EP1382665A1 - Use of phospate compounds - Google Patents

Abstract

Phosphate pre-mixes for use in washing and detergent agents contain (wt) at least 50 % pentasodium triphosphate (STP), less than 5 % Na pyrophosphate and a maximum of 18% water and are in the form of agglomerates of primary particles. An Independent claim is also included for preparation of phosphate pre-mixes by agglomerating anhydrous STP powder (and optionally also further washing or detergent agent ingredients) with 12-28 wt.% water in a high-speed mixer and then drying the product in a fluidized bed with product temperature below 60 degreesC to a free-water content below 5 wt.%.

Description

The present invention relates to phosphate compounds which are suitable for incorporation into Detergent tablets are suitable, and detergent tablets, which contain such compounds. Next is a manufacturing process for specified such phosphate compounds.

Alkali phosphates are generally suitable as phosphorus-containing builder substances for Detergents and cleaning agents. In particular, trisodium phosphate, tetrasodium diphosphate, Disodium dihydrogen diphosphate, pentasodium triphosphate, so-called Sodium hexametaphosphate, oligomeric trisodium phosphate with Degrees of oligomerization in the range from 5 to 1000, in particular 5 to 50, and mixtures made from sodium and potassium salts. The most common of these is pentasodium triphosphate used.

When incorporating pentasodium triphosphate (STP) into detergents or cleaning agents it should be noted that its hydration is a strongly exergonic process, which increases Overheating of detergent and cleaning agent components can result. Accordingly, the hydration of the STP is usually at least partially pre mixing with other ingredients.

In the published patent application DE 29 13 145 a continuous process for Preparation of a detergent granulate described in the anhydrous pentasodium triphosphate with a high phase II content in a continuous mixer is sprayed with a substoichiometric amount of water. After a dwell the phosphate is mixed in a second mixer with sodium silicate and possibly sodium carbonate mixed and granulated with renewed addition of water and then in one Steam-saturated atmosphere is moved 5 to 15 min before the product is cooled becomes.

In the patent DE 32 49 902 a continuous process is described in the pentasodium triphosphate with an at least stoichiometric amount of water is added and then left in a closed container until the Degree of hydration has reached at least 70%. Finally, the particles are on a water content of less than 5% by weight which can be split off at 50 ° C. is dried.

Spray drying a slurry from a water-soluble inorganic phosphate with a polymeric polycarboxylate is in patent application DE 38 18 660 described. The resulting hollow spheres serve as carriers for nonionic surfactant, which the balls are sprayed on in amounts of 2 to 40% by weight. Is pentasodium triphosphate one of the suitable phosphates.

Document GB-A-1466868 relates to a process for the production of porous granular Materials and granules produced by the process, which in a Detergent formulation can be installed. The powder used for granulation contains alkali metal tripolyphosphates and a binder, e.g. Water. This binder, that is necessary to bring about the granulation is added after the powdered tripolyphosphate has been formed into an annular bed; the Granulated product is then kept in motion and z. B. in a fluidized bed dried.

The German patent application DE-A-29 25 137 discloses homogeneous, dust-free and free-flowing detergent and cleaning agent granules based on Pentasodium tripolyphosphate, which is practically free of hydrolysis products from Are polyphosphate, and a process for their continuous production. This Granules contain, among other components, 50 to 80% by weight Pentasodium tripolyphosphate and 10 to 25% by weight, in particular 9 to 19% by weight Water. The ratio of ortho- and sodium pyrophosphate to total phosphate is 0.005 to 0.08% by weight.

From the German patent application DE-A-44 35 743 is a process for the production a multi-component granulate for use in detergents and cleaning agents known in which in a continuous agglomeration mixer a powder Detergent component with the addition of a binder to granulate particles is granulated. Then drying takes place in a drying device, for example in a fluid bed dryer. A made by this process phosphate-containing multi-component granules contain 15 to 50% by weight Sodium tripolyphosphate and 3 to 15% by weight of water, in particular 4 to 8% by weight Water.

A granular composition that contains a hydrate-forming phosphate, preferably Pentasodium triphosphate, 0.1-23 wt .-% water and 2 to 125 ppm surfactant is described in European patent EP-B-259 291. This is made Granules, for example in a mixer, in which an aqueous solution of the surfactant the phosphate is given. Essential to the invention is the surfactant content which leads to that the proportion of free water to hydrate water in the product in favor of Hydrate water shifts. The degree of conservation of the pentasodium triphosphate is also this process between 84 and 94% of the phosphate content. Such a low one Degree of phosphate conservation and the associated high pyrophosphate content leads to the Use of such granules when washing dishes to undesirably strong Glass corrosion.

It has now been found that phosphate compounds which contain little pyrophosphate i.e. have a high degree of phosphate retention and are present as agglomerates, are excellent for incorporation into moldings of detergents and cleaning agents are suitable and even improve the dissolution behavior of these moldings.

Accordingly, a first object of the invention are phosphate compounds for Use in detergents or cleaning agents that contain at least 50% by weight Pentasodium triphosphate, less than 5% by weight sodium pyrophosphate and maximum Contain 18 wt .-% water and exist as agglomerates of primary particles.

Due to its high calcium binding capacity, pentasodium triphosphate (STP), which is in anhydrous crystalline form or as hexahydrate, particularly Interest as a builder in detergents and cleaning agents, and should accordingly as The main constituent can be contained in the compounds according to the invention. The content of STP is at least 50% by weight, preferably over 70% by weight and especially preferably even more than 80% by weight of the total compounds.

Due to the desired high content of STP, the content of the compounds should increase other phosphates, especially ortho-, meta- and pyrophosphates. Less than 5% by weight, in particular even less than 3% by weight, of these are preferred Phosphates contained in the compound. The proportion of these phosphates is expressed about the degree of conservation of the pentasodium triphosphate in the compound (STP degree of conservation). It is preferably at least 95%, particularly preferably even at least 97%. In particular, a high pyrophosphate content leads to the use of such Compounds in dishwashing detergents to undesirably reinforce the Glass corrosion. The inventive compounds avoid such disadvantages, in which contain less than 5% by weight of sodium pyrophosphate, it being preferred if the sodium pyrophosphate content is even less than 3% by weight or less.

In addition to phosphate, the compound contains a proportion of water that is a maximum of 18% by weight. can be. However, preferred compounds contain a maximum of 15% by weight of water, a water content of at most 13% by weight can also be preferred. If particularly phosphate-rich compounds are to be produced, one can even Water content of at most 11 wt .-% may be preferred. The water is in the Compounds for the most part as hydrate water. The content is Pentasodium triphosphate hexahydrate preferably between 20 and 70 wt .-% of the content of total pentasodium triphosphate. The free water content of the compounds, i.e. water not bound as hydrate water should be as low as possible. He is preferably at most 5% by weight, with free water contents of at most 3% by weight can be particularly preferred. In a special, preferred embodiment the free water content should even be below 1.5% by weight. The free water is already released below 100 ° C and can therefore at this temperature be determined.

In addition to these components, the compounds can contain other ingredients of washing and / or Detergents included. These can preferably be substances that Have cobuilder properties. Here are primarily polycarboxylates, to name in particular polymeric polycarboxylates, and phosphonates.

Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol. In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out 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 molar masses measured against polystyrene sulfonic acids are generally almost twice as high as the molar masses specified 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 with molecular weights 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. Such polymeric polycarboxylates are preferably contained in the compounds since they are not only effective as cobuilders but can also serve as agglomeration aids. The (co) polymeric polycarboxylate content of the compounds is preferably 0.5 to 20% by weight, in particular 3 to 15% by weight.

To improve water solubility, the polymers can also allylsulfonic acids, such as for example in EP-B-727448 allyloxybenzenesulfonic acid and methallylsulfonic acid, included as a monomer. Biodegradable are also particularly preferred Polymers made up of more than two different monomer units, for example those which according to DE-A-43 00 772 as monomer salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or as in DE-C-42 21 381 Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives contain. Other preferred copolymers are those described in the German Patent applications DE-A-43 03 320 and DE-A-44 17 734 are described and as Monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and Have vinyl acetate.

Hydroxyalkane and aminoalkane phosphonates in particular can be used as phosphonates be included. Among the hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a cobuilder. It is preferred used as the sodium salt, the disodium salt being neutral and the tetrasodium salt alkaline (pH 9) reacts. Preferred aminoalkane phosphonates are Ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues in question. You will prefer in the form of neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP. As a builder, the class of phosphonates preferably uses HEDP, and is accordingly also then preferably contained in the compounds if these compounds as Builder compounds are designed, i.e. as a predominant or sole builder in laundry or cleaning agents are suitable. The aminoalkanephosphonates have a clear lower calcium binding capacity than HEDP, however, due to their Heavy metal binding capacity used for bleach stabilization. Accordingly it can, especially if the compounds are used together with bleach should also be preferred that aminoalkane phosphonates, especially DTPMP, or Mixtures of the aforementioned phosphonates are included. The salary of the Compounds of total phosphonates are preferably 0.3 to 20% by weight.

Even though the compounds are designed as builder compounds, it is preferred that these compounds contain no silicates, especially no sodium silicates, or insoluble ones Contain aluminosilicates. Accordingly, the compounds are primarily suitable for use in agents that contain phosphate as the main builder. Should be in the middle other inorganic builders are included, they are preferably separated from the Phosphate compounds introduced. Other ingredients of washing and Cleaning agents, in particular surfactants, can be contained in the compounds, however, they are preferably only present in small amounts or not at all. In particular, the nonionic surfactants frequently used as granulation aids are in the Compounds preferably not included.

Their shape is essential for the properties of the compounds according to the invention. she exist as agglomerates that are formed from primary particles. The middle Particle size of the agglomerates, as can be seen from a sieve analysis, is included preferably in the range of 0.2 to 1.0 mm, in particular in the range of 0.3 up to 0.8 mm. The average diameter of the primary particles is preferred Embodiments here by a factor of 5, preferably even by a factor 10, less than the average particle size of the agglomerates. Because of this special In terms of structure, the compounds themselves are easily and quickly soluble. The compounds show usually has a bulk density in the range 600 to 1000 g / l, the Bulk weight of the compounds is preferably between 700 and 900 g / l. This The special form of the compounds also places special demands on Manufacturing process for such compounds.

A second subject of the invention is accordingly a method for the production of such phosphate compounds, which is characterized in that anhydrous, powdered pentasodium triphosphate in a high speed mixer with 12 up to 28% by weight of water, based on the pentasodium triphosphate, and if appropriate other ingredients of washing and / or cleaning agents is agglomerated and the agglomerate immediately afterwards in a fluid bed dryer at a Product temperature below 50 ° C to a free water content of below 5% by weight is dried.

Under powdery, anhydrous pentasodium triphosphate (STP) commercial pentasodium triphosphate qualities understood, the maximum 1 wt .-% May contain moisture. There are two of the anhydrous form of the STP Modifications, referred to as Phase I, are metastable at room temperature High temperature modification as well as phase II stable at room temperature The two phases also differ in terms of their rate of hydration. Phase I absorbs water much faster than Phase II The heat released during the hydration process heats up pentasodium triphosphate may become so strong during this process that it may decompose the Triphosphate is coming. Because this decomposition is undesirable, most do Hydration procedure for STP a certain ratio of phase I to phase II required to avoid overheating. Usually must predominantly Phase II are present to prevent decomposition of the STP during hydration can be. The present procedure is largely independent of the share of two phases, it can be with any ratio of phase I to phase II be performed. Particularly high levels of triphosphate should be achieved However, it is also advantageous with this method if more than 50% by weight of the phosphate is present as phase II.

The phosphate powder is placed in a high-speed mixer, which is preferably designed as a free-fall mixer. The term "high speed" in this context means that such mixer with a speed of several revolutions per second, preferably than 1500 rpm ^-1, mix. The residence time of the phosphate in the mixer is only a short time, preferably less than 20 seconds; if a free-fall mixer is used as the mixer, preferably even less than 2 seconds, in particular less than 1.5 seconds. During this time, the phosphate powder is sprayed with water or an aqueous solution, 12 to 28% by weight, preferably 15 to 20% by weight, of the phosphate weight being applied as water. In a special variant of the method, less than 18% by weight of water is applied.

Are the phosphate other ingredients already described above Detergents and / or cleaning agents are mixed, so these are in one Embodiment of the invention in dry form with the anhydrous phosphate powder mixed and then introduced into the high-speed mixer. In a another preferred embodiment, an aqueous solution of at least one of the Ingredients used for spraying in the high-speed mixer. You can other ingredients have already been dry mixed with the phosphate.

The mixer turns the wet compound into one without wasting time Drying device, which is designed as a fluid bed drying, transferred. In the simplest case if a free fall mixer is used, the compound will be noticed directly from the mixer the fluid bed. Drying in the fluidized bed takes place under mild conditions, whereby the product temperature during the entire process is preferably below 60 ° C is below 45 ° C. This is achieved by a suitable choice of the supply air temperature. It is the optimal supply air temperature depending on the dimension of the fluid bed and the amount of air supplied. However, it has been shown that in general with a Supply air temperature of maximum 130 ° C overheating of the product can be avoided can. However, the supply air temperature is preferably a maximum of 100 ° C. In a The embodiment releases the heat of hydration of the triphosphate Drying used and the supply air is not preheated. But also if preheated supply air supplied, the process always has the advantage of the heat of hydration to use at the same time for drying and accordingly with compared to others Processes with little additional energy. Through this mild Conditions, especially the low product temperature, will cause decomposition of the Triphosphate largely prevented. After drying, preferably still lie at least 95% by weight of the phosphate as triphosphate. The drying takes place until the free water content is at most 5% by weight, preferably at maximum 3% by weight. As a rule, the required length of stay is Agglomerates in the fluid bed dryer between 30 and 60 minutes.

A return can follow the fluid bed drying. Fine fractions can if necessary together with the filter dusts from the fluid bed dryer be fed to the agglomeration stage, while coarse grain before recycling is preferably ground in a hammer mill and after the fluid bed drying at least a third of the distance, preferably after more than two thirds of the Distance, is fed again.

The phosphate compound described above is ideal for Incorporation in detergent tablets such as Detergent tablets for washing textiles, detergent tablets for machine dishwashing or cleaning hard surfaces, Bleach tablets for use in washing machines or dishwashers, Water softening tablets or stain tablets.

Another object of the present invention is therefore the use of Phosphate compounds after mixing with finely divided processing components pressed into detergent tablets in a manner known per se to improve the stability and solubility of washing and Detergent tablets. By using the phosphate compounds according to the invention, which after mixing with other components to wash and Detergent tablets are pressed, the physical properties the molded body, in particular the mechanical stability and the solubility behavior, be significantly improved. This allows washing and low pressure pressures Manufacture detergent tablets that have sufficient mechanical stability Have packaging, transport and handling, compared to use In this way, conventional phosphates can add equally stable tablets lower pressures are produced, so that the wear on the Tableting machines significantly reduced and their lifespan extended.

Another object of the present invention are washing and Detergent tablets made of compressed particulate washing, and Detergents which contain a phosphate compound according to the invention.

It is of course possible to use the phosphate compounds according to the invention to be used in a mixture with conventional and commercially available phosphates. However, the majority of the phosphate contained in the shaped bodies preferably originates from the phosphate compounds according to the invention. Washing and Detergent tablets which have at least 80% by weight, preferably at least 90 % By weight and particularly preferably the total amount contained in the shaped body Amount of phosphate in the form of phosphate compounds according to the invention are included therefore preferred.

Depending on the intended use, the phosphate compounds can be those of the invention Detergent tablets in varying amounts in the tablets be included. Here, detergent tablets are preferred which, based on the weight of the molded body, 10 to 90 wt .-%, preferably 20 to 80 % By weight and in particular 25 to 70% by weight of the phosphate compound.

In order to facilitate the disintegration of highly compressed moldings, disintegration aids, so-called tablet disintegrants, can be incorporated into them in order to shorten the disintegration times. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt " Textbook of pharmaceutical technology " (6th edition, 1987, p. 182-184), tablet disintegrants or disintegration accelerators 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 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. overflowing 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.

In a preferred variant of the invention, the washing and Detergent tablets do not contain any disintegration aids. You are alone the incorporation of the phosphate compound according to the invention is sufficiently high Dissolution speed.

In another, also preferred variant, the washing and Detergent tablets 0.5 to 10 wt .-%, preferably 3 to 7 wt .-% and in particular 4 to 6% by weight of one or more disintegration auxiliaries, in each case 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, viewed formally, 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 disintegrants in granular or optionally contain cogranulated form, are in the German Patent applications DE 197 09 991 and DE 197 10 254 as well as international Patent application WO98 / 40463 described. These writings are also closer 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 coarser ones 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 another 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 receive 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 microfine celluloses delivers the microcrystalline celluloses that Have primary particle sizes of approx. 5 µm and, for example, 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.

In addition to the ingredients mentioned, phosphate compound and disintegration aid can the detergent tablets according to the invention additionally one or several substances from the groups of bleaching agents, bleach activators, enzymes, pH regulators, Fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, Silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, Color transfer inhibitors, corrosion inhibitors and silver preservatives included. These substances are described below.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate are of particular importance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced. If such bleach tablets are to be used for textile washing, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, regardless of which other ingredients are contained in the shaped bodies. If cleaning tablets or bleach tablets for machine dishwashing are manufactured, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxyaloacidoperoxycaproic acid (Pε) )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipinic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxydiperoxybiperyldoxybiperyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutanoic acid, 4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Chlorine or. Can also be used as bleaching agents in moldings for automatic dishwashing Bromine-releasing substances are used. Among the appropriate chlorine or bromine releasing materials come, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with Cations such as potassium and sodium are considered. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

To be one when washing or cleaning at temperatures of 60 ° C and below To achieve improved bleaching effects, bleach activators can be used in the detergent tablets according to the invention are incorporated. As Bleach activators can be compounds that are aliphatic under perhydrolysis conditions Peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid become. Substances containing O and / or N-acyl groups of the number of carbon atoms mentioned are suitable and / or optionally substituted benzoyl groups. Are preferred polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), Carboxylic anhydrides, especially phthalic anhydride, acylated polyvalent 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 salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.

Enzymes come from the class of proteases, lipases, amylases, Cellulases or their mixtures in question. Bacterial strains are particularly suitable or mushrooms such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus-derived enzymatic agents. Proteases are preferably from Subtilisin type and in particular proteases derived from Bacillus lentus, used. There are enzyme mixtures, for example of protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, in particular, however, cellulase-containing mixtures of particular interest. Also Peroxidases or oxidases have proven to be suitable in some cases. The Enzymes can be adsorbed on carriers and / or embedded in coating substances, to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules in the moldings according to the invention for example about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight. To the most commonly used enzymes include lipases, amylases, cellulases and Proteases. Preferred proteases are e.g. B. BLAP®140 from Biozym, Optimase®-M-440 and Opticlean®-M-250 from Solvay Enzymes; Maxacal®CX and Maxapem® or Esperase® from Gist Brocades or Savinase® from Novo. Especially suitable cellulases and lipases are Celluzym® 0.7 T and Lipolase® 30 T from Novo Nordisk. Duramyl® and Termamyl® are particularly used as amylases 60 T, and Termamyl® 90 T from Novo, Amylase-LT® from Solvay Enzymes or Maxamyl® P5000 from Gist Brocades. Other enzymes can also be used become.

In addition, the detergent tablets can also contain components contain, which have a positive influence on 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 with an inventive Detergent containing this oil and fat-dissolving component has been washed. To 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 from 15 to 30 wt .-% and hydroxypropoxyl groups from 1 to 15 % By weight, in each case based on the nonionic cellulose ether, and those from the prior art 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.

The moldings can, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed Compounds which instead of the morpholino group a diethanolamino group, a Carry a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also 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) diphenyl. Mixtures of the aforementioned brighteners can be used.

Dyes and fragrances are the detergent tablets according to the invention added to improve the aesthetic impression of the products and to the consumer, in addition to the softness performance, a visually and sensory "typical and to provide a distinctive "product. As perfume oils or fragrances individual fragrance compounds, e.g. synthetic products of the type Esters, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are e.g. benzyl acetate, Phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. To the ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g. the Jonone, ∝-isomethylionon and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons mainly include the terpenes such as 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 included as they are available from plant sources, e.g. 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 content of the detergent tablets according to the invention is usually in the range of dyes below 0.01% by weight, while fragrances up to 2% by weight of the can make up the entire wording.

The fragrances can be incorporated directly into the agents according to the invention But it can also be advantageous to apply the fragrances to the carrier, which have 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.

In order to improve the aesthetic impression of the agents according to the invention, they can be dyed with suitable dyes. Preferred dyes, their selection the expert has no difficulty, have a high storage stability and Insensitivity to the other ingredients of the agent and to light as well no pronounced substantivity towards textile fibers in order not to dye them.

Dishwasher detergent tablets according to the invention can be used to protect the dishes or the machine contain corrosion inhibitors, especially silver protection agents have a special meaning in the field of automatic dishwashing. In general, silver protection agents selected from the group of triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the Transition metal salts or complexes are used. Particularly preferred to benzotriazole and / or alkylaminotriazole are used. One finds in In addition, detergent formulations often contain active chlorine agents that corrode significantly reduce the silver surface. In chlorine-free cleaners especially oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, Gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds. Also salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. The are preferred here Transition metafl salts selected from the group of manganese and / or Cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the Cobalt (acetate) complexes, the cobalt (carbonyl) complexes; the chlorides of cobalt or Manganese and manganese sulfate. Zinc compounds can also be used for prevention corrosion on the wash ware.

Special ingredients that can be used in moldings according to the invention for machine dishwashing or cleaning hard surfaces are substances which prevent surfaces from being soiled again and / or facilitate the detachment of dirt after a single use (so-called “soil release compounds”).
The soil release connections that can be used include all connections known in the prior art. Cationic polymers, such as, for example, hydroxypropyltrimethylammonium guar, are particularly suitable; Copolymers of aminoethyl methacrylate and acrylamide and copolymers of dimethyldiallylammonium chloride. and acrylamide, polymers with imino groups, cationic cellulose derivatives, cationic homo- and / or copolymers (monomer units: quaternized ammonium alkyl methacrylate groups).

The cationic polymers are particularly preferably selected from cationic Polymers of copolymers of monomers such as trialkylammonium alkyl (meth) acrylate or -acrylamide; Dialkyldiallyldiammoniumsalze; polymeranalogous Reaction products of ethers or esters of polysaccharides with ammonium side groups, in particular guar, cellulose and starch derivatives; Polyadducts of Ethylene oxide with ammonium groups; quaternary ethyleneimine polymers and polyesters and Polyamides with quaternary side groups as soil release compounds. In the context of this application, natural ones are also exceptionally preferred Polyuronic acids and related substances, as well as polyampholytes and hydrophobized Polyampholytes, or mixtures of these substances.

In the moldings according to the invention, all of those described above can be used Ingredients are used; in addition to the phosphate compounds according to the invention other builders can also be contained in the moldings. In the Detergent tablets according to the invention can be used in addition to Phosphate compounds water-soluble and water-insoluble builders, especially for binding of calcium and magnesium can be used. Thereby are for detergent tablets preferred water-soluble builder because they work on dishes and hard surfaces in the Usually less tend to form insoluble residues. Usual builders working in Within the scope of the invention between 10 and 90 wt .-% based on the total Preparation can be present, in addition to the builders mentioned above low molecular weight polycarboxylic acids and their salts, the carbonates and silicates. To water-insoluble builders include the zeolites, which can also be used as well as mixtures of the aforementioned builder substances. In addition to the phosphate compounds of trisodium citrate and / or Sodium carbonate and / or sodium bicarbonate and / or gluconate and / or silicate Builder from the class of disilicates and / or metasilicates or layered silicates used.

Alkali carriers can be present as further constituents. Are considered to be alkali carriers Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, Alkali silicates, alkali metasilicates, and mixtures of the aforementioned Substances, in the sense of this invention preferably the alkali carbonates, in particular Sodium carbonate, sodium bicarbonate or sodium sesquicarbonate used become.

a) Herstellung eines erfindungsgemäßen Phosphat-Compounds nach einem erfindungsgemäßen Verfahren,

b) Abmischen des in Schritt a) hergestellten Compounds mit weiteren Inhaltsstoffen von Wasch- und Reinigungsmitteln zu einem zu verpressenden Vorgemisch,

c) Verpressen zu Formkörpern.

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

a) production of a phosphate compound according to the invention by a process according to the invention,

b) mixing the compound produced in step a) with further ingredients of detergents and cleaning agents into a premix to be pressed,

c) pressing into shaped bodies.

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

As already mentioned above, the washing and Detergent tablets according to the phosphate compounds according to the invention Intended use in varying amounts. The invention is also completely analogous Processes preferred in which the phosphate compound produced in step a) 10 to 90% by weight, preferably 20 to 80% by weight and in particular 25 to 70% by weight of the compressing premix.

Depending on the application, the phosphate compound according to the invention is used in step b) mixed with other ingredients of detergents and cleaning agents and for Molded body pressed. Methods according to the invention are preferred here, which thereby are characterized in that the phosphate compound produced in step a) in step b) with at least one oxygen bleach selected from the group of Alkali perborates, alkali percarbonates, organic peracids and hydrogen peroxide is mixed. The bleaches in question were described above.

In detergent tablets for the automatic cleaning of dishes can also other bleaching agents are used. In such cases, the invention Preferred processes in which the phosphate compound produced in step a) with at least one bleaching agent selected from the group of trichlorocyanuric acids, the Dichloro- or Monochlorcyanurate, the hypochlorite, and other common chlorine-containing Bleach is mixed.

The bleaching performance of moldings containing bleach is preferably such as Detergent tablets, detergent tablets or bleach tablets by the Use of bleach activators increased. This is the method according to the invention preferred, in which the phosphate compound produced in step a) with at least a bleach activator, preferably from the group of polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), the N-acylimides, especially N-nonanoylsuccinimide (NOSI), the acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methylsulfate (MMA) and / or the bleach-enhancing Transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably from the group of the manganese and / or cobalt salts and / or complex, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and / or the manganese sulfate is mixed.

In preferred process variants, that produced in step a) Foam inhibitor granules in step b) with at least one surfactant-containing granulate a premix to be pressed with a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l. in the Preferred methods within the scope of the present invention therefore include the Pressing a particulate premix of at least one phosphate compound, at least one surfactant-containing granulate and at least one admixed powdery component. The production of granules containing surfactants can be carried out using conventional technical granulation processes such as compacting, Extrusion, mixer granulation, pelleting or fluidized bed granulation take place.

In preferred process variants, the granules containing surfactant are sufficient Teilchengrößenkriterien. Methods according to the invention are preferred in which the 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.

In addition to the active substances (anionic and / or nonionic and / or cationic and / or amphoteric surfactants) preferably also contain the surfactant granules Carriers that particularly preferably come from the group of builders. Particularly advantageous processes are characterized in that the surfactant Granules contain anionic and / or nonionic surfactants and builders and Total surfactant contents of at least 10% by weight, preferably at least 20% by weight has in particular at least 25% by weight.

Depending on the intended use of the moldings according to the invention, the proportion of Select surfactant granules and the surfactant content of the granules higher or lower. If the phosphate compound according to the invention already contains surfactants, these are included the calculation of the total surfactant content. Usually the Surfactant content of detergent tablets between 10 and 40 wt .-%, preferably between 12.5 and 30% by weight and in particular between 15 and 25% by weight, while Detergent tablets for automatic dishwashing between 0.1 and 10% by weight, preferably between 0.5 and 7.5% by weight and in particular between 1 and 5 Wt .-% surfactants. Bleach tablets and water softener tablets are usually free of surfactants.

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

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 with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 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. 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 Caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, Stearic acid or behenic acid.

The 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 fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior 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 in themselves are nonionic surfactants (description see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Soaps are particularly suitable as further anionic surfactants. Are suitable saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural Fatty acids, e.g. 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.

When choosing the anionic surfactants, there is no freedom of formulation in the way. Preferred surfactant granules have However, a soap content of 0.2 wt .-%, based on the total weight of the Detergent tablets produced in step d) exceeds. Prefers Anionic surfactants to be used are the alkylbenzenesulfonates and Fatty alcohol sulfates, preferred detergent tablets 2 to 20% by weight, preferably 2.5 to 15% by weight and in particular 5 to 10% by weight of fatty alcohol sulfate (s), each based on the weight of the detergent tablets

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or can 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 fat 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, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Usable: Alkylpolyglycosides satisfy the general formula RO (G) _z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
Linear alkyl polyglucosides, ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.

The surfactant granules can preferably contain alkyl polyglycosides, with levels of APG over 0.2 wt .-%, based on the entire molded body, are preferred. Particularly preferred detergent tablets contain APG in amounts of 0.2 to 10 % By weight, preferably 0.2 to 5% by weight and in particular 0.5 to 3% by weight.

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 in particular not more than half of it.

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.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.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes.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] 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 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.

Regardless of whether anionic or nonionic surfactants or mixtures of these classes of surfactants and optionally amphoteric or cationic surfactants in The surfactant granules used are preferred according to the method of the invention which the surfactant content of the surfactant-containing granules is 5 to 60% by weight, preferably 10 up to 50 wt .-% and in particular 15 to 40 wt .-%, each based on the Granules of surfactant. moldings

It has already been mentioned above that in addition to the phosphate compounds in the moldings further builder substances can be included. Accordingly, it can be in the frame the invention may also be preferred if in step b) further builder substances; the preferably contain at least one aluminosilicate and / or a layered silicate with which Phosphate compound are mixed.

The aluminosilicate is preferably finely crystalline, synthetic and bound water-containing zeolites, in particular zeolite A, X and / or P. As zeolite P, for example, zeolite MAP ^(R) (commercial product from Crosfield) is used. However, zeolite Y and mixtures of A, X, Y and / or P are also suitable. Such a mixture of zeolite A and zeolite X is commercially available, for example, under the name Vegobond AX® (from Condea Augusta SpA). The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its production. In the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. 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.

Layered silicates are preferably crystalline, layered sodium silicates of the general formula NaMSi _x O _{2x + 1} .yH 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 understood. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

As already mentioned above, the washing and Detergent tablets further ingredients of detergents and cleaning agents included, so that preferred process variants are to be carried out analogously. An im Process preferred in the context of the present invention is characterized in that that the premix additionally a disintegration aid, preferably a Disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10 wt .-%, 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 Premix contains, it being additionally preferred that the premix additionally one or more substances from the group of 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 and silver protection agents.

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

The moldings according to the invention are first produced by dry Mixing the components, which can be partially or completely pre-granulated, and then Inform, in particular pressing to tablets, taking on conventional methods can be used. To make the Shaped body according to the invention, the premix in a so-called die compacted between two stamps to form a solid compact. This process, which takes place in The following, briefly referred to as tableting, is divided into four sections: Dosage, compression (elastic deformation), plastic deformation and ejection.

First of all, the premix is introduced into the die, the filling quantity and thus the weight and the shape of the molding being formed being determined by the position of the lower punch and the shape of the pressing tool. The constant metering, even at high molding throughputs, is preferably achieved by volumetric metering of the premix. As the tableting continues, the upper punch touches the premix and lowers further towards 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.

Eccentric tablet presses are preferred for small production quantities used, in which the stamp or stamps are attached to an eccentric, the in turn is mounted on an axis with a certain rotational speed. The Movement of this ram is with the operation of a standard four-stroke engine comparable. The pressing can be done with an upper and lower stamp However, several stamps can also be attached to an eccentric disc, the Number of die holes has been expanded accordingly. The throughputs of Eccentric presses vary from a few hundred to a maximum of 3000 tablets depending on the type per hour.

For larger throughputs, rotary tablet presses are selected in which a larger number of matrices are arranged in a circle on a so-called die table. The number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available. Each die on the die table is assigned an upper and lower punch, and again the pressure can be built up actively only by the upper or lower punch, but also by both stamps. The die table and the stamps move about a common vertical axis, the stamps being brought into the positions for filling, compression, plastic deformation and ejection by means of rail-like curved tracks during the rotation. At locations where 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, only a semicircle having to be run through to produce a tablet. For the production of two- and multi-layer molded articles, 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 tablets per hour.

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

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 and 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 separated from one another Individual elements can be formed, the predetermined dosage of the washing and / or Detergent corresponds. However, it is also possible to form compacts, which connect a plurality of such mass units in one compact, wherein the easy separability in portions by predetermined predetermined breaking points smaller units is provided. For the use of textile detergents in machines training of the type common in Europe with horizontally arranged mechanics the 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 pressing pieces.

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 moldings can be dosed directly into the induction bowl without a dosing aid, where it dissolves during the induction process. Of course, there is also a The detergent tablets can be used without any problems using a dosing aid Preferred within the scope of the present invention.

Another preferred molded body that can be produced has a plate or panel-like structure with alternating thick long and thin short segments, see above that individual segments of this "bolt" at the predetermined breaking points, the short display thin segments, can be canceled and entered into the machine can. This principle of the "bar-shaped" molded article detergent can also be used in other geometric shapes, such as vertical triangles, the are connected to each other only on one of their sides, can be realized.

But it is also possible that the different components do not become one uniform tablet are pressed, but that molded bodies are obtained, the have multiple layers, i.e. at least two layers. It is also there possible that these different layers have different dissolving speeds exhibit. This can result in advantageous application properties of the Moldings result. If, for example, components are contained in the moldings are, which mutually influence each other negatively, it is possible that one component to integrate in the faster soluble layer and the other component in one incorporate slower soluble layer so that the first component already has reacted when the second goes into solution. The layer structure of the moldings can this is done both in stacks, with the inner layer (s) dissolving the edges of the molded body already occurs when the outer layers are still are not completely solved, but it can also be a complete wrapping of the inner Layer (s) can be achieved through the layer (s) further out, what to prevent early release 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, i.e. 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 the envelope-shaped molded body, however, the outermost layers free of peroxy bleach are. Furthermore, it is also possible to use peroxy bleach and any present Bleach activators and / or enzymes spatially in a molded body separate. Such multilayered moldings have the advantage that they are not only via a detergent dispenser or a dosing device which is added to the wash liquor given, can be used; rather, in such cases it is also possible to put the molded body 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 the detergent composition to be pressed or the reach the entire molded body. The body to be coated can do this be sprayed with aqueous solutions or emulsions, for example, or over the process of melt coating received a 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 σ = 2 P πDt

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 molded body causes, D is the molded body diameter in meters and t is the height of the moldings.

Examples Phosphate compounds

Pentasodium triphosphate powder was used to produce the phosphate compounds a pure substance content of 98.3% and 0.3% by weight of water in a free-fall mixer (Flexomix®; company Schugi), which ran at a speed of 2600 rpm, with a 10% solution of a polyacrylate-maleate copolymer (Sokalan CP5®; BASF) sprayed. The agglomerate fell from the mixer into a fluidized bed and was at one Product temperature of 40 ° C within 45 minutes to a total water content dried by 13 wt .-%. The granules obtained had a raspberry shape Structure, the average particle diameter of the agglomerate particles around 550 microns was, but the primary particles forming the agglomerate almost smaller by a factor of 10 were than the average particle diameter of the agglomerates. The dates of the Granules obtained are given in Table 1.

The phosphate content in Table 1 was determined from the total phosphorus content (in the case of C4, the phosphorus contained in the phosphonate was subtracted here) and the total water content was measured at 160 ° C. Free water is the moisture that is split off up to 100 ° C, the stated crystal water content is the difference between the two values. A crystal water content of 8.1% by weight was determined for C1 using thermoanalytical methods (DTA-TG; heating rate: 10 K / min). Composition and physical parameters of the phosphate compounds (nb: not determined) compound C1 C2 C3 C4 Phosphate content [% by weight] 84.5 86.5 84.5 85.2 STP content [% by weight] 97.5 98.0 97.3 97.6 Copolymer [wt%] 2.5 1.5 1.5 1.5 HEDP - - - 1.3 Total moisture [% by weight] where: 13 12 14 12 free water [% by weight] 4.5 nb nb nb Water of crystallization [% by weight] 8.5 nb nb nb Bulk density [g / l] 760 820 800 790 Particle size distribution [% by weight] nb nb > 1.6 mm <1 <1 > 0.8 mm 13 10 > 0.4 mm 30 32 > 0.2 mm 45 49 <0.2 mm 11 8th d ₅₀ [mm] 0.55 nb nb 0.56

All of the compounds produced were easily soluble and quickly dissolved in water.

moldings

Shaped bodies were produced with Compound C1. For this purpose, the phosphate compound was mixed with further processing components and pressed on an eccentric tablet press according to Table 3. The composition of the premix to be pressed (and thus the composition of the moldings) can be found in Table 2. In addition to the specified ingredients, the moldings contained auxiliaries such as binders, disintegration aids, colorants and fragrances, fillers and water. Comparative Example V had the same formulation, but here phosphate and copolymer were used separately from one another, the phosphate being used in the form of a commercially available granulate with a free water content of more than 7% by weight. In the comparative example, considerably higher compression pressures were required to produce tablets of comparable hardness (see Table 3). Premix [wt%] phosphate 49 copolymer 3 phosphonate 1 Sodium hydroxide monohydrate 9 enzymes 4 surfactants 2 silicate 4 TAED 2

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. The measurement was carried out on a hardness tester CT5 (Holland) with punch diameters of 8 mm.

The dissolution time of the tablets was determined in a household dishwasher. The tablets were placed in the machine basket before the main rinse began placed, with the basket in the same place in all tests Machine. A 50 ° C program was used and the time until complete dissolution of the tablet is determined by tracking conductivity.

The experimental data of the individual tablet series are shown in Table 3. Properties of dishwasher tablets E1 E2 E3 E4 V Pressure [kN] 30 44 46 45 70 Tablet hardness [kg] - after pressing 10 15 20 17 13 - after 1 week 17 22 30 30 17 - after 4 weeks 22 34 36 38 17 - after 7 weeks 20 40 41 44 18 Dissolution time (min) - after pressing 6 8th 10 9 10 - after 1 week 6 9 10 10 12 - after 4 weeks 8th 10 11 12 12 - after 7 weeks 8th 10 12 11 12 Correlation hardness / dissolution time after pressing 17 19 20 19 13 - after 1 week 28 24 30 30 14 - after 4 weeks 28 34 33 32 14 - after 7 weeks 25 40 34 40 15

The correlation between hardness and dissolution time given in Table 3 is obtained by the value for the tablet hardness by the for the dissolution time to value obtained at the corresponding point in time and this factor by 10 is multiplied. The tablets are at the same time as hard as possible and one Fastest possible resolution desired. The factor used here provides one Possibility to optimize both parameters at the same time. It turns out that this factor is significantly better at all times in the examples according to the invention than in the comparative example.

Claims (25)

Use of a phosphate compound which is at least 50% by weight Pentasodium triphosphate, less than 5% by weight sodium pyrophosphate and maximum Contains 18% by weight of water and is present as an agglomerate of primary particles Improved stability of detergent tablets. Use according to claim 1, characterized in that the phosphate compounds contain 0.5 to 20% by weight of a polymeric polycarboxylate. Use according to one of claims 1 or 2, characterized in that the phosphate compounds contain 0.3 to 20% by weight of phosphonate. Use according to one of claims 1 to 3, characterized in that the phosphate compounds contain no nonionic surfactant and no silicate. Use according to one of Claims 1 to 4, characterized in that the phosphate compounds have a bulk density in the range 600 to 1000 g / l and the agglomerates have an average particle size in the range from 0.2 to 1.0 mm, preferably from the range 0.3 to 0.8 mm. Process for the preparation of phosphate compounds which are used according to one of Claims 1 to 5, characterized in that anhydrous, powdery pentasodium triphosphate in a high-speed mixer with 12 to 28% by weight of water, based on the pentasodium triphosphate, and optionally further ingredients of Washing and / or cleaning agents is agglomerated and the agglomerate is then immediately dried in a fluid bed drying at a product temperature below 60 ° C. to a free water content of below 5% by weight. Process for the preparation of phosphate compounds according to Claim 6, characterized in that the residence time of the phosphate in the high-speed mixer is less than 20 seconds and the agglomeration is carried out with 15 to 20% by weight of water. Process for the preparation of phosphate compounds according to one of claims 6 or 7, characterized in that the residence time of the agglomerate in the fluid bed dryer is between 10 and 60 minutes and the supply air temperature is below 130 ° C, preferably below 100 ° C. Process for the preparation of phosphate compounds according to one of claims 6 to 8, characterized in that further ingredients of washing and / or cleaning agents are mixed in dry form with the phosphate powder and the mixture is then agglomerated. Process for the preparation of phosphate compounds according to one of claims 6 to 9, characterized in that the water is used in the form of an aqueous solution of further ingredients of detergents and / or cleaning agents and the residence time of the phosphate in the high-speed mixer is less than 2 seconds , Use of phosphate compounds according to one of claims 1 to 5 or use of phosphate compounds produced by a process according to one of claims 6 to 10 for the production of detergent tablets, characterized in that at least 80% by weight, preferably at least 90% by weight and particularly preferably the total amount of the amount of phosphate contained in the shaped body is provided in the form of the aforementioned phosphate compounds. Use according to Claim 11, characterized in that 10 to 90% by weight, preferably 20 to 80% by weight and in particular 25 to 70% by weight, of the phosphate compound are used, based on the weight of the molded body. Use according to one of claims 11 or 12, characterized in that in addition a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 to 7 % By weight and in particular from 4 to 6% by weight, in each case based on the weight of the shaped body, is used. Use according to one of claims 11 to 13, characterized in that one or more substances from the groups of bleaching agents, bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors , Color transfer inhibitors, corrosion inhibitors and silver protection agents are used. A method for producing stability-improved detergent tablets by using phosphate compounds according to any one of claims 1 to 5, characterized by the steps a) production of a phosphate compound by a process according to one or more of claims 6 to 10, b) mixing the compound produced in step a) with further ingredients of detergents and cleaning agents into a premix to be pressed, c) pressing into shaped bodies. Process according to Claim 15, characterized in that the phosphate compound produced in step a) makes up 10 to 90% by weight, preferably 20 to 80% by weight and in particular 25 to 70% by weight of the premix to be pressed. Method according to one of claims 15 or 16, characterized in that the phosphate compound prepared in step a) is mixed in step b) with at least one oxygen bleaching agent selected from the group consisting of alkali perborates, alkali percarbonates, organic peracids and hydrogen peroxide. Method according to one of claims 15 to 17, characterized in that the phosphate compound produced in step a) is mixed with at least one bleaching agent selected from the group consisting of trichlorocyanuric acids, dichloro- or monochlorocyanurates, hypochlorites, and other customary chlorine-containing bleaching agents , Method according to one of claims 15 to 18, characterized in that the phosphate compound produced in step a) with at least one bleach activator, preferably from the group of polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), of N-acylimides, in particular N- Nonanoylsuccinimide (NOSI), the acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methylsulfate (MMA) and / or the bleach-enhancing transition metal complexes M, especially with the bleach-enhancing transition metal complexes , Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes , the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and / or manganese sulfate is mixed. Method according to one of claims 15 to 19, characterized in that the phosphate compound produced in step a) with at least one surfactant-containing granulate to form a premix to be pressed with a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l is combined. A method according to claim 20, characterized in that the surfactant-containing granules have particle sizes between 100 and 2000 µm, preferably between 200 and 1800 µm, particularly preferably between 400 and 1600 µm and in particular between 600 and 1400 µm. Method according to one of claims 20 or 21, characterized in that the surfactant-containing granules contain anionic and / or nonionic surfactants and builders and total surfactant contents of at least 10% by weight, preferably at least 20% by weight and in particular at least 25% by weight. -%, having. Method according to one of claims 15 to 22, characterized in that in step b) further builder substances, which preferably contain at least one aluminosilicate and / or a layered silicate, are mixed with the phosphate compound. Process according to one of claims 15 to 23, characterized in that the premix additionally contains a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably of 3 up to 7 wt .-% and in particular from 4 to 6 wt .-%, each based on the weight of the premix. Method according to one of claims 15 to 24, characterized in that the premix additionally one or more substances from the group of enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors Contains corrosion inhibitors and silver protection agents.