DE19915321A1 - Detergent tablets, useful for laundering textiles, in automatic dishwasher, for cleaning surface or as bleach, water softening or scouring tablets, contain bentonite with specified particle size range as disintegration aid and hardener - Google Patents

Abstract

Laundry and other detergents tablets of compressed particulate detergent contain 0.1-20 wt.% bentonite, at least 70 wt.% of which consists of 400-1600 mu m particles. Independent claims are also included for (a) the production of detergent tablets by pressing a premix containing bentonite as above; (b) the use of bentonite, in which >= 70 wt.% of the particles have a size of 400-1600 mu m, for increasing the hardness and reducing the disintegration time of detergent tablets.

Description

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

Detergent tablets are widely described in the prior art and are enjoying increasing popularity with consumers because of their ease of dosing. Tabletted detergents and cleaning agents have a number of advantages compared to powdered ones Advantages: They are easier to dose and handle and because of their compact structure advantages in storage and transportation. Also in the patent lite Accordingly, detergent tablets are comprehensively described. A Problem that always occurs when using washing and cleaning active moldings occurs again, the too low disintegration and dissolution rate of the moldings is below Conditions of use. Since sufficiently stable, i.e. H. shape and break-resistant shape body can only be produced by relatively high pressure, it comes to a strong compression of the molded body components and to a resultant one delayed disintegration of the shaped body in the aqueous liquor and thus to one slow release of the active ingredients in the washing or cleaning process. The ver Delayed disintegration of the moldings also has the disadvantage that it is usual Washing and cleaning product tablets do not go through the household detergent dispenser Let washing machines rinse in, as the tablets will not be in a sufficiently fast time Secondary particles that are small enough to get out of the detergent dispenser into the wash disintegrate drum to be washed up. Provide molded body that is given a predetermined Hardness is characterized by short disintegration times and thus also across the dispenser Allowing household washing machines to dose was one of the tasks of the present Invention. Another object of the invention was to provide an additive for tablet Provide animal-ready premixes, the production of flushable washing and Rei Cleaning agent tablets allows, even if these tablets have higher disintegration times exhibit. Usually, detergent tablets that do not dissolve disintegrated into their secondary particles within 60 seconds, no longer into their Be constituents, so that such tablets in the form of hard, moist lumps in the detergent chamber and are no longer rinsed out by repeated addition of water become.

To overcome the dichotomy between hardship, i. H. Transport and handling stability The prior art has many approaches to solving the problem, and easy disintegration of the moldings has been developed. A particularly well-known from pharmacy and in the field of Detergent tablets and detergent tablets an extensive approach is the incorporation of be certain disintegration aids that facilitate the entry of water or upon entry swell by water or generate gas or have a disintegrating effect in some other way. Other proposed solutions from the patent literature describe the compression of Vor mixing of certain particle sizes, the separation of individual ingredients from be agreed other ingredients as well as the coating of individual ingredients or des entire molding with binders. Also the idea of more easily soluble ingredients in to incorporate the shaped body and thus accelerate the disintegration of the shaped body is in in the patent literature. In addition to easily soluble salts such as acetates, citrates, etc. are z. T. also easily soluble nonionic ingredients mentioned.

The use of sheet silicates as a disintegration aid is also out of the phar known pharmaceutical literature, the specific problems of washing and Naturally, cleaning agents are not taken into account. The state of the art Finding documents dealing with the incorporation of bentonites in detergents grasp, use these layered silicates to achieve an avivage effect. In Reini The property of bentonite is assigned to agents for machine dishwashing wrote to reduce water stains on wash ware. Enzymatic dishwashing detergents tablets, the surfactant, alkali salt, enzyme and 0.5 to 25 wt .-% layered structure Clay mineral, preferably smectite, kaolin, ilite, chlorite, attapulgite or (mixed-layer) Hectorite, montmorillonite, bentonite are contained in EP 139 329 (Unilever) wrote.

Disintegration-promoting properties of bentonites in detergents and cleaning agents molded bodies are not described in the prior art.

It has now been found that detergent tablets with the ge named advantages when they get bentonite within a certain part size range included. Surprisingly, such moldings can be passed through Their short disintegration times, even with high hardness levels, are household-wise via the detergent dispenser in washing machines.

The invention relates to detergent tablets made from compressed particulate detergents and cleaning agents containing bentonites in quantities of 0.1 to 20 % By weight, based on the weight of the molding, with at least 70 % By weight of the bentonite particles have particle sizes between 400 and 1600 μm.

Bentonites are contaminated clays that were formed by the weathering of volcanic tuffs are. Due to their high content of montmorillonite, bentonites have valuable properties properties such as swellability, ion exchange capacity and thixotropy. It is possible Lich, to modify the properties of the bentonite according to the intended use ren. Bentonites are common as a clay component in tropical soils and are used as sodium Bentonite e.g. B. mined in Wyoming / USA. Sodium bentonite has the most favorable uses technical properties (swellability), so that its use in the Rah Men of the present invention is preferred. Naturally occurring calcium Bentonites come, for example, from Mississippi / USA or Texas / USA or from Lands hat / D. The naturally obtained Ca-bentonites are artificially produced by exchanging Ca converted against Na into the more swellable Na bentonites.

The main components of bentonites are so-called montmorillonites, which can also be used in pure form in the context of the present invention. Montmorillo nites are clay minerals belonging to the phyllosilicates and here to the dioctahedral smectites, which crystallize in a monoclinic-pseudohexagonal manner. Montmorillonites form predominantly white, gray-white to yellowish, completely amorphous appearing, easily friable masses that swell in water but do not become plastic, which are determined by the general formulas

Al ₂ [(OH) ₂ / Si ₄ O ₁₀ ] .nH ₂ O or

Al ₂ O ₃ .4SiO ₂ .H ₂ O.nH ₂ O or

Al ₂ [(OH) ₂ / Si ₄ O ₁₀ (dried at 150 °)

can be described.

Montmorillonites have a three-layer structure consisting of two tetrahedral layers that are electrostatically crosslinked via the cations of an octahedral intermediate layer. The layers are not rigidly connected, but can be replaced by reversible storage of water (in 2-7 times the amount) and other substances such as B. alcohols, glycols, pyridine, α-picoline, ammonium compounds, hydroxy-aluminosilicate ions, etc. swell. The ones given above. Formulas are only approximate formulas, since montmorillonites have a large ion exchange capacity. Al can be exchanged for Mg, Fe ²⁺ , Fe ³⁺ , Zn, Cr, Cu and other ions. Such a substitution results in a negative charge in the layers, which is balanced ^{by other cations, especially Na +} and Ca ^2+.

The structure of the phyllosilicates, in which a central layer of octahedral coordinated cations is sandwiched by 2 layers of [(Si, Al) O ₄ ] tetrahedra, can be varied widely by numerous substitutions in the octahedral layer. In addition to mostly Al ³⁺ (montmorillonite - dioctahedral layered silicate), the octahedron layer can also contain, for example, Mg ²⁺ (saponite - trioctahedral layered silicate) or Fe ³⁺ (nontronite - dioctahedral layered silicate). It also contains cations such as Zn ²⁺ (sauconite - trioctahedral sheet silicate), Ni ²⁺ (nickel sauconite - trioctahedral sheet silicate) and Li ⁺ (hectorite - trioctahedral sheet silicate). Substitutions can also be observed in the tetrahedral ^{layer, for example Si 4+} can be partially replaced by Al ³⁺ (in the case of beidellite - dioctahedral sheet silicate) and also by Fe ³⁺ (in the case of nontronite - dioctahedral sheet silicate). These substitutions result in an imbalance in the charge balance, which is balanced out by exchangeable cations, usually sodium, calcium and potassium, including magnesium, between the layer packages.

The general formulas for dioctahedral phyllosilicates can thus be

(K, Ca, Na, Mg) ^{i +} [Si _4-x (Al, Fe ³⁺ ) _x O ₁₀ ] [(Al, Fe ³⁺ ) _2-y (Mg, Fe ²⁺ ) _{y + z} (OH) ₂ ]

with i = about 0.6 to 0.2 per O ₁₀ (OH) ₂ and furthermore i = x + y-2z and for trioctahedral phyllosilicates

(K, Ca, Na, Mg) ^{i +} [Si _4-x Al _x O ₁₀ ] [(Mg, Fe ²⁺ ) _3-y (Al, Fe ³⁺ ) _yz (OH) ₂ ]

specify with i = x-y + 3z and 0.6 <i <0.2.

In the context of the present invention, bentonites are preferably used in the classic Senses, i.e. clays with a high montmorillonite content, are used. Preferred washing and Detergent tablets contain phyllosilicates with a montmorillo as bentonite nit content of more than 60 wt .-%, preferably of more than 75 wt .-% and in particular those of more than 90 wt .-%, each based on the weight of the phyllosilicate.

If this is not undesirable for reasons of cost, pure Insert montmorillonite. Detergent tablets that are pure as bentonite Containing montmorillonites are also preferred according to the invention.

The layer spacing of phyllosilicates can be determined by incorporating certain compounds gen, as this depends on the charge of the elementary layers and from the interlayer cations - can swell, d. H. the base distance of their Three-layer packages through the storage of water molecules or long-chain organics large molecules to over 15 Å. So can according to the invention Chemically modified bentonites are used, with detergents and cleaning agents Shaped bodies are preferred which are modified by quaternary ammonium compounds Contains bentonite.

Preferred amounts of the bentonites used in the washing and cleaning agents according to the invention agent moldings are within narrower ranges, so that washing and cleaning agent tablets are preferred which contain the bentonite in amounts of 0.2 to 17.5% by weight, preferably from 0.5 to 15% by weight, and more preferably from 1 to 10% by weight, each based on the weight of the molding.

The content of the bentonite particles that are outside of the specified particle size range are rich, is preferably smaller, so that detergent tablets are preferred in which at least 80 wt .-%, preferably at least 85 wt .-% and in particular at least 90% by weight of the bentonite particle size contained in them have between 400 and 1600 µm.

The particle size distribution of the bentonites used according to the invention is preferably se even tighter, so that detergent tablets with at least 70 % By weight, preferably at least 80% by weight and in particular at least 90% by weight the bentonites contained in them have particle sizes between 400 and 1200 µm, are preferred.

An even narrower particle size distribution of the bentonites used according to the invention can be beneficial. Another preferred embodiment of the present invention Application therefore provides detergent tablets which are characterized by this are that a maximum of 40 wt .-%, preferably a maximum of 30 wt .-% and in particular ma ximal 20 wt .-% of the bentonite contained in them particle sizes below 600 microns have, it is preferred that at least 30 wt .-%, preferably at least 40 % By weight and in particular at least 50% by weight of the bentonite particle sizes above 800 µm.

According to the invention, it is also possible to granulate the bentonites with other raw materials and adjust to the required particle spectrum through grinding and sieving operations. According to the invention, it is therefore also possible to use compounds which contain at least 50% by weight, based on the compound, consist of bentonite, these compounds then denote the must meet particle size criteria according to the invention, d. i.e. that at least 70 % By weight of the compounds have particle sizes between 400 and 1600 μm. Invent According to the invention, detergent tablets containing them are also preferred Bentonite-containing compounds containing at least 50 wt .-% bentonite, each based on the weight of the compound, at least 70% by weight of the Compounds have particle sizes between 400 and 1600 µm.

Further ingredients with which bentonite becomes bentonite which can be used according to the invention Compounds containing compounds that can be processed are, for example, bleaching agents such as Na trium perborate monohydrate, sodium perborate tetrahydrate and sodium percarbonate, bleach activators such as tetraacetylethylenediamine (TAED), builders such as sodium carbonate, amorphous sodium silicates, sodium phosphates or zeolites and other ingredients of Detergents and cleaning agents, in particular from the groups of organic solid acids ren, the polymers and the adjusting agents or pH corrections.

It is possible within the scope of the present invention to incorporate acidic constituents into the molded body to incorporate. If the moldings contain carbonates, the acid is caused by the reaction re released with the carbonate carbon dioxide, this "effervescent effect" being disintegrated can have an ons-promoting effect. Usually, oligomeric oligomers are used in effervescent systems used acids such as succinic acid, maleic acid and especially citric acid. In preferred embodiments of the present invention is the washing and cleaning The active agent tablets are not, however, an "effervescent tablet", d. H. preferred washing and Detergent tablets are free from oligomeric oligocarboxylic acids, in particular Citric acid.

It is also technically possible to coat the shaped body with a coating that has the covers the entire molded body. Such coated detergent and cleaning agent form bodies can be applied by spraying a melt or a solution of the coating material produced the shaped body or immersion of the shaped body in the melt or solution become. In preferred embodiments of the present invention, the washing and detergent tablets, however, not with a coating that covers the entire Molded body coated, coated.

In order to further facilitate the disintegration of the moldings according to the invention, it is possible to use additional disintegration aids, so-called tablet disintegrants, in these incorporated in order to shorten the disintegration times even more. Taking pills Teln or decay accelerators are according to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of Pharmaceutical Technology" (6th edition, 1987, pp. 182-184) Excipients understood that are necessary for the rapid disintegration of tablets in water or gastric juice and ensure that the pharmaceuticals are released in an absorbable form.

These substances, which are also known as "explosives" because of their effect, ver increase their volume when water enters, whereby on the one hand their own volume increases (Swelling), on the other hand, a pressure can also be generated via the release of gases which breaks the tablet into smaller particles. Well-known disintegration aid Medium are, for example, carbonate / citric acid systems, with others also being organic Acids can be used. Swelling disintegration aids are for example synthetic polymers such as polyvinylpyrrolidone (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 additional ones cher disintegration aids, each based on the weight of the molding.

In the context of the present invention, cellulose-based disintegrants are used as preferred additional disintegration agents, so that preferred detergent tablets have such a cellulose-based disintegration agent in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, viewed formally, represents a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approx. 500 to 5000 glucose units and consequently have average molar masses of 50,000 to 500,000. Cellulose derivatives that can be obtained from cellulose by polymer-analogous reactions can also be used as cellulose-based disintegrants in the context of the present invention. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which Hy droxy hydrogen atoms have been substituted. Celluloses in which the hydroxyl groups have been replaced by functional groups that 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 cellulose-based disintegrants, but are used in a mixture with cellulose. The cellulose derivative content of 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 the cellulose-based disintegrant.

The cellulose used as an additional disintegration aid is preferred not used in finely divided form, but rather before being mixed with the ones to be pressed Premixes converted into a coarser form, for example granulated or compacted. Detergent tablets, the disintegrants in granular or given if contained in co-granulated form, German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) as well as the international patent report WO 98/40463 (Henkel). These writings are also more detailed for the production of granulated, compacted or co-granulated cellulose disintegrants remove. The particle sizes of such disintegrants are mostly 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 aforementioned and in coarser disintegration aids described in more detail in the cited publications on Cellu Losebasis are preferred as disintegration aids in the context of the present invention medium and commercially available, for example, under the name Arbocel® TF-30- HG available from Rettenmaier.

As another cellulose-based disintegrant or as part of this compo In some cases, microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under such 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 deaggregation of the microfine cellulos 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 negotiable.

In the context of the present invention, preferred form of detergent and cleaning agent bodies also contain another disintegration aid, preferably a Des integration aids based on cellulose, preferably in granular, co-granulated or compacted form, in amounts from 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 molded body.

Another object of the present invention is a process for the production of Washing and cleaning agent tablets by molding a particle shaped premix, which is characterized in that the premix bentonites in Amounts from 0.1 to 20 wt .-%, based on the premix, contains, at least 70% by weight of the bentonite particles have particle sizes between 400 and 1600 μm.

Analogous to what has been said about the detergents and cleaning agents according to the invention Moldings are also preferred in the method according to the invention, variants in which the premix bentonites, preferably phyllosilicates with a montmorillonite content of more than 60% by weight, preferably of more than 75% by weight and in particular of more than 90 wt .-%, each based on the weight of the phyllosilicate, in amounts of 0.5 to 15% by weight, preferably from 1 to 10% by weight.

Also with regard to the particle size distribution of the process according to the invention The bentonite introduced applies analogously to what has already been said above. In preferred methods, white sen at least 70 wt .-%, preferably at least 80 wt .-% and in particular min at least 90% by weight of the bentonite particle sizes introduced into the premix between between 400 and 1200 µm.

In preferred variants of the method, premixes are pressed which, in addition to the inven Bentonites used as intended additionally contain surfactant-containing granulate (s) and a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular which have at least 700 g / l. The production of the surfactant-containing granules can be done there with customary technical granulation processes such as compaction, extrusion, Wed shear granulation, pelleting or fluidized bed granulation take place.

Granulation can be used in a wide variety of applications in the detergent and cleaning products industry apparatus commonly used are carried out. For example, it is possible Lich, to use the rounders common in pharmacy. In such a turntable appa temperatures, the residence time of the granules is usually less than 20 seconds. Also conventional mixers and mixing granulators are suitable for granulation. As Wed Both high-shear mixers and normal mixers can shear Mixers with lower rotational speeds can be used. Suitable mixers are for example Eirich® mixers of the R or RV series (trademarks of the machines factory Gustav Eirich, Hardheim), the Schugi® Flexomix, the Fukae® FS-G mixer (Wa trademark of Fukae Powtech, Kogyo Co., Japan), the Lödige® FM, KM and CB Mixer (trademark of Lödige Maschinenbau GmbH, Paderborn) or the Drais - Series T or K-T (trademark of Drais-Werke GmbH, Mannheim). The dwell times of the granules in the mixers are in the range of less than 60 seconds, with the Residence time also depends on the speed of rotation of the mixer. Shorten here the dwell times change accordingly, the faster the mixer runs. They 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, will linger set times of up to 20 minutes, with dwell times below 10 minutes because of the Process economics are preferred.

Preferred granulation processes for the production of surfactant-containing granules are described in Mi shear granulators, in which some mixer parts or the entire mixer are heated to temperatures that are at least 20 ° C above the temperature that have the substances to be granulated at the beginning of the granulation process. So will Granulated solids that were stored at 20 ° C and at this temperature in the Wed get shear, it is preferred that some or all of the mixer parts at least one Temperature of 40 ° C. Overall, however, a temperature of 120 ° C for the Mixer parts or the entire mixer are not exceeded. Will only parts of the Mixer heated to the temperatures mentioned, these are preferably the mixers walls or the mixer tools. The former can be through a heatable jacket, the latter can be brought to the desired temperature by built-in heating elements.

In the production of surfactant-containing granulates, all or some of them are also preferred heated mixers the use of non-aqueous granulation aids, esp special nonionic surfactants with a melting point in the range of 20 to 50 ° C exhibit. By the preferred granulation process described, the bulk can Increase the weight of the surfactant granules, while at the same time unwanted caking on the wall can be significantly reduced on the mixer walls. The use of such herge put surfactant granules in tablettable premixes leads to washing and cleaning agent moldings, which are compared to mixtures that herge conventionally contained granules, characterized by a further reduced disintegration time.

In preferred process variants, the surfactant-containing granulate is sufficient for a certain part size criteria. Thus, methods according to the invention are preferred in which the th sidhaltige granules particle sizes between 100 and 2000 microns, preferably between 200 and 1800 microns, particularly preferably between 400 and 1600 microns and in particular between between 600 and 1400 µm.

In addition to the active ingredients (anionic and / or nonionic and / or cationic and / or amphoteric surfactants), the surfactant granules preferably also contain carrier fe, which particularly preferably come from the group of builders. Particular advantage Adhesive processes are characterized in that the surfactant-containing granules are anionic and / or contains nonionic surfactants and builders and total surfactant contents of at least 10% by weight, preferably at least 20% by weight and in particular at least at least 25% by weight.

These surface-active substances come from the group of anionic, non-ionic between, zwitterionic or cationic surfactants, with anionic surfactants from ökono mixed reasons and due to their range of services are clearly preferred.

The anionic surfactants used are, for example, those of the sulfonate and sulfate type. Surfactants of the sulfonate type are preferably C _9-13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from C _12-18 monoolefins with terminal or internal double bonds by sulfonation with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products are considered. _{Alkane sulfonates obtained from C 12-18} alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization, are also suitable. Likewise, the esters of α-sulfo fatty acids (ester sulfonates), z. B. the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids ge suitable.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Taking fatty acid glyce rinestern are the mono-, di- and tri-esters as well as their mixtures to be understood as they are at the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or can be obtained in the transesterification of triglycerides with 0.3 to 2 mol of glycerol. Before Additional sulfated fatty acid glycerol esters are the sulfation products of saturated fat acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, Ca prinic acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid _{half esters of the C 12} -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ Oxo alcohols and those half esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis and which have a degradation behavior similar to that of the appropriate 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. No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C _12-18 -Fatty alcohols with 1 to 4 EO are suitable. Due to 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 represent the 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 of these. Particularly preferred sulphosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols which, considered in isolation, represent nonionic surfactants (see description below). In turn, 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 in particular come into consideration 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 especially from natural ones 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 their form Sodium or potassium salts, especially in the form of the sodium salts.

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

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

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with 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 is linear or preferably in the 2-position May be methyl-branched or contain linear and methyl-branched radicals in the mixture, as they are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin with 12 to 18 carbon atoms, e.g. B. from coconut, palm, tallow 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 _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 of these, 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 mean values which, for a specific product, can be a whole number or a fractional number. 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 are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Another class of preferably used nonionic surfactants, which either as all 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 with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as for example in the Japanese Pa tent application JP 58/217598 are described or preferably according to the in the International patent application WO-A-90/13533 prepared method described become.

Another class of nonionic surfactants which can be used advantageously are the alkyl polyglycosides (APG). Usable alkypolyglycosides satisfy the general formula RO (G) _z , in which R represents a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol that stands for a Glyko seeinheit 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, that is to say alkyl polyglycosides, are preferably used in de The polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.

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

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 alkali nolamide may be suitable. The amount of these nonionic surfactants is before preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of it.

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

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

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

in which R for a linear or branched alkyl or alkenyl radical with 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 oxy-alkyl radical with 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 radical.

[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 the international application WO-A-95/07331 by reaction with fatty acid remethylesters in the presence of an alkoxide as a catalyst in the desired polyhy droxyfettsäureamide are transferred.

Regardless of whether anionic or nonionic surfactants or mixtures of these Surfactant classes and optionally amphoteric or cationic surfactants in the surfactant granulate lat are used, processes according to the invention are preferred in which the surfactant content of the surfactant-containing granules produced in step a) 5 to 60% by weight, preferably wise 10 to 50 wt .-% and in particular 15 to 40 wt .-%, each based on the Surfactant granules.

The surfactant granules can vary in the detergent tablets Quantities are used. Process according to the invention in which the proportion of the surfactant containing granules on the detergent tablets 40 to 95 wt .-%, preferably 45 to 85% by weight and in particular 55 to 75% by weight, each based on is the weight of the detergent tablets, are preferred.

In addition to the washing-active substances, builders are the most important ingredients of Detergents and cleaning agents. In the surfactant granules, but also as part of the Premixes can all be commonly used in detergents and cleaning agents Builders may be included, in particular zeolites, silicates, carbonates, organic Cobuilders and - where there are no ecological prejudices against their use - also the Phosphates.

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

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ module of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, which are release 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 even lead to particularly good builder properties if the silicate particles give blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted in such a way that the products have microcrystalline areas of size 10 to a few hundred nm, values up to a maximum of 50 nm and in particular up to a maximum of 20 nm being preferred. Such so-called X-ray amorphous silicates, which also have a dissolution delay compared to conventional What sergläsern, are described, for example, in German patent application DE-A-44 00 024. Compressed / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates are particularly preferred.

If desired, the amount of zeolite introduced by the surfactant granulate can be used of the P- and / or X-type further zeolite are incorporated into the premix, by adding zeolite as a make-up component. The fine crystalline used ne, synthetic zeolite containing bound water is preferably a zeolite of type A, P, X or Y. However, zeolite X and mixtures of A are also suitable, X and / or P. Suitable zeolites have an average particle size of less than 10 µm (volume distribution; measuring 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 can also be used as builder sub punching possible, provided that such use is not avoided for ecological reasons should be. Among the large number of commercially available phosphates, the Alka Limetallphosphate with particular preference of pentasodium or pentapotassium tri phosphate (sodium or potassium tripolyphosphate) in detergents and cleaning agents Industry the greatest importance.

Alkali metal phosphates is the summary name for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid H ₃ PO ₄ can be distinguished in addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts or lime incrustations in fabrics and also contribute to cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white powders that are very easily soluble in water, which lose the water of crystallization when heated and convert to weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ) at 200 ° C, and to sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below), skip over. NaH ₂ PO _{4 has an} acidic reaction; it is formed when phosphoric acid is adjusted to a pH value of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt with a density of 2.33 gcm ^-3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is easily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes into the diphosphate Na ₄ P ₂ O ₇ when heated more strongly. Disodium hydrogen phosphate is made by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm ^-3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is easily soluble in water with an alkaline reaction and is herge by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 gcm ^-3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises z. B. when He heats Thomas slag with coal and potassium sulfate. Despite the higher price, the more easily soluble and therefore highly effective potassium phosphates are often preferred to corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also stated 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) . Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed when disodium phosphate is heated to <200 ° or when phosphoric acid is reacted with soda in a stoichiometric ratio and the solution is dehydrated by spraying. The decahydrate complexes heavy metal salts and hardness builders and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH being 1% Solution at 25 ° is 10.4.

Condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ results in higher mol. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphos phate and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used for the latter in particular: fused or calcined phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is a non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa-O] _{n ) which is anhydrous or crystallizes with 6 H 2 O} -Na with n = 3. In 100 g of water at room temperature about 17 g, at 60 ° about 20 g, at 100 ° about 32 g of the anhydrous salt; after two hours of heating the solution to 100 °, hydrolysis results in about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with soda solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including Lime soaps, etc.) Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% by weight solution (<23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates, which can also be used in the context of the present invention. These arise, for example, when sodium trimetaphosphate is hydrolyzed with KOH:

(NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

According to the invention, these are exactly like sodium tripolyphosphate and potassium tripolyphosphate or mixtures of these two can be used; also mixtures of sodium tripolyphos phate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and Sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tri polyphosphate and sodium potassium tripolyphosphate can be used according to the invention.

Organic co-builders can be used in the automatic dishwashing according to the invention in particular mediate polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, As paraginic acid, polyacetals, dextrins, other organic cobuilders (see below) and Phosphonates are used. These classes of substances are described below.

Organic builder substances that can be used are, for example, those in the form of their sodium salts which can be used polycarboxylic acids, polycarboxylic acids being such carboxylic acids be understood that carry more than one acid function. For example, this is Citro nenic 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 and 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 possess besides their buil the effect is typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or Detergents. Citric acid, succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these may be mentioned.

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

The molar masses given for polymeric polycarboxylates are in the sense of this document to weight average molecular weights MW of the respective acid form, the basic were also determined by means of gel permeation chromatography (GPC), with a UV Detector was used. The measurement was carried out against an external polyacrylic acid re-standard, which due to its structural relationship with the examined Poly meren delivers realistic molecular weight values. This information differs significantly from the Molecular weight data in which polystyrene sulfonic acids are used as the standard. The molar masses measured against polystyrene sulfonic acids are usually significantly higher than the molar masses given in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 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 10,000 g / mol, and particularly preferably from 3000 to 5000 g / mol, are preferred be.

Also suitable are copolymeric polycarboxylates, in particular 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 that contain 50 to 90% by weight acrylic acid and 50 to 10% by weight maleic acid. Your relative mole Pellet 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 used either as a powder or as an aqueous solution can be used. The content of (co) polymeric polycarboxylates in the agents is above preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

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

Biodegradable polymers made of more than two ver different monomer units, for example those which are used as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or the as Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives contain.

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

Likewise, 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, they also have a Have a bleach-stabilizing effect.

Further suitable builder substances are polyacetals, which are obtained by reacting Dial dehydrogenates with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl have groups, can be obtained. Preferred polyacetals are made from Dialde hyden such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from Polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid obtained.

Other suitable organic builders 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 customary, for example acid or enzyme, catalytic lysed procedures are performed. It is preferably a hydrolysis pro products with average molar masses in the range from 400 to 500,000 g / mol. There is a poly saccharide with a dextrose equivalent (DE) in the range from 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 cose syrups 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. Oxidized dextrins of this type and processes for their production are, for example, from the 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 the 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 mindisuccinat, are further suitable co-builders. Ethylenediamine-N, N'- disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and Gly are also preferred in this context cerintrisuccinate. Suitable use amounts are zeolite-containing and / or silicate-containing gen formulations at 3 to 15% by weight.

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

Another class of substances with co-builder properties are the phosphonates. Da in particular it is hydroxyalkane or aminoalkane phosphonates. Under of the hydroxyalkanephosphonates is the 1-hydroxyethane-1,1-diphosphonate (HEDP) of of particular importance as a co-builder. It is preferably used as the sodium salt, whereby the disodium salt reacts neutrally and the tetrasodium salt reacts alkaline (pH 9). As Aminoalkanephosphonates are preferably ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriaminepentamethylene phosphonate (DTPMP) and their higher Ho mologist in question. They are preferably in the form of the neutrally reacting sodium salts, z. B. as the hexasodium salt of EDTMP or as the hepta- and octasodium salt of DTPMP, used. The preferred builder from the class of phosphonates is HEDP ver turns. The aminoalkanephosphonates also have a pronounced heavy metal bin decapacity. Accordingly, it can, especially if the agents also contain bleach hold, be preferred to use aminoalkanephosphonates, in particular DTPMP, or To use mixtures of the phosphonates mentioned.

In addition, all compounds that are capable of forming complexes with alkaline earth to train ions can be used as co-builders.

Before the particulate premix is compressed into detergents and cleaning agents The premix with finely divided surface treatment agents can form shaped bodies be "powdered". This can be for the texture and physical properties both the premix (storage, compression) and the finished washing and rice nigungsmittelformkörper be advantageous. Fine powdering agents are available well known in the art, mostly zeolites, silicates or other inorganic salts can be used. However, the premix with finely divided zeolite is preferred "powdered", with zeolites of the faujasite type being preferred. As part of the present According to the invention, the term "zeolite of the faujasite type" characterizes 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, p. 92). In addition to zeolite X, there are also zeolite Y and faujasite as well Mixtures of these compounds can be used, with pure zeolite X being preferred. Also mixtures or cocrystals of zeolites of the faujasite type with other zeolites Lithen, which do not necessarily have to belong to the zeolite structure group 4, are as Abpu can be used change agent, it is advantageous if at least 50 wt .-% of the Ab powdering agent 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, the granular Kompo contains nents and subsequently added powdery substances, the or one of the subsequently added powdery components a zeolite of the faujasite type with particle sizes below 100 µm, preferably below 10 µm and in particular is below 5 µm and at least 0.2% by weight, preferably at least 0.5% by weight and in particular more than 1% by weight of the premix to be compressed.

In addition to the ingredients mentioned, surfactant, builder and disintegration aid, or In the process according to the invention, the particulate to be compressed can be used in its place Premix additionally one or more substances from the group of bleaches, bleach activators, enzymes, pH adjusters, fragrances, perfume carriers, fluorescent agents, color substances, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, ver contain graying inhibitors, color transfer inhibitors and corrosion inhibitors.

Sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance among the compounds which serve as bleaching agents and produce H ₂ O _{2 in water.} Other useful bleaching agents are, for example, sodium percarbonate, peroxypyro phosphates, citrate perhydrates and _{peracid salts or peracids that provide H 2} O ₂ , such as per benzoate, peroxophthalate, diperazelaic acid, phthaloimino peracid or diperdodecanedi acid. When using the bleaching agents, too, it is possible to dispense with the use of surfactants and / or builders, so that pure bleaching agent tablets can be produced. If cleaning or bleach tablets for machine dishwashing are produced, then bleaches from the group of organic bleaches can also be used. Typical organic bleaching agents are the diacyl peroxides, such as e.g. B. dibenzoyl peroxide. Further typical organic bleaching agents are the peroxy acids, the examples being particularly 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 monoper phthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxyla rinsic acid, peroxystearic acid, ε-hexycapthalimoperic acid, ε-phthalapthalimoperic 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, 2-oxy-diperoxy-azelaic acid, diperoxy-diperoxy-diperoxy, diperoxy-diperoxy-diperoxy-diperoxy-diperoxy-diperoxy, diperoxy 1,4-diacid, N, N-terephthaloyl-di (6-aminopercaproic acid) can be used.

As a bleaching agent in moldings for machine dishwashing, chlorine or 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, Dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with Cations such as potassium and sodium can be considered. Hydantoin compounds such as 1,3-dichloro-5,5- dimethylhydanthoin are also suitable.

To be able to use a verbes when washing or cleaning at temperatures of 60 ° C and below To achieve an effective bleaching effect, bleach activators can be incorporated into the inventive Detergent tablets are incorporated. As bleach activators can nen compounds which under perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or given otherwise substituted perbenzoic acid can be used. Substan are suitable zen, the O- and / or N-acyl groups of said number of carbon atoms and / or optionally carry substituted benzoyl groups. Multiple acylated alkylenediamines are preferred, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, esp special tetraacetylglycoluril (TAGU), N-acylimide, especially N-nonanoyl succinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or iso nonanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular Phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol coli diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to or in place of conventional bleach activators, you can also use so-called bleach catalysts are incorporated into the shaped bodies. With this fabric fen are bleach-intensifying transition metal salts or transition metal complexes such as Mn-, Fe-, Co-, Ru- or Mo-salen 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 available as bleach catalysts can be used.

In particular, enzymes from the class of hydrolases such as protea come as enzymes sen, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned are possible. All of these hy drolasen wear in the laundry to remove stains such as protein, fat or starchy stains and graying. Cellulases and other Glykosylhy Drolasen can also be done by removing pilling and microfibrils Contribute to the preservation of color and to increasing the softness of the textile. To bleach or to Oxidoreductases can also be used to inhibit color transfer. Special those are well suited from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as from their genetically modified variants obtained enzymatic active ingredients. Before Proteases of the subtilisin type and in particular proteases derived from Ba cillus lentus are used. Here are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enes enzymes or from protease, amylase and lipase or lipolytic enzymes or Protease, lipase or lipolytic enzymes and cellulase, but in particular Protease and / or lipase-containing mixtures or mixtures with lipolytically acting Enzymes of particular interest. Examples of such lipolytic enzymes are the well-known cutinases. Peroxidases or oxidases have also come to an agreement Cases proven to be suitable. Suitable amylases include in particular alpha- Amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferred wise cellobiohydrolases, endoglucanases and -glucosidases, which also cellobiases ge are called, or mixtures of these are used. Since different cellulase Differentiating types by their CMCase and Avicelase activities can be distinguished by ge Targeted mixtures of the cellulases set the desired activities.

The enzymes can be adsorbed on carrier substances or embedded in coating substances in order to to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5% by weight, preferably 0.5 to be about 4.5% by weight.

In addition, the detergent tablets can also contain components which have a positive effect on the ability of textiles to be washed out with oil and grease (so-called called supposed repellents). This effect is particularly noticeable when a textile becomes dirty is that already several times with a detergent according to the invention that this Contains oil and grease dissolving components, has been washed. Among the preferred oil and Fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methylhydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and of hydroxypropoxyl groups from 1 to 15 wt .-%, each based 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, esp special polymers made from 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 acid and terephthalic acid are preferred re-polymers.

The shaped bodies can be derivatives of diaminostilbene disulfonic acid as optical brighteners or contain their alkali metal salts. Suitable are e.g. B. Salts of 4,4'-bis (2-anilino-4- morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or a similar structure Compounds which, instead of the morpholino group, have a diethanolamino group, a Me thylamino group; carry an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyryl type can be present, z. B. the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyls, 4,4'-bis (4-chloro-3-sulfostyryl) - diphenyls, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls. Mixtures of the pre called brighteners can be used.

Dyes and fragrances are the detergent and cleaning agent form according to the invention bodies added to improve the aesthetic impression of the products and the In addition to performance, consumers have a visual and sensory “typical and unmistakable” feature As perfume oils or fragrances, individual Fragrance compounds, e.g. B. the synthetic products of the ester, ether, Alde type hyde, ketones, alcohols and hydrocarbons can be used. Fragrance compound genes of the ester type are e.g. B. benzyl acetate, phenoxyethyl isobutyrate, p-tert.- Butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl carbinylacetate, phenylethyl acetate, Linalyl benzoate, benzyl formate, ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, Styrallyl propionate and benzyl salicylate. The ethers include, for example, benzylethyl lether, to the aldehydes z. B. the linear alkanals with 8-18 carbon atoms, citral, citronel lal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, Lilial and Bourgeo nal, to the ketones z. B. the ionones, ∝-Isomethylionon and Methylcedrylketon, to the Alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and ter pineol, the hydrocarbons mainly include terpenes such as limonene and Pinene. However, mixtures of different fragrances are preferably used which create an appealing fragrance together. Such perfume oils can also be natural che fragrance mixtures contain as they are available from vegetable sources, z. B. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Are also suitable Muscat, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well Orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The content of the detergent and cleaning agent form according to the invention is usually in the range grains of dyes below 0.01 wt .-%, while fragrances up to 2 wt .-% of the ge the entire formulation.

The fragrances can be incorporated directly into the agents according to the invention, it but it can also be advantageous to apply the fragrances to a carrier that ensures the adhesion of the perfume on the laundry and a slower release of fragrance for ensure a long-lasting fragrance of the textiles. As such carrier materials have been found at for example cyclodextrins proven, with the cyclodextrin-perfume complexes in addition can still be coated with other auxiliaries.

In order to improve the aesthetic impression of the agents according to the invention, they can colored with suitable dyes. Preferred dyes, the choice of which is the A person skilled in the art poses no difficulty, have a high storage stability and unemp sensitivity to the other ingredients of the remedy and to light as well as none pronounced substantivity towards textile fibers so as not to stain them.

The moldings according to the invention are first produced by the dry process Mixing the ingredients, which can be pre-granulated in whole or in part, and on Closing information, in particular compression into tablets, whereby on conventionally which procedures can be used. For the production of the invention The pre-mix is molded into a so-called die between two punches condensed into a solid grain primate. This process, hereinafter referred to briefly as a tablet is divided into four sections: Dosing, compression (elasti c deformation), plastic deformation and ejection.

First, the premix is introduced into the die, with the filling quantity and thus the weight and shape of the resulting shaped body due to the position of the lower one Stamp and the shape of the pressing tool can be determined. The consistent dosage tion, even with high throughputs of molded bodies, is preferably carried out via a volumetric Dosing of the premix reached. In the further course of the tableting, the touches Upper punch the premix and lowers further in the direction of the lower punch. At this compression the particles of the premix are pressed closer to each other where at the void volume within the filling between the punches continuously decreases. From a certain position of the upper punch (and thus from a certain th pressure on the premix) the plastic deformation begins, in which the particles flow together and it comes to the formation of the shaped body. Depending on the physical Depending on the properties of the premix, some of the premix particles will also be reduced presses and there is sintering of the premix at even higher pressures. At increasing pressing speed, so high throughput, the phase of the elasti rule deformation is shortened more and more, so that the resulting moldings more or may have less large cavities. In the last step of the tableting, the finished molded body pressed out of the die by the lower punch and through subsequent transport devices are transported away. At this point it is just that Weight of the molded body finally determined because the compacts due to physical Processes (stretching back, crystallographic effects, cooling, etc.) their shape and size can still change.

Tableting takes place in commercially available tablet presses, which are principally equipped with single or double stamps can be equipped. In the latter case, not only the waiter will ram used to build up pressure, the lower ram also moves during the Pressing process on the upper punch, while the upper punch presses down. For Eccentric tablet presses are preferably used for small production quantities which the punch or stamps are attached to an eccentric disk, which in turn is attached to a Axis is mounted with a certain rotational speed. The movement of this The ram is comparable to the way a conventional four-stroke engine works. The Ver Pressing can be done with one upper and one lower punch, but more can also be used be attached to an eccentric disc, the number of Matrizenbohrun 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 one chooses rotary tablet presses, with which on a so-called called the die table a larger number of dies is arranged in a circle. The The number of dies varies, depending on the model, between 6 and 55, although larger dies are also available are commercially available. Each die on the die table is an upper and a lower assigned stamp, in turn the pressing pressure active only through the upper or lower stamp, but can also be built up by both stamps. The matrix table and the Punches move around a common vertical axis, whereby the punches with the help of rail-like cam tracks during the revolution in the positions for Be filling, compression, plastic deformation and ejection. At the stel len on which a particularly serious raising or lowering of the stamp is required This is (filling, compressing, ejecting), these cam paths are through additional che low-pressure pieces, pull-down rails and lifting tracks are supported. The filling Development of the die takes place via a rigidly arranged feed device, the so-called Filling shoe which is connected to a storage container for the premix. The press The pressure on the premix is individual via the press paths for the upper and lower punches adjustable, whereby the pressure build-up due to the rolling of the punch shaft heads past ver adjustable pressure rollers happens.

Rotary presses can also verse with two filling shoes to increase throughput hen, where only a semicircle must be run through to produce a tablet the must. To produce two-layer and multi-layer moldings, several fillers are used shoes arranged one behind the other without the lightly pressed first layer in front of the further filling is ejected. By appropriate process management are on this Wei se also coat and dot tablets can be produced, which have an onion skin-like structure have, in the case of the point tablets the top of the core or core layers is not covered and thus 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 for pressing at the same time the. The throughputs of modern rotary tablet presses are over a million molds body per hour.

When tableting with rotary presses, it has proven to be advantageous to use the Ta perform pelleting with the lowest possible weight fluctuations of the tablet. In this way, the fluctuations in the hardness of the tablet can also be reduced. Minor Weight fluctuations can be achieved in the following ways:

Use of plastic inserts with small thickness tolerances

• - Low number of revolutions of the rotor
• - Big filling shoes
• - Adjustment of the filling shoe wing speed to the speed of the rotor
• - Filling shoe with constant powder height
• - Decoupling of the filling shoe and powder feed

To reduce caking of the stamps, all of the technical be recognized non-stick coatings. Plastic coatings are particularly advantageous, Plastic inserts or plastic stamps. Rotating punches have also proven to be an advantage proved liable, with the upper and lower punches being designed to be rotatable if possible should. In the case of rotating stamps, a plastic insert can usually be dispensed with become. Here the stamp surfaces should be electropolished.

It was also found that long pressing times are advantageous. These can be with pressure rails, several pressure rollers or low rotor speeds. Since the Fluctuations in hardness of the tablet caused by fluctuations in the compressive forces den, systems should be used that limit the pressing force. Here elasti cal stamps, pneumatic compensators or resilient elements are incorporated in the force path are set. The pressure roller can also be designed to be resilient.

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, Horn & Noack Pharmatechnik GmbH, Worms, IMA Packaging systems GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms. Other providers are for example Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Li verpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy N. V., Halle (BE / LU) and Me diopharm Kamnik (SI). The hydraulic double, for example, is particularly suitable Druckpresse HPF 630 from LAEIS, D. Tableting tools are for example from the companies Adams Tablettierwerkzeuge, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber & Sons GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharmatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Werkzeugbau, Tamm. Other providers are z. B. the Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).

The shaped bodies can ge in a predetermined spatial shape and predetermined size be manufactured. Practically all practically manageable designs come as the spatial shape considerations, for example training as a table, rods or bars form, cube, cuboid 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 form of presentation from the tablet to to compact cylinder pieces with a ratio of height to diameter above 1.

The portioned compacts can each be used as separate individual elements be designed that the predetermined dosage of the washing and / or cleaning medium corresponds. But it is also possible to form compacts that have a plurality connect such mass units in a compact, in particular by vorgege At the same predetermined breaking points, smaller portioned units can be easily separated hen is. For the use of laundry detergents in machines of the type common in Europe with horizontally arranged mechanics, the formation of the portioned compacts as Tablets, in cylinder or cuboid shape, may be useful, with a diameter / height Ratio in the range of about 0.5: 2 to 2: 0.5 is preferred. Commercially available hydrau Like presses, eccentric presses or rotary presses are particularly suitable devices special for the production of such compacts.

The three-dimensional shape of another embodiment of the molded body is in its dimensions adapted to the dispenser of standard household washing machines, so that the Shaped bodies can be dosed directly into the dispensing compartment without a dosing aid, wherever it dissolves during the wash-in process. But it goes without saying that there is also a mission the detergent tablet easily possible via a dosing aid and within the scope of the present invention preferred.

Another preferred molded body that can be produced has a plate or Tabular structure with alternating thick long and thin short segments, so that individual segments of this "bolt" at the predetermined breaking points, which thin the short ones Segments can be displayed, canceled and entered into the machine. This The principle of the “bar-shaped” molded body detergent can also be used in other geometrical rule shapes, for example perpendicular triangles, which 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 form a uniform Tablet are compressed, but that moldings are obtained that have several layers ten, i.e. at least two layers. It is also possible that this ver different layers have different dissolution rates. From this you can advantageous application properties of the shaped bodies result. If at For example, components are contained in the moldings that mutually nega tive influence, so it is possible to have one component in the more rapidly soluble layer to integrate and to incorporate the other component in a more slowly soluble layer th, so that the first component has already reacted by the time the second goes into solution. The layer structure of the molded body can be done in a stack, with a lo The process of solving the inner layer (s) at the edges of the molding already takes place if the outer layers are not yet completely dissolved, but it can also be a complete covering of the inner layer (s) by the outer layer (s) Layer (s) are reached, resulting in a prevention of the early resolution of Be constituents 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, where a peroxy bleach is contained in at least one of the inner layers, while in the case of the stack-shaped shaped body the two cover layers and in the case of the envelope-shaped body Shaped body, however, the outermost layers are free from peroxy bleach. Farther it is also possible to use peroxy bleaches and bleach activators which may be present and / or to spatially separate enzymes from one another in a shaped body. Such more Layered molded bodies have the advantage that they do not only have a dispensing compartment or via a metering device which is added to the wash liquor can be; rather, in such cases it is also possible to direct the molded body th contact with the textiles in the machine without staining Bleach and the like would be feared.

Similar effects can also be achieved by coating individual components the detergent and cleaning agent composition to be compressed or the whole Achieve molded body. For this purpose, the body to be coated can, for example, with aqueous solutions or emulsions are sprayed, or via the method of Melt coating obtained a coating.

After pressing, the detergent tablets have a high level of stability. The breaking strength of cylindrical shaped bodies can be determined from the measurable variable of the diametrical breaking stress. This can be determined according to

Here, σ stands for the 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 Cause breakage of the molding, D is the molding diameter in meters and t is the Height of the moldings.

Another object of the present invention is the use of bentonites, after mixing with other processing components in a manner known per se are pressed into detergent tablets to increase the hardness and reducing the disintegration time of detergent tablets, wherein at least 70% by weight of the bentonite particles, particle sizes between 400 and 1600 μm exhibit. Through the use of the aforementioned bentonites, which after mixing with other Components are compressed to detergent tablets, the physical properties of the moldings can be significantly improved, such as the following the following examples.

Examples

Granulation in a 50 liter ploughshare mixer from Lödige produced a ten sidhaltiges granules (composition see Table 1) produced, which as a basis for a particulate premix was used. Following the granulation were the granules in a fluidized bed apparatus from Glatt at an inlet air temperature dried at 60 ° C over a period of 30 minutes. After drying were Fine parts <0.4 mm and coarse grain parts <1.6 mm are screened off.

This premix was made by mixing the surfactant-containing granules with bleach tel, bleach activator and other treatment components. The invent molded bodies E according to the invention contained processed bentonite. For this purpose a Bentonite of the type Ex0030 from Süd-Chemie on a roller compactor from the company Alexanderwerk compacted into a scab. The scab was then placed in a sieve granulator broken and sieved between 400 and 1600 µm. The comparison molded body per V contained the unprocessed commercial product. The particle size distribution of the The bentonite used is shown in Table 2.

The premixes were made into tablets (diameter: 44 mm in a Korsch eccentric press) mm, height: 22 mm, weight: 37.5 g). The pressure was set so that that in each case two series of moldings were obtained (E, E 'and V, V') which are in differ in their hardness. The composition of the premixes to be injected (and thus the shaped body) is shown in Table 3.

Table 1

Composition of the surfactant granulate [% by weight]

Table 2

Sieve numbers of the bentonites used [mm% by weight]

Table 3

Composition of the premixes [% by weight]

Tabelle 4

Waschmitteltabletten [physikalische Daten]

Durch den erfindungsgemäßen Einsatz der Desintegrationshilfsmittel (Bentonite) werden die Zerfallszeiten im Vergleich zu handelsüblichen Produkten deutlich verbessert. The hardness of the tablets was measured after two days of storage by deforming the tablet until it broke, the force acting on the side surfaces of the tablet and determining the maximum force that the tablet withstood. To determine the tablet disintegration, the tablet was placed in a beaker with water (600 ml of water, temperature 25 ° C.) and the time to complete tablet disintegration was measured. The experimental data are shown in Table 4.

Table 4

Detergent tablets [physical data]

By using the disintegration aids (bentonites) according to the invention, the disintegration times are significantly improved in comparison with commercially available products.

Claims (18)

1. Detergent tablets made from compacted particulate detergent and cleaning agents, characterized in that they contain bentonites in amounts of 0.1 to 20% by weight, based on the weight of the molding, with at least 70% by weight the bentonite particles have particle sizes between 400 and 1600 µm. 2. detergent tablets according to claim 1, characterized in that that they are bentonite phyllosilicates with a montmorillonite content of more than 60 % By weight, preferably more than 75% by weight and in particular more than 90 % By weight, each based on the weight of the phyllosilicate. 3. Washing and cleaning agent tablets according to one of claims 1 or 2, characterized characterized in that they contain pure montmorillonite as bentonite. 4. Washing and cleaning agent tablets according to one of claims 1 to 3, characterized characterized in that they are modified by quaternary ammonium compounds Bento nite included. 5. detergent tablets according to any one of claims 1 to 4, characterized characterized in that they prefer the bentonite in amounts of 0.2 to 17.5% by weight wise from 0.5 to 15 wt .-% and in particular from 1 to 10 wt .-%, each based on the weight of the molding included. 6. detergent tablets according to one of claims 1 to 5, characterized characterized in that at least 80 wt .-%, preferably at least 85 wt .-% and in particular at least 90% by weight of the bentonite particle size contained in them have between 400 and 1600 µm. 7. detergent tablets according to one of claims 1 to 6, characterized characterized in that at least 70 wt .-%, preferably at least 80 wt .-% and in particular at least 90% by weight of the bentonite particle size contained in them ßen have between 400 and 1200 µm. 8. detergent tablets according to one of claims 1 to 7, characterized characterized in that a maximum of 40 wt .-%, preferably a maximum of 30 wt .-% and ins particular maximum 20 wt .-% of the bentonite particle sizes contained in them below 600 microns, it is preferred that at least 30 wt .-%, before preferably at least 40% by weight and in particular at least 50% by weight of the bento nite particle sizes above 800 microns. 9. Washing and cleaning agent tablets according to one of claims 1 to 8, characterized characterized in that they contain bentonite-containing compounds which are at least 50 % By weight bentonite, based in each case on the weight of the compound, wherein at least 70% by weight of the compounds, particle sizes between 400 and 1600 µm exhibit. 10. Washing and cleaning agent tablets according to one of claims 1 to 9, characterized characterized in that they also have a disintegration aid, preferably a Disintegration aid based on cellulose, preferably in granular, co-granulated form ter or compacted form, in amounts of 0.5 to 10% by weight, preferably of 3 up to 7% by weight and in particular from 4 to 6% by weight, based in each case on the shape body weight, included. 11. Process for the production of detergent tablets by form giving compression of a particulate premix, characterized in that that the premix bentonite in amounts of 0.1 to 20 wt .-%, based on the Premix, contains, wherein at least 70 wt .-% of the bentonite particles particle size have between 400 and 1600 µm. 12. The method according to claim 11, characterized in that the premix bentonite, preferably phyllosilicates with a montmorillonite content of more than 60% by weight, preferably more than 75% by weight and in particular more than 90% by weight, each based on the weight of the phyllosilicate, in amounts of 0.5 to 15% by weight, preferably contains from 1 to 10% by weight. 13. The method according to any one of claims 11 or 12, characterized in that at least at least 70% by weight, preferably at least 80% by weight and in particular at least 90% by weight of the bentonite introduced into the premix particle sizes between 400 and 1200 µm. 14. The method according to any one of claims 11 to 13, characterized in that the part Chen-like premix additionally contains surfactant-containing granulate (s) and a Bulk weight of at least 500 g / l, preferably at least 600 g / l and in particular which has at least 700 g / l. 15. The method according to claim 15, characterized in that the surfactant-containing granules 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. 16. The method according to any one of claims 15 or 16, characterized in that the Surfactant-containing granules, anionic and / or nonionic surfactants and builders contains and total surfactant contents of at least 10 wt .-%, preferably at least at least 20% by weight and in particular at least 25% by weight. 17. The method according to any one of claims 12 to 17, characterized in that the part Chen-like premix additionally one or more substances from the group of Bleaches, bleach activators, enzymes, pH adjusters, fragrances, perfume carriers, Fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion contains sion inhibitors. 18. Use of bentonites to increase hardness and reduce disintegration time of detergent tablets, at least 70% by weight of the Bentonite particles have particle sizes between 400 and 1600 µm.