DE19828577A1 - Production of laundry detergent tablets useful in domestic washing machine - Google Patents

Abstract

Production of laundry detergent moldings by mixing a granulate, containing surfactant and finely-divided preparation components, then press molding. The surfactant granulate contains a zeolite of the P and/or X type. An Independent claim is also included for the zeolite of zeolites of the P and/or X type in surfactant granulates, which increase the stability and solubility of laundry detergent moldings when mixed with finely-divided preparation components.

Description

The present invention relates to a process for the production of moldings which have washing and cleaning properties. In particular, the invention relates a process for the production of detergent tablets for the Tex washing in a household washing machine, briefly referred to as detergent tablets become.

Commercial detergents and cleaning agents are nowadays in the form of liquid pro products or solids. A distinction is made in the latter form of offer conventional powders or concentrates, for example by granulation or extrusion are available. Compared to conventional powders, concentrated washing and Cleaning agents have the advantage that a reduced packaging effort must be and less doses per wash cycle. Be too due to the reduced pack sizes, the transport and storage costs are reduced. The highly concentrated form in which detergents and cleaning agents are currently used in some Countries offered in the market are compressed washing and cleaning agents molded body. While water softeners and machine dishwashing detergents in this area botsform are widespread, there are various problems with textile detergents that to date have prevented wide distribution and consumer acceptance. Due to the significantly higher surfactant levels are usually the form of the form problems occurring in the body. Washing mitts are particularly problematic tablets that contain alkoxylated nonionic surfactants, as this class of surfactants  has a negative effect on the solubility of the tablets - on the other hand, they are precisely these Surfactants are expressly desired because of their high washing power.

In particular, the dichotomy between a sufficiently hard molded body and one Sufficiently fast disintegration time is a central problem. Because sufficiently stable, d. H. shape and break resistant molded body only by relatively high compression pressures can be put, there is a strong compression of the molded parts and a consequent delayed disintegration of the shaped body in the aqueous Liquor and thus too slow a release of the active substances in the washing or Cleaning process. The delayed disintegration of the molded body continues to have Disadvantage that conventional detergent tablets do not have the A Have the washing-up chamber rinsed in by household washing machines as the tablets are not in decay into secondary particles that are small enough to turn off on sufficiently quickly rinsing chamber to be washed into the washing drum.

A variety of approaches exist in the prior art to solve this problem. Next the use of special ingredients that are intended to promote disintegration Coating of individual ingredients as well as sieving the premix to be pressed proposed.

For example, EP-A-0 466 484 (Unilever) discloses detergent tablets in which the ver pressing premix has particle sizes between 200 and 1200 microns, with upper and the lower limit of the particle sizes do not differ by more than 700 µm. About the waiter Surface treatment of individual ingredients is not described in this document.

EP-A-0 522 766 (Unilever) also relates to moldings made from a compact, partially Chen-shaped detergent composition containing surfactants, builders and disintegra tion aids (for example based on cellulose), at least some of the particles is coated with the disintegrant, which both binder and disintegrate onseffect when dissolving the moldings in water shows. This font also shows the general difficulty, molded articles with adequate stability and good at the same time To produce solubility. The particle size in the mixture to be compressed should be above  are half of 200 µm, the upper and lower limits of the individual particle sizes being around should not differ from each other by more than 700 µm.

DE 40 10 533 (Henkel KGaA) discloses a process for the production of compacts from pre-compressed granules. This is done in a first stage Extrusion and cutting produced granules, if necessary with further content and excipients are mixed and tabletted. The proportion of the pre-compressed granulate in the Presslings in this document is up to 100%. Pretreatment of the optional on set mixing components is not disclosed.

The detergent tablets produced according to the documents mentioned have one sufficient hardness, but have decay rates that exceed a dosage not allow a detergent dispenser of a household washing machine. In the cited Prior art documents have dissolution times of less than 10 minutes and return values below 50% are described as good, with such values for the use of Detergent tablets through the dispenser are completely inadequate.

Another disadvantage of the molded articles produced according to the prior art lies in their lack of resistance to shock loads. Across from Pressure that is slowly increasing on them makes the tablets sufficiently stable For example, they burst when falling on hard ground. In case or in Transport of the tablets can also occur edge breaking symptoms against which the conventional tablets are not sufficiently stable. In addition, usual washing and detergent tablets have the disadvantage that they harden or zer during storage flow so that they must be protected from the ambient air, which is usually is realized by individual packaging.

The present invention was based on the object of a method for the production of detergent tablets, which makes it possible to form to produce bodies that are free from the disadvantages mentioned. It should be simple che and highly reproducible way laundry detergent tablets can be, which have a high hardness, by a fast dissolution rate  distinguish and also via the induction chamber of household washing machines are settable. The hardness should not only relate to a high diametrical breaking stress limit, but also stability during transport (rubbing / shaking) and falling ensure the molded body.

In addition, the shaped articles produced by the process to be provided are said to be no change in their advantageous property profile even with open storage ren, so that airtight packaging of individual tablets can be dispensed with.

It has now been found that detergent tablets with the ge advantages mentioned, if you press premixes, which consist of a ten granules containing zeolite P and / or zeolite X and other autbe mounting components exist.

The invention therefore relates to a process for the production of washing and cleaning agents molded body by mixing a surfactant-containing granulate with finely divided Processing components and subsequent shaping pressing in itself known manner, in which the surfactant-containing granules are a zeolite of the P and / or X type contains.

The production of surfactant-containing granules is widely described in the prior art where in addition to extensive patent literature, numerous review articles and mono graphics can be used. This is how W Hermann de Groot, I. Adami, G. F. Moretti "The Manufacture of Modern Detergent Powders", Hermann de Groot Academic Publisher, Wassenaar, 1995 various spray drying, mixing and granulating processes ren for the production of detergents and cleaning agents.

For energetic reasons, it is preferred in the context of the present invention if the surfactant-containing granules are not spray dried, but by a granulation process ren is manufactured. In addition to the conventional granulation and agglomeration processes, carried out in a wide variety of mixing granulators and mixing agglomerators press agglomeration processes can also be used, for example.  

The granulation can be found in a wide variety of industries in the detergent and cleaning agent industries usually used apparatus can be carried out. For example, it is possible Lich to use the rounding agents common in pharmacy. In such a turntable app temperatures, the residence time of the granules is usually less than 20 seconds. Also conventional mixers and mixing granulators are suitable for granulation. As Wed Shearers can use both high-intensity shear mixers and normal ones Mixers with lower circulation speeds can be used. Suitable mixers are, for example, Eirich® mixers of the R or RV series (trademarks of the machines factory Gustav Eirich, Hardheim), the Schugi® Flexomix, the Fukae® FS-G mixer (Wa trademark of Fukae Powtech, Kogyo Co., Japan), the Lödige® FM, KM and CB Mixer (trademark of Lödige Maschinenbau GmbH, Paderborn) or the Drais® Series T or K-T (trademark of Drais-Werke GmbH, Mannheim). The dwell times the granules in the mixers are in the range of less than 60 seconds, the Dwell time also depends on the speed of rotation of the mixer. Shorten this the faster the mixer runs, the dwell times accordingly. These are preferably Residence times of the granules in the mixer / rounder are less than one minute, preferably less than 15 seconds. In slow running mixers, e.g. B. a Lödige KM, become lingering times of up to 20 minutes, with dwell times of less than 10 minutes due to the Process economics are preferred.

In the press agglomeration process, the surfactant-containing granules are under pressure and compressed under the influence of shear forces and homogenized and then discharged form-giving from the apparatus. The most technically significant press agglomerates tion processes are extrusion, roller compaction, pelleting and ta blett. In the context of the present invention, preferably for the preparation of the surfactant Pressed agglomeration processes containing granules are extrusion, the whale zen compacting and pelleting.

In a preferred embodiment of the invention, the surfactant-containing granules preferably continuously a planetary roller extruder or a 2-shaft extruder or 2-screw extruder with co-rotating or counter-rotating screw guidance fed, its housing and its extruder pelletizing head to the predetermined extru  dier temperature can be heated. Under the shear of the extruder screws the premix is under pressure, which is preferably at least 25 bar, at extreme high throughputs depending on the apparatus used but also below condensed, plasticized, in the form of fine strands through the perforated nozzle plate in the Extruder head extruded and finally the extrudate using a rotating tee knife preferably to approximately spherical to cylindrical granules nert. The hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granule size. In this embodiment, the Production of granules of a substantially uniformly predeterminable part size, in particular the absolute particle sizes of the intended use purpose may be adapted. Important embodiments see the production of uniform granules in the millimeter range, for example in the range from 0.8 to 5 mm and in particular in the range from about 1.0 to 3 mm. The length / diameter The ratio of the primary granules chipped off is an important factor tion form in the range from about 1: 1 to about 3: 1. It is further preferred that the pla to supply static primary granules to a further shaping processing step; there at edges present on the crude extrudate are rounded off, so that ultimately spherical until approximately spherical extrudate grains can be obtained. Alternatively, you can Extrusions / pressings also in low pressure extruders, in the Kahl press or in Be extruder be carried out.

In a further preferred embodiment of the present invention, the Her adjustment process for the surfactant-containing granules by means of a roller compacting leads. Here, the surfactant-containing granulate is targeted between two smooth or vertically Rolls of defined shape dosed and between the two whale zen rolled under pressure into a leaf-shaped compact, the so-called Schülpe. The rollers exert a high line pressure on the premix and can vary depending on Required to be additionally heated or cooled. When using smooth rollers he one keeps smooth, unstructured cuffs, while using struktu structured rolls or structured pellets or individual pellets can, in which, for example, certain forms of the later granules or molded articles can be specified by. The cuff band is subsequently knocked off  and crushing process broken into smaller pieces and this way too Granules are processed by further known surfaces treatment process further remunerated, in particular in approximately spherical shape can be brought.

In a further preferred embodiment of the present invention, the Her position of the surfactant-containing granules by means of pelleting. Here will The surfactant-containing granules are applied to a perforated surface and applied using a pressure body through the holes. In common embodiments of Pellt The tenside-containing granulate is compressed under pressure, plasticized, using a rotating roller in the form of fine strands pressed through a perforated surface and finally crushed to a granulate with a knock-off device. Here are the Different configurations of the pressure roller and perforated die are conceivable. So For example, flat perforated plates are used as well as concave or con vex ring matrices through which the material passes through one or more pressure rollers is pressed through. The press rolls can also be conical in the plate machines, in the ring-shaped devices, dies and press roll (s) can run in the same direction or against have a common sense of rotation. A ge for performing the method according to the invention A suitable apparatus is described, for example, in German published patent application DE 38 16 842 (Schlüter GmbH). The ring die press disclosed in this document exists from a rotating ring die interspersed with press channels and at least one with whose inner surface is operatively connected to the press roller, which is the die space guided material through the press channels in a material discharge. Here are ring die and press roller can be driven in the same direction, resulting in reduced shear stress and thus a lower temperature increase of the premix can be achieved. Self ver Of course, it is also possible to work with heatable or coolable rollers when pelleting to set a desired temperature of the premix.

The surfactant-containing granules contain fillers and carriers as well as optional additives setting ingredients of detergents and cleaning agents and additional granulation auxiliaries surfactants. These surface-active substances come from the group of anionic, nonionic, zwitterionic or cationic surfactants, anionic  Surfactants due to economic reasons and due to their range of services 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 having an end or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfofatty acids (ester sulfonates), e.g. B. the α-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids is suitable.

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

As alk (en) yl sulfates, the alkali and especially the sodium salts of the sulfuric acid semiesters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ - Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, straight-chain alkyl radical produced on a chemical basis, 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 in accordance with US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN, are 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 _9-1 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. Are suitable saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural Fatty acids, e.g. B. coconut, palm kernel or tallow fatty acids, derived soap mixtures.

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

In the context of the present invention, surfactant granules are process end products of the intermediate step a) preferably, the 5 to 50 wt .-%, preferably 7.5 to 40 wt .-% us in particular 10 to 20 wt .-% anionic surfactant (s), each based on the Granu lat, included.

When choosing the anionic surfactants that are in the process end products of the Zwi step a) are used, the freedom of formulation cannot be complied with the framework in the way. However, preferred surfactant granules have a Ge hold on soap, the 0.2 wt .-%, based on the total weight of the in step d) provided detergent tablets, exceeds. Preferred to use Anionic surfactants are the alkylbenzenesulfonates and fatty alcohol sulfates, with be preferred detergent tablets 2 to 20 wt .-%, preferably 2.5 to 15% by weight and in particular 5 to 10% by weight of fatty alcohol sulfate (s), in each case based on the weight of the detergent tablets

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol residue is linear or preferably in the 2-position May be methyl branched or may contain linear and methyl branched radicals in the mixture, as are usually present in oxoalko radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-13 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _{12 - 18} alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and _C12-18 alcohol containing 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these 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.

Another class of preferred nonionic surfactants, which are used either as allei some nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and pro poxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as described, for example, in Japanese Pa tentanmeldung JP 58/217598 are described or which preferably according to the in ternational patent application WO-A-90/13533 who produced the.

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

Linear alkyl polyglucosides, ie alkyl polyglycosides, are preferably used in de the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.

The process end products of intermediate step a) can preferably be alkyl polyglycosides contain, with contents of APG over 0.2 wt .-%, based on the total molding per, are preferred. Particularly preferred detergent tablets are ent hold APG in amounts of 0.2 to 10 wt .-%, preferably 0.2 to 5 wt .-% and esp special from 0.5 to 3 wt .-%.

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 alka  nolamides may be suitable. The amount of these nonionic surfactants is before preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of it.

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

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

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

in the R for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ¹ for a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R ² for a linear, branched or cyclic alkyl radical or represents an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-14 alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated derivatives of this Re stes.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example, after the teaching of international application WO-A-95/07331 by reaction with fatty acid remethyl esters in the presence of an alkoxide as a catalyst in the desired polyhy droxy fatty acid amides are transferred.

Regardless of whether anionic or nonionic surfactants or mixtures of these Classes of surfactants and, if applicable, amphoteric or cationic surfactants in the surfactant granule lat are used, methods according to the invention are preferred, in which the surfactant content of the surfactant-containing granules produced in step a) 5 to 60% by weight, preferably as 10 to 50 wt .-% and in particular 15 to 40 wt .-%, each based on the ten sidgranulate.

The surfactant granules can vary in the laundry detergent and cleaning product tablets Amounts are used. Processes according to the invention in which the proportion of the surfactant containing granules on the detergent tablets 40 to 95% by weight, preferably 45 to 85% by weight and in particular 55 to 75% by weight, in each case based on the weight of the detergent tablets is preferred.

According to the invention, the surfactant granules contain those in the process according to the invention are used, a zeolite of the P and / or X type.

Zeolite P belongs to the zeolite structure group 1 (compare Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, page 72) and can through the secondary imaging unit of a single four-ring (S4R). In the context of the present invention, the zeolites of the zeolite structure group 1 are interchangeable, so that in addition to the synthetic zeolite P, the mineral or synthetic zeolites Analcime, Wairakit, Viseit, Kehoeit, Harmotom, Phillipsit, Gismondin, Garronit, Paulingit, Laumonit and Yugawaralit can be used as Zeo lith P-type. However, pure zeolite P is preferably used, which can be described by the formula Na ₆ (AlO ₂ ) ₆ (SiO ₂ ) ₁₀ ] 15 H ₂ O. The two most common types of zeolite P are a cubic and a tetragonal modification, the cubic zeolite P also being referred to in the literature as zeolite B or zeolite P _c , while the teragonal type is called P _t .

Zeolite P has a density of 2.01 gcm ^-3 and the structure has a void volume of 41%. The three-dimensional network of the zeolite P used in the process according to the invention has pores of 2.6 Å (dehydrated) or 3.1.4.4 Å and 2.8. 4.9 Å (hydrated). Zeolite MAP® (commercial product from Crosfield) is particularly preferred as zeolite P.

Together with the zeolites X and Y, the mineral faujasite belongs to the faujasite types within the zeolite structure group 4, which by the double six-ring subunit D6R is marked (Compare Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, page 92). To the zeolite structure group 4 In addition to the faujasite types mentioned, the minerals chabazite and gmelinite also count as well as the synthetic zeolites R (chabazite type), S (gmelinite type), L and ZK-5. The the latter two synthetic zeolites have no mineral analogues. All representatives of the zeolite structure group 4 mentioned can be within the scope of the present exchange for zeolite X, using the same as for the P-type zeolites Zeolite X is clearly preferred.

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

Mixtures or cocrystallisates of zeolites of the P and / or X type with others Zeolites, which do not necessarily have to belong to the zeolite structure group 1 or 4 usable according to the invention, the advantages of the method according to the invention particularly This is particularly evident when at least 50% by weight of that is contained in the surfactant granulate NEN zeolite consist of one or more P and / or X type zeolites. The Aluminum silicates that are used in the process according to the invention are more commercial available, and the methods for their representation are in standard monographs be wrote.

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

Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ .x H ₂ O,

K ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .x H ₂ O,

Ca ₄₀ Na ₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .x H ₂ O,

Sr ₂₁ Ba ₂₂ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .x H ₂ O,

in which x can take values between 0 and 276 and the pore sizes from 8.0 to 8.4 Å have.

A co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X), which is available from CONDEA Augusta S. pA under the brand name VEGOBOND AX, is also commercially available and can preferably be used in the process according to the invention ® is distributed 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 content of the surfactant-containing granules of zeolite of the P and / or X type can vary other optional ingredients vary. Within the scope of the present invention Processes preferred in which the content of the surfactant-containing granules of zeolite P and / or zeolite × 20 to 80% by weight, preferably 25 to 70% by weight and in particular 30 to 50% by weight, based in each case on the surfactant granules, is.

The surfactant granules containing zeolite P and / or X are then mixed with further Processing components mixed into a premix, which is then washed and Detergent tablets can be pressed. The premix to be pressed can be used as processing components in addition to the ingredients already mentioned further ingredients common in washing and cleaning agents, in particular from Group of builders, disintegration aids, bleach, bleach activators, en zymes, pH adjusting agents, fragrances, perfume carriers, fluorescent agents, dyes, foamin inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors ren, color transfer inhibitors and corrosion inhibitors included.

In addition to the washing-active substances, builders are the most important ingredients of Detergents and cleaning agents. In the washing and cleaning agents according to the invention Molded bodies can usually all be used in washing and cleaning agents Th builders may be included, especially zeolites, silicates, carbonates, organic Cobuilder and - where there are no ecological prejudices against their use - also that 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 × 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0164 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 ₂ Si ₂ O ₅ .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 ₂ O: 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, can also be used are delayed 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, compaction / 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 in such a way that the products have microcrystalline ranges 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 release delay compared to the conventional water glass glasses, are described, for example, in German patent application DE-A-44 00 024. Particularly preferred are compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates.

If desired, the amount of zeolite introduced by the surfactant granules P and / or X-type additional zeolite are incorporated into the premix, by adding zeolite as a treatment component. The fine crystals used ne, synthetic and bound water-containing zeolite is preferably a zeolite of type A, P, X or Y. However, zeolite X and mixtures of A, X are also suitable and / or P. Suitable zeolites have an average particle size of less than 10 μm  (Volume distribution; measurement method: Coulter Counter) and preferably contain 18 up 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 buildersub punching possible, provided that such use is not avoided for ecological reasons should be. The sodium salts of orthophosphates, the py rophosphates and especially the tripolyphosphates.

Usable organic builders are, for example, those in the form of their sodium salt ze usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutar acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, as well as mixing from 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 this.

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

These substances, which are also referred to as "explosives" due to their effect, ver increase their volume when water enters, and on the one hand increases their own volume (Swelling), on the other hand, a pressure can be generated via the release of gases which can break the tablet into smaller particles. Well-known disintegration aid medium are, for example, carbonate / citric acid systems, but also other organic ones Acids can be used. Swelling disintegration aids are, for example synthetic polymers such as polyvinyl pyrrolidone (PVP) or natural polymers or mo  differentiated natural substances such as cellulose and starch and their derivatives, alginates or casein Derivatives.

Preferred detergent tablets contain 0.5 to 10% by weight preferably 3 to 8% by weight and in particular 4 to 6% by weight of a disintegration aid means, each based on the weight of the molded body.

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent and cleaning agent moldings contain such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 8% by weight and in particular Contain 4 to 6 wt .-%. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, formally speaking, represents a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.

The cellulose derivatives mentioned are preferably not used alone as disintegration agents tel based on cellulose, but used in a mixture with cellulose. The Ge the content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the disintegrant Cellulose base. Cellulose-based disintegrant is particularly preferred ne cellulose used, which is free of cellulose derivatives.  

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

It is in the process according to the invention for the later washing and cleaning agents Shaped bodies are advantageous if the premix to be pressed has a bulk density points that comes close to the usual compact detergent. In particular, it is preferred that the premix to be compressed has a bulk density of at least 500 g / l, preferably has at least 600 g / l and in particular above 700 g / l.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as per benzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced. If such bleach tablets are to be used for textile washing, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, irrespective of which other ingredients are contained in the moldings. If cleaning tablets or bleach tablets for machine dishwashing are manufactured, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as. B. dibenzoyl peroxide. Other typical organic bleaching agents are peroxyacids; the alkyl peroxy acids and the aryl peroxy acids are mentioned as examples. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, s-phthalimidthanoic acidoperoximinoxy acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacynoic acid, diperoxydiacid acid, diperoxane -1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

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

To be a better choice when washing or cleaning at temperatures of 60 ° C and below To achieve the greatest bleaching effect, bleach activators can be used as the sole component or be incorporated as an ingredient of component b). Can be used as bleach activators Compounds containing aliphatic peroxocarboxylic acids under perhydrolysis conditions preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or given if substituted perbenzoic acid result, are used. Suitable substances are the O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally sub carry substituted benzoyl groups. Multi-acylated alkylenediamines, ins special tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5- Diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular Tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5- Diacetoxy-2,5-dihydrofuran.  

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

Enzymes come from the class of proteases, lipases, amylases, cellulases or their mixtures in question. Bacterial strains or are particularly well suited Mushrooms such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus enzymatic agents. Proteases of the subtilisin type and esp special proteases obtained from Bacillus lentus. Here are En enzyme mixtures, for example of protease and amylase or protease and lipase or Protease and cellulase or from cellulase and lipase or from protease, amylase and Li pase or protease, lipase and cellulase, but especially cellulase-containing Mi of particular interest. Peroxidases or oxidases are also in one proven cases. The enzymes can be adsorbed on carriers and / or be embedded in coating substances to protect them against premature decomposition. Of the Proportion of the enzymes, enzyme mixtures or enzyme granules in the inventive Shaped bodies can, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 % By weight.

In addition, the detergent tablets can also ent components hold, which positively influence the oil and fat washability from textiles (so-called called soil repellents). This effect is particularly evident when a textile is dirty is already several times with a detergent according to the invention, this Contains oil and fat-dissolving component, was washed. Among the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methylhydroxy-propyl cellulose with a proportion of methoxyl groups from 15 to 30 wt .-% and of hydroxypropoxyl groups from 1 to 15 wt .-%, each bezo gene on the nonionic cellulose ether, as well as those known from the prior art  Polymers of phthalic acid and / or terephthalic acid or their derivatives, in particular special polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Especially be of these, the sulfonated derivatives of phthalic and terephthalic acids are preferred re-polymers.

The moldings can be derivatives of diaminostilbenedisulfonic acid as optical brighteners or their alkali metal salts. Are suitable for. B. Salts of 4,4'-bis (2-anilino-4- morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or the like Compounds which, instead of the morpholino group, a diethanolamino group, a Me wear thylamino group, an anilino group or a 2-methoxyethylamino group. Wei thereafter brighteners of the substituted diphenylstyryl type may be present, e.g. B. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) - diphenyls, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyls. Mixtures of the pre named brighteners can be used.

Dyes and fragrances become the detergent and cleaning agent form according to the invention added bodies to improve the aesthetic impression of the products and Ver In addition to the softness performance, users need a visually and sensory "typical and unmatched interchangeable "product. As perfume oils or fragrances can individual fragrance compounds, e.g. B. the synthetic products of the ester type, Ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Smell Compounds of the ester type are e.g. B. benzyl acetate, phenoxyethyl isobutyrate, p tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allylcyclohexylpropio nat, styrallyl propionate and benzyl salicylate. Ethyls include, for example, benzyls ethyl ether, to the aldehydes z. B. the linear alkanals with 8-18 C atoms, Citral, Citro nellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, Lilial and Bour geonally, to the ketones e.g. B. the Jonone, cc-isomethyl ionone and methyl cedryl ketone the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and Terpineol, the hydrocarbons mainly include terpenes such as limonene and pinene. However, mixtures of different fragrances are preferably used,  which together create an appealing fragrance. Such perfume oils can also na contain natural fragrance genetics, such as are available from plant sources, e.g. B. 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, lin flower oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil such as 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 But it can also be advantageous to apply the fragrances to carriers that increase the adhesion of the Reinforcing perfumes on the laundry and slower fragrance release for longer maintain the fragrance of the textiles. Such carrier materials have, for example se cyclodextrins have proven themselves, with the cyclodextrin-perfume complexes additionally other auxiliaries can be coated.

In order to improve the aesthetic impression of the agents according to the invention, they can can be colored with suitable dyes. Preferred dyes, the selection of which Specialist poses no difficulty, has a high storage stability and is unstable sensitivity to the other ingredients of the agents and to light and none pronounced substantivity towards textile fibers so as not to stain them.

Before pressing the particulate premix into detergent and cleaning agent The premix can be shaped 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 washing and cleaning molded article may be advantageous. Finely divided powdering agents are known in the art Well-known technology, mostly zeolites, silicates or other inorganic salts be set. However, the premix is preferred with finely divided zeolite "powdered", with zeolites of the faujasite type being preferred. As part of the present  the invention denotes the term "faujasite type zeolite" all three zeolites that form the faujasite subgroup of zeolite structure group 4 (compare Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, To ronto, 1974, page 92). In addition to the zeolite X, there are also zeolite Y and faujasite as well Mixtures of these compounds can be used, the pure zeolite X being preferred.

Within the scope of the present invention are processes for the production of washing and Preferred detergent tablets, in which the or one of the subsequently added mixed finely divided processing components with a zeolite of the faujasite type Chen sizes below 100 microns, preferably below 10 microns and in particular below 5 µm and at least 0.2% by weight, preferably at least 0.5% by weight and in particular which makes up more than 1% by weight of the premix to be pressed.

To produce the moldings according to the invention, the premix is in a so-called called die between two stamps compressed into a solid compressed. This The process, which is briefly referred to below as tableting, is divided into four Sections: dosage, compression (elastic deformation), plastic deformation and Expel.

First, the premix is introduced into the die, the filling quantity and thus the weight and shape of the resulting molded body through the position of the lower one Stamp and the shape of the press tool can be determined. The constant dose tion even at high molding throughputs is preferably a volumetric Dosage of the premix reached. In the further course of tabletting, the Upper stamp the premix and continues to lower towards the lower stamp. At this compression, the particles of the premix are pressed closer together where at the void volume within the filling between the punches continuously decreases. From a certain position of the upper stamp (and thus from a certain pressure on the premix) begins the plastic deformation, in which the particles flow together and the molded body is formed. Depending on the physi properties of the premix, some of the premix particles are also broken down presses and the premix is sintered at even higher pressures. At  increasing press speed, i.e. high throughput, the phase of elasti 's deformation is continuously shortened, so that the resulting molded body more or may have smaller cavities. In the last step of tableting the Finished molded articles are pressed out of the die by the lower punch and through subsequent transport devices transported away. At this point, it's just that Weight of the molded body finally determined, because the compacts due to physical Processes (stretching, crystallographic effects, cooling etc.) their shape and size can still change.

Tableting takes place in commercially available tablet presses, which are basically or double stamps can be equipped. In the latter case, not only the waiter stamp used to build up pressure, also the lower stamp moves during the Pressing process towards the upper punch, while the upper punch presses down. For Small production quantities are preferably used with eccentric tablet presses which the one or more stamps are attached to an eccentric, which in turn on one Axis is mounted with a certain rotational speed. The movement of this Press ram is comparable to the way a conventional four-stroke engine works. The Ver pressing can be done with one upper and one lower stamp, but several can also be used re stamp on an eccentric disk, the number of die holes gen is expanded accordingly. 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 on a so-called called matrix table a larger number of matrices is arranged in a circle. The The number of matrices varies between 6 and 55, depending on the model, with larger matrices also are commercially available. Each die on the die table is a top and bottom stamp assigned, again the pressing pressure active only by the upper or lower stamp, but can also be built up by both stamps. The matrix table and the Stamps move around a common vertical axis, the stamp with the help of rail-like cam tracks during the circulation in the positions for Be filling, compression, plastic deformation and discharge. On the stel len, where a particularly serious raising or lowering the stamp  is necessary (filling, compressing, ejecting), these cam tracks are replaced by additional che low-pressure pieces, Nierderzugschienen and lifting tracks supported. The Befill The matrix is developed via a rigidly arranged feed device, the so-called Filling shoe, which is connected to a reservoir for the premix. The pressure the pre-mix can be set individually using the press paths for the upper and lower punches bar, the pressure build-up by rolling the stamp sheep heads past adjustable ren pressure rollers happens.

Rotary presses can also use two filling shoes to increase throughput hen be, with only one semicircle to manufacture a tablet that must. Several fillers are used to produce two-layer and multi-layer moldings shoes arranged one behind the other without the slightly pressed first layer in front of the further filling is ejected. By appropriate process control are in this way also coated and dot tablets can be produced, which have an onion-shell-like structure ben, 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 are also included Single or multiple tools can be equipped 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 a million tablets per hour.

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

The portioned compacts can each be separate individual elements be formed, the predetermined dosage of washing and / or cleaning medium corresponds. However, it is also possible to form compacts that have a plurality connect such mass units in a compact, in particular by vorege bene predetermined breaking points the easy separability of portioned smaller units hen is. For the use of textile detergents in machines of the type common in Europe with horizontally arranged mechanics, the formation of the portioned compacts as Tablets, in the shape of a cylinder or cuboid, with a diameter / height Ratio in the range of about 0.5: 2 to 2: 0.5 is preferred. Commercial hydrau Lik presses, eccentric presses or rotary presses are suitable devices in particular especially for the production of such compacts.

The spatial shape of another embodiment of the shaped body is in its dimensions the induction chamber of commercial household washing machines adapted so that the Shaped bodies can be metered directly into the induction chamber without a metering aid, where it dissolves during the induction process. Of course, there is also a stake the detergent tablets are easily possible via a dosing aid and within the present invention preferred.

Another preferred shaped body that can be produced has a plate or panel-like structure with alternating thick long and thin short segments, so that individual segments of this "bar" at the predetermined breaking points, the short thin Display segments, can be canceled and entered into the machine. This Principle of the "bar-shaped" shaped body detergent can also be used in other geometric Shapes, for example vertical triangles, only on one side are connected alongside each other, can be realized.  

But it is also possible that the various components do not become one Tablet are pressed, but that molded bodies are obtained that have several layers ten, i.e. at least two layers. It is also possible that these ver different layers have different dissolving speeds. From this you can advantageous application properties of the molded articles result. If at for example, components are contained in the moldings, which are mutually nega tiv influence, so it is possible to find a component in the more rapidly soluble layer to integrate and incorporate the other component in a slower soluble layer ten, so that the first component has already reacted when the second goes into solution. The layer structure of the moldings can be stacked, with one solder process of the inner layer (s) at the edges of the molded body already takes place, if the outer layers are not yet completely detached, it can also be one complete coating of the inner layer (s) by the outer layer (s) Layer (s) can be reached, which prevents the premature dissolution of Be components of the inner layer (s).

In a further preferred embodiment of the invention, a molded body consists of at least three layers, ie two outer and at least one inner layer, wherein at least one of the inner layers contains a peroxy bleach, while in the case of the stacked shaped body, the two outer layers and in the case of the shell-shaped one Shaped bodies, however, the outermost layers are free of peroxy bleach. Farther it is also possible to use peroxy bleach and any bleach activators present and / or to separate enzymes spatially from one another in a shaped body. Such more Layered moldings have the advantage that they do not have only one induction chamber or who uses a metering device which is added to the washing liquor that can; rather, in such cases it is also possible to direct the molded body To give contact to the textiles in the machine without staining Bleach and the like would be feared.

Similar effects can also be achieved by coating individual components of the detergent and cleaning agent composition to be pressed, or all of them Reach shaped body. For this purpose, the bodies to be coated can be coated, for example  aqueous solutions or emulsions are sprayed, or via the process of Get a coating on the melt coating.

After pressing, the detergent tablets have a high level of 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

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 is the Breakage of the shaped body causes, D is the shaped body diameter in meters and t is the Height of the molded body.

Another object of the present invention is the use of zeolite from P and / or X type in surfactant-containing granules, which after mixing with finely divided Preparation components for washing and cleaning agents in a manner known per se molded bodies are pressed to improve the stability and solubility of washing and detergent tablets. By using the types of zeolites mentioned in Detergent and cleaning agent granules, which after mixing with other components th are pressed into detergent tablets, the physi The properties of the moldings can be significantly improved, such as the following Evidence of examples.

Examples

A polymer compound was produced by spray drying and used as the basis for one granules containing sid were used. The tower powder was made with other components (Zeolite, fatty alcohol sulfate, NaOH, anionic surfactant, nonionic surfactant, silicate, polymer) in a SO- Liter ploughshare mixer from the company Lödige granulated. The amounts of hard used substances and liquids as well as the order of addition in the mixer are in the table 3 specified. In the granulation batches E1 and E2 according to the invention, zeolite P or X are used; in Comparative Example V, the surfactant granules with zeolite A manufactured.

Following the granulation, the granules were in a fluidized bed apparatus The company Glatt at a supply air temperature of 60 ° C over a period of 30 minutes dries. After drying, fine particles <0.6 mm and coarse particles <1.6 mm sieved. To determine the water content of the granules, 2 g of Gra nulats heated for 10 minutes at 130 ° C on an MA 30 device from Sartorius and the drying loss determined gravimetrically.

The surfactant granules E1 and E2 or V1 were then egg with other components nem pressable premix prepared, after which the Ver. in a Korsch eccentric press pressing into tablets (diameter: 44 mm, height: 22 mm, weight: 37.5 g) was carried out. The compression pressure was set so that he two series of moldings were kept (E1, E2 and V1 or E1 ', E2' and Vl '), which differ in their hardness the. The composition of the spray-dried polymer compound is shown in Table 1 Composition of the premixes to be pressed (and thus the shaped body) shows Table 4.  

Table 1

Composition of the polymer compound [% by weight]

Table 2

Zeolite types used

Table 3

Composition of the granulation batches [g]

Table 4

Composition of the detergent tablets [% by weight]

The hardness of the tablets became after two days of storage by deforming the tablet measured to break, the force acting on the side surfaces of the tablet and the maximum force that the tablet withstood was determined.

To determine tablet disintegration, the tablet was placed in a beaker with water placed (600 ml of water, temperature 30 ° C) and the time until the tablet is completely case measured.

The experimental data are shown in Table 5:  

Table 5:

Physical data of the detergent tablets

With comparable hardness, the detergent tablets therefore disintegrate contain a surfactant-containing granulate which contains a zeolite of the P or X type ten, significantly faster than detergent tablets; where that is Zeolite A-based surfactant granules.

Claims (9)

1. Process for the production of detergent tablets by mixing a surfactant-containing granulate with finely divided preparation components and subsequent molding in a manner known per se, characterized in that the surfactant-containing granulate contains a zeolite of the P and / or X type. 2. The method according to claim 1, characterized in that the surfactant-containing granules was not produced by spray drying. 3. The method according to any one of claims 1 or 2, characterized in that the content of the surfactant-containing granules of zeolite P and / or zeolite × 20 to 80% by weight preferably 25 to 70 wt .-% and in particular 30 to 50 wt .-%, each based on the surfactant granules. 4. The method according to any one of claims 1 to 3, characterized in that the surfactant content of the surfactant-containing granules 5 to 60% by weight, preferably 10 to 50% by weight and in particular 15 to 40% by weight, based in each case on the surfactant granules. 5. The method according to any one of claims 1 to 4, characterized in that the proportion of the surfactant-containing granules on the detergent tablets 40 to 95% by weight, preferably 45 to 85% by weight and in particular 55 to 75% by weight, each Weil is based on the weight of the detergent tablets. 6. The method according to any one of claims 1 to 5, characterized in that the ver pressing premix a bulk density of at least 500 g / l, preferably min at least 600 g / l and in particular above 700 g / l. 7. The method according to any one of claims 1 to 6, characterized in that the or one of the subsequently mixed, finely divided processing components is a zeolite of the faujasite type with particle sizes below 100 microns, preferably below 10 microns  and in particular below 5 microns and at least 0.2 wt .-%, preferably at least at least 0.5% by weight and in particular more than 1% by weight of the pre-pressed material mixes. 8. The method according to any one of claims 1 to 7, characterized in that the ver pressing premix continues one or more substances from the group of bleaching activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, Dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners ler, graying inhibitors, color transfer inhibitors and corrosion inhibitors contains. 9. Use of zeolite of the P and / or X type in surfactant-containing granules which after mixing with finely divided preparation components in known per se Be pressed into detergent tablets, for stability and solubility improvement of detergent tablets.