DE19918722A1 - Detergent formed bodies, e.g. tablets, include percarbamide which acts both as a bleach and as an agent to improve the hardness and decomposition properties - Google Patents

Abstract

A percarbamide is used to increase the hardness of detergent formed bodies and to reduce their decomposition time. An Independent claim is also included for a method of preparing the detergent formed body.

Description

The present invention relates to detergent tablets which Bleach included. In particular, the invention relates to moldings such as Detergent tablets, detergent tablets, bleach tablets or Water softener tablets with bleach.

Detergent and cleaning agent compositions in the form of moldings, tablets in particular have long been known in the prior art and have been widely described. In addition to a number of advantages, the shape of the molded article also has a number of advantages Disadvantages affecting both the manufacture and use as well as consumer acceptance can affect. The main advantages of moldings such as the elimination of Dimension of the required amount of product by the consumer, the higher density and thus the reduced packaging and storage effort and a not to be underestimated Disadvantages such as the dichotomy between acceptable hardness and sufficiently rapid disintegration and dissolution of the moldings as well as numerous technological difficulties in manufacturing and packaging relativized.

In particular, the dichotomy between a sufficiently hard molded body and one Sufficiently fast disintegration time is a central problem. Because sufficiently stable, d. H. Shaped and unbreakable molded articles only through relatively high compression pressures  can be produced, there is a strong compression of the Molded parts and a resulting delayed disintegration of the Shaped body 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 Shaped body has the further disadvantage that conventional washing and Detergent tablets not through the detergent dispenser of household washing machines Allow to be flushed in, as the tablets do not quickly become secondary particles disintegrate, which are small enough to move from the dispenser into the washing drum to be washed in.

To overcome the dichotomy between hardness, i. H. Transport and Handling stability and easy disintegration of the moldings are state of the art many solutions have been developed. A well-known in particular from pharmacy and is an extensive approach in the field of detergent tablets the incorporation of certain disintegration aids that prevent the entry of water facilitate or swell upon entry of water or gas evolving or in another form act disintegrating. Other proposed solutions from the patent literature describe the Compression of premixes of certain particle sizes, the separation of individual ones Ingredients of certain other ingredients as well as the coating of individual ones Ingredients or the entire molded body with binders.

For example, EP-A-0 522 766 (Unilever) discloses molded bodies made of a compact, particulate detergent composition containing surfactants, builders and Disintegration aids (for example based on cellulose), at least a part the particle is coated with the disintegrant, which is both binder and Disintegration effect when dissolving the moldings in water shows. This font also points to the general difficulty of molding with adequate stability to produce good solubility at the same time. The particle size to be compressed Mixture should be above 200 microns, with upper and lower limits of individual particle sizes should not differ from each other by more than 700 µm.

Other publications that deal with the production of detergent tablets, are EP-A-0 716 144 (Unilever), the molded articles with an external shell  describes water-soluble material, as well as EP-A-0 711 827 (Unilever), which as Ingredient contain a citrate with a defined solubility.

The use of binders, which may have an explosive effect (in particular Polyethylene glycol) is disclosed in EP-A-0 711 828 (Unilever), which Detergent tablets describes which by pressing a particulate Detergent composition at temperatures between 28 ° C and the melting point of the binding material are produced, always below the melting temperature is pressed. From the examples of this document it can be seen that the according to their Molded articles produced have higher breaking strengths when increased Temperature is pressed.

Detergent tablets, in which individual ingredients are separated from others, are also described in EP-A-0 481 793 (Unilever). The one in this writing disclosed detergent tablets containing sodium percarbonate, that of all others Components that could affect its stability are physically separate. 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 made by pressing particulate material be, which has particle sizes in the range of 200 to 2000 microns, the The upper and lower limits of the particle sizes should not differ by more than 700 µm. 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 washing and Detergent tablets, which are bleaches with an average particle size Contain above 400 microns and are preferably free of less than 200 microns. As Examples and comparative examples are only molded articles in this application disclosed which contain sodium perborate.

None of the cited prior art documents dealing with washing and Deal with detergent tablets, the use of percarbamide  described. None of the documents mentioned is concerned with the improvement of the Solubility of detergent tablets through the targeted use of Percarbamide.

The present invention is therefore based on the task of washing and To provide detergent tablets, which are characterized by a high hardness and have excellent decay properties. This washing and Detergent tablets should also be dosed through the induction chamber can without the consumer disadvantages due to residues in the Adult detergent dispenser and too little detergent in the wash water. Besides these Shaping-specific properties should also include washing and cleaning services the molded article according to the invention should be exemplary. The beneficial properties of Shaped bodies should not use additives that merely improve the Shaped body properties serve to be achieved, but through the targeted use of Fabrics that also have an effect in the washing and cleaning process.

The invention relates to molded detergent and cleaning product bodies Particulate detergents and cleaning agents containing percarbamide.

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

The hydrogen peroxide content of the percarbamide is theoretically 36.16% by weight, Powdered commercial products usually have hydrogen peroxide contents of at least 35% by weight. From this an active oxygen content (AO) is calculated 17% by weight (theoretical) or ≧ 16.5% by weight in commercially available powders. 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. In principle, industrial production takes place in the same way, in that finely divided urea is mixed 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, for example, from Degussa, Solvay-Interox and Peroxid-Chemie GmbH, Pullach, and is mainly used in hair bleaching and coloring agents, as a disinfectant (for example for contact lenses) and partly as a wound treatment agent.

The laundry detergent and cleaning product 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 from 7.5 to 25 and in particular from 10 to 20% by weight, in each case based on the weight of the molded article.

The percarbamide is preferably used within certain particle size ranges used. According to the invention, detergent tablets are preferred which the percarbamide has an average particle size above 0.3 mm.

The average particle size is one in the context of the present invention arithmetical size, which results from the multiplication of the percentage of one Sieve fraction with the mesh size of the sieve results. The individual values of such averages can scatter strongly, for example if extremely small and extremely large particles coexist. In the context of the present invention, however, it is preferred that the particle size distribution of the percarbamide does not scatter widely, but rather narrowly is around the mean. Fine particles in particular should be largely excluded be so that in the context of the present invention washing and Detergent tablets are preferred, in which the contained in them  Percarbamide has an average particle size above 0.3 mm and preferably is 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 less than 1% by weight and in particular less than 0.5% by weight.

It is not only preferred in the context of the present invention that dust and Fine parts of the percarbamide are largely absent, the content should also be Particles with a size below 0.4 mm are kept as small as possible. There are such Detergent tablets are preferred in which the percarbamide less than 30% by weight, preferably less than 20% by weight and in particular less than 10 % By weight of 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 of one Has size above 10.8 mm, it being particularly preferred that the percarbamide is substantially free of particles larger than 1.6 mm.

As a result, the proportion of larger percarbamide particles should be as high as possible. Here it is again preferred if the particles of the percarbamide are not only larger than 0.4 mm, but are significantly larger, for example larger than 0.8 mm. Still, it should Percarbamide of course not in the form of coarse lumps in the washing and Detergent tablets of the present invention are incorporated. Out practical aspects have particle sizes of the percarbamide below 2.0 mm proven, it is preferred if that in the washing and Detergent tablets contain percarbamide substantially free of particles Sizes above 1.6mm is - see above.

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

It is possible within the scope of the present invention to include acidic constituents in the Incorporate molded bodies. If the moldings contain carbonates, is by reaction the acid with the carbonate or bicarbonate carbon dioxide released, wherein this "shower effect" can promote disintegration. Usually in Effervescent systems oligomeric oligocarboxylic acids such as succinic acid, maleic acid and especially citric acid used. In preferred embodiments of the In the present invention, however, the detergent tablet is not "Effervescent tablet", i.e. H. 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. Such coated washing and Detergent tablets can by spraying a melt or solution of the Coating material on the molded body or immersing the molded body in the melt or solution can be prepared. In preferred embodiments of the present The laundry detergent and cleaning product tablets are, however, not with one Coating, which covers the entire molded body, coated.

As already mentioned above, detergent tablets are; their Decay times are above 60 seconds, usually almost completely insoluble and therefore no longer washable. Due to high pressures at the Manufacture can be made with any premix tablets, which disintegration times have above 60 seconds and according to previous experience are unsatisfactory in terms of application technology. So far was the pressure and with it the maximum achievable hardness of the tablets is limited. By the invention Percarbamide can also be used to produce harder tablets, which despite Decay times of over 60 seconds still decay into secondary particles and thus let it wash in. Although it is possible according to the invention to make the tablets so hard pressing that disintegration times over two minutes can be achieved is over application technology perspective (washing cycle of household washing machines)  Manufacture of molded articles according to the invention, which have disintegration times below 100 Have seconds. Even with the use according to the invention are easy and quick disintegrating tablets are preferred so that in the context of the present invention washing and detergent tablets that are in water at 30 ° C in less than 60 seconds completely disintegrate into their secondary particles which are so small that they overlap Have the detergent dispenser in a household washing machine, especially are preferred.

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

These substances, which are also known as "explosives" due to their effectiveness, increase their volume when water enters, and on the one hand increases their own volume (Swelling), on the other hand, a pressure can be generated via the release of gases which can break the tablet into smaller particles. Well-known Disintegration aids are, for example, carbonate / citric acid systems, wherein other organic acids can also be used. Swell end Disintegration aids are, for example, synthetic polymers such as Polyvinylpyrrolidone (PVP) or natural polymers or modified 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 Disintegration aid, each based on the weight of the molded body.

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

The cellulose used as disintegration aid is preferably not in finely divided form used, but before mixing to the to be pressed Premixes are converted into a coarser form, for example granulated or compacted. Detergent tablets, the explosives in granular or optionally contain cogranulated form, are in the German Patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) as well the international patent application WO 98/40 463 (Henkel). These writings are also more details on the production of granulated, compacted or co-granulated 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 coarser mentioned above and described in more detail in the cited documents  Disintegration aids based on cellulose are within the scope of the present invention preferably used as a disintegration aid and commercially, for example, at the name Arbocel® TF-30-HG available from Rettenmaier.

As a further disintegrant based on cellulose or as part of it Component can be used microcrystalline cellulose. This microcrystalline Cellulose is made by partial hydrolysis of celluloses under such conditions get that only the amorphous areas (about 30% of the total cellulose mass) of the Attack and completely dissolve celluloses, but the crystalline areas (approx. 70%) leave undamaged. A subsequent disaggregation by hydrolysis emerging micro-fine cellulosic supplies the microcrystalline celluloses that Have primary particle sizes of about 5 microns and, for example, to granules with a average particle size of 200 microns are compactible.

Preferred washing and Detergent tablets 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 from 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the molded body weight.

To develop the desired bleaching performance, the washing and Detergent tablets of the present invention percarbamide. Of course it is also possible according to the invention to add further bleaching agents to those according to the invention Incorporate detergent tablets, in particular the usual bleaching agents from the group sodium perborate monohydrate, Sodium perborate tetrahydrate and sodium percarbonate have proven effective. If that Percarbamide is to be used together with other bleaching agents Mixture of percarbamide and sodium percarbonate has been tried and tested Weight ratio of percarbamide to sodium percarbonate with advantage in the range of 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 peroxycarbonate. Sodium percarbonate forms a white, water-soluble powder with a density of 2.14 gcm ^-3 , which easily breaks down into sodium carbonate and bleaching or oxidizing oxygen.

Sodium carbonate peroxohydrate was first made in 1899 by precipitation with ethanol from a Obtained solution of sodium carbonate in hydrogen peroxide, but mistakenly as Peroxycarbonate viewed. It was not until 1909 that the compound was Deposition bond recognized, nevertheless has the historical designation "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): % Mother liquor, is then centrifuged off and dried in fluid bed dryers at 90 ° C. The bulk density of the finished product can vary between 800 and 1200 g / l depending on the manufacturing process. As a rule, the percarbonate is stabilized by an additional coating. Coating processes and substances 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 Solvay Interox, Degussa, Kemira or Akzo.

As with all bleaching agents used, the percarbamide content is Shaped bodies on this substance depend on the intended use of the shaped bodies. While Usual universal detergent in tablet form between 5 and 30 wt .-%, preferably  between 7.5 and 25% by weight and in particular between 12.5 and 22.5% by weight Containing percarbamide, the content of bleach or bleach booster tablets between 15 and 50% by weight, preferably between 22.5 and 45% by weight us in particular between 30 and 40% by weight.

In addition to the percarbamide and the optional additional bleaching agents can the detergent tablets according to the invention Contain bleach activator (s), which is preferred in the context of the present invention. Bleach activators are incorporated into detergents and cleaning agents in order to Wash at temperatures of 60 ° C and below an improved bleaching effect to reach. As bleach activators, compounds that are under Perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 C- Atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted Perbenzoic acid result, are used. Suitable substances are O- and / or N- Acyl groups of the number of carbon atoms mentioned and / or optionally substituted Wear benzoyl groups. Multi-acylated alkylenediamines are preferred, in particular Tetraacetylethylene diamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl 2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular Tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxyjbenzenesulfonat (n- or iso-NOBS), carboxylic anhydrides, in particular Phthalic anhydride, acylated polyhydric alcohols, especially triacetin; Ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, too so-called bleaching catalysts can be incorporated into the moldings. With these Fabrics are bleach-enhancing transition metal salts or Transition metal complexes such as Mn, Fe, Co, Ru or Mo Salene 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 moldings according to the invention contain bleach activators, they contain in each case based on the entire molded body, between 0.5 and 30% by weight, preferably between 1 and 20% by weight and in particular between 2 and 15% by weight one or more bleach activators or bleach catalysts. Depending on These quantities can vary in the intended use of the moldings produced. So are in typical universal detergent tablets bleach activator contents between 0.5 and 10 % By weight, preferably between 2 and 8% by weight and in particular between 4 and 6 % By weight is common, while bleach tablets may have higher contents, for example between 5 and 30% by weight, preferably between 7.5 and 25% by weight and in particular can have between 10 and 20 wt .-%. The specialist is in his Freedom of formulation is not restricted and can be stronger or weaker bleaching detergent tablets, detergent tablets or Manufacture bleach tablets by reducing the levels of bleach activator and bleach varies.

A particularly preferably used bleach activator is the N, N, N ', N'- Tetraacetylethylenediamine, which is widely used in detergents and cleaning agents. Accordingly, preferred detergent tablets are thereby characterized in that as a bleach activator tetraacetylethylenediamine in the above Amounts are used.

In addition to the ingredients mentioned, the washing and Detergent tablets contain other ingredients, the amounts of which vary according to Align the intended use of the molded body. So are especially substances from the groups the surfactants, the builders and the polymers for use in the invention Detergent tablets are suitable. The expert will not be here either Difficulties arise in the individual components and their quantities to select. How to make a universal detergent tablet higher amounts of surfactant (s) included, while in the case of bleach tablets they may even be used entirely can be dispensed with. The amount of builder (s) used also varies depending on the intended use.  

In the detergent tablets according to the invention, all can builders usually used in detergents and cleaning agents, especially zeolites, silicates, carbonates, organic cobuilders and - where none There are ecological prejudices against their use - including 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 x2 , 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-91/08 171 .

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024.

Compacted / compacted amorphous silicates, compounded, are particularly preferred amorphous silicates and over-dried X-ray amorphous 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 S. pA under the brand name VEGOBOND AX® and by the formula

n Na ₂ O. (1-n) K ₂ O. Al ₂ O _3. (2-2.5) SiO _2. (3.5-5.5) H ₂ O

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

It goes without saying that the generally known phosphates are also used as Builder substances possible, provided that such use is not for ecological reasons should be avoided. Have among the variety of commercially available phosphates the alkali metal phosphates with particular preference for pentasodium or Pentapotassium triphosphate (sodium or potassium tripolyphosphate) in the washing and Detergent industry the most important.

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 _{4 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 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white, water-soluble powders that lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₄ , at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below), NaH ₂ PO ₄ reacts acidic; it forms when phosphoric acid is adjusted to pH 4.5 with sodium hydroxide solution and the mash is sprayed in. 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 readily soluble in water.

Disodium hydroigen 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 to diphosphate Na ₄ P ₂ O ₇ 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 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 ) 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 readily soluble in water with an alkaline reaction and is produced 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 gcm ^-3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises e.g. B. when heating Thomas slag with coal and potassium sulfate. Despite the higher price in the detergent industry, the more soluble, therefore highly effective; Potassium phosphates often preferred over corresponding sodium compounds.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1836 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 by heating disodium phosphate to <200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers 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 value being 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 O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O. -Na with n = 3. In 100 g of water about 17 g dissolve at room temperature, at 60 ° about 20 g, at 100 ° about 32 g of the water free of crystal water; 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 O ₁₀ + H ₂ O

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

As organic cobuilders in the washing and Detergent tablets, in particular polycarboxylates / polycarboxylic acids, polymers Polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used. These classes of substances will described below.

Usable organic builders are, for example, those in the form of their Polycarboxylic acids that can be used are sodium salts, with polycarboxylic acids being such 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), if 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. The acids have besides theirs Builder effect typically also the property of an acidifying component and thus also serve to set a lower and milder pH value of washing or detergents. In particular, citric acid, succinic acid, To name glutaric acid, adipic acid, gluconic acid and any mixtures of these.

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

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), a UV detector being used. 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 Have 2000 to 20,000 g / mol. Because of their superior solubility, can this group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, preferably his.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As Copolymers of acrylic acid with maleic acid have proven particularly suitable Contain 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your 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 either as a powder or as an aqueous solution be used. The amount 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 allylsulfonic acids, such as for example allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer contain.

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

Further preferred copolymers are those which are described in German patent applications DE- A-43 03 320 and DE-A-44 17 734 are described and preferably as monomers Have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate. Likewise, further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors. Are particularly preferred Polyaspartic acids or their salts and derivatives, of which in the German Patent application DE-A-195 40 086 discloses that in addition to cobuilder Properties also have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which are obtained by converting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 Have hydroxyl groups can be obtained. Preferred polyacetals are made from Dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained 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 obtained by partial hydrolysis of starches can be. The hydrolysis can be carried out according to conventional methods, for example acid or enzyme lysed procedures are carried out. It is preferably hydrolysis pro Products with average molecular weights in the range of 400 to 500,000 g / mol. There is one Polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, particularly preferred from 2 to 30, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which have a DE of 100 owns. Both maltodextrins with a DE between 3 and 20 can be used 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.

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-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as international patent applications WO 92 / 18542, WO 93/08 251, WO 93/16 110, WO 94/28 030, WO 95/07 303, WO 95/12 619 and WO 95/20 608. 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 are also preferred Ethylene diamine disuccinate are other suitable cobuilders. Here, ethylenediamine N, N'-disuccinate (EDDS) preferably in the form of its sodium or magnesium salts used. Glycerol disuccinates are also preferred in this context and glycerol trisuccinates. Suitable amounts are in zeolite and / or formulations containing silicate at 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 have at least 4 carbon atoms and at least one Contain hydroxy group and a maximum of two acid groups. Such cobuilders will described, for example, in international patent application WO 95/20 029.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a cobuilder. It is preferably used as the sodium salt the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). As Aminoalkane phosphonates preferably come from ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher Homologues in question. They are preferably in the form of neutral reactions Sodium salts, e.g. B. as the hexasodium salt of EDTMP or as hepta- and octa- DTPMP sodium salt used. As a builder, the class becomes the Phosphonates preferably used HEDP. The aminoalkane phosphonates also have a pronounced heavy metal binding capacity. Accordingly, it can, in particular if the agents also contain bleach, aminoalkanephosphonates are preferred, use in particular DTPMP, or mixtures of the phosphonates mentioned use.

In addition, all compounds that are able to complex with To train alkaline earth ions are used as cobuilders.

The amount of builders 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 wt .-% and in particular between 30 and 55 wt .-%), for example detergent tablets (usually 10 to 50% by weight, preferably 12.5 to 45% by weight and in particular between 17.5 and 37.5% by weight).  

Preferred detergent tablets furthermore contain one or more Surfactant (s). Can in the detergent tablets according to the invention anionic, nonionic, cationic and / or amphoteric surfactants respectively Mixtures of these are used. Are preferred from application technology View mixtures of anionic and nonionic surfactants. The total surfactant content the shaped body is 5 to 60% by weight, based on the weight of the shaped body, wherein Surfactant contents above 15% by weight are preferred.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and disulfonates such as are obtained, for example, from C _12-18 monoolefins having a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfofatty acids (ester sulfonates), e.g. B. the α-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under Fatty acid glycerol esters are the mono-, di- and triesters as well as their mixtures understand how they are produced by esterification of a monoglycerin with 1 up to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerin be preserved. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example the Capron acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C _12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols which, viewed in isolation, 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. Are suitable saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural Fatty acids, e.g. B. coconut, palm kernel or tallow fatty acids, derived soap mixtures.  

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

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 linearly or preferably 2-branched methyl or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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 which stands 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 either as sole nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the Alkyl chain, especially fatty acid methyl esters, such as those found in Japanese Patent application JP 58/217598 are described or preferably according to the in the international patent application WO-A-90/13 533 become.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the Fatty acid alkanolamides can be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of it.

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

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

The group of polyhydroxy fatty acid amides also includes compounds of the formula (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 oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example, according to the teaching of the international application WO-A-95/07 331 by implementation with Fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are transferred.

In the context of the present invention, detergent tablets are shaped preferred which contain anionic (s) and nonionic (s) surfactant (s), wherein application technology advantages from certain proportions, in which the individual classes of surfactants can be used.

For example, detergent tablets are particularly preferred where 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, the 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 molding weight, contain.

From an application point of view, it can be advantageous if certain classes of surfactants in some phases of the detergent tablets or in whole Molded articles, d. H. in all phases, are not included. Another important one Embodiment of the present invention therefore provides that at least one phase the molded body is free of nonionic surfactants.

Conversely, the content of individual phases or the entire phase can also be used Molded body, d. H. all phases, achieved a positive effect on certain surfactants become. The introduction of the alkyl polyglycosides described above has proven to be proven to be advantageous, so that detergent tablets are preferred, in which contains at least one phase of the shaped body alkyl polyglycosides.

Similar to the non-ionic surfactants, the omission of anionic surfactants from individual or all phases of washing and Detergent tablets result, which are better for certain areas of application own. It is therefore also within the scope of the present invention Detergent tablets are conceivable in which at least one phase of the tablets is free of anionic surfactants.

In addition to the ingredients mentioned, bleach, bleach activator, builder, surfactant and Disintegration aids, the washing and Detergent tablets further ingredients common 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.

To the aesthetic impression of the washing and To improve detergent tablets, they can be mixed with suitable dyes be colored. Preferred dyes, the selection of which none of the expert Difficulties have a high storage stability and insensitivity  compared to the other ingredients of the agents and against light and no pronounced Substantivity towards textile fibers so as not to stain them.

Preferred for use in the washing and Detergent tablets are all colorants that are oxidatively destroyed in the washing process and mixtures of these with suitable blue dyes, so-called. Shades of blue. It has proven to be advantageous to use colorants in water or are soluble in liquid organic substances at room temperature. Are suitable for example anionic colorants, e.g. B. anionic nitroso dyes. A possible one Colorant is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020), which as a commercial product, for example as Basacid® Green 970 from Fa. BASF, Ludwigshafen, is available, as well as mixtures of these with suitable blue Dyes. 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 1 S (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. Generally speaking, 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 washing or cleaning agents varies. In the case of readily water-soluble colorants, e.g. B. the above-mentioned Basacid® green or the above-mentioned Sandolan® blue, colorant concentrations are typically selected in the range of a few 10 ₂ to 10 _-3 wt .-%. In the preferred because of their brilliance, but less water-soluble pigment dyes, for. B. the above-mentioned Pigmosol® dyes, the suitable concentration of the colorant in washing or cleaning agents, however, is typically a few 10 ^-3 to 10 ^-4 wt .-%.

The moldings can be optical brighteners of the derivative type of the diaminostilbene contain sulfonic acid or its alkali metal salts. Are suitable for. B. salts of 4,4'- Bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure, which instead of the morpholino group Diethanolamino group, a methylamino group, an anilino group or a 2- Wear methoxyethylamino group. Brighteners of the substituted type can also be used Diphenylstyryle may be present, e.g. B. 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 washing and Detergent tablets 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, based in each case on the entire shaped body.

Fragrances are added to the agents according to the invention in order to improve the aesthetics Improve product impression and consumer in addition to the performance of the Product a visually and sensory "typical and distinctive" product for To make available. Individual as perfume oils or fragrances Fragrance compounds, e.g. B. the synthetic products of the ester, ether, Aldehydes, ketones, alcohols and hydrocarbons can be used.

Fragrance compounds of the ester type are e.g. B. benzyl acetate, Phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl carbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. To the ethers include, for example, benzyl ethyl ether, the aldehydes z. B. the linear alkanals 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. B. the Jonone, ∝- Isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons  mainly include the terpenes like limes and pinene. However, are preferred Mixtures of different fragrances are used, which together make an appealing Generate fragrance. Such perfume oils can also contain natural fragrance mixtures contain as they are accessible from plant sources, e.g. B. pine, citrus, jasmine, Patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, Chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, 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 inventive washing and Detergent tablets of fragrances up to 2% by weight of the total formulation. The fragrances can be incorporated directly into the agents according to the invention but can also be advantageous to apply the fragrances to the carrier, which increase the liability of the perfume on the laundry and by a slower fragrance release for long-lasting fragrance of the textiles. As such carrier materials have become For example, cyclodextrins have proven to be the cyclodextrin-perfume complexes can also be coated with other auxiliaries.

Enzymes in particular come from the hydrolase classes such as that Proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases contribute to the removal of stains such as protein, greasy or starchy stains and graying. Cellulases and others Glycosyl hydrolases can also be removed by removing pilling and Microfibrils help to maintain color and increase the softness of the textile. Oxidoreductases can also be used for bleaching or for inhibiting color transfer be used. Bacterial strains or fungi such as are particularly well suited Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and those obtained from its genetically modified variants enzymatic agents. Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus are used. Are there 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 lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic Enzymes and cellulase, but especially protease and / or lipase-containing Mixtures or mixtures with lipolytically active enzymes of particular Interest. Examples of such lipolytically active enzymes are the known ones Cutinases. Peroxidases or oxidases have also been found to be suitable in some cases proven. Suitable amylases include in particular alpha-amylases, iso- Amylases, pullulariases and pectinases. As cellulases are preferred Cellobiohydrolases, endoglucanases and glucosidases, also called cellobiases are used, or mixtures of these. Because there are different types of cellulase can distinguish through their CMCase and Avicelase activities, through targeted Mixtures of cellulases to set the desired activities. The enzymes can be adsorbed on carriers or embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5% by weight.

In addition, the detergent tablets can also contain components contain, which positively influence the oil and fat washability from textiles (so-called soil repellents). This effect is particularly evident when a textile is soiled, which has previously been repeatedly washed with a detergent according to the invention, that contains this oil and fat-dissolving component. Among 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, each based on the nonionic cellulose ether, and those from the prior art Technically known polymers of phthalic acid and / or terephthalic acid or their Derivatives, in particular polymers of ethylene terephthalates and / or Polyethylene glycol terephthalates or anionically and / or nonionically modified Derivatives of these. Of these, the sulfonated derivatives of are particularly preferred Phthalic acid and terephthalic acid polymers.  

Another object of the present invention is a method for producing Detergent tablets by molding a Particulate premix, which is characterized in that the premix Percarbamide in amounts of 1 to 40 wt .-%, based on the premix.

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

Also with regard to the particle size distribution of the process according to the invention Percarbamids introduced apply analogously to what has already been said above. It is also completely analog to transfer the use of further ingredients to the method according to the invention. In preferred method, the particulate premix additionally contains surfactant (s) Granulate (s) and has a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l.

Regarding the preferred particle size of the percarbamide, refer to the above Executions referenced. In preferred methods according to the invention, this Granules containing surfactants Particle sizes between 100 and 2000 microns, preferably between 200 and 1800 µm, particularly preferably between 400 and 1600 µm and in particular between 600 and 1400 µm.

The other ingredients of the washing and Detergent tablets can be introduced into the method according to the invention to which reference is made to the above statements. Preferred procedures are characterized in that the particulate premix additionally one or several 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, Contains graying inhibitors, color transfer inhibitors and corrosion inhibitors.  

The moldings according to the invention are first produced by dry means Mixing of the components, which can be partially or completely pre-granulated, and on concluding information, in particular pressing into tablets, with conventional che procedures can be used. For the production of the invention The pre-mix is molded in a so-called die between two stamps compacted into a solid compressed. This process, briefly referred to below as Tabletting is divided into four sections: dosage, compression (elastic deformation), plastic deformation and ejection.

First, the premix is introduced into the die, the filling quantity and thus the weight and shape of the resulting molded body through the position of the lower one Stamp and the shape of the press tool can be determined. The constant one Dosage even at high molding throughputs is preferably over a volumetric dosage of the premix reached. In the further course of tableting the upper stamp touches the premix and continues to lower in the direction of the Lower stamp. With this compression, the particles of the premix become closer pressed together, the void volume within the filling between the Stamping decreases continuously. From a certain position of the upper stamp (and from a certain pressure on the premix) the plastic begins Deformation in which the particles flow together and it to form the molded body is coming. Depending on the physical properties of the premix, a part also becomes the premixed particles are crushed and there is a pressure at even higher pressures Sintering the premix. With increasing press speed, i.e. high Throughput quantities, the phase of elastic deformation is shortened more and more, so that the resulting shaped bodies can have more or less large cavities. In the last step of tableting, the finished molded article is made using the lower stamp pressed out of the die and by subsequent transport devices transported away. At this point, only the weight of the molded body is final determined because the compacts due to physical processes (stretching, crystallographic effects, cooling etc.) can still change their shape and size. Tableting takes place in commercially available tablet presses, which are basically or double stamps can be equipped. In the latter case, not only Upper stamp used to build up pressure, the lower stamp also moves during  of the pressing process towards the upper punch, while the upper punch presses down. Eccentric tablet presses are preferably used for small production quantities, where the stamp or stamps are attached to an eccentric disc, which in turn an axis with a certain rotational speed is mounted. The movement this ram is comparable to the operation of a conventional four-stroke engine. The pressing can be done with an upper and lower stamp, but it can also several stamps can be attached to an eccentric disc, the number of Die holes are expanded accordingly. The throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs, rotary tablet presses are selected, on which one so-called die table a larger number of dies is arranged in a circle. The number of matrices varies between 6 and 55, depending on the model, with larger ones as well Matrices are commercially available. Each die on the die table is a top and Assigned lower stamp, whereby again the pressure is active only by the upper or Lower stamps, but also built up by both stamps karin. The matrix table and the stamps move about a common vertical axis, the Stamp with the help of rail-like cam tracks during the circulation in the positions for filling, compression, plastic deformation and ejection. To the Places where there is a particularly serious increase or decrease in the stamp is necessary (filling, compacting, ejecting), these cam tracks are additional low-pressure pieces, low-tension rails and lifting tracks supported. The The die is filled via a rigidly arranged feed device so-called filling shoe, which is connected to a reservoir for the premix. The pressure on the premix is via the press paths for upper and lower punches individually adjustable, the pressure build-up by rolling the Stamp shaft heads happen on adjustable pressure rollers.

Rotary presses can also be used with two filling shoes to increase the throughput be provided, with only a semicircle to produce a tablet must become. Several are used to produce two-layer and multi-layer moldings Filling shoes arranged one behind the other without the slightly pressed first layer in front of the further filling is ejected. Appropriate litigation is based on this Way to produce coated and dot tablets, the onion-like  Have structure, whereby in the case of the point tablets the top of the core or Core layers are not covered and thus remain visible. Also Rotary tablet presses can 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 for pressing at the same time. The throughputs are more modern Rotary tablet presses are over one million tablets per hour.

When tableting with rotary 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 of the technology is available to reduce the build-up of stamps known non-stick coatings. Plastic coatings are particularly advantageous, Plastic inlays or plastic stamps. Rotating stamps have also turned out to be proven to be advantageous, the upper and lower punches being rotatable if possible should be. With rotating stamps, a plastic insert can usually be used to be dispensed with. The stamp surfaces should be electropolished here.

It was also shown that long pressing times are advantageous. You can use Pressure rails, several pressure rollers or low rotor speeds can be set. Because the fluctuations in hardness of the tablet due to the fluctuations in the pressing forces systems should be used that limit the pressing force. Here can elastic stamps, pneumatic compensators or resilient elements in the Kraftweg be used. 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 Verpackungssysteme 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, Liverpool (GB) I. Holand Ltd., Nottingham (GB), Courtoy N.V., Halle (BE / LU) and Mediopharm Kamnik (SI). For example, the hydraulic one is particularly suitable Double printing press HPF 630 from LAEIS, D. are tabletting tools for example from Adams Tablettierwerkzeuge, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber & Söhne GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharmatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Werkzeugbau, Tamm available. Other providers are e.g. B. Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).

The moldings can be in a predetermined spatial shape and a predetermined size are manufactured. Practically all sensibly manageable come as a room shape Configurations into consideration, for example, the training as a board, the staff or Bar shape, cubes, cuboids and corresponding room elements with flat side surfaces as well as in particular cylindrical configurations with 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 separate individual elements be formed, the predetermined dosage of the washing and / or Corresponds to detergent. But it is also possible to form compacts, the one Connect a plurality of such mass units in one compact, in particular by predetermined breaking points make it easy to separate portioned smaller units is provided. For the use of textile detergents in machines of in Europe usual type with horizontally arranged mechanics can the training of portioned compacts as tablets, in cylindrical or cuboid form, are expedient,  a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred is. Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices in particular for the production of such compacts.

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

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

But it is also possible that the various components do not become one Tablet are pressed, but that shaped bodies are obtained, which 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 performance properties of the shaped bodies result. If, for example, components are contained in the moldings, the affect each other negatively, so it is possible to have one component in the faster integrate soluble layer and the other component into a slower soluble Work in layer so that the first component has already reacted when the second goes into solution. The layer structure of the moldings can be stacked, a dissolution process of the inner layer (s) at the edges of the molded body already then occurs when the outer layers are not yet completely dissolved, but it can also a complete covering of the inner layer (s) by the further outwards  lying layer (s) can be reached, which prevents the early Solution of components of the inner layer (s) leads.

In a further preferred embodiment of the invention, a molded body consists of at least three layers, ie two outer and at least one inner layer, wherein at least one of the inner layers contains a peroxy bleach, while in the case of the stacked shaped body, the two outer layers and in the case of the shell-shaped one Shaped bodies, however, the outermost layers are free of peroxy bleach. Farther it is also possible to use peroxy bleach and any bleach activators present and / or to separate enzymes spatially from one another in a shaped body. Such multilayered moldings have the advantage that they do not have only one Detergent dispenser or via a metering device, which is added to the wash liquor will be used; rather, it is also possible in such cases, the Put molded articles in direct contact with the textiles in the machine without Stains from bleach and the like would be feared.

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

After pressing, the detergent tablets have a high stability. The breaking strength of cylindrical shaped bodies can be determined via the measured variable of the diametrical breaking load. This can be determined according to

Here σ stands for diametral fracture stress (DFS) in Pa, P is the force in N which leads to the pressure exerted on the molded body, which is the Breakage of the shaped body causes, D is the shaped body diameter in meters and t is the Height of the molded body.  

Another object of the present invention is the use of percarbamide to increase the hardness and reduce the disintegration time of washing and Detergent tablets. This use of percarbamide according to the invention leads to Shaped bodies with advantageous properties, as the examples below show. With regard to preferred embodiments of the use according to the invention (Particle sizes, other ingredients, composition of the premix, etc.) applies analogously to what was said above for the method according to the invention.  

For the production of detergent tablets containing percarbamide, a Granular surfactant mixed with other processing components and placed on an eccentric Tablet press pressed into shaped bodies. The composition of the surfactant granules is given in Table 1 below, the composition of the material to be pressed Premix (and thus the composition of the shaped bodies) can be found in Table 2.

Table 1

Granular surfactant [% by weight]

Table 2

Premix [wt%]

The tablettable premixes E and V were added in a Korsch eccentric press Tablets (diameter: 44 mm, height: 22 mm, weight: 37.5 g) pressed. It was 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 until it broke, where the force applied to the side surfaces of the tablet and the maximum force that the tablet withstood, was determined.

To determine tablet disintegration, the tablet was placed in a beaker with water placed (600 ml of water, temperature 30 ° C) and the time to complete Tablet disintegration measured. The experimental data of the individual tablet series shows Table 3

Table 3

Detergent tablets [physical data]

Claims (14)

1. Detergent tablets made of compressed particulate detergent and cleaning agent, characterized in that they contain percarbamide. 2. Detergent tablets according to claim 1, characterized in that they contain percarbamide in amounts of 1 to 40% by weight, preferably 5 to 30 % By weight, particularly preferably from 7.5 to 25 and in particular from 10 to 20% by weight, each based on the weight of the molded part. 3. Detergent tablets according to one of claims 1 or 2, characterized characterized in that the percarbamide contained in them has an average particle size has above 0.3 mm and preferably substantially free of particles with sizes is below 0.2 mm. 4. Detergent tablets according to one of claims 1 to 3, characterized characterized in that the percarbamide less than 30 wt .-%, preferably less than 20% by weight and in particular less than 10% by weight of particles of one 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 has, wherein it is particularly preferred that the percarbamide is substantially free of Particles with sizes above 1.6 mm. 5. Detergent tablets according to one of claims 1 to 4, characterized characterized in that they contain percarbamide-containing compounds, which at least 60 wt .-% percarbamide, each based on the weight of the compound. 6. Detergent tablets according to one of claims 1 to 5, characterized characterized in that they are free of oligomeric oligocarboxylic acids, in particular Citric acid. 7. Detergent tablets according to one of claims 1 to 6, characterized characterized in that they additionally contain a disintegration aid, preferably a Disintegration aids based on cellulose, preferably in granular form,  cogranulated or compacted form, in quantities of 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the weight of the molded body. 8. Detergent tablets according to one of claims 1 to 7, characterized characterized in that they are surfactant (s), preferably anionic (s) and / or nonionic surfactant (s), in amounts from 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 wt .-%, each based on the weight of the molded body. 9. Process for the production of detergent tablets by shaping compression of a particulate premix, thereby characterized in that the premix percarbamide in amounts of 1 to 40 wt .-%, 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. 11. The method according to any one of claims 9 or 10, characterized in that the Particulate premix additionally contains granules (s) containing surfactant and a Bulk density of at least 500 g / l, preferably at least 600 g / l and in particular has at least 700 g / l. 12. The method according to claim 11, characterized in that the surfactant-containing granules Particle sizes between 100 and 2000 microns, preferably between 200 and 1800 µm, particularly preferably between 400 and 1600 µm and in particular between 600 and 1400 µm; having. 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, Contains color transfer inhibitors and corrosion inhibitors. 14. Use of percarbamide to increase the hardness and reduce the Disintegration time of detergent tablets.