the result is polymers with different structural units. Processes according to the invention are preferred here in which solutions or suspensions of polyurethane are used which have structural units of the formula (III)

- [OC (O) -NH-R ¹ -NH-C (O) -OR ² ] _k - (III),

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

Here, the diisocyanates described as preferred can be reacted with all the diols described as preferred to give polyurethanes, so that in preferred methods according to the invention, polyurethanes are used as adhesion promoters which have one or more of the structural units (IIIa) to (IIIh):

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

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

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

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

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

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

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

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

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

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

In preferred embodiments of the present invention, the polyurethanes have molar masses from 5000 to 150,000 gmol ^-1 , preferably from 10,000 to 100,000 gmol ^-1 and in particular from 20,000 to 50,000 gmol ^-1 . Corresponding methods are preferred according to the invention.

In the method according to the invention, in the first step using conventional press technology single-phase or multi-phase molded articles which have a cavity, provided with adhesion promoter in the subsequent process steps and with a Core is filled.

This first step of the method according to the invention is briefly described below purifies.

In the first, a particulate premix, which contains ingredients of washing and cleaning agents, in a so-called The die is compacted between two punches to form a solid compact. This process, which is briefly referred to below as tableting, is divided into four sections: Dosage, compression (elastic deformation), plastic deformation and ejection.

First, the premix is introduced into the die, the filling quantity and thus the weight and shape of the resulting molded body through the position of the lower one Stamp and the shape of the press tool can be determined. The constant dose tion even at high molding throughputs is preferably a volumetric Dosage of the premix reached. In the further course of tabletting, the  Upper stamp the premix and continues to lower towards the lower stamp. With this compression, the particles of the premix are pressed closer together, the void volume within the filling between the punches being continuous decreases. From a certain position of the upper stamp (and thus from a be correct pressure on the premix) begins the plastic deformation, at which the parti flow together and the molded body is formed. Depending on the physi Kalische properties of the premix also becomes part of the premix particles crushed and sintering of the premix occurs at even higher pressures. With increasing pressing speed, i.e. high throughputs, the phase of elastic deformation is continuously shortened, so that the resulting shaped body more or may have smaller cavities. The final step of tableting is the finished molded body is pressed out of the die by the lower punch and transported away by subsequent transport devices. At this point is single Lich the weight of the molded body finally determined, since the compacts due to physi calic processes (stretching, crystallographic effects, cooling etc.) their shape and can still change size.

Tableting takes place in commercially available tablet presses, which are basically or double stamps can be equipped. In the latter case, not only Upper stamp used to build up pressure, the lower stamp also moves during of the pressing process towards the upper punch, while the upper punch presses down. Eccentric tablet presses are preferably used for small production quantities det, in which the stamp or stamps are attached to an eccentric, which in turn is mounted on an axis with a certain rotational speed. The movement this ram is comparable to the operation of a conventional four-stroke engine. The pressing can be done with an upper and lower stamp, but it can also several stamps can be attached to an eccentric disc, the number of Die holes are expanded accordingly. The throughputs of eccentric presses especially Depending on the type, they range from a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs, rotary tablet presses are selected, in which on a so-called called matrix table a larger number of matrices is arranged in a circle. The The number of matrices varies between 6 and 55, depending on the model, with larger matrices also are commercially available. Each die on the die table is a top and bottom assigned to the stamp, the pressing pressure again being active only through the upper or lower stamp,  but can also be built using both stamps. The matrix table and the stamps move about a common vertical axis, whereby the stamps with the help of rail-like cam tracks during the circulation in the position for filling, compression, plastic deformation and ejection. On the places where a particularly serious raising or lowering of the stem pel is required (filling, compacting, ejecting), these cam tracks are followed by additional low-pressure pieces, low-tension rails and lifting tracks supported. The The die is filled via a rigidly arranged feed device, the so-called called filling shoe, which is connected to a reservoir for the premix. The Press pressure on the premix is indivi over the press paths for upper and lower punches Duell adjustable, the pressure build-up by rolling the punch shaft heads happens on adjustable pressure rollers.

Rotary presses can also be equipped with two filling shoes to increase the throughput are seen, with only a semicircle to produce a tablet must become. Several are used to produce two-layer and multi-layer moldings Filling shoes arranged one behind the other without the slightly pressed first layer in front the further filling is ejected. Appropriate litigation is based on this Way to produce coated and dot tablets that have an onion-like on have construction, whereby in the case of the point tablets the top of the core or the core layers is not covered and therefore remains visible. Also rotary tablet presses can be equipped with single or multiple tools so that, for example, an outer Circle with 50 and an inner circle with 35 holes simultaneously for pressing be used. The throughputs of modern rotary tablet presses are over one Million moldings per hour.

Ta suitable for the first process step in the context of the present invention Blotting machines are available, for example, from the Apparatebau Holzwarth company GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen GmbH, Berlin, Mapag Maschinenbau AG, Bem (CH) and Courtoy N.V., Halle (BE / LU). For example, the Hydraulic double printing press HPF 630 from LAEIS, D.

The moldings can ge in a predetermined spatial shape and a predetermined size be manufactured. Practically all sensibly manageable designs come as a spatial form  considered, for example, the training as a board, the bars or bars shape, cubes, cuboids and corresponding room elements with flat side surfaces as well in particular cylindrical configurations with a circular or oval cross cut. This last embodiment covers the presentation form from the tablet to to compact cylinder pieces with a ratio of height to diameter above 1.

The spatial shape of another embodiment of the shaped body is in its dimensions the induction chamber of commercial household washing machines adapted so that the moldings can be dosed directly into the induction chamber without a dosing aid, where it dissolves during the induction process. Should cleaning according to the invention medium tablets for machine dishwashing, one is recommended rectangular base, in which the height of the molded body is smaller than the smaller one Side of the rectangle. Rounded corners are preferred with this offer.

It is also possible, however, that the various components do not become one Chen tablet are pressed, but that molded bodies are obtained, the several Have layers, that is, at least two layers. It is also possible that these different layers have different dissolving speeds. here This can result in advantageous performance properties of the molded articles ren. If, for example, components are contained in the moldings that change affect negatively, so it is possible to have a component in the faster integrate soluble layer and the other component into a slower soluble Incorporate layer so that the first component has already reacted when the second goes into solution. The layer structure of the shaped bodies can be both stack-like take place, a dissolving process of the inner layer (s) on the edges of the mold body already occurs when the outer layers have not yet completely dissolved , but it can also completely encase the inner layer (s) by the each layer (s) lying further out can be reached, which leads to a prevention the early dissolution of components of the inner layer (s).

After the pressing, the base moldings have a high stability. The Bruchfe strength cylindrical shaped body can be detected via the measured variable of the diametrical fracture stress. This can be determined according to

The premix to be pressed can usually all be in washing and cleaning agents Contain contained ingredients, the composition depending varies from the intended use of the later molded body. So contain detergent remove higher amounts of surfactants than detergent tablets for mechanical Dishwashing, while bleach tablets and water softening tablets are more common be formulated without surfactants. The amount and type of builders used, Bleach, etc. may vary depending on the intended use. Independently most detergent tablets contain their intended use one or more substances from the group of builders. In the basic moldings can NEN as builders all Ge usually used in washing and cleaning agents builders are included, in particular thus zeolites, silicates, carbonates, organic co builder and also the phosphates.

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

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed and have secondary washing properties. The dissolution delay compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / sealing or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Particularly preferred are compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates.

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

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

can be described. The zeolite can be used both as a builder in a granu laren compound used, as well as a kind of "powdering" of the entire ver pressing mixture are used, usually both ways to Incorpo ration of the zeolite can be used in the premix. Suitable zeolites have one average particle size of less than 10 µm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight bound water.

It goes without saying that the generally known phosphates are also used as builders Substances possible, provided that such use is not ver should be avoided. The sodium salts of orthophospha are particularly suitable te, the pyrophosphates and especially the tripolyphosphates.

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

Usable organic builders are, for example, those in the form of their sodium salts of polycarboxylic acids, such polycarboxylic acids being among polycarboxylic acids be understood that carry more than one acid function. For example, these are Citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, malein acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, as well as Mi created from these. Preferred salts are the salts of polycarboxylic acids such as Citro Nenoic acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and Mi created from these.

The acids themselves can also be used. The acids have besides theirs Builder effect typically also the property of an acidifying component and thus also serve to set a lower and milder pH value of washing or detergents. In particular, citric acid, succinic acid and glutar are used here acid, adipic acid, gluconic acid and any mixtures of these.

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

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

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

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As a special copolymers of acrylic acid with maleic acid, 50 contain up to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative Molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

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

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

Biodegradable polymers of more than two are also particularly preferred various monomer units, for example those which are salts of the monomers Acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or the as monomeric salts of acrylic acid and 2 alkylallylsulfonic acid as well as sugar derivatives contain.

Further preferred copolymers are those which preferably contain acrolein as monomers and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Likewise, further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors. Po are particularly preferred lyaspartic acids or their salts and derivatives, in addition to cobuilder properties also have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which are obtained by converting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 Hy have droxyl groups, can be obtained. Preferred polyacetals are made from Dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.  

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be. The hydrolysis can be carried out according to conventional methods, for example acid or enzyme catalyzed processes are carried out. It is preferably hydrolyz Seproducts with average molecular weights in the range of 400 to 500000 g / mol. There is one Polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular preferred from 2 to 30, DE being a common measure of the reducing we kung a polysaccharide compared to dextrose, which has a DE of 100, is. Both maltodextrins with a DE between 3 and 20 and dry glu can be used cosesirupe with a DE between 20 and 37 as well as so-called yellow dextrins and White dextrins with higher molar masses in the range from 2000 to 30000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

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

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

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a cobuilder. It is preferably used as the sodium salt sets, the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9).  

Preferred aminoalkane phosphonates are ethylenediaminetetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of neutral reactions Sodium salts, e.g. B. as the hexasodium salt of EDTMP or as hepta- and octa- Sodium salt of the OTPMP. As a builder, the class becomes the phospho nate prefers HEDP. The aminoalkanephosphonates also have an embossed heavy metal binding capacity. Accordingly, it can, especially if the agents also contain bleach, preferably aminoalkane phosphonates, in particular DTPMP to use, or to use mixtures of the phosphonates mentioned the.

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

In base moldings for machine dishwashing produced according to the invention Water-soluble builders are preferred because they work on dishes and hard surfaces in the world Usually less tend to form insoluble residues. Usual builders working in machine dishwashing tablets according to the invention between 10 and 90% by weight % based on the premix to be pressed may be present molecular polycarboxylic acids and their salts, the homopolymers and copolymers Polycarboxylic acids and their salts, the carbonates, phosphates and silicates. Preferred who for the production of moldings for machine dishwashing trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicar bonate and / or gluconates and / or silicate builders from the class of disilicates and / or metasilicates used. A builder system is particularly preferred a mixture of tripolyphosphate and sodium carbonate. Also particularly preferred is a builder system that is a mixture of tripolyphosphate and sodium carbonate Contains sodium disilicate.

In the context of the present invention, process variants are preferred in which the particulate premix builder compressed into trough tablets in the first step Amounts from 20 to 80% by weight, preferably from 25 to 75% by weight and in particular from 30 to 70% by weight, based in each case on the premix.

In addition to the builders described above, the premix can also be used mentioned contain detergent substances, especially for detergent tablets  are important ingredients. Depending on the molded body to be produced, the answer is: questions, whether and if so which surfactants are used, different answers possible. Moldings for washing textiles can usually be found under various surfactants from the groups of anionic, nonionic, cationic and contain amphoteric surfactants, while molded articles for machine dishes rinse preferably contain only low-foaming nonionic surfactants and what Serum softening tablets or bleach tablets are free of tensides. The specialist are involved in the incorporation of the surfactants into the premix to be pressed with regard to the There are no limits to the freedom of formulation.

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

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

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

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

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

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

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

If detergent tablets are produced within the scope of the present invention, that is it is preferred that this be 5 to 50% by weight, preferably 7.5 to 40% by weight special 10 to 20 wt .-% anionic surfactant (s), each based on the molded body important, included.

When selecting the anionic surfactants that are used in the washing and Detergent tablets are used, the freedom of formulation does not stand in the way. Preferred detergent tablets however, have a soap content of 0.2 wt .-%, based on the total Ge weight of the molded body. Anionic surfactants to be used with preference the alkylbenzenesulfonates and fatty alcohol sulfates, preferred detergents molded bodies 2 to 20% by weight, preferably 2.5 to 15% by weight and in particular 5 to 10% by weight Fatty alcohol sulfate (s), each based on the weight of the molded body

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol residue is linear or preferably in the 2-position May be methyl branched or may contain linear and methyl branched radicals in the mixture, as are usually present in oxoalko radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 - alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _{12- 14} alcohol with 3 EO and _C12-18 alcohol containing 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these non-ionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Alkypolyglycosides that can be used satisfy the general formula RO (G) _z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol which stands for a glycosyl unit with 5 or 6 carbon atoms, preferably for glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 170 and 2.0 and in particular between 1.1 and 1.4.

Linear alkyl polyglucosides, ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.

The base moldings produced according to the invention can preferably alkyl polyglycosides contain, with APG contents of the shaped bodies exceeding 0.2% by weight, based on the entire molded body, are preferred. Particularly preferred washing and cleaning molded tablets contain APG in amounts of 0.2 to 10 wt .-%, preferably 0.2 to 5% by weight and in particular from 0.5 to 3% by weight.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N- dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkano lamides can be suitable. The amount of these nonionic surfactants is preferred not more than that of the ethoxylated fatty alcohols, especially not more than that Half of it.

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

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

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

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

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

In principle, all surfactants can also be used as surfactants in the production of moldings for automatic dishwashing. Preferred for this application, however, are the nonionic surfactants described above and above all the low-foaming nonionic surfactants. The alkoxylated alcohols are particularly preferred, especially the ethoxylated and / or propoxylated alcohols. Since the person skilled in the art generally understands by alkoxylated alcohols the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the sense of the present invention, the longer-chain alcohols (C ₁₀ to C ₁₈ , preferably between C ₁₂ and C ₁₆ , such as C ₁₁ -, C ₁₂ -, C ₁₃ -, C ₁₄ -, C ₁₅ -, C ₁₆ -, C ₁₇ - and C ₁₈ -alcohols). As a rule, n moles of ethylene oxide and one mole of alcohol form a complex mixture of addition products of different degrees of ethoxylation, depending on the reaction conditions. A further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. If desired, final etherification with short-chain alkyl groups, such as preferably the butyl group, can also give the substance class of the “closed” alcohol ethoxy latates, which can also be used for the purposes of the invention. For the purposes of the present invention, very particularly preferred are highly ethoxylated fatty alcohols or their mixtures with end-capped fatty alcohol ethoxylates.

Will the inventive method for the production of detergent tablets for machine dishwashing used, it is preferred that in the first step pressed particulate premix surfactant (s), preferably nonionic (s) sid (e), in amounts of 0.5 to 10 wt .-%, preferably from 0.75 to 7.5 wt .-% and contains in particular from 1.0 to 5% by weight, based in each case on the premix.

Regardless of the intended use of the moldings to be produced, it can be advantageous if the pre-pressed in the first step of the method according to the invention has certain physical properties. In particular, inventions are hereby Processes according to the invention are preferred, which are characterized in that the step a) pressed pre-mixed particulate a bulk density above 600 g / l, before preferably above 700 g / l and in particular above 800 g / l.

The particle size distribution of the premix can also influence the properties have the basic molded body. Preferred methods are characterized in that the in the first step, particulate premix pressed a particle size distribution having less than 10 wt .-%, preferably less than 7.5 wt .-% and ins especially less than 5% by weight of the particles larger than 1600 µm or smaller than 200 µm are. The particle size distribution is preferably that compressed in step a) Premixed even more closely, so that particularly preferred processes are characterized thereby net are that the particulate premix pressed in step a) a particle size has an outer distribution in which more than 30% by weight, preferably more than 40% by weight  and in particular more than 50% by weight of the particles have a particle size between 600 and have 1000 µm.

As already described at the beginning, the first step can of course not only be single-phase moldings are produced, but also multi-phase or multi-layer Shaped bodies which are produced in a manner known per se by adding several different particulate premixes are pressed together. Is special Here, the production of two-layer moldings in step a) by two different che particulate premixes are pressed together, one of which is one or contains several bleaches and the other contains one or more enzymes. Selbstverständ It is not only possible to separate bleach and oxidation-sensitive substances zen (enzymes, colors and fragrances) can be realized in this way, but also the separation of bleach and bleach activator by two different particles shaped premixes are pressed together, one of which is one or more Bleach and the other contains one or more bleach activators.

The ingredients mentioned and other ingredients of detergents and cleaning agents such as disintegration aids, silver protection agents, optical brighteners, Color transfer inhibitors, corrosion inhibitors, pH adjusting agents, surfactants, enzymes, buttocks polymers, fluorescent agents, foam inhibitors, anti-redeposition agents, graying inhibitors Bitter and mixtures thereof can be contained in the premixes contained in the er most step are pressed in a conventional manner. These fabrics will be next described below.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdo decanedioic 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, the use of sodium percarbonate is preferred, irrespective of which other constituents are contained in the moldings. If cleaning or bleaching agents are produced for machine dishwashing, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as. B. dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimonic acid [peroxycapa Phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamido-peroxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxy dicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyacetic acid diperoxy acid, diperoxyacid diperoxyacid diperoxyacid diacid acid, diperoxyacetic acid diperoxyacid diperoxyacid diacid acid, diperoxyacetic acid diperoxyacid diacid acid, diperoxyacid diacid acid diperoxyacid diacid acid, diperoxyacetic acid diperoxyacid diacid acid, diperoxyacid diacid acid, diperoxyacid diacid acid, diperoxyacid diacid acid, diperoxyacetic acid diperoxyacid, phthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Chlorine or. Can also be used as bleaching agents in moldings for automatic dishwashing Bromine-releasing substances are used. Among the appropriate chlorine or bromine releasing materials come for example heterocyclic N-bromine and N- Chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with Cations such as potassium and sodium are considered. Hydantoin compounds such as 1,3-dichloro 5,5- dimethylhydanthoin are also suitable.

To be a better choice when washing or cleaning at temperatures of 60 ° C and below To achieve the greatest bleaching effect, bleach activators can be pressed into the pre-press be mixed in. As bleach activators, compounds that are under Perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 C- Atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbene result in zoic acid. Suitable substances are O- and / or N- Acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl carry groups. Multi-acylated alkylenediamines, in particular tetraa, are preferred cetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4- dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylgly koluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phe nolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso- NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyvalent  Alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5- dihydrofuran.

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

Premixes for detergent tablets include, in particular, enzymes from the classes of hydrolases such as proteases, esterases, lipases or lipolytic acting enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases help to remove stains such as protein, greasy or starchy stains. Oxidoreductases can also be used for bleaching be used. Bacterial strains or fungi such as are particularly well suited Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and those obtained from its genetically modified variants enzymatic agents. Proteases of the subtilisin type and esp special proteases obtained from Bacillus lentus. Are there Enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipoly enzymes or protease having a table action, lipase or enzymes having a lipolytic action, in particular, however, protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipoly Enzymes with a table effect are the well-known cutinases. Also peroxidases or oxidases have proven to be suitable in some cases. Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases.

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

Premixes for detergent tablets come in addition to those mentioned above Enzymes are also considered cellulases. Cellulases and other glycosyl hydrolas can be removed by removing pilling and microfibrils for color preservation and Contribute to increasing the softness of the textile. As cellulases are preferred Cellobiohydrolases, endoglucanases and glucosidases, also called cellobiases are used, or mixtures of these. Because there are different types of cellulase distinguish through their CMCase and Avicelase activities, through targeted Mi cellulases the desired activities can be set.

Shaped body according to the invention for machine cleaning dishes can be used to protect the dishes or the Korrosi machine onsinhibitoren contain, with silver protection in the field of machine dishes rinsing have a special meaning. The known substances can be used the state of the art. In general, silver protection agents in particular can be selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, the Alkylaminotriazoles and the transition metal salts or complexes are used. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. you often finds active chlorine-containing agents in detergent formulations Can significantly reduce corroding of the silver surface. In chlorine-free cleaners oxygen and nitrogenous organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydro quinone, gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds. Also salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. The transitions are preferred here metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the Cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or Manganese and manganese sulfate. Zinc compounds can also be used for prevention corrosion on the wash ware.

In addition, premixes for detergent tablets produced according to the invention can also contain components that make oil and fat washable from textiles posi influence (so-called soil repellents). This effect is particularly evident when a textile is soiled that has previously been used several times with an inventive Detergent containing this oil and fat-dissolving component has been washed. To  The preferred oil and fat dissolving components include, for example, nonionic Cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of Methoxyl groups from 15 to 30% by weight and hydroxypropoxyl groups from 1 to 15% by weight, each based on the nonionic cellulose ether, as well as those from the prior art known polymers of phthalic acid and / or terephthalic acid or their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene Lenglykolterephthalaten or anionically and / or nonionically modified derivatives of this. Of these, the sulfonated derivatives of phthalic acid and the terephthalic acid polymers.

The premix to be pressed can be produced when manufacturing textile detergent articles len wants, as optical brighteners derivatives of diaminostilbenedisulfonic acid or their alkali contain lime salts. Are suitable for. B. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5- triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similar compounds, which instead of the morpholino group, a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group. Furthermore, on lighter of the substituted diphenyl styrene type, e.g. B. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chloro styryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brighteners can also be used.

Fragrances can be added to the detergent tablets according to the invention be set to improve the aesthetic impression of the resulting products and a senso to the consumer in addition to the cleaning performance and the color impression to provide a "typical and distinctive" product. As perfume oils or fragrances, individual fragrance compounds, e.g. B. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type become. Fragrance compounds of the ester type are e.g. B. benzyl acetate, phenoxyethy lisobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allyl cyclohe xyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example Benzyl ethyl ether, to the aldehydes z. B. the linear alkanals with 8-18 C atoms, citral, Citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. B. the Jonone, ∝-isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and  Terpineol, the hydrocarbons mainly include terpenes such as limonene and pinene. However, mixtures of different fragrances are preferably used, which together create an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures as they are available from plant sources are, e.g. B. pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also ge suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, Linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the premix, but it can also be advantageous to apply the fragrances on carriers that affect the adhesion of the perfume reinforce the laundry and through a slower fragrance release for long-lasting The scent of the textiles Cyclo, for example, have become such carrier materials dextrine has proven itself, with the cyclodextrin-perfume complexes additionally with others Auxiliaries can be coated.

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

These substances, which are also referred to as "explosives" due to their effect, ver increase their volume when water enters, and on the one hand increases their own volume (Swelling), on the other hand, a pressure can be generated via the release of gases which can break the tablet into smaller particles. Well-known disintegration aid Medium are, for example, carbonate / citric acid systems, with other organi cal acids can be used. Swelling disintegration aids are included for example synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polyme re or modified natural products such as cellulose and starch and their derivatives, alginates or Casein derivatives.  

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

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

The cellulose used as disintegration aid is preferably not finely divided form, but before mixing into the premixes to be pressed converted into a coarser form, for example granulated or compacted. washing and detergent tablets, the disintegrant in granular or optionally co contain granulated form, are in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel). These writings are also more details on the production of granulated, compacted or cogranulated  To remove cellulose disintegrant. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 µm and in particular at least 90% by weight between 400 and 1200 µm. The coarser ones mentioned above and described in more detail in the cited documents Disintegration aids based on cellulose are within the scope of the present invention preferably used as a disintegration aid and commercially, for example, at the name Arbocel® TF-30-HG available from Rettenmaler.

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

The base moldings produced in the first step can have any geometric shape assume, in particular concave, convex, biconcave, biconvex, cubic, te tragonal, orthorhombic, cylindrical, spherical, segment-like, disks shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, five-, hexagonal and octagonal prismatic and rhombohedral shapes are preferred. Also completely irregular base areas such as arrow or animal shapes, trees, clouds, etc. will be realized. If the shaped bodies according to the invention have corners and edges, so they are preferably rounded. As an additional optical differentiation is a Embodiment with rounded corners and beveled ("chamfered") edges vorzugt.

The cavity in the base moldings can also have any shape. she can cut through the molded part, d. H. an opening on different sides, for example have on the top and bottom of the molded body, but it can not pass through the entire molded body going cavity, the opening of only one molded body side is visible, which is preferred according to the invention. The shape of the cavity can also be in wide limits can be freely chosen. For reasons of procedural economy  Troughs with an opening on one side of the molded body have proven themselves. Also the shape of the trough can be chosen freely, preference being given to moldings in which at least one Trough a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disc-shaped, tetrahedral, dodecahedral, octa cathedral, conical, pyramidal, ellipsoid, pentagonal, hexagonal and octagonal prismatic as well rhombohedral shape can take. Completely irregular trough shapes such as arrow or animal forms, trees, clouds etc. can be realized. As with the shape bodies are troughs with rounded corners and edges or with rounded corners and chamfered edges preferred.

The geometric forms of implementation mentioned above can be used as desired combine each other. In this way, molded bodies with a rectangular or square base can be used surface and circular cavities are produced as well as round shaped bodies octagonal troughs, with no limit to the variety of possible combinations are set. For reasons of process economy and aesthetic consumption Trough moldings in which the moldings are particularly preferred base area and the hole cross-section have the same geometric shape, for example se molded body with a square base and a centrally integrated square Cavity.

It is particularly advantageous in the context of the present invention if the core fits into the cavity with a positive fit and no visually disturbing wide gaps be formed. Processes in which the core (s) fit into the cavity (s) of the base molding can be / are preferred.

The size of the trough in comparison to the entire molded body depends on the ge desired use of the molded body. Depending on how big the later to be inserted is sticky core and whether a smaller or larger amount of washing or cleaning dosing agent, the size of the cavity can vary. Independent of Methods of use according to the invention are preferred in which the volume of the core (or cores) 0.05 to 1 times, preferably 0.1 to 0.75 times and in particular 0.15 to 0.5 times the volume of the base molding accounts.  

In addition to the volume ratio mentioned, a mass ratio of the two can also be used Parts are given, the two values on the densities of the base molding or correlate the core with each other. Regardless of the density of the individual parts Processes are preferred in which the weight ratio of the base molding to core 1: 1 to 100: 1, preferably 2: 1 to 80: 1, particularly preferably 3: 1 to 50: 1 and is in particular 4: 1 to 30: 1.

Analogous information can also be given for the surfaces, each from the base molded body or from the core are visible. Here, methods are preferred in which the externally visible surface of the core 1 to 25%, preferably 2 to 20%, esp preferably 3 to 15% and in particular 4 to 10% of the total surface of the mold body

The core and the base molding are preferably colored to be optically distinguishable. In addition to the optical differentiation, application-related advantages can be achieved through un Different solubilities of the different shaped body areas can be achieved. Detergent tablets in which the core dissolves faster than that Base moldings are preferred according to the invention. By incorporating certain Be On the one hand, the solubility of the core can be accelerated in a targeted manner, on the other on the one hand, the release of certain ingredients from the detergent component lead to advantages in the washing or cleaning process.

Of course, detergent tablets are also preferred, de the core loosens later in the washing program than the basic molded body. performance benefits This delayed release can be achieved, for example, by using With the help of a slower soluble core, active substance (s) are only released in later rinses be set. For example, in machine dishwashing, long more soluble cores are achieved that further active substance (s) in the rinse cycle Is available. Through additional substances such as non-ionic surfactants, acidification detergents, soil release polymers etc. can be used to improve the rinse aid results. Incorporation of perfume is also possible without any problems; by its delayed In dishwashers, release can cause the "lye odor" that often occurs in Opening the machine can be eliminated.  

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

The cores to be inserted into the cavity provided with adhesion promoters can - as already mentioned - contain each of the above-mentioned active substances. The manufacture of the Cores can be made in different ways, using methods such as tableting, Casting, injection molding, sintering, extruding and pelleting are preferred. Selbstver Suitable mixtures of substances can of course only be prilled or pastilled and subsequently pressed.

The cores can be loaded with suitable materials before they are inserted into the cavity be layered, based on methods and materials known to those skilled in the art can be gripped.

Claims (11)

1. A process for the production of multi-phase detergent tablets, in which, in a first step, base tablets are produced which have at least one cavity into which adhesion promoters are / are metered in in a second step, before the cavity (s) are added in a third step (one) core (s) is filled, characterized in that solutions, dispersions, emulsions or melts which have a viscosity below 3000 mPas are used as adhesion promoters in a second step. 2. The method according to claim 1, characterized in that the adhesion promoter at the Processing a viscosity below 2500 mPas, preferably below Have 2000 mPas and in particular below 1000 mPas. 3. The method according to any one of claims 1 or 2, characterized in that the Adhesion promoter at a temperature between 10 and 130 ° C, preferably between 20 and 110 ° C and in particular between 20 and 90 ° C who metered into the cavity the. 4. The method according to any one of claims 1 to 3, characterized in that as detention mediator one or more substances from the groups of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) can be used. 5. The method according to any one of claims 1 to 3, characterized in that as detention mediator solutions of polyhydric alcohols and / or solid at room temperature Sugars are used, with solutions being preferred which are based on the Solution at least 30 wt .-%, preferably at least 40 wt .-% and in particular which contain at least 50 wt .-% solid (s). 6. The method according to claim 5, characterized in that solutions of sorbitol are used which, based on the solution at least 50 wt .-%, preferred have at least 60% by weight and in particular at least 70% by weight of sorbitol hold.   7. The method according to any one of claims 1 to 3, characterized in that as adhesion promoters solutions or suspensions of polyurethanes made from diisocyanates (I) and diols (II)
O = C = NR ¹ -N = C = O (I),
HOR ² -OH (II),
are used, the diols being selected at least in part from polyethylene glycols (IIa) and / or polypropylene glycols (IIb)
H- (O-CH ₂ -CH ₂ ) _n -OH (IIa),
and R ¹ and R ² independently of one another represent a substituted or unsubstituted, straight-chain or branched alkyl, aryl or alkylaryl radical having 1 to 24 carbon atoms and n each number from 5 to 2000. 8. The method according to claim 7, characterized in that solutions or suspensions of polyurethanes from diisocyanates (I) and diols (II) are used
O = C = NR ¹ -N = C = O (I),
HOR ² -OH (II),
where R ¹ for a methylene-ethylene-propylene, butylene, pentylene group or for - (CH ₂ ) ₆ - or for 2,4- or 2,6-C ₆ H ₃ -CH ₃ , or for C ₆ H ₄ -CH ₂ -C ₆ H ₄ or isophorone (3,5,5-trimethyl-2-cyclohexenone) and R ^{2 is} selected from - CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n - or -CH ₂ -CH ₂ - (O-CH (CH ₃ ) -CH ₂ ) _n - with n = 4 to 1999. 9. The method according to any one of claims 7 or 8, characterized in that solutions or suspensions of polyurethanes are used which have structural units of the formula (III)
- [OC (O) -NH-R ¹ -NH-C (O) -OR ² ] _k - (III),
in which R ^{1 stands} for - (CH ₂ ) ₆ - or for 2,4- or 2,6-C ₆ H ₃ -CH ₃ , or for C ₆ H ₄ -CH ₂ -C ₆ H ₄ and R ² is selected from -CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n - or -CH (CH ₃ ) -CH ₂ - (O-CH (CH ₃ ) -CH ₂ ) _n -, where n is a Number from 5 to 199 and k is a number from 1 to 2000. 10. The method according to any one of claims 1 to 9, characterized in that the Vo lumen of the core (or cores) 0.05 to 1 times, preferably 0.1 to 0.75 times and in particular 0.15 to 0.5 times the volume of the basic shape body. 11. The method according to any one of claims 1 to 10, characterized in that the / The core (s) are positively fitted into the cavity (s) of the base molding can / can.