EP1322743B1 - Recessed tablets and method for the production thereof - Google Patents

Abstract

Laundry or dishwasher detergent tablets comprise at least one cavity, nonionic surfactants in the range from 5 to 25% by weight, based on the tablet and 0.1% to 70% by weight of sulfonated copolymers.

Description

The invention relates to detergent tablets in the form of well tablets, i. Tablets having at least one cavity on one of their surfaces. The invention also relates a method of making well tablets or well tabs. It is in a (usually the upper) side of a large volume tablet imprinted a trough, which in a subsequent Confectioning be filled with a different material, in particular poured out can.

In the preparation of mortar tablets occur very special problems, since the tablet surface not exactly, but profiled. This results for the different surface geometries the corresponding embossing element different pressure and Abrasionsverhältnisse. Because the tendency to adhere to substances to be pressed on the embossing element among other things, the specific surface pressure and the surface geometry determined Depending on the pressure vectors, certain parts of a stamping element profile are particularly prone to Buildup or caking. Such attachments result in the sequence of many pressings Roughnesses of the tablet surfaces increase in the corresponding places, too Deviations in the proportions of the substances and also cause tablet breakage can. If a tablet breaks in the tableting press, this leads to considerable impairments of the manufacturing process.

One way to solve this problem is the geometry of the cavity or trough to choose so that buildup and edge breakage are avoided at the trough edge. Often are however, from technical (eg volume of the well at a given tablet size) or more aesthetic View the possibilities of variation extremely limited. Also a surface finish of the Press punches with non-stick materials can be used to reduce the tendency to stick. However, the materials known in the prior art have the disadvantage of short service lives which necessitate frequent replacement of tools. That of the invention The underlying technical problem is the mixture to be tabletted by addition certain substances to be designed so that adhesions to the pressing tool and breakage be reduced or avoided altogether at the edges of the cavity. This problem is invented achieved in that in the mixtures to be tabletted use of nonionic surfactants and in particular nonionic surfactant mixtures in certain ranges. In multiphase (in particular multi-layered) tablets suffices a corresponding addition to the mixture, which forms the phase which has contact with the ram at the final crimping, which presses the cavity into the tablets.

The present invention relates to washing or cleaning agent tablets comprising at least one cavity, wherein the content of the tablets of nonionic surfactants having a melting point above 20 ° C 5.5 to 25 % By weight, based in each case on the tablet.

The use of nonionic surfactants in the stated amounts leads to a reduction in the Appearances on the non-planning pressing tool and a significantly reduced occurrence edge chipping phenomena at the trough edges. For multi-phase tablets is enough a corresponding composition of the phase comprising the cavity, i. of the premix, which comes into contact with the non-planned ram at the final crimping. There in precompacting steps (such as in the preparation of two-layer tablets) the first premix is only slightly compressed by pressing with the stamp, no adhesion or occur here Edge break phenomena on. Only at the final compression, the forces are so great that the problems mentioned are to be feared.

Another object of the present invention are therefore also multi-phase washing or Detergent tablets comprising at least one cavity, wherein the content of the phase, the the cavity has, to nonionic surfactants having a melting point above 20 ° C 5.5 to 25 wt .-%, is.

In a tableting process naturally only one body can be made, the vertical has lateral boundary surfaces (possibility of ejection from the die). Usually For example, the bottom and "top" surfaces are horizontal, i. they and the edge surface (s) are orthogonal each other. Tablets having at least one cavity (so-called mortar tablets), possess this cavity for the reasons mentioned above at its top or bottom. Out Due to the simplified ejection process from the die is the lower punch (and thus the Bottom) mostly designed plan, while on the upper punch at least one survey which impresses the cavity in the top of the tablet. The tablets according to the invention (hereinafter also referred to as "base molding") may be any geometric shape in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segmented, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, octagonal and octagonal prismatic and rhombohedral forms are preferred. Also completely irregular bases like arrow or animal shapes, trees, clouds can be realized. Indicates the basic shaped body Corners and edges, so these are preferably rounded. As an additional optical Differentiation is an embodiment with rounded corners and beveled ("chamfered") Edges preferred.

The shape of the trough can be chosen freely, with tablets being preferred in which at least a trough a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segmented, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, pentagonal, octagonal, prismatic and rhombohedral Can take shape. Also completely irregular trough shapes like arrow or animal forms, trees, Clouds can be realized. As with the basic moldings are wells with rounded Corners and edges or with rounded corners and chamfered edges preferred.

The problem of edge rupture on the trough edges and the adhesion to the Elevations of the ram occurs increasingly when the contact angle of the trough is larger. On the other hand, a contact angle lying near 90 ° is preferred since shallow wells / cavities have only small volumes, while "steep" cavities with small opening area can have large volumes. The solution according to the invention is especially in such Problem cases suitable. Appropriate washing or cleaning agent tablets characterized in that the cavity has lateral boundary walls which are orthogonal to the Base area are preferred embodiments.

Between the extremes of a hemispherical or semi-ellipsoidal trough (no straight lateral Boundary surfaces) or a cylindrical recess (straight lateral boundary surfaces, which meet orthogonally on a trough bottom standing parallel to the base surface) various transitions possible. In general, the problems occur increasingly when the lateral Boundary surfaces are straight, i. when the shortest connecting line from the trough edge to the hollow bottom is a straight line and no curve. Here, the advantages of the invention occur more clearly, corresponding tablets according to the invention are preferred. At the straight lateral boundary walls, in turn, the problems become clearer, the steeper these are (see above), which leads in extreme cases to the above-described angles of 90 ° (Angle less than 90 ° between trough bottom and lateral boundary line are not technically possible, otherwise the bottom surface of the trough would be larger than the opening area). In this In extreme cases, the benefits of the invention are most apparent. However, you can also create hollows with "straight" side walls and non-orthogonal angles, which is technically preferred. Such wells, which have a cone, have advantages in later Filling operations, so that tablets according to the invention, in soft angle as explained above between 90 and 120 °, preferably between 91 and 110 °, more preferably between 92 and 100 ° and in particular between 93 and 98 °, are preferred.

The size of the trough or cavity in comparison to the entire shaped body depends on the desired use of the shaped body. Depending on whether and with which substances in which aggregate states the trough or cavity is to be filled, the size of the trough vary. Regardless of the purpose, washing and cleaning tablets are used preferred in which the volume ratio of base molding to trough volume in the range from 1: 1 to 100: 1, preferably from 2: 1 to 80: 1, more preferably from 3: 1 to 50: 1 and especially from 4: 1 to 30: 1.

Similar statements can be made to the surface portions of the base molding or Make the trough opening on the entire surface of the molding. Here are washing or Detergent tablets in which the surface of the cavity opening is 1 to 25%, preferably 2 to 20%, more preferably 3 to 15% and in particular 4 to 10% of the total surface makes up the tablet.

If, for example, the overall shaped body has dimensions of 20 × 20 × 40 mm and thus a total surface area of 40 cm ² , well fillings are preferred which have a surface area of 0.4 to 10 cm ² , preferably 0.8 to 8 cm ² , more preferably of 1.2 to 6 cm ² and in particular from 1.6 to 4 cm ² .

The well tablets according to the invention contain nonionic surfactant (s). In addition, you can they are anionic, cationic (especially in the case of detergent tablets) and / or amphoteric surfactants or mixtures thereof. Preferred are from an application point of view for detergent tablets mixtures of anionic and nonionic surfactants. The total surfactant content of detergent tablets is 5.5 to 60 Wt .-%, based on the molding weight, with surfactant contents above 15 wt .-% preferred are.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C _12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration. 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. Among fatty acid glycerol esters are the mono-, di- and triesters and their mixtures to understand how they are in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example, the caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, Palmitic acid, stearic acid or behenic acid.

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. Also, 2,3-alkyl sulfates prepared, for example, according to U.S. Patents 3,234,258 or 5,075,041, which can be obtained as commercial products of the Shell Oil Company under the name DAN®, are suitable anionic surfactants.

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. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) yl-succinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

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 from 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, available. Preferably, the anionic surfactants are in the form of their sodium or potassium salts, especially in the form of the sodium salts.

In automatic dishwashing detergents, surfactants are usually low-foaming surfactants nonionic surfactants used. In detergent tablets according to the invention therefore have Representatives of the groups of anionic, cationic or amphoteric surfactants a lower Importance. The nonionic surfactants which according to the invention both in the Detergent tablets as well as detergent tablets in amounts of 5.5 to 25 wt .-% in the Means are included, are described below.

In particularly preferred embodiments of the present invention, the detergent tablets according to the invention comprise nonionic surfactants from the group of the alkoxylated alcohols. As such nonionic surfactants, preference is given to using 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 is linear or preferably methyl-branched in the 2-position may contain or linear and methyl-branched radicals in the mixture, 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 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 alone nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester.

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 alkanolamide may be suitable. The amount of these nonionic surfactants is preferably no longer than that of the ethoxylated fatty alcohols, especially not more than half of them.

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. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Further suitable surfactants are polyhydroxy fatty acid amides of the formula (I)

wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R ^{1 is} hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 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.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R' für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

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

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

The automatic dishwashing detergent tablets according to the invention contains a nonionic surfactant which has a melting point above Room temperature. The washing or cleaning agent tablets contain nonionic surfactant (s) having a melting point above 20 ° C, preferably above of 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, in amounts of 5.5 to 25 wt .-%, preferably from 5.5 to 20 wt .-%, preferably from 6.0 to 17.5 wt .-%, especially preferably from 6.5 to 15 wt .-% and in particular from 7.0 to 12.5 wt .-%, each based on the tablet or the phase that has the cavity.

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

Preferred nonionic surfactants to be used at room temperature are from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures thereof Surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Drawing such (PO / EO / PO) nonionic surfactants Beyond that 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. Appropriate detergent tablets characterized in that the nonionic surfactant (s) is / are ethoxylated nonionic surfactant (s) selected from C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol were obtained (n), are therefore preferred.

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 bis to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Surfactants. Detergents or cleaning tablets, the ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 Wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant are preferred embodiments of the present invention. Especially preferred Nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols, which in addition Having polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part such nonionic surfactant molecules preferably makes up more than 30% by weight, especially preferably more than 50 wt .-% and in particular more than 70 wt .-% of the total molecular weight such nonionic surfactants.

Further particularly preferably used nonionic surfactants with melting points above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend, the 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 which can be used with particular preference are, for example available 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 for a value of at least 15 is detergent tablets, which are characterized in that they nonionic surfactants of 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, are therefore preferred.

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. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined 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 last-mentioned 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.

In summary, detergent or detergent tablets are preferred, which are characterized in that they or the phase having the cavity 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, x is n-butyl, 2-butyl or 2-methyl-2-butyl, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, surfactants of the type R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² in which x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

a) 1,0 bis 4,0 Gew.-% nichtionischer Tenside aus der Gruppe der alkoxylierten Alkohole,

b) 4,0 bis 24,0 Gew.-% nichtionischer Tenside aus der Gruppe der hydroxylgruppenhaltigen alkoxylierten Alkohole ("Hydroxymischether"),

jeweils bezogen auf die gesamte Tablette bzw. die Phase, die die Kavität aufweist, aufweisen.With particular preference, mixtures of different nonionic surfactants are used in the tablets according to the invention. Washing or cleaning agent tablets which have a content of

a) 1.0 to 4.0% by weight of nonionic surfactants from the group of the alkoxylated alcohols,

b) 4.0 to 24.0% by weight of nonionic surfactants from the group of hydroxyl-containing alkoxylated alcohols ("hydroxy mixed ethers"),

each based on the entire tablet or the phase having the cavity have.

The nonionic surfactants from group a) have already been described in detail above, with particular preference for the automatic dishwashing compositions containing the abovementioned mixtures, C _12-14 fatty alcohols with 5EO and 4PO and C _12-18 fatty alcohols with an average of 9 EO have proven to be outstanding. With similar preference end-capped nonionic surfactants, in particular C _12-18 fatty alcohol-9 EO-butyl ether, can be used.

Surfactants from group b) show outstanding clear rinse effects and reduce stress corrosion cracking on plastics. Furthermore, they have the advantageous property that their network behavior is constant over the entire usual temperature range. Particularly preferred the surfactants from the group b) hydroxyl-containing alkoxylated alcohols, as described in EP 300 305 are described, the disclosure of which is expressly incorporated herein. All there Hydroxymischether disclosed are invariably with preference as a surfactant from the group b) in the According to the invention preferred dishwashing detergents contain.

a) 1,5 bis 3,5 Gew.-%, vorzugsweise 1,75 bis 3,0 Gew.-% und insbesondere 2,0 bis 2,5 Gew.-% nichtionischer Tenside aus der Gruppe der alkoxylierten Alkohole,

b) 4,5 bis 20,0 Gew.-%, vorzugsweise 5,0 bis 15,0 Gew.-% und insbesondere 7,0 bis 10,0 Gew.-% nichtionischer Tenside aus der Gruppe der hydroxylgruppenhaltigen alkoxylierten Alkohole ("Hydroxymischether"),

jeweils bezogen auf die gesamte Tablette bzw. die Phase, die die Kavität aufweist.The amounts in which the surfactants from groups a) and b) may be present in dishwashing detergent tablets preferred according to the invention vary depending on the desired product and are preferably within narrower ranges. Particularly preferred detergent tablets contain

a) 1.5 to 3.5 wt .-%, preferably 1.75 to 3.0 wt .-% and in particular 2.0 to 2.5 wt .-% of nonionic surfactants selected from the group of alkoxylated alcohols,

b) 4.5 to 20.0 wt .-%, preferably 5.0 to 15.0 wt .-% and in particular 7.0 to 10.0 wt .-% of nonionic surfactants from the group of hydroxyl-containing alkoxylated alcohols (" hydroxy mixed "),

in each case based on the entire tablet or the phase having the cavity.

The incorporation of the nonionic surfactant (s / e) in the compositions of the invention may be different Art done. The surfactants may, for example, in the molten state on the otherwise ready-to-use pre-mix to be compressed are sprayed on or the premix in the form of compounds or surfactant formulations. Especially it is preferred to use particulate premixes of high-surfactant particles, so-called "rinse aid particles" admit.

a) 20 bis 90 Gew.-% einer oder mehrerer Trägermaterialien aus der Gruppe der Gerüststoffe,

b) 10 bis 40 Gew.-% eines oder mehrerer nichtionischer Tenside sowie

c) 0 bis 70 Gew.-% weiterer Wirk- und Hilfsstoffe,

enthält.These "rinse aid particles" can be added as a particulate component to the premix to be compressed, wherein both the amount of rinse aid particles and their content of nonionic surfactants, the amount of surfactants in the final product (or in the relevant phase of the final product) can be influenced. Premixes for pressing into washing or cleaning agent tablets according to the invention or phases thereof preferably contain a particulate rinse aid, based on its weight

a) 20 to 90% by weight of one or more support materials from the group of builders,

b) 10 to 40 wt .-% of one or more nonionic surfactants and

c) 0 to 70% by weight of other active ingredients and auxiliaries,

contains.

Particularly preferred rinse aid particles contain as carrier (e) a) one or more substances from the groups of phosphates, carbonates, bicarbonates and / or silicates in quantities of From 25 to 85% by weight, preferably from 35 to 82.5% by weight and in particular from 45 to 80% by weight, each based on the weight of the particulate rinse aid, contains These substances described below.

Among the phosphates, in turn, the alkali metal phosphates are particularly preferred as support materials for the rinse aid particles. Alkali metal phosphates 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, moreover, contribute to the cleaning performance.

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

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm ^-3 , loss of water at 95 °), 7 moles (density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 moles water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na ₄ P ₂ O ₇ . Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is readily soluble in water

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

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

Condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ results in higher mol. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: hot or cold phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or with 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH: (NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

These phosphates are according to the invention just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two can be used; also mixtures of sodium tripolyphosphate and Sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate are used according to the invention.

Other ingredients used instead of or in addition to phosphates as support materials may be carbonates and / or bicarbonates, wherein the alkali metal salts and among which especially the potassium and / or sodium salts are preferred. Preferred washing or Detergent tablets contain carbonate (s) and / or bicarbonate (s), preferably Alkali carbonates, more preferably sodium carbonate, in amounts of 25 to 75 wt .-%, preferably from 30 to 60 wt .-% and in particular from 35 to 50 wt .-%, each based on the mass of rinse aid particles contained in them.

Other ingredients which, instead of or in addition to the said phosphates and / or Carbonates / bicarbonates may be included in the detergent tablets are Silicates, wherein the alkali metal silicates and including 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} .yH 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 are 2, 3 or 4. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x has the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 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". This means that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

The washing or cleaning agent tablets according to the invention can be used as carrier materials or in the remaining solid matrix also contain zeolites, with preferred agents no zeolite as Carrier material in the rinse aid particles and particularly preferred detergent tablets even do not contain any zeolite. In laundry detergent tablets according to the invention is the use of zeolite however preferred.

Zeolites have the general formula M _{2 / n} O ^· Al ₂ O ₃ ^· x SiO ₂ ^· y H 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. The zeolite structures are formed by linking AlO ₄ tetrahedra with SiO ₄ tetrahedra, this network being occupied by cations and water molecules. The cations in these structures are relatively mobile and can be exchanged to varying degrees by other cations. Depending on the type of zeolite, the intercrystalline "zeolitic" water can be released continuously and reversibly, while with some zeolite types, structural changes are accompanied by water release or uptake.

In the structural subunits, the "primary binding units" (AlO ₄ tetrahedra and SiO ₄ tetrahedra) form so-called "secondary binding units", which are in the form of single or multiple rings. For example, 4-, 6- and 8-membered rings (referred to as S4R, S6R and S8R) occur in different zeolites, others are joined via four- and six-membered double ring prisms (most common types: D4R as quadrangular or D6R as hexagonal prism ). These "secondary subunits" combine different polyhedra called Greek letters. The most common is a Vielflächner, which is composed of six squares and eight equilateral hexagons and which is referred to as "β". With these units, a variety of different zeolites can be realized. So far, 34 natural zeolite minerals and about 100 synthetic zeolites have been known.

The best known zeolite, zeolite 4 A, is a cubic composite of β-cages linked by D4R subunits. It belongs to the zeolite structure group 3 and its three-dimensional network has pores of 2.2 Å and 4.2 Å size, the formula unit in the unit cell can be with Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] ^· 27 H ₂ O describe.

When zeolites are used, faujasite-type zeolites are preferably used. Together with zeolites X and Y, the mineral faujasite belongs to the faujasite types within the zeolite structure group 4, which is characterized by the double-six-membered subunit D6R (cf. Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974 , page 92). In addition to the faujasite types mentioned, the zeolite structural group 4 also includes the minerals chabazite and gmelinite as well as the synthetic zeolites R (chabazite type), S (gmelinite type), L and ZK-5. The latter two synthetic zeolites have no mineral analogs.

Faujasite-type zeolites are composed of β-cages linked tetrahedrally via D6R subunits, with the β-cages resembling the carbon atoms in the diamond. The three-dimensional network of the faujasite-type zeolites used in the process according to the invention has pores of 2.2 and 7.4 Å, the unit cell also contains 8 cavities of about 13 Å diameter and can be represented by the formula Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] ^. 264 H ₂ O. The network of zeolite X contains a void volume of about 50%, based on the dehydrated crystal, which represents the largest void space of all known zeolites (zeolite Y: about 48% void volume, faujasite: about 47% void volume). (All data from: Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, pages 145, 176 , 177 ).

In the context of the present invention, the term "faujasite-type zeolite" denotes all three zeolites forming the faujasite subgroup of zeolite structure group 4. In addition to the zeolite Thus, according to the invention, X are also zeolite Y and faujasite as well as mixtures of these compounds can be used according to the invention, wherein the pure zeolite X is preferred

Also, mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites, the not necessarily belong to the zeolite structure group 4, can be used according to the invention, the advantages of the method according to the invention are particularly evident when at least 50% by weight of the powdering agent consists of a faujasite-type zeolite. It is also conceivable, for example, that the minimum amount of a zeolite of the faujasite type (0.5 wt .-%, based on the weight of the resulting molding) and the remainder Abwudermittel conventional zeolite A used But is preferred in any case that the Powdered agent consists solely of one or more faujasite-type zeolites, Zeolite X is again preferred.

The aluminum silicates used in the washing or cleaning tablets according to the invention are commercially available, and the methods of their presentation are in Standard monographs are described.

Examples of commercially available X-type zeolites can be described by the following formulas: Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] ^.xH ₂ O, K ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] ^.xH ₂ O, Ca ₄₀ Na ₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] ^xH ₂ O, Sr ₂₁ Ba ₂₂ [(AlO _{2) 86} (SiO _{2) 106]} ^· x H ₂ O,

where x can take values between 0 and 276 and have pore sizes of 8.0 to 8.4 Å.

For example, a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) which is marketed by the company CONDEA Augusta SpA under the brand name VEGOBOND AX® is also commercially available and preferably usable in the context of the process according to the invention and by the formula nNa ₂ O ^• (1-n) K ₂ O ^• Al ₂ O ₃ ^• (2 - 2.5) SiO ₂ ^• (3.5-5.5) H ₂ O can be described.

Also Y-type zeolites are commercially available us can be, for example, by the formulas Na ₅₆ [(AlO ₂ ) ₅₆ (SiO ₂ ) ₁₃₆ ] ^xH ₂ O, K ₅₆ [(AlO ₂ ) ₅₆ (SiO ₂ ) ₁₃₆ ] ^xH ₂ O, where x is numbers between 0 and 276 and has pore sizes of 8.0 Å.

The abovementioned builder substances can be used as carrier materials in the rinse aid particles be included, or they may be additional or only part of the "other" Washing or cleaning tablets.

As a second component, the rinse aid particles contained in the washing or Detergent tablets can be used nonionic surfactant (s) already have been described in detail above. Also in the event that the inventive Detergents or cleansing tablets contain the nonionic surfactant (s) in the form of separate rinse aid particles those tablets are preferred in which the particulate rinse aid as nonionic Surfactants b) Mixtures of alkoxylated alcohols and hydroxy mixed ethers in amounts of From 10 to 35% by weight, preferably from 10.5 to 30% by weight and in particular from 11 to 20% by weight, each based on the weight of the particulate rinse aid contains.

The well tablets according to the invention may contain further ingredients which are either as Active ingredients or excipients localized in the rinse aid particles or incorporated in other ways in the agents are. These substances are described below and may each be further Active ingredients or auxiliaries may be contained in the rinse aid particles, but they may also be added or only exclusively part of the "remaining" mortar tablets.

When rinse aid particles are used detergent or cleaner tablets according to the invention preferred in which the particulate Klarspüier as further active ingredients and / or auxiliaries c) a or more substances from the groups of dyes, fragrances, defoamers, polymers, scale inhibitors, Silver protectants, enzymes and / or mixtures thereof in amounts of 5 to 60 Wt .-%, preferably from 10 to 50 wt .-% and in particular from 15 to 30 wt .-%, respectively based on the weight of the particulate rinse aid.

In addition to the substances mentioned above, bleaching agents, bleach activators, co-builders, Chelating and complexing agents, water-softening substances, acidifying and / or alkalizing agents as well as adjusting, separating and anti-caking agents as constituents of the mortar tablets according to the invention prefers. In the case of the first three substances mentioned, it is advantageous not to use them into the rinse aid particles.

In summary, wellbill tablets according to the invention are preferred, which are characterized are that they continue to contain one or more substances from the groups of surfactants, enzymes, Bleaching agents, bleach activators, corrosion inhibitors, scale inhibitors, cobuilders color and / or Fragrances, soil release polymers, optical brighteners, color transfer or grayness inhibitors in amounts of 25 to 70 wt .-%, preferably from 30 to 60 wt .-% and in particular from 40 to 50 wt .-%, each based on the weight of the total composition.

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.

Sodium carbonate peroxohydrate was first obtained from solution in 1899 by precipitation with ethanol of sodium carbonate in hydrogen peroxide but erroneously considered as peroxycarbonate. It was not until 1909 that the compound was recognized as a hydrogen peroxide addition compound, Nonetheless, the historical name "sodium percarbonate" has prevailed in practice The bulk density of the finished product, depending on the manufacturing process between 800 and 1200 g / l vary. As a rule, the percarbonate is stabilized by an additional coating. coating process and fabrics used for coating are widely described in the patent literature. In principle, all commercial percarbonate types can be used according to the invention such as Solvay lnterox, Degussa, Kemira or Akzo Tobe offered.

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 compositions. Bleaching agents from the group of organic bleaching agents can also be used in the compositions according to the invention. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. 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-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutan-1, 4-diacid, N, N-terephthaloyl-di (6-aminopercapronate) can be used.

As a bleaching agent and chlorine or bromine releasing substances can be used. Among the suitable chlorine or bromine-releasing materials are, for example, heterocyclic N-bromine and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or salts thereof with cations such as Potassium and sodium are considered. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

To improve when washing or cleaning at temperatures of 60 ° C and below To achieve bleaching effect, bleach activators can be incorporated. Bleach activators that For example, compounds that support one or more of the bleaching agent's effects N- or O-acyl groups, such as substances from the class of anhydrides, the ester, 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).

As bleach activators, compounds which are aliphatic under perhydrolysis conditions Peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, can be used. Are suitable Substances which contain O- and / or N-acyl groups of said C atom number and / or optionally bear substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), Carboxylic anhydrides, especially phthalic anhydride, acylated polyvalent Alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), and enol ester, as well as acetylated sorbitol and Mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular Pentaacetylglucose (PAG), Pentaacetylfruktose, Tetraacetylxylose and Octaacetyllactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated Lactams, for example N-benzoyl-caprolactam. Hydrophilic substituted acyl acetals and Acyllactams are also preferably used. Also combinations of conventional Bleach activators can be used.

In addition to or in place of the conventional bleach activators, so-called Bleaching catalysts are incorporated. These substances are bleach-enhancing Transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes are known as Bleach catalysts usable.

Bleach activators from the group of the multiply acylated alkylenediamines, in particular Tetraacetylethylenediamine (TAED), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), preferably in amounts to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, especially 2 to 8 wt .-% and especially preferably 2 to 6 wt .-% based on the total agent used.

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

Further preferred well tablets are characterized in that they silver protectants the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, 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 total agent included.

The corrosion inhibitors mentioned can be used to protect the items to be washed or the machine are also incorporated into the well tablets, wherein in the field of machine dishwashing Silver protectants have a special meaning. Can be used, the known Substances of the prior art. In general, especially silver protectants can be selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and the transition metal salts or complexes. Especially preferred benzotriazole and / or alkylaminotriazole are to be used. One finds in cleaner formulations In addition, frequently active chlorine-containing agents that corrode the silver surface can significantly reduce. In chlorine-free cleaner are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. Hydroquinone, Pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these connection classes. Also salt and complex inorganic compounds, such as salts The metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred are the Transition metal salts selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and the Manganese sulfate. Also, zinc compounds can be used to prevent corrosion on the dishes be used.

As enzymes are in particular those from the classes of hydrolases such as proteases, Esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures the enzymes mentioned in question. All of these hydrolases contribute to the removal of stains such as proteinaceous, fatty or starchy stains. To bleach can also Oxidoreductases are used. Particularly suitable are from bacterial strains or Fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens and enzymatically derived from their genetically modified variants Agents. Preferably, subtilisin-type proteases and in particular proteases, used from Bacillus lentus. These are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples for such lipolytic enzymes are the known cutinases. Also peroxidases or oxidases have been found to be suitable in some cases. To the suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases.

The enzymes may be adsorbed to carriers or embedded in encapsulating substances to them to protect against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules may, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-%, each based on the total mean amount.

Other ingredients that may be part of the compositions of the invention are, for example Co-builders, dyes, fragrances, soil-release compounds, soil repellents, antioxidants, Fluorescers, foam inhibitors, silicone and / or paraffin oils. These substances will be described below.

Useful organic builders are, for example, those usable in the form of their sodium salts Polycarboxylic acids, understood by polycarboxylic acids such carboxylic acids which carry more than one acidity function. For example, these are citric acid, adipic acid, Succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, Aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use of ecological Reasons are not objectionable, as well as mixtures of these. Preferred salts are the salts polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, Sugar acids and mixtures of these.

The acids themselves can also be used. The acids have besides their builder effect typically also the property of an acidifying component and thus also serve for Setting a lower and milder pH of detergents or cleaners. Especially here are citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and to name any mixtures of these.

Other suitable builders are polymeric polycarboxylates, for example the alkali metal salts the polyacrylic acid or the polymethacrylic acid, for example those with a relative Molecular weight of 500 to 70000 g / mol.

For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrosulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, this group may again, the short-chain polyacrylates, the molecular weights of 2000 to 10,000 g / mol, and especially preferably from 3000 to 5000 g / mol, have to be preferred.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As especially suitable have proven copolymers of acrylic acid with maleic acid, the 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Their molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol, and in particular 30,000 to 40,000 g / mol.

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

To improve the water solubility, the polymers may also allylsulfonic, such as Allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.

Also particularly preferred are biodegradable polymers of more than two different Monomer units, for example those containing as monomers salts of acrylic acid and the Maleic acid and vinyl alcohol or vinyl alcohol derivatives or the salts of acrylic acid as monomers and the 2-alkylallylsulfonic acid and sugar derivatives.

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

Likewise, as further preferred builder substances are polymeric aminodicarboxylic acids, their To name salts or their precursors. Particularly preferred are polyaspartic acids or their salts and derivatives, which in addition to cobuilder properties also a bleach-stabilizing Have effect.

Further suitable builder substances are polyacetals, which are prepared by reaction of dialdehydes with polyol carboxylic acids having 5 to 7 C atoms and at least 3 hydroxyl groups, can be obtained. Preferred polyacetals are selected from dialdehydes such as glyoxal, glutaraldehyde, Terephthalaldehyde and mixtures thereof and from Polyolcarbonsäuren such as gluconic acid and / or glucoheptonic acid.

Further suitable organic builder substances are dextrins, for example oligomers or Polymers of carbohydrates that can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes be performed. Preferably, they are hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. This is a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, especially from 2 to 30 preferred, wherein DE a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 is. Useful are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins having higher molecular weights in the range of 2000 to 30,000 g / mol.

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

Also oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable cobuilders. Here, ethylenediamine-N, N'-disuccinate (EDDS) is preferred used in the form of its sodium or magnesium salts. Further preferred are in In this context, also glycerol disuccinates and glycerol trisuccinates. Suitable quantities are in zeolithhaltigen and / or silicate-containing formulations at 3 to 15 wt .-%.

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

Another class of substances with co-builder properties are the phosphonates in particular hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates For example, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, wherein the disodium salt neutral and the tetrasodium salt is alkaline (pH 9). As Aminoalkanphosphonate are preferably Ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. They are preferably in shape the neutral reacting sodium salts, eg. B. as hexasodium salt of EDTMP or as hepta- and Octa-sodium salt of DTPMP used. As a builder is from the class of phosphonates preferred to use HEDP. The aminoalkanephosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it may, especially if the means also bleach may be preferred to use Aminoalkanphosphonate, in particular DTPMP, or Use mixtures of the above phosphonates.

In addition, all compounds capable of forming complexes with alkaline earth ions can be used as co-builders.

In order to improve the aesthetic impression of the agents according to the invention, they can be whole or partially (e.g., only single layers or the well fill) colored with suitable dyes become. Preferred dyes, the selection of which does not cause any difficulty for the skilled person, have a high storage stability and insensitivity to the other ingredients the agent and against light and no pronounced substantivity to the treated Substrates such as crockery parts, so as not to stain them.

Preferred for use in laundry detergent tablets according to the invention are all colorants which are in Washing process can be oxidatively destroyed as well as mixtures thereof with suitable blue Dyes, so-called blue tint. It has proved to be advantageous to use dyes which are in Water or at room temperature in liquid organic substances are soluble. Are suitable for example, anionic colorants, e.g. anionic nitrosofarads. A possible dye is, for example, naphthol green (Color Index (Cl) Part 1: Acid Green 1, part 2: 10020), which is known as Commercial product, for example, as Basacid® Green 970 from BASF, Ludwigshafen, available is, as well as mixtures of these with suitable blue dyes. As more colorants come Pigmosol® Blue 6900 (Cl 74160), Pigmosol® Green 8730 (Cl 74260), Basonyl® Red 545 FL (Cl 45170), Sandolan® Rhodamine EB400 (Cl 45100), Basacid® Yellow 094 (Cl 47005), Sicovit® Patent Blue 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acid Blue 183), Pigment Blue 15 (Cl 74160), Supranol® Blue GLW (CAS 12219-32-8, Cl Acidblue 221)), Nylosan® Yellow N-7GL SGR (CAS 61814-57-1, Cl Acidyellow 218) and / or Sandolan® Blue (Cl Acid Blue 182, CAS 12219-26-0) for use.

When choosing the colorant, it must be taken into account that the colorants do not have too high an affinity for the textile surfaces and, in particular, for synthetic fibers. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. In the case of readily water-soluble colorants, for example the abovementioned Basacid® Green or the abovementioned Sandolan® Blue, colorant concentrations in the range from a few 10 ^-2 to 10 ^-3 % by weight are typically selected. In the case of the particularly preferred, but less readily water-soluble, pigment dyes, for example the abovementioned Pigmosol® dyes, the suitable concentration of the colorant in detergents or cleaners is typically between 10 ^-3 and 10 ^-4 % by weight. ,

Fragrances are added to the compositions of the invention to give the aesthetic impression of Improve products and give the consumer a visual and in addition to the performance of the product sensory "typical and distinctive" product to provide. As perfume oils or fragrances may be individual fragrance compounds, e.g. the synthetic products of the type the esters, ethers, aldehydes, ketones, alcohols and hydrocarbons are used. fragrance compounds the type of esters are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, Linalyl acetate, dimethylbenzyl-carbinyl acetate, phenylethyl acetate, linalyl benzoate, Benzylformiat, Eihylmethylphenyl-glycinate, Allylcyclohexylpropionat, Styrallylpropionat and Benzyl salicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the ionone, α-isomethylionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes Limes and pinas. However, preference is given to using mixtures of different fragrances, which together create an appealing scent. Such perfume oils can also be natural Fragrance mixtures as available from vegetable sources, e.g. Pine, Citrus, Jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, Chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, Olibanumöl, Galbanumöl and Labdanumöl as well as orange blossom oil, neroliol, orange peel oil and Sandalwood oil.

Usually, the content of the detergents according to the invention of fragrances is up to 2 Wt .-% of the total formulation. The fragrances can be directly in the agents according to the invention but it may also be advantageous to apply the perfumes to carriers, which increase the adhesion of the perfume on the laundry and by a slower fragrance release ensure a long-lasting fragrance of the textiles. As such carrier materials, for example Cyclodextrins proven, the cyclodextrin-perfume complexes additionally with other excipients can be coated.

As foam inhibitors, which can be used in the inventive compositions come For example, soaps, paraffins or silicone oils, optionally on support materials can be applied.

The detergent tablets according to the invention may contain one or more optical (s) Contain brightener. These substances, which are also called "whiteners" are used in modern Detergent used since even freshly washed and bleached white laundry a slightly yellowish. Optical brighteners are organic dyes that are part of the invisible Convert UV radiation of sunlight into longer wavelength blue light. The emission This blue light complements the "gap" in the light reflected from the textile, so that one with optical Brightener treated textile makes the eye whiter and brighter because of the mechanism of action of brighteners presupposes their application to the fibers, a distinction is made according to the "to be colored" Fibers, for example, brighteners for cotton, polyamide or polyester fibers. The commercial ones Brighteners suitable for incorporation into detergents are essentially included therein five structural groups on the stilbene, the diphenylstilbene, the coumarin-quinoline, the diphenylpyrazole group and the group of the combination of benzoxazole or benzimidazole with conjugated Systems. Suitable are e.g. Salts of 4,4'-bis [(4-anilino-6-morpholino-s-triazin-2-yl) amino] stilbene-2,2'-disulfonic acid or similar compounds which replace the Morpholino group a diethanolamino group, a methylamino group, an anilino group or carry a 2-methoxyethylamino group. In addition, brighteners of the substituted type can be used Diphenylstyryls be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls. Also mixtures The aforementioned brightener can be used.

In order to facilitate the disintegration of highly compressed tablets, it is possible disintegration aids, so-called tablet disintegrants to incorporate into this to shorten the disintegration times. These Substances are suitable, for example, for the release of individual tablet areas accelerate other areas. Among tablet disintegrants and decay accelerators are understood to be excipients for the rapid disintegration of tablets in water or gastric juice and provide for the release of the pharmaceuticals in absorbable form.

These substances, which are also referred to as "explosives" due to their effect, increase their size when water enters their volume, on the one hand increases the intrinsic volume (swelling), on the other hand also, via the release of gases, a pressure can be generated which the tablet is in smaller particles disintegrate. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

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

Disintegrating agents based on cellulose are used as preferred disintegrating agents in the present invention, so that preferred washing and cleaning agent tablets contain such cellulose-based disintegrating agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular 4 contain up to 6 wt .-%. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and formally represents a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5,000 Glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives.

The cellulose used as disintegration assistant is preferably not in finely divided form but before blending into the pre-mixes to be pressed into a coarser one Form transferred, for example, granulated or compacted. The particle sizes of such disintegrating agents are usually above 200 microns, preferably at least 90 wt .-% between 300 and 1600 microns and in particular at least 90 wt .-% between 400 and 1200 microns. The mentioned above and described in more detail in the cited documents coarser Disintegrationshilfsmittel Cellulosic are preferred in the context of the present invention as disintegration aids and commercially available, for example, under the name Arbocel® TF-30-HG available from Rettenmaier.

As another disintegrating agent based on cellulose or as a component of this component can microcrystalline cellulose. This microcrystalline cellulose is made by partial Obtained hydrolysis of celluloses under such conditions that only the amorphous regions (ca. 30% of the total cellulose mass) of the celluloses attack and completely dissolve the crystalline ones Areas (about 70%) but leave undamaged. A subsequent disaggregation of The micro-crystalline celluloses, the primary particle sizes, produce the micro-fine celluloses produced by the hydrolysis of about 5 microns and, for example, to granules with a medium Particle size of 200 microns are compacted.

In the context of the present invention, preferred washing and cleaning agent tablets additionally a disintegration aid, preferably a cellulose disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10 wt .-%, preferably from 3 to 7 wt .-% and in particular from 4 to 6 wt .-%, respectively based on the weight of the tablet.

The detergent tablets according to the invention can moreover be a gas-evolving Effervescent system incorporated into one or more of the masses to be processed incorporated becomes. The gas-evolving effervescent system may consist of a single substance, which releases a gas on contact with water. Among these compounds is in particular the To name magnesium peroxide, which releases oxygen on contact with water. Usually exists however, the gas-releasing effervescent system itself comprises at least two components, which react with each other to form gas. While here a variety of systems thinking and is executable that release, for example, nitrogen, oxygen or hydrogen, the both in the detergent and cleaner tablets used according to the invention be selected on the basis of economic as well as ecological aspects. preferred Effervescent systems consist of alkali metal carbonate and / or bicarbonate as well an acidifying agent which is suitable from the Aikatimetailsalzen in aqueous solution of carbon dioxide release.

In the alkali metal carbonates or bicarbonates, the sodium and potassium salts are made Cost reasons over the other salts clearly preferred. Of course you have to not the respective pure alkali metal carbonates or bicarbonates are used; Rather, mixtures of different carbonates and bicarbonates from washing technical Interest be preferred.

In preferred washing and cleaning agent tablets are used as effervescent 2 to 20 wt .-%, preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or -hydrogencarbonats and 1 to 15, preferably 2 to 12 and in particular 3 to 10 wt .-% an Acidifizierungsmittels, each based on the total tablets used. The salary individual masses of the substances mentioned may well be higher.

Acidifying agents which release carbon dioxide from the alkali salts in aqueous solution are For example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used. However, preferred are organic Acidifizierungsmittel used, wherein the citric acid is a particularly preferred Acidifizierungsmittel. However, it is also possible in particular to use the other solid mono-, oligo- and polycarboxylic acids. Again preferred from this group are tartaric acid, succinic acid, malonic acid, adipic acid, Maleic acid, fumaric acid, oxalic acid and polyacrylic acid. Organic sulfonic acids such as sulfamic acid are also usable. Commercially available and as Acidifizierungsmittel in Sokalan® DCS (Trademark BASF), a mixture of succinic acid (max 31 wt .-%), glutaric acid (max 50 wt .-%) and adipic acid (max 33 wt%).

In the context of the present invention, detergent tablets and cleansing agent tablets are preferred those as Acidifizierungsmittel in the effervescent system, a substance from the group of organic di-, tri-and Oligocarbonsäuren or mixtures of these are used.

Grayness inhibitors have the task of removing the dirt removed from the fiber in the fleet to keep it suspended and thus prevent the dirt from being rebuilt. These are water-soluble colloids mostly organic nature suitable, for example, the water-soluble salts polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids or the Cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also water-soluble, Acidic group-containing polyamides are suitable for this purpose. Continue to leave use soluble starch preparations and other than the above starch products, e.g. degraded starch, aldehyde levels, etc. Also polyvinylpyrrolidone is useful. Prefers however, cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof in amounts of 0.1 to 5 wt .-%, based on the means used

As textile fabrics, in particular of rayon, rayon, cotton and their mixtures, to Knittem own, because the Einzelfasem against sagging, kinking. Pressing and squeezing are sensitive to transverse to the fiber direction, the well tablets synthetic crease inhibitors contain. These include, for example, synthetic products based on fatty acids, Fatty acid esters. Fatty acid amides, alkylol esters, alkylolamides or fatty alcohols which usually reacted with ethylene oxide, or products based on lecithin or modified Organophosphate.

To combat microorganisms, the well tablets may contain antimicrobial agents. Here one differentiates depending on the antimicrobial spectrum and mechanism of action between bacteriostats and bactericides, fungiostats and fungicides, etc. Important substances These groups include, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and Phenolmercuriacetat, which can be completely dispensed with these compounds.

Unwanted changes caused by oxygen and other oxidative processes To prevent the agents and / or the treated textiles, the agents can antioxidants contain. This class of compounds includes, for example, substituted phenols, Hydroquinones, catechols and aromatic amines as well as organic sulfides, polysulfides, Dithiocarbamates, phosphites and phosphonates.

Increased comfort may result from the additional use of antistatic agents which the agents prepared according to the invention are additionally attached. Antistatic agents increase the Surface conductivity and thus allow improved drainage of formed charges. External antistatic agents are usually substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. This mostly surfactant antistatic agents can be converted into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) Divide antistatic agents. The lauryl (or stearyl) dimethylbenzylammonium chlorides are suitable as antistatic agents for textiles or as an additive to detergents, with an additional finishing effect is achieved.

To improve the water absorbency, the rewettability of the treated Textiles and to facilitate the ironing of the treated textiles can in the mortar tablets Silicone derivatives are used. These additionally improve the rinsing behavior of the Agent by their foam-inhibiting properties. Preferred silicone derivatives are, for example Polydialkyl- or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes, optionally be derivatized and are then amino-functional or quaternized or Si-OH-, Have Si-H and / or Si-Cl bonds. The viscosities of the preferred silicones are included 25 ° C in the range between 100 and 100,000 centistokes, with the silicones in quantities between 0.2 and 5 wt .-%, based on the total agent can be used.

Finally, the mortar tablets according to the invention may also contain UV absorbers on apply the treated textiles and improve the lightfastness of the fibers. Links, which have these desired properties are, for example, by non-radiative Deactivation of effective compounds and derivatives of benzophenone with substituents in 2- and / or 4-position. Furthermore, substituted benzotriazoles, in the 3-position phenyl-substituted Acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes as well as natural substances such as umbelliferone and the body's own urocanic acid suitable.

The mortar tablets according to the invention are particularly suitable for further ingredients in the To incorporate cavity. In this case, for example, a liquid poured into the trough caused by cooling, solidification, chemical reaction, delayed water retention, Change the rheological properties, etc. is solidified. But it is also possible, particulate To provide fillings for the cavity, which are fastened in the cavity by adhesion promoter become. A special case of this is the insertion of a single particle (hereinafter also referred to as "core"), either by the use of adhesion promoters or by physical Forces in the cavity are liable. Last but not least, a particulate premix can enter the trough pressed in and also form a phase there. When using adhesion promoters can these are introduced into the well either before the dosage of the cavity filling, or afterwards ( "Spray effect"). The application of adhesion promoters is particularly necessary if the subsequently applied active substances alone do not have sufficient adhesiveness to remain at least partially in the cavity and the mechanical loads to withstand packaging, transport and handling without abrasion. The bonding agent Thus, in the case of cores that are not sufficiently adhesive, it is used to "stick" these substances or compounds.

As a primer substances can be used to the molding surfaces to which they applied give sufficient adhesiveness ("stickiness"), so that in the subsequent process step permanently attached to the surface of applied substances. In principle, they offer themselves Here the mentioned in the relevant adhesive literature and in particular in the monographs thereto Substances, wherein in the context of the present invention, the application of Melting, which act at higher temperatures adhesion, but not after cooling more sticky, but firm, has a special meaning.

Melting of one or more substances with a melting range of 40 ° C to 75 ° C are as Adhesion promoters preferred.

At the adhesion promoter various requirements are made, on the one hand the Schmelzbeziehungsweise Solidification behavior, on the other hand, however, the material properties in the solidified area at ambient temperature. As applied to the molding Layer of adhesion promoter, the "stuck" active substances during transport or storage permanently should, it has a high stability against, for example, in packaging or transport have occurring impact loads. The bonding agents should therefore either at least partially have elastic or at least plastic properties in order to an occurring Impact stress by elastic or plastic deformation to respond and not to break. The Adhesion promoters should have a melting range (solidification range) in such a temperature range have, in which the applied active materials are not exposed to high thermal stress become. On the other hand, however, the melting range must be sufficiently high to at least slightly elevated temperature nor to provide effective adhesion of the applied active ingredients. According to the invention, the coating substances preferably have a melting point above 30 ° C. The width the melting range of the primer also has an immediate effect on the Procedure: The provided with primer body must in the following Process step are brought into contact with the applied active substances, In the meantime, the adhesion must not be lost. After absorption of the active substances the adhesion should be reduced as quickly as possible in order to avoid unnecessary loss of time or Caking and stagnation in subsequent process steps or handling and Avoid packaging. In the case of the use of melts, the reduction of the Adherence by cooling (for example, blowing cold air) are supported.

It has proved to be advantageous if the adhesion promoters do not have a sharply defined melting point show how it usually occurs in pure, crystalline substances, but one under Circumstances have several degrees Celsius melting range.

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

The above properties are usually met by so-called waxes. Under "Waxing" is understood to mean a number of natural or artificial substances, usually melt above 40 ° C without decomposition and relatively little above the melting point low viscosity and non-stringy. They have a strong temperature-dependent Consistency and solubility.

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

Natural waxes include, for example, vegetable waxes such as candelilla wax, Carnauba wax, japan wax, esparto wax, cork wax, guaruma wax, rice germ oil wax, Sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, Shellac wax, spermaceti, lanolin (woolwax), or raffia fat, mineral waxes such as ceresin or Ozokerite (ground wax), or petrochemical waxes such as petrolatum, paraffin waxes or Microcrystalline waxes.

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

Synthetic waxes are generally polyalkylene waxes or polyalkylene glycol waxes Understood. Compounds which can also be used as adhesion promoters are compounds from other classes of substances, which are the meet the requirements regarding the softening point. As suitable synthetic Compounds, for example, have higher esters of phthalic acid, in particular Dicyclohexyl phthalate, which is commercially available under the name Unimoll® 66 (Bayer AG), proved. Also suitable are synthetically produced waxes from lower carboxylic acids and Fatty alcohols, for example dimyristyl tartrate, sold under the name Cosmacol® ETLP (Condea) Conversely, synthetic or partially synthetic esters of lower alcohols are also available Fatty acids can be used from natural sources. For example, the Tegin® 90 falls into this class of substances (Goldschmidt), a glycerol monostearate palmitate. Also shellac, for example shellac KPS three-ring SP (Kalkhoff GmbH) can be used according to the invention as a primer.

Likewise to the waxes in the context of the present invention are, for example, the Calculated so-called wax alcohols. Wax alcohols are higher molecular weight, water-insoluble Fatty alcohols with usually about 22 to 40 carbon atoms. The waxy alcohols come for example in the form of wax esters of higher molecular weight fatty acids (wax acids) as the main constituent many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), Cetyl alcohol, myristyl alcohol or melissyl alcohol. The in step b) optional If appropriate, adhesion promoters to be applied may also contain wool wax alcohols, among which Triterpenoid- and steroid alcohols, such as lanolin, understands, for example, under the Trade name Argowax® (Pamentier & Co) is available. Also at least proportionately as Component of the adhesion promoter can be used 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.

The adhesion promoters preferably contain paraffin wax in the predominant proportion. It means that preferably at least 50% by weight of the adhesion promoters, preferably more, of paraffin wax consist. Particularly suitable are paraffin wax contents in the adhesion promoter of about 60 wt .-%, about 70 wt .-% or about 80 wt .-%, with even higher levels of, for example, more than 90 wt .-% are particularly preferred.

Paraffin waxes have, compared to the other mentioned, natural waxes in the context of present invention has the advantage that in an alkaline detergent environment no Hydrolysis of waxes takes place (as can be expected, for example, in the Wachsestem) 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 having a melting point of more than 70 ° C, more preferably more than 60 ° C on. Shares of high-melting alkanes in the paraffin can fall below this Melting temperature in the cleaning agent unwanted wax residue on the zu leave cleansing surfaces or the goods to be cleaned. Such wax residues usually lead to an unsightly appearance of the cleaned surface and therefore should be avoided.

Preferably, the content of the paraffin wax used is at ambient temperature (in the Usually about 10 to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes as high as possible. The more solid wax components are present in a wax at room temperature, the more useful it is in the context of the present invention as a primer. With increasing proportion of fixed Wax constituents increases the strength of the adhesive layer against shocks or Friction on other surfaces, resulting in a longer-lasting clinging of the wrapped Active ingredients results in high levels of oils or liquid wax components can lead to a Weakening of the particle adhesion, whereby the adhered active substances differ from the shaped body to solve.

In addition to paraffin as the main constituent, the adhesion promoters may contain one or more of the above mentioned waxes or waxy substances. Basically, the bonding agents should be such that the "adhesive layer" is at least largely insoluble in water. The solubility in water at a temperature of about 30 ° C should not exceed about 10 mg / l, and preferably below 5 mg / l.

If a temperature-controlled release of the adhered active substances is desired, the Adhesion promoters the lowest possible solubility in water, even in water at elevated temperature, have as possible to a temperature-independent release of the coated active ingredients largely avoided.

The adhesion promoters can be pure substances or substance mixtures. In the latter case, the Melt contain varying amounts of adhesion promoters and excipients.

The principle described above serves the delayed detachment of the "glued" Active substances at a certain time, for example in the cleaning of a Dishwasher and can be particularly advantageous to use when in the main rinse with lower temperature (for example 55 ° C) is rinsed, so that the active substance from the Adhesive layer is only released in the rinse cycle at higher temperatures (about 70 ° C).

However, the said principle can also be reversed to the effect that the active substance (s) of The adhesive layer does not delay, but accelerates to be released. This can be easier Achieve way in that as a primer not Löseverzögerer, sondem dissolution accelerator be used so that the adhered active substances do not dissolve more slowly from the molding, but faster. In contrast to the poorly water-soluble described above Bonding agents, preferred adhesion promoters are readily soluble in water for rapid release. The Water solubility of the adhesion promoter can be significantly increased by certain additives, for example, by incorporation of slightly soluble salts or effervescent systems. Such Dissolution-accelerated adhesion promoter (with or without additives 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 become. Detailed comments can be found below.

As adhesion promoter for the accelerated release of the active substances from the washing and cleaning agent molding In particular, synthetic waxes from the group of polyethylene glycols are suitable and polypropylene glycols.

Polyethylene glycols (abbreviation PEG) which can be used according to the invention are polymers of ethylene glycol which are of general formula III H- (O-CH ₂ -CH ₂ ) _n -OH satisfy, where n can assume values between 1 (ethylene glycol) and over 100,000. Decisive in the assessment of whether a polyethylene glycol is used according to the invention, is the state of aggregation of the PEG, ie the melting point of the PEG must be above 30 ° C, so that the monomer (ethylene glycol) and the lower oligomers with n = 2 to approx 16 can not be used because they have a melting point below 30 ° C. The polyethylene glycols with higher molecular weights are polymolecular, ie they consist of groups of macromolecules with different molecular weights. For polyethylene glycols there are various nomenclatures that can lead to confusion. Technically common is the indication of the average relative molecular weight following the indication "PEG", so that "PEG 200" characterizes a polyethylene glycol having a relative molecular weight of about 190 to about 210. According to this nomenclature, the commercially available polyethylene glycols PEG 1550, PEG 3000, PEG 4000 and PEG 6000 are preferably used in the context of the present invention.

For cosmetic ingredients, a different nomenclature is used, in which the abbreviation PEG is hyphenated and directly followed by the hyphen a number corresponding to the number n in the above formula III. According to this nomenclature (so-called INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 ^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997) according to the invention, for example, PEG-32, PEG-40, PEG-55, PEG- 60, PEG-75, PEG-100, PEG-150 and PEG-180 are preferably used according to the invention.

Commercially available are polyethylene glycols, for example under the trade name Carbowax® PEG 540 (Union Carbide), Emkapol® 6000 (ICI Americas), Lipoxol® 3000 MED (HUBS America), Polyglycol® E-3350 (Dow Chemical), Lutrol® E4000 (BASF) and the corresponding trade names with higher numbers.

genügen, wobei n Werte zwischen 1 (Propylenglycol) und ca. 1000 annehmen kann. Ähnlich wie bei den vorstehend beschriebenen PEG kommt es bei der Bewertung, ob ein Polypropylenglycol erfindungsgemäß einsetzbar ist, auf den Aggregatzustand des PPG an, d.h. der Schmelzpunkt des PPG muß oberhalb von 30 °C liegen, so daß das Monomer (Propylenglycol) sowie die niederen Oligomere mit n = 2 bis ca. 15 nicht einsetzbar sind, da sie einen Schmelzpunkt unterhalb von 30°C aufweisen.Polypropylene glycols which can be used according to the invention (abbreviated PPG) are polymers of propylene glycol which are of general formula IV

satisfy, where n can assume values between 1 (propylene glycol) and about 1000. Similar to the PEG described above, the evaluation of whether a polypropylene glycol is used according to the invention, on the physical state of the PPG, ie the melting point of the PPG must be above 30 ° C, so that the monomer (propylene glycol) and the lower Oligomers with n = 2 to about 15 can not be used because they have a melting point below 30 ° C.

In addition to the preferably used as adhesion promoters PEG and PPG are of course also Other substances can be used provided they have a sufficiently high water solubility and a Melting point above 30 ° C.

Preferred adhesion promoters according to the invention are one or more substances from the groups the paraffin waxes, preferably with a melting range of 50 ° C to 55 ° C, and / or the Polyethylene glycols (PEG) and / or polypropylene glycols (PPG) and / or the natural waxes and / or the fatty alcohols.

In addition to melting, other substances can be applied as adhesion promoters. For this For example, concentrated salt solutions are suitable after application of the active ingredients Crystallization or evaporation / evaporation are transferred into an adhesion-promoting salt crust. Of course, supersaturated solutions or solutions can also be used of salts in solvent mixtures.

Also suitable as adhesion promoters are solutions or suspensions of water-soluble or dispersible polymers, preferably polycarboxylates. The substances mentioned were further already described above due to their co-builder characteristics.

Other particularly suitable adhesion promoters are solutions of water-soluble substances the group (acetalated) polyvinyl alcohol, polyvinylpyrrolidone, gelatin and mixtures thereof.

Polyvinyl alcohols, referred to as PVAL for short, are polymers of the general structure [-CH ₂ -CH (OH) -] _n in small proportions also structural units of the type [-CH ₂ -CH (OH) -CH (OH) -CH ₂ ] contain. Since the corresponding monomer, the vinyl alcohol, is not stable in free form, polyvinyl alcohols are prepared via polymer-analogous reactions by hydrolysis, but especially by alkaline-channeled transesterification of polyvinyl acetates with alcohols (preferably methanol) in solution. These technical processes also make PVAL accessible. which contain a predeterminable residual amount of acetate groups.

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

The water solubility of PVAL can be improved by post-treatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid, Reduce borax and thus set specifically to desired values. Also the rheological properties PVAL solutions can be modified by changing the molecular weight or concentration adjust to the desired values, depending on how the solution is applied as a primer shall be.

beschreiben.Polyvinylpyrrolidones, referred to as PVP for short, may be represented by the general formula

describe.

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

Gelatine is a polypeptide (molecular weight: approx. 15,000-> 250,000 g / mol), primarily by hydrolysis of the collagen contained in the skin and bones of animals under acid or alkaline Conditions is won. The amino acid composition of gelatin corresponds largely that of the collagen from which it was obtained and varies depending on it Provenance. The use of gelatin as the water-soluble coating material is particularly useful in the Pharmaceutical in the form of hard or soft gelatin capsules extremely widespread.

In the context of the present invention, adhesion promoters from the group starch are also preferred and starch derivatives, cellulose and cellulose derivatives, in particular methylcellulose and mixtures thereof.

Starch is a homoglycan, wherein the glucose units are linked α-glycosidically. Strength is composed of two components of different molecular weight: from about 20-30% straight chain Amylose (M.W., about 50,000-150,000) and 70-80% branched-chain amylopectin (M.W. 300,000-2,000,000), in addition there are still small amounts of lipids, phosphoric acid and cations contain. While the amylose due to binding in 1,4-position long, helical, forms chains with about 300-1200 glucose molecules, the chain branches in the Amylopectin after an average of 25 glucose building blocks by 1,6-binding to a branch-like Formations with about 1500-12000 molecules of glucose. In addition to pure strength are for the production water-soluble bag in the present invention also starch derivatives by polymer-analogous reactions of starch are available. Such chemically modified starches include, for example, products of esterifications or etherifications in which hydroxy-hydrogen atoms were substituted. But also strengths in which the hydroxy groups have been replaced by functional groups that are not bound by an oxygen atom, can be used as starch derivatives. For example, fall into the group of starch derivatives Alkali starches, carboxymethyl starch (CMS), starch esters and ethers, and amino starches.

Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulosic adhesion promoters usable in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.

Preferred adhesion promoters which can be used as aqueous solution consist of a Polymer having a molecular weight between 5000 and 500,000 daltons, preferably between 7500 and 250,000 daltons, and more particularly between 10,000 and 100,000 daltons. The after drying the bonding agent between the individual molding body areas (Muldenwandung and second Part) present layer of the adhesion promoter preferably has a thickness of 1 to 150 microns, preferably from 2 to 100 μm, particularly preferably from 5 to 75 μm and in particular from 10 up to 50 μm, up.

After application of the primer further active substances can be inserted into the cavity become. The active substances can be applied in solid, highly viscous or plastic form become.

The application of solid active substances in the cavity succeeds with apparatuses, for example from the confectionery industry are known. If a particulate solid is introduced into the cavity, so more than one body inserted into the hollow so are the introduced into the hollow Active substances based on this area hereinafter referred to as "sprinkles".

Depending on the type of spread dosage and depending on the shape and size of the sprinkles is the Metering accuracy with which a certain amount of additional active substance is applied, different high. In general, this dosing accuracy when applying crumbs with a certain fluctuation range of approx. +/- 10%. As active substances for those in the cavity solid crumbles to be introduced have proven to be particularly effective in the washing or cleaning should dissolve quickly, for example, enzymes.

As already mentioned, the crumbs can be produced in different shapes and sizes. In principle, under "crumbling" is also the gluing of a single metering unit in the cavity to understand, with this single metering unit naturally has a higher volume as the single volume of dosing units, which are introduced several times into the cavity. in the Thus, for example, a hemispherical crumb in the context of the present invention Mulde be glued. Also other forms for "Sprinkles" and moldings such as cubes, cuboids, Semi-ellipsoids, cylinder segments, prisms, etc. are thinkable and realizable.

However, preferred embodiments provide that the number of crumbs, which in the trough glued, is greater than 1. Such sprinkles then advantageously have the dimensions conventional washing and cleaning agent in powder, granule, extrudate, flake or platelet form and are glued in multiple numbers.

The introduction of further active substance in the cavity in the form of a single dosing unit is also prefers. So according to the invention is easily possible, two separately prepared moldings, which are form-fitting on or ineinanderfügbar, to glue together, wherein one of the moldings an inventive mortar tablet is. In addition to the insertion of individual dosing units, produced by other methods, such as casting, extrusion, compression molding, etc. In particular, separately manufactured tablets are available as a single dosing unit at.

A particularly preferred embodiment of the present invention provides that the Muldentablette has a cavity whose bottom and / or side surfaces optionally with adhesion promoter be provided, after which a separately prepared and in the cavity matching shaped body is glued. Alternatively, the application of the adhesion promoter can also be individual surfaces of the To be adhered molded body.

The cavity in the well tablet can - as already mentioned - have any shape. she can divide the shaped body, i. an opening at the top and bottom of the molding but it can also be a cavity that does not pass through the entire molded body, the opening of which is only visible on a molded body side.

The application of adhesion promoter can either in the molding with cavity or in the molding take place, which fills the cavity. Bonding agent is preferred in the cavity of the molding brought in.

This procedure is well feasible Muldenformkörpern because the dosage simply by Dripping of liquid adhesion promoters in the trough can be realized. Suitable dosing systems for the large-scale dosing small amounts of liquid in cavities are those skilled in the art well known.

Often it is technically easier to apply adhesion promoter to the cavity filling Make moldings. In such cases, it is preferred to apply primer to one or more Apply surfaces, preferably on one surface, to the individual dosing unit.

This application of adhesion promoter on preferably an area of the individual metering unit can be done in different ways. For example, it is possible to use the separate dosing unit in the dipping process one-sidedly with adhesive to wet and then in the cavity to place. This technology is technologically easy to implement, but carries the risk that Adhesive contaminates the surface of the molding with cavity. The amount of glue can controlled in this variant by varying the rheological properties of the adhesion promoter become.

Another and preferred in the context of the present invention, adhesion promoters on preferably to apply an area of the individual metering unit, is this metering unit past adhesive dosing systems and then place in the cavity. This is achieved by adhesion promoter dosing nozzles, impregnated with primer brushes or Nonwovens or by rolling. The latter method design is particularly easy to implement, that the separate dosing unit has only a small contact surface to the roller The adhesion promoter can be dosed from the interior of the roller, but it is also possible, the bonding agent at a point from the point of contact of the roller with the separate metering units away, apply to the roller.

The filling of the cavity can fill the cavity completely, but it can also fill the cavity stand out or only partially fill them, leaving the imagination of the product developers no Limits are set. By varying the shape of the well tablets according to the invention, the Shape of the trough or the hole and the shape of the separate dosing unit can be varied Produce molded body variations that are visually very different from each other.

With the mold bodies, the adhesion of the separate metering unit in the cavity decreases with decreasing Touchpad. Maximum adhesion between the two moldings is achieved if the molded body and the separate dosing unit without gaps fit together form-fitting.

Completely analogous to the above-described preparation of two-phase Formkörpem by On or sticking together of two separately pressed Formkörpem can also be three-phase Shaped bodies are produced. Here is either the pasting of two separately prepared Moldings in a well tablet with two cavities, but it is also possible and preferred to prepare a biphasic, for example a two-layer, gauze tablet and to insert another molded body in this.

The said principle can be correspondingly applied to further multi-phase detergent tablets expand. Thus, for example, four-phase moldings can be produced by two biphasic moldings (inventive two-phase mold body and two-phase "Kem") are interconnected.

As regards the composition of the second part optionally to be introduced into the cavity, are the design possibilities also no limits. For example, it is possible to incorporate certain ingredients into the second part so as to remove them from the ingredients in the Separate debit tablets according to the invention. Of course, the second part can also contain several ingredients or in themselves a complete detergent or cleaning composition be. It is particularly preferred in the context of the present invention, if the second part is made up so that it in the washing or cleaning process an additional Effect unfolds. For automatic dishwashing detergents it is preferred to use "kernels" to be used in the well tablets which serve the function of a "pre-rinse phase", a "performance booster" or a "final rinse phase", i. at predetermined times in the cleaning cycle Certain ingredients (in the first case, for example, enzymes, in the second case, for example Bleaching agent and in the third case, for example, surfactants or scale-inhibiting polymers or Acids). It is particularly preferred to incorporate ingredients in the "core" which the make additional dosage unnecessary otherwise necessary means, for example Rinse aid or regenerating salt. In the former case, the "core" represents a final rinse phase, in In the latter case, salt substitutes are incorporated into the "core" necessary for binding the Provide water hardness and thus allow rinsing with hard water, without causing limescale on the dishes or machine parts comes.

Washing or cleaning agent tablets according to the invention are therefore particularly preferred additionally have a second part, the shape of a core or on or in the first part ("base tablet") glued body and preferably one or more substances from the group of builders, acidifiers, chelating agents or scale-inhibiting agents Contains polymers.

Builders and acidifiers have already been described above. Another possible Group of ingredients for the second part are the chelating agents. Chelating agents are substances that form cyclic compounds with metal ions, where a single Ligand occupies more than one coordination site on a central atom, i. H. at least "bidentate" is. In this case, normally stretched verbs are formed by complex formation over a lon to rings closed. The number of bound ligands depends on the coordination number of the central lone.

Common and preferred chelate complex images within the scope of the present invention are for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Also complexing polymers, ie polymers which are either in the Main chain or self-supporting to this functional groups that act as ligands can and with suitable metal atoms usually to form chelate complexes react,. are used according to the invention. The polymer-bound ligands of the resulting Metal complexes can come from just one macromolecule or different ones Belong to polymer chains. The latter leads to the networking of the material, provided that the complex-forming Polymers were not previously crosslinked via covalent bonds.

Complexing groups (ligands) of conventional complex-forming polymers are iminodiacetic acid, Hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic, amidoxime, aminophosphoric, (cycl.) Polyamino, mercapto, 1,3-dicarbonyl and crown ether radicals with z. T. very specific. Activities towards ions of different metals. Many base polymers too commercially significant complexing polymers are polystyrene, polyacrylates, polyacrylonitriles, Polyvinyl alcohols, polyvinylpyridines and polyethyleneimines. Also natural polymers like cellulose, Starch or chitin are complexing polymers. In addition, these may be due to polymer analogues Transformations are provided with additional ligand functionalities.

(i) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt,

(ii) stickstoffhaltigen Mono- oder Polycarbonsäuren,

(iii) geminalen Diphosphonsäuren,

(iv) Aminophosphonsäuren,

(v) Phosphonopolycarbonsäuren,

(vi) Cyclodextrine

in Mengen oberhalb von 0,1 Gew.-%, vorzugsweise oberhalb von 0,5 Gew.-%, besonders bevorzugt oberhalb von 1 Gew.-% und insbesondere oberhalb von 2,5 Gew.-%, jeweils bezogen auf das Gewicht des zweiten Teils, enthält.In the context of the present invention, washing or cleaning agent tablets having a "second part" inserted in the cavity are particularly preferred, in which the second part comprises one or more chelate complexing agents from the groups of

(i) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5,

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

(iii) geminal diphosphonic acids,

(iv) aminophosphonic acids,

(v) phosphonopolycarboxylic acids,

(vi) cyclodextrins

in amounts above 0.1 wt .-%, preferably above 0.5 wt .-%, more preferably above 1 wt .-% and in particular above 2.5 wt .-%, each based on the weight of second part, contains.

a) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt wie Gluconsäure,

b) stickstoffhaltige Mono- oder Polycarbonsäuren wie Ethylendiamintetraessigsäure (EDTA), N-Hydroxyethylethylendiamintriessigsäure, Diethylentriaminpentaessigsäure, Hydroxyethyliminodiessigsäure, Nitridodiessigsäure-3-propionsäure, Isoserindiessigsäure, N,N-Di-(β-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-asparaginsäure oder Nitrilotriessigsäure (NTA),

c) geminale Diphosphonsäuren wie 1-Hydroxyethan-1,1-diphosphonsäure (HEDP), deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon und 1-Aminoethan-1,1-diphosphonsäure, deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon,

d) Aminophosphonsäuren wie Ethylendiamintetra(methylenphosphonsäure), Diethylentriaminpenta(methylenphosphonsäure) oder Nitrilotri(methylenphosphonsäure),

e) Phosphonopolycarbonsäuren wie 2-Phosphonobutan-1,2,4-tricarbonsäure sowie

f) Cyclodextrine.

In the context of the present invention, all complexing agents of the prior art can be used. These can belong to different chemical groups. Preferably, used individually or in admixture with each other:

a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, such as gluconic acid,

b) nitrogen-containing mono- or polycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, nitridodiacetic acid-3-propionic acid, isoserinediacetic acid, N, N-di- (β-hydroxyethyl) -glycine, N- (1,2- Dicarboxy-2-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid or nitrilotriacetic acid (NTA),

c) geminal diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), their higher homologues having up to 8 carbon atoms and hydroxy- or amino-containing derivatives thereof and 1-aminoethane-1,1-diphosphonic acid whose higher homologues with up to 8 carbon atoms and hydroxyl- or amino-containing derivatives thereof,

d) aminophosphonic acids, such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) or nitrilotri (methylenephosphonic acid),

e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid and

f) cyclodextrins.

As polycarboxylic acids a) are in the context of this patent application carboxylic acids - also monocarboxylic acids - understood, in which the sum of carboxyl and contained in the molecule Hydroxyl groups is at least 5. Complexing agent from the group of nitrogen-containing polycarboxylic acids, especially EDTA, are preferred. In the invention required alkaline pH values of the treatment solutions, these Komplexbilner are at least partially as anions. It is irrelevant whether they are introduced in the form of acids or in the form of salts become. In the case of use as salts are alkali, ammonium or alkylammonium salts, especially sodium salts, preferred.

In the case of the scale-inhibiting polymers as an ingredient of the second part are in particular Detergent tablets preferred, characterized in that the second part one or more scale-inhibiting polymers from the group of cationic homoders Copolymers, in particular hydroxypropyltrimethylammonium guar; Copolymers of aminoethyl methacrylate and acrylamide, copolymers of dimethyldiallylammonium chloride and acrylamide, Polymers with imino groups, polymers, which are quaternized as monomer units Ammoniumalkylmethacrylatgruppen cationic polymers of monomers such as trialkylammonium alkyl (meth) acrylate or -acrylamide; Dialkyldiallyldiammoniumsalze; polymer-analogous reaction products of ethers or esters of polysaccharides having pendant ammonium groups, in particular Guar, cellulose and starch derivatives; Polyadducts of ethylene oxide with ammonium groups; quaternary ethyleneimine polymers and polyesters and polyamides having pendant quaternary groups in amounts above 5 wt .-%, preferably above 10 wt .-%, particularly preferably above 20 wt .-% and in particular above 25 wt .-%, each based on the Weight of the second part, contains.

i) ungesättigten Carbonsäuren

ii) Sulfonsäuregruppen-haltigen Monomeren

iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren

in Mengen oberhalb von 5 Gew.-%, vorzugsweise oberhalb von 10 Gew.-%, besonders bevorzugt oberhalb von 20 Gew.-% und insbesondere oberhalb von 25 Gew.-%, jeweils bezogen auf das Gewicht des zweiten Teils, enthält, bevorzugte Ausführungsformen der vorliegenden Erfindung.Another preferred ingredient for the second part are certain sulfonic acid group-containing copolymers. So are washing or cleaning tablets, the second part of one or more copolymers

i) unsaturated carboxylic acids

ii) sulfonic acid group-containing monomers

iii) optionally further ionic or nonionic monomers

in amounts above 5 wt .-%, preferably above 10 wt .-%, more preferably above 20 wt .-% and in particular above 25 wt .-%, each based on the weight of the second part, contains, preferred Embodiments of the present invention.

In the context of the present invention, unsaturated carboxylic acids of the formula V are preferred as the monomer, R ¹ (R ² ) C = C (R ³ ) COOH in the R ¹ to R ³ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids which can be described by the formula V are in particular acrylic acid (R ¹ = R ² = R ³ = H), methacrylic acid (R ¹ = R ² = H, R ³ = CH ₃ ) and / or maleic acid (R ¹ = COOH; R ² = R ³ = H) is preferred.

In the sulfonic acid-containing monomers, those of the formula VI are preferred, R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H in R ⁵ to R ⁷ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas Vla, Vlb and / or Vlc, H ₂ C = CH-X-SO ₃ H H ₂ C = C (CH ₃ ) -X-SO ₃ H HO ₃ SX (R ⁶⁾ C = C (R ⁷⁾ -X-SO ₃ H in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₂ CH ₃ ) in formula Vla), 2-acrylamido-2-propanesulfonic acid (X = -C ( O) NH-C (CH ₃ ) ₂ in formula Via), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula Vla), 2 -Methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula VIb), 3-methacrylamido-2-hydroxypropanesulfonic acid (X = -C (O) NH-CH ₂ CH (OH) CH ₂ - in formula VIb), allylsulfonic acid (X = CH ₂ in formula Vla), methallylsulfonic acid (X = CH ₂ in formula VIb), allyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula Vla), methallyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula VIb), 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid (X = CH ₂ in formula VIb), styrenesulfonic acid (X = C ₆ H ₄ in formula VIA), vinylsulfonic acid (X not present in formula Vla), 3-sulfopropyl acrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in Formula Vla), 3-Sul fopropyl methacrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in formula VIb), sulfomethacrylamide (X = -C (O) NH- in formula VIb), sulfomethylmethacrylamide (X = -C (O) NH-) CH ₂ - in formula VIb) and water-soluble salts of said acids.

As further ionic or nonionic monomers are in particular ethylenically unsaturated Compounds considered. The content is preferably that used according to the invention Polymers of monomers of group iii) less than 20 wt .-%, based on the polymer. Particularly preferred polymers contained in the second part consist only of monomers of Groups i) and ii).

i) einer oder mehrerer ungesättigter Carbonsäuren aus der Gruppe Acrylsäure, Methacrylsäure und/oder Maleinsäure

ii) einem oder mehreren Sulfonsäuregruppen-haltigen Monomeren der Formeln VIa, VIb und/oder Vlc: H₂C=CH-X-SO₃H H₂C=C(CH₃)-X-SO₃H HO₃S-X-(R⁶)C=C(R⁷)-X-SO₃H in der R⁶ und R⁷ unabhängig voneinander ausgewählt sind aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂ und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_nmit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)-

iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren.

Particularly preferred laundry detergent or detergent tablets contain one or more copolymers in the second part

i) one or more unsaturated carboxylic acids from the group of acrylic acid, methacrylic acid and / or maleic acid

ii) one or more sulfonic acid group-containing monomers of the formulas VIa, VIb and / or VIc: H ₂ C = CH-X-SO ₃ H H ₂ C = C (CH ₃ ) -X-SO ₃ H HO ₃ SX (R ⁶⁾ C = C (R ⁷⁾ -X-SO ₃ H in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -

iii) optionally further ionic or nonionic monomers.

The copolymers contained in the second part may contain the monomers from groups i) and ii) and, where appropriate, (iii) in varying amounts, all representatives of the Group i) with all representatives from group ii) and all representatives from the group iii) can be combined. Particularly preferred polymers have certain structural units on, which are described below.

Thus, for example, washing or cleaning agent tablets according to the invention are preferred which are characterized in that one or more copolymers are contained in the second part, the structural units of the formula VII - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative. Copolymerizing the sulfonic acid-containing acrylic acid derivative with methacrylic acid, one arrives at another polymer whose use in the second part of the cleaning agents according to the invention is also preferred and characterized in that one or more copolymers are used, the structural units of formula VIII - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ CHC (O) -Y-SO ₃ H] _p - in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. For example, washing or cleaning agent tablets according to the invention are preferred, the second part of which comprises one or more copolymers which contain structural units of the formula IX - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals containing 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, preferably, also a preferred embodiment of the present invention, just as detergent or detergent tablets are preferred, which are characterized in that the second part contains one or more copolymers, the structural units of the formula X. - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

Instead of acrylic acid and / or methacrylic acid or in addition thereto, maleic acid can also be used as a particularly preferred monomer from group i). This gives way to inventively preferred washing or cleaning agent tablets, which are characterized in that one or more copolymers are contained in the second part, the structural units of the formula XI - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is, are preferred and to detergent tablets, which are characterized in that the second part contains one or more copolymers, the structural units of the formula XII - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

In the polymers, the sulfonic acid groups can be completely or partially in neutralized form, i.e. that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups against metal ions, preferably alkali metal ions and in particular against sodium ions, can be exchanged. Appropriate detergents characterized are that the sulfonic acid groups in the copolymer partially or fully neutralized, are according to the invention prefers.

The monomer distribution in the copolymers according to the invention contained in the second part is in the case of copolymers which contain only monomers from groups i) and ii), preferably in each case 5 to 95 wt .-% i) or ii), particularly preferably 50 to 90 wt .-% monomer from the group i) and 10 to 50 wt .-% of monomer from group ii), each based on the polymer.

In the case of terpolymers, particular preference is given to those which contain from 20 to 85% by weight of monomer Group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer Group iii).

The molecular weight of the polymers according to the invention contained in the second part can be varied in order to adapt the properties of the polymers to the desired end use. Preferred cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

In addition to the added benefit of being able to do without the dosage of Regeneriersalz make the preferred products according to the invention described above also the additional Dosing a rinse aid superfluous.

The parent application detergent tablets according to the invention, the at least a cavity and 5.5 to 25 wt .-% of nonionic (s) surfactant (s) having a melting point above 20 ° C, each based on the Tablet, may also be designed multiphase, wherein the content of the phase, the the cavity has, on nonionic surfactants from 5.5 to 25 wt .-%, is. Both the as- The multiphase washing or cleaning agent tablets according to the invention can additionally a second part having the shape of a core or one on the first Part ("base tablet") glued body has and preferably one or more substances from the group of builders, acidifiers, chelating agents or scale-inhibiting agents Contains polymers.

The above-described sulfonic acid-containing polymers cause their incorporation in the washing or cleaning tablets according to the invention a further additional benefit. It is initially irrelevant whether the sulfonic acid-containing polymers in the surfactant-rich Muldentablette ("basic tablet") itself or in another part ("core") or in both Parts are included. Other particular advantages, however, can be found in the distribution of the polymer on the two parts result.

Thus, cleaning agents according to the invention are preferred which, in addition to the nonionic surfactants have a content of sulfonic acid-containing polymers. In inventive Means of this embodiment causes the after the main rinse cycle and the intermediate rinses in the machine remaining amounts of surfactants adequate drainage behavior in the final rinse cycle, so that the effluent from the wash water leaves no stains during drying. In addition, the sulfonic acid group-containing polymer used acts as an effective softener, so that can be rinsed with non-softened water even in high hardness areas without it comes to coverings on the dishes or machine. The rinse requires when using this inventive agent is not charged with additional intentionally added rinse aid to be, and also on the use of regenerating salt can be omitted. In the The products described in this additional application are thus genuine '3in1' products, which are the Combine cleaner, rinse aid and regenerating salt in one medium.

i) ungesättigten Carbonsäuren

ii) Sulfonsäuregruppen-haltigen Monomeren

iii) gegebenenfalls weiteren ionischen oder nichtionogenen Monomere

enthalten.Another object of the present invention are therefore detergent or cleaner tablets according to the invention, which additionally comprises from 0.1 to 70 wt .-% of copolymers

i) unsaturated carboxylic acids

ii) sulfonic acid group-containing monomers

iii) optionally further ionic or nonionic monomers

contain.

In the case of multiphase tablets, a corresponding one is sufficient analogously to the above information Composition of the phase comprising the cavity, i. of the premix, which with the non-planning punch at the final compression comes into contact. As in precompression steps (For example, in the preparation of two-layer tablets) the first premix by Andrükken with the stamp is only slightly compressed, occur here no adhesion or edge breakage phenomena on. Only at the final compression, the forces are so great that the above Problems are to be feared.

Earlier, the use of sulfonated Cpolymere in a second part, which has already been as "core" in the surfactant-rich mortar tablet ("base tablet") is inserted or glued. The However, sulfonated copolymers can be incorporated not only in the "core" but also in the base tablet, cores optionally present in the base tablets, the copolymer (s) contain or be free from it.

Regardless of where the / the sulfonated copolymers in the inventive washing or Detergent tablets are preferred, such detergent or cleaning tablets are preferred, the sulfonated copolymer (s) in amounts of 0.25 to 50 wt .-%, preferably from 0.5 to 35% by weight, more preferably from 0.75 to 20% by weight and especially from 1 to 15 wt .-%, each based on the total tablet included.

The sulfonated copolymers are broadly described above, so that reference may be made to the statements there. In general, washing or cleaning agent tablets which contain one or more copolymers which are structural units of the formulas VII and / or VIII and / or IX and / or X and / or XI and / or XII are also preferred - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

Particularly preferred sulfonic acid-containing monomers are as already above mentions 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propane-sulfonic acid, 2-acrylamido-2-methyl-1-propane-sulfonic acid, 2-Methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, Allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, Methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen-1-sulfonic acid, Styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, Sulfomethacrylamid, sulfomethylmethacrylamide and water-soluble salts of said Acids.

As can be seen from the above statements, a "core" in the surfactant-rich depression tablet glued, which also contain the sulfonated or the copolymer (s) can. Here are those detergent or detergent tablets are preferred, in addition to a second part having the shape of a core or one on the first part ("base tablet") glued body and - based on the weight of the core - 1 to 80 wt .-%, preferably 2.5 to 70 wt .-%, particularly preferably 5 to 60 wt .-% and in particular 10 to 50% by weight of the sulfonated copolymer (s / e).

Irrespective of whether a "core" is inserted or glued into the tablets according to the invention the tablets themselves may contain the sulfonated copolymer (s). Here are inventive Detergents or detergent tablets preferred in which the well tablet ("Base tablet") based on their weight 0.5 to 30 wt .-%, preferably 1 to 25 wt .-%, especially preferably from 2.5 to 20% by weight and in particular from 4 to 15% by weight of the sulphonated one Copolymer (s / e) contains.

It is particularly preferred if a core is present and both the core and the base tablet containing the sulfonated copolymer (s). The polymer is particularly advantageous not uniformly distributed in core and base tablet, but is mainly localized in the base tablet Here, washing or cleaning agent tablets according to the invention are preferred in which both the base tablet and the core contain the sulfonated copolymer (s), wherein at least 50% by weight, preferably at least 60% by weight and in particular at least 65% % By weight of the total sulfonated copolymer (s / e) contained in the tablet in the base tablet is included.

For earlier products, parts of the product had to be removed by appropriate measures such as Be protected from premature release into the application fleet, so that a controlled release of individual ingredients was achieved by the measures. Surprisingly, this is the case with the washing or cleaning agent tablets according to the invention not required, so that both the base tablet and optionally contained Core no coating is required to effect a rinse effect and on regenerating salt to be able to do without. Particularly preferred washing or cleaning agent tablets according to the invention are therefore characterized in that the core has no coating.

In addition to the combination of the inventively used sulfonic acid-containing polymers with nonionic surfactants in high amounts, agents according to the invention have been found to be particularly suitable in addition to the sulfonated copolymers other homo- and / or copolymeric polycarboxylic acids or contain polycarboxylates.

Also suitable are combinations of the sulfonated copolymers with heteroatom-containing Polymers or copolymers, especially those with amino or phosphono groups.

Here, washing or cleaning agent tablets according to the invention are particularly preferred, which additionally 0.1 to 30 wt .-% homo- and / or copolymeric polycarboxylic acids or their salts and / or heteroatom-containing polymers / copolymers, in particular those having amino or phosphono groups contain.

The corresponding homo- or copolymeric polycarboxylic acids or polycarboxylates are further described in detail above as a co-builder. The combination of the two polymers in these invention Means is particularly effective, since the sulfonated polymers in particular phosphate-containing Counteract deposits, while the carboxylate-containing polymers precipitation prevent calcium carbonate. In combination, both types of polymers show a synergistic Effect against deposits on the dishes and the machine parts.

The combination with amino- and / or phosphonogruppenhaltigen polymers / copolymers advantageous in builder systems, which only partially. phosphate-based, e.g. Phosphate / citrate mixing systems.

The time required for operating a domestic dishwasher at two intervals Dosage (After a certain number of rinses, the regeneration salt must be in the Water softening system of the machine are refilled), can be with the above-described inventive means to summarize a single operation, as well after a higher number of rinsing cycles, the dosage of another product (regenerating salt) and thus a double dosing is not necessary.

In addition to the added benefit of being able to do without the dosage of Regeneriersalz make the preferred products according to the invention described above also the additional. Dosing a rinse aid superfluous.

Another object of the present invention is a process for the preparation of washing or Detergent tablets having at least one cavity, wherein a particulate premix, its content of nonionic surfactants having a melting point above 20 ° C 5.5 to 25 wt .-%, each based on the premix, is pressed in a conventional manner to depression tablets.

As described in detail above, is sufficient for multi-phase / multi-layer tablets corresponding Niotensidgehalt in the phase / layer, which in the final compression contact with the Preßstempel has, which impresses the cavity. Another object of the present invention is Therefore, a method for producing multiphase washing or cleaning agent tablets with at least one cavity, in which several particulate premixes in per se known Be pressed into well tablets, wherein the content of the premix, the final compression the tablet is contacted with the stamp for the injection of the cavity, a Content of nonionic surfactants of from 5.5 to 25% by weight, in each case based on the premix, having a melting point above 20 ° C. having.

The tableting of the mono- or multiphase well tablets is analogous to conventional Tablettings, except that the pressing surface of at least one press ram is not is plan, but has at least one survey that the cavity (s) in the inventive Molded body. It has proved to be advantageous if the compressed premix meets certain physical criteria. For example, preferred methods characterized in that to be compressed particulate premixes a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l.

Also, the particle size of the compressed premix preferably satisfies certain criteria: Processes in which particulate premixes have particle sizes between 100 and 2000 μm, preferably between 200 and 1800 microns, more preferably between 400 and 1600 microns and especially between 600 and 1400 μm, are preferred according to the invention. One more Narrowed particle size in the premixes to be compressed may be more advantageous for obtaining Molded body properties are set. In preferred variants for the inventive Method to be compressed particulate premixes have a particle size distribution at, wherein less than 10 wt .-%, preferably less than 7.5 wt .-% and in particular less than 5 wt .-% of the particles are greater than 1600 microns or less than 200 microns. Here are narrower particle size distributions more preferred. Particularly advantageous process variants are characterized in that the to be compressed particulate premixtures a Particle size distribution, wherein more than 30 wt .-%, preferably more than 40 wt .-% and more preferably more than 50% by weight of the particles have a particle size between 600 and 1000 have μm.

When carrying out the tabletting, the process preferred according to the invention is not specified limited that only a particulate premix is pressed into a shaped body. Rather, this process step can also be extended to the effect that in known per se Way multilayer molded body produces by mixing two or more premixes prepares that are pressed together. In this case, the first-filled premix becomes light pre-compressed to get a smooth top and after filling in the second premix Endverpreßt the finished molded body. In the case of three-layered or multi-layered shaped bodies, the following occurs each pre-mix addition, one more pre-compression before adding the last pre-mix the molding is end-pressed. Preferably, the cavity described above is in Basic shaped body a trough, so that preferred embodiments of the first invention Method characterized in that multilayer moldings having a trough, be prepared in a conventional manner by several different particulate Premixes are pressed together. This must (if the upper punch the non-plane Preßstempel is) only the last premix meet the criteria of the invention - it can however, it may be desired that several or all premixes, despite otherwise different composition contain at least 5 wt .-% of nonionic surfactant (s).

The production of the moldings takes place first by the dry mixing of the ingredients, which may be pre-granulated in whole or in part, and subsequent informing, in particular Compress to tablets, using conventional methods. to Preparation of the shaped bodies according to the invention is the premix in a so-called template compressed between two stamps to a fixed compressed. This process, in the following short referred to as tableting, is divided into four sections: dosage, compaction (elastic deformation), plastic deformation and ejection.

First, the premix is introduced into the die, wherein the filling amount and thus the Weight and the shape of the resulting molded body by the position of the lower punch and the shape of the pressing tool can be determined. The constant dosage even at high Moldings throughputs are preferably via volumetric metering of the premix reached. As the tableting progresses, the upper punch touches the pre-mix and continues to lower in the direction of the lower punch. In this compression, the particles become of the premix is pressed closer to each other, wherein the void volume within the Filling between the punches decreases continuously. From a certain position of the upper punch (and thus from a certain pressure on the premix) begins the plastic deformation, in which the particles flow together and it comes to the formation of the molded body je according to the physical properties of the premix also becomes part of the premix particles crushed and it comes at even higher pressures to sinter the premix. at increasing press speed, so high throughputs, the phase of the elastic Deformation further shortened, so that the resulting moldings more or less large May have cavities. In the last step of tabletting the finished molding pushed out by the lower punch from the die and by subsequent transport facilities carried away. At this time, only the weight of the molded article is final determined because the compacts due to physical processes (re-stretching, crystallographic Effects, cooling) can change their shape and size.

The tableting is carried out in commercial tablet presses, which in principle with single or Double stamping can be equipped. In the latter case, not only the upper punch to Pressure build-up used, also the lower punch moves during the pressing process on the Upper stamp too, while the upper punch presses down. For small production quantities Eccentric tablet presses are preferably used, in which the one or the stamp on an eccentric disc are fixed, which in turn on an axis with a certain rotational speed is mounted. The movement of these punches is the operation of a usual Four-stroke engine comparable. The compression can each with a top and bottom stamp take place, but it can also be attached more stamp on an eccentric disc, wherein the number of die holes is extended accordingly. The throughputs of eccentric presses vary according to type from a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs you can choose rotary tablet presses, where on a so-called Matrizentisch a larger number of matrices is arranged in a circle. The number of matrices varies from 6 to 55 depending on the model, although larger dies are commercially available. Each die on the die table is assigned a top and bottom stamp, again the pressing pressure active only by the upper or lower punch, but also constructed by both stamp can be. The die table and the punches move around a common vertical standing axis, wherein the punches by means of rail-like cam tracks during the Circulated to positions for filling, compaction, plastic deformation and ejection become. At the places where a particularly serious increase or decrease in the Stamp is required (filling, compaction, ejection), these curved paths by additional Low pressure pieces, Nierderzugschienen and Aushebebahnen supported. The filling the die takes place via a rigidly arranged supply device, the so-called filling shoe, the is connected to a reservoir for the premix. The pressing pressure on the premix is individually adjustable via the pressing paths for upper and lower punches, whereby the pressure build-up by passing the stamp shank heads past adjustable pressure rollers.

Concentric presses can also be equipped with two filling shoes to increase throughput be, with the preparation of a tablet only a semicircle must be run through. to Production of two-layered and multi-layered moldings, several filling shoes in a row arranged without the slightly pressed first layer ejected before further filling becomes. By suitable process control coat and point tablets can be produced in this way, which have a onion-bowl-like structure, wherein in the case of the point tablets the Top of the core or the core layers is not covered and thus 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 at the same time for pressing to be used. The throughputs of modern rotary tablet presses are over one Million moldings per hour.

• Verwendung von Kunststoffeinlagen mit geringen Dickentoleranzen
• Geringe Umdrehungszahl des Rotors
• Große Füllschuhe
• Abstimmung des Füllschuhflügeldrehzahl auf die Drehzahl des Rotors
• Füllschuh mit konstanter Pulverhöhe
• Entkopplung von Füllschuh und Pulvervorlage

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

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

To reduce Stempelanbackungen offer all known from the art non-stick coatings at. Particularly advantageous are plastic coatings, plastic inserts or plastic stamp. Rotary stamps have proved to be advantageous, wherein after Possibility of upper and lower punches should be rotatable. With rotating stamps can be dispensed with a plastic insert usually. Here should be the stamp surfaces be electropolished.

It has also been shown that long pressing times are advantageous. These can be with pressure rails, several pressure rollers or low rotor speeds are set. Because the hardness fluctuations The tablet should be caused by the fluctuations of the pressing forces should systems be applied, which limit the pressing force. Here can elastic punches, pneumatic Compensators or resilient elements are used in the force path. Also, the pressure roller be performed resilient.

Tableting machines suitable for the purposes of the present invention are available, for example at the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMA Packaging Systems GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Presses AG, Berlin, as well as Romaco GmbH, Worms. Other providers include Dr. med. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bem (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy N.V., Halle (BE / LU) and Mediopharm Kamnik (SI). Particularly suitable is, for example, the Hydraulic double pressure press HPF 630 of the company LAEIS, D. Tabletting tools are for example by the companies Adams tabletting tools, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Sons GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Werkzeugbau, Tamm available. Other providers are e.g. the Senss AG, Reinach (CH) and the Medicopharm, Kamnik (SI).

The moldings can - as already mentioned above - in a predetermined spatial form and be made of a predetermined size. As a form of space virtually all useful manageable Embodiments into consideration, for example, the training as a blackboard, the bar or bar form, Cube, cuboid and corresponding room elements with flat side surfaces and in particular cylindrical embodiments with a circular or oval cross-section. These last embodiment detects the presentation form of the tablet up to compact cylinder pieces with a height to diameter ratio above 1.

But it is also possible that the various components do not become a single tablet be pressed, but that moldings are obtained, the more layers, so at least two layers. It is also possible that these different layers have different dissolution rates. This can be advantageous application technology Properties of the moldings result. For example, if components in the moldings are mutually negative influence, so it is possible, the one Integrate component in the faster soluble layer and the other component into one incorporate slower soluble layer so that the first component has already reacted, when the second goes into solution. The layer structure of the molded body can be both stacked take place, wherein a solution process of the inner layer (s) at the edges of the molding already it then happens when the outer layers are not yet completely dissolved, but it can also a complete encasement of the inner layer (s) by the further outer layer (s) Layer (s) are achieved, resulting in a prevention of premature solution of components the inner layer (s) leads.

In a further preferred embodiment of the invention, a shaped body consists of at least three layers, so two outer and at least one inner layer, wherein at least in one of the inner layers a peroxy bleach is contained, while in the stacked one Shaped body, the two outer layers and the envelope-shaped body the outermost However, layers are free of peroxy bleach. Furthermore, it is also possible peroxy bleach and optionally existing bleach activators and / or enzymes spatially in one Separate molded bodies from each other.

After pressing, the washing or cleaning agent tablets have a high stability. The breaking strength of cylindrical shaped bodies can be detected by the measurand of the diametric breaking load. This is determinable σ = 2 P π dt

Herein, σ is the diametrical fracture stress (DFS) in Pa, P ist the force in N, which leads to the pressure exerted on the molding, the breakage of the molding D is the shape diameter in meters and t is the height of the moldings.

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 on the one hand increase the storage stability of the ingredients, in the case of moldings with cavities and inserted second part on the other hand surprisingly long-term adhesion of the Significantly improve trough filling. A further subject of the present invention is therefore a combination of (one or more) washing or cleaning agent tablets according to the invention and a packaging system containing the washing or cleaning agent tablet (s), the packaging system having a moisture vapor transmission rate of 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%.

The packaging system of the combination of detergent tablet (s) 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 FDDR = 24 · 10000 A · x y [ G / m 2 / 24 H ] 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 (12114.4) 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.

The relative equilibrium humidity of 85% at 23 ° C can be, for example, in laboratory chambers with humidity control to +/- 2% r.L. depending on the device type. set exactly. Also over saturated Solutions of certain salts form in closed systems at a given temperature constant and well-defined relative humidities resulting in the phase equilibrium between partial pressure of water, saturated solution and soil body based.

The combinations according to the invention of washing or cleaning agent tablet (s) and packaging system can, of course, in turn in secondary packaging, such as cardboard or trays, with no secondary requirements on the secondary packaging have to be asked. 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.

The packaging system of the combination according to the invention encloses depending on the embodiment of the invention one or more washing or cleaning agent tablet (s). It is according to the invention preferred to make either a shaped body such that it is an application unit of the washing or cleaning agent, and to pack this tablet individually, or to pack the number of tablets in a packaging unit, which in sum is an application unit includes. At a target dosage of 80 g detergent or cleaning agent it is According to the invention, it is possible to prepare an 80 g washing or cleaning agent tablet and to package individually, but it is also possible according to the invention, two 40 g each heavy To pack washing or cleaning agent tablets in a packaging in order to form a product according to the invention Combination to arrive. Of course, this principle can be extended so that According to the invention, combinations also include three, four, five or even more washing or cleaning agent tablets contained in a packaging unit. Of course, two or three more detergent tablets in a package different compositions exhibit. In this way it is possible to spatially separate certain components to separate, for example, to avoid stability problems.

The packaging system of the combination according to the invention can be made of the most diverse Materials exist and assume any external forms. For economic reasons and however, for ease of processing, packaging systems are preferred which the packaging material has a low weight, easy to work and inexpensive is. In inventively preferred combinations, the packaging system consists of a Bag or bag of single-layer or laminated paper and / or plastic film.

The washing or cleaning agent tablets may be unsorted, i. as a loose bed, in a bag of the materials mentioned are filled. It is for aesthetic reasons and preferably for sorting the combinations in secondary packaging, the detergent tablets one by one or several sorted into sacks or bags to fill. For individual Application units of washing or cleaning agent tablets, which are in a bag or Bags, the term "flow pack" has become common in the art. Such "flow packs" can then - optionally again sorted - optionally be packed in outer packaging, which underlines the compact form of the tablet.

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 which can be used in the context of the present invention as a packaging system, for example, in Hans Domining House "The Plastics and their properties", 3rd edition , VDI Verlag, Dusseldorf, 1988 , page 193 indicated. 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 a packaging system a bag or bag of single-layer or laminated plastic film with 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, in addition to the films mentioned or papers also wax-coated papers in the form of cardboard boxes as a packaging system for the washing or cleaning agent tablets it is preferred in the context of the present invention, when the Verpakkungssystem does not include boxes of wax-coated paper. The term "packaging system indicates in the context of the present invention is always the primary packaging of Detergents or shaped bodies, i. the packaging, which on its inside directly with the Shaped surface is in contact. At an optional secondary packaging are no requirements provided so that all the usual materials and systems can be used here.

As already mentioned above, the washing or cleaning agent tablets of the invention Combination depending on their intended use further ingredients of Waschoder Detergents in varying amounts. Regardless of the purpose of the tablets it is inventively preferred that the detergent tablets or a detergent Equilibrium moisture content of less than 30% at 35 ° C / exhibit.

The relative equilibrium humidity of the washing or cleaning agent tablets can after the following methods A water-impermeable 1-liter jar with a lid, which has a closable opening for the introduction of samples was, with a total of 300 g washing or cleaning agent tablets are filled and kept at a constant 23 ° C for 24 h to ensure a uniform temperature of vessel and substance. The water vapor pressure in the room above the moldings can then 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 designed resealable. Also combinations where the packaging system has a micro perforation can be realized according to the invention with preference.

The compositions according to the invention can be used in all household dishwashing machines be used, with respect to the program choice, there are no limitations. The beneficial effects are found in both low-temperature programs such as 45 ° C programs or Achieved at 50/55 ° C or 60/65 ° C programs.

Another object of the present invention is therefore a method for the purification of Dishes in a domestic dishwasher, in which one or more inventive Detergent tablet (s) is introduced into the main cleaning cycle of the machine.

The introduction into the main cleaning gear can by filling the dosing with the tablet (s), wherein by opening the dosing after a possible Vorreinigungsgang the tablet (s) is released into the machine. It is alternatively possible bring the tablet (s) directly into the machine and thus already in an optional Pre-cleaning procedure to release active substance. Alternatively, it can also be on a Vorreinigungsgang be waived. By means of the invention no need in the rinse cycle additional rinse aid to be dosed. inventive methods in which the Klarspttlgang the machine is carried out without the deliberate addition of further rinse aid are therefore preferred.

The term "further rinse aid" encompasses liquid commercially available rinse aids which are from Consumers given at intervals of several rinsing cycles in a reservoir of the machine must be released and programmatically released from there. This intentional addition a rinse aid and the required for this second dosing step at intervals of some rinse cycles are not required by the use of the agents according to the invention.

a) Kontaktieren des verschmutzten Spülguts mit einer wäßrigen Reinigungsflotte aus Wasser und Reinigungsmitteltabletten, wobei die Reinigungsmitteltabletten 5 bis 25 Gew.-% nichtionische(s) Tensid(e) enthalten,

b) Abpumpen der Reinigungsflotte und Kontaktieren des Spülguts mit einem Klarspülgang.

Another object of the present invention is a method for cleaning dishes in a domestic dishwasher using detergent tablets, comprising the steps

a) contacting the soiled items with an aqueous cleaning solution of water and detergent tablets, the detergent tablets containing 5 to 25% by weight of nonionic surfactant (s),

b) pumping out the cleaning liquor and contacting the items to be washed with a rinse cycle.

As already mentioned, the advantages of the present invention are achieved even if the Main cleaning and the rinse cycle are interrupted by intermediate rinses. preferred Methods are therefore characterized in that between steps a) and b) one or more intermediate rinses done.

Again, the additional deliberate dosage of commercially available rinse aid is not required so that processes are preferred in which in step b) no further rinse aid intentionally is added.

Completely analogous to washing methods according to the invention for washing textiles in household washing machines Further objects of the present invention. Here, instead of detergent tablets according to the invention detergent tablets used according to the invention.

Claims (23)

1. Laundry or dishwasher detergent tablets comprising at least one cavity, characterized in that they contain 5.5 to 25% by weight, based on the tablet, of nonionic surfactants with a melting point above 20°C.
2. Multiphase laundry or dishwasher detergent tablets comprising at least one cavity, characterized in that the phase with the cavity contains 5.5 to 25% by weight, based on the tablet, of nonionic surfactants with a melting point above 20°C.
3. Laundry or dishwasher detergent tablets as claimed in claim 1 or 2, characterized in that the cavity has lateral boundary walls which are orthogonal to its base.
4. Laundry or dishwasher detergent tablets as claimed in any of claims 1 to 3, characterized in that the surface area of the cavity opening makes up 1 to 25%, preferably 2 to 20%, more preferably 3 to 15% and most preferably 4 to 10% of the total surface area of the tablet.
5. Laundry or dishwasher detergent tablets as claimed in any of claims 1 to 4, characterized in that they contain nonionic surfactant(s) with a melting point above 25°C, preferably between 25 and 60°C and more preferably between 26.6 and 43.3°C in quantities of 5.5 to 20% by weight, preferably in quantities of 6.0 to 17.5% by weight, more preferably in quantities of 6.5 to 15% by weight and most preferably in quantities of 7.0 to 12.5% by weight, based on the tablet or the phase with the cavity.
6. Laundry or dishwasher detergent tablets as claimed in any of claims 1 to 5, characterized in that the nonionic surfactant(s) is/are ethoxylated nonionic surfactant(s) obtained from C_6-20 monohydroxyalkanols or C_6-20 alkylphenols or C_16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and, more particularly, more than 20 mol ethylene oxide per mol alcohol.
7. Laundry or dishwasher detergent tablets as claimed in any of claims 1 to 6, characterized in that they or the phase with the cavity contain(s) ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule make up as much as 25% by weight, preferably as much as 20% by weight and more particularly as much as 15% by weight of the total molecular weight of the nonionic surfactant.
8. Laundry or dishwasher detergent tablets as claimed in any of claims 1 to 7, characterized in that they or the phase with the cavity contain(s) nonionic surfactants corresponding to the following formula: R¹O[CH₂CH(CH₃)O]_x[CH₂CH₂O]_y[CH₂CH(OH)R²] in which R¹ is a linear or branched aliphatic hydrocarbon radical containing 4 to 18 carbon atoms or mixtures thereof, R² is a linear or branched hydrocarbon radical containing 2 to 26 carbon atoms or mixtures thereof, x has a value of 0.5 to 1.5 and y has a value of at least 15.
9. Laundry or dishwasher detergent tablets as claimed in any of claims 1 to 8, characterized in that they or the phase with the cavity contain(s) end-capped poly(oxyalkylated) nonionic surfactants corresponding to the following formula: R¹O[CH₂CH(R³)O]_x[CH₂]_kCH(OH)[CH₂]_jOR² in which R¹ and R² are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals containing 1 to 30 carbon atoms, R³ stands for H or for a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x has a value of 1 to 30, k and j have values of 1 to 12 and preferably 1 to 5,
   surfactants of the following type: R¹O(CH₂CH(R³)O]_xCH₂CH(OH)CH₂OR² in which x is a number of 1 to 30, preferably 1 to 20 and more particularly 6 to 18 being particularly preferred.
10. Laundry or dishwasher detergent tablets as claimed in any of claims 1 to 9, characterized by a content of

    a) 1.0 to 4.0% by weight of nonionic surfactants from the group of alkoxylated alcohols,

    b) 4.0 to 24.0% by weight of nonionic surfactants from the group of hydroxyfunctional alkoxylated alcohols ("hydroxy mixed ethers"),

    based on the tablet as a whole or on the phase with the cavity.
11. Laundry or dishwasher detergent tablets as claimed in claim 10 containing

    a) 1.5 to 3.5% by weight, preferably 1.75 to 3.0% by weight and more particularly 2.0 to 2.5% by weight of nonionic surfactants from the group of alkoxylated alcohols,

    b) 4.5 to 20.0% by weight, preferably 5.0 to 15.0% by weight and more particularly 7.0 to 10.0% by weight of nonionic surfactants from the group of hydroxyfunctional alkoxylated alcohols ("hydroxy mixed ethers"),

    based on the tablet as a whole or on the phase with the cavity.
12. Laundry or dishwasher detergent tablets as claimed in any of claims 1 to 11, characterized in that they additionally comprise a second part which is in the form of a core or a body bonded onto or into the first part ("basic tablet") and which preferably contains one or more substances from the group of builders, acidifying agents, chelating agents or scale-inhibiting polymers.
13. Laundry or dishwasher detergent tablets as claimed in any of claims 1 to 12, characterized in that they additionally contain 0.1 to 70% by weight of copolymers of

    i) unsaturated carboxylic acids,

    ii) monomers containing sulfonic acid groups,

    iii) optionally other ionic or nonionic monomers.
14. Laundry or dishwasher detergent tablets as claimed in any of claims 1 to 13, characterized in that they contain the sulfonated copolymer(s) in quantities of 0.25 to 50% by weight, preferably in quantities of 0.5 to 35% by weight, more preferably in quantities of 0.75 to 20% by weight and most preferably in quantities of 1 to 15% by weight, based on the tablet as a whole.
15. Laundry or dishwasher detergent tablets as claimed in any of claims 1 to 14, characterized in that they contain one or more copolymers containing structural units corresponding to formulae VII and/or VIII and/or IX and/or X and/or XI and/or XII: -[CH₂-CHCOOH]_m-[CH₂-CHC(O)-Y-SO₃H]_p- -[CH₂-C(CH₃)COOH]_m-[CH₂-CHC(O)-Y-SO₃H]_p- -[CH₂-CHCOOH]_m-[CH₂-C(CH₃)C(O)-Y-SO₃H]_p- -[CH₂-C(CH₃)COOH]_m-[CH₂-C(CH₃)C(O)-Y-SO₃H]_p- -[HOOCCH-CHCOOH]_m-[CH₂-CHC(O)-Y-SO₃H]_p- -[HOOCCH-CHCOOH]_m-[CH₂-C(CH₃)C(O)O-Y-SO₃H]_p- in which m and p are whole natural numbers of 1 to 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals containing 1 to 24 carbon atoms, spacer groups in which Y represents -O-(CH₂)_n- with n = 0 to 4, -O-(C₆H₄)-, -NH-C(CH₃)₂- or -NH-CH(CH₂CH₃)- being preferred.
16. Laundry or dishwasher detergent tablets as claimed in any of claims 1 to 15, characterized in that they additionally comprise a second part which is in the form of a core or a body bonded onto or into the first part ("basic tablet") and which contains - based on the weight of the core - 1 to 80% by weight, preferably 2.5 to 70% by weight, more preferably 5 to 60% by weight and most preferably 10 to 50% by weight of the sulfonated copolymer(s).
17. Laundry or dishwasher detergent tablets as claimed in any of claims 1 to 16, characterized in that the cavity tablet ("basic tablet") contains, based on its weight, 0.5 to 30% by weight, preferably 1 to 25% by weight, more preferably 2.5 to 20% by weight and most preferably 4 to 15% by weight of the sulfonated copolymer(s).
18. Laundry or dishwasher detergent tablets as claimed in claim 16 or 17, characterized in that both the basic tablet and the core contain the sulfonated copolymer(s), at least 50% by weight, preferably at least 60% by weight and, more particularly, at least 65% by weight of the total of sulfonated copolymer(s) in the tablet being present in the basic tablet.
19. Laundry or dishwasher detergent tablets as claimed in any of claims 16 to 18, characterized in that the core does not have a coating.
20. Laundry or dishwasher detergent tablets as claimed in any of claims 1 to 19, characterized in that they additionally contain 0.1 to 30% by weight of homo- and/or copolymeric polycarboxylic acids or salts thereof and/or heteroatom-containing polymers/copolymers, more particularly those containing amino or phosphono groups.
21. Laundry or dishwasher detergent tablets as claimed in any of claims 1 to 18, characterized in that they additionally contain 0.1 to 30% by weight of polymers/copolymers containing amino or phosphono groups.
22. A process for the production of laundry or dishwasher detergent tablets having at least one cavity, characterized in that a particulate premix containing 5.5 to 25% by weight, based on the premix, of nonionic surfactants with a melting point above 20°C is tabletted in known manner to form cavity tablets.
23. A process for the production of multiphase laundry or dishwasher detergent tablets having at least one cavity in which several particulate premixes are tabletted in known manner to form cavity tablets, characterized in that the premix which, in the final pressing of the tablet, is contacted with the punch for forming the cavity contains 5.5 to 25% by weight, based on the premix, of nonionic surfactants with a melting point above 20°C.