EP1051474B1 - Multiphase detergent tablets - Google Patents

Abstract

The invention relates to shaped bodies of detergent with two or more phases, consisting of compacted particulate detergents comprising tenside(s), builder(s) and optionally, other detergent constituents. The tenside content of the individual phases of the shaped body vary by more than 3 wt. % in relation to the weight of the individual phase. The phase(s) containing more tenside contain(s) greater quantities of a constituent with an oil absorption capacity of at least 20g/100g than the phase(s) containing less tenside. This combination of the tenside content and the oil absorption constituent in the individual phases of the shaped body produces multiphase shaped bodies with excellent characteristics.

Description

The present invention relates to multi-phase detergent tablets. In particular, the invention relates to multi-phase detergent tablets intended for washing of textiles used in a household washing machine and briefly as detergent tablets be designated.

Because of the convenience of their dosage and other packaging benefits, Transport and storage, the offer form of highly compressed molded bodies has a variety of advantages that make it seem desirable in this form of washing and washing Provide cleaning agents. To detergent tablets, which often abbreviated as detergent tablets, there is a wide prior art, the in particular the task arises of addressing a central problem of the "tablet" offer form overcome: The dichotomy between the hardness of the molded body on the one hand and its rate of decay on the other hand. Adequate hardness is required for packaging, storage, Transport and handling of the moldings essential while the disintegration properties influence the washing process decisively and a sufficiently fast disintegration for the Formation of a sufficiently concentrated wash liquor is absolutely necessary.

The problem of finding a technically reasonable compromise between hardness and decay is made more difficult with multi-phase moldings: it can be from washing or cleaning technology Reasons to be beneficial certain detergent ingredients separate from each other. However, this separation requires a different physical Property profile of the different phases in the molded body. In extreme cases, the Adhesion between the phases become so low that multiphase molded articles do not have more manufactured. Too different hardness of different phases would result cause individual phases to be more severely damaged due to packaging, transport or handling than other phases. In addition, there is also a too different decay and The dissolution rate of individual phases is not desirable, since otherwise active substances from the poorer disintegrating or soluble phase in the washing process are not available. Furthermore, it may be desirable that the individual phases of the molded body differ Have surfactant levels, so a wider range of recipe choices to own.

It is therefore of central importance in the case of multiphase detergent tablets, that all phases adhere to each other, a sufficient and possibly the same hardness and show a sufficiently fast and possibly identical decay and dissolution profile, too if the surfactant levels in the individual phases vary widely. Proposed solutions to this Problems are currently not described in the prior art.

Detergent tablets in which individual ingredients are present separately from others are also described in EP-A-0 481 793 (Unilever). The detergent tablets disclosed in this document contain sodium percarbonate, which is spatially separated from all other components that could influence its stability. Statements about hardness and / or decay depending on the phase composition are not made in this document.

EP-A-0 466 485 (Unilever) describes detergent tablets which have resulted from the compression of two granules containing surfactant. One granulate contains the total amount of anionic surfactants, while the second surfactant granulate is preferably free of anionic surfactants. This document also does not comment on hardness and / or decay depending on the phase composition.

The present invention was based on the object of multiphase detergent tablets to provide, which overcome the disadvantages mentioned. In particular multi-phase detergent tablets are to be provided, which in all phases have a high hardness as well as a high rate of disintegration and dissolution, regardless of how much the surfactant levels vary in the individual phases.

It has now been found that multiphase detergent tablets with have an outstanding property profile produced if the surfactant content varies in the individual phases of the surfactant-rich phase (s) in the preparation of the compressing premix larger amounts of absorbent are added than the less surfactant phase (s).

The invention now relates to two-phase or multi-phase detergent tablets made of compressed particulate detergent and cleaning agent, comprising Surfactant (s), builder (s) and optionally further detergent and cleaning agent components, in which the surfactant content of the individual phases of the moldings, based on the Weight of the individual phase, varied by more than 3 wt .-%, being in the phase (s) with the higher surfactant content a component A with an oil absorption capacity of at least 20g / 100g and an average particle size of less than 50 microns, based on the weight the phase is contained in higher amounts than in the phase (s) with a lower surfactant content.

In the context of the present application, the variation in the surfactant content means more than 3% by weight, based on the weight of the individual phases, that the absolute values of the surfactant content vary in the phases by more than 3% by weight. So a phase contains 20% by weight Surfactant (s), the surfactant content of the other phase (s) must be selected so that the Width of the variation by the value 20 is more than 3% by weight. In other words, the Percentage numerical value of the surfactant content of the lower surfactant phase from the percentage numerical value of the Subtracted surfactant content of the respective surfactant-rich phase, the result of each of Phase to phase must be> 3. In a four-phase tablet, this would be at a surfactant level of 12% by weight in the surfactant-poorest phase means that the next phases, for example Report surfactant contents of 15.1% by weight, 18.2% by weight and 21.3% by weight.

It is also possible in the context of the present invention that a phase is completely free of Is surfactants (corresponding to a surfactant content of 0% by weight, based on this phase). The The next phase must then - in order to meet the criteria according to the invention - a surfactant content of more than 3% by weight.

As the surfactant content increases, the individual phases of the laundry detergent according to the invention contain Detergent tablets increasing proportions of component A with an oil absorption capacity of at least 20g / 100g, with the proviso that the more tenis-rich Phase based on the overall composition of the phase a higher proportion of this Has component. It is preferred in the context of the present invention that the content the more surfactant-rich phase (s) on component A by at least 0.3% by weight, preferably by at least 0.5% by weight and in particular by at least 1% by weight on the weight of the individual phase, is higher than in the phase (s) with less surfactant. Based the fact can be based on the example of the four-phase shaped body listed above Clarify as follows: contains the phase with the lowest surfactant content in addition to the 12% by weight Surfactant 1.5% by weight of component A, the second phase would contain at least 1.8% by weight (preferably 2.0% by weight and in particular 2.5% by weight) of this component A. The content The third phase of component A depends on the real content thereof Component in the second phase - here too the difference is preferably at least 0.3% by weight, more preferably at least 0.5% by weight and in particular at least 1.0 Wt .-%. The same applies to the fourth phase.

In addition to the absolute content of the individual phases of surfactant (s) and the component (s) A, which refers to the composition of each phase, is also the ratio the quantities in the individual phases are mutually variable. As part of the present Invention are detergent tablets preferred, in which the quantitative ratio of component A between the individual phases is greater than the quantitative ratio of the surfactants between the relevant phases.

If the example mentioned above is used again for clarification, the ratio is the surfactant levels between phase 2 and phase 1 15.1 to 12.0 = 1.26 to 1. Here is now preferred that the second phase compared to the first so much of component A contains that the ratio of this component in the two phases is greater than 1.26. contains For example, if phase 1 is 1.5% by weight of component A, phase 2 should be more than that 1.26 times this value, ie contain at least 1.9% by weight of this component. ever according to the level of surfactant and oil absorption component in each phase now, one can vary the contents of the other phases of these substances so that they meet the criteria mentioned. In a phase that is free of an oil absorption component or is free from surfactants, makes relationships mathematical no sense, which is why absolute values in the sense of the preferred embodiments explained above find application of the present invention.

The oil absorption components contained in the individual surfactant-containing phases of the molded body according to the invention have an oil absorption capacity of at least 20g / 100g. However, preference is given to using oil absorption components which have a higher oil absorption capacity have. Detergent tablets are preferred which the component A contained in them has an oil absorption capacity of at least 50g / 100g, preferably at least 80g / 100g, particularly preferably at least 120g / 100g and in particular has at least 140g / 100g

The oil absorption capacity is a physical property of a substance that can be determined using standardized methods. For example, there are British standard methods BS1795 and BS3483: Part B7: 1982, both of which refer to the ISO 787/5 standard. In the test methods, a balanced sample of the substance in question is placed on a plate and refined flaxseed oil (density: 0.93 gcm-3) from a burette is added dropwise. After each addition, the powder is mixed intensively with the oil using a spatula, the addition of oil being continued until a paste of smooth consistency is obtained. This paste should flow or run without crumbling. The oil absorption capacity is now the amount of the added oil, based on 100g absorbent and is given in ml / 100g or g / 100g, whereby conversions about the density of the linseed oil are easily possible.

The oil absorption component preferably has the smallest possible average particle size, since the active surface increases with decreasing particle size. Preferred washing and Detergent tablets contain a component with an oil absorption capacity of at least 20g / 100g, which preferably has an average particle size of less than 20 µm has less than 10 microns.

A large number of substances are suitable as an oil absorption component. There is a big one Number of both inorganic and organic substances that have a large oil absorption capacity exhibit. Examples include finely divided substances obtained by precipitation are called. For example, silicates, aluminosilicates, Calcium silicates, magnesium silicates and calcium carbonate use. But also diatomaceous earth (Diatomaceous earth) and finely divided cellulose fibers or derivatives thereof are within the scope of present invention can be used. Preferred detergent tablets, are characterized in that component A contained in them is selected from silicates and / or aluminosilicates, in particular from the group of silicas and / or Zeolites.

Here, for example, finely divided zeolites can be used, but also pyrogenic silicas (Aerosil®) or silicas that were obtained by precipitation.

In the context of the present invention, the individual phases of the shaped body can have different spatial shapes. The simplest possible implementation is in two- or multi-layer tablets, with each layer of the shaped body representing a phase. However, it is also possible, according to the invention, to produce multiphase molded articles in which individual phases have the form of inclusions in (another) other phase (s). In addition to so-called "ring-core tablets", coated tablets or combinations of the above-mentioned embodiments are possible, for example. Examples of multi-phase moldings can be found in the illustrations in EP-A-0 055 100 (Jeyes), which describes toilet cleaning blocks. The currently most widespread spatial form of multi-phase tablets is the two- or multi-layer tablet. In the context of the present invention, it is therefore preferred that the phases of the shaped body have the form of layers.

In the present invention, it is essential to the invention that the surfactant content of the individual Phases of the molded body by more than 3 wt .-%, based on the weight of the individual Phase, varies and the more surfactant-rich phase (s) contain more oil absorption component than the lower surfactant phase (s). The sum is used to determine the surfactant content of the surfactants contained in the phase in question, regardless of the order what type of surfactants it is. Contains one phase, for example, anionic and nonionic surfactants, the total surfactant content of the phase is the sum of the amounts of anionic and nonionic surfactants.

The surfactants can be incorporated in the individual phases of the shaped bodies in pure form become. This is no problem, for example, with soaps or other easily processable surfactants possible. With many surfactants, however, it is advisable not to incorporate the pure surfactants, but surfactant compounds. These compounds, depending on the application, if possible should have high surfactant contents, can be done by conventional methods such as spray drying, Granulation or compounding can be made. It goes without saying a combination of several surfactant granules or a combination of surfactant granules possible with pure surfactants.

In the context of the present invention, it is preferred that the surfactant (s) contain surfactant-containing Granules (e) are introduced into the phases of the shaped body.

In further embodiments of the present invention can now be different for each phase Surfactant granules are used. But it is also possible that each phase has its own The surfactant content is obtained from a single granulate, which therefore applies to all phases of the molded body is included. In the context of the present invention, this is a further preferred embodiment, in which the same surfactant granules are used in all phases of the molded body becomes.

The simplest conceivable embodiment of the present invention now sees a two-phase Tablet in which the phases are in layers and in which in both layers the same surfactant granules are used in different amounts. These moldings, which have two layers, which contain the same surfactant granulate, can be in easily manufacture conventional tablet presses.

In the detergent tablets according to the invention, anionic, nonionic, cationic and / or amphoteric surfactants or mixtures of these are used. Mixtures of are preferred from an application point of view anionic and nonionic surfactants. The total surfactant content of the moldings is 5 up to 60% by weight, based on the weight of the shaped body, surfactant contents above 15% by weight are preferred.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C _12-18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with 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. Among fatty acid glycerol esters the mono-, di- and triesters and their mixtures are to be understood as they are in the Manufactured by esterification of a monoglycerin with 1 to 3 moles of fatty acid or the transesterification of triglycerides with 0.3 to 2 mol of glycerol can be obtained. preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 up 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 are the alkali and especially the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

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

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

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

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

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or can 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 fat 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, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, 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 preferred nonionic surfactants, either as the sole nonionic surfactant or used 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 esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably described in the international patent application Methods described in WO-A-90/13533.

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

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Other suitable surfactants are polyhydroxy fatty acid amides of the formula (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.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder Propxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula (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 oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated Derivatives of this remainder.

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

In the context of the present invention, detergent tablets are preferred, which contain anionic (s) and nonionic (s) surfactant (s), application technology Advantages from certain proportions in which the individual surfactant classes are used will result.

For example, detergent tablets are particularly preferred which the ratio of anionic surfactant (s) to nonionic surfactant (s) between 10: 1 and 1:10, preferably is between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2.

From an application point of view, it can have advantages if certain classes of surfactants are used some phases of the detergent tablets or in the entire tablet, i.e. in all phases, are not included. Another important embodiment of the present The invention therefore provides that at least one phase of the shaped body is free of nonionic Is surfactants.

Conversely, however, the content of individual phases or of the entire molded body, i.e. all phases, a positive effect can be achieved on certain surfactants. The bringing in the alkyl polyglycosides described above have proven to be advantageous, so that detergent tablets are preferred in which at least one phase the molded body contains alkyl polyglycosides.

Similar to the nonionic surfactants can also be left out of anionic Surfactants from individual or all phases of detergent tablets result that are more suitable for certain areas of application. It is therefore in the frame the present invention also conceivable detergent tablets, which at least one phase of the shaped body is free of anionic surfactants.

In addition to the washing-active substances, builders are the most important ingredients of Detergents and cleaning agents. In the detergent tablets according to the invention can all be used in washing and cleaning agents Builders may be included, in particular thus zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - also the phosphates.

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

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 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. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024 . Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula n Na ₂ ^O. (1-n) K ₂ ^O. Al ₂ O ₃ ^. (2-2.5) SiO ₂ ^. (3.5-5.5) H ₂ O can be described. The zeolite can be used both as a builder in a granular compound and can also be used for a kind of "powdering" of the entire mixture to be compressed, usually using both ways of incorporating the zeolite into the premix. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It goes without saying that the generally known phosphates are also used as builder substances possible, provided that such use is not avoided for ecological reasons should be. The sodium salts of orthophosphates, pyrophosphates, are particularly suitable and especially the tripolyphosphates.

Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that 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. In order to facilitate the disintegration of highly compressed moldings, disintegration aids, so-called tablet disintegrants, can be incorporated into them in order to shorten the disintegration times. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, pp. 182-184), tablet disintegrants or disintegration accelerators are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in resorbable form.

These substances, which are also referred to as "explosives" due to their effectiveness, increase their volume in the event of water ingress, on the one hand increasing their own volume (swelling), on the other hand, a pressure can be generated via the release of gases, which the tablet disintegrates into smaller particles. Well-known disintegration aids are for example carbonate / citric acid systems, with other organic acids also being used can be. Swelling disintegration aids are, for example, synthetic Polymers such as polyvinyl pyrrolidone (PVP) or natural polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives.

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

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets have 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, viewed formally, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which 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. 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 of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.

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. Detergent tablets which contain disintegrants in granular or, if appropriate, cogranulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO 98/40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants. 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-mentioned coarser disintegration aids based on cellulose and described in more detail in the cited documents are preferably to be used as disintegration aids in the context of the present invention and are commercially available, for example, under the name Arbocel® TF-30-HG from Rettenmaier.

As another disintegrant based on cellulose or as a component of this component microcrystalline cellulose can be used. This microcrystalline cellulose will obtained by partial hydrolysis of celluloses under such conditions that only the attack the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses completely dissolve, but leave the crystalline areas (approx. 70%) undamaged. A subsequent one Disaggregation of the microfine celluloses resulting from the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 μm and, for example can be compacted into granules with an average particle size of 200 μm.

Detergent tablets, which are additionally a disintegration aid, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 up to 7% by weight and in particular from 4 to 6% by weight, in each case based on the weight of the shaped body, contained are particularly preferred in the context of the present invention.

The production of washing and cleaning-active moldings is done by using Pressure on a mixture to be pressed, which is located in the cavity of a press. in the simplest case of molded article production, which is referred to below simply as tableting the mixture to be tabletted is directly, i.e. without previous granulation pressed. The advantages of this so-called direct tableting are its simple and inexpensive Application, since no further process steps and therefore no further Attachments are needed. However, these advantages are offset by disadvantages. So a powder mixture that is to be tabletted directly must have sufficient plastic deformability possess and have good flow properties, furthermore it may be used during the Storage, transportation and filling of the die have no tendency to separate demonstrate. These three requirements are only extraordinary for many substance mixtures difficult to master, so that direct tableting, especially in the manufacture of Detergent tablets are not often used. The usual way of making detergent tablets are therefore based on powdery components ("Primary particles"), which by means of suitable processes to secondary particles with higher Particle diameter can be agglomerated or granulated. These granules or mixtures different granules are then made with individual powdered additives mixed and fed to the tableting. Depending on the design of the phases of the multi-phase Detergent and cleaning product tablets are gradually made with different molds Premixes filled. When making multilayer tablets, one can apply light pressure between the pre-mix filling for the next shift Have advantages. One of them is in the production of ring-core shaped articles or coated tablets such pre-pressing with shaping is almost indispensable.

Preferred washing and cleaning agents in the context of the present invention are obtained by compressing particulate premixes from at least one surfactant Granules and at least one subsequently mixed powdered component. The surfactant-containing granules can be processed using conventional granulation processes such as mixer and plate granulation, fluidized bed granulation, extrusion, pelleting or compacting getting produced. It is for the later detergent tablets advantageous if the premixes to be pressed have a bulk density, that comes close to the usual compact detergent. In particular, it is preferred that the premix to be pressed has a bulk density of at least 500 g / l, preferably has at least 600 g / l and in particular above 700 g / l. Another advantage can result from a narrower particle size distribution of the surfactant granules used. Detergent and cleaning product tablets are within the scope of the present invention preferred, in which the granules particle sizes between 10 and 4000 microns, preferably have between 100 and 2000 microns and in particular between 600 and 1400 microns.

Another object of the present invention is therefore a method for manufacturing two-phase or multi-phase detergent tablets, which surfactant (s), builders (e) and optionally contain further detergent and cleaning agent components, by pressing known per se, which is characterized in that it is carried out by pressing a particulate premix consisting of at least one surfactant-containing granulate and at least one a subsequently admixed powdery component were obtained, wherein the surfactant content of the individual phases of the moldings, based on the weight of the individual Phase varied by more than 3% by weight and in the phase (s) with the higher surfactant content a component A with an oil absorption capacity of at least 20g / 100g and an average particle size of less than 50 microns, based on the weight of the phase, in higher Amounts are contained in the phase (s) with a lower surfactant content.

The above applies to the variation of the surfactant content and preferred values Analogous information also for the method according to the invention.

Preferred processes are characterized in that the granules are made using conventional ones Granulation processes such as mixer and plate granulation, fluid bed granulation, extrusion, Pelleting or compacting were made. In particularly preferred processes the granules have particle sizes between 10 and 4000 μm, preferably between 100 and 2000 µm and in particular between 600 and 1400 µm.

The particle size distribution of the subsequently mixed powder-form processing components can be varied, with methods preferred in which the subsequently mixed powdered component (s) containing component A.

Before pressing the particulate premix into detergent tablets can the premix with finely divided surface treatment agents be "powdered". This can affect the nature and physical properties of the premix (storage, pressing) as well as the finished detergent tablets be an advantage. Finely divided powdering agents are known in the art Well-known technology, mostly using zeolites, silicates or other inorganic salts become. However, the premix is preferably "powdered" with finely divided zeolite, faujasite type zeolites are preferred. Within the scope of the present invention The term "faujasite type zeolite" denotes all three zeolites that make up the faujasite subgroup of the zeolite structure group 4 (compare Donald W. Breck: "Zeolite Molecular Sieves ", John Wiley & Sons, New York, London, Sydney, Toronto, 1974. Page 92). In addition to zeolite X, there are also zeolite Y and faujasite and mixtures of these Compounds can be used, the pure zeolite X being preferred.

Mixtures or cocrystallizates of faujasite-type zeolites with other zeolites, which do not necessarily belong to the zeolite structure group 4 are used as powdering agents can be used, it being advantageous if at least 50% by weight of the powdering agent are made from a faujasite type zeolite.

These powdering agents can of course have an oil absorption capacity of more have as 20g / 100g, where they can replace or supplement the oil absorption component. When the powdering agent is used in addition to the oil absorption components and have an oil absorption capacity of more than 20g / 100g, they are at The calculation of the share in the individual phases must of course be taken into account.

In the context of the present invention, detergent tablets are preferred, which consist of a particulate premix, the granular components and subsequently contains powdered substances, the or one of the subsequently admixed powdered components a zeolite of the faujasite type with particle sizes is below 100 µm, preferably below 10 µm and in particular below 5 µm and at least 0.2% by weight, preferably at least 0.5% by weight and in particular more than 1 Makes up% by weight of the premix to be pressed.

The finely divided processing components with the particle sizes mentioned above can be mixed dry with the premix to be pressed. But it is also possible and preferably, by adding small amounts of liquids to the surface of the "stick" coarser particles. These powdering processes are state of the art broadly described and familiar to the expert. As liquid components that are used for adhesion mediation suitable powdering agents, for example nonionic surfactants or aqueous solutions of surfactants or other detergents and cleaning agents be used. In the context of the present invention, it is preferred as a liquid Adhesion promoter between finely divided powdering agent and the coarse particles of perfume use.

In addition to the ingredients mentioned, surfactant, builder and disintegration aid can the detergent tablets according to the invention further in detergents usual ingredients from the group of bleaching agents, bleach activators, enzymes, Fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, Anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and contain corrosion inhibitors.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.

To improve the bleaching effect when washing at temperatures of 60 ° C and below To achieve, bleach activators can be used as the sole component or as an ingredient of Component b) are incorporated. As bleach activators, compounds that are under Perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid result, are used. Substances containing O- and / or N-acyl groups are suitable carry the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylenediamine, are preferred (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, in particular Triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, so-called Bleaching catalysts can be incorporated into the moldings. Acting on these substances it is bleach-enhancing transition metal salts or transition metal complexes such as for example Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.

Enzymes come from the class of proteases, lipases, amylases, cellulases or their mixtures in question. From bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus Agents. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. Here are enzyme mixtures, for example from protease and amylase or protease and lipase or protease and Cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, Lipase and cellulase, but especially cellulase-containing mixtures of particular Interest. Peroxidases or oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules in the moldings according to the invention can, for example about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

In addition, the detergent tablets can also contain components which have a positive influence on the oil and fat washability from textiles (so-called soil repellents). This effect is particularly evident when a textile that is already soiled previously several times with a detergent according to the invention that this oil and fat-dissolving Contains component that has been washed. Among the preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and on hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic Cellulose ether, as well as the polymers of phthalic acid known from the prior art and / or terephthalic acid or its derivatives, in particular polymers Ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionically modified derivatives of these. Of these, those are particularly preferred sulfonated derivatives of phthalic acid and terephthalic acid polymers.

The moldings can, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed Compounds which, instead of the morpholino group, have a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group. Farther brighteners of the substituted diphenylstyryl type may be present, e.g. the alkali salts 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls. Mixtures of the aforementioned brighteners can be used.

Dyes and fragrances are added to the agents according to the invention in order to improve the aesthetics Improve impression of the products and the consumer in addition to the softness performance to provide visually and sensory "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 be used. Fragrance compounds of the ester type are e.g. benzyl acetate, Phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. To the etheme include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with 8-18 Carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, Lilial and bourgeonal, to the ketones e.g. the Jonone, α-isomethylionon and methylcedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes like lime and pinene. However, mixtures of different fragrances are preferred used, which together create an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures, such as those obtainable from plant sources are, 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 Orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The dye content of the plasticizers according to the invention is usually lower 0.01% by weight, while fragrances make up up to 2% by weight of the total formulation can.

The fragrances can be incorporated directly into the agents according to the invention, it can but it may also be advantageous to apply the fragrances to carriers, which increase the adhesion of the perfume reinforce on the laundry and through a slower fragrance release for long-lasting Ensure the fragrance of the textiles. Cyclodextrins, for example, have become such carrier materials proven, the cyclodextrin-perfume complexes additionally with others Auxiliaries can be coated.

For the aesthetic impression of the detergent tablets according to the invention To improve, they can be colored with suitable dyes. preferred Dyes, the selection of which is not difficult for the person skilled in the art, have a high level Storage stability and insensitivity to the other ingredients of the agent and against light as well as no pronounced substantivity towards textile fibers to stain. Since the subject of the present invention multi-phase detergent tablets concerns, the coloring of individual phases is of increased importance to underline the different effects of individual phases. Examples for the effectiveness of such coloring and for the success of statements well known from the denture cleaner advertising.

The moldings according to the invention are first produced by dry Mixing the components of the individual phases, which are partially or completely pre-granulated can, and then bringing information, in particular compression to tablets, whereby conventional methods for the production of multi-phase molded articles can be used can. The premixes are used to produce the multiphase moldings according to the invention in a so-called matrix between two stamps to form a solid compressed product compacted. This process, which is briefly referred to below as tabletting, is structured divided into four sections: metering, compression (elastic deformation), plastic deformation and expelling.

Tableting takes place in commercially available tablet presses, which are basically single or Double stamps can be equipped. In the latter case, it is not only the upper stamp used to build up pressure, the lower punch also moves during the pressing process towards the upper stamp while the upper stamp presses down. For little ones Production quantities are preferably eccentric tablet presses in which the or the stamps are attached to an eccentric disc, which in turn is on an axis a certain rotational speed is mounted. The movement of this ram is comparable to the way a conventional four-stroke engine works. The pressing can be done with one upper and one lower stamp; however, several stamps can also be on one Eccentric disk can be attached, the number of die holes correspondingly expanded is. The throughputs of eccentric presses vary from a few hundred to depending on the type maximum 3000 tablets per hour.

For larger throughputs, rotary tablet presses are selected, on which a so-called Matrix table a larger number of matrices is arranged in a circle. The number of Matrices vary between 6 and 55 depending on the model, although larger matrices are also commercially available are available. Each die on the die table is assigned an upper and lower stamp, where again the pressure is active only through the upper or lower stamp, but also can be built by both stamps. The die table and the stamps move around a common vertical axis, the stamp using rail-like Curve tracks during the circulation in the positions for filling, compression, plastic Deformation and discharge are brought. In places where one is special serious raising or lowering of the stamp is necessary (filling, compacting, Eject), these cam tracks are by additional low-pressure pieces, kidney rails and lift tracks supported. The matrix is filled with a rigid one arranged feed device, the so-called filling shoe, which with a storage container for the premixes are connected. The pressure on the respective premix is over the Press paths for upper and lower punches individually adjustable, whereby the pressure build-up the stamp shaft heads roll past adjustable pressure rollers.

Rotary presses can also be used with two or more filling shoes to increase the throughput be provided. For the production of two-layer and multi-layer moldings several filling shoes arranged one behind the other without the slightly pressed first layer is ejected before further filling. Appropriate process management is based on this In this way, coated tablets and dot tablets can also be produced, which have an onion-shell-like structure have, whereby in the case of the point tablets the top of the core or the core layers is not covered and therefore remains visible. Rotary tablet presses can also be or multiple tools can be equipped so that, for example, an outer circle with 50th 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.

Tableting machines suitable for the purposes of the present invention are, for example available from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH presses GmbH, Berlin, Mapag Maschinenbau AG, Bern (CH) and Courtoy N.V., Halle (BE / LU). The hydraulic double-pressure press HPF, for example, is particularly suitable 630 from LAEIS, D.

The moldings can be made in a predetermined spatial shape and size being made up of several phases, i.e. Layers, inclusions or cores and rings exist. Practically all useful configurations come as a spatial form into consideration, for example the formation as a board, the shape of bars or bars, Cubes, cuboids and corresponding room elements with flat side surfaces as well as in particular cylindrical configurations with 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.

The portioned compacts can each be separate individual elements be formed, the predetermined dosage of detergents and / or cleaning agents equivalent. However, it is also possible to form compacts that have a plurality of such mass units connect in a compact, in particular by predetermined breaking points the easy separability of portioned smaller units is provided. For the Use of textile detergents in machines of the type common in Europe with horizontal arranged mechanics can form the portioned compacts as tablets, in cylindrical or cuboid shape may be appropriate, with a diameter / height ratio in the range from about 0.5: 2 to 2: 0.5 is preferred. Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, particularly for manufacturing such compacts.

The spatial shape of another embodiment of the shaped body is in its dimensions Detergent dispenser of commercial household washing machines adapted so that the molded body can be dosed directly into the induction bowl without a dosing aid dissolves during the induction process. It goes without saying that the Detergent tablets easily possible using a dosing aid.

Another preferred multi-phase molded body that can be produced has one plate-like or panel-like structure with alternating thick long and thin short segments, so that individual segments of this "multi-phase bolt" at the predetermined breaking points, the represent the short thin segments, broken off and entered into the machine can. This principle of the "bar-shaped" shaped detergent can also be used in others geometric shapes, for example vertically standing triangles, which only on one their sides are connected alongside each other, can be realized. Here it offers itself for optical reasons, the triangular base that connects the individual segments, form as one phase, while the triangle tip forms the second phase. A different coloring of both phases is particularly attractive in this embodiment.

After pressing, the detergent tablets have a high stability. The breaking strength of cylindrical shaped bodies can be determined via the measured variable of the diametrical breaking load. This can be determined according to σ = 2 P π dt

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

Examples:

By mixing surfactant-containing granules with pulverulent preparation components, premixes were produced which were pressed into two-phase detergent tablets in a Korsch tablet press. The surfactant granules 1, 2 and 3 were produced in a 130 liter ploughshare mixer (Gebrüder Lödige, Paderbom) and then dried in a fluidized bed dryer. After the coarse particles (≥ 1.6 mm) and the fine particles (≤ 0.4 mm) had been sieved, the surfactant granules were mixed with the preparation components in a paddle mixer.
The composition of the surfactant granules is shown in Table 1. Surfactant granules [% by weight] Granules 1 Granules 2 Granules 3 C _9-13 alkyl benzene sulfonate 21.2 18.6 19.4 C _12-18 fatty alcohol sulfate 8.5 5.4 5.2 C _12-18 fatty alcohol with 7 EO - 5.7 4.8 C _12-16 alkyl glucoside, degree of oligomerization 1.1 - - 1.0 Soap 1.6 1.6 1.6 sodium 17.0 16.6 17.0 sodium silicate 5.6 5.4 5.6 Zeolite A (anhydrous active substance) 28.5 29.9 28.5 optical brightener 0.3 0.3 0.3 Na-hydroxyethane-1,1-diphosphonate 0.8 0.8 0.8 Acrylic acid-maleic acid copolymer 5.6 5.4 5.6 Water, salts rest rest rest

The premixes (surfactant granules + treatment components) were used on a Korsch rotary press produced two-layer detergent tablets, the proportion of the first layer 75% by weight of the total mass and the proportion of the second layer 25% by weight the total mass of the tablet was. The diameter of the tablets was 44 mm.

Tables 2, 3 and 4 below show the compositions of the detergent tablets broken down by phase. The values in the columns of the table indicate the amount of the substance in question in the respective phase of the tablet, ie the values in one column add up to 100%. The amount of the substance in question in the entire tablet can be easily calculated from the proportion of the individual phases. In accordance with the different tablet weights (37.5 g ± 1%, due to slight fluctuations in the feed of the premix into the die of the press), the tablet hardness fluctuated by approx. ± 10%, the disintegration times by approx. 5 seconds. The tablet hardness and disintegration times are listed in the respective tables. Detergent tablets: composition [% by weight], physical data example 1 inventively Comparative example Layer 1 Layer 2 Layer 1 Layer 2 Granules 1 64.0 50.7 64.2 51.3 Sodium perborate monohydrate 23.7 - 23.7 - tetraacetylethylenediamine - 29.0 - 29.0 Enzyme granules * - 10.0 - 10.0 foam inhibitor 3.5 1.1 3.5 1.1 Repelotex-SRP-4 ** 1.1 1.1 1.1 1.1 Perfume 0.5 0.5 0.5 0.5 Zeolite A 2.2 1.4 2.0 2.0 cellulose **** 5.0 5.0 5.0 5.0 surfactant 20.03% 15.87% 20.09% 16.06% Surfactant content (tablet) 18.99% 19.09% Difference in surfactant content 4.16% 4.03% Ratio of surfactant levels 1.26: 1 1.25: 1 Ratio zeolite A *** 1.57: 1 1: 1 tablet hardness 36-48 N 39-47 N disintegration time 17-23 s > 60 s Detergent tablets: composition [% by weight], physical data Example 2 inventively Comparative example Layer 1 Layer 2 Layer 1 Layer 2 Granules 2 65.8 42.1 66.8 41.1 Sodium perborate monohydrate 17.8 17.8 17.8 17.8 tetraacetylethylenediamine - 29.0 - 29.0 Enzyme granules * 3.3 - 3.3 - foam inhibitor 3.5 3.5 3.5 3.5 Repelotex-SRP-4 ** 1.1 1.1 1.1 1.1 Perfume 0.5 0.5 0.5 0.5 Zeolite A 3.0 1.0 2.0 2.0 cellulose **** 5.0 5.0 5.0 5.0 surfactant 20.60% 13.18% 20.91% 12.86% Surfactant content (tablet) 18.74% 18.90% Difference in surfactant content 7.42% 8.05% Ratio of surfactant levels 1.56: 1 1.63: 1 Ratio zeolite A *** 3: 1 1: 1 tablet hardness 36-48 N 37-49 N disintegration time 20 - 28 s > 60 s Detergent tablets: composition [% by weight], physical data Example 3 erfindungsgemäB Comparative example Layer 1 Layer 2 Layer 1 Layer 2 Granules 3 65.1 43.8 66.3 42.5 Sodium perborate monohydrate 7.0 50.0 7.0 50.0 tetraacetylethylenediamine 9.8 - 9.8 - enzyme granules 3.3 - 3.3 - foam inhibitor 4.7 - 4.7 - Repelotex-SRP-4 1.4 - 1.4 - Perfume 0.5 0.5 0.5 0.5 Zeolite A 3.2 0.7 2.0 2.0 cellulose 5.0 5.0 5.0 5.0 surfactant 20.83% 14.02% 21.22% 13.60% Surfactant content (tablet) 19.13% 19.31% Difference in surfactant content 6.81% 7.62% Ratio of surfactant levels 1.48: 1 1.56: 1 Ratio zeolite A 4.57: 1 1: 1 tablet hardness 43 - 51 N 38-47 N disintegration time 14-19 s > 60 s

Claims (23)

1. Two- or multiphase washing and cleaning composition shaped bodies made of compacted particulate washing and cleaning composition comprising surfactant(s), builder(s) and optionally further washing and cleaning composition constituents, characterized in that the surfactant content of the individual phases of the shaped bodies, based on the weight of the individual phase, varies by more than 3% by weight, where, in the phase(s) with the higher surfactant content, a component A with an oil-absorption capacity of at least 20 g/100 g and an average particle size of less than 50 µm, based on the weight of the phase, is present in larger amounts than in the phase(s) with a lower surfactant content.
2. Washing and cleaning composition shaped bodies according to Claim 1, characterized in that the content of component A in the phase(s) with a higher surfactant content is at least 0.3% by weight, preferably at least 0.5% by weight and in particular at least 1% by weight, based on the weight of the individual phase, higher than that in the phase(s) with a lower surfactant content.
3. Washing and cleaning composition shaped bodies according to one of Claims 1 or 2, characterized in that the relative quantitative ratio of component A between the individual phases is greater than the relative quantitative ratio of the surfactants between the relevant phases.
4. Washing and cleaning composition shaped bodies according to one of Claims 1 to 3, characterized in that the component A present therein has an oil-absorption capacity of at least 50 g/100 g, preferably at least 80 g/100 g, particularly preferably at least 120 g/100 g and in particular at least 140 g/100 g.
5. Washing and cleaning composition shaped bodies according to one of Claims 1 to 4, characterized in that the component A present therein has an average particle size of less than 20 µm, preferably less than 10 µm.
6. Washing and cleaning composition shaped bodies according to one of Claims 1 to 5, characterized in that the component A present therein is chosen from silicates and/or aluminosilicates, in particular from the group of silicas and/or zeolites.
7. Washing and cleaning composition shaped bodies according to one of Claims 1 to 6, characterized in that the phases of the shaped body have the form of layers.
8. Washing and cleaning composition shaped bodies according to one of Claims 1 to 7, characterized in that the surfactant(s) are introduced into the phases of the shaped bodies via surfactant-containing granulate(s).
9. Washing and cleaning composition shaped bodies according to Claim 8, characterized in that the same surfactant granulate is used in all of the phases of the shaped bodies.
10. Washing and cleaning composition shaped bodies according to Claim 8 and 9, characterized in that the shaped bodies have two layers which contain the same surfactant granulate in different amounts.
11. Washing and cleaning composition shaped bodies according to one of Claims 1 to 10, characterized in that they comprise anionic and nonionic surfactant(s).
12. Washing and cleaning composition shaped bodies according to Claim 11, characterized in that the ratio of anionic surfactant(s) to nonionic surfactant(s) is between 10:1 and 1:10, preferably between 7.5:1 and 1:5 and in particular between 5:1 and 1:2.
13. Washing and cleaning composition shaped bodies according to one of Claims 1 to 12, characterized in that at least one phase of the shaped bodies is free from nonionic surfactants.
14. Washing and cleaning composition shaped bodies according to one of Claims 1 to 13, characterized in that at least one phase of the shaped bodies comprises alkyl polyglycosides.
15. Washing and cleaning composition shaped bodies according to one of Claims 1 to 14, characterized in that at least one phase of the shaped bodies is free from anionic surfactants.
16. Washing and cleaning composition shaped bodies according to one of Claims 1 to 15, characterized in that they additionally comprise a disintegration auxiliary, preferably a disintegration auxiliary based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the shaped body weight.
17. Washing and cleaning composition shaped bodies according to one of Claims 1 to 16, further comprising one or more substances from the group of bleaches, bleach activators, enzymes, pH extenders, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, greying inhibitors, colour transfer inhibitors and corrosion inhibitors.
18. Process for the preparation of two- or multiphase washing and cleaning composition shaped bodies which comprise surfactant(s), builder(s) and optionally further washing and cleaning composition constituents by compression known per se, characterized in that they have been obtained by compression of a particulate premix made of at least one surfactant-containing granulate and at least one subsequently mixed-in pulverulent component, where the surfactant content of the individual phases of the shaped bodies, based on the weight of the individual phase, varies by more than 3% by weight and, in the phase(s) with the higher surfactant content a component A with an oil-absorption capacity of at least 20 g/100 g and an average particle size of less than 50 µm, based on the weight of the phase, is present in larger amounts than in the phase(s) with a lower surfactant content.
19. Process according to Claim 18, characterized in that the granulates have been prepared by means of customary granulation processes, such as mixer granulation and plate granulation, fluidized-bed granulation, extrusion, pelleting or compaction.
20. Process according to one of Claims 18 or 19, characterized in that the granulates have particle sizes between 10 and 4000 µm, preferably between 100 and 2000 µm and in particular between 600 and 1400 µm.
21. Process according to one of Claims 18 to 20, characterized in that the subsequently mixed-in pulverulent component(s) comprise the component A.
22. Process according to one of Claims 18 to 21, characterized in that the premix to be compressed has a bulk density of at least 500 g/l, preferably at least 600 g/l and in particular above 700 g/l.
23. Process according to one of Claims 18 to 22, characterized in that one of the subsequently mixed-in pulverulent components is a zeolite of the faujasite type with particle sizes below 100 µm, preferably below 10 µm and in particular below 5 µm and constitutes at least 0.2% by weight, preferably at least 0.5% by weight and in particular more than 1% by weight, of the premix to be compressed.