EP1322743A1

EP1322743A1 - Recessed tablets and method for the production thereof

Info

Publication number: EP1322743A1
Application number: EP01969736A
Authority: EP
Inventors: Thomas Holderbaum; Bernd Richter; Christian Nitsch; Rolf Bayersdörfer
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2000-09-28
Filing date: 2001-09-19
Publication date: 2003-07-02
Anticipated expiration: 2021-09-19
Also published as: DE50104563D1; EP1322743B1; DE10108153A1; ATE282688T1; WO2002026926A1; US20030186828A1; US7205266B2; AU2001289894A1; ES2232663T3

Abstract

The invention relates to detergent or cleanser tablets, which have at least one cavity and whose content of non-ionic surfactants ranges from 5 to 25 wt. % with regard to the tablet. In multi-phase tablets, it is sufficient to add an appropriate material to the mixture that forms the phase containing the cavity. The invention also relates to a method for producing recessed tablets.

Description

"Tray tablets and process for their manufacture ' ¹

The invention relates to detergent tablets in the form of tray tablets, i.e. Tablets that have at least one cavity on one of their surfaces. The invention also relates to a method for producing tray tablets or tray tabs. In this case, a depression is embossed into one (usually the upper) side of a large-volume tablet, which can be filled with another material, in particular poured out, in a subsequent confectioning process.

Very special problems arise in the manufacture of trough tablets, since the tablet surface is not flat, but profiled. This results in different pressure and abrasion ratios for the different surface geometries of the corresponding embossing element. Since the tendency for substances to be pressed to adhere to the embossing element depends, inter alia, on the specific surface pressure and the pressure vectors determined by the surface geometry, certain parts of an embossing element profile are particularly prone to buildup or caking. In the sequence of many pressings, such buildup leads to increasing roughness of the tablet surfaces at the corresponding points, which can lead to deviations in the proportions of the substances and also to tablet breakage. If a tablet breaks in the tablet press, this leads to considerable impairments of the manufacturing process.

One way to solve this problem is to choose the geometry of the cavity or trough in such a way that buildup and edge breakage at the edge of the trough are avoided. However, from a technical point of view (e.g. volume of the trough for a given tablet size) or aesthetically, the possible variations are extremely limited. Surface finishing of the press ram with non-stick materials can also be used to reduce the tendency to stick. However, the materials known in the prior art have the disadvantage of a short service life, which necessitates frequent tool changes. The technical problem on which the invention is based is to design the mixture to be tabletted by adding certain substances in such a way that buildup on the pressing tool and signs of breakage at the edges of the cavity are reduced or avoided entirely. This problem is solved according to the invention by using nonionic surfactants and in particular nonionic surfactant mixtures in certain quantitative ranges in the mixtures to be tabletted. In the case of multi-phase (in particular multi-layer) tablets, it is sufficient to add them to the mixture which forms the phase which, during the final compression, is in contact with the ram which presses the cavity into the tablets. The present invention relates to detergent tablets comprising at least one cavity, the tablet content of nonionic surfactants being 5 to 25% by weight, based in each case on the tablet.

The use of nonionic surfactants in the amounts mentioned leads to a reduction in the adherence to the non-planar pressing tool and to a significantly reduced occurrence of edge breakage at the edges of the trough. In the case of multi-phase tablets, an appropriate composition of the phase which has the cavity, i.e. of the pre-mix that comes into contact with the non-flat press ram during final pressing. Since the first premix is only slightly compressed by pressing with the stamp during pre-compression steps (for example in the production of two-layer tablets), no adhesion or edge breakage phenomena occur here. Only at the final pressing do the forces become so great that the problems mentioned are to be feared.

The present invention therefore also relates to multiphase detergent or cleaning agent containers comprising at least one cavity, the nonionic surfactant content of the phase comprising the cavity being 5 to 25% by weight.

Naturally, only one body can be produced in a tabletting process, which has vertical lateral boundary surfaces (possibility of ejection from the die). The bottom and “lid” surface are usually horizontal, ie they and the edge surface (s) are orthogonal to one another. Tablets which have at least one cavity (so-called trough tablets) have this cavity on their top or for the reasons mentioned above For reasons of the simplified ejection process from the die, the lower punch (and thus the underside) is usually designed to be flat, while there is at least one elevation on the upper punch which impresses the cavity into the top of the tablet. The tablets according to the invention (hereinafter also called “Base moldings”) can assume any geometric shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, five hexagonal and octagonal prismatic as well as rhombohedrisc he forms are preferred. Completely irregular base areas such as arrow or animal shapes, trees, clouds, etc. can also be realized. If the base molding has corners and edges, these are preferably rounded. As an additional optical differentiation, an embodiment with rounded corners and beveled (“chamfered”) edges is preferred.

The shape of the trough can also be chosen freely, tablets being preferred in which at least one trough is a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, hexagonal and octagonal-prismatic and rhombohedral in shape. Completely irregular trough shapes such as arrow or animal shapes, trees, clouds, etc. can also be realized. As with the basic shaped bodies, troughs with rounded corners and edges or with rounded corners and chamfered edges are preferred.

The problem of the edge breaking phenomena at the edges of the trough and the adherence to the elevations of the press punches occurs increasingly when the edge angle of the trough increases. On the other hand, a contact angle close to 90 ° is preferred, since flat troughs / cavities have only small volumes, while "steep" cavities can have large volumes with a small opening area. The solution according to the invention is particularly suitable for such problem cases Detergent or cleaning agent tablets, which are characterized in that the cavity has lateral boundary walls which are orthogonal to the base area, are preferred embodiments.

A variety of transitions are possible between the extremes of a hemispherical or semi-ellipsoidal trough (no straight lateral boundary surfaces) or a cylindrical trough (straight lateral boundary surfaces, which meet a trough bottom parallel to the base surface). In general, the problems arise when the lateral boundary surfaces are straight, i.e. when the shortest connecting line from the edge of the bowl to the bowl floor is a straight line and not a curve. Since the advantages according to the invention become clearer here, corresponding tablets according to the invention are preferred. In the case of the straight side boundary walls, the problems become clearer the steeper they are (see above), which in extreme cases leads to the angles of 90 ° described above (angles smaller than 90 ° between the trough floor and the side boundary line are not technically possible, otherwise the floor area of the trough would be larger than the opening area). In this extreme case, the advantages according to the invention emerge most clearly. However, troughs with "straight" side walls and non-orthogonal angles can also be produced, which is technically preferred. Such troughs, which have a cone, have advantages in later filling processes, so that tablets according to the invention, in which the angle explained above between 90 and 120 °, preferably between 91 and 110 °, particularly preferably between 92 and 100 ° and in particular between 93 and 98 °, are preferred.

The size of the trough or cavity compared to the entire molded article depends on the intended use of the molded article. The size of the trough can vary depending on whether and with which substances in which physical states the trough or cavity is to be filled. Regardless of the intended use, detergent tablets are preferred in which the volume ratio of the base tablet to the trough volume is in the range from 1: 1 to 100: 1, preferably from 2: 1 to 80: 1, particularly preferably from 3: 1 to 50: 1 and is in particular from 4: 1 to 30: 1. Similar statements can be made about the surface proportions that the base molding or the trough opening make up on the total surface of the molding. Detergent or cleaning agent tablets are preferred here, in which the surface of the cavity opening accounts for 1 to 25%, preferably 2 to 20%, particularly preferably 3 to 15% and in particular 4 to 10% of the total surface area of the tablet.

If, for example, the overall shaped body has dimensions of 20 x 20 x 40 mm and thus a total surface area of 40 cm ² , trough fillings are preferred which have a surface area of 0.4 to 10 cm ² , preferably 0.8 to 8 cm ² , particularly preferably of 1, 2 to 6 cm ² and in particular from 1, 6 to 4 cm ² .

The tray tablets according to the invention contain nonionic surfactant (s). In addition, they can contain anionic, cationic and / or amphoteric surfactants or mixtures of these (especially if detergent tablets are involved). From an application point of view, preference is given to mixtures of anionic and nonionic surfactants in detergent tablets. The total surfactant content of detergent tablets is 5 to 60% by weight, based on the weight of the shaped body, with surfactant contents above 15% by weight being preferred.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C ₉ . ₁₃ alkylbenzene sulfonates, olefinsulfonates finsulfonate, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from C ₁₂ -ι ₈ monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation , into consideration. Also suitable are alkanesulfonates, from C ₁₂ -ι ₈ - are obtained alkanes, for example by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures, such as those produced 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 Glycerin can be obtained. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid. As alk (en) yl sulfates, the alkali and especially the sodium salts of the sulfuric acid half esters of C ₁₂ -C 8 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂ o -Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₂ -C ₁₆ alkyl sulfates and C ₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred from a washing-technical point of view. 2,3-Alkyl sulfates, which are manufactured according to the US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C ₇ ethoxylated with 1 to 6 mol of ethylene oxide. ₂₁ alcohols, such as 2-methyl-branched C ₉ . _ι alcohols with an average of 3.5 moles of ethylene oxide (EO) or C ₁₂ . ₁₈ fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

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

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

The anionic surfactants, including the soaps, can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts. In dishwasher detergents, only weakly foaming nonionic surfactants are usually used as surfactants. In cleaning agent tablets according to the invention, representatives from the groups of anionic, cationic or amphoteric surfactants are therefore of less importance. The nonionic surfactants, which according to the invention are contained in the detergents tablets as well as detergent tablets in amounts of 5 to 25% by weight, are described below.

In particularly preferred embodiments of the present invention, the washing or cleaning agent tablets according to the invention contain nonionic surfactants from the group of the alkoxylated alcohols. Such nonionic surfactants are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is branched linearly or preferably in the 2-position methyl may or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ . ₁₄ alcohols with 3 EO or 4 EO, Cg-n-alcohol with 7 EO, Cι - ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Cι ₂ . 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 -ι ₈ -alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl ester. Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

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

R

I

R-CO-N- [Z] (I)

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

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

R ¹ -0-R ²

R-CO-N- [Z] (II)

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, where C.,. ₄ -alkyl or phenyl radicals are preferred and [Z] represents a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.

[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 into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst. It is particularly preferred for detergent tablets according to the invention for machine dishwashing that they contain a nonionic surfactant which has a melting point above room temperature. Here, washing or cleaning agent tablets are preferred which contain non-ionic surfactant (s) with a melting point above 20 ° C., preferably above 25 ° C., particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43.3 ° C, in amounts of 5.5 to 20 wt .-%, preferably from 6.0 to 17.5 wt .-%, particularly preferably from 6.5 to 15 and in particular from 7.0 to 12 , 5 wt .-%, each based on the tablet or the phase containing the cavity.

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

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

In a preferred embodiment of the present invention, the nonionic surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has resulted. Corresponding detergent or cleaning agent tablets, which are characterized in that the nonionic surfactant (s) is / are ethoxylated nonionic surfactant (s), which are made from C ₆ . ₂₀ monohydroxyalkanols or C ₆ . ₂ o-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 are accordingly preferred.

A particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C _16th ₂₀ alcohol), preferably a C-is-alcohol and at least 12 moles, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide won. Among these, the so-called "narrow ranks ethoxylates" (see above) are particularly preferred. The nonionic surfactant, which is solid at room temperature, preferably additionally has propylene oxide units in the molecule. Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. Detergent or cleaning agent tablets containing ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule make up up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight, of the total molecular weight of the nonionic surfactant , are preferred embodiments of the present invention. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols, which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molar mass of such nonionic surfactants.

Other nonionic surfactants with melting points above room temperature which are particularly preferably used contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which contains 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol of propylene oxide and 25% by weight. -% of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

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

Another preferred surfactant can be represented by the formula

R ¹ 0 [CH ₂ CH (CH ₃ ) 0] _x [CH ₂ CH ₂ 0] _y [CH ₂ CH (OH) R ² ]

describe in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x denotes values between 0.5 and 1, 5 and y represents a value of at least 15. Detergent or cleaning agent tablets, which are characterized in that they contain nonionic surfactants of the formula

R ¹ 0 [CH ₂ CH (CH ₃ ) 0] _x [CH ₂ CH ₂ 0] _y [CH ₂ CH (OH) R ² ]

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

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

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

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

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

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

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x CH ₂ CH (OH) CH ₂ OR ²

simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 have} 9 to 14 carbon atoms, R ^{3 represents} H and x assumes values from 6 to 15. In summary, detergent or cleaning agent tablets are preferred, which are characterized in that they or the phase which has the cavity, end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

contain in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5, with surfactants of the type

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x CH ₂ CH (OH) CH ₂ OR ²

in which x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

Mixtures of different nonionic surfactants are particularly preferably used in the tablets according to the invention. Washing or cleaning agent tablets are particularly preferred which contain 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 hydroxyl-containing alkoxylated alcohols (“hydroxy mixed ethers”), in each case based on the entire tablet or the phase which has the cavity.

The nonionic surfactants from group a) have already been described in detail above, with C _{12 being} particularly suitable for machine dishwashing detergents which contain the abovementioned mixtures. ₁₄ fatty alcohols with 5EO and 4PO and C ₁₂ -ι ₈ fatty alcohols with an average of 9 EO have proven to be outstanding. Endgroup-closed nonionic surfactants, in particular C _12, are similarly preferred. ₁₈ -Fatty alcohol-9 EO-butyl ether, can be used.

Surfactants from group b) show outstanding rinse aid effects and reduce stress corrosion cracking on plastics. Furthermore, they have the advantageous property that their wetting behavior is constant over the entire usual temperature range. The surfactants from group b) are particularly preferred alkoxylated alcohols containing hydroxyl groups, as described in EP 300 305, the disclosure of which is expressly included here. All of the hydroxy mixed ethers disclosed there are, without exception, preferably present as surfactant from group b) in the dishwasher detergents preferred according to the invention. The amounts in which the surfactants from groups a) and b) can be contained in dishwasher tablets preferred according to the invention vary depending on the desired product and are preferably within narrow ranges. Particularly preferred washing or cleaning agent tablets contain a) 1.5 to 3.5% by weight, preferably 1.7 to 3.0% by weight and in particular 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 in particular 7.0 to 10.0% by weight of nonionic surfactants from the group of alkoxylated alcohols containing hydroxyl groups (“hydroxy mixed ethers”), in each case based on the entire tablet or the phase which has the cavity.

The nonionic surfactant (s) can be introduced into the agents according to the invention in different ways. The surfactants can be sprayed, for example, in the molten state onto the premix, which is otherwise ready to be pressed, or added to the premix in the form of compounds or surfactant preparation forms. It is particularly preferred to add particulate premixes of particles containing high surfactants, so-called “rinse aid particles”.

These "rinse aid particles" can be added as a particulate component to the premix to be compressed, it being possible for the amount of surfactants in the end product (or in the relevant phase of the end product) to be influenced both by the amount of rinse aid particles and by their content of nonionic surfactants. Premixes for compression into detergent tablets according to the invention or phases thereof preferably contain a particulate rinse aid which, based on its weight, a) 20 to 90% by weight of one or more carrier materials from the group of builders, b) 10 to 40% by weight. % of one or more nonionic surfactants and c) 0 to 70% by weight of further active ingredients and auxiliaries.

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

Among the phosphates, the alkali metal phosphates are again particularly preferred as carrier materials for the rinse aid particles. Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which metaphosphoric acids (HP0 ₃ ) _n and orthophosphoric acid H ₃ P0 are used in addition to can distinguish molecular representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues and also contribute to cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ P0, exists as a dihydrate (density 1.91, preferably ^"3 , melting point 60 °) and as a monohydrate (density 2.04, preferably ^{" 3} ). Both salts are white powders that are very easily soluble in water, which lose water of crystallization when heated and into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ 0 ₇ ) at 200 ° C, and at higher temperatures in sodium trimethane phosphate (Na ₃ P ₃ 0 ₉ ) and Maddrell's salt (see below). NaH ₂ P0 _{4 is} acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ P0, is a white salt with a density of 2.33 ^"3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KP0 ₃ ) _x ] and is easily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPÖ ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gladly ^"3 , water loss at 95 °), 7 mol. (Density 1, 68 gladly ^{" 3} , melting point 48 ° with loss of 5 H ₂ 0) and 12 mol. Water ( Density 1, 52 like ^"3 , melting point 35 ° with loss of 5 H ₂ 0), becomes anhydrous at 100 ° and changes to diphosphate Na P ₂ 0 ₇ when heated. Disodium hydrogenphosphate is used by neutralizing phosphoric acid with soda solution produced by phenolphthalein as an indicator Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HP0 ₄ , is an amorphous, white salt, which is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ P0 ₄ , are colorless crystals which like dodecahydrate a density of 1.62 ^"3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20 % P ₂ 0 ₅ ) have a melting point of 100 ° C. and, in anhydrous form (corresponding to 39-40% P ₂ 0 ₅ ), a density of 2.536 ^"3 . Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or three-base potassium phosphate), K ₃ P0 ₄ , is a white, deliquescent, granular powder with a density of 2.56 ^"3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It forms eg when heating Thomas slag with coal and potassium sulfate Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ 0 ₇ , exists in anhydrous form (density 2.534 like ^'3 , melting point 988 °, also given 880 °) and as decahydrate (density 1, 815-1, 836 like ^{' 3} , melting point 94 ° with loss of water) For substances are colorless, in water with alkaline shear reaction soluble crystals. Na ₄ P ₂ 0 ₇ is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ 0 ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 ^"3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.

Condensation of NaH ₂ P0 ₄ or KH ₂ P0 ₄ produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of names are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (0) (ONa) -0] _π that crystallizes with 6 H ₂ 0 -Na with n = 3. Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% by weight solution (> 23% P ₂ 0 ₅ , 25% K ₂ 0). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates, which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

(NaP0 ₃ ) ₃ + 2 KOH ^■ »Nas- ^ PaO« + H ₂ 0

According to the invention, these phosphates can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention. Other ingredients that can be used instead of or in addition to phosphates as carrier materials are carbonates and / or hydrogen carbonates, the alkali metal salts and, in particular, the potassium and / or sodium salts being preferred. Preferred detergent or cleaning agent tablets contain carbonate (s) and / or hydrogen carbonate (s), preferably alkali carbonates, particularly preferably sodium carbonate, in amounts of 25 to 75% by weight, preferably 30 to 60% by weight and in particular 35 to 50% by weight .-%, each based on the mass of the rinse aid particles contained in them.

Other ingredients that can be contained in the cleaning agent tablets instead of or in addition to the phosphates and / or carbonates / bicarbonates mentioned are silicates, the alkali metal silicates and, in particular, the amorphous and / or crystalline potassium and / or sodium disilicate being preferred.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x 0 _{2x + 1} y H ₂ 0, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ 0 ₅ "yH ₂ 0 are preferred.

Amorphous sodium silicates with a module Na ₂ 0: Si0 ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

The washing or cleaning agent tablets according to the invention can also contain zeolites as carrier materials or in the remaining solid matrix, preferred agents not containing any zeolite as carrier material in the rinse aid particles and particularly preferred cleaning agent tablets at all does not contain zeolite. In contrast, the use of zeolite is preferred in detergent tablets according to the invention.

Zeolites have the general formula

M _{∑ /} nO 'Al ₂ 0 ₃ ^• x Si0 ₂ "y H ₂ 0

where M is a cation of valence n, x stands for values that are greater than or equal to 2 and y can assume values between 0 and 20. The zeolite structures are formed by linking Al0 ₄ tetrahedra with Si0 ₄ tetrahedra, this network being occupied by cations and water molecules. The cations in these structures are relatively mobile and can be exchanged for other cations in different degrees. Depending on the type of zeolite, the intercrystalline “zeolitic” water can be released continuously and reversibly, while for some types of zeolite structural changes are also associated with the water release or uptake.

In the structural subunits, the "primary binding units" (Al0 ₄ tetrahedra and Si0 tetrahedra) form so-called "secondary binding units", which have the form of one or more rings. For example, 4-, 6- and 8-membered rings appear in different zeolites (referred to as S4R, S6R and S8R), other types are connected via four- and six-membered double ring prisms (most common types: D4R as a square prism or D6R as a hexagonal prism ). These "secondary subunits" connect different polyhedra, which are denoted by Greek letters. The most common is a polyhedra, which is composed of six squares and eight equilateral hexagons and which is referred to as "ß". A variety of different zeolites can be realized with these units. To date, 34 natural zeolite minerals and around 00 synthetic zeolites are known.

The best known zeolite, zeolite 4 A, is a cubic combination of ß-cages that are linked by D4R subunits. It belongs to the zeolite structure group 3 and its three-dimensional network has pores of 2.2 A and 4.2 A in size, the formula unit in the unit cell can be characterized with Na ₁₂ [(AI0 ₂ ) ₁₂ (Si0 ₂ ) ₁₂ ] ' Describe 27 H ₂ 0.

If zeolites are used, faujasite-type zeolites are preferably used. Together with the 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-ring subunit D6R (compare 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 structure group 4 also includes the minerals chabazite and gmelinite and the synthetic zeolites R (chabazite type), S (gmelinite type) , L and ZK-5. The latter two synthetic zeolites have no mineral analogues. Faujasite-type zeolites are made up of ß-cages which are tetrahedral linked by D6R subunits, the ß-cages being arranged similar to 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 A, the unit cell also contains 8 cavities with a diameter of approx. 13 A and can be calculated using the formula Na ₈₆ [ (AIO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] ^' 264 H ₂ 0. The network of zeolite X contains a void volume of approximately 50%, based on the dehydrated crystal, which represents the largest empty space of all known zeolites (zeolite Y: approx. 48% void volume, faujasite: approx. 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 “zeolite of the faujasite type” denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4. In addition to the zeolite X, zeolite Y and faujasite and mixtures of these compounds can also be used according to the invention, the pure zeolite X is preferred.

Mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites which do not necessarily have to belong to the zeolite structure group 4 can also be used according to the invention, the advantages of the process according to the invention being particularly evident when at least 50% by weight of the powdering agent consist of a zeolite of the faujasite type. It is also conceivable, for example, that the minimum amount of a faujasite-type zeolite (0.5% by weight, based on the weight of the shaped body formed) is used and conventional zeolite A is used as the remaining powdering agent. In any case, however, it is preferred that the powdering agent consists exclusively of one or more zeolites of the faujasite type, zeolite X again being preferred.

The aluminum silicates which can be used in the washing or cleaning agent tablets according to the invention are commercially available, and the methods for their presentation are described in standard monographs.

Examples of commercially available X-type zeolites can be described by the following formulas:

Na ₈₆ [(AIO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] ^■ x H ₂ 0,

K ₈ 6 [(AIO ₂ ) ₈ 6 (SiO ₂ ) ₁₀ 6] ^' x H ₂ 0,

Ca ₄₀ Na ₆ [(AIO ₂ ) ₈₆ (SiO ₂ ) ₁₀ 6] ^' x H ₂ 0, Sr ₂₁ Ba ₂₂ [(AIO ₂ ) ₈₆ (SiO ₂ ) ₁₀ 6] ^' x H ₂ 0,

in which x can have values between 0 and 276 and have pore sizes of 8.0 to 8.4 A.

Preferably commercially available and within the scope of the inventive method is used, for example, a co-crystallizate of zeolite X and zeolite A (ca. 80 wt .-% zeolite X) which is marketed by CONDEA Augusta SpA under the trade name VEGOBOND AX ^® and through the formula

nNa ₂ ö ^• (1-n) K ₂ 0 ^■ Al ₂ 0 ₃ ^■ (2 - 2.5) Si0 ₂ ^■ (3.5 - 5.5) H ₂ 0

can be described.

Y-type zeolites are also commercially available and can be expressed, for example, by the formulas

Na ₅₆ [(Al0 ₂ ) ₅₆ (Si0 ₂ ) ₁₃₆ ] 'x H ₂ 0,

K56 [(AI0 ₂ ) ₅₆ (Si0 ₂ ) ₁₃ 6] ^■ x H ₂ 0,

in which x stands for numbers between 0 and 276 and have a pore size of 8.0 A.

The builder substances mentioned above can be contained as carrier materials in the rinse aid particles, but they can also be an additional or only an integral part of the “other” detergent or cleaning agent tablets.

As a second constituent, the rinse aid particles which can be used in the washing or cleaning agent tablets according to the invention contain nonionic surfactant (s) which have already been described in detail above. Even in the event that the washing or cleaning agent tablets according to the invention contain the nonionic surfactant (s) in the form of separate rinse aid particles, tablets are preferred in which the particulate rinse aid as nonionic surfactants b) mixtures of alkoxylated alcohols and hydroxy mixed ethers in amounts of 10 to 35% by weight, preferably from 10.5 to 30% by weight and in particular from 11 to 20% by weight, in each case based on the weight of the particulate rinse aid.

The trough tablets according to the invention can contain further ingredients, which are either localized as active ingredients or auxiliary substances in the rinse aid particles or incorporated into the agents in another way. are worked. These substances are described below and can each be present in the rinse aid particles as further active ingredients or auxiliaries, but they can also be an additional or only an integral part of the “other” depression tablets.

When using rinse aid particles, detergent tablets according to the invention are preferred, in which the particulate rinse aid as further active ingredients and / or auxiliary substances c) one or more substances from the groups of dyes, fragrances, defoamers, polymers, deposit inhibitors, silver preservatives, enzymes and / or mixtures thereof in amounts of 5 to 60% by weight, preferably 10 to 50% by weight and in particular 15 to 30% by weight, in each case based on the weight of the particulate rinse aid.

In addition to the substances mentioned above, bleaching agents, bleach activators, cobuilders, cheat and complexing agents, water-softening substances, acidifying and / or alkalizing agents, as well as adjusting agents, release agents and anti-caking agents are also preferred as constituents of the tray tablets according to the invention. In the case of the first three substances, it is advantageous not to incorporate them into the rinse aid particles.

In summary, trough tablets according to the invention are preferred, which are characterized in that they also contain one or more substances from the groups of surfactants, enzymes, bleaching agents, bleach activators, corrosion inhibitors, scale inhibitors, cobuilders, colorants and / or fragrances, soil-release polymers, optical brighteners , Color transfer or graying 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.

Sodium percarbonate is of particular importance among the compounds which serve as bleaching agents and supply H ₂ 0 ₂ in water. "Sodium percarbonate" is a non-specific term for sodium carbonate peroxohydrates which, strictly speaking, are not "percarbonates" (ie salts of percarbonic acid) but hydrogen peroxide adducts with sodium carbonate. The merchandise has the average composition 2 Na ₂ C0 ₃ -3 H ₂ 0 ₂ and is therefore not peroxycarbonate. Sodium percarbonate often forms a white, water-soluble powder with a density of 2.14 ^"3 , which easily breaks down into sodium carbonate and bleaching or oxidizing oxygen.

Sodium carbonate peroxohydrate was first obtained in 1899 by ethanol precipitation from a solution of sodium carbonate in hydrogen peroxide, but was mistakenly regarded as peroxy carbonate. The compound was only recognized as a hydrogen peroxide addition compound in 1909, but the historical name "sodium percarbonate" has become established in practice. The bulk density of the finished product can vary between 800 and 1200 g / l depending on the manufacturing process additional coating stabilized. Processes and substances used for coating are widely described in the patent literature. In principle, according to the invention, all commercially available types of percarbonate can be used, such as those offered by Solvay Interox, Degussa, Kemira or Akzo.

Other useful bleaching agents are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and H ₂ 0 ₂ -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid 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 agents. Bleaching agents from the group of organic bleaching agents can also be used in the agents according to the invention. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkyl peroxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxyiminoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipinic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1, 12-diperoxycarboxylic acid, 1, 9-diperoxyazelaic acid, diperocyseboxybrasic acid, Decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Chlorine or bromine-releasing substances can also be used as bleaching agents. Suitable chlorine or bromine-releasing materials include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

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

Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-di-acetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU ), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin 5-diace-oxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), and enol esters as well as acetylated sorbitol and mannitol or their mixtures (SORMAN), acylated sugar derivatives, in particular penta-acetylglucose (PAG), penta-acetylfructose, Tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-ben zoylcaprolactam. Hydrophilically substituted acylacetals and acyllactams are also preferably used. Combinations of conventional bleach activators can also be used.

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

Bleach activators from the group of multi-acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n-) or iso-N-NOB are preferred -Methyl-morpholinium-acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 2 to 8% by weight and particularly 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 consisting of manganese and / or cobalt salts and / or complexes, particularly preferably cobalt (ammin ) Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese Sulfates are used in conventional amounts, preferably in an amount of up to 5% by weight, in particular from 0.0025% by weight to 1% by weight and particularly preferably from 0.01% by weight to 0.25% by weight. -%, based in each case on the total average. But in special cases, more bleach activator can be used.

Further preferred depression tablets are characterized in that they contain silver protective agents from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes, particularly preferably benzotriazole and / or alkylaminotriazole, in amounts of 0.01 up to 5% by weight, preferably from 0.05 to 4% by weight and in particular from 0.5 to 3% by weight, in each case based on the total agent.

The corrosion inhibitors mentioned can also be incorporated into the trough tablets to protect the items to be washed or the machine, silver protection agents being of particular importance in the field of automatic dishwashing. The known substances of the prior art can be used. In general, silver protective agents selected from the group consisting of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkyl laminotriazoles and the transition metal salts or complexes can be used. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. In addition, active chlorine-containing agents are often found in cleaner formulations, which can significantly reduce the corroding of the silver surface. In chlorine-free cleaners, especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preferred here are the transition metal salts which are selected from the group consisting of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can also be used to prevent corrosion on the wash ware.

Particularly suitable enzymes are those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically acting enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as stains containing protein, fat or starch. Oxidoreductases can also be used for bleaching. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example se 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 especially protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases.

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

Further ingredients that can be part of the agents according to the invention are, for example, cobuilders, dyes, fragrances, soil release compounds, soil repellents, antioxidants, fluorescent agents, foam inhibitors, silicone and / or paraffin oils, etc. These substances are described below.

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

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

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

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

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.

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

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

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

Also particularly preferred are biodegradable polymers composed of more than two different monomer units, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers ,

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

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Polyaspartic acids or their salts and derivatives are particularly preferred which, in addition to cobuilder properties, also have a bleach-stabilizing effect. Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used.

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

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

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

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9). Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylene phosphonate (DTPMP) as well as their higher homologues in question. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition, all compounds that are able to form complexes with alkaline earth metal ions can be used as cobuilders.

In order to improve the aesthetic impression of the agents according to the invention, they can be colored in whole or in part (e.g. only individual layers or the cavity filling) with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity towards the treated substrates such as, for example, dishes, so as not to stain them.

Preferred for use in detergent tablets according to the invention are all colorants which can be oxidatively destroyed in the washing process, and also mixtures thereof with suitable blue dyes, so-called blue toners. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. For example, anionic colorants, for example anionic nitroso dyes, are suitable. One possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020)., That is as a commercial product, for example as Basacid ^® Green 970 from BASF, Ludwigshafen available, as well as mixtures thereof with suitable blue dyes. Other colorants include 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 ^® Patentblau 85 E 131 (Cl 42051), Acid Blue 183 (CAS 12217-22-0, Cl Acidblue 183), Pigment Blue 15 (Cl 74160), Supranol ^® Blau 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).

When choosing the colorant, care must be taken to ensure that the colorants do not have too strong an affinity for the textile surfaces and especially for synthetic fibers. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stabilities against oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depends on the Solubility and thus also the sensitivity to oxidation, the concentration of the colorant in the washing or cleaning agents varies. For highly soluble dyes, for example, the above-mentioned Basacid ^® Green or the above-mentioned Sandolan Blue ^®, are typically selected dye concentrations in the range of some 10 ^"2 to ^{10" 3} wt .-%. In the due to their brilliance, particularly preferred, but are less readily water-soluble pigment dyes, for example the above-mentioned Pigmosol ^® ATTO-dyes, the appropriate concentration of the colorant is in washing or cleaning agents, however, typically a few 10 ^"3 to ^{10" 4} wt .-% ,

Fragrances are added to the agents according to the invention in order to improve the aesthetic impression of the products and, in addition to the performance of the product, to provide the consumer with a visually and sensorially "typical and distinctive" product. As perfume oils or fragrances, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallyl propylate and benzyl acetate. The ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanols with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the Jonones, oc-isomethylionon and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures as are available from plant 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, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrance content of the cleaning agents according to the invention is usually up to 2% by weight of the total formulation. The fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries. Foam inhibitors that can be used in the agents according to the invention are, for example, soaps, paraffins or silicone oils, which can optionally be applied to carrier materials.

The detergent tablets according to the invention can contain one or more optical brighteners. These fabrics, which are also called "whiteners", are used in modern laundry detergents because even freshly washed and bleached white laundry has a slight yellow tinge. Optical brighteners are organic dyes that convert part of the invisible UV radiation from sunlight into longer-wave blue light. The emission of this blue light complements the "gap" in the light reflected by the textile, so that a textile treated with an optical brightener appears whiter and brighter to the eye. Since the action mechanism of brighteners presupposes that they are drawn onto the fibers, a distinction is made depending on the "dyed" fibers, for example brighteners for cotton, polyamide or polyester fibers. The commercial brighteners suitable for incorporation in detergents essentially comprise five structural groups: the stilbene, the diphenylstilbene, the coumarin-quinoline, the diphenylpyrazoline group and the group of the combination of benzoxazole or benzimidazole with conjugated systems. Suitable are for example salts of ^4,4'-bis [(4-anilino-6-morpholino-s-triazin-2-yl) amino] stilbene-2,2 ^'disulfonic acid or compounds of similar composition which instead of the morpholino Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, for example 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). Mixtures of the aforementioned brighteners can also be used.

In order to facilitate the disintegration of highly compressed tablets, disintegration aids, so-called tablet disintegrants, can be incorporated into them in order to shorten the disintegration times. These substances are suitable, for example, to accelerate the release of individual tablet areas compared to other areas. Tablet disintegrants or disintegration accelerators are understood to mean auxiliary substances which ensure the rapid disintegration of tablets in water or gastric juice and the release of the pharmaceuticals in an absorbable form.

These substances, which are also referred to as "explosives" due to their effect, increase their volume when water enters, whereby on the one hand the intrinsic volume increases (swelling) and on the other hand a pressure can be generated by the release of gases, which breaks the tablet into smaller particles disintegrates. Well-known disintegration aids are, for example, carbonate citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives. Preferred detergent and cleaning agent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration auxiliaries, in each case based on the tablet weight.

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

The cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be pressed. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 μm and in particular at least 90% by weight between 400 and 1200 μm. The above and described in more detail in the documents cited coarser disintegration aids, are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ^® TF-30-HG from Rettenmaier available in the present invention.

Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions that only affect the amorphous areas (approx. Attack and completely dissolve 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged. A subsequent disaggregation of the microfine celluloses produced by the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 μm and can be compacted, for example, into granules with an average particle size of 200 μm.

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

The detergent and cleaning agent tablets according to the invention can also contain a gas-developing effervescent system which is incorporated into one or more of the masses to be processed. The gas-developing shower system can consist of a single substance that releases a gas when it comes into contact with water. Among these compounds, magnesium peroxide should be mentioned in particular, which releases oxygen on contact with water. Usually, however, the gas-releasing bubble system in turn consists of at least two components that react with one another to form gas. While a large number of systems are conceivable and executable here, which release nitrogen, oxygen or hydrogen, for example, the effervescent system used in the detergent and cleaning agent tablets according to the invention can be selected on the basis of both economic and ecological aspects. Preferred effervescent systems consist of alkali metal carbonate and / or hydrogen carbonate and an acidifying agent which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.

In the case of the alkali metal carbonates or bicarbonates, the sodium and potassium salts are clearly preferred over the other salts for reasons of cost. Of course, the pure alkali metal carbonates or bicarbonates in question do not have to be used; rather, mixtures of different carbonates and bicarbonates may be preferred for reasons of washing technology.

In preferred washing and cleaning agent tablets, 2 to 20% by weight, preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or hydrogen carbonate and 1 to 15, preferably 2 to 12 and in particular, are used as the effervescent system 3 to 10% by weight of an acidifying agent, in each case based on the total tablets, used. The content of individual substances in the substances mentioned may well be higher. Acidifiers which release carbon dioxide from the alkali salts in aqueous solution are, for example, boric acid and alkali metal bisulfates, alkali metal dihydrogen phosphates and other inorganic salts. However, organic acidifying agents are preferably used, citric acid being a particularly preferred acidifying agent. However, the other solid mono-, oligo- and polycarboxylic acids can also be used in particular. Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are preferred from this group. Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight).

In the context of the present invention, detergent tablets are preferred in which a substance from the group of the organic di-, tri- and oligocarboxylic acids or mixtures thereof are used as acidifying agents in the effervescent system.

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

Since textile fabrics, in particular rayon, rayon, cotton and their mixtures, can be wrinkled because the individual fibers prevent bending and kinking. If squeezing and squeezing across the grain are sensitive, the tray tablets can contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

To combat microorganisms, the trough tablets can contain antimicrobial agents. A distinction is made depending on the antimicrobial spectrum and mechanism of action between bacteriostatics and bactericides, fungiostatics and fungicides etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylariyl sulfonates, halophenols and phenol mercuric acetate, although these compounds can also be dispensed with entirely.

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

Increased wearing comfort can result from the additional use of antistatic agents, which are additionally added to the agents produced according to the invention. Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve. External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. The lauryl (or stearyl) dimethylbenzylammonium chlorides are suitable as antistatic agents for textiles or as an additive to detergents, with an additional avivage effect.

Silicone derivatives can be used in the trough tablets to improve the water absorption capacity, the rewettability of the treated textiles and to facilitate the ironing of the treated textiles. These additionally improve the rinsing behavior of the agents due to their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. The viscosities of the preferred silicones at 25 ° C. are in the range between 100 and 100,000 centistokes, the silicones being used in amounts between 0.2 and 5% by weight, based on the total agent.

Finally, the tray tablets according to the invention can also contain UV absorbers, which absorb onto the treated textiles and improve the light resistance of the fibers. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position. Also substituted are benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, 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 urocanoic acid are suitable.

The trough tablets according to the invention are particularly suitable for incorporating further ingredients into the cavity. Here, for example, a liquid can be poured into the trough, which is solidified by cooling, solidification, chemical reaction, time-delayed water binding, change in the rheological properties, etc. However, it is also possible to provide particulate fillings for the cavity, which are fixed in the cavity by adhesion promoters. A special case of this is the insertion of a single particle (hereinafter also referred to as the "core"), which adheres either through the use of adhesion promoters or through physical forces in the cavity. Last but not least, a particulate premix can be pressed into the well and there also one When using adhesion promoters, these can either be introduced into the cavity before the cavity filling is metered in, or afterwards (“spray adhesive effect”). The application of adhesion promoters is particularly necessary if the active substances to be applied subsequently do not have sufficient adhesion on their own to remain at least partially in the cavity and to withstand the mechanical loads during packaging, transport and handling without abrasion. In the case of cores which are not sufficiently adhesive, the adhesion promoter serves to "stick" these substances or compounds.

Substances can be used as adhesion promoters which impart sufficient adhesive power ("stickiness") to the shaped body surfaces to which they are applied, so that the substances applied in the subsequent process step adhere permanently to the surface. In principle, the relevant ones in the relevant adhesive literature and in particular are available here substances mentioned for this purpose in the monographs, in the context of the present invention the application of melts which have an adhesion-promoting effect at elevated temperature but are no longer sticky after cooling but are solid, are of particular importance.

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

Various requirements are placed on the adhesion promoters, which relate on the one hand to the melt or solidification behavior, but on the other hand also to the material properties in the solidified area at ambient temperature. Since the layer of the adhesion promoter applied to the molded body is intended to hold the "glued" active substances permanently during transportation or storage, it must have a high stability against, for example, shock loads occurring during packaging or transportation. The adhesion promoters should therefore either have at least partially elastic or at least plastic properties in order to react to an occurring shock load through elastic or plastic deformation and not to break Adhesion promoters should have a melting range (solidification range) in such a temperature range in which the active substances to be applied are not exposed to excessive thermal stress. On the other hand, however, the melting range must be sufficiently high to still offer effective adhesion of the applied active substances at at least a slightly elevated temperature. According to the invention, the coating substances preferably have a melting point above 30 ° C. The width of the melting range of the adhesion promoters also has direct effects on the implementation of the process: the molded article provided with the adhesion promoter must be brought into contact with the active substances to be applied in the subsequent process step - in the meantime, the adhesiveness must not be lost. After the active substances have been absorbed, the adhesive strength should be reduced as quickly as possible in order to avoid unnecessary loss of time or to prevent caking and congestion in subsequent process steps or handling and packaging. If melts are used, the reduction in adhesion can be supported by cooling (e.g. blowing with cold air).

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

The adhesion promoters preferably have a melting range which is between approximately 45 ° C. and approximately 75 ° C. In the present case, this means that the melting range occurs within the specified temperature interval and does not indicate the width of the melting range. The width of the melting range is preferably at least 1 ° C., preferably about 2 to about 3 ° C.

The properties mentioned above are usually fulfilled by so-called waxes. "Waxing" is understood to mean a number of natural or artificially obtained substances which generally melt above 40 ° C. without decomposition and which are relatively low-viscosity and not stringy even a little above the melting point. They have a strongly temperature-dependent consistency and solubility.

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

Natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walnut, lanolin (wool wax), or broom wax, mineral wax or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes. The chemically modified waxes include hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.

Synthetic waxes are generally understood to mean polyalkylene waxes or polyalkylene glycol waxes. Compounds from other classes of substance that meet the requirements regarding the softening point can also be used as adhesion promoters. As suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl, which is commercially available under the name Unimoll 66 ^® (Bayer AG), proved. Are also suitable Synthetic waxes of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ^® ETLP (Condea). Conversely, synthetic or partially synthetic esters from lower alcohols with fatty acids from native sources can also be used. Tegin ^® 90 (Goldschmidt), a glycerol monostearate palmitate, falls into this class of substances. Shellac, for example Shellac-KPS-Dreiring-SP (Kalkhoff GmbH), can also be used as an adhesion promoter according to the invention.

The so-called wax alcohols are also included in the waxes in the context of the present invention, for example. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols with usually about 22 to 40 carbon atoms. The wax alcohols occur, for example, in the form of wax esters of higher molecular fatty acids (wax acids) as the main component of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The step b) optionally applied adhesion promoter may optionally also contain wool wax alcohols which are understood to be triterpenoid and steroid alcohols, for example lanolin understood, which is obtainable for example under the trade name Argowax ^® (Pamentier & Co). In the context of the present invention, fatty acid glycerol esters or fatty acid alkanolamides can also be used, at least in part, as a constituent of the adhesion promoter, but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds.

The majority of the adhesion promoters contain paraffin wax. This means that preferably at least 50% by weight of the adhesion promoters, preferably more, consist of paraffin wax. Paraffin wax contents in the adhesion promoter of approximately 60% by weight, approximately 70% by weight or approximately 80% by weight are particularly suitable, with even higher proportions of, for example, more than 90% by weight being particularly preferred.

Paraffin waxes have the advantage over the other natural waxes mentioned in the context of the present invention that there is no hydrolysis of the waxes in an alkaline detergent environment (as is to be expected, for example, from the wax esters), since paraffin wax contains no hydrolyzable groups. Paraffin waxes consist mainly of alkanes and low levels of iso- and cycloalkanes. The paraffin to be used according to the invention preferably has essentially no constituents with a melting point of more than 70 ° C., particularly preferably of more than 60 ° C. Portions of high-melting alkanes in the paraffin can leave undesired wax residues on the surfaces to be cleaned or the goods to be cleaned if the melting temperature in the detergent solution drops below this. Such wax residues usually lead to an unsightly appearance on the cleaned surface and should therefore be avoided.

Preferably, the paraffin wax content of alkanes, isoalkanes and cycloalkanes which are solid at ambient temperature (generally about 10 to about 30 ° C.) is as high as possible. The more solid wax components present in a wax at room temperature, the more useful it is as an adhesion promoter in the context of the present invention. With increasing proportion of solid wax constituents, the resilience of the adhesion promoter layer to impacts or friction on other surfaces increases, which leads to a longer-lasting holding of the coated active substances. High proportions of oils or liquid wax components can weaken the particle adhesion, causing the glued active substances to detach from the molded body.

In addition to paraffin, the adhesion promoters can also contain one or more of the above-mentioned waxes or wax-like substances as the main constituent. In principle, the adhesion promoters should be such that the “adhesive layer” is at least largely water-insoluble. The solubility in water should not exceed about 10 mg / l at a temperature of about 30 ° C. and should preferably be below 5 mg / l.

If a temperature-controlled release of the adhered active substances is desired, the adhesion promoters should have as little water solubility as possible, even in water at an elevated temperature, in order to avoid as far as possible a temperature-independent release of the coated active substances.

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

The principle described above serves to delay the detachment of the “glued” active substances at a certain point in time, for example in the cleaning cycle of a dishwasher, and can be used particularly advantageously when washing in the main wash cycle at a lower temperature (for example 55 ° C.) so that the active substance is rinsed out the adhesive layer is only released in the rinse cycle at higher temperatures (approx. 70 ° C). However, the principle mentioned can also be reversed in that the active ingredient (s) are not released by the adhesive layer, but are released faster. This can be achieved in a simple manner in that dissolving retarders, rather than dissolving accelerators, are used as adhesion promoters, so that the glued-on active substances do not detach from the shaped body more slowly, but faster. In contrast to the poorly water-soluble adhesive agents described above, preferred adhesive agents are readily water-soluble for the rapid detachment. The water solubility of the adhesion promoters can be increased significantly by certain additives, for example by incorporating easily soluble salts or shower systems. Such accelerated adhesion promoters (with or without the addition of other solubility improvers) lead to a rapid detachment and release of the active substances at the beginning of the cleaning cycle.

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

Synthetic waxes from the group of polyethylene glycols and polypropylene glycols are particularly suitable as adhesion promoters for the accelerated release of the active substances from the detergent tablets.

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

H- (0-CH ₂ -CH ₂ ) _n -OH (III)

are sufficient, where n can have values between 1 (ethylene glycol) and over 100,000. The decisive factor in the assessment of whether a polyethylene glycol can be used according to the invention is the physical state of the PEG, i.e. 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 approximately 16 cannot be used, since they have a melting point below 30 ° C. The higher molecular weight polyethylene glycols are polymolecular, i.e. they consist of groups of macromolecules with different molecular weights. There are various nomenclatures for polyethylene glycols that can lead to confusion. The specification of the average relative molecular weight following the specification "PEG" is customary in technical terms, so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210. According to this nomenclature, the technically customary polyethylene glycols PEG 1550, PEG 3000, PEG 4000 and PEG 6000 can preferably be used in the context of the present invention.

A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and a number follows the hyphen directly after the hyphen Number n in formula III above corresponds. According to this nomenclature (so-called INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 * Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997) PEG-32, PEG-40, PEG-55, PEG- 60, PEG-75, PEG-100, PEG-150 and PEG-180 can preferably be used according to the invention.

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

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

H- (0-CH-CH ₂ ) _n -OH (IV)

CH,

are sufficient, where n values can be between 1 (propylene glycol) and approx. 1000. Similar to the PEG described above, the assessment of whether a polypropylene glycol can be used according to the invention depends on the physical state of the PPG, i.e. 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 approx. 15 cannot be used, since they have a melting point below 30 ° C.

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

Adhesion promoters preferred according to the invention are one or more substances from the groups of the paraffin waxes, preferably with a melting range from 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 also be applied as adhesion promoters. For this purpose, concentrated salt solutions are suitable, for example, which after application of the active substances are converted into an adhesion-promoting salt crust by crystallization or evaporation / evaporation. It is of course also possible to use supersaturated solutions or solutions of salts in solvent mixtures. Solutions or suspensions of water-soluble or water-dispersible polymers, preferably polycarboxylates, can also be used as adhesion promoters. The substances mentioned have already been described above because of their cobuilder properties.

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

Polyvinyl alcohols, abbreviated as PVAL, are polymers of the general structure

[-CH ₂ -CH (OH) -] _n

which 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 in solution via polymer-analogous reactions by hydrolysis, but technically in particular by alkaline-channeled transesterification of polyvinyl acetates with alcohols (preferably methanol). These technical processes also make PVAL accessible which contain a predeterminable residual proportion of acetate groups.

Commercial PVAL (for example Mowiol ^® types from Hoechst) are commercially available as white-yellowish powders or granules with degrees of polymerization in the range of approximately 500-2500 (corresponding to molar masses of approximately 20,000-100,000 g / mol) and have different degrees of hydrolysis from 98-99 and 87-89 mole%, respectively. They are therefore partially saponified polyvinyl acetates with a residual acetyl group content of approx. 1-2 or 1-13 mol%.

The water solubility of PVAL can be reduced by post-treatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus adjust to the desired values. The rheological properties of PVAL solutions can also be adjusted to the desired values by changing the molar mass or concentration, depending on how the solution is to be applied as an adhesion promoter.

Polyvinylpyrrolidones, abbreviated as PVP, can be identified by the general formula

describe.

PVP are made by radical polymerization of 1-vinyl pyrrolidone. Commercial PVPs have molar masses in the range of approx. 2500-750,000 g / mol and are offered as white, hygroscopic powders or as aqueous solutions.

Gelatin is a polypeptide (molecular weight: approx. 15,000-> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions. The amino acid composition of the gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance. The use of gelatin as a water-soluble coating material is extremely widespread, especially in the pharmaceutical industry in the form of hard or soft gelatin capsules.

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

Starch is a homoglycan, with the glucose units linked α-glycosidically. Starch is made up of two components of different molecular weights: approx. 20-30% straight-chain amylose (MW. Approx. 50,000-150,000) and 70-80% branched-chain amylopectin (MW. Approx. 300,000-2,000,000) still contain small amounts of lipids, phosphoric acid and cations. While the amylose forms long, helical, intertwined chains with about 300-1200 glucose molecules due to the binding in the 1,4-position, the chain in the amylopectin branches after an average of 25 glucose units through 1,6-binding to form a knot-like structure with about 1500-12000 molecules of glucose. In addition to pure starch, for the production of water-soluble bags within the scope of the present invention, starch derivatives are also obtainable from starch by polymer-analogous reactions. Such chemically modified starches include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Starches in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as starch derivatives. The group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and starches and amino starches. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) n and, formally speaking, is a ß-1,4 polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. In the context of the present invention, cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions can also be used as cellulose-based adhesion promoters. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.

Preferred adhesion promoters, which can be used as an aqueous solution, consist of a polymer with a molecular weight between 5000 and 500,000 daltons, preferably between 7500 and 250,000 daltons and in particular between 10,000 and 100,000 daltons. The layer of the adhesion promoter which is present between the individual shaped body regions (trough wall and second part) after the adhesion promoter has dried preferably has a thickness of 1 to 150 μm, preferably 2 to 100 μm, particularly preferably 5 to 75 μm and in particular 10 to 50 μm , on.

After the adhesion promoter has been applied, further active substances can be inserted into the cavity. The active substances can be applied in solid, highly viscous or plastic form.

Solid active substances can be applied to the cavity using apparatuses that are known, for example, from the confectionery industry. If a particulate solid is introduced into the cavity, that is to say more than one body is inserted into the cavity, the active substances introduced into the cavity are hereinafter referred to as “sprinkles” based on this area.

Depending on the type of sprinkle dosing and the shape and size of the sprinkles, the dosing accuracy with which a certain amount of further active substance is applied varies. In general, this dosing accuracy when applying sprinkles is subject to a certain fluctuation range of approx. +/- 10%. As active substances for such solid sprinkles to be introduced into the cavity, substances which have proven themselves in washing or Should dissolve cleaning cycle quickly, for example enzymes.

As already mentioned, the sprinkles can be produced in different shapes and sizes. In principle, the term "scattering" also means gluing a single dosing unit into the to understand vity, whereby this individual dosing unit naturally has a higher volume than the individual volume of dosing units which are introduced several times into the cavity. In the context of the present invention, for example, a hemispherical crumble can be glued into the trough. Other shapes for “sprinkles” and shaped bodies such as cubes, cuboids, semi-ellipsoids, cylinder segments, prisms, etc. are also conceivable and feasible.

However, preferred embodiments provide that the number of sprinkles that are glued into the trough is greater than 1. Such sprinkles then advantageously have the dimensions of conventional detergents and cleaning agents in powder, granule, extrudate, flake or plate form and are "glued" in multiple numbers.

The introduction of further active substance into the cavity in the form of a single dosage unit is also preferred. Thus, according to the invention, it is easily possible to glue together two separately produced molded bodies which can be positively attached or inserted into one another, one of the molded bodies being a tray tablet according to the invention. In addition to the insertion of individual dosing units, which have been produced by other methods, for example casting, extrusion, compression molding, etc., separately manufactured tablets are particularly suitable as a single dosing unit.

A particularly preferred embodiment of the present invention provides that the tray tablet has a cavity, the bottom and / or side surfaces of which are optionally provided with an adhesion promoter, after which a separately produced molded body which fits into the cavity is glued in place. Alternatively, the adhesion promoters can also be applied to individual surfaces of the molded body to be glued.

The cavity in the depression tablet can - as already mentioned - have any shape. It can cut through the molded part, i.e. have an opening on the top and bottom of the molded body, but it can also be a cavity that does not go through the entire molded body, the opening of which is only visible on one side of the molded body.

Adhesion promoter can be applied either to the molded article with cavitation or to the molded article that fills the cavity. Adhesion promoter is preferably introduced into the cavity of the molded body.

This procedure can be easily implemented in the case of mold bodies, since the metering can be carried out simply by dropping liquid adhesion promoters into the mold. Suitable dosing systems for large-scale dosing of small amounts of liquid into cavities are well known to the person skilled in the art. It is often technically easier to apply adhesion promoter to the molded body filling the cavity. In such cases, it is preferred to apply adhesion promoter to one or more surfaces, preferably to one surface, of the individual metering unit.

This application of adhesion promoter to preferably one surface of the individual dosing unit can take place in different ways. For example, it is possible to wet the separate dosing unit with adhesive on one side and then place it in the cavity. This technique is technologically simple to implement, but carries the risk that adhesive will contaminate the surface of the molded body with cavitation. In this variant, the amount of adhesive can be controlled by varying the rheological properties of the adhesion promoters.

A further possibility, which is preferred in the context of the present invention, of applying adhesion promoters to preferably one surface of the individual metering unit consists in passing this metering unit past adhesive metering systems and then placing them in the cavity. This is achieved by means of nozzles metering the adhesion promoter, brushes or fleeces impregnated with adhesion promoters or by rollers. The latter process design is particularly easy to implement in that the separate metering unit has only a small contact area with the roller. The adhesion promoter can be metered in from the inside of the roller, but it is also possible to apply the adhesion promoter to the roller at a point which is away from the point of contact of the roller with the separate metering units.

The filling of the cavity can completely fill the cavity, but it can also protrude from the cavity or fill it only partially, with no limits to the imagination of the product developers. By varying the shape of the tray tablets according to the invention, the shape of the trough or the hole and the shape of the separate metering unit, it is possible to produce a wide variety of molded body variations which differ greatly in appearance.

In the case of the trough shaped bodies, the adhesion of the separate dosing unit in the cavity decreases with a decreasing contact area. Maximum adhesion between the two shaped bodies is achieved if the trough shaped body and the separate dosing unit fit into one another without gaps.

Completely analogous to the production of two-phase moldings described above by gluing or gluing two separately pressed moldings to one another, three-phase moldings can also be produced. Here, it is either advisable to glue two separately produced molded articles in a tray tablet with two cavities, but it is also possible and preferred to produce a two-phase, for example a two-layer, gauze tablet and insert another molded article into it. The principle mentioned can be extended accordingly to further multiphase detergent tablets. For example, four-phase shaped articles can be produced by connecting two two-phase shaped articles (two-phase trough shaped articles according to the invention and two-phase “core”) to one another.

With regard to the composition of the second part that can optionally be inserted into the cavity, there are also no limits to the design options. It is possible, for example, to introduce certain ingredients into the second part in order to separate them from the ingredients in the trough tablets according to the invention. Of course, the second part can also contain several ingredients or can be a complete detergent or cleaning agent composition. In the context of the present invention, it is particularly preferred if the second part is assembled in such a way that it has an additional effect in the washing or cleaning process. In the case of detergents for automatic dishwashing, it is preferred to use "cores" in the trough tablets, which have the function of a nonslush phase ", a" performance booster "or a" rinse aid phase ", i.e. Release certain ingredients at predetermined times in the cleaning cycle (in the first case, for example, enzymes, in the second case, for example, bleaching agents and in the third case, for example, surfactants or deposit-inhibiting polymers or acids). It is particularly preferred to incorporate ingredients into the "core" that make the additional dosage of other necessary means unnecessary, for example rinse aid or regeneration salt. In the former case, the "core" represents a rinse aid phase, in the latter case salt substitutes are used in the " Kern "incorporated, which bind the water hardness and thus allow washing with hard water, without there being limescale deposits on the dishes or machine parts.

Detergent or cleaning agent tablets according to the invention are therefore particularly preferred which additionally have a second part which has the shape of a core or a body glued onto or into the first part (“base tablet”) and preferably one or more substances from the group of builders Contains acidifying agents, chelating agents or the deposit-inhibiting polymers.

Builders and acidifying agents have already been described above. Another possible group of ingredients for the second part are the chelating agents. Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination point on a central atom, ie being at least “bidentate”. In this case Normally, stretched verbs are formed into rings by complex formation via an ion. The number of ligands bound depends on the coordination number of the central ion. Common and preferred chelate complexing agents in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Complex-forming polymers, that is to say polymers which carry functional groups either in the main chain itself or laterally to it, which can act as ligands and which generally react with suitable metal atoms to form chelate complexes, can be used according to the invention. The polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or can belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.

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

In the context of the present invention, particular preference is given to detergent tablets with a “second part” used in the cavity, 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) phosphonopoyl carboxylic acids,

(vi) cyclodextrins

in amounts above 0.1% by weight, preferably above 0.5% by weight, particularly preferably above 1% by weight and in particular above 2.5% by weight, in each case based on the weight of the second part.

All complexing agents of the prior art can be used in the context of the present invention. These can belong to different chemical groups. The following are preferably used individually or in a mixture: a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, such as gluconic acid, b) nitrogen-containing mono- or polycarboxylic acids, such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, 3-nitridodiacetic acid, nitridodiacetic acid , N, N-Di- (ß-hydroxyethyl) glycine, N- (1, 2-dicarboxy-2-hydroxyethyl) glycine, N- (1, 2-dicarboxy-2-hydroxyethyl) aspartic acid or nitrilotriacetic acid (NTA), c) geminal diphosphonic acids such as 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), their higher homologues with up to 8 carbon atoms as well as derivatives thereof containing hydroxy or amino groups and 1-aminoethane-1, 1- diphosphonic acid, its higher homologs with up to 8 carbon atoms and derivatives thereof containing hydroxyl or amino groups, d) aminophosphonic acids such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (m ethylene phosphonic acid) or nitrilotri (methylene phosphonic acid), e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1, 2,4-tricarboxylic acid and f) cyclodextrins.

In the context of this patent application, polycarboxylic acids a) are understood to mean carboxylic acids - also monocarboxylic acids - in which the sum of carboxyl and the hydroxyl groups contained in the molecule is at least 5. Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. At the alkaline pH values of the treatment solutions required according to the invention, these complexing agents are at least partially present as anions. It is immaterial whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali metal, ammonium or alkylammonium salts, in particular sodium salts, are preferred.

In the case of the deposit-inhibiting polymers as an ingredient of the second part, washing or cleaning-agent tablets are particularly preferred, which are characterized in that the second part comprises one or more deposit-inhibiting polymers from the group of the cationic homo- or copolymers, in particular hydroxypropyltrimethylammonium guar; Copolymers of aminoethyl methacrylate and acrylamide, copolymers of dimethyldiallylammonium chloride and acrylamide, polymers with imino groups, polymers which have quaternized ammonium alkyl methacrylate groups as monomer units, cationic polymers of monomers such as trialkylammonium alkyl (meth) acrylate or acrylamide; Dialkyldiallyldiammoniumsalze; polymer-analogous reaction products of ethers or esters of polysaccharides with ammonium side groups, in particular guar, cellulose and starch derivatives; Polyadducts of ethylene oxide with ammonium groups; quaternary ethyleneimine polymers and polyesters and polyamides with quaternary side groups in amounts above 5% by weight, preferably above 10% by weight, particularly preferably above 20% by weight and in particular above 25% by weight, in each case based on the weight of the second part. Another preferred ingredient for the second part are certain copolymers containing sulfonic acid groups. Detergent tablets, the second part of which are one or more copolymers, are also tablets

i) unsaturated carboxylic acids ii) monomers containing sulfonic acid groups iii) optionally further ionic or nonionic monomers

in amounts above 5% by weight, preferably above 10% by weight, particularly preferably above 20% by weight and in particular above 25% by weight, based in each case on the weight of the second part 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 (V),

in which 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 represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids that can be described by 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) preferred.

In the case of the monomers containing sulfonic acid groups, preference is given to those of the formula VI

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (VI),

in which 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 represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally available spacer group is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) - NH-C (CH ₃ ) ₂ - and -C (0) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas Via, VIb and / or Vlc,

H ₂ C = CH-X-S0 ₃ H (via),

H ₂ C = C (CH ₃ ) -X-S0 ₃ H (VIb),

H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (Vlc),

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 represents an optionally present spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and - C (0) -NH- CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid (X = -C (0) NH-CH (CH ₂ CH ₃ ) in the formula Via), 2-acrylamido-2-propanesulfonic acid (X = -C ( 0) NH-C (CH ₃ ) ₂ in formula Via), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = -C (0) NH-CH (CH ₃ ) CH ₂ - in formula Via), 2 -Methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (0) NH- CH (CH ₃ ) CH ₂ - in formula VIb), 3-methacrylamido-2-hydroxypropane sulfonic acid (X = -C (Ö) NH-CH ₂ CH (OH) CH ₂ - in formula VIb), allylsulfonic acid (X = CH ₂ in formula Via), methallylsulfonic acid (X = CH ₂ in formula VIb), allyloxybenzenesulfonic acid (X = -CH ₂ -0-C ₆ H ₄ - in formula Via), methallyloxybenzenesulfonic acid (X = -CH ₂ -0-C ₆ H - in formula VIb), 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2- propen1-sulfonic acid (X = CH ₂ in formula VIb), styrene sulfonic acid (X = C ₆ H ₄ in formula via), vinyl sulfonic acid (X not present in formula via), 3-sulfopropyl acrylate (X = -C (0 ) NH-CH ₂ CH ₂ CH ₂ - in the form el Via), 3-sulfopropyl methacrylate (X = -C (0) NH- CH ₂ CH ₂ CH ₂ - in formula VIb), sulfomethacrylamide (X = -C (0) NH- in formula VIb), sulfomethyl methacrylamide (X = -C (0) NH-CH ₂ - in formula VIb) and water-soluble salts of the acids mentioned.

Other ionic or nonionic monomers that can be used are, in particular, ethylenically unsaturated compounds. The group iii) content of the polymers used according to the invention is preferably less than 20% by weight, based on the polymer. Polymers particularly preferably contained in the second part consist only of monomers of groups i) and ii).

In the second part, particularly preferred detergent or cleaning agent tablets contain one or more copolymers i) one or more unsaturated carboxylic acids from the group consisting of acrylic acid, methacrylic acid and / or maleic acid

ii) one or more monomers of the formulas Via, VIb and / or Vlc containing sulfonic acid groups:

H ₂ C = CH-X-S0 ₃ H (via),

H ₂ C = C (CH ₃ ) -X-S0 ₃ H (VIb),

H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (Vlc),

> in which R ⁶ and R ⁷ are selected independently of one another from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally present spacer group, which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and -C (0) -NH-CH (CH ₂ CH ₃ ) -

iii) optionally further ionic or nonionic monomers.

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

For example, detergent or cleaning agent tablets according to the invention are preferred, which are characterized in that the second part contains one or more copolymers, the structural units of the formula VII

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (Ö) -Y-S0 ₃ H] _p - (VII),

contain, in which m and p each represent an integer between 1 and 2000 and Y stands for a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -0- (CH ₂ ) _n - with n = 0 to 4, for -0- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

These polymers are produced by copolymerization of acrylic acid with an acrylic acid derivative containing sulfonic acid groups. If the sulfonic acid group-containing acrylic acid derivative is copolymerized with methacrylic acid, another polymer is obtained, the use of which in the second part of the cleaning agents according to the invention is also preferred and is therefore characterized is that one or more copolymers are used, the structural units of formula VIII

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (VIII),

Completely analogously, acrylic acid and / or methacrylic acid can also be copolymerized with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. So washing or cleaning agent tablets according to the invention are preferred, the second part of one or more copolymers, the structural units of the formula IX

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p - (IX),

contains, in which m and p each represent an integer between 1 and 2000 and Y stands for a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -0- (CH ₂ ) _n - with n = 0 to 4, for -0- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is, are also preferred, a preferred embodiment of the present invention, just as washing or cleaning agent 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 (0) -Y-S0 ₃ H] _p - (X),

Instead of or in addition to acrylic acid and / or methacrylic acid, maleic acid can also be used as a particularly preferred monomer from group i). In this way, washing or cleaning agent tablets preferred according to the invention are obtained, which thereby 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 (0) -Y-S0 ₃ H] _p - (XI),

contain, in which m and p each represent an integer between 1 and 2000 and Y stands for a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -0- (CH ₂ ) _n - with n = 0 to 4, for -0- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or - NH-CH (CH ₂ CH ₃ ) - stands, are preferred and for washing or cleaning agent 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 (0) 0-Y-S0 ₃ H] _p - (XII),

The sulfonic acid groups in the polymers may be wholly or partly in neutralized form, i.e. that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by sodium ions. Corresponding cleaning agents which are characterized in that the sulfonic acid groups in the copolymer are partially or fully neutralized are preferred according to the invention.

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

In the case of terpolymers, those which contain 20 to 85% by weight of monomer from group i), 10 to 60% by weight of monomer from group ii) and 5 to 30% by weight of monomer from group iii) are particularly preferred ,

The molar mass of the polymers contained in the second part according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use. Before- Drawn cleaning agents are characterized in that the copolymers have molar masses from 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 additional benefit of being able to dispense with the addition of regeneration salt, the preferred products according to the invention described above also make the additional addition of a rinse aid unnecessary.

The parent application detergent or cleaning agent tablets according to the invention, which comprise at least one cavity and contain 5 to 25% by weight of nonionic surfactant (s), in each case based on the tablet, can also be of a multi-phase design, the content of the phase, which has the cavity of 5 to 25% by weight of nonionic surfactants. Both the single-phase and the multi-phase detergent tablets according to the invention can additionally have a second part which has the shape of a core or a body glued onto or into the first part (“base tablet”) and preferably one or more substances from the Group of builders, acidifiers, chelating agents or deposit-inhibiting polymers.

The above-described polymers containing sulfonic acid groups bring about a further additional benefit when incorporated into the washing or cleaning agent tablets according to the invention. It is initially irrelevant whether the polymers containing sulfonic acid groups are contained in the tensile trough tablet (“base tablet”) itself or in a further part (“core”) or in both parts. However, further particular advantages can result from the distribution of the polymer over the two parts.

Thus, cleaning agents according to the invention are preferred which, in addition to the nonionic surfactants, contain polymers containing sulfonic acid groups. In the inventive agents of this embodiment, the amounts of surfactants remaining in the machine after the main rinse cycle and the intermediate rinse cycles result in an adequate drainage behavior in the rinse cycle, so that the water running off the dishes does not leave any stains on drying. In addition, the sulfonic acid group-containing polymer used acts as an effective softener, so that even in high hardness areas it can be rinsed with non-softened water without causing deposits on the items to be washed or the machine. When using these agents according to the invention, the rinse aid does not need to be loaded with additional deliberately added rinse aid, and the use of regeneration salt can also be dispensed with. The products described in this additional application thus represent real "3-in-1" products that combine the conventional detergents, rinse aid and regeneration salt agents in one. The present invention therefore furthermore relates to detergent tablets according to the invention which additionally contain 0.1 to 70% by weight of copolymers of i) unsaturated carboxylic acids ii) monomers containing sulfonic acid groups iii) optionally further ionic or nonionic monomers.

In the case of multi-phase tablets, a corresponding composition of the phase which has the cavity, i.e. of the pre-mix that comes into contact with the non-flat ram during final pressing. Since the first premix is only slightly compressed by pressing with the stamp during pre-compression steps (for example in the manufacture of two-layer tablets), there are no signs of adhesion or edge breakage. Only at the final pressing do the forces become so great that the problems mentioned are to be feared.

The use of sulfonated copolymers was already described above in a second part, which is inserted or glued as the "core" in the surfactant-rich tray tablet ("base tablet"). The sulfonated copolymers can, however, not only be incorporated into the "core", but also into the base tablet, it being possible for cores present in the base tablets to contain or be free of the copolymer (s).

Regardless of where the sulfonated copolymer (s) are contained in the washing or cleaning agent tablets according to the invention, those washing or cleaning agent tablets are preferred which contain the sulfonated copolymer (s) in amounts of 0.25 to 50% by weight. %, preferably from 0.5 to 35% by weight, particularly preferably from 0.75 to 20% by weight and in particular from 1 to 15% by weight, in each case based on the entire tablet.

The sulfonated copolymers are described broadly above, so that reference can be made to the statements there. In general, detergent tablets are also preferred here, which contain one or more copolymers which have structural units of the formulas III and / or IV and / or V and / or VI and / or VII and / or VIII

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (VII),

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (VIII),

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p - (IX),

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (XI),

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) 0-Y-S0 ₃ H] _p - (XII), contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -0- (CH ₂ ) _n - with n = 0 to 4, for -0- (C ₆ H ₄ ) -, for -NH- C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

As already mentioned above, particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propane sulfonic 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-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenl-sulfone- acid, styrene sulfonic acid, vinyl sulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethyl methacrylamide and water-soluble salts of the acids mentioned.

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

Regardless of whether a "core" is inserted or glued into the tablets according to the invention, the tablets themselves can contain the sulfonated copolymer (s). Here, detergent or cleaning agent tablets according to the invention are preferred, in which the tray tablet ( “Base tablet”), based on its weight, 0.5 to 30% by weight, preferably 1 to 25% by weight, particularly preferably 2.5 to 20% by weight and in particular 4 to 15% by weight, of the contains the sulfonated copolymer (s / e).

It is particularly preferred if a core is present and both the core and the base tablet contain the sulfonated copolymer (s). With particular advantage, the polymer is not distributed equally in the core and base tablet, but is predominantly localized in the base tablet. Here, detergent tablets according to the invention are preferred, in which both the base tablet and the core contain the sulfonated copolymer (s), 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 is contained in the base tablet. In the case of earlier products, parts of the product had to be protected from early release into the application fleet by suitable measures, such as coating, so that the measures achieved a controlled release of individual ingredients. Surprisingly, this is not necessary in the detergent or cleaning agent tablets according to the invention, so that no coating is required either for the base tablet or for the core which may be present in order to achieve a rinse aid effect and to be able to dispense with regenerating salt. 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 polymers containing sulfonic acid groups used according to the invention with nonionic surfactants in large quantities, agents according to the invention which, in addition to the sulfonated copolymers, contain further homo- and / or copolymeric polycarboxylic acids or polycarboxylates have been found to be particularly suitable.

Combinations of the sulfonated copolymers with heteroatom-containing polymers or copolymers, in particular those with amino or phosphono groups, are also suitable.

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

The corresponding homo- or copolymeric polycarboxylic acids or polycarboxylates are described in detail above as cobuilders. The combination of the two polymers in these agents according to the invention is particularly effective since the sulfonated polymers counteract, in particular, phosphate-containing deposits, while the carboxylate-containing polymers prevent the precipitation of calcium carbonate. In combination, both types of polymer show a synergistic effect against deposits on the dishes and machine parts.

The combination with polymers and copolymers containing amino and / or phosphono groups is advantageous in builder systems which only partially are phosphate based, e.g. Phosphate / citrate mixing systems.

The two dosing processes required to operate a household dishwasher at intervals (after a certain number of rinsing processes, the regeneration salt must be refilled in the water softening system of the machine) can be combined into a single process using the inventive agents described above, since also after a higher number of rinsing cycles, the dosing of another product (regeneration salt) and therefore a double dosing process is not necessary.

In addition to the added benefit of being able to dispense with the addition of regenerating salt, the preferred products according to the invention described above also make the additional addition of a rinse aid superfluous.

Another object of the present invention is a process for the production of detergent or cleaning agent tablets with at least one cavity, in which a particulate premix whose content of nonionic surfactants is 5 to 25% by weight, in each case based on the premix, is known per se Way is pressed into trough tablets.

As described in detail above, in the case of multi-phase / multi-layer tablets, a corresponding non-ionic surfactant content in the phase / layer is sufficient, which during the final compression has contact with the press die which impresses the cavity. Another object of the present invention is therefore also a process for the production of multiphase detergent or cleaning agent tablets with at least one cavity, in which several particulate premixes are pressed into trough tablets in a manner known per se, the content of the premix being used in the final compression of the tablet is contacted with the stamp for pressing in the cavity, has a nonionic surfactant content of 5 to 25% by weight, based in each case on the premix.

The tableting of the single-phase or multiphase trough tablets proceeds analogously to conventional tableting, with the exception that the pressing surface of at least one ram is not flat, but rather has at least one elevation which shapes the cavity (s) in the shaped bodies according to the invention. It has proven advantageous here if the compressed premix meets certain physical criteria. Preferred processes are characterized, for example, in that particulate premixes to be compressed have a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l.

The particle size of the compressed premix preferably also meets certain criteria: Methods in which particulate premixes have particle sizes between 100 and 2000 μm, preferably between 200 and 1800 μm, particularly preferably between 400 and 1600 μm and in particular between 600 and 1400 μm are preferred according to the invention , A further narrowed particle size in the premixes to be pressed can be adjusted in order to obtain advantageous molded body properties. In preferred variants for the process according to the invention, particulate premixes to be compressed have a particle size distribution in which less than 10% by weight, preferably less than 7.5% by weight and in particular less than 5% by weight of the particles larger than 1600 μm or less than 200 μm. Here are narrower particle size distributions more preferred. Particularly advantageous process variants are characterized in that the particulate premixes to be compressed have a particle size distribution in which more than 30% by weight, preferably more than 40% by weight and in particular more than 50% by weight of the particles have a particle size between 600 and 1000 μm.

When tableting is carried out, the method preferred according to the invention is not restricted to the fact that only a particulate premix is pressed into a shaped body. Rather, this process step can also be expanded to the effect that multilayer molded articles are produced in a manner known per se by preparing two or more premixes which are pressed together. In this case, the premix which has been filled in first is lightly pre-pressed in order to obtain a smooth upper surface and, after the second premix has been filled in, is finally pressed to give the finished shaped body. In the case of three-layer or multi-layer molded articles, a further pre-compression is carried out after each addition of the premix before the molded article is finally pressed after the addition of the last premix. Preferably, the above-described cavity in the base molding is a trough, so that preferred embodiments of the first method according to the invention are characterized in that multilayered moldings which have a trough are produced in a manner known per se by pressing several different particulate premixes onto one another. In this case (if the upper punch is the non-planar press punch) only the last premix has to meet the criteria according to the invention - however, it may be desirable that several or all premixes contain at least 5% by weight nonionic surfactant (s) despite an otherwise different composition.

The molded articles are first produced by dry mixing the constituents, which can be wholly or partially pre-granulated, and then providing information, in particular pressing them into tablets, whereby conventional methods can be used. To produce the moldings according to the invention, the premix is compacted in a so-called die between two punches to form a solid compressed product. This process, which is briefly referred to as tableting in the following, is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection.

First of all, the premix is introduced into the die, the filling quantity and thus the weight and the shape of the molding being formed being determined by the position of the lower punch and the shape of the pressing tool. The constant metering, even at high molding throughputs, is preferably achieved by volumetric metering of the premix. As the tableting continues, the upper punch touches the premix and lowers further in the direction of the lower punch. During this compression, the particles of the premix are pressed closer together, the void volume within the filling between the punches continuously decreasing. From a certain position of the top The plastic deformation begins (and thus from a certain pressure on the premix), in which the particles flow together and the molded body is formed. Depending on the physical properties of the premix, some of the premix particles are crushed and sintering of the premix occurs at even higher pressures. With increasing pressing speed, that is to say high throughput quantities, the phase of elastic deformation is shortened further and further, so that the resulting shaped bodies can have more or less large cavities. In the last step of tableting, the finished molded body is pressed out of the die by the lower punch and transported away by subsequent transport devices. At this point in time, only the weight of the molded body is finally determined, since the compacts can still change their shape and size due to physical processes (stretching, crystallographic effects, cooling, etc.).

Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double stamps. In the latter case, not only is the upper stamp used to build up pressure, the lower stamp also moves towards the upper stamp during the pressing process, while the upper stamp presses down. For small production quantities, eccentric tablet presses are preferably used, in which the stamp or stamps are attached to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed. The movement of these rams is comparable to that of a conventional four-stroke engine. The pressing can take place with one upper and one lower punch, but several punches can also be attached to one eccentric disc, the number of die holes being correspondingly increased. The throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs, rotary tablet presses are selected in which a larger number of dies is arranged in a circle on a so-called die table. The number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available. Each die on the die table is assigned an upper and lower punch, and again the pressure can be built up actively only by the upper or lower punch, but also by both stamps. The die table and the stamps move around a common vertical axis, the stamps being brought into the positions for filling, compression, plastic deformation and ejection by means of rail-like curved tracks during the rotation. Wherever a particularly serious lifting or lowering of the punches is required (filling, compacting, ejecting), these cam tracks are supported by additional low-pressure pieces, low-tension rails and lifting tracks. The die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix. The pressing pressure on the premix can be individually adjusted via the pressing paths for the upper and lower punches, the pressure being built up by rolling the punch shaft heads past adjustable pressure rollers. Rotary presses can also be provided with two filling shoes to increase the throughput, with only a semicircle having to be run through to produce a tablet. For the production of two- and multi-layer moldings, several filling shoes are arranged one behind the other without the slightly pressed first layer being ejected before further filling. With suitable process control, jacket and dot tablets can also be produced in this way, which have an onion-shell-like structure, the top side of the core or the core layers not being covered in the case of the dot tablets and thus remaining visible. Rotary tablet presses can also be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used simultaneously for pressing. The throughputs of modern rotary tablet presses are over one million tablets per hour.

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

- Use of plastic inserts with small thickness tolerances

- Low number of revolutions of the rotor

- Big filling shoes

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

- Filling shoe with constant powder height

- Decoupling of filling shoe and powder feed

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

It was also shown that long pressing times are advantageous. These can be set with pressure rails, several pressure rollers or low rotor speeds. Since the fluctuations in the hardness of the tablet are caused by the fluctuations in the pressing forces, systems should be used which limit the pressing force. Here elastic stamps, pneumatic compensators or resilient elements can be used in the force path. The pressure roller can also be designed to be resilient. Tableting machines suitable within the scope of the present invention are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Hörn & Noack Pharmatechnik GmbH, Worms, IMA Verpackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms. Other providers include Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy NV, Halle (BE / LU) and Mediopharm Kamnik (Sl). For example, the hydraulic double-pressure press HPF 630 from LAEIS, D. Tablettierwerkzeuge are, for example, from the companies Adams Tablettierwerkzeuge, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Söhne GmbH, Hamburg, Hofer GmbH, Weil, Hörn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Werkzeugbau, Tamm available. Other providers include Senss AG, Reinach (CH) and Medicopharm, Kamnik (Sl).

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

However, it is also possible that the various components are not pressed into a uniform tablet, but that shaped bodies are obtained which have several layers, that is to say at least two layers. It is also possible that these different layers have different dissolving speeds. This can result in advantageous performance properties of the molded articles. If, for example, components are contained in the moldings which have a mutually negative effect, it is possible to integrate one component in the more rapidly soluble layer and to incorporate the other component in a more slowly soluble layer, so that the first component has already reacted. when the second goes into solution. The layer structure of the shaped bodies can be stacked, with the inner layer (s) already loosening at the edges of the shaped body when the outer layers have not yet been completely detached, but it is also possible for the inner layer (s) to be completely encased ) can be achieved by the outer layer (s), which leads to the premature detachment of components of the inner layer (s).

In a further preferred embodiment of the invention, a shaped body consists of at least three layers, ie two outer and at least one inner layer, at least A peroxy bleaching agent is contained in one of the inner layers, while the two outer layers in the case of the stacked shaped body and the outermost layers in the case of the shell-shaped shaped body are free of peroxy bleaching agent. Furthermore, it is also possible to spatially separate peroxy bleaching agents and any bleach activators and / or enzymes that may be present in a molded body.

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

2P πDt

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

The detergent or cleaning agent tablets according to the invention can be packaged after production, the use of certain packaging systems having proven particularly useful, since these packaging systems on the one hand increase the storage stability of the ingredients, and on the other hand surprisingly also in the case of moldings with cavities and inserted second part, the long-term liability of Improve well filling significantly. Another object 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 permeability rate of 0.1 g / m ² / Day to less than 20 g / m ² / day if the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%.

The packaging system of the combination of detergent or cleaning agent tablet (s) and packaging system according to the invention has a moisture vapor permeability rate of 0.1 g / m ² / day to less than 20 g / m ² / day when the packaging system is at 23 ° C. and a relative Equilibrium moisture of 85% is stored. The specified temperature and humidity conditions are the test conditions that are mentioned in the DIN standard 53122, whereby according to DIN 53122 minimal deviations are permitted (23 ± 1 ° C, 85 ± 2% relative humidity). The moisture vapor permeability rate of a given packaging system or material can be determined by further standard methods and is, for example, also in the ASTM standard E-96-53T ("Test for measuring Water Vapor transmission of Materials in Sheet form") and in the TAPPI standard T464 m-45 ("Water Vapor Permeability of Sheet Materials at high temperature an Humidity"). The measuring principle of common methods is based on water absorption me of anhydrous calcium chloride, which is stored in a container in the appropriate atmosphere, the container being sealed at the top with the material to be tested. The moisture vapor permeability rate can be determined from the surface of the container which is sealed with the material to be tested (permeation surface), the weight gain of the calcium chloride and the exposure time

24-10000

FDDR = ^Z "- ^WW ° ^ [gfmX24h} A y ^{[ä J}

calculate, 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 humidity, often referred to as “relative air humidity”, is 85% at 23 ° C. when measuring the moisture vapor permeability rate within the scope of the present invention. The capacity of air for water vapor increases with temperature up to a respective maximum content, the so-called saturation content, and is given in g / m ^3. For example, 1 m ^{3 of} air at 17 ° is saturated with 14.4 g of water vapor, at a temperature of 1 ° there is already saturation with 10 g of water vapor Percentage expressed ratio of the actual water vapor content to the saturation content corresponding to the prevailing temperature. For example, if air contains 17 ° 12 g / m ³ water vapor, then the relative air humidity = (12 / 14.4) - 100 = 83% If one cools this air, then the saturation (100% r.L.) is reached at the so-called dew point (in the example: 14 °), ie at After cooling, a precipitate is formed in the form of fog (dew). Hygrometers and psychrometers are used for the quantitative determination of moisture.

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

The combinations of detergent or cleaning agent tablet (s) and packaging system according to the invention can of course in turn be packaged in secondary packaging, for example cardboard boxes or trays, with no further requirements being placed on the secondary packaging. Secondary packaging is therefore possible, but not necessary.

Packaging systems preferred within the scope of the present invention have a moisture vapor permeability rate of 0.5 g / m ² / day to less than 15 g / m ² / day. Depending on the embodiment of the invention, the packaging system of the combination according to the invention encloses one or more washing or cleaning agent tablets. It is preferred according to the invention either to design a shaped body in such a way that it comprises an application unit of the detergent or cleaning agent, and to pack this tablet individually, or to pack the number of tablets in a packaging unit which in total comprises one application unit. With a nominal dosage of 80 g of detergent or cleaning agent, it is therefore possible according to the invention to produce and individually pack an 80 g washing or cleaning agent tablet, but it is also possible according to the invention to pack two 40 g washing or cleaning agent tablets in one package to arrive at a combination according to the invention. This principle can of course be expanded so that combinations according to the invention can also contain three, four, five or even more detergent or cleaning agent tablets in one packaging unit. Of course, two or more washing or cleaning agent tablets in one package can have different compositions. In this way it is possible to spatially separate certain components from one another, for example in order to avoid stability problems.

The packaging system of the combination according to the invention can consist of a wide variety of materials and can take any external shape. For economic reasons and for reasons of easier processability, however, packaging systems are preferred in which the packaging material is light in weight, easy to process and inexpensive. In combinations preferred according to the invention, the packaging system consists of a sack or pouch made of single-layer or laminated paper and / or plastic film.

The detergent or cleaning agent tablets can be unsorted, i.e. as a loose fill, be filled into a bag made of the materials mentioned. However, for aesthetic reasons and to sort the combinations in secondary packaging, it is preferred to fill the detergent or cleaning agent tablets individually or in groups in sacks or bags. For individual application units of detergent or cleaning agent tablets that are in a sack or bag, the term "flow pack" has become common in technology. Such "flow packs" can then - again preferably sorted - optionally be packaged in outer packaging, whatever the compact form of the tablet underlines.

The sacks or bags made of single-layer or laminated paper or plastic film, which are preferably to be used as a packaging system, can be designed in a wide variety of ways, for example as a blown-up bag without a central seam or as a bag with a central seam which is sealed by heat (hot fusion), adhesives or adhesive tapes become. Single-layer bag or sack materials are the known papers, which can optionally be impregnated, and plastic films, which can optionally be co-extruded. Plastic films that are used as a packaging system in the context of the present invention can, for example, be given in Hans Domininghaus "The plastics and their properties", 3rd edition, VDI Verlag, Düsseldorf, 1988, page 193. Figure 111 shown there also gives indications of the water vapor permeability of the materials mentioned.

Combinations which are particularly preferred in the context of the present invention contain, as a packaging system, a sack or pouch made of single-layer or laminated plastic film with a thickness of 10 to 200 μm, preferably 20 to 100 μm and in particular 25 to 50 μm.

Although it is possible to use wax-coated papers in the form of cardboard boxes as packaging systems for the detergent or cleaning agent tablets in addition to the films or papers mentioned, it is preferred in the context of the present invention if the packaging system does not include boxes made of wax-coated paper. In the context of the present invention, the term ner packaging system always denotes the primary packaging of the cleaning agents or moldings, i.e. the packaging, which is in direct contact with the molded body surface on the inside. No requirements are placed on an optional secondary packaging, so that all common materials and systems can be used here.

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

The relative equilibrium moisture content of the detergent or cleaning agent tablets can be determined using customary methods, the following procedure being chosen in the context of the present investigations: A water-impermeable 1-liter container with a lid, which has a closable opening for introducing samples , was filled with a total of 300 g detergent or cleaning agent tablets and kept at a constant 23 ° C for 24 h to ensure a uniform temperature of the vessel and substance. The water vapor pressure in the space above the moldings can then be determined using a hygrometer (Hygrotest 6100, Testoterm Ltd., England). The water vapor pressure is now measured every 10 minutes until two successive values show no deviation (equilibrium moisture). The above 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 to be reclosable. Combinations in which the packaging system has a microperforation can also be preferably implemented according to the invention. The compositions according to the invention can be used in all household dishwashers, with no restrictions on the choice of program. The advantageous effects are achieved in low-temperature programs such as 45 ° C programs or glass programs as well as in 50/55 ° C or 60/65 ° C programs.

Another object of the present invention is therefore a method for cleaning dishes in a domestic dishwasher, in which one or more detergent tablets (s) according to the invention are introduced into the main cleaning cycle of the machine.

It can be introduced into the main cleaning cycle by filling the dosing chamber with the tablet (s), the tablet (s) being released into the machine by opening the dosing chamber after a possible pre-cleaning cycle. Alternatively, it is also possible to insert the tablet (s) directly into the machine and thus release active substance in an optional pre-cleaning cycle. Alternatively, a pre-cleaning cycle can also be dispensed with. By means of the agents according to the invention, no additional rinse aid needs to be metered in the rinse aid, methods according to the invention in which the rinse aid of the machine is carried out without the intentional addition of further rinse aid are therefore preferred.

The term "further rinse aid" includes liquid commercial rinse aid which must be placed in a storage container of the machine by the consumer at intervals of several rinsing cycles and released from there under program control. This deliberate addition of a rinse aid and the required second metering step are at intervals of a few rinsing cycles not required due to the use of the agents according to the invention.

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 wash ware with an aqueous cleaning liquor composed 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 wash ware with a rinse cycle.

As already mentioned, the advantages of the present invention are achieved even if the main cleaning cycle and the rinse cycle are interrupted by intermediate rinse cycles. Preferred methods are therefore characterized in that one or more intermediate rinse cycles take place between steps a) and b). Here, too, the additional deliberate addition of commercially available rinse aid is not necessary, so that processes are preferred in which no further rinse aid is intentionally added in step b).

Completely analogously, washing processes according to the invention for washing textiles in household washing machines are further objects of the present invention. Here, detergent tablets according to the invention are used instead of detergent tablets according to the invention.

Claims

claims:

1. washing or cleaning agent tablets, comprising at least one cavity, characterized in that the tablet content of nonionic surfactants is 5 to 25% by weight, based in each case on the tablet.

2. Multi-phase washing or cleaning agent tablets, comprising at least one cavity, characterized in that the content of the phase, which has the cavity, of nonionic surfactants is 5 to 25% by weight.

3. washing or cleaning agent tablets according to one of claims 1 or 2, characterized in that the cavity has lateral boundary walls which are orthogonal to the base.

4. washing or cleaning agent tablets according to one of claims 1 to 3, characterized in that the surface of the cavity opening makes up 1 to 25%, preferably 2 to 20%, particularly preferably 3 to 15% and in particular 4 to 10% of the total surface of the tablet ,

5. washing or cleaning agent tablets according to one of claims 1 to 4, characterized in that they nonionic (s) surfactant (s) with a melting point above 20 ° C, preferably above 25 ° C, particularly preferably between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C, in amounts of 5.5 to 20 wt .-%, preferably from 6.0 to 17.5 wt .-%, particularly preferably from 6.5 to 15 and in particular from 7.0 to 12.5% by weight, based in each case on the tablet or the phase which has the cavity.

6. washing or cleaning agent tablets according to any one of claims 1 to 5, characterized in that the nonionic surfactant (s) is / are ethoxylated (s) nonionic surfactant (s), which / which from C ₆ - ₂₀ - monohydroxyalkanols or C ₆ - ₂ o-alkylphenols or C ₁₆ - ₂ o-fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.

7. washing or cleaning agent tablets according to one of claims 1 to 6, characterized in that they or the phase which has the cavity contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably make up up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant.

8. washing or cleaning agent tablets according to one of claims 1 to 7, characterized in that they or the phase which has the cavity, nonionic surfactants of the formula R ¹ 0 [CH ₂ CH (CH ₃ ) 0] _x [CH ₂ CH ₂ 0] _y [CH ₂ CH (OH) R ² ]

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

9. washing or cleaning agent tablets according to one of claims 1 to 8, characterized in that they or the phase which has the cavity, end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x CH ₂ CH (OH) CH ₂ OR ²

10. washing or cleaning agent tablets according to one of claims 1 to 9, characterized by a content of a) 1, 0 to 4.0 wt .-% nonionic surfactants from the group of alkoxylated alcohols, b) 4.0 to 24.0 % By weight of nonionic surfactants from the group of the hydroxyl-containing alkoxylated alcohols (“hydroxy mixed ethers”), in each case based on the entire tablet or the phase which has the cavity.

11. washing or cleaning agent tablets according to claim 10, containing a) 1.5 to 3.5 wt .-%, preferably 1.75 to 3.0 wt .-% and in particular 2.0 to 2.5 wt .-% 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 in particular 7.0 to 10.0% by weight of nonionic surfactants from the group of the hydroxyl-containing alkoxylated alcohols (“hydroxy mixed ethers”) in each case based on the entire tablet or the phase which has the cavity.

12. Detergent or cleaning agent tablets according to one of claims 1 to 11, characterized in that they additionally have a second part which has the shape of a core or a body glued to or in the first part (“base tablet”) and preferably one or contains several substances from the group of builders, acidifying agents, chelating agents or the deposit-inhibiting polymers.

13. Detergent or cleaning agent tablets according to any one of claims 1 to 12, characterized in that they additionally 0.1 to 70 wt .-% of copolymers of i) unsaturated carboxylic acids ii) sulfonic acid group-containing monomers iii) optionally further ionic or nonionic monomers contain.

14. Detergent or cleaning agent tablets according to one of claims 1 to 13, characterized in that they contain the sulfonated copolymer (s) in amounts from 0.25 to 50% by weight, preferably from 0.5 to 35 % By weight, particularly preferably from 0.75 to 20% by weight and in particular from 1 to 15% by weight, in each case based on the entire tablet.

15. washing or cleaning agent tablets according to one of claims 1 to 14, characterized in that they contain one or more copolymers, the structural units of the formulas VII and / or VIII and / or IX and / or X and / or XI and / or XII

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (VII),

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (VIII),

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p - (IX),

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (XI),

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) 0-Y-S0 ₃ H] _p - (XII),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -0- (CH ₂ ) _n - with n = 0 to 4, for -0- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

16. Detergent or cleaning agent tablets according to one of claims 1 to 15, characterized in that they additionally have a second part which has the shape of a core or a body glued to or in the first part ("base tablet") and - related on the weight of the core - 1 to 80% by weight, preferably 2.5 to 70% by weight, particularly preferably add 5 to 60 wt .-% and in particular 10 to 50 wt .-%, of the sulfonated copolymer (s / e) contains.

17. Detergent or cleaning agent tablets according to one of claims 1 to 16, characterized in that the tray tablet (“base tablet”) based on its weight is 0.5 to 30% by weight, preferably 1 to 25% by weight, particularly preferably 2.5 to 20 wt .-% and in particular 4 to 15 wt .-%, of the sulfonated copolymer (s / e) contains.

18. Detergent or cleaning agent tablets according to one of claims 16 or 17, characterized in that both the base tablet and the core contain the sulfonated copolymer (s), 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 is contained in the base tablet.

19. Detergent or cleaning agent tablets according to one of claims 16 to 18, characterized in that the core has no coating.

20. Detergent or cleaning agent tablets according to one of claims 1 to 19, characterized in that they additionally 0.1 to 30 wt .-% homo- and / or copolymeric polycarboxylic acids or their salts and / or heteroatom-containing polymers / copolymers, especially those contain with amino or phosphono groups.

21. Detergent or cleaning agent tablets according to one of claims 1 to 18, characterized in that they additionally contain 0.1-30% by weight of amino- or phosphono-group-containing polymers / copolymers.

22. A process for the preparation of washing or cleaning agent tablets with at least one cavity, characterized in that a particulate premix whose content of nonionic surfactants is 5 to 25% by weight, based in each case on the premix, in a manner known per se Trough tablets are pressed.

23. A process for the production of multi-phase detergent or cleaning agent tablets with at least one cavity, in which several particulate premixes are pressed into trough tablets in a manner known per se, characterized in that the content of the premix, which is used for the final compression of the tablet with the stamp for the Pressing the cavity is contacted, has a nonionic surfactant content of 5 to 25 wt .-%, each based on the premix.