WO2000065017A1 - Detergent tablets containing bleaching agents - Google Patents

Abstract

The invention relates to detergent forms that are characterised by a high degree of hardness and at the same time, by a short decomposition time. According to the invention, the detergent forms contain percarbamide. To this end, the percarbamide is mixed with other components and then compacted into the detergent forms.

Description

 "Detergent tablets containing bleach"

The present invention relates to detergent tablets which contain bleach. In particular, the invention relates to shaped articles such as detergent tablets, detergent tablets, bleach tablets or

Water softener tablets with bleach.

Detergent and cleaning agent compositions in the form of molded articles, in particular tablets, have long been known in the prior art and have been widely described. In addition to a number of advantages, the form of the molded article also has disadvantages which can affect both the manufacture and use as well as the consumer acceptance. The main advantages of foils such as the fact that the consumer does not have to measure the required amount of product, the higher density and thus the reduced packaging and storage costs and an aesthetic aspect that should not be underestimated are thereby offset by disadvantages such as the dichotomy between acceptable hardness and sufficiently rapid disintegration and Dissolution of the moldings and numerous technological difficulties in production and packaging put into perspective.

In particular, the dichotomy between a sufficiently hard molded body and a sufficiently fast disintegration time is a central problem. Since sufficiently stable, that is to say shape and break-resistant molded articles can only be produced by relatively high compression pressures, there is a strong compression of the molded article components and consequent delayed disintegration of the molded article in the aqueous liquor and thus to a slow release of the active substances in the Washing or cleaning process. The delayed disintegration of the moldings has the further disadvantage that conventional washing and Do not allow detergent tablets to be washed in via the induction chamber of household washing machines, since the tablets do not disintegrate into secondary particles that are small enough to be washed into the washing drum from the induction chamber.

To overcome the dichotomy between hardness, i.e. Transport and handling stability, and easy disintegration of the moldings, many solutions have been developed in the prior art. A particularly well-known approach from pharmacy and extended to the field of detergent tablets is the incorporation of certain disintegration aids which facilitate the access of water or which swell or develop gas or other forms upon access of water. Other proposed solutions from the patent literature describe the compression of premixes of certain particle sizes, the separation of individual ingredients from certain other ingredients, and the coating of individual ingredients or of the entire shaped body with binders.

For example, EP-A-0 522 766 (Unilever) discloses moldings made from a compact, particulate detergent composition containing surfactants, builders and disintegration aids (for example based on cellulose), at least some of the particles being coated with the disintegration agent, which is both binder and also shows disintegration effects when the moldings are dissolved in water. 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.

Further documents which deal with the production of detergent film bodies are EP-A-0 716 144 (Unilever), which describes moldings with an external casing made of water-soluble material, and EP-A-0 711 827 (Unilever) , which contain a citrate with a defined solubility as an ingredient. The use of binders which optionally disintegrating effect (more particularly polyethylene glycol) is A-0 EP-711 828 (Unilever) disclosed in, the detergent tablets described, which by compressing a particulate ^'shaped detergent composition at temperatures between 28 ° C and the melting point of the binding material are produced, always pressing below the melting temperature. From the examples in this document it can be seen that the moldings produced in accordance with their teaching have higher breaking strengths when compression is carried out at elevated temperature.

Detergent tablets in which individual ingredients are present separately from others are also described in EP-A-0 481 793 (Unilever). The detergent tablets disclosed in this document contain sodium percarbonate, which is spatially separated from all other components that could influence its stability. Information on the particle size of the bleaching agent cannot be found in this document.

European patent application EP-A-0 466 484 (Unilever) claims detergent tablets which are produced by pressing particle-shaped material which has particle sizes in the range from 200 to 2000 μm, the upper and lower limits of the particle sizes being not more than 700 μm should differ. The use of bleaching agents is only mentioned as optional in this document, particle size ranges for the bleaching agents are not specified.

The older German patent application DE 198 06 200.1 (Henkel) describes detergent tablets which contain bleaches with an average particle size above 400 μm and are preferably free of fractions below 200 μm. As examples and comparative examples, only moldings which contain sodium perborate are disclosed in this application.

The use of percarbamide is not described in any of the cited prior art documents dealing with detergent tablets. None of the documents mentioned is concerned with the improvement of the Solubility of detergent tablets through targeted use of percarbamide.

The present invention is therefore based on the object of providing detergent tablets which are distinguished by high hardness and have excellent disintegration properties. These laundry detergent and cleaning product form bodies should also be able to be metered through the dispensing chamber without the consumer suffering disadvantages as a result of residues in the dispensing chamber and too little detergent in the wash liquor. In addition to these molded body-specific properties, the washing and cleaning performance of the molded bodies according to the invention should also be exemplary. The advantageous properties of the molded body should not be achieved by additives which only serve to improve the molded body properties, but by the targeted use of substances which also have an effect in the washing and cleaning process.

The invention relates to shaped detergents and cleaning agents made from compressed particulate detergents and cleaning agents which contain percarbamide.

The percarbamide contained in the molded bodies according to the invention is a urea peroxohydrate, which can be described by the formula H2N-CO-NH ₂ Η2O2. Percarbamide comes in the form of white crystals which decompose in the presence of moisture above 40 ° C, is easily soluble in water (800g per liter of water at 20 ° C) and has a melting point of 80-90 ° C (with decomposition ) on. The bulk weight of the commercial product is approx. 600 g / 1.

The hydrogen peroxide content of the percarbamide is theoretically 36.16% by weight, and powdery commercial products usually have hydrogen peroxide contents of at least 35% by weight. An active oxygen content (AO) of 17% by weight (theoretically) or> 16.5% by weight in commercially available powders is calculated from this. Additions of sodium or ammonium dihydrogen phosphate or zinc sulfate improve the thermal stability of the percarbamide. Percarbamide, which is often referred to as "solid hydrogen peroxide" due to its high AO content, was first obtained from Tanatar in 1908 by pouring 30% H ₂ O ₂ into a solution of urea in water and then cooling it. The industrial production takes place in principle in the same way, by mixing finely divided urea with 35% hydrogen peroxide in the presence of stabilizers. Percarbamide is obtained from the resulting solutions by freezing and concentrating. The raw product separated from the mother liquor is carefully dried at 30 to 40 ° C. Another technical Process for the production of percarbamide consists in spraying 35% H ₂ O ₂ onto a moving bed of urea particles (fluidized bed granulation) Percarbamide is commercially available from Degussa, Solvay-Interox and Peroxid-Chemie GmbH, Pullach mainly in hair bleaching and coloring agents, as a disinfectant el (for example for contact lenses) and partially used as a wound treatment agent.

The detergent tablets according to the invention preferably contain the percarbamide in amounts of 1 to 40% by weight, preferably 5 to 30% by weight, particularly preferably 7.5 to 25 and in particular 10 to 20% by weight, each based on the molded body weight.

The percarbamide is preferably used within certain particle size ranges. Preferred detergent tablets according to the invention are those in which the percarbamide has an average particle size above 0.3 mm.

In the context of the present invention, the average particle size is a computational size which results from the multiplication of the percentage of a sieve fraction by the mesh size of the sieve. The individual values of such mean values can vary widely if, for example, extremely small and extremely large particles are present side by side. In the context of the present invention, however, it is preferred that the particle size distribution of the percarbamide does not vary widely, but is relatively narrow around the mean. In particular, fine fractions should be largely excluded, so that detergent tablets are preferred in the context of the present invention, in which the contained therein Percarbamide has an average particle size above 0.3 mm and is preferably substantially free of particles with sizes below 0.2 mm.

In the context of the present invention, “substantially free” means contents below 2% by weight, preferably below 1% by weight and in particular below 0.5% by weight.

It is not only preferred in the context of the present invention that dust and fine fractions of the percarbamide are largely absent, the content of particles with a size below 0.4 mm should also be kept as small as possible. Preference is given to detergent tablets in which the percarbamide contains less than 30% by weight, preferably less than 20% by weight and in particular less than 10% by weight, of particles having a size below 0.4 mm and preferably more than 10% by weight, preferably more than 20% by weight and in particular more than 30% by weight, of particles of a size above 0.8 mm, it being particularly preferred that the percarbamide be substantially free of particles of sizes above 1, Is 6 mm.

As a result, the proportion of larger percarbamide particles should be as high as possible. Here again, it is preferred if the particles of the percarbamide are not only larger than 0.4 mm, but significantly larger, for example larger than 0.8 mm. Nevertheless, the percarbamide should of course not be incorporated in the form of coarse lumps in the detergent tablets of the present invention. From a practical point of view, particle sizes of the percarbamide below 2.0 mm have proven successful, it being preferred if the percarbamide contained in the detergent tablets is substantially free of particles with sizes above 1.6 mm - see above.

It is also possible according to the invention to granulate the percarbamide with other raw materials and to adjust it to the preferred particle spectrum by grinding and sieving operations. According to the invention, it is therefore also possible to use compounds which consist of at least 60% by weight, based on the compound, of percarbamide, these compounds preferably meeting the particle size criteria mentioned. According to the invention, detergent tablets are also preferred Contain percarbamide-containing compounds which contain at least 60% by weight percarbamide, in each case based on the weight of the compound.

It is possible within the scope of the present invention to incorporate acidic constituents into the molded body. If the moldings contain carbonates, carbon dioxide is released by reaction of the acid with the carbonate or hydrogen carbonate, this "effervescent effect" being able to promote disintegration. Usually, oligomeric oligocarboxylic acids such as succinic acid, maleic acid and in particular cifronic acid are used in effervescent systems. Preferred embodiments of the present invention however, the detergent tablets do not have an "effervescent tablet", ie preferred detergent tablets are free of oligomeric oligocarboxylic acids, especially citric acid.

It is also technically possible to coat the molded body with a coating that covers the entire molded body. Coated detergent tablets of this type can be produced by spraying a melt or solution of the coating material onto the molded article or by 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 that covers the entire tablet.

As already mentioned above, detergents and cleaning agents are molded; the disintegration times of which are above 60 seconds, usually almost completely insoluble and therefore no longer washable. With sufficient high compression pressures during production, tablets can be produced with each premix, which have disintegration times of more than 60 seconds and which, according to previous experience, are unsatisfactory in terms of application technology. So far, the compression pressure and with it the achievable hardness of the tablets have been limited. The use of percarbamide according to the invention also makes it possible to produce harder tablets which, despite disintegration times of over 60 seconds, still disintegrate into secondary articles and can thus be washed in. Although it is possible according to the invention to veφressen the tablets so hard that disintegration times over two minutes can be achieved, is over From an application point of view (induction cycle of household washing machines), the production of molded articles according to the invention which have disintegration times of less than 100 seconds is preferred. Even with the use according to the invention, tablets which disintegrate quickly and easily are preferred, so that in the context of the present invention, detergent tablets which in water at 30 ° C. in less than 60 seconds completely disintegrate into their secondary particles which are so small that they separate Let it wash in via the dispenser of a household washing machine, are particularly preferred.

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

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

Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration auxiliaries, in each case based on the molded article weight. Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred washing and cleaning agent shaped bodies such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 contain up to 6 wt .-%. Pure cellulose has the formal gross composition (C ₆ Hιoθ ₅ ) _n and is formally considered 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 hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the disintegrant based on cellulose.

The cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be treated. Detergent tablets, which contain disintegrants in granular or, optionally, granulated 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 documents also contain more information on the production of granulated, compacted or cogranulated To remove cellulose disintegrant. 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 produced by the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 μm and can be compacted, for example, into granules with an average particle size of 200 μm.

Detergent tablets 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 molded body weight.

In order to develop the desired bleaching performance, the detergent tablets of the present invention contain percarbamide. Of course, it is also possible according to the invention to incorporate further bleaching agents into the detergent tablets according to the invention, the usual bleaching agents from the group sodium perborate monohydrate, sodium perborate tetrahydrate and sodium percarbonate having proven particularly useful. If the percarbamide is to be used together with other bleaching agents, one has Mixture of percarbamide and sodium percarbonate has proven itself, the weight ratio of percarbamide to sodium percarbonate advantageously being in the range from 1: 100 to 100: 1.

“Sodium percarbonate” is a non-specific term for sodium carbonate peroxohydrates, which strictly speaking are not “percarbonates” (ie salts of percarbonic acid) but hydrogen peroxide adducts with sodium carbonate. The merchandise has the average composition 2 Na ₂ CO ₃ -3 H ₂ O ₂ and is therefore not peroxy carbonate. Sodium percarbonate often forms a white, water-soluble powder with a density of 2.14 ^"3 , which easily breaks down into sodium carbonate and bleaching or oxidizing oxygen.

Sodium carbonate peroxohydrate was first obtained in 1899 by ethanol precipitation from a solution of sodium carbonate in hydrogen peroxide, but was mistakenly regarded as peroxy carbonate. It was not until 1909 that the compound was recognized as a hydrogen peroxide addition compound, but the historical name "sodium percarbonate" has become established in practice.

The industrial production of sodium percarbonate is mainly produced by precipitation from an aqueous solution (so-called wet process). Here, aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium percarbonate is precipitated by salting-out agents (predominantly sodium chloride), crystallization aids (for example polyphosphates, polyacrylates) and stabilizers (for example Mg ²⁺ ions). The precipitated salt, which still contains 5 to 12% by weight of mother liquor, is then centrifuged off and dried at 90 ° C. in fluid bed dryers. The bulk density of the finished product can vary between 800 and 1200 g / 1 depending on the manufacturing process. As a rule, the percarbonate is stabilized by an additional coating. Coating processes and materials used for coating are widely described in the patent literature. In principle, according to the invention, all commercially available types of percarbonate can be used, such as those offered by the companies Solvay Interox, Degussa, Kemira or Akzo. With percarbamide - as with all bleaching agents used - the content of the molded body in this substance depends on the intended use of the molded body. While conventional universal detergents in tablet form contain between 5 and 30% by weight, preferably between 7.5 and 25% by weight and in particular between 12.5 and 22.5% by weight of percarbamide, the contents are in bleach or bleach booster tablets between 15 and 50% by weight, preferably between 22.5 and 45% by weight and in particular between 30 and 40% by weight.

In addition to the percarbamide and the optionally additionally used bleaching agents, the detergent tablets according to the invention can contain bleach activator (s), which is preferred in the context of the present invention. Bleach activators are incorporated into detergents and cleaning agents to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable are substances 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, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially 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 triacetoxy and 2,5-diacetyloxy and 2,5-glycethylacetyl, ethylene glycol 2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be incorporated into the moldings. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also 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 be used as bleaching catalysts.

If the molded articles according to the invention contain bleach activators, they each contain, based on the total molded article, between 0.5 and 30% by weight, preferably between 1 and 20% by weight and in particular between 2 and 15% by weight, of one or more Bleach activators or bleach catalysts. These quantities can vary depending on the intended use of the molded articles produced. For example, bleach activator contents of between 0.5 and 10% by weight, preferably between 2 and 8% by weight and in particular between 4 and 6% by weight, are common in typical universal detergent tablets, while bleach tablets contain quite high contents, for example between 5 and 30% by weight, preferably between 7.5 and 25% by weight and in particular between 10 and 20% by weight. The person skilled in the art is not restricted in its freedom of formulation and can thus produce more or less bleaching detergent tablets, detergent tablets or bleach tablets by varying the bleach activator and bleach content.

A particularly preferred bleach activator is N, N, N ', N'-tetraacetylethylenediamine, which is widely used in detergents and cleaning agents. Accordingly, preferred shaped detergents and cleaning agents are characterized in that tetraacetylethylenediamine is used as the bleach activator in the amounts mentioned above.

In addition to the ingredients mentioned, the detergent tablets according to the invention can contain further ingredients, the amounts of which depend on the intended use of the tablets. In particular, substances from the groups of surfactants, builders and polymers are suitable for use in the detergent tablets according to the invention. Here too, the person skilled in the art will have no difficulty in selecting the individual components and their amounts. For example, a universal detergent tablet will contain higher amounts of surfactant (s), while a bleach tablet might even use it entirely can be dispensed with. The amount of builder (s) used also varies depending on the intended use.

The detergent tablets according to the invention can contain all of the builders customarily used in detergents and cleaning agents, in particular thus 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 + ι H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ "yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171 .

Amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus 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 "amoφh" is also understood to mean "roentgenamoφh". 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 are added

Electron diffraction experiments provide washed-out or even sharp diffraction maxima. This is to be integrated so that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Particularly preferred are compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray silicates.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula

nNa ₂ O ^' (ln) K ₂ O ^• Al ₂ O ₃ ^' (2 - 2.5) SiO ₂ ^' (3.5 - 5.5) H ₂ O

can be described. The zeolite can be used both as a builder in a granular compound and can also be used for a kind of "powdering" of the entire mixture to be eaten, usually using both ways of incohering the zeolite into the premix. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Of course, it is also possible to use the generally known phosphates as builders, provided that such use should not be avoided for ecological reasons. Among the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium phosphate (sodium or potassium tripolyphosphate), have the greatest importance in the detergent and cleaning agent industry. Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO ₃ ) n and orthophosphoric acid H ₃ PO in addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues and also contribute to cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 like ^"3 , melting point 60 °) and as a monohydrate (density 2.04 like ^{" 3} ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ) at 200 ° C, in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO is acidic; it occurs when phosphoric acid is adjusted to a pH 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, is a white salt with a density of 2.33 ^"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 gladly ^"3 , water loss at 95 °), 7 mol. (Density 1.68 gladly ^{" 3} , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 ^'3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to the diphosphate Na P ₂ O when heated more strongly. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO, is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO, are colorless crystals that like a dodecahydrate a density of 1.62 ^"3 and a melting point of 73-76 ° C (decomposition), as a decahydrate (corresponding to 19-20% P ₂ O) a melting point of 100 ° C and in anhydrous form (corresponding to 39- ^ 0% P ₂ O ₅ ) have a density of 2.536 ^"3. Trisodium phosphate is readily soluble in water with an alkaline reaction and is prepared by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH Tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 ^"3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

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

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow 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 Oιo (sodium tripolyphosphate), is a water-free, non-hygroscopic, white, crystallizing with 6 H ₂ O, Water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered 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% strength 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 occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH - ^ Na ₃ K ₂ P ₃ Oιo + H ₂ O

According to the invention, these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.

Organic cobuilders which can be used in the detergent tablets according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.

Usable organic builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, polycarboxylic acids being those Carboxylic acids are understood that carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric 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 acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value for detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

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

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

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group. Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 2,000 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. The content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

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

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

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

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A-195 40 086 that in addition to cobuilder properties they also have a bleach-stabilizing effect.

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

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE between 3 and 20 and dry glucose 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 can be used.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0427 349, EP-A-0472 042 and EP-A-0 542 496 and international patent applications WO 92/18542 , WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608. 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.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable cobuilders. Ethylene diamine N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates are also preferred in this context and glycerol trisuccinates. Suitable amounts for use in formulations containing zeolite and / or silicate are 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such cobuilders are described, for example, in international patent application WO 95/20029.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, l-hydroxyethane-l, l-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9). Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition, all compounds that are able to form complexes with alkaline earth metal ions can be used as cobuilders.

The amount of builder is usually between 10 and 70% by weight, preferably between 15 and 60% by weight and in particular between 20 and 50% by weight. Again, the amount of builders used depends on the intended use, so that bleach tablets can have higher amounts of builders (for example between 20 and 70% by weight, preferably between 25 and 65% by weight. and in particular between 30 and 55% by weight), for example detergent tablets (usually 10 to 50% by weight, preferably 12.5 to 45% by weight and in particular between 7.5 and 37.5% by weight).

Preferred detergent tablets also contain one or more surfactant (s). Anionic, nonionic, cationic and / or amphoteric surfactants or mixtures of these can be used in the detergent tablets according to the invention. Mixtures of anionic and nonionic surfactants are preferred from an application point of view. The total surfactant content of the molded article is from 5 to 60% by weight, based on the weight of the molded article, with surfactant contents above 15% by weight being preferred.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. As surfactants of the sulfonate type, preference is given to C _{9 3} alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C _{2 8} monoolefins with an end or internal double bond Sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates which are obtained from C ₁ -C ₈ -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures, as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfated products of saturated fatty acids having 6 to 22 carbon atoms, for example capric acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid. As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C ₂ -C ₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the Co-C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. For reasons of washing technology, the C ₂ -C ₆ alkyl sulfates and C ₂ -C ₅ alkyl sulfates and C ₄ -C ₅ alkyl sulfates are preferred. In addition, 2,3-alkyl sulfates, which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C ethoxylated with 1 to 6 mol of ethylene oxide. ₂ -Alcohols, such as 2-methyl-branched C ₉ -n alcohols with an average of 3.5 mol of ethylene oxide (EO) or -C ₂ -ι 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.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, Ci ₂ -ι alcohols with 3 EO or 4 EO, C9-11 alcohol with 7 EO, Cι ₃ -ι alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci ₂ -ι alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-1 4 alcohol containing 3 EO and Ci2-ι ₈ alcohol containing 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol for a Glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

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

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

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

R ¹

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

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ^ 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 are usually obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent ones Acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride can be obtained.

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

R ^] -OR

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

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, Ci-t-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 rest.

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

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

For example, detergent tablets are particularly preferred in which the ratio of anionic surfactant (s) to nonionic surfactant (s) is between 10: 1 and 1:10, is preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2. Preference is also given to detergent tablets which contain surfactant (s), preferably anionic (s) and / or nonionic (s) surfactant (s), in amounts of 5 to 40% by weight, preferably 7.5 to 35% by weight .-%, particularly preferably from 10 to 30 wt .-% and in particular from 12.5 to 25 wt .-%, each based on the molded body weight.

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

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

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

In addition to the constituents mentioned, bleaching agent, bleach activator, builder, surfactant and disintegration aid, the detergent tablets according to the invention can contain further ingredients customary in detergents and cleaning agents from the group of dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, anti-redeposition agents, graying inhibitors, Color transfer inhibitors and corrosion inhibitors included. In order to improve the aesthetic impression of the detergent tablets according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a 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.

Preferred for use in the detergent tablets according to the invention are all colorants which can be oxidatively destroyed in the washing process, and also mixtures thereof with suitable blue dyes, so-called blue toners. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. For example, anionic colorants, e.g. anionic nitroso dyes. A possible colorant is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part

2: 10020), which is available as a commercial product, for example as Basacid Green 970 from BASF, Ludwigshafen, and mixtures of these with suitable blue dyes. Other colorants are Pigmosol Blue 6900 (CI 74160), Pigmosol ^® Green 8730 (CI 74260), Basonyl ^® Red 545 FL (CI 45170), Sandolan ^® Rhodamine EB400 (CI 45100), Basacid ^® Yellow 094 (CI 47005), Sicovit ^® Patent Blue 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), Pigment Blue 15 (CI 74160), Supranol ^® Blue GLW (CAS 12219-32-8, CI Acidblue 221) ), Nylosan ^® yellow N-

7GL SGR (CAS 61814-57-1, CI Acidyellow 218) and or Sandolan ^® Blau (CI Acid Blue 182, CAS 12219-26-0).

When choosing the colorant, care must be taken to ensure that the colorants do not have too strong an affinity for the textile surfaces and especially for synthetic fibers. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stabilities against oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergent or Detergents. In the case of colorants which are readily water-soluble, for example the above-mentioned basacid green or the likewise above-mentioned sandolan blue, colorant concentrations in the range from a few 10 ^"2 to 10 ^{" 3} % by weight are typically chosen. In contrast, in the case of the pigment dyes which are particularly preferred on account of their brilliance, but less readily water-soluble, for example the pigmosol dyes mentioned above, the suitable concentration of the colorant in washing or cleaning agents is typically a few 10 ^"3 to 10 ^{" 4} % by weight.

The moldings can contain optical brighteners of the type of derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. 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. The optical brighteners are in the detergent tablets according to the invention in concentrations between 0.01 and 1% by weight, preferably between 0.05 and 0.5% by weight and in particular between 0.1 and 0.25% by weight. %, each based on the entire molded body, used.

Fragrances are added to the agents according to the invention in order to improve the aesthetic impression of the products and, in addition to the performance of the product, to provide the consumer with a visually and sensorially "typical and distinctive" product. Individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl benzylatepylpionate, allyl cyclohexyl propyl pionate. To the ethers include, for example, benzylethyl ether, the aldehydes include, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones include, for example, the jonones, oc-isomethylionone and methyl cedryl ketone the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and teφineol, the hydrocarbons mainly include teφenes 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, linden blossom 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 fragrance content of the detergent tablets according to the invention is usually 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.

Particularly suitable enzymes are those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxidoreductases can also be used for bleaching or for inhibiting color transfer. Bacterial strains or fungi such as are particularly well suited Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases. The enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.5 to about 4.5% 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, based in each case the nonionic cellulose ether, as well as from the prior art Polymers of phthalic acid and or terephthalic acid or of their derivatives known in the 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.

Another object of the present invention is a process for the production of detergent shaped bodies by shaping molding a particulate premix, which is characterized in that the premix contains percarbamide in amounts of 1 to 40% by weight, based on the premix.

Analogous to the explanations for the detergent tablets according to the invention, variants are also preferred in the method according to the invention in which the premix percarbamide in amounts of 5 to 30% by weight, preferably 7.5 to 25 and in particular 10 to 20% by weight. -%, each based on the weight of the premix.

The statements made above also apply analogously to the particle size distribution of the percarbamide introduced into the process according to the invention. The use of further ingredients can also be transferred completely analogously to the process according to the invention. In preferred processes, the particulate premix additionally contains surfactant-containing granules and has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g / 1.

With regard to the preferred particle size of the percarbamide, reference is made to the above statements. In preferred methods according to the invention, the surfactant-containing granulate has 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.

The further ingredients of the detergent tablets according to the invention can also be incorporated into the method according to the invention to which reference is made to the above statements. Preferred processes are characterized in that the particulate premix additionally contains one or more substances from the group of bleach activators, disintegration aids, enzymes, pH-adjusting agents, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors Contains corrosion inhibitors.

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

For larger throughputs, rotary tablet presses are selected in which a larger number of dies is arranged in a circle on a so-called die table. The number of 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 around a common vertical axis, the stamps being brought into the positions for filling, compression, plastic deformation and ejection by means of rail-like curved tracks during the rotation. 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 pressing pressure on the premix can be individually adjusted via the pressing paths for the upper and lower punches, the pressure being built up by rolling the punch 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.

When tableting with concentricity presses, it has proven to be advantageous to carry out the tabletting with the smallest possible fluctuations in the weight of the tablet. The fluctuations in hardness of the tablet can also be reduced in this way. Small fluctuations in weight 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

- Matching the filler paddle speed to the speed of the rotor

- Filling shoe with constant powder height

- Decoupling of filling shoe and powder feed

All non-stick coatings known from the art are suitable for reducing stamp caking. Plastic coatings, plastic inserts or plastic stamps are particularly advantageous. Rotating punches have also proven to be advantageous, with the upper and lower punches being rotatable if possible should be. In the case of rotating stamps, a plastic insert can generally be dispensed with. The stamp surfaces should be electropolished here.

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

Tableting machines suitable in the context of the present invention are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Hörn & Noack Pharmatechnik GmbH, Worms, IMA Veφackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms. Other providers include Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Liveφool (GB), I. Holand Ltd., Nottingham (GB), Courtoy NV, Halle (BE / LU) and Mediopharm Kamnik (SI ). For example, the hydraulic double pressure press HPF 630 from LAEIS is particularly suitable. D. Tableting tools are, for example, from Adams Tablettierwerkzeuge, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Söhne GmbH, Hamburg, Hofer GmbH, Weil, Hom & Noack, Pharmatechnik GmbH, Worms, Ritter Pharmatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Werkzeugbau, Ta-mm available. Other providers are e.g. Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).

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 of the tablet up 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 approximately 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 induction chamber of commercially available household washing machines, so that the molded body can be metered directly into the induction chamber without metering aid, where it dissolves during the induction 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 single tablet, but that shaped bodies are obtained that have several Have layers, that is, 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, for example, components are contained in the moldings that mutually influence one another negatively, 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. when 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, that is to say 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 stacked molded body the two outer layers and in the shell-shaped molded body the outermost layers, however, 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

2R σ = iτDt

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, which causes the molded body to break, D is the molded body diameter in meters and t is the height of the molded body.

Another object of the present invention is the use of percarbamide to increase the hardness and reduce the disintegration time of detergent tablets. This use of percarbamide according to the invention leads to moldings with advantageous properties, as the examples below show. With regard to preferred embodiments of the use according to the invention (particle sizes, further ingredients, composition of the premix, etc.), what has been said above for the method according to the invention applies analogously.

Examples:

For the production of percarbamide-containing detergent tablets, a surfactant granulate was mixed with other processing components and pressed on a eccentric tablet press to form tablets. The composition of the surfactant granules is given in Table 1 below, the composition of the premix to be treated (and thus the composition of the shaped bodies) can be found in Table 2.

Table 1: Surfactant granules [% by weight]

Table 2: Premix [% by weight]

Shaped body E according to the invention: carbamide peroxide from Peroxid-Chemie, Pullach

Comparative Example V: sodium perborate monohydrate from Degussa

** Terephthalic acid-ethylene glycol-polyethylene glycol ester (Rhodia, Rhône-Poulenc)

The tablet-like premixes E and V were pressed in a Korsch eccentric press into tablets (diameter: 44 mm, height: 22 mm, weight: 37.5 g). The pressure was adjusted so that three series of molded bodies were obtained (E, E ', E "and V, V, V"), which differ in their hardness.

The hardness of the tablets was measured by deforming the tablet to fracture, the force acting on the side surfaces of the tablet and the maximum force that the tablet was able to withstand.

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. The experimental data of the individual tablet series is shown in Table 3:

Table 3: Detergent tablets [physical data]

Claims

Claims:

1. washing and cleaning agent shaped body made of compressed particulate washing and cleaning agent, characterized in that they contain percarbamide.

2. Detergent and molded article according to claim 1, characterized in that it contains percarbamide in amounts of 1 to 40% by weight, preferably 5 to 30% by weight, particularly preferably 7.5 to 25 and in particular 10 to 20 wt .-%, each based on the molded body weight.

3. Detergent and molded article according to one of claims 1 or 2, characterized in that the percarbamide contained in them has an average particle size above 0.3 mm and is preferably substantially free of particles with sizes below 0.2 mm.

4. Detergent and molded article according to one of claims 1 to 3, characterized in that the percarbamide less than 30 wt .-%, preferably less than 20 wt .-% and in particular less than 10 wt .-% particles of a size below 0 , 4 mm and preferably more than 10% by weight, preferably more than 20% by weight and in particular more than 30% by weight, of particles having a size above 0.8 mm, it being particularly preferred that the percarbamide be substantially free of particles larger than 1.6 mm.

5. Detergent and molded article according to one of claims 1 to 4, characterized in that they contain percarbamide-containing compounds which contain at least 60% by weight of percarbamide, in each case based on the weight of the compound.

6. washing and cleaning agent shaped body according to one of claims 1 to 5, characterized in that they are free of oligomeric oligocarboxylic acids, especially citric acid.

7. washing and cleaning agent molded article according to one of claims 1 to 6, characterized in that it additionally contains a disintegration aid, preferably a Disintegration aids based on cellulose, 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 4 to 6% by weight, in each case based on the Molded body weight, included.

8. Detergent and molded article according to one of claims 1 to 7, characterized in that it contains surfactant (s), preferably anionic (s) and / or nonionic (s) surfactant (s), in amounts of 5 to 40% by weight. %, preferably from 7.5 to 35% by weight, particularly preferably from 10 to 30% by weight and in particular from 12.5 to 25% by weight, in each case based on the molded body weight.

9. A process for the production of detergent tablets by shaping a particulate premix, characterized in that the premix contains percarbamide in amounts of 1 to 40% by weight, based on the premix.

10. The method according to claim 9, characterized in that the premix percarbamide in amounts of 5 to 30 wt .-%, preferably from 7.5 to 25 and in particular from 10 to 20 wt .-%, each based on the weight of the premix , contains.

1 1. The method according to any one of claims 9 or 10, characterized in that the particulate premix additionally contains surfactant-containing granules (s) and a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g / 1.

12. The method according to claim 1 1, 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.

13. The method according to any one of claims 9 to 12, characterized in that the particulate premix additionally one or more substances from the group of bleaching agents, bleach activators, disintegration aids, enzymes, pH adjusting agents, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils , Anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.

14. Use of percarbamide to increase the hardness and reduce the disintegration time of detergent tablets.