DE19902425A1 - Compressed laundry and other detergent tablets, useful for laundry, in dishwasher, for cleaning hard surface or as bleach, water softening or stain removal tablets, are made from granulate with higher than equilibrium water content - Google Patents

Abstract

Compressed laundry and other detergent tablets contain a surfactant granulate with a water content at least 5% higher than the equilibrium water content of the same granulate. Independent claims are also included for (a) the use of surfactant granulates with a water content at least 5% higher than the equilibrium content for improving the stability and solubility of (laundry) detergent tablets made by mixing the granulate with finely-divided dressing components and pressing; (b) the production of the tablets.

Description

The present invention is in the field of compact molded articles which are washable. and have cleaning-active properties. Such detergent and cleaning agent form bodies include, for example, detergent tablets for washing textiles, Detergent tablets for automatic dishwashing or hard cleaning Surfaces, bleach tablets for use in washing machines or dishwashers, Water softening tablets or stain tablets. In particular, concerns the Erfin dung Detergent tablets that are used to wash textiles in one Household washing machine used and briefly referred to as detergent tablets.

Detergent tablets are widely described in the prior art are becoming increasingly popular with consumers because of the simple dosage. Tableted detergents and cleaning agents have a number of powdered detergents Advantages: They are easier to dose and handle and because of their compact structure Advantages in storage and transport. Even in the Patentlite As a result, laundry detergent and cleaning product tablets are comprehensively described. On Problem that always occurs when using washing and cleaning active moldings occurs again, the too slow disintegration and dissolving speed of the shaped body is below Conditions of use. Because sufficiently stable, d. H. shape and break resistant shape body can only be produced by relatively high pressure, it comes to a strong compression of the molded parts and to a consequent delayed disintegration of the shaped body in the aqueous liquor and thus to one slow release of the active substances in the washing or cleaning process. The ver  hesitated disintegration of the moldings has the disadvantage that usual Detergent tablets not over the induction chamber of household Have the washing machine rinsed in as the tablets will not wash in quickly enough Secondary particles disintegrate that are small enough to go from the induction chamber into the wash drum to be washed in. Another problem, particularly with washing and Detergent tablets occur, the friability of the tablets or their often insufficient stability against abrasion. So can be sufficiently stable, d. H. hard detergent tablets are produced, but these are often the Strain on packaging, transport and handling, d. H. Fall and rubbing stress not sufficiently grown, so that edge breakage and signs of abrasion Appearance of the molded body or even to a complete destruction lead the molded structure.

To overcome the dichotomy between hardness, i. H. Transport and handling stabilizer lity, and easy disintegration of the moldings are many solutions in the prior art has been developed. A well known from the pharmacy and in the field of Detergent tablets are an extensive approach to incorporation Certain disintegration aids that facilitate the access of water or upon entry swell from water or develop gas or disintegrate in another form. Other proposed solutions from the patent literature describe the pressing of Vor Mixing certain particle sizes, the separation of individual ingredients from be agreed other ingredients as well as the coating of individual ingredients or the entire molded body with binders.

For example, EP 687 464 (Allphamed Arzneimittel-Gesellschaft) describes effervescent tablets, be standing from at least one active ingredient or combination of active ingredients, at least a binder, possibly carriers such as flavors, colors, fragrances, soft matter chern, bleaches and effervescent additives, propylene glycol or Gly cerin, preferably in amounts of 0.004 to 2.5% by weight. Likewise Processes for producing these effervescent tablets are claimed. According to the statements this document can also be used with the teaching according to the invention  Manufacture effervescent tablet without the binders used to form a carbon dioxide would result in loss of shower additives.

European patent application EP 711 828 (Unilever) describes detergent tablets, which contain surfactant (s), builders (e) and a polymer that acts as a binding and disintegrating agent on aids works. The binders disclosed in this document are said to be at room temperature be solid and be fed to the premix to be pressed as a melt. Be preferred binders are the higher molecular weight polyethylene glycols.

The use of particles that are too little water based on their equilibrium moisture content included, is described in German patent application DE 197 09 411.2 (Henkel). This document teaches synergistic effects between polyethylene glycols and over-drying amorphous silicates.

Solutions to the problem of the friability and abrasion stability of washing and cleaning medium shaped bodies are only in the prior art in the older German Pa tent registration DE 198 41 146.4 (Henkel KGaA). The Lö disclosed herein approach consists in the incorporation of liquid, non-surfactant binders into the compressing premixes.

The present invention was based on the object of providing moldings which are characterized by short disintegration times with a given hardness and are thus also have it dispensed via the induction chamber of household washing machines. Additional Lich to these requirements, the moldings should be against increased stability Fall and rubbing loads, d. H. an improved, d. H. reduced friability possess and have a reduced abrasion behavior.

It has now been found that the water content used in the premixes upcoming surfactant granules have a decisive influence on the abrasion stability of the Has detergent tablets. The use of the surfactant granules mentioned late does not affect the breaking hardness of the detergent tablets or only to a minor extent.  

The present invention relates to detergent tablets compacted, particulate detergent and cleaning agent containing ent surfactant granules keep, whose water content is at least 5 percent higher than the water content the same surfactant granules at equilibrium moisture.

The water content of a surfactant granulate (hereinafter synonymous with the term "water value "used) in the context of the present invention denotes the weight % of water in the respective granulate, which at 200 ° C using Karl Fischer Titration (KF titration) is determined. The equilibrium moisture (also below Equilibrium moisture)) of a granulate is the water content, which is at Drying in a fluidized bed apparatus with a supply air temperature of 80 ° C and one Supply air humidity of x <0.015. To determine the equilibrium moisture content, a Granules dried under the specified conditions and samples of the granules in time interval titrated according to Karl Fischer. If by doubling the Drying time the further decrease in water value is below 2%, the same has weight moisture adjusted.

Both the water content of the equilibrium moisture and the water content of the Moist granules to be used according to the invention relate to the particular one Granules. If a surfactant granulate with equilibrium moisture content has a water content of 10% by weight, 100 grams of these granules contain 90 grams of constituents, which are not titrated as water at the KF tration at 200 ° C. A granulate whose Water value above that at equilibrium moisture, for example at 11% by weight %, is consequently contains only 89 g of components per 100 g of granules which Tration at 200 ° C should not be titrated as water. The above value of 5 Percent by which the water content of the surfactant granules must be higher according to the invention, as the water value of the same surfactant granules at the equilibrium moisture content is as to understand relative information that relates to the water value at equilibrium moisture becomes. So it is not 5 percentage points, but 5 percent relative to Water value at equilibrium moisture. In the above example (water content at equilibrium moisture content 10% by weight, based on the granules with equilibrium  moist) granules to be used according to the invention thus have water contents above 10.5% by weight, based on the wetter granules.

In preferred laundry detergent and cleaning product tablets, the water value in IH NEN surfactant granules compared to the water value of the same surfactant granules the equilibrium moisture is higher. So are detergent tablets preferred in which the surfactant granules have a water content which is at least 6 Percent, preferably by at least 7.5 percent and in particular by at least 10 Percent is higher than the water content of the same surfactant granulate in the same weight moisture.

The water content of the surfactant granules can vary depending on the composition, whereby Water values above the equilibrium moisture z. B. by increased water addition during granulation or an appropriate driving style of the drying process (Ver time, supply air temperature) can be set. Depending on the co composition (which determines the equilibrium moisture) and depending on the relative Deviation of the water value from the equilibrium moisture can according to the invention more or less "moist" granules are used. With the recipe variation of the Surfactant granules can serve as an indication that preferred washing and cleaning medium shaped bodies are characterized in that the surfactant granules have a water content at the equilibrium moisture content of 5 to 15% by weight, preferably 7.5 to 12.5% by weight % and in particular from 9 to 11% by weight, in each case based on the surfactant granules points.

The water values of the detergent tablets according to the invention actually used surfactant granules are at least 5 percent higher forth than the aforementioned water values of the surfactant granules at equilibrium wet. The numbers above are for the water values of surfactant grade to be used Accordingly, nulate with a factor <1.05, preferably <1.06, especially before multiply <1.075 and especially <1.1. Accordingly, are according to the invention Detergent tablets are preferred, which are characterized in that the surfactant granules used have a water content of 5.25 to 16.5% by weight, preferably two  se from 7.9 to 18.15% by weight and in particular from 9.45 to 12.1% by weight, in each case based on the surfactant granules.

According to the teaching of the present invention, the surfactant-free compo nenten of a detergent tablets with one over the peer weight-damp lying water value can be used. This way too Produce abrasion-resistant moldings. But it turned out that the higher what especially in the case of components such as enzymes, bleaches, bleach activators and foam inhibitors can lead to deterioration in storage stability. in the In the context of the present invention it is therefore preferred if only the surfactant or surfactants granules (e) have the increased water value.

In addition to that according to the invention in the surfactant granules via the equilibrium moisture In addition, water contained in the surfactant granules naturally contain surfactants. These can nen from the groups of anionic, nonionic, cationic or amphoteric ten side originate, of course also mixtures of the surfactant types mentioned for Can come into play. Regardless of the type of surfactant used, the tenside grades In preferred laundry detergent and cleaning product tablets, surfactant contents of 5 to 60% by weight. preferably from 10 to 50% by weight and in particular from 15 to 40% by weight, each based on the weight of the surfactant granules.

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 a terminal 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.

The alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut 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, 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 are - C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates of preferably. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from 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 _9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C _12-18 -Fatty alcohols with 1 to 4 EO, are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

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

Soaps are particularly suitable as further anionic surfactants. 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, detergent tablets are shaped preferred, in which the content of the surfactant granules of anionic surfactants 5 to 45 % By weight. preferably 10 to 40% by weight and in particular 15 to 35% by weight, in each case based on the weight of the surfactant granules.

When choosing the anionic surfactants, there is no question of freedom of formulation framework conditions in the way. However, preferred surfactant granules have one Content of soap on the 0.2 wt .-%, based on the total weight of the washing and Detergent tablets, exceeds. Anionic surfactants to be used with preference the alkylbenzenesulfonates and fatty alcohol sulfates, with preferred washing and rice Detergent tablets 2 to 20 wt .-%, preferably 2.5 to 15 wt .-% and esp special 5 to 10 wt .-% fatty alcohol sulfate (s), each based on the weight of the Detergent tablets are included.  

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 _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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 are preferably according to the in the international patent application WO-A-90/13533 become.

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Alkyl polyglycosides which 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, C 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 surfactant granules can preferably contain alkyl polyglycosides, with levels of APG over 0.2 wt .-%, based on the entire molded body, are preferred. Especially preferred detergent tablets contain APG in amounts of 0.2 to 10% by weight, preferably 0.2 to 5% by weight and in particular 0.5 to 3% by weight.

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 (I),

in the R-CO for an aliphatic acyl radical having 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 acyl rank 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)

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 is an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example, according to 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.

According to the invention, detergent tablets are preferred in which the Nonionic surfactant content of the surfactant granules 1 to 15% by weight, preferably 2.5 up to 10 wt .-% and in particular 5 to 7.5 wt .-%, each based on the weight of the Granules of surfactant.

In addition to that according to the invention in the surfactant granules via the equilibrium moisture In addition, water and surfactant (s) contained in the surfactant granules generally contain wide re ingredients of washing and cleaning agents. For storage-stable and free-flowing To obtain surfactant granules, it is preferred if in the preparation of the surfactant granules  latex carriers are added, which contain surfactant granules. Other ingredients of washing and cleaning agents, especially so-called Small components such as optical brighteners, polymers, defoamers, phosphonates, color and fragrances, can be part of the surfactant granules. These substances continue to grow described below.

The surfactant granules can vary in the laundry detergent and cleaning product tablets Amounts are used. Detergent tablets according to the invention, which the surfactant granules in amounts of 40 to 95 wt .-%, preferably from 45 to 85 % By weight and in particular from 55 to 75% by weight, in each case based on the shaped body importance, contain, are preferred.

Another object of the present invention is a method for producing Detergent tablets by mixing a granule containing surfactant lats with finely divided preparation components and subsequent shaping Ver press in a manner known per se, in which the surfactant-containing granules have a water content which is at least 5 percent higher than the water content of the same surfactant granules at the equilibrium moisture.

In the process according to the invention, too, the surfactant granules advantageously have egg NEN water content of 5.25 to 16.5 wt .-%, preferably from 7.9 to 18.15 wt .-% and in particular from 9.45 to 12.1% by weight, based in each case on the surfactant granules.

The production of surfactant-containing granules is widely described in the prior art, wherein in addition to extensive patent literature, numerous review articles and monogra phien 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. Method, in which the surfactant-containing granules by granulation, agglomeration, press agglomerates on or a combination of these methods are therefore preferred.

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. Conventional mixers and mixing granulators are also suitable for granulation. As Mixers can be both high-intensity mixers ("high-shear mixer") and nor male mixers with lower circulation speeds can be used. Suitable Wed. Shearers are, for example, Eirich® mixers of the R or RV series (trademark of Ma Schinenfabrik Gustav Eirich, Hardheim), the Schugi® Flexomix, the Fukae® FS-G mixer (Trademark of Fukae Powtech, Kogyo Co., Japan), the Lödige® FM, KM and CB Mixer (trademark of Lödige Maschinenhau 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 compacted under the influence of shear forces and homogenized and connected discharged form-giving from the apparatus. The most technically significant press day Glomeration processes are extrusion, roller compaction, pelleting and tableting. In the context of the present invention preferably for the production of  Press agglomerating processes containing surfactant-containing granules are extrusion Roll compacting and pelleting.

In a preferred embodiment of the invention, the surfactant-containing granule lat preferably continuously a planetary roller extruder or a 2-shaft Extruder or twin-screw extruder with co-rotating or counter-rotating screws guide fed, its housing and its extruder pelletizing head on the vorbe correct extrusion temperature can be heated. Under the shear of the Ex The pre-mix is screwed under pressure, preferably at least 25 bar at extremely high throughputs depending on the apparatus used can also lie below, compressed, plasticized, in the form of fine strands through the hole extruded nozzle plate in the extruder head and finally rotate the extrudate using a the knives preferably to approximately spherical to cylindrical granules scaled down. 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 succeeds essentially uniformly tunable particle size, the absolute particle sizes in particular intended use can be adapted. Important embodiments can be seen here the production of uniform granules in the millimeter range, for example in the Be range from 0.8 to 5 mm and in particular in the range from about 1.0 to 3 mm. The country ge / diameter ratio of the chipped primary granules is one important embodiment in the range of about 1: 1 to about 3: 1. Furthermore, it is before moves, the still plastic primary granules for further shaping processing feed step; edges present on the crude extrudate are rounded off so that ultimately spherical to approximately spherical extrudate grains can be obtained. Alternatively, extrusions / pressings can also be carried out in low-pressure extruders, in the Press or in the extruder.

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 Schülpenband is subsequently by an Ab Whipping and crushing process broken into smaller pieces and can in this way se to be processed into granules, which 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 carried out by 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 pellet 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 into granules with a chopping 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 roller (s) can run in the same direction or have opposite sense of rotation. A to carry out the inventive method A suitable apparatus is described, for example, in German published application DE 38 16 842 (Schlüter GmbH). The ring die press disclosed in this document consists of a rotating, through which press channels penetrated and at least a press roller, which is in operative connection with the inner surface of the die material fed through the press channels into a material discharge. Here are Ring die and press roller can be driven in the same direction, resulting in a reduced shear load stung and thus lower temperature increase of the premix can be realized. Yourself  understandable can also be used for pelleting with heatable or coolable rollers tet to set a desired temperature of the premix.

The surfactant granules are then combined with other processing components The premix is mixed, which is then pressed into detergent tablets can be. The premix to be pressed can be used as processing components in addition to the ingredients already mentioned, other übli in detergents and cleaning agents che ingredients, especially from the group of builders, disintegration aids, Bleaching agents, bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluo Resence agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, opti brighteners, graying inhibitors, color transfer inhibitors and corrosion hibitors included. However, all or part of the substances mentioned can already exist Be part of the surfactant granules.

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 Shaped bodies can all usually 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.

It has been shown that the effect of improving wear resistance is stronger if the surfactant granules only contain small amounts of carbonates. Preferred washing and Detergent tablets therefore contain surfactant granules that contain a sodium or Potassium carbonate content of less than 15% by weight, preferably less than 10 % By weight and in particular less than 5% by weight, in each case based on the surfactant gray nulate.

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 are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates 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 the international patent application WO-A-91/08171 .

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 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 deliver 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 delay in dissolution compared to the conventional water 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 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 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.

As organic cobuilders in the washing and cleaning agents according to the invention Telformkörper in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxy latex, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used. These classes of substances are described below ben.

Usable organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, with such carboxylic acids under polycarboxylic acids can be understood that carry more than one acid function. For example, these are Citro Nenoic acid, adipic acid. Succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, Fumaric acid. Sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if one such use is not objectionable for ecological reasons, as well as mixtures from these. Preferred salts are the salts of polycarboxylic acids such as citric acid, Adi Pinic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of the sen.

The acids themselves can also be used. The acids have besides their buil the effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or Detergents. In particular, citric acid, succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.  

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

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

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2000 to 20,000 g / mol. Because of their superior solubility, the This group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, preferably his.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As a special copolymers of acrylic acid with maleic acid, 50 to Contain 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative mole Cooling mass, based on free acids, is generally from 2000 to 70,000 g / mol preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

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

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

Biodegradable polymers of more than two ver. Are also particularly preferred different monomer units, for example those that act as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives contain.

Further preferred copolymers are those which are described in German patent applications DE- A-43 03 320 and DE-A-44 17 734 are described and preferably as monomers Have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Likewise, further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors. Polyas are particularly preferred paraginic acids or their salts and derivatives, of which in the German patent application dung DE-A-195 40 086 discloses that, in addition to cobuilder properties, it also has a have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which are produced by the implementation of Dial dehyden with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl have groups that can be obtained. Preferred polyacetals are from Dialde hyden such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from Obtained polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be. The hydrolysis can be carried out according to conventional methods, for example acid or enzyme lysed procedures are carried out. It is preferably hydrolysis pro Products with average molecular weights in the range of 400 to 500,000 g / mol. There is a poly saccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30 preferred, DE being a common measure of the reducing effect  of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and dry glu can be used cosesirupe with a DE between 20 and 37 as well as so-called yellow dextrins and White dextrins with higher molar masses in the range from 2000 to 30000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are able to oxidize at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 and international patent applications WO 92/18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608 are known. An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Also oxydisuccinates and other derivatives of disuccinates, preferably ethylenedia mindisuccinate are other suitable cobuilders. Here, ethylenediamine-N, N'- disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and Gly are also preferred in this context cerintrisuccinate. Suitable amounts are in zeolite and / or silicate salts gene formulations at 3 to 15 wt .-%.

Other useful organic cobuilders are, for example, acetylated hydroxycarbon acids or their salts, which may optionally also be in lactone form, and which have at least 4 carbon atoms and at least one hydroxyl group and maxi contain two acid groups. Such cobuilders are used, for example, in the inter national patent application WO 95/20029.

Another class of substances with cobuilder properties are the phosphonates it is in particular hydroxyalkane or aminoalkanephosphonates. Under the hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) from of particular importance as a cobuilder. It is preferably used as the sodium salt  the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). As Aminoalkane phosphonates preferably come from ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher Ho mologist in question. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP, used. HEDP is preferred as a builder from the phosphonate class turns. The aminoalkanephosphonates also have a pronounced heavy metal bin de assets. Accordingly, it can, especially if the agent also ent bleach hold, be preferred to use aminoalkane phosphonates, in particular DTPMP, or To use mixtures of the phosphonates mentioned.

In addition, all compounds that are capable of complexing with alkaline earth train ions as cobuilders.

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 7% by weight and in particular 4 to 6% by weight of one or more disinfectants Gration aids, 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 laundry detergents and cleaning agents form such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% 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, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably used not only as cellulose-based disintegrants, but rather in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free from cellulose derivatives is particularly preferably used as a cellulose-based disintegrant.

The cellulose used as disintegration aid is preferably not finely divided form, but before mixing into the premixes to be pressed converted into a coarser form, for example granulated or compacted. Washing and Detergent tablets, the disintegrant in granular or optionally cogranu  Contained form, are in the German patent applications DE 197 09 991 (Ste fan Herzog) and DE 197 10 254 (Henkel) and the international patent application WO98 / 40463 (Henkel). These writings are also more detailed information on the Her position of granulated, compacted or cogranulated cellulose disintegrants men. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 µm and in particular to at least 90% by weight between 400 and 1200 µm. The above and in the writings cited described coarser disintegration aids on cellulose In the context of the present invention, bases are preferred as disintegration aids used and commercially, for example under the name Arbocel® TF-30-HG by available from Rettenmaier.

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.

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 washing textiles, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, regardless of what 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 bleaches are the diacyl peroxides, such as. B. dibenzoyl peroxide. Other typical organic bleaching agents are the peroxy acids, examples of which include the alkyl peroxy acids and the aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, per oxystearic acid, ε-phthalimidanoic 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, diperocysebacyldiperoxyacidoxydiperoxyacid, diperoxyacyldiperoxyacid, diperoxyacid, diperoxyacetic acid, -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. 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. Brighteners of the substituted diphenylstyryl type may also 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 to the body to improve the aesthetic impression of the products and the In addition to the softness performance, consumers are visually and sensory "typical and un confusable "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. The ethers 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, ∝-isomethyl ionone and methyl cedryl ketone, too 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 mixtures as they are accessible 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 content of the detergent and cleaning agent form according to the invention is usually Bodies of dyes below 0.01% by weight. while fragrances up to 2 wt .-% of the ge can make up the entire wording.

The fragrances can be incorporated directly into the agents according to the invention but can also be advantageous to apply the fragrances to the carrier, which increase the liability of the perfume on the laundry and by a slower fragrance release for long-lasting fragrance of the textiles. As such carrier materials have been found for example, cyclodextrins have proven themselves, with the cyclodextrin-perfume complexes additionally can be coated with other auxiliaries.

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 rice shaped detergent be advantageous. Fine powdering agents are in the stand well-known in the art, mostly zeolites, silicates or other inorganic salts be used. However, the premix is preferred with finely divided zeolite "powdered", with zeolites of the faujasite type being preferred. As part of the present Invention, the term "faujasite-type zeolite" denotes all three zeolites, which 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 mm 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.

In preferred methods according to the invention, the premix to be pressed has Bulk density of at least 500 g / l, preferably at least 600 g / l and in particular especially above 700 g / l, and still contains one or more substances from the Group of bleaching agents, bleach activators, disintegration aids, enzymes, pH Adjusting agents, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, Silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, Color transfer inhibitors and corrosion inhibitors.

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, compacting, ejecting), these cam tracks are replaced by additional che low-pressure pieces, pull-down rails and lifting tracks supported. The filling 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 press pressure on the premix is individual via the press paths for upper and lower punches adjustable, the pressure build-up by rolling the stamp shaft heads past ver adjustable 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- and multi-layer moldings shoes arranged one behind the other without the slightly pressed first layer in front of the further filling is emitted: Through appropriate process control, this way se also coated and dot tablets can be produced, which have an onion-shell-like structure have, whereby in the case of the point tablets the top of the core or the core layers is not covered and therefore remains visible. Rotary tablet presses 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 simultaneously used for pressing the. The throughputs of modern rotary tablet presses are over a million forms body per hour.

Tableting machines suitable for the purposes of the present invention are, for example available from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH 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 detergent can also in other geometri forms, for example vertical triangles that only on one of their Sides are connected alongside one another, 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 via a metering device which is added to the wash liquor can be; rather, it is also possible in such cases to direct the molded body into the machine without causing stains 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 with, 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 Tensidgra nulates whose water content is at least 5 percent higher than the water content the same surfactant granulate at the equilibrium moisture content and after mixing with finely divided preparation components in a manner known per se for washing and cleaning molded agent bodies are pressed, to improve stability and solubility of detergent tablets. By using the opposite of theirs Equilibrium moisture humid surfactant granules, which after mixing with other Components can be pressed into detergent tablets, the physical properties of the moldings can be improved, such as the following Examples show:

Examples

A tower powder containing surfactants was produced by spray drying and used as the basis for granules containing surfactants were used. The tower powder was mixed with other com components (zeolite, FAS granulate, nonionic surfactant, polymer) in a 130 liter Ploughshare mixer granulated by Lödige. The amounts of solids used and liquids and the order of addition to the mixer are shown in Table 2 given.

Following the granulation, the granules were placed in an Aeromatic Fluidized bed apparatus at a supply air temperature of 80 ° C with a supply air humidity of x = 0.008 dried. For the three drying times of 10, 20 and 40 minutes, a 30 kg granulation batch divided into 10 kg drying batches in order to avoid falsification to obtain the results from different wet granules. After drying the granules were removed with a drying time of 10 minutes (E) or 20 minutes (V) Fine particles <0.6 mm and coarse particles <1.6 mm sieved. The Wasserge hold of the granules depending on the drying time was determined by Karl Fischer Titration determined at 200 ° C and is given in Table 3.

The surfactant granules E and V were then pressed together with other components prepared premix, after which the pressing in a Korsch eccentric press Tablets (diameter: 44 mm, height: 22 mm, weight: 37.5 g) took place. It was the pressure was adjusted so that two series of molded articles were obtained (E1, E2 or V 1 and V2), which differ in their hardness. The measured values of the tablet The hardness and decay times are the mean values of a double determination, whereby the individual values for each molded body type varied by a maximum of 2 N or 2 s. The assembly The spray-dried tower powder shows Table 1 the composition of the Compressing premixes (and thus the shaped body) are shown in Table 4.  

Table 1

Composition of the spray-dried tower powder [% by weight]

Table 2

Granulation approach

Table 3

Water content of the surfactant granules after drying

The water value of the granulate E according to the invention was thus 11% above the equilibrium weight moisture.

Table 4

Composition of the premixes [% 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 abrasion stability was determined by placing a tablet on a sieve with the Mesh width 1.6 mm was placed. This sieve was then Test sieve machine used and with an amplitude of 2 mm over 120 seconds claimed. By weighing the tablet on the sieve before and after the bean wear can be calculated in%. The experimental data are shown in Table 5:

Table 5

Detergent tablets [physical data]

While the tablet hardness and disintegration times of the shaped bodies E and V are the same Range, the shaped bodies E according to the invention show a significantly better stability act against the frictional load caused by the vibrating screen. The application technology proprietary are made by using the wetter surfactant granules according to the invention consequently further improved.

Claims (15)

1. Detergent tablets made of compressed, particulate detergents and cleaning agents, characterized in that they contain a surfactant granulate, the water content of which is at least 5 percent higher than the water content of the same surfactant granules at the equilibrium moisture content. 2. Detergent tablets according to claim 1, characterized in that the surfactant granules have a water content that is at least 6 percent, preferably by at least 7.5 percent and in particular by at least 10 percent is higher than the water content of the same surfactant granules at equilibrium wet. 3. Detergent tablets according to one of claims 1 or 2, characterized characterized in that the surfactant granules have a water content at equilibrium moisture from 5 to 15% by weight, preferably from 7.5 to 12.5% by weight and in particular from 9 to 11% by weight, based in each case on the surfactant granules. 4. Detergent tablets according to one of claims 1 to 3, characterized characterized in that the surfactant granules used have a water content of 5.25 to 16.5% by weight, preferably from 7.9 to 18.15% by weight and in particular from 9.45 to 12.1% by weight, based in each case on the surfactant granules. 5. Detergent tablets according to one of claims 1 to 4, characterized characterized in that the surfactant granules preferably from 5 to 60 wt .-% surfactant as from 10 to 50 wt .-% and in particular from 15 to 40 wt .-%, each based on the weight of the surfactant granules. 6. Detergent tablets according to one of claims 1 to 5, characterized characterized in that the content of the surfactant granules of anionic surfactants 5 to 45 % By weight, preferably 10 to 40% by weight and in particular 15 to 35% by weight, in each case based on the weight of the surfactant granules.   7. Detergent tablets according to one of claims 1 to 6, characterized characterized in that the content of the surfactant granules of nonionic surfactants 1 to 15% by weight, preferably 2.5 to 10% by weight and in particular 5 to 7.5% by weight, each Weil based on the weight of the surfactant granules. 8. Detergent tablets according to one of claims 1 to 7, characterized characterized in that the content of the surfactant granules of sodium and / or potassium car bonat below 15 wt .-%, preferably below 10 wt .-% and in particular below 5 % By weight, based in each case on the weight of the surfactant granules. 9. Detergent tablets according to one of claims 1 to 8, characterized characterized in that the surfactant granules in amounts of 40 to 95 wt .-%, before preferably from 45 to 85 wt .-% and in particular from 55 to 75 wt .-%, each be pulled on the molded body weight, included. 10. Process for the production of detergent tablets by Ab Mixing granules containing surfactants with finely divided processing components and subsequent shaping pressing in a manner known per se, thereby ge indicates that the surfactant-containing granules have a water content around is at least 5 percent higher than the water content of the same surfactant granules the equilibrium moisture. 11. The method according to claim 10, characterized in that the surfactant granules Water content from 5.25 to 16.5% by weight, preferably from 7.9 to 18.15% by weight and in particular from 9.45 to 12.1% by weight, based in each case on the surfactant granules points. 12. The method according to any one of claims 10 or 11, characterized in that the Granules containing surfactants by granulation, agglomeration, press agglomeration or a Combination of these processes is made.   13. The method according to any one of claims 10 to 12, characterized in that that too compressing premix a bulk density of at least 500 g / l, preferably of has at least 600 g / l and in particular above 700 g / l. 14. The method according to any one of claims 10 to 13, characterized in that the compressing premix further one or more substances from the group of Bleaching agents, bleach activators, disintegration aids, enzymes, pH adjusting agents, Fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color over contains wear inhibitors and corrosion inhibitors. 15. Use of surfactant granules, the water content of which is at least 5 percent higher is the water content of the same surfactant granules at equilibrium moisture and that after mixing with finely divided processing components in itself are known to be pressed into detergent tablets, to Sta Improvement in the balance and solubility of detergent tablets.