EP1141191B1 - Phosphate 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 suitable for incorporation in Washing or cleaning product tablets are suitable, and detergent tablets, containing such compounds. Next is a manufacturing method for stated such phosphate compounds.

In general, alkali phosphates are suitable as phosphorus-containing builders for Detergents and cleaners. In particular, trisodium phosphate, tetrasodium diphosphate, Disodium dihydrogen diphosphate, pentasodium triphosphate, so-called Sodium hexametaphosphate, oligomeric trisodium phosphate with Oligomerisierungsgrade in the range of 5 to 1000, in particular 5 to 50, and mixtures used from sodium and potassium salts. The most common of these is pentasodium triphosphate used.

In the incorporation of pentasodium triphosphate (STP) in washing or Cleaning agents should be noted that its hydration is a highly exergonic This process leads to overheating of detergent and cleaning agent components can. Accordingly, the hydration of the STP usually becomes at least partial before mixing with other ingredients

In the published patent application DE 29 13 145 a continuous process for Preparation of a detergent granules 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 stay The phosphate is in a second mixer with sodium silicate and optionally sodium carbonate mixed and granulated with renewed addition of water and then in a steam-saturated atmosphere for 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 at least a stoichiometric amount of water is transferred and then left in a closed container until the Level of hydration has reached at least 70%. Finally, the particles are on dried at 50 ° C water content of less than 5 wt .-% dried.

Spray-drying a slurries from a water-soluble inorganic phosphate with a polymeric polycarboxylate is described in the patent application DE 38 18 660. The resulting hollow spheres serve as a carrier for nonionic surfactant, which acts on the spheres in amounts of 2 to 40 wt .-% is sprayed. Pentasodium triphosphate is included one of the suitable phosphates.

Document GB-A-1466868 relates to a process for the preparation of porous granulated Materials and granules made by the process which are incorporated in a detergent formulation to be built in. The powder used for granulation contains alkali metal tripolyphosphates and a binder, e.g. Water. This binder, the cause the granulation is required is added after the powdered tripolyphosphate has been formed into a circular bed; the granulated Product is then kept in motion and z. B. dried in a fluidized bed.

The German patent application DE-A-29 25 137 discloses homogeneous, dust-free and free-flowing Washing and cleaning agent granules based on pentasodium tripolyphosphate, which are virtually free of hydrolysis products of the polyphosphate, as well as a Process for their continuous production. These granules contain, among others Components, 50 to 80% by weight of pentasodium tripolyphosphate and 10 to 25% by weight, in particular 9 to 19 wt .-% water. The ratio of ortho and sodium pyrophosphate to the total phosphate is 0.005 to 0.08 wt .-%.

From the German patent application DE-A-44 35 743 is a process for the preparation a multi-component granules for use in detergents and cleaners known in which in a continuous Agglomeriermischer a powder detergent component Granulated with the addition of a binder to granules becomes. Subsequently, the drying takes place in a drying device, for example in a fluid bed dryer. A prepared by this process phosphate-containing Multi-component granules containing 15 to 50 wt .-% sodium tripolyphosphate and 3 to 15% by weight of water, in particular 4 to 8% by weight of water.

A granular composition containing a hydrate-forming phosphate, preferably Pentasodium triphosphate, 0.1 to 23 wt .-% water and 2 to 125 ppm of surfactant is described in European patent EP-B-259 291. This is manufactured 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 water of hydration in the product in favor of the water of hydration shifts. The degree of preservation of the pentasodium triphosphate is with this Method between 84 and 94% of the phosphate content. Such a low phosphate balance and associated high pyrophosphate content results in use such granules when washing dishes to undesirably strong glass corrosion.

Now it was found that phosphate compounds. which contain little pyrophosphate, i. have a high degree of phosphate retention, and are present as agglomerates ideal for incorporation in moldings of detergents and cleaners and even improve the dissolution behavior of these moldings.

A first subject of the invention are accordingly phosphate compounds for Use in detergents or cleaners containing at least 50% by weight Pentasodium triphosphate, less than 5 wt .-% sodium pyrophosphate and maximum Contain 18% by weight of water and are present as agglomerates of primary particles, characterized in that the content of the compounds in free water at most 5% by weight, preferably at most 3% by weight, and the content of pentasodium triphosphate hexahydrate between 20 and 70% by weight of Total content of pentasodium triphosphate is.

Due to its high calcium binding capacity, pentasodium triphosphate (STP), which is anhydrous in crystalline form or as hexahydrate, of particular Interest as a builder in detergents and cleaners, and is accordingly intended as Be contained main component in the compounds of the invention. The content of STP is at least 50% by weight, preferably over 70% by weight, and especially preferably even more than 80 wt .-% of the total compounds.

Due to the desired high content of STP content of the compounds should other phosphates, especially ortho-, meta- and pyrophosphates be low. Preference is given to less than 5% by weight, in particular even less than 3% by weight, of these Phosphates contained in the compound. Expressed is the proportion of these phosphates on the degree of retention of the pentasodium triphosphate in the compound (STP preservation level). It is preferably at least 95%, more preferably even at least 97%. In particular, a high pyrophosphate content leads to the use of such Compounds in dishwashing agents to an unwanted reinforcement of Glass corrosion. Such disadvantages avoid the compounds according to the invention, in containing less than 5% by weight of sodium pyrophosphate, it being preferred that when the sodium pyrophosphate content is even less than 3% by weight or lower.

In addition to phosphate, the compound contains a proportion of water which is not more than 18% by weight. can amount. However, preferred compounds contain water too much 15 wt .-%, wherein a water content of at most 13 wt .-% also be preferred can. If particularly phosphate-rich compounds are to be produced, then it is even possible a water content of at most 11 wt .-% may be preferred. The water is in the Compounds for the most part as water of hydration ago. The content is Pentasodium triphosphate hexahydrate between 20 and 70 wt .-% of the content of pentasodium triphosphate in total. The content of the compounds in free water, i.e. not as water of hydration bound water should be as low as possible. He is not more than 5% by weight, with a maximum free water content of 3% by weight may be preferred. In a special, preferred Embodiment, the content of free water should be less than 1.5 wt .-%.

The free water is released already below 100 ° C and can therefore at This temperature can be determined.

In addition to these ingredients, the compounds may contain other ingredients of laundry and / or Detergents included. These may preferably be substances which Cobuildereigenschaften have. Here are primarily polycarboxylates, in particular polymeric polycarboxylates, and to call phosphonates.

Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol. In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molar masses 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 with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally almost twice as high as the molecular weights 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, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again 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 from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol. Such polymeric polycarboxylates are preferably included in the compounds because they are not only effective as co-builders but can also serve as agglomeration aids. The content of (co) polymeric polycarboxylates in the compounds is preferably 0.5 to 20% by weight, in particular 3 to 15% by weight.

To improve the water solubility, the polymers may also be allyl sulfonic acids, for example, in EP-B-727448 allyloxybenzenesulfonic acid and Methallylsulfonic acid, as a monomer. Especially preferred are also biodegradable polymers from more than two different monomer units, for example, those according to DE-A-43 00 772 as monomers salts of Acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives. Further preferred copolymers are those described in 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 vinyl acetate.

As phosphonates in particular hydroxyalkane and Aminoalkanphosphonate be included. Among the hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a co-builder. It is preferably used as the sodium salt, wherein the disodium salt is neutral and the tetrasodium salt alkaline (pH 9) reacts. As Aminoalkanphosphonate are preferably Ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of neutral sodium salts, e.g. B. as hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. As a builder is doing this The class of phosphonates preferably uses HEDP, and is accordingly then preferably included in the compounds, if these compounds as Builder compounds are designed, i. as predominant or sole builder in wash or Detergents 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 Aminoalkanphosphonate, in particular DTPMP, or Mixtures of the mentioned phosphonates are included. The salary of Compounds of total phosphonates is preferably 0.3 to 20 wt .-%.

Even if the compounds. are designed as builder compounds, it is preferred that these compounds do not contain silicates, especially no sodium silicates, or insoluble A-luminosilicates contain. Accordingly, the compounds are mainly for Use in agents that contain phosphate as the main builder. Should-in the means more inorganic builders are included, they are preferably separated from the Introduced phosphate compounds. Other ingredients of detergents and cleaners, especially surfactants, may be included in the compounds, wherein they but preferably only in small amounts or not at all. especially the Frequently used as granulating aids nonionic surfactants are preferred in the compounds not included.

Essential for the invention. Properties of the compounds is their form. she are present as agglomerates, which are formed from primary particles. The mean particle size The agglomerates, as it emerges from a sieve analysis, is preferably in the range of 0.2 to 1.0 mm, especially in the range of 0.3 to 0.8 mm. The mean diameter of the primary particles is in preferred embodiments about a factor of 5, preferably even a factor of 10, less than the mean particle size of the agglomerates. Because of this special structure are the Compounds themselves easily and quickly soluble. The compounds usually have one Bulk density in the range 600 to 1000 g / l, wherein the bulk density of the compounds preferably between 700 and 900 g / l. This particular form of compounds also places special demands on a manufacturing process for such compounds.

A second subject of the invention is accordingly a process for the preparation Such phosphate compounds, which is characterized in that anhydrous, powdery Pentasodium triphosphate in a high speed mixer with 12 to 28 wt .-% water, based on the pentasodium triphosphate, and optionally further Ingredients of detergents and / or cleaning agents is agglomerated and the Agglomerate immediately afterwards in a fluidized bed drying at a product temperature dried below 60 ° C to a content of free water of less than 5 wt .-%.

Under powdered, anhydrous pentasodium triphosphate (STP) are thereby understood commercial pentasodium triphosphate qualities, the maximum 1 wt .-% May contain moisture. There are two of the anhydrous form of STP Modifications, referred to as Phase I, metastable at room temperature High temperature modification and the stable at room temperature phase II. This Both phases also differ in their rate of hydration. Phase I absorbs water much faster than Phase II Hydration process liberated heat heats pentasodium triphosphate during this process may be so strong that it may decompose the Triphosphate is coming. Since this decomposition is undesirable, is at most Hydration method for STP a specific ratio of phase I to phase II necessary to avoid overheating. In general, must be predominantly Phase II to prevent decomposition of the STP during hydration can be. The present method is largely independent of the proportion of both phases, it can with any ratio of phase I to phase II be performed. Are particularly high Triphosphaterhaltungsgrade achieved However, it is also advantageous in 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 tumbler mixer. The term "high speed" means that such mixers at a speed of several revolutions per second, preferably above 1500 Umin ^-1 , mix. The residence time of the phosphate is in the mixer 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, wherein 12 to 28 wt .-%, preferably 15 to 20 wt .-%, of the phosphate weight is applied as water. In a specific variant of the process, less than 18% by weight of water is applied.

Are the phosphate even more, already described above ingredients of Blended with detergents and / or cleaning agents, they 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. one In another preferred embodiment, an aqueous solution of at least one of Ingredients used for spraying in high-speed mixer. It can other ingredients have already been mixed dry with the phosphate.

From the mixer, the wet compound without loss of time in a drying device, which is designed as a fluidized bed drying, transferred. In the simplest case, if one Free-fall mixer is used, the compound falls directly from the mixer to the fluidized bed. The drying in the fluidized bed is carried out under mild conditions, the product temperature preferably even below 60 ° C during the entire process 45 ° C. This is achieved by a suitable choice of the supply air temperature optimum supply air temperature depending on the size of the fluidized bed and the supplied Air volume. However, it has been shown that generally with a supply air temperature a maximum of 130 ° C overheating of the product can be avoided. Preferably, however, the supply air temperature is a maximum of 100 ° C. In one embodiment becomes the released heat of hydration of the triphosphate for drying used and the supply air not preheated. But even if preheated supply air supplied However, the process still has the advantage, the heat of hydration simultaneously to use for drying and accordingly with compared to other methods little additional energy supplied. Through these mild conditions, especially the low product temperature, a decomposition of the triphosphate largely prevented. After drying, preferably still at least 95 wt .-% of the phosphate as a triphosphate ago. The drying takes place until, until the content of free water is not more than 5% by weight, preferably not more than 3% by weight, lies. In general, the required residence time of the agglomerate is in the Fluid bed dryer between 10 and 60 minutes.

On the fluidized bed drying can be followed by a return. Fine parts can optionally together with the filter dusts from the fluid bed dryer turn the Grobkom preferred before recycling is ground in a hammer mill and the fluidized bed drying after at least one third of the route, preferably after more than two thirds of the route, again is supplied.

The above - described phosphate compound is excellent for Incorporation in detergent tablets, such as Detergent tablets for washing textiles, detergent tablets for automatic dishwashing or cleaning of hard surfaces, Bleach moldings for use in washing machines or dishwashers, Water softening tablets or patch salt tablets.

Another object of the present invention is therefore the use of Phosphate compounds, which after mixing with finely divided treatment components pressed in a conventional manner to washing and Reinigungsmittefformkörpem be used to improve the stability and solubility of washing and Reinigungsmittelformkörpem. Through the use of the phosphate compounds according to the invention, after mixing with other components to washing and Cleaning agent molding can be pressed, the physical properties the shaped body, in particular the mechanical stability and the solubility behavior, be significantly improved. This can be washed and pressed with low pressures Prepare detergent tablets which have sufficient mechanical stability in packaging, transport and handling. Opposite the insert Conventional phosphates can in this way equal stable tablets lower pressing pressures are produced, so that the wear on the Tabletting significantly reduced and their life is extended.

Another object of the present invention are also washing and Detergent shaped body of compacted particulate washing and Detergents containing a phosphate compound according to the invention.

It is of course possible here, the phosphate compounds of the invention in mixture with conventional and commercially available phosphates. Preferably, however, the majority of the phosphate contained in the moldings comes from the phosphate compounds according to the invention. Washing and Reinigungsmitteiformkörper which at least 80 wt .-%, preferably at least 90th Wt .-% and particularly preferably the total amount contained in the molding Phosphate amount in the form of phosphate compounds according to the invention are included therefore preferred.

Depending on the intended use, the phosphate compounds can be used according to the invention Detergents and cleaning agent tablets in varying amounts in the Formkörpem be included. In this case, washing and cleaning agent tablets are preferred which, based on the weight of the molding, 10 to 90 wt .-%, preferably 20 to 80 Wt .-% and in particular 25 to 70 wt .-% of the phosphate compound.

In order to facilitate the disintegration of highly compacted moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrating agents, in order to shorten the disintegration times. According to Römpp (9th edition, volume 6, page 4440) and Voigt "Textbook of Pharmaceutical Technology" (6th edition, 1987, pages 182-184), excipients are understood to mean excipients which are suitable for rapid disintegration of tablets in water or gastric juice and for the release of the drugs in resorbable form.

These substances, which are also called "explosives" because of their effect, enlarge their volume when water enters, on the one hand increases the intrinsic volume (Swelling), on the other hand also on the release of gases pressure to be generated may cause the tablet to disintegrate into smaller particles. Well-known Disintegration aids are, for example, carbonate / citric acid systems, wherein also other organic acids can 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 no disintegration aids. They show alone the incorporation of the phosphate compound according to the invention a sufficiently high Dissolution speed up.

In another, likewise preferred variant contain the washing and Detergent tablets 0.5 to 10 wt .-%, preferably 3 to 7 wt .-% and in particular 4 to 6 wt .-% of one or more Cesintegrationshilfsmittel, respectively based on the molding body weight.

As preferred disintegrating agents, cellulose-based disintegrating agents are used in the present invention, so that preferred washing and Reinigungsmittelformkörper- such disintegrating agent based on cellulose in amounts of 0.5 to 10 wt .-%, preferably 3 to 7 wt .-% and in particular 4 to 6 wt .-% included. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and formally represents a β-1,4-polyacetate of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives.

The cellulose used as disintegration aid is preferably not in used finely divided form, but before admixing to be pressed Premixes converted into a coarser form, for example, granulated or compacted. Detergents and cleaning agents, the disintegrators in granular or optionally cogranulated form are in the German Patent applications DE 197 09 991 and DE 197 10 254 and the international Patent Application WO98 / 40463. These writings are also closer Information on the production of granulated, compacted or cogranulated Remove cellulose explosives. The particle sizes of such disintegrating agents are usually above 200 microns, preferably at least 90 wt .-% between 300 and 1600 microns and in particular at least 90 wt .-% between 400 and 1200 microns. The coarser ones mentioned above and described in more detail in the cited documents Cellulosic disintegration aids are within the scope of the present invention preferably used as a disintegration aid and in the trade, for example, under the name Arbocel® TF-30-HG of the company Rettenmaier available.

Another disintegrating agent based on cellulose or as part of this Component may be used microcrystalline cellulose. This microcrystalline Cellulose is produced by partial hydrolysis of celluloses under such conditions containing only the amorphous regions (30% of the total cellulose mass) of the Celluloses attack and completely dissolve, but the crystalline areas (70%) leave undamaged. Subsequent deaggregation by hydrolysis resulting micro-fine celluloses provides the microcrystalline celluloses, the Primary particle sizes of about 5 microns and, for example, with granules a mean particle size of 200 microns are compacted.

For the purposes of the present invention, preferred washing and Detergent tablets also contain a disintegration aid, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, respectively based on the molding body weight ,.

In addition to the ingredients listed phosphate compound and disintegration aids can the detergent tablets according to the invention additionally one or more substances from the groups of bleaches, bleach activators, enzymes, pH adjusters, fragrances, perfume carriers, fluorescers, dyes, Foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, Grayness inhibitors, color transfer inhibitors, corrosion inhibitors and Contain silver protectants. These substances are described below.

Among the compounds which serve as bleaches and deliver in water H ₂ O ₂ , the sodium perborate tetrahydrate, the sodium perborate monohydrate and the sodium percarbonate have particular significance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid 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, irrespective of which further ingredients are contained in the shaped bodies. When cleaning or bleaching tablets for automatic dishwashing are prepared, it is also possible to use bleaching agents from the group of organic bleaching agents. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. 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-phthalimidoperoxycaproic acid [Phthaloiminoperoxyhexanoic acid (PAP ), o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutan-1, 4-diacid, N, N-terephthaloyl-di (6-aminopercaproic acid) can be used.

As bleaching agents in machine dishwashing moldings, chlorine may also be used or bromine-releasing substances are used. Under the appropriate chlorine or Bromo-releasing materials include, for example, heterocyclic N-bromo and N-chloroamides, for example, trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or salts thereof with Cations such as potassium and sodium into consideration. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable

To wash or clean at temperatures of 60 ° C and below To achieve improved bleaching action, bleach activators can be incorporated into the Detergent tablets according to the invention are incorporated. When Bleach activators may be compounds that are under perhydrolysis conditions aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, be used. Suitable substances are the O- and / or N-acyl groups of bear C-atomic number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular Tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (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 may also so-called bleach catalysts are incorporated into the moldings. In these Substances are bleach-enhancing transition metal salts or Transition metal complexes such as Mn, Fe, Co, Ru or Mo saline 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 ammine complexes are useful as bleach catalysts.

Enzymes are those from the class of proteases, lipases, amylases, Cellulases or mixtures thereof in question. Particularly suitable are from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. Preferably, proteases are from Subtilisin type and in particular proteases derived from Bacillus lentus, used. These are enzyme mixtures, for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or protease, amylase and lipase or protease, lipase and cellulase, but especially cellulase-containing mixtures of particular interest. Also Peroxidases or oxidases have proven to be suitable in some cases. The Enzymes can be adsorbed to carriers and / or embedded in encapsulating substances be to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules in the moldings of the invention can for example, 0.1 to 5 wt .-%, preferably 0.1 to 2 wt .-% amount. The most commonly used enzymes include lipases, amylases, cellulases and proteases. Preferred proteases are, for. B. BLAP®140 Fa. 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 the company. Novo Nordisk. Particular use as amylases is found in Duramyl® and Termamyl® 60 T, and Termamyl® 90 T from Novo, Amylase-LT® from Solvay Enzymes or Maxamyl® P5000 from Gist Brocades. Other enzymes can be used become.

In addition, the detergent tablets may also contain components which positively influence the oil and Fettauswaschbarkeit from textiles (so-called soil repellents). This effect becomes particularly apparent when a textile is contaminated, which previously several times with an inventive Detergent containing this oil and fat dissolving component was washed. To the preferred oil and fat dissolving components include, for example, nonionic Cellulose ethers such as methylcellulose and methylhydroxy-propylcellulose with a proportion at methoxyl groups from 15 to 30 wt .-% and hydroxypropoxyl groups from 1 to 15 wt .-%, each based on the nonionic cellulose ether, and from the State of the art known polymers of phthalic acid and / or terephthalic acid or of their derivatives, in particular polymers of ethylene terephthalates and / or Polyethylene glycol terephthalates or anionic and / or nonionic modified Derivatives of these. Particularly preferred of these are the sulfonated derivatives of Phthalic acid and the terephthalic acid polymers.

The moldings can be used as optical brighteners derivatives of Diaminostilbendisulfonsäure 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 Methylamino group, an anilino group or a 2-Methoxyethylaminogruppe carry. Furthermore, brighteners of the substituted diphenylstyrene type may be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls. Also mixtures of The aforementioned brighteners can be used.

Dyes and fragrances are the washing and Reinigungsmittelformkörpem invention added to improve the aesthetic appearance of the products and the consumer in addition to the softness a visually and sensory "typical and unmistakable "product as perfume oils or fragrances For example, individual perfume compounds, e.g. the synthetic products of the type Esters, ethers, aldehydes, ketones, alcohols and hydrocarbons are used. Fragrance compounds of the ester type are known e.g. benzyl acetate, Phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. To the Ethem include, for example, benzyl ethyl ether, to the aldehydes e.g. the linear alkanals with 8-18 carbon atoms. Citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the ionone, α-isomethylionone 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, preference is given Used mixtures of different fragrances, which together create an appealing Create a fragrance. Such perfume oils can also be natural fragrance mixtures as 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, lime blossom oil, juniper berry oil, Vetiver oil, Olibanum oil, Galbanum oil and Labdanum oil and Orange blossom oil, Neroliol, Orange peel oil and sandalwood oil.

Usually, the content of the detergent tablets according to the invention is Dyes below 0.01 wt .-%, while perfumes up to 2 wt .-% of entire formulation can make.

The fragrances can be incorporated directly into the compositions according to the invention However, it may also be advantageous to apply the fragrances to carriers, the adhesion of the perfume on the lingerie and by a slower release of fragrance for long-lasting fragrance of the textiles. As such carrier materials have become For example, cyclodextrins have proven useful, with the cyclodextrin-perfume complexes additionally can be coated with other excipients.

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

Dishwashing agent shaped bodies according to the invention can be used to protect the items to be washed or the machine contain corrosion inhibitors, with particular silver protectants have special significance in the field of automatic dishwashing. In general, especially silver protectants 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 too use are benzotriazole and / or alkylaminotriazole. One finds in In addition, cleaner formulations often include active chlorine containing agents Corrosion of the silver surface can significantly reduce. In chlorine-free cleaner are particularly oxygen- and nitrogen-containing organic redox-active Compounds such as di- and trihydric phenols, e.g. Hydroquinone, pyrocatechol, Hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these Classes of compounds. Also salt and complex inorganic compounds, such as Salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are frequently used. Preferred are here the transition metal salts, which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate. Likewise, zinc compounds be used to prevent corrosion of items to be washed.

Special ingredients which are used in machine bodies according to the invention Dishwashing or cleaning hard surfaces can be used Substances that prevent the re-soiling of surfaces and / or the Easily remove dirt after a single use (so-called "soil release compounds").

Among the usable soil release compounds are all in the prior art known compounds. Particularly suitable are cationic polymers, such as for example, hydroxypropyltrimethylammonium guar; 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 Polymers of copolymers of monomers such as trialkylammonium alkyl (meth) acrylate or -acrylamide; Dialkyldiallyldiammoniumsalze; polymeranalogous Reaction products of ethers or esters of polysaccharides with pendant ammonium 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. Exceptionally preferred in the context of this application are also natural 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 the above-described Ingredients are used; in addition to the phosphate compounds of the invention Other builders may also be included in the moldings. In the Detergent tablets according to the invention may be used in addition to Phosphate Compounds Water-soluble and water-insoluble builders especially for Binding of calcium and magnesium are used. Here are for Detergent Tablets Water-soluble builders preferred as they are on dishes and Hard surfaces usually tend to be less susceptible to insoluble residues form. Typical builders which in the context of the invention comprise between 10 and 90% by weight. are present in relation to the entire preparation, in addition to the already Buildem mentioned above, the low molecular weight polycarboxylic acids and their salts, the Carbonates and silicates. Water-insoluble buildem include the zeolites, which also can be used, as well as mixtures of the aforementioned builders. Preference is given in addition to the phosphate compounds according to the invention Trisodium citrate and / or sodium carbonate and / or sodium bicarbonate and / or Gluconates and / or silicatic builders from the class of disilicates and / or Metasilicates or the layered silicates used.

As further constituents alkali carriers may be present. To be considered as alkali carriers Alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, Alkatimetallsesquicarbonate, alkali silicates, alkali metal silicates, and mixtures of the abovementioned substances, preference being given in the context of this invention to the alkali metal carbonates, especially sodium carbonate, sodium bicarbonate or sodium sesquicarbonate be used.

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 Formkörpem.

Another object of the present invention is a process for the preparation of washing and Reinigungsmittelformkörpem, characterized by the steps

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

b) mixing the compound prepared in step a) with further ingredients of detergents and cleaners to form a premix to be compressed,

c) pressing into shaped bodies.

In the first process step, as described in detail above, a phosphate compound is produced. In selecting the machines and process parameters suitable for this process step, the person skilled in the art can use literature-known machines and apparatus 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 inventive washing and Detergent tablets the phosphate compounds of the invention depending on Intended use in varying quantities. Completely analogous are also inventive Preferred method in which the prepared in step a) phosphate compound 10 bis 90 wt .-%, preferably 20 to 80 wt .-% and in particular 25 to 70 wt .-% of the constituting the compressing premix.

Depending on the application, the phosphate compound according to the invention in step b) mixed with other ingredients of detergents and cleaners and for Molded body pressed. In this case, methods according to the invention are preferred which are characterized characterized in that the phosphate compound prepared 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 bleaching agents in question were described above.

In detergent moldings for the machine cleaning of dishes can also other bleaching agents are used. In such cases are inventive Preferred method in which the phosphate compound prepared in step a) with at least one bleaching agent selected from the group of trichlorocyanuric acids, dichloro- or monochlorocyanurates, hypochlorites, and other usual ones chlorine-containing bleaching agent is mixed.

Preferably, the bleaching performance of bleach-containing Formkörpem as Detergent tablets, detergent tablets or bleach tablets through the Use of bleach activators increased. Such are methods according to the invention preferred in which the phosphate compound prepared in step a) with at least a bleach activator, preferably from the group of the multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED). the N-acylimides, especially 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, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably from the group of manganese and / or cobalt salts and / or complexes, more 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) Phosphate compound with at least one surfactant-containing granules too a premix to be compressed with a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l combined. in the Therefore, preferred methods of the present invention include the Pressing a particulate premix of at least one phosphate compound, at least one surfactant-containing granules and at least one admixed powdered component. The preparation of surfactant-containing granules can by conventional technical Granulationsverfähren such as compaction, Extrusion, mixer granulation, pelleting or fluidized bed granulation done.

The surfactant-containing granules are sufficient in preferred process variants Teilchengrößenkriterien. Thus, methods according to the invention are preferred in which the surfactant-containing granules particle sizes between 100 and 2000 microns, preferably between 200 and 1800 microns, more preferably between 400 and 1600 microns and especially between 600 and 1400μm, has.

In addition to the active substances (anionic and / or nonionic and / or cationic and / or amphoteric surfactants) preferably still contain the surfactant granules Carriers which more preferably originate from the group of builders. Particularly advantageous methods are characterized in that the surfactant-containing Granules containing anionic and / or nonionic surfactants and builders and Total surfactant contents of at least 10% by weight, preferably at least 20% by weight in particular at least 25% by weight.

Depending on the intended use of the shaped body 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 also included the calculation of the total surfactant content. Usually it is Tenside content of detergent tablets between 10 and 40 wt .-%, preferably between 12.5 and 30% by weight and especially between 15 and 25% by weight while Detergent tablets for automatic dishwashing between 0.1 and 10 wt .-%, 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 surfactants come from the group of anionic, nonionic, zwitterionic or cationic surfactants, with anionic surfactants for economic reasons and because of their range of services clearly preferred are.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C _12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Under Fatty acid glycerol esters are the mono-, di- and triesters and mixtures thereof as understood in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol to be obtained. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 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.

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. Also, 2,3-alkyl sulfates prepared, for example, according to U.S. Patents 3,234,258 or 5,075,041, which can be obtained as commercial products of the Shell Oil Company under the name DAN®, are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C _7-21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C _12-18 . Fatty alcohols with 1 to 4 EO are suitable. They are used in detergents due to their high Schaumverhattens only in relatively small amounts, for example in amounts of 1 to 5 wt .-%.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) yl-succinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

As further anionic surfactants are particularly soaps into consideration. 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 soaps may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or Triethanolamine. Preferably, the anionic surfactants are in the form their sodium or potassium salts, in particular in the form of the sodium salts.

When selecting the anionic surfactants, the freedom from formulation is none to be observed in the way. Preferred surfactant granules have However, a content of soap, which is 0.2 wt .-%, based on the total weight of In step d) produced detergent and cleaner molding exceeds. Preferred anionic surfactants are the alkylbenzenesulfonates and Fatty alcohol sulfates, preferred detergent tablets being from 2 to 20% by weight, preferably from 2.5 to 15% by weight and in particular from 5 to 10% by weight of fatty alcohol sulphate (e), in each case based on the weight of the detergent tablets

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

Another class of preferred nonionic surfactants used either as sole nonionic surfactant or in combination with other nonionic surfactants Surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 Carbon atoms in the alkyl chain, especially fatty acid methyl esters, as they For example, in Japanese Patent Application JP 58/217598 are described or preferably according to the method described in International Patent Application WO-A-90/13533 be prepared described methods.

Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG). Usable alkylpolyglycosides satisfy the general formula RO (G) _z , in which R is a linear or branched, in particular in the 2-position methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably 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.
Preference is given to using linear alkyl polyglucosides, that is to say alkyl polyglycosides in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.

The surfactant granules may preferably contain alkylpolyglycosides, wherein contents of APG over 0.2 wt .-%, based on the total molding, are preferred. Particularly preferred detergent tablets contain APG in amounts of from 0.2 to 10 Wt .-%, preferably 0.2 to 5 wt .-% and in particular from 0.5 to 3 wt .-%.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the Fatty acid alkanolamides may 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.Further suitable surfactants are polyhydroxy fatty acid amides of the formula (I)

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

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 the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with 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 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 may then be, for example according to the teaching of international application WO-A-95/07331 by reaction with Fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxyfatty acid amides are transferred.

Regardless of whether anionic or nonionic surfactants or mixtures of These surfactant classes and optionally amphoteric or cationic surfactants in Tensidgranulat are used, methods of the invention are preferred in the surfactant content of the surfactant-containing granules 5 to 60 wt .-%, preferably 10 to 50 wt .-% and in particular 15 to 40 wt .-%, each based on the Surfactant granules, is.

It has already been mentioned above that in addition to the phosphate compounds in the moldings Other builders may be included. Accordingly, it may be in the Also be preferred within the scope of the invention, if in step b) more Builders, preferably at least one aluminosilicate and / or a Layered silicate, are mixed with the phosphate compound.

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. Also suitable, however, are zeolite Y and mixtures of A, X, Y and / or P. 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 else as undried, still moist, stabilized suspension of its preparation. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols having 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Among 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 sheet 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 is 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 cleaners included, so that preferred variants of the method are analog. An im Under the present invention preferred method is characterized in that that the premix additionally a disintegration aid, preferably a Cellulosic disintegration aids, preferably granular, co-granulated or compacted form, in amounts of from 0.5 to 10% by weight, preferably from 3 to 7 Wt .-% and in particular from 4 to 6 wt .-%, each based on the weight of Premix, it being additionally preferred that the premix additionally one or more substances from the group of enzymes, pH adjusters, fragrances, Perfume carriers, fluorescers, dyes, foam inhibitors, silicone oils, Anti redeposition agents, optical brighteners, grayness inhibitors, color transfer inhibitors, Contains corrosion inhibitors and silver protectants.

Prior to compression of the particulate premix into detergent tablets, the premix may be "powdered" with finely divided surface treatment agents. This may be advantageous for the nature and physical properties of both the premix (storage, compression) and the finished detergent tablets. Fine particulate powdering agents are well known in the art, with mostly zeolites, silicates or other inorganic salts are used. Preferably, however, the premix is "powdered" with finely divided zeolite, with 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 structural group 4 (cf. Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York , London, Sydney, Toronto, 1974, page 92). In addition to zeolite X, it is thus also possible to use zeolite Y and faujasite and also mixtures of these compounds, the pure zeolite X being preferred.
Mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites, which need not necessarily belong to the zeolite structure group 4, can be used as a powdering agent, it being advantageous if at least 50 wt .-% of the powdery powder of a zeolite of faujasite Type persist.

The production of the shaped body according to the invention is initially carried out by the dry Mixing the ingredients, which may be pre-granulated in whole or in part, and subsequent Informing, in particular pressing into tablets, wherein conventional methods can be used. For the production of Shaped body according to the invention is the premix in a so-called template compressed between two stamps to a fixed compressed. This process, in the hereinafter referred to as tableting, is divided into four sections: Dosing, compaction (elastic deformation), plastic deformation and ejection.

First, the premix is introduced into the die, wherein the filling amount and thus the weight and the shape of the resulting shaped body are determined by the position of the lower punch and the shape of the pressing tool. The constant dosage even at high molding throughputs is preferably achieved via a volumetric metering of the premix. As the tableting progresses, the upper punch contacts the pre-mix and continues to descend toward the lower punch. In this compression, the particles of the premix are pressed closer to each other, with the void volume within the filling between the punches decreasing continuously. From a certain position of the upper punch (and thus from a certain pressure on the premix) begins the plastic deformation, in which the particles flow together and it comes to the formation of the molding. Depending on the physical properties of the premix, some of the premix particles are also crushed, and even higher pressures cause sintering of the premix. With increasing pressing speed, so high throughput amounts, the phase of the elastic deformation is shortened more and more, so that the resulting moldings may have more or less large cavities. In the last step of tableting, the finished molded body is pushed out of the die by the lower punch and carried away by subsequent transport means. At this time, only the weight of the shaped body is finally determined because the compacts due to physical processes (re-expansion, crystallographic effects, cooling) can change their shape and size.
The tableting is carried out in commercial tablet presses, which can be equipped in principle with single or double punches. In the latter case, not only the upper punch is used to build up pressure, and the lower punch moves during the pressing on the upper punch, while the upper punch presses down. For small production quantities, eccentric tablet presses are preferably used in which the die or punches are attached to an eccentric disc, which in turn is mounted on an axis at a certain rotational speed. The movement of these punches is comparable to the operation of a conventional four-stroke engine. The compression can be done with a respective upper and lower punch, but it can also be attached more stamp on an eccentric disc, the number of Matrizenbohrungen is extended accordingly. The throughputs of eccentric presses vary depending on the type of a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs, rotary tablet presses are selected in which a larger number of dies 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 commercially available. Each die on the die table is assigned an upper and lower punch, in turn, the pressing pressure can be actively built only by the upper or lower punch, but also by both stamp. The die table and the punches move about a common vertical axis, the punches are brought by means of rail-like cam tracks during the circulation in the positions for filling, compression, plastic deformation and ejection. At the points where a particularly serious increase or decrease of the stamp is required (filling, compaction, ejection), these curved paths are supported by additional low-pressure pieces, Nierderzugschienen and lifting tracks. The filling of the die via a rigidly arranged supply device, the so-called filling shoe, which is connected to a reservoir for the premix. The pressing pressure on the premix is individually adjustable via the compression paths for upper and lower punches, wherein the pressure build-up is done by the Vorbeirollen the stamp shank heads on adjustable pressure rollers.
Concentric presses can be provided with two Füllschuhen to increase the throughput, with the production of a tablet only a semicircle must be traversed. To produce two-layered and multi-layered shaped bodies, several filling shoes are arranged one after the other without the slightly pressed-on first layer being ejected before further filling. By suitable process control coat and point tablets can be produced in this way, which have a zwiebelschalenartigen structure, wherein in the case of the point tablets, the top of the core or the core layers is not covered and thus remains visible. Even 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 are used simultaneously for pressing. The throughputs of modern rotary tablet presses amount to over one million moldings per hour.

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

The moldings can be in a predetermined spatial form and predetermined size be made. As a form of space virtually all useful manageable Embodiments into consideration, for example, the training as a blackboard, the rod or Barrel shape, cubes, cuboids and corresponding room elements with flat side surfaces and in particular cylindrical embodiments with circular or oval cross-section. This last embodiment detects the Darbletungsform 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 each other Be formed individual elements that the predetermined dosage of the washing and / or Cleaning agent corresponds. Likewise, it is possible to train briquettes, which connect a plurality of such mass units in a compact, wherein in particular by predetermined breaking points the easy separability portioned smaller units is provided. For the use of textile detergents in machines of the type common in Europe with horizontally arranged mechanics may be the training the portioned compacts as tablets, in cylindrical or cuboid form be expedient a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred is. Commercially available hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for producing such compacts.

The spatial form of another embodiment of the moldings is in their dimensions the Einspülkammer adapted from commercial household washing machines, so that the moldings can be metered directly into the dispensing chamber without dosing aid, where it dissolves during the flushing process. Of course, but also one Use of detergent tablets via a dosing easily possible and im Within the scope of the present invention.

Another preferred molded article which can be produced has a plate or tabular structure with alternately thick long and thin short segments, see above that individual segments of this "bar" at the predetermined breaking points, the short thin segments, aborted and entered into the machine can. This principle of the "bar-shaped" molding detergent can also in other geometric shapes, such as vertical triangles, the are connected together only on one of their sides, realized become.

But it is also possible that the various components not one uniform tablet be pressed, but that moldings are obtained, the several layers, so at least two layers have. And that's it possible that these different layers have different dissolution rates exhibit. From this, advantageous application properties of the Shaped bodies result. For example, if components are contained in the moldings are mutually negatively affecting, so it is possible that one component integrate into the faster soluble layer and the other component into one incorporate slower soluble layer, so that the first component already abreacted when the second goes into solution. The layer structure of the molded body can doing both stacked, with a solution process of the inner layer (s) on The edges of the shaped body already takes place when the outer layers are still not completely solved, but it can also be a complete covering of the inner Layer (s) are achieved by the respective outer layer (s), which to prevent premature dissolution of constituents of the inner layer (s) leads.

In a further preferred embodiment of the invention, a shaped body is made 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 stack-shaped molded body, the two outer layers and the shell-shaped moldings, the outermost layers, however, free of peroxy bleach are. Furthermore, it is also possible, peroxy bleach and optionally present Bleach activators and / or enzymes spatially in a molding of each other separate. Such multilayer molded articles have the advantage that they not only via a dispenser or via a metering device, which in the wash liquor given can be used; rather, it is also possible in such cases to give the shaped body in direct contact with the textiles in the machine, without that stains caused by bleach and the like are to be feared.

Similar effects can also be achieved by coating individual constituents the detergent composition to be compressed or the reach entire molding. For this purpose, the body to be coated For example, be sprayed with aqueous solutions or emulsions, or over the process of melt coating obtained a coating.

After pressing, the detergent tablets have a high stability. The breaking strength of cylindrical shaped bodies can be detected by the measurand of the diametric breaking load. This is determinable σ = 2 P πDt

Here, σ stands for the diametrical fracture stress (DFS) in Pa, P is the force in N which leads to the pressure exerted on the molding, which is the pressure Fraction of the molded body caused, D is the molding diameter in meters and t is the height of the moldings.

Examples Phosphate compounds

For the preparation of phosphate compounds was pentasodium triphosphate powder with a pure substance content of 98.3% and 0.3 wt .-% 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 dropped from the mixer into a fluidized bed and became at one Product temperature of 40 ° C within 45 minutes to a total water content dried by 13 wt .-%. The resulting granules had a raspberry-shaped Structure, wherein the average particle diameter of the agglomerate particles by 550 .mu.m However, the primary particles forming the agglomerate are almost a factor of 10 smaller were as the average particle diameter of the agglomerates. The data of obtained granules are given in Table 1.

The phosphate content in Table 1 was determined from the total phosphorus content (in C4, the phosphorus contained in the phosphonate was removed 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 specified water content is the difference between the two values. By means of thermoanalytical methods (DTA-TG, heating rate: 10 K / min) a crystallized water content of 8.1% by weight was determined for C1. Composition and physical parameters of 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 [% by weight] 2.5 1.5 1.5 1.5 HEDP - - - 1.3 Total moisture [wt .-%] where: 13 12 14 12 free water [% by weight] 4.5 nb nb nb Crystal water [% 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 compounds prepared were readily soluble and quickly dissolved in water.

moldings

Moldings were produced with compound C1. For this purpose, the phosphate compound was mixed with further treatment components and pressed on an eccentric tablet press according to Table 3. The composition of the premix to be compressed (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, dyes and fragrances, fillers and water. Comparative Example V had the same formulation, but here phosphate and copolymer were used separately, the phosphate was used in the form of a commercial granules with a free water content of about 7 wt .-%. To produce tablets of comparable hardness, significantly higher pressing pressures were required in the comparative example (see Table 3). Premix [% by weight] 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 deformation of the tablet until fracture, the force acting on the side surfaces of the tablet and the maximum force, the the tablet withstood, was detected. The measurement was carried out on a hardness tester CT5 (Holland) with punch diameter of 8 mm.

The determination of the dissolution time of the tablets was carried out in a household dishwasher. The tablets were placed in the basket of the machine before starting the main wash cycle The basket is in all attempts in the same place in the Machine was. It was used a 50 ° C program and the time until the completely dissolving the tablet over the pursuit of conductivity.

The experimental data of the individual tablet series are shown in Table 3. Characteristics of the dishwasher tablets E1 E2 E3 E4 V Pressing 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 becomes by the value for the tablet hardness by the for the dissolution time to the corresponding time value is divided and this factor with 10 is multiplied. At the same time the tablets are as hard as possible and one fastest possible resolution desired. The factor used here provides one Possibility to optimize both parameters simultaneously. It turns out that this factor in the inventive examples at all times significantly better than at the comparative example.

Claims (28)

1. Phosphate compound for use in detergents, containing at least 50% by weight of pentasodium triphosphate, less than 5% by weight of sodium pyrophosphate and a maximum of 18% by weight of water, the compounds being present in the form of agglomerates of primary particles, characterized in that the content in the compound of free water is not more than 5% by weight, preferably not more than 3% by weight, and the content of pentasodium triphosphate hexahydrate is between 20 and 70% by weight of the content of pentasodium triphosphate overall.
2. Phosphate compound according to Claim 1, characterized in that the compound contains 0.5 to 20% by weight of a polymeric polycarboxylate.
3. Phosphate compound according to either of Claims 1 and 2, characterized in that the compound contains 0.3 to 20% by weight of phosphonate.
4. Phosphate compound according to one of Claims 1 to 3, characterized in that the compound does not contain any nonionic surfactant or any silicate.
5. Phosphate compound according to one of Claims 1 to 4, characterized in that the compound has a bulk density in the 600 to 1000 g/l range and the agglomerates have an average particle size from the range of 0.2 to 1.0 mm, preferably from the 0.3 to 0.8 mm range.
6. Process for producing phosphate compounds according to one of Claims 1 to 5, characterized in that anhydrous, pulverulent pentasodium triphosphate.is agglomerated in a high-speed mixer with 12 to 28% by weight of water, based on the pentasodium triphosphate, and optionally further ingredients of detergents, and the agglomerate is immediately subsequently dried to a content of free water of below 5% by weight in a fluidized-bed drying step at a product temperature below 60°C.
7. Process for producing 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.
8. Process for producing phosphate compounds according to either of Claims 6 and 7, characterized in that the residence time of the agglomerate in the fluidized-bed drier is between 10 and 60 minutes and the air supply temperature is below 130°C, preferably below 100°C.
9. Process for producing phosphate compounds according to one of Claims 6 to 8, characterized in that further ingredients of detergents are mixed in dry form with the phosphate powder and the mixture is subsequently agglomerated.
10. Process for producing 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 the residence time of the phosphate in the high-speed mixer is less than 2 seconds.
11. Use of phosphate compounds according to one of Claims 1 to 5 for improving the solubility of detergent tablets, expressed by an improved hardness/dissolution time correlation factor, which is obtained by dividing the value for the tablet hardness by the value obtained for the dissolution time at the appropriate time and multiplying this factor by 10.
12. Use of phosphate compounds according to one of Claims 1 to 5 for improving the mechanical stability of detergent tablets.
13. Detergent tablet composed of compacting particulate detergent, characterized in that it comprises a phosphate compound according to one of Claims 1 to 5 or a process product according to one of Claims 6 to 10.
14. Detergent tablet according to Claim 13, characterized in that it contains at least 80% by weight, preferably at least 90% by weight and more preferably the entirety of the amount of phosphate present in the tablet in the form of phosphate compounds according to one of Claims 1 to 5 or a process product according to one of Claims 6 to 10.
15. Detergent tablet according to either of Claims 13 and 14, characterized in that it contains, based on the weight of the tablet, 10 to 90% by weight, preferably 20 to 80% by weight and in particular 25 to 70% by weight, of the phosphate compound.
16. Detergent tablet according to one of Claims 13 to 15, characterized in that it additionally contains a disintegration assistant, preferably a disintegration assistant based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably of 3 to 7% by weight and in particular of 4 to 6% by weight, based in each case on the tablet weight.
17. Detergent tablet according to one of Claims 13 to 16, characterized in that it additionally comprises one or more substances from the groups of the bleaches, bleach activators, enzymes, pH modifiers, fragrances, perfume carriers, fluorescers, dyes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, greying inhibitors, dye transfer inhibitors, corrosion inhibitors and silver protectants.
18. Process for producing detergent tablets, characterized by the steps of

    a) producing a phosphate compound by a process according to one or more of Claims 6 to 10,

    b) blending the compound produced in step a) with further ingredients of detergents to give a premix to be compacted,

    c) compaction to tablets.
19. Process according to Claim 18, 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 compacted.
20. Process according to either of Claims 18 and 19, characterized in that the phosphate compound produced in step a) is mixed in step b) with at least one oxygen bleach selected from the group of the alkali metal perborates, alkali metal percarbonates, the organic peracids and hydrogen peroxide.
21. Process according to one of Claims 18 to 20, characterized in that the phosphate compound produced in step a) is mixed with at least one bleach selected from the group of the trichlorocyanuric acids, the dichloro- or monochlorocyanurates, the hypochlorites, and other customary chlorine bleaches.
22. Process according to one of Claims 18 to 21, characterized in that the phosphate compound produced in step a) is mixed with at least one bleach activator, preferably from the group of the polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), the N-acylimides, in particular N-nonanoylsuccinimide (NOSI), the acylated phenolsulphonates, in particular n-nonanoyl- or isononanoyloxybenzene-sulphonate (n- and iso-NOBS respectively), n-methylmorpholinioacetonitrile methylsulphate (MMA) and/or the bleach-boosting transition metal complexes, in particular having 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 complexes, more preferably the cobalt(ammine) complexes, the cobalt(acetate) complexes, the cobalt(carbonyl) complexes, the chlorides of cobalt or of manganese and/or of manganese sulphate.
23. Process according to one of Claims 18 to 22, characterized in that the phosphate compound produced in step a) is combined with at least one surfactant-containing granule to give a premix to be compacted having a bulk density of at least 500 g/l, preferably at least 600 g/l and in particular at least 700 g/l.
24. Process according to Claim 23, characterized in that the surfactant-containing granule has particle sizes between 100 and 2000 µm, preferably between 200 and 1800 µm, more preferably between 400 and 1600 µm and in particular between 600 and 1400 µm.
25. Process according to either of Claims 23 and 24, characterized in that the surfactant-containing granule comprises anionic and/or nonionic surfactants and builders, and has total surfactant contents of at least 10% by weight, preferably at least 20% by weight and in particular at least 25% by weight.
26. Process according to one of Claims 18 to 25, characterized in that further builder substances which preferably comprise at least one aluminosilicate and/or one sheet silicate are mized with the phosphate compound in step b).
27. Process according to one of Claims 18 to 26, characterized in that the premix additionally comprises a disintegration assistant, preferably a disintegration assistant based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably of 3 to 7% by weight and in particular of 4 to 6% by weight, based in each case on the weight of the premix.
28. Process according to one of Claims 18 to 27, characterized in that the premix additionally comprises one or more substances from the groups of the enzymes, pH modifiers, fragrances, perfume carriers, fluorescers, dyes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, greying inhibitors, dye transfer inhibitors, corrosion inhibitors and silver protectants.