WO1999038949A1 - Multiphase detergent tablets - Google Patents

Abstract

The invention relates to two- or multiphase detergent forms consisting of compressed particulate detergents comprising tenside(s), builder(s) and optionally, other detergent constituents. The tenside content of the individual phases of the detergent form does not vary by more than 3 wt. % in relation to the weight of the individual phase. By aligning the tenside contents of the individual phases of the form as far as possible in this way, it is possible to obtain multiphase detergent forms with excellent properties.

Description

 'Multi-phase detergent tablets'

The present invention relates to multi-phase detergent tablets. In particular, the invention relates to multiphase detergent tablets which are used for washing textiles in a household washing machine and are referred to for short as detergent tablets.

Due to the convenience of their dosage and other advantages with regard to repackaging, transport and storage, the form of highly compressed molded articles has a number of advantages which make it desirable to also provide washing and cleaning agents in this form. For detergent tablets, which are often referred to briefly as detergent tablets, there is a broad state of the art, which has the particular task of overcoming a central problem of the "tablet" offer form: the dichotomy between the hardness of the tablet and its rate of decay on the other hand. Adequate hardness is essential for packaging, storage, transport and handling of the molded articles, while the disintegration properties have a decisive influence on the washing process and a sufficiently rapid disintegration is imperative for the formation of a sufficiently concentrated wash liquor.

The problem of finding a technically reasonable compromise between hardness and decay is further complicated in the case of multi-phase molded articles: certain washing and cleaning agent ingredients can be advantageous for washing or cleaning reasons 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 can become so low that multi-phase moldings can no longer be produced. Too different hardness of different phases would lead to individual phases being more damaged than other phases due to packaging, transport or handling. In addition, a too different disintegration and dissolution rate of individual phases is not desirable, since otherwise active substances from the poorer disintegrating or soluble phase are not available in the washing process.

It is therefore of central importance in the case of multiphase detergent tablets that all phases adhere to one another, have a sufficient and, if possible, the same hardness and a sufficiently fast and, if possible, identical disintegration and dissolution profile. Proposed solutions to this problem 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 arisen from the molding of two granules containing surfactants. 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 providing multi-phase detergent tablets which overcome the disadvantages mentioned. In particular multi-phase detergent tablets are to be provided, which have a high hardness and a high rate of disintegration and dissolution in all phases.

It has now been found that multi-phase detergent and cleaning product bodies with an outstanding property profile can be produced if the surfactant contents in the individual phases are largely matched to one another.

The invention now relates to two-phase or multi-phase washing and cleaning agent molded articles made of compressed particulate washing and cleaning agent, comprising surfactant (s), builder (s) and, if appropriate, further washing and cleaning agent components in which the surfactant content of the individual phases of the molded article is not more than 3 wt .-%, based on the weight of the individual phase, varies.

In the context of the present application, the variation by not more than 3% by weight, based on the weight of the individual phases, means that the absolute values of the surfactant content in the phases do not vary by more than 3% by weight. If one phase contains 20% by weight of surfactant (s), the surfactant content of the other phase (s) must be selected so that the width of the variation around the value 20 is a maximum of 3% by weight. In other words, the percentage numerical value of the surfactant content of the phase with the least surfactant content is subtracted from the percentage number value of the surfactant content of the phase richest in surfactant, the result having to be <3.

In preferred detergent tablets, the surfactant content of the individual phases varies by less than 3% by weight. Detergent tablets are preferred in which the surfactant content of the individual phases of the tablet is not more than 2% by weight, preferably not more than 1.5% by weight and in particular not more than 1% by weight. , based on the weight of the individual phase, varies.

In particular, detergent tablets are preferred in which the surfactant content of the individual phases of the tablet is identical. Since the products mentioned are large-scale products that are produced on a tonne scale for unit weights that are usually less than 100 grams, this is a small one Fluctuation in the surfactant content of individual phases cannot be completely excluded. Within the scope of the present invention, an "identical" surfactant content in the individual phases is also present when there are fluctuations of a few tenths by weight.

The individual phases of the molded body can have different spatial shapes within the scope of the present invention. The simplest possible implementation is in two- or multi-layer tablets, with each layer of the molded body representing a phase. However, according to the invention, it is also possible to produce multi-phase molded bodies in which individual phases have the form of inclusions in (another) 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 molded bodies 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 molded body have the shape of layers.

In the present invention, it is essential to the invention that the surfactant content of the individual phases of the molded body does not vary by more than 3% by weight, based on the weight of the individual phase. When determining the surfactant content, the sum of the surfactants contained in the phase in question is used, regardless of the type of surfactant involved. For example, if a phase contains 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 into the individual phases of the molded body in pure form. This is easily possible, for example, with soaps or other easily workable surfactants. With many surfactants, however, it is advisable not to incorporate the pure surfactants, but rather surfactant compounds. These compounds, which should have as high a surfactant content as possible depending on the application, can be produced by customary processes such as spray drying, granulation or compounding. It goes without saying a combination of several surfactant granules or a combination of surfactant granules with pure surfactants is possible.

In the context of the present invention, it is preferred that the surfactant (s) are introduced into the phases of the molded body via granules (s) containing surfactant.

In further embodiments of the present invention, different surfactant granules can now be used for each phase. However, it is also possible that each phase obtains its surfactant content from a single granulate, which is thus contained in all phases of the molded article. 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 article.

The simplest conceivable embodiment of the present invention now provides a two-phase tablet in which the phases are present as layers and in which the same surfactant granules are used in both layers. These molded articles, which have two layers and contain the same surfactant granulate, can be easily produced in conventional tablet presses.

Anionic, nonionic, cationic and / or amphoteric surfactants or mixtures of these can be used in the detergent tablets according to the invention. Mixtures of anionic and nonionic surfactants are preferred from an application point of view. The total surfactant content of the molded article is from 5 to 60% by weight, based on the weight of the molded article, 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 -Alkylbenzolsul- sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfide, obtained, for example, from C ₁₂ _ ₁₈ -Monoolefmen with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent al- receives potassium or acid hydrolysis of the sulfomerization products into consideration. Alkanesulfonates which are derived from C ₁₂ are also suitable. ₁₈ alkanes can be obtained, 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. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol become. Preferred sulfated fatty acid glycerol esters are the sulfate 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.

Alk (en) yl sulfates are the alkali and especially the sodium salts of the Schwefelsäurehalbester C _I2 -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or _{C] 0} -C ₂₀ - Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials. From the washing, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ are - C ₁₅ alkyl sulfates. In addition, 2,3-alkyl sulfates, which are produced for example according to U.S. 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 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 . _π alcohols containing on average 3.5 mol ethylene oxide (EO) or C ₁₂ _ ₁₈ fatty alcohols with 1 to 4 EO, are also suitable. she are used in cleaning agents due to their high foaming behavior 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 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.

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 may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols are native original 8th

Jump 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 preferred. The preferred ethoxylated alcohols include, for example, _C2 . ₁₄ - alcohols with 3 EO or 4 EO, C _9. ,, - 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 of these, such as mixtures of C ₁₂ . ₁₄ alcohol with 3 EO and C _I2 " 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 ranks 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, carbon 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, as described for example in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533.

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, especially not more than half of them.

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

R ^J

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 ^ OR 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 oxyalkyl group having 1 to 8 carbon atoms, where C, _ ₄ - alkyl or phenyl groups being preferred, and [Z] is a linear polyhydroxyalkyl residue, whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this rest. 10

[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, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

For the purposes of the present invention, detergent tablets are preferred which contain anionic (s) and nonionic (s) surfactant (s), with application technology advantages being able to result from certain quantitative ratios in which the individual classes of surfactants are used.

For example, detergent tablets are particularly preferred in which 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.

From an application point of view, it can be advantageous if certain classes of surfactant are present in some phases of the detergent tablets or in the entire molded article, i.e. in all phases, are not included. A further important embodiment of the present invention therefore provides that at least one phase of the molded article is free from nonionic surfactants.

Conversely, a positive effect can also be achieved by the content of individual phases or of the entire molded body, ie all phases, of certain surfactants. The introduction of the alkyl polyglycosides described above has proven to be advantageous, so that detergent tablets are preferred in which at least one phase of the tablets contains alkyl polyglycosides. 11

Similar to the nonionic surfactants, the omission of anionic surfactants from individual or all phases can result in detergent tablets which are better suited for certain areas of application. It is therefore also conceivable within the scope of the present invention for detergent tablets to be made in which at least one phase of the tablet is free from anionic surfactants.

In addition to the wash-active substances, builders are the most important ingredients in detergents and cleaning agents. The washing and cleaning agent shaped bodies according to the invention can contain all builders normally used in washing and cleaning agents, in particular thus zeolites, silicates, carbonates, organic co-builders 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} H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are. 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 disilicate Na ^ i ^ "yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171.

Amorphous sodium silicates with a Na ^: SiO ₂ modulus of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, which delay the dissolution, can also be used are 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 "amoφh" is also understood to mean "roentgenamoφh". This means that the silicates do not give sharp X-ray reflections in X-ray diffraction experiments as they do for crystalline substances. 12

zen are typical, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be integrated in such a way 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 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. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray silicates.

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

nN ^ O '(ln) 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 veφressed, usually both ways of incoφoration of the zeolite in 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 is of course also possible to use the generally known phosphates as builder substances, provided that such use is not avoided for ecological reasons 13

should be. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.

Usable organic builders are, for example, the polycarboxylic acids that 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), 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.

In order to facilitate the disintegration of highly compressed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, 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, p. 182-184), tablet disintegrants or accelerators of decay 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 absorbable form.

These substances, which are also referred to as "explosives" due to their effectiveness, 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 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 molded article weight. 14

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred washing and cleaning agent shaped bodies 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, represents 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 of 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 treated. Detergent tablets containing 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 PCT / EP 98/1203 (Henkel) . These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants. The particle size 15

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 which only attack and completely dissolve the amorphous areas (approx. 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, which 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 of 4 to 6% by weight, based in each case on the weight of the molded body, are particularly preferred in the context of the present invention.

The production of washable and cleaning-active molded articles takes place by applying pressure to a mixture to be veφressing, which is located in the cavity of a press. In the simplest case of molded article production, which is referred to simply as tableting below, the mixture to be tabletted is pressed directly, ie without prior granulation. The advantages of this so-called direct tableting are its simple and inexpensive application, since no further process steps and consequently no further plants are required. However, these advantages are offset by disadvantages. For example, a powder mixture that is to be tabletted directly must have sufficient plastic 16

possess formability and have good flow properties, furthermore it must not show any tendency to separate during storage, transport and filling of the die. These three requirements are extremely difficult to master with many substance mixtures, so that direct tableting is not often used, particularly in the production of detergent tablets. The usual way of producing detergent tablets is therefore based on powdery components (“primary particles”) which are agglomerated or granulated by suitable processes to form secondary particles with a larger particle diameter. These granules or mixtures of different granules are then mixed with individual powdery additives and fed to the tableting. Depending on the design of the phases of the multi-phase detergent tablets, the die is gradually filled with different premixes. In the manufacture of multi-layer tablets, a slight application of pressure between the pre-mix filling can have advantages for the next layer. In the production of ring-core shaped bodies or coated tablets, such pre-evaporation with shaping is almost indispensable.

Preferred detergent tablets in the context of the present invention are obtained by squeezing particulate premixes from at least one surfactant-containing granulate and at least one subsequently admixed powdery component. The surfactant-containing granules can be produced using conventional granulation processes such as mixer and plate granulation, fluidized bed granulation, extrusion, pelletizing or compacting. It is of advantage for the later detergent and molded product bodies if the premixes to be dispensed have a bulk density that comes close to that of conventional compact detergents. In particular, it is preferred that the premix to be veφress has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular above 700 g / 1. Another advantage can result from a narrower particle size distribution of the surfactant granules used. In the context of the present invention, detergent tablets are preferred in which the granules have particle sizes between 10 and 4000 μm, preferably between 100 and 2000 μm and in particular between 600 and 1400 μm. 17

The particle size distribution of the subsequently admixed pulverulent preparation components can also be varied, preference being given to detergent tablets in which the subsequently admixed pulverulent component (s) have the same particle size distribution as the granules used.

Can formköφern Before Veφressung of particulate ^'shaped premix to detergent and cleaning the premix be with fine-particle surface treatment agents "dusted". This can be of advantage for the quality and physical properties of both the premix (storage, molding) as well as the finished detergent tablets. Finely divided powdering agents are well known in the art, mostly zeolites, silicates or other inorganic salts being used. However, the premix is preferably “powdered” with finely divided zeolite, zeolites of the faujasite type being preferred. In the context of the present invention, the term “faujasite-type zeolite” denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4 (see Donald W. Breck: “Zeolite Molecular Sieves”, John Wiley & Sons, New York) , London, Sydney, Toronto, 1974, page 92). In addition to the zeolite X, zeolite Y and faujasite and mixtures of these compounds can also be used, the pure zeolite X being preferred.

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

In the context of the present invention, detergent tablets are preferred which consist of a particulate premix which contains granular components and subsequently admixed powdery substances, the or one of the subsequently admixed powdery components being a zeolite of the faujasite type with particle sizes below 100 μm, is preferably below 10 μm and in particular below 5 μm and is 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 treated. 18th

The finely divided processing components with the above-mentioned particle sizes can be dry mixed into the premix to be treated. However, it is also possible and preferred to "stick" them to the surface of the coarser particles by adding small amounts of liquid substances. These powdering processes are widely described in the prior art and are familiar to the person skilled in the art. Non-ionic surfactants or aqueous solutions of surfactants or other detergent ingredients can be used, for example, as liquid components which are suitable for promoting the adhesion of the powdering agents. In the context of the present invention, it is preferred to use perfume as the liquid adhesion promoter between the finely divided powdering agent and the coarse-grained particles.

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

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 peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C. and below, bleach activators can be incorporated as the sole constituent or as an ingredient of component b). 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. Substances containing O- and / or N-acyl groups are suitable 19

carry the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular l, 5-diacetyl-2,4-dioxohexahydro-l, 3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetoxy and 2,5-diacetyloxy and 2,5-glycolacetyl, ethylene glycol 2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be incorporated into the moldings. 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.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymatic active substances obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are 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 in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules in the shaped bodies according to the invention can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight. 20th

In addition, the detergent tablets can also contain components that positively influence the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component. 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 of hydroxypropoxyl groups of 1 to 15% by weight in each case based on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

The shaped bodies can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-moφholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which, instead of the Moφholino group, have a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group. In addition, brighteners of the substituted diphenylstyryl type may be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2- sulfostyryl) diphenyls. Mixtures of the aforementioned brighteners can also be used.

Dyes and 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 softness, to provide the consumer with a visually and sensorially "typical and unmistakable" product. Individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl 21

carbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, AUylcyclohexylpropionat, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the Jonone, oc-isomethylionon and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and Teφineol, to the hydrocarbons belong mainly the Teφene like Limonen and Pinen. 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, lentil flower 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 dye content of the plasticizers according to the invention is usually less than 0.01% by weight, while fragrances can make up up to 2% by weight of the entire 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.

In order to improve the aesthetic impression of the detergent tablets according to the invention, 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 long shelf life and are insensitive to the other ingredients of the compositions and to light, and also have no pronounced substantivity towards textile fibers 22

stain. Since the subject matter of the present invention relates to multi-phase detergent tablets, the coloring of individual phases is of greater importance in order to underline the different active character of individual phases. Examples of the effectiveness of such coloring and of the success of statements on this are well known from the denture cleaner advertising.

The molded articles according to the invention are first produced by dry mixing the constituents of the individual phases, which can be wholly or partially pre-granulated, and then providing information, in particular compresses to tablets, whereby conventional methods for producing multi-phase molded articles can be used. To produce the multi-phase molded bodies according to the invention, the premixes are compressed in a so-called die between two punches to form a solid compact. 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.

Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches. 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 punch or stamps are fastened 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 stamp, but several stamps 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 23

Matrices vary 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. At locations where a particularly serious lifting or lowering of the punches is required (infestation, compression, ejection), these cam tracks are supported by additional low-pressure pieces, low-pressure 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 premixes. The pressing pressure on the respective premix can be individually adjusted via the pressing paths for the upper and lower punches, the pressure building up by the rolling of the punch shaft heads past adjustable pressure rollers.

Rotary presses can also be equipped with two or more filling shoes to increase the throughput. For the production of two-layer and multi-layer molded bodies, 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 molded articles per hour.

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, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen GmbH, Berlin, Mapag Maschinenbau AG, Bern (CH) and Courtoy NV, Halle 24

(BE / LU). For example, the hydraulic double pressure press HPF 630 from LAEIS, D. is particularly suitable.

The shaped bodies can be manufactured in a predetermined spatial shape and size, whereby they always consist of several phases, i.e. Layers, inclusions or cores and rings exist. 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.

The portioned compacts can each be designed as separate individual elements that correspond to the predetermined dosage of the detergents and / or cleaning agents. It is also possible, however, to form compacts which connect a plurality of such mass units in one compact, the portioned smaller units being easy to separate, in particular by predetermined predetermined breaking points. For the use of laundry detergents in machines of the type customary in Europe with horizontally arranged mechanics, the portioned compacts as tablets, in cylinder or cuboid form can be expedient, 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, in particular for the production of such pressed articles.

The spatial shape of another embodiment of the molded body is adapted in its dimensions to the detergent dispenser of commercially available household washing machines, so that the molded body can be metered directly into the dispenser without metering aid, where it dissolves during the dispensing process. Of course, the detergent tablets can also be used without problems using a dosing aid. 25th

Another preferred multi-phase molded body that can be produced has a plate-like or panel-like structure with alternately thick long and thin short segments, so that individual segments of this "multi-phase lock" are broken off at the predetermined breaking points, which represent the short thin segments and can be entered into the machine. This principle of the "bar-shaped" shaped body detergent can also be realized in other geometric shapes, for example vertically standing triangles, which are connected to one another only on one of their sides along the side. For optical reasons, it makes sense to design the triangular base that connects the individual segments as one phase, while the triangle tip forms the second phase. 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

2P σ = πDt

Herein σ 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 molded body.

Examples: Premixes were prepared by mixing surfactant-containing granules with pulverulent preparation components, which were pressed in a Korsch tablet press into two-phase detergent tablets. The surfactant granules 1, 2 and 3 were produced in a 130-liter ploughshare mixer (Gebrüder Lödige, Paderborn) 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 processing components in a paddle mixer. The composition of the surfactant granules is shown in Table 1. Table 1: Surfactant granules [% by weight]

Granules 1 Granules 2 Granules 3

26

C ₉ . ₁₃ alkyl benzene sulfonate 21.2 18.6 19.4

C ₁₂ .. ₈ 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 1.0 degree of oligomerization 1.1

Soap 1.6 1.6 1.6

Sodium carbonate 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

Two-layer detergent tablets were produced from the premixes (surfactant granules + processing components) on a Korsch rotary press, the proportion of the first layer being 75% by weight of the total mass and the proportion of the second layer being 25% by weight of the total mass of the tablet. 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% and the disintegration times by approx. 5 seconds. The tablet hardness and disintegration times are listed in the respective tables. 27

Table 2: Detergent tablets: composition [% by weight], physical data

Example 1 Comparative Example According to the Invention

Layer 1 Layer 2 Layer 1 Layer 2

Granules 1 60.0 60.0 64.2 51.3

Sodium perborate monohydrate 23.7 - 23.7 -

Tetraacetylethylenediamine 2.6 22.5-29.0

Enzyme granules * - 10.0 - 10.0

Foam inhibitor 4.7-3.5 1.1

Repelotex-SRP-4 ** 1.5 - 1.1 1.1

Perfume 0.5 0.5 0.5 0.5

Zeolite A 2.0 2.0 2.0 2.0

Cellulose *** 5.0 5.0 5.0 5.0

Surfactant content 18.78% 18 _» 7% 20.09% 16.05

Teosidge (tablet) 18 8% \ m%

Tablet hardness 43 - 55 N 39 - 47 N

Disintegration time 13 - 18 sec> 60 sec

Protease, cellulase, amylase, lipase on carrier (starch), coated

** Repelotex-SRP-4 is a terephthalic acid-ethylene glycol-polyethylene glycol ester of

Rhönen-Poulenc.

*** compacted cellulose (particle size: 90% by weight> 400 μm)

Table 3: Detergent tablets: composition [% by weight], physical data

Example 2 Comparative Example According to the Invention

Layer 1 Layer 2 Layer 1 Layer 2

Granules 2 60.0 60.1 66.8 41.1

Sodium perborate monohydrate 17.8 17.8 17.8 17.8

Tetraacetylethylenediamine 10.1 - - 29.0

28

Enzyme granules - 10.0 3.3 -

Foam inhibitor 3.5 3.5 3.5 3.5

Reρelotex-SRP-4 1.1 1.1 1.1 1.1

Perfume 0.5 0.5 0.5 0.5

Zeolite A 2.0 2.0 2.0 2.0

Cellulose * 5.0 5.0 5.0 5.0

Tessidgehalέ 18.78% 18.81% 20.91% 12.86%

Surfactant content (tablet) 18 _* 79% 18.90%

Tablet hardness 40-50N 37-49N

Disintegration time 16-22 sec> 60 sec

compacted cellulose (particle size: 90% by weight> 400 μm)

29

Table 4: Detergent tablets: composition [% by weight], physical data

Example 3 Comparative Example According to the Invention

Layer 1 Layer 2 Layer 1 Layer 2

Granules 3 60.1 60.1 66.3 42.5

Sodium perborate monohydrate 14.5 27.8 7.0 50.0

Tetraacetylethylenediamine 10.0 - 9.8 -

Enzyme granules 3.3 - 3.3 -

Foam inhibitor 3.5 3.5 4.7 -

Repelotex-SRP-4 1.1 1.1 1.4 -

Perfume 0.5 0.5 0.5 0.5

Zeolite A 2.0 2.0 2.0 2.0

Cellulose * 5.0 5.0 5.0 5.0

Ts ^ £ ge & at the shift 19.23% 19.23% 21 _> 22 o 13.60%

Tensi aged (pochard) 19.23% 19.32%

Tablet hardness 43-51N 38-47N

Disintegration time 13 -17 sec> 60 sec

compacted cellulose (particle size: 90% by weight> 400 μm)

Claims

30 patent claims:

1. Two-phase or multi-phase detergent shaped body made of compressed particulate detergent and cleaning agent, comprising surfactant (s), builder (s) and optionally further detergent and cleaning agent components, characterized in that the surfactant content of the individual phases of the molded body around not more than 3% by weight, based on the weight of the individual phase, varies.

2. Detergent and molded article according to claim 1, characterized in that the surfactant content of the individual phases of the molded article is not more than 2% by weight, preferably not more than 1.5% by weight and in particular not more than 1 % By weight, based on the weight of the individual phase, varies.

3. Detergent and molded article according to one of claims 1 or 2, characterized in that the surfactant content of the individual phases of the molded article is identical.

4. Detergent and shaped body according to one of claims 1 to 3, characterized in that the phases of the shaped body have the shape of layers.

5. Detergent and molded article according to one of claims 1 to 4, characterized in that the surfactant (s) are introduced via surfactant-containing (s) granules (e) in the phases of the molded article.

6. Detergent and molded article according to claim 5, characterized in that the same surfactant granules are used in all phases of the molded article.

7. washing and cleaning agent molded article according to claim 4 and 6, characterized in that the molded article have two layers which contain the same surfactant granules. 31

8. Detergent form according to one of claims 1 to 7, characterized in that they contain anionic (s) and nonionic (s) surfactant (s).

9. Detergent and molded article according to claim 8, 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.

10. Detergent and molded article according to one of claims 1 to 6, characterized in that at least one phase of the molded article is free of nonionic surfactants.

11. Detergent and molded article according to one of claims 1 to 6, characterized in that at least one phase of the molded article contains alkyl polyglycosides.

12. Detergent and molded article according to one of claims 1 to 11, characterized in that at least one phase of the molded article is free from anionic surfactants.

13. Washing and cleaning agent molded article according to one of claims 1 to 12, characterized in that they have been obtained by molding a particulate premix comprising at least one surfactant-containing granulate and at least one subsequently admixed powdery component.

14. Washing and cleaning agent molded article according to claim 13, characterized in that the granules were produced using conventional granulating processes such as mixer and plate granulation, fluidized bed granulation, extrusion, pelletizing or compacting.

15. Detergent and molded article according to one of claims 13 or 14, characterized in that the granules have particle sizes between 10 and 4000 microns, preferably between 100 and 2000 microns and in particular between 600 and 1400 microns. 32

16. Detergent and molded article according to one of the claims 13 to 15, characterized in that the powder (s) component (s) subsequently mixed in have the same particle size distribution as the granules used.

17. Detergent and molded article according to one of the claims 13 to 16, characterized in that the premix to be veφressende a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular above 700 g / 1.

18. Detergent form according to one of claims 13 to 17, characterized in that the or one of the subsequently admixed powdery components is a faujasite-type zeolite with particle sizes below 100 μm, preferably below 100 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% by weight of the premix to be pressed.

19. Detergent form according to one of claims 1 to 18, characterized in that it additionally contains 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 from 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the molded body weight.

20. Washing and cleaning agent shaped body according to one of claims 1 to 19, further comprising one or more substances from the group of builders, bleaching agents, bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.