WO2000027959A1 - Cleaning agent and detergent shaped bodies with granulates with anti-foaming agents - Google Patents

Abstract

Cleaning agent and detergent shaped bodies, characterized by a high degree of hardness and a short decomposition time with good anti-foaming characteristics. The inventive shaped bodies contain foam inhibiting granulates that are obtained by means of wet granulation. A foam inhibiting granulate is produced by means of wet granulation, mixed with other constituents and pressed to form cleaning agent and detergent shaped bodies.

Description

'Detergent tablets with defoamer granules' ¹

The present invention is in the field of compact moldings which have washing and cleaning properties. Such detergent tablets comprise, for example, detergent tablets for washing textiles, detergent tablets for machine dishwashing or hard surface cleaning, bleach tablets for use in washing machines or dishwashers, water softening tablets or stain remover tablets. In particular, the invention relates to detergent tablets which are used for washing textiles in a household washing machine and are briefly referred to as detergent tablets.

Detergent tablets are widely described in the prior art and are becoming increasingly popular with consumers because of the ease of dosing and handling, so that this type of product is becoming increasingly established in the market for detergents and cleaning agents in addition to the conventional powder products. A fundamental problem in the form of high-density molded articles is their reduced disintegration time, which is accompanied by increasing hardness, and thus deteriorated solubility. With the majority of the commercial products and also in the majority of the descriptions in the prior art, the disintegration times of the detergent tablets are so high that the tablets cannot be washed in via the induction chests of household washing machines because they do not pass into secondary particles sufficiently quickly that are small enough to be washed in. Such moldings must either be put directly into the laundry, with or without a metering aid (for example a sachet), where the contact between the laundry and the slowly dissolving molding can lead to textile damage due to high local concentrations of bleaching agent and enzymes. To provide moldings which, with a given hardness, are characterized by short disintegration Marking times and thus can also be dosed via the induction chamber of household washing machines was an object of the present invention.

There is a wide range of prior art for detergent tablets, in which a wide variety of solutions are proposed to overcome the dichotomy between hardness and disintegration time. One approach to this lies in the particle size of the premixes to be pressed.

For example, EP-A-0 466 484 (Unilever) discloses detergent tablets in which the premix to be compressed has particle sizes between 200 and 1200 μm, the upper and lower limits of the particle sizes not differing by more than 700 μm. Nothing is said in this document about the surface treatment of individual ingredients.

EP-A-0 522 766 (Unilever) also relates to moldings made from a compacted, particulate detergent composition containing surfactants, builders and disintegration aids, at least some of the particles being coated with the disintegration agent which has both binder and disintegration activity Dissolving the molded body in water shows. This document also indicates the general difficulty of producing moldings with adequate stability and good solubility at the same time. The particle size in the mixture to be pressed should be above 200 μm, the upper and lower limits of the individual particle sizes should not differ from one another by more than 700 μm.

The abovementioned documents show that a premix to be compressed should have a relatively homogeneous particle size distribution on the one hand and should be relatively coarse-grained on the other. With a large number of raw materials, however, the large-scale use in tableting premixes is not possible without problems, since the performance of the ingredients is reduced as a result. For example, foam inhibitors are added to the detergents and cleaning agents in finely divided form in order to control the foam formation even at low washing temperatures and thus prevent the washing liquor from overflowing. The use of coarser foam inhibitor compounds therefore leads especially at the washing temperatures of 30 and 40 ° C to undesirably high foaming.

A further object of the present invention was therefore to find an incorporation form for foam inhibitors in detergent tablets, in which on the one hand the above-mentioned requirements for the molded article are met, but on the other hand the defoamer performance is not impaired.

The above-mentioned tasks can be solved if wet-granulated foam inhibitor granules are incorporated into the detergent tablets.

The invention relates to detergent tablets made of compressed particulate detergents and cleaning agents which contain a wet-granulated foam inhibitor granulate.

In the context of the present invention, foam inhibitors (anti-foaming agents, anti-foaming agents, foam dampers, foam brakes) are understood to be substances which are added to foaming liquids in order to reduce or prevent their foaming. The foam inhibitors are either surface-active substances that displace the foaming agents from the interface without generating foam themselves (e.g. soaps), or products that increase the surface tension of the water, e.g. natural fats and oils or fatty alcohols. The use of foam inhibitors is indispensable both in the household (machine dishwashing detergent, detergent) and in industry (manufacture of paper, sugar, etc.). In low-foaming detergents and cleaning agents, the high foaming power of the anionic surfactants contained therein is generally achieved by using long-chain soaps, e.g. Sodium behenate reduced; In the meantime, defoamers based on paraffin or silicone have become more important because the defoaming performance of the soaps is heavily dependent on the water hardness.

The term “foam inhibitor active substance” characterizes the substance or the compound which the desired foam-reducing or -controlling properties Has shafts, for example the paraffin or silicone oil. The foam inhibitors are usually not added to the washing and cleaning agents as a pure active substance, but in the form of compounds in which the foam inhibitor active substance is present together with other substances. In the case of liquid foam inhibitor active substances in particular, such "foam inhibitor compounds" of active substance and carrier material are present.

In the context of the present invention, foam inhibitor active substances or foam inhibitor compounds are converted by wet granulation into a "foam inhibitor granulate" which, according to the invention, is contained in the detergent tablets. The term "granulate" always denotes a product in connection with foam inhibitors wet granulation, ie a compression process using a liquid granulation aid. Foam inhibitors or foam inhibitor compounds compacted on dry paths, for example by roller compaction or pelletizing, are not referred to in the context of the present application as “granules” but rather as “agglomerates” or “compactates”.

Paraffins and silicones are preferably used as foam inhibitor active substances in the context of the present invention, which can be present in a known manner in a mixture with finely divided bisfatty acid amides and / or silicas, paraffins and silicones largely liquid at room temperature being preferred. In preferred foam inhibitor granules, the content of foam inhibitor active substance is 1 to 30% by weight, based on the granulate, so that detergent tablets are preferred in which the foam inhibitor granules are 1 to 30% by weight based on the weight of the granules .-%, preferably 2 to 25 wt .-% and in particular 3 to 20 wt .-% foam inhibitors from the group of paraffins and / or silicones.

As described above, the foam inhibitor granules can be obtained by wet granulation of pure foam inhibitor active substances or from foam inhibitor compounds. Usually foam inhibitor compounds are used, which are granulated. In addition to the foam inhibitor active substances, the foam inhibitor granules used according to the invention preferably contain further substances, in particular carriers. germ materials. Detergent tablets in which the foam inhibitor granules as carrier material for the paraffin (s) and / or silicone (s) contain one or more substances from the group of sulfates, carbonates, bicarbonates, silicates and citrates, the Alkali metal salts are preferred and the sodium salts are particularly preferred are preferred in the context of the present invention.

Corresponding foam inhibitor granules or processes for their preparation are described, for example, in patent applications DE 196 20 249, WO97 / 34983 and WO98 / 09701 (all Henkel). Reference is expressly made to these documents here with regard to further process parameters, ingredients and amounts.

When the foam inhibitor granules are produced by wet granulation, further ingredients of detergents and cleaning agents can be incorporated into the foam inhibitor granules via the granulation aid (“granulating liquid”) or via additives. For example, it is possible to add further so-called small components via the foam inhibitor granules in It is preferred if the foam inhibitor granules contain substances from the group of polymers as further ingredients of detergents and cleaning agents, These polymers can contribute to improving the primary washability by inhibiting the color transfer or by repositioning the dirt prevent the liquor from spilling onto the textile, but polymers with cobuilder properties can also improve the secondary washability, disilicate, carboxymethyl cellulose (CMC) and polycarboxylates are considered as preferred polymers Examples are homo- and copolymers of acrylic acid. Polyacrylates, acrylic acid / maleic acid copolymers and acrylic phosphinates are particularly preferred. Polyacrylates are, for example, under the names Versicol ^® E5, Versicol ^® E7 and Versicol ^® E9 (trademark of the Allied Colloids), Narlex ^® LD 30 and Narlex ^® LD 34 (trademark of the national adhesives), Acrysol ^® LMW-10, Acrysol ^® LMW-20, Acrysol LMW-45 ^® and Acrysol ^® Al-N (trademark of Rohm & Haas), and Sokalan ^® PA-20, PA-40 Sokalan ^®, Sokalan ^® PA 70 and Sokalan ^® PA-110 (trademark of BASF) commercially available. Ethylene / maleic acid copolymers are sold under the name EMA ^® (trademark of Monsanto), methyl vinyl ether / maleic acid copolymers under the name Gantrez ^® AN 119 (trademark of GAF Corp.) and acrylic acid / maleic acid copolymers under the names Sokalan ^® CP5 and Sokalan ^® CP7 (trademark of BASF). Acrylic phosphates are available as DKW ^® (trademark of National Adhesives) and Belperse ^® types (trademark of Ciba-Geigy). In combination with the polymers mentioned or as the sole polymer, it is also possible to use graft copolymers which are obtained by grafting polyalkylene oxides with molecular weights between 2000 and 100000 with vinyl acetate. The acetate groups can optionally be saponified up to 15%. Polymers of this type, as EP-A-0219048 (BASF) are described in European patent application, under the name Sokalan ^® HP22 (trademark of BASF). In the case of wet granulation for the production of the foam inhibitor granules, silicate solutions (so-called water glasses), polycarboxylate solutions, mixtures of CMC / water and water are particularly suitable as granulating liquids, the first-mentioned granulating liquids being preferred over the latter two.

Preferred detergent tablets in the context of the present invention are characterized in that the foam inhibitor granules contain further ingredients of detergents and cleaning agents, in particular polymers, in amounts of 0.5 to 20% by weight, preferably of 1 to 10 Wt .-% and in particular from 2.5 to 7.5 wt .-%, each based on the foam inhibitor granules.

According to the invention, the detergent tablets contain a wet-granulated foam inhibitor granulate. Although it is possible to introduce the foam inhibitor active substance (s) only partially via the granules used according to the invention and to a further extent in the conventional way, it is preferred according to the invention if the detergent tablets are at least 80% by weight, preferably at least 90 % By weight and particularly preferably the total amount of the defoamer contained in the shaped body in the form of wet-granulated foam inhibitor granules.

Depending on the amount of surfactant contained in the moldings, the desired defoamer performance and the content of the foam inhibitor granules Foam inhibitor active substance can contain the wet-granulated foam inhibitor granules in the detergent tablets according to the invention in varying amounts, the person skilled in the art having no limits with regard to his freedom from formulations. Preferred detergent tablets contain 1 to 15% by weight, preferably 2 to 10% by weight and in particular 2.5 to 7.5% by weight, of the wet-granulated foam inhibitor granules as a general formulation. In this case, detergent tablets are preferred which, based on the weight of the body, comprise 0.01 to 5% by weight, preferably 0.1 to 2.5% by weight and in particular 0.5 to 1% by weight of foam inhibitor - Contain active substance.

In order to facilitate the disintegration of highly compressed moldings, disintegration aids, so-called tablet disintegrants, can be incorporated into them in order to shorten the disintegration times. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, p. 182-184), tablet disintegrants or accelerators of decay are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in absorbable form.

These substances, which are also referred to as "explosives" due to their effectiveness, increase their volume when water enters, whereby on the one hand the intrinsic volume increases (swelling), and on the other hand a pressure can be generated by the release of gases, which breaks the tablet into smaller particles disintegrates. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives.

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

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

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

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

It is also technically possible to coat the molded body with a coating that covers the entire molded body. Such coated detergent tablets can be produced by spraying a melt or solution of the coating material onto the molded article or immersing the molded article in the melt or solution. In preferred embodiments of the present invention, however, the detergent tablets are not coated with a coating which covers the entire tablet. By using the wet granulated foam inhibitor granulate according to the invention and optionally supported by the use of disintegration aids, detergent tablets can be produced according to the invention which disintegrate into their constituents extremely quickly in water at high hardness. In the context of the present invention, particular preference is given to detergent tablets which disintegrate completely in water at 30 ° C. in less than 60 seconds into their secondary particles, which are so small that they can be washed in via the washing-in chamber of a household washing machine.

Another object of the present invention is a method for producing detergent tablets, characterized by the steps

a) production of a foam inhibitor granulate by wet granulation, b) mixing of the granulate produced in step a) with further ingredients of detergents and cleaning agents to form a premix to be pressed, c) pressing into shaped bodies.

In the first step of the process, a foam inhibitor granulate is produced by wet granulation. When selecting the machines and process parameters suitable for this process step, the person skilled in the art can fall back on machines and apparatuses known from the literature as well as process engineering operations, as described, for example, in W. Pietsch, "Size Enlargement by Agglomeration", Verlag Wiley, 1991, and the literature cited therein are.

In preferred processes, process step a) is carried out in the following substeps:

al) adsorbing foam inhibitor active substance onto carrier material, a2) optionally mixing the foam inhibitor compound formed in step a1) with further ingredients of washing and cleaning agents, a3) Granulation with the addition of a granulating liquid.

Process step a1) corresponds to the above-described production of foam inhibitor compounds from foam inhibitor active substance (s). In preferred processes, process step a1) is carried out as spraying or spraying on a melt, an emulsion or a solution of solid foam inhibitor active substance or as spraying or spraying liquid foam inhibitor active substance onto moving carrier material particles or as spray drying of a carrier material foam inhibitor slurry.

As already mentioned in the description of the detergent tablets according to the invention, preferred foam inhibitor active substances are those from the group of paraffins and / or silicones. Processes according to the invention, in which, in process step a1), foam inhibitors from the group of paraffins and / or silicones, preferably paraffins and / or silicones which are liquid at room temperature, in amounts of 1 to 30% by weight, preferably 5, as the foam inhibitor active substance up to 25% by weight and in particular from 10 to 20% by weight, based in each case on the weight of the compound, are preferred. In such processes, one or more substances from the group of the sulfates, carbonates, bicarbonates, silicates and citrates are preferably used as the carrier material for the foam inhibitor active substance, the alkali metal salts being preferred and the sodium salts being particularly preferred.

In process step a2), the foam inhibitor compound is optionally mixed with further ingredients of detergents and cleaning agents. Substances from the group of builders, cobuilders and polymers are preferably used here in amounts of 5 to 40% by weight, preferably 10 to 35% by weight and in particular 15 to 30% by weight, in each case based on the mixture of Foam inhibitor compound and other ingredients used. These builders, cobuilders and polymers are described below.

In the last process step of the production of the foam inhibitor granules, the solid mixture is granulated with the addition of a granulating liquid. The person skilled in the art can use all liquids known to him as granulation aids, with both for example, nonionic surfactants, polyethylene glycols or other liquids can be used. In particularly preferred processes, water or an aqueous solution of one or more ingredients of detergents and cleaning agents in a weight ratio of granulating liquid to solid amount of 1: 100 to 2: 1, preferably 1:50 to 1: 1 and in particular 1:20, is used as the granulating liquid up to 1: 2.

The process for producing the detergent tablets comprises mixing the foam inhibitor granules with further components to form a premix, which is pressed in the last process step. In preferred processes, the foam inhibitor granulate produced in step a) makes up 1 to 15% by weight, preferably 2 to 10% by weight and in particular 2.5 to 7.5% by weight of the premix to be pressed.

In preferred process variants, the foam inhibitor granulate produced in step a) is combined in step b) with at least one surfactant-containing granulate to form a premix to be pressed with a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g / 1 . In the context of the present invention include preferred method, therefore, the compression of a teilchenfb ^'RMI gen premixture of at least one foam inhibitor granules, at least one surfactant-sidhaltigen granules and at least one blended powder component. The granules containing surfactant can be produced by conventional industrial granulation processes such as compacting, extrusion, mixer granulation, pelletization or fluidized bed granulation.

In preferred process variants, the surfactant-containing granulate satisfies certain particle size criteria. Methods according to the invention are preferred in which the surfactant-containing granules have particle sizes between 100 and 2000 μm, preferably between 200 and 1800 μm, particularly preferably between 400 and 1600 μm and in particular between 600 and 1400 μm. In addition to the active substances (anionic and / or nonionic and / or cationic and / or amphoteric surfactants), the surfactant granules preferably also contain carriers which particularly preferably come from the group of builders. Particularly advantageous processes are characterized in that the surfactant-containing granules contain anionic and / or nonionic surfactants and builders and have total surfactant contents of at least 10% by weight, preferably at least 20% by weight and in particular at least 25% by weight.

These surface-active substances come from the group of anionic, nonionic, zwitterionic or cationic surfactants, anionic surfactants being clearly preferred for economic reasons and because of their range of services.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Suitable surfactants of the sulfonate type are preferably C _9-13 - alkyl benzene sulfonates, Olefϊnsulfonate, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from _2- Cι ι ₈ -Monoolefmen with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates, which are for example obtained from _2- Cι ι ₈ alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid. As alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid semiesters of the -C ₈ -C fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the CIO-C o-oxo alcohols and those Half-secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The Cι -C ₆ alkyl sulfates and C ₁₂ - Cis alkyl sulfates and Cι ₄ -Cι ₅ alkyl sulfates are preferred for washing technology reasons. In addition, 2,3-alkyl sulfates, which are produced for example according to US -Patentschriften 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C ethoxylated with 1 to 6 mol of ethylene oxide. ₂₁ alcohols, such as 2 -methyl-branched C ₉ π alcohols with an average of 3.5 moles of ethylene oxide (EO) or C ₁₂ i ₈ 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- ι ₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof. Soaps are particularly suitable as further anionic surfactants. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.

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

In the context of the present invention, surfactant granules are preferred as process end products of intermediate step a), which each contain 5 to 50% by weight, preferably 7.5 to 40% by weight and in particular 10 to 20% by weight of anionic surfactant (s) based on the granules.

When choosing the anionic surfactants that are used in the end products of the process in intermediate step a), there are no general conditions to be observed that prevent freedom of formulation. Preferred surfactant granules, however, have a soap content which exceeds 0.2% by weight, based on the total weight of the detergent tablets produced in step d). The preferred anionic surfactants are the alkylbenzenesulfonates and fatty alcohol sulfates, preferred detergent tablets 2 to 20% by weight, 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 an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical has a methyl or linear branching in the 2-position may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm or tallow fat, are or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol is preferred. The preferred ethoxylated alcohols include, for example, C _2-1 alcohols with 3 EO or 4 EO, C _9- alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12- 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of _2- Cι ι ₄ alcohol containing 3 EO and Cι _2-18 - 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 of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). 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, C atoms and G is Is a symbol which stands for a glycosine 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, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used. The end products of the process of intermediate step a) can preferably contain alkyl polyglycosides, with APG contents of more than 0.2% by weight, based on the total molded body, being preferred. Particularly 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.

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

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

Rl

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

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

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

R ^! -OR ^2nd

R-CO-N- [Z] (III) in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, with C _-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, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Irrespective of whether anionic or nonionic surfactants or mixtures from these classes of surfactants and, if appropriate, amphoteric or cationic surfactants are used in the surfactant granules, processes according to the invention are preferred in which the surfactant content of the surfactant-containing granules produced in step a) is 5 to 60% by weight. %, preferably 10 to 50% by weight and in particular 15 to 40% by weight, in each case based on the surfactant granules.

The surfactant granules can be used in the detergent tablets in varying amounts. Processes according to the invention in which the proportion of the surfactant-containing granules in the detergent tablets is 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. and detergent tablets are preferred.

In addition to the wash-active substances, builders are the most important ingredients in detergents and cleaning agents. In the surfactant granules, but also as part of the Premix or as a component in the foam inhibitor granules used according to the invention can contain all builders normally used in detergents and cleaning agents, in particular thus zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - the phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{x +} ι Η O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na Si ₂ O ₅ ^' yH 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 modulus Na O: SiO from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are delayed in dissolution, can also be used and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water have serge glasses are described for example in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

If desired, in addition to the amount of zeolite of the P and / or X type introduced by the surfactant granules, further zeolite can be incorporated into the premix by adding zeolite as a treatment component. The finely crystalline, synthetic and bound water-containing zeolite used is preferably a type A, P, X or Y zeolite. However, zeolite X and mixtures of A, X and / or P are also suitable. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It is of course also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.

Usable organic builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

The detergent tablets according to the invention can also contain, as additional cobuilders and graying inhibitors, 0.5 to 5% by weight, preferably 1 to 3% by weight, of a polycarboxylate polymer which contains (meth) acrylate and / or maleate Contains units. These anionic polymers can be used in their acid form or in the partially or completely neutralized salt form. Preferred polymers are homo- and copolymers of acrylic acid. Polyacrylates are particularly preferred here, Acrylic acid / maleic acid copolymers and acrylic phosphinates. Polyacrylates are, for example, under the names Versicol ^® E5, Versicol ^® E7 and Versicol ^® E9 (trademark of Allied Colloids), Narlex ^® LD 30 and Narlex ^® LD 34 (trademark of national adhesives), Acrysol ^® LMW-10, Acrysol ^® LMW- 20, Acrysol ^® LMW-45 and Acrysol ^® Al-N (trademark of Rohm & Haas) as well as Sokalan ^® PA-20, Sokalan ^® PA-40, Sokalan ^® PA-70 and Sokalan ^® PA-110 (trademark of BASF) available in the stores. Ethylene / maleic acid copolymers are sold under the name EMA ^® (trademark of Monsanto), methyl vinyl ether / maleic acid copolymers under the name Gantraz ^® AN 119 (trademark of GAF Coφ.) And acrylic acid / maleic acid copolymers under the name Sokalan ^® CP5 and Sokalan ^® CP7 (trademark of BASF). Acrylic phosphinates are available as DKW ^® (trademark of National Adhesives) and Belperse ^® - types (trademark of Ciba-Geigy). In combination with the polymers mentioned or as the sole graying inhibitor, it is also possible to use graft copolymers which are obtained by grafting polyalkylene oxides with molecular weights between 2000 and 100,000 with vinyl acetate. The acetate groups can optionally be saponified up to 15%. Polymers of this type, as EP-A-0219048 (BASF) are described in European patent application, under the name Sokalan ^® HP22 (trademark of BASF).

Before the particulate premix is pressed into detergent tablets, the premix can be "powdered" with finely divided surface treatment agents. This can be of advantage for the nature and physical properties of both the premix (storage, pressing) and the finished detergent tablets. Finely divided powdering agents are well known in the art, mostly zeolites, silicates or other inorganic salts being used. However, the premix is preferably “powdered” with finely divided zeolite, zeolites of the faujasite type being preferred. In the context of the present invention, the term “faujasite-type zeolite” denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4 (see Donald W. Breck: “Zeolite Molecular Sieves”, John Wiley & Sons, New York) , London, Sydney, Toronto, 1974, page 92). In addition to the zeolite X, zeolite Y and faujasite and mixtures of these compounds can also be used, the pure zeolite X being preferred. Mixtures or cocrystallisates of zeolites of the faujasite type with other zeolites which do not necessarily have to belong to the zeolite structural group 4 can also be used as powdering agents, it being advantageous if at least 50% by weight of the Powder consist of a zeolite of the faujasite type.

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

As already mentioned above, detergent tablets are preferred which additionally contain a disintegration aid. Processes according to the invention in which the premix additionally contains a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the weight of the premix, are preferred. In addition to the constituents mentioned, surfactant, builder and disintegration aid, or in their place in the process according to the invention, the particulate premixes to be treated can additionally contain one or more substances from the group of bleaching agents, bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, Dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.

Among the compounds which provide HO in water and provide bleaching agents, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O-providing peracidic salts or peracids, such as peracids. benzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced. If such bleach tablets are to be used for textile washing, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, regardless of which other ingredients are contained in the molded articles. 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 dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monophthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidopercapid [Phthaloiminoperoxyhexanoic 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-diperoxyacelic acid oxyacid, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Chlorine or bromine-releasing substances can also be used as bleaching agents in molded articles for automatic dishwashing. Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- 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.

In order to achieve an improved bleaching effect when washing or cleaning at temperatures of 60 ° C. and below, bleach activators can be incorporated as the sole component or as an ingredient of component b). Can be used as bleach activators Compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are polyacylated alkylenediamines, in particular tetraacetylethylene diamine (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 phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetate, ethylene glycol, Diacetoxy-2,5-dihydrofuran.

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

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest. Peroxidases or oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules in the inventive Molded bodies can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

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

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

Dyes and fragrances are added to the detergent tablets according to the invention in order to improve the aesthetic impression of the products and, in addition to the softness, to provide the consumer with a visually and sensorially "typical and unmistakable" product. As perfume oils or fragrances, NEN single fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert.-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allylcyclohexylproylatepyll-propyll-propyl-allyl-propyl-allyl-propyl-allyl-propyl-allyl-propyl-allyl-propyl-allyl-propyl-allyl-propyl-allyl-propyl-allyl. The ethers include, for example, benzylethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones, for example, the ionone, c -Isomethyl ionone and methyl cedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and teφineol, the hydrocarbons mainly include tephenols such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lentil flower oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

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

The fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.

In order to improve the aesthetic impression of the agents according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which No problem for a person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity towards textile fibers in order not to dye them.

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

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

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

For larger throughputs, rotary tablet presses are selected in which a larger number of dies is arranged in a circle on a so-called die table. The number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available. Each die on the die table is assigned an upper and lower punch, and again the pressure can be built up actively only by the upper or lower punch, but also by both stamps. The die table and the stamps move about a common vertical axis, the stamps being brought into the positions for filling, compaction, plastic deformation and ejection by means of rail-like cam tracks during the rotation. Wherever a particularly serious lifting or lowering of the punches is required (filling, compacting, ejecting), these cam tracks are supported by additional low-pressure pieces, low-tension rails and lifting tracks. The die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix. The pressure on the premix is individual via the press paths for the upper and lower punches adjustable, whereby the pressure builds up by rolling the stamp shaft heads past adjustable pressure rollers.

Rotary presses can also be provided with two filling shoes to increase the throughput, with only a semicircle having to be run through to produce a tablet. For the production of two-layer and multi-layer molded bodies, several filling shoes are arranged one behind the other without the slightly pressed first layer being ejected before further filling. With suitable process control, jacket and dot tablets can also be produced in this way, which have an onion-shell-like structure, the top side of the core or the core layers not being covered in the case of the dot tablets and thus remaining visible. Rotary tablet presses can also be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used simultaneously for pressing. The throughputs of modern rotary tablet presses are over one million molded articles per hour.

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

The molded body can be manufactured in a predetermined spatial shape and a predetermined size. Practically all practical configurations can be considered as the spatial shape, for example, the design as a board, the bar or bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross section. This last embodiment covers the presentation form from the tablet to compact cylinder pieces with a ratio of height to diameter above 1. The portioned compacts can each be designed as separate individual elements that correspond to the predetermined dosage of the detergents and / or cleaning agents. It is also possible, however, to form compacts which connect a plurality of such mass units in one compact, the portioned smaller units being easy to separate, in particular by predetermined predetermined breaking points. For the use of textile detergents in machines of the type customary in Europe with horizontally arranged mechanics, the portioned compacts can be designed as tablets, in cylindrical or cuboid form, with a diameter / height ratio in the range from about 0.5: 2 to 2: 0.5 is preferred. Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for the production of such pressed articles.

The spatial shape of another embodiment of the molded body is adapted in its dimensions to the detergent dispenser of commercially available household washing machines, so that the molded body can be metered directly into the dispenser without metering aid, where it dissolves during the dispensing process. However, it is of course also possible to use the detergent tablets without problems using a metering aid and is preferred in the context of the present invention.

Another preferred molded body that can be produced has a plate-like or plate-like structure with alternating thick long and thin short segments, so that individual segments of this "bolt" at the predetermined breaking points, which represent the short thin segments, broken off and into the Machine can be entered. This principle of the "bar-shaped" shaped body detergent can also be realized in other geometric shapes, for example vertically standing triangles, which are connected to one another only on one of their sides along the side.

However, it is also possible that the various components are not pressed into a uniform tablet, but that shaped bodies are obtained which have several layers, that is to say at least two layers. It is also possible that these different layers have different dissolving speeds. This can result in advantageous application properties of the molded body. If both for example, components are contained in the moldings that mutually influence each other negatively, so it is possible to integrate one component in the more rapidly soluble layer and to incorporate the other component in a more slowly soluble layer, so that the first component has already reacted if the second goes into solution. The layer structure of the molded body can take place in a stack-like manner, with the inner layer (s) already loosening at the edges of the molded body when the outer layers have not yet been completely removed, but it is also possible for the inner layer (s) to be completely encased ) can be achieved by the layer (s) lying further outwards, which leads to the premature dissolution of components of the inner layer (s).

In a further preferred embodiment of the invention, a molded body consists of at least three layers, i.e. two outer and at least one inner layer, at least one peroxy bleaching agent being contained in at least one of the inner layers, while in the case of the stap egg-shaped molded body, the two outer layers and in the case of the shaped body however, the outermost layers are free of peroxy bleach. Furthermore, it is also possible to spatially separate peroxy bleaching agents and any bleach activators and / or enzymes that may be present in a molded body. Such multilayer molded bodies have the advantage that they can be used not only via a dispensing chamber or via a metering device which is added to the washing liquor; rather, in such cases it is also possible to put the molded body into direct contact with the textiles in the machine without the risk of bleaching from bleaching agents and the like.

Similar effects can also be achieved by coating individual constituents of the detergent and cleaning agent composition to be treated or the entire molded article. For this purpose, the bodies to be coated can, for example, be sprayed with aqueous solutions or emulsions, or else they can be coated using the melt coating method. After pressing, the detergent tablets have a high stability. The breaking strength of cylindrical shaped bodies can be determined via the measured variable of the diametrical breaking load. This can be determined according to

2P πDt

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

The present invention furthermore relates to the use of wet-granulated foam inhibitor granules which, after mixing with finely divided processing components, are pressed in a manner known per se to form detergent tablets, for improving the stability and solubility of detergent tablets. By using the foam inhibitor granules mentioned, which are mixed after mixing with other components to form detergent tablets, the physical properties of the molded articles can be significantly improved, as the examples below demonstrate.

Examples:

Granulation in a 50-liter ploughshare mixer from Lödige produced granules containing tensides (for composition, see Table 1), which was used as the basis for a particulate premix. Following the granulation, the granules were dried in a fluidized bed apparatus from Glatt at a supply air temperature of 60 ° C. over a period of 30 minutes. After drying, fine particles <0.4 mm and coarse particles> 1.6 mm were screened off.

The particulate premix was produced by blending the surfactant-containing granules with bleach, bleach activator and other processing components. As a further processing component, the particulate premix contained a foam inhibitor concentrate which was used in the form of wet granules in the case of the molded bodies E according to the invention, in the form of a compact in the case of comparative example VI and in the form of non-granulated powder in the case of comparative example V2.

A mixture of paraffin on carrier material and a polymer on carrier material was used as the foam inhibitor concentrate. The first-mentioned mixture was produced according to the teaching of international patent application WO97 / 34983 (Henkel) and had an active substance content (paraffin) of 15% by weight, the powdery product having a bulk density of 700 g / l. The polymer on a carrier material is a terephthalic acid-ethylene glycol-polyethylene glycol ester which has been applied to sodium sulfate as a carrier. The powdery product with 70 wt .-% polymer and 30 wt .-% sodium sulfate, which has a bulk density of 1020 g / 1, is commercially available under the name Repelotex ^® -SRP-4 (trademark of Rhodia, Rhone-Poulenc) .

For comparative example V2, a mixture of the two powdery products was used, the proportions of which are shown in the table in the ready-to-press premix. For comparative example VI, a mixture of 76% by weight of the paraffm carrier powder and 24% by weight of the polymer carrier powder was compacted to form a slug on a compacting roller of the Alexanderwerk type. Then followed grinding the slug on a sieve granulator, the ground slug being sieved between 0.6 and 1.6 mm. For the inventive Example E, the two powder of a wet granulation were subjected by adding 5 kg of a mixture of 76 wt .-% of Paraffm carrier powder and 24 wt .-% of the polymer support powder with 1 kg of a polymer solution (Sokalan ^® -CP 5: Acrylic acid-maleic acid copolymer, 40% in water) was granulated in a 20 liter Lödige ploughshare mixer with chopper. The granules were then dried in a smooth fluidized bed at a supply air temperature of 80 ° C. for 30 minutes and sieved between 0.6 and 1.6 mm after drying. All in all, the premixes to be contained contained 4.6% by weight of the defoaming powder (V2) or compactate (VI) or granulate (E). The premixes were pressed in a Korsch eccentric tablet (diameter: 44 mm, height: 22 mm, weight: 37.5 g). The pressure was adjusted so that two series of molded bodies were obtained (E, E 'or VI, VI' and V2, V2 '), which differ in their hardness. Table 2 shows the composition of the premixes to be treated (and thus the shaped body).

Table 1: Composition of the surfactant granules [% by weight]

Table 2: Composition of the premixes [% by weight]:

15% by weight of active substance, see WO97 / 34983

** 70% by weight terephthalic acid-ethylene glycol-polyethylene glycol ester on 30% by weight sodium sulfate (Repelotex ^® -SRP-4 from Rhodia, Rhône-Poulenc)

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

After two days of storage, the hardness of the tablets was measured by deforming the tablet until it broke, the force acting on the side surfaces of the tablet and the maximum force which the tablet withstood being determined.

To determine the tablet disintegration, the tablet was placed in a beaker with water (600 ml of water, temperature 30 ° C.) and the time until the tablet disintegrated completely. To determine the defoamer performance, two tablets were placed in the dispenser of a household washing machine (AEG Öko-Lavamat) and a 60 ° C main wash program was started. The foam formation was then assessed through the porthole or via the half-opened induction chamber, the grades 0 (“no foam”) to 6 (“foam standing in the induction chamber”) being used. The experimental data are shown in Table 3:

Table 3: Detergent tablets with foam inhibitors [physical data]

Table 3 shows that the disintegration time of molded articles which contain a granulated or compacted foam inhibitor system (E, VI) is reduced compared to molded articles in which the foam inhibitor is used in finely divided form, with comparable hardness. However, the use of the compacted foam inhibitor system in the moldings of Comparative Example VI at low washing temperatures leads to unacceptable foam notes, i.e. at 40 ° C the defoamer performance is insufficient. Only the granulated foam inhibitor according to the invention in the molded bodies E shows at the same time a very good defoamer performance and improved disintegration times at high hardness levels.

Claims

Claims:

1. washing and cleaning agent molded body made of compressed particulate washing and cleaning agent, characterized in that they contain a wet granulated foam inhibitor granulate.

2. Detergent form according to claim 1, characterized in that the foam inhibitor granules based on the weight of the granules 1 to 30 wt .-%, preferably 2 to 25 wt .-% and in particular 3 to 20 wt .-% foam inhibitors contains from the group of paraffins and / or silicones.

3. washing and cleaning agent form according to claim 2, characterized in that the foam inhibitor granules as a carrier material for the paraffin (s) and / or silicone (s) one or more substances from the group of sulfates, carbonates, hydrogen carbonates, Contains silicates and citrates, the alkali metal salts being preferred and the sodium salts being particularly preferred.

4. washing and cleaning agent molded article according to one of claims 1 to 3, characterized in that the foam inhibitor granules further ingredients of washing and cleaning agents, in particular polymers, in amounts of 0.5 to 20 wt .-%, preferably from 1 to 10 wt .-% and in particular from 2.5 to 7.5 wt .-%, each based on the foam inhibitor granules.

5. Washing and cleaning agent molded articles according to one of claims 1 to 4, characterized in that they contain at least 80% by weight, preferably at least 90% by weight and particularly preferably the total amount of defoamer contained in the molded article in the form of wet-granulated foam inhibitor granules .

6. Detergent and molded article according to one of claims 1 to 5, characterized in that it is based on the weight of the molded article 1 to 15 wt .-%, preferably 2 to 10 wt .-% and in particular 2.5 to 7.5 % By weight of the wet-granulated foam inhibitor granules.

7. Detergent and molded article according to one of claims 1 to 6, characterized in that it is based on the weight of the molded article 0.01 to 5 wt .-%, preferably 0.1 to 2.5 wt .-% and in particular 0 , 5 to 1 wt .-% foam inhibitor active substance.

8. Detergent and molded article according to one of claims 1 to 7, characterized in that it additionally contains a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight. , preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the molded body weight.

9. Detergent and molded article according to one of claims 1 to 8, characterized in that they are not coated with a coating which covers the entire molded article.

10. Washing and cleaning agent molded article according to one of claims 1 to 9, characterized in that it completely disintegrates into its secondary articles in water at 30 ° C in less than 60 seconds.

11. A process for the production of detergent tablets, characterized by the steps

a) production of a foam inhibitor granulate by wet granulation, b) mixing of the granulate produced in step a) with further ingredients of detergents and cleaning agents to form a premix to be treated, c) molding to shaped articles.

12. The method according to claim 11, characterized in that process step a) is carried out in the following substeps: al) adsorbing foam inhibitor active substance onto carrier material, a2) optionally mixing the foam inhibitor compound formed in step a1) with further ingredients of washing and cleaning agents, a3) granulating with the addition of a graining liquid.

13. The method according to claim 12, characterized in that process step al) as spraying or spraying on a melt, an emulsion or a solution of solid foam inhibitor active substance or as spraying or spraying on liquid foam inhibitor active substance onto moving carrier material particles or as spray drying of a carrier material. Foam inhibitor slurries is carried out.

14. The method according to claim 12 or 13, characterized in that in process step a1) as foam inhibitor active substance, foam inhibitors from the group of paraffins and / or silicones, preferably paraffins and / or silicones which are liquid at room temperature, in amounts of 1 to 30% by weight .-%, preferably from 5 to 25% by weight and in particular from 10 to 20% by weight, in each case based on the weight of the compound.

15. The method according to any one of claims 12 to 14, characterized in that one or more substances from the group of sulfates, carbonates, bicarbonates, silicates and citrates are used as the carrier material for the foam inhibitor active substance, the alkali metal salts being preferred and the sodium salts being particularly preferred are preferred.

16. The method according to any one of claims 12 to 15, characterized in that in process step a2) further ingredients of detergents and cleaning agents, preferably from the group of builders, cobuilders and polymers, in amounts of 5 to 40 wt .-%, preferably from 10 to 35% by weight and in particular from 15 to 30% by weight, based in each case on the mixture of foam inhibitor compound and further ingredients.

17. The method according to any one of claims 12 to 16, characterized in that the granulating liquid is water or an aqueous solution of one or more ingredients of detergents and cleaning agents in a weight ratio of granulating liquid to the amount of solids of 1: 100 to 2: 1, preferably 1:50 up to 1: 1 and in particular from 1:20 to 1: 2.

18. The method according to any one of claims 11 to 17, characterized in that the foam inhibitor granules produced in step a) 1 to 15 wt .-%, preferably 2 to 10 wt .-% and in particular 2.5 to 7.5 wt .-% % of the premix to be dispensed.

19. The method according to any one of claims 11 to 18, characterized in that the foam inhibitor granules produced in step a) in step b) with at least one surfactant-containing granules to a premix to be veφressende with a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g / 1 is combined.

20. The method according to claim 19, characterized in that the surfactant-containing granules have particle sizes between 100 and 2000 microns, preferably between 200 and 1800 microns, particularly preferably between 400 and 1600 microns and in particular between 600 and 1400 microns.

21. The method according to any one of claims 19 or 20, characterized in that the surfactant-containing granules contains anionic and / or nonionic surfactants and builders and total surfactant contents of at least 10 wt .-%, preferably at least 20 wt .-% and in particular at least 25 % By weight.

22. The method according to any one of claims 11 to 21, characterized in that the premix additionally comprises a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the weight of the premix.

23. The method according to any one of claims 11 to 22, characterized in that the premix additionally one or more substances from the group of bleaching agents, bleach activators, enzymes, pH adjusting agents, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, contains optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.

24. Use of wet-granulated foam inhibitor granules to improve the stability and solubility of detergent tablets.