DE10134309A1 - Production of bi- or multi-phase shaped detergents involves pretreatment of one or more ingredients to give a flowable particulate pre-mix prior to extrusion - Google Patents

Abstract

At least one of the ingredients used in the production of bi- or multi-phase shaped detergents by extrusion of a strand followed by cutting to length is pre-treated by shearing or compressing to give a flowable particulate pre-mix.

Description

The present invention relates to a novel method for the production of two or multiphase detergent tablets.

Detergent tablets, such as those produced by tableting or Extrusion are enjoyed by consumers because of their simple Dosage unbroken popularity. Their compact structure gives them Detergents over powdered products have a number of advantages, for example during storage and transportation. There is therefore a wide range of Technology for detergent tablets, which can also be found in an extensive range Patent literature is reflected. Developments in this area involve separation various incompatible ingredients of detergent compositions in different phases of the molded body or the release of certain ingredients under defined conditions in the washing or cleaning cycle, a process that also takes place in the German usage is called "controlled release". In addition to those from the Pharmaceuticals well known core / shell tablets and ring / core tablets in particular multilayered molded articles, which are used today for all areas of Washing and cleaning or hygiene are offered.

That in the field of detergents and cleaning agents for the production of the moldings mentioned or parts of these moldings, the most commonly used process is tableting which is a particulate pre-mix using pressure into a compact tablet is transferred. In addition to tableting, however, extrusion is also becoming increasingly popular Importance. Here, a solid particulate premix under high pressures plasticized and carried out by hole shapes, after which a shaping by Cut off and possible post-treatment. In contrast to tableting, where the particle bed quais is "sintered", and the moldings still have a hollow volume own, the extrusion leads too much due to the high pressures of 100 bar and above compact particles or pieces, the internal volume of which is significantly reduced. The in Extrusion processes disclosed in the prior art usually lead to washing and Detergent granules that stand out in comparison to conventional washing powders characterized by a higher active ingredient density, but the same disadvantage Have dosing properties.

For example, the German utility model application DE 298 11 135 (Henkel) describes extruded Detergent granules which are characterized by at least one through opening. Such cleaning agents are characterized by a during the dissolving process comparatively constant surface and ensure during the Cleaning process a substantially constant concentration of the over a long time resulting wash liquor on washing and cleaning active. Substances.

But also single-phase detergent tablets without separation of active ingredients are described in the prior art.

The subject of German patent application DE 196 49 565 (Knoll) is a method for Production of detergent and cleaning agent granules or single-phase detergent and Detergent tablets by extrusion of a particulate premix. A There is no spatial separation of incompatible ingredients in such moldings possible.

The present application was based on the task of a novel technical simple process for the preparation of two or multi-phase washing and Provide detergent tablets, which regarding the choice of ingredients of the Detergent offers the greatest possible flexibility. In particular, when using this process the processing of pressure, temperature and shear sensitive substances just as possible as the processing of incompatible ingredients. Such a method should advantageously also continue to implement Allow "controlled release" mechanisms.

It has now been found that a new kind can be found to solve the aforementioned problems Extrusion process is suitable.

The present invention therefore relates to a process for producing two or three multiphase detergent tablets with at least two different composite deformable masses are produced, this a head tool are fed in and brought together into a two-phase or multi-phase strand and this strand after exiting from the outlet opening of the head tool by means of a Cutting device is cut to a predetermined length, thereby characterized in that at least one of the deformable masses by the action of Shear and compression forces, such as those that work in extruders, from one Particulate, free-flowing premix is provided.

In a preferred embodiment of the method according to the invention, at least one, but not all deformable mass due to the action of shear and Compaction forces provided from a particulate, free-flowing premix.

Such deformable, preferably plastic, not by the action of shear and Masses provided by compressive forces can, after the shaping processing, too usually only prints in the range between 2 and 20, preferably between 4 and 15 bar and in particular between 6 and 10 bar are necessary according to different Harden mechanisms. In a preferred within the scope of the present invention The hardening of this deformable mass (s) is carried out by delayed processes Water binding, crystallization, evaporation of a solvent or solidification.

Curing by is particularly preferred in the process according to the invention Solidification, preferably through the use of softenable substances that unite Have melting range (solidification range) in such a temperature range in which the remaining ingredients of the masses to be processed none too high thermal Exposed to stress. On the other hand, the melting range must be sufficiently high to be a manageable molded body at at least slightly elevated temperature provide. In preferred compositions according to the invention, the melt or softenable substances have a melting point above 30 ° C.

Such masses softenable under the influence of temperature are also easy assemble the desired additional ingredients with a melting or softenable substance mixed and the mixture to temperatures in the softening range this material is heated and shaped at these temperatures. Especially waxes, paraffins, Polyalkylene glycols etc. used.

It has proven to be advantageous if the meltable or softenable substances do not sharply defined melting point, as is usually the case with pure, crystalline substances occurs, but a melting range that may include several degrees Celsius exhibit. The meltable or softenable substances preferably have one Melting range, which is between about 45 ° C and about 75 ° C. That means in the present Case that the melting range occurs within the specified temperature interval and does not denote the width of the melting range. Preferably, the width of the Melting range at least 1 ° C, preferably about 2 to about 3 ° C.

The properties mentioned above are usually fulfilled by so-called waxes. Under "Waxing" is understood to mean a number of natural or artificially obtained substances that are used in the Usually melt above 40 ° C without decomposition and a little above the melting point are relatively low viscosity and non-stringy. You have a strong temperature-dependent consistency and solubility.

According to their origin, the waxes are divided into three groups, the natural waxes, chemically modified waxes and synthetic waxes.

Natural waxes include, for example, vegetable waxes such as candelilla wax, Carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, Rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as Beeswax, shellac wax, walrus, lanolin (wool wax), or pretzel fat, mineral waxes such as ceresin or ozokerite (earth wax), or petrochemical waxes such as petrolatum, Paraffin waxes or micro waxes.

The chemically modified waxes include hard waxes such as Montanester waxes, Sassol waxes or hydrogenated jojoba waxes.

Synthetic waxes generally include polyalkylene waxes or Understand polyalkylene glycol waxes. As meltable or softenable substances for the through Compounds from other classes of material can also be used as cooling-curing compounds, that meet the stated softening point requirements. As suitable synthetic compounds, for example, have higher esters of phthalic acid, in particular Dicyclohexylphthalate, which is commercially available under the name Unimoll® 66 (Bayer AG) is proven. Synthetic waxes made from lower carboxylic acids and are also suitable Fatty alcohols, for example dimyristyl tartrate, which is sold under the name Cosmacol® ETLP (Condea) is available. Conversely, synthetic or semi-synthetic esters are also made lower alcohols with fatty acids from native sources can be used. It falls into this class of substances for example the Tegin® 90 (Goldschmidt), a glycerol monostearate palmitate. Also shellac, for example Shellac-KPS-Dreiring-SP (Kalkhoff GmbH) is according to the invention as a melt or softenable substances.

The waxes, for example, are also included in the scope of the present invention so-called wax alcohols. Wax alcohols are high molecular weight, water-insoluble Fatty alcohols usually with about 22 to 40 carbon atoms. The wax alcohols are coming for example in the form of wax esters of higher molecular weight fatty acids (wax acids) than Main ingredient of many natural waxes. Examples of wax alcohols are Lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The The solid particles coated according to the invention can optionally also be coated Wool wax alcohols, including triterpenoid and steroid alcohols, for example Lanolin, which means, for example, under the trade name Argowax® (Pamentier & Co) is available. Also at least partially as part of the meltable or softenable Substances can be used in the context of the present invention or fatty acid glycerol esters Fatty acid alkanolamides but also, if appropriate, water-insoluble or only slightly water-soluble Polyalkylene glycol.

Particularly preferred meltable or softenable substances in those to be processed Masses are those from the group of polyethylene glycols (PEG) and / or Contains polypropylene glycols (PPG), with polyethylene glycols with molecular weights between 1500 and 36,000 preferred, those with molecular weights from 2000 to 6000 are particularly preferred and those with molecular weights of 3000 to 5000 are particularly preferred. Corresponding too Processes which are characterized in that the plastically deformable mass (es) at least one substance from the group of polyethylene glycols (PEG) and / or Polypropylene glycols (PPG) contains / are preferred.

Here, compositions to be processed according to the invention are particularly preferred which contain propylene glycols (PPG) and / or polyethylene glycols (PEG) as the only meltable or softenable substances. Polypropylene glycols (abbreviation PPG) which can be used according to the invention are polymers of propylene glycol which have the general formula I


are sufficient, where n can have values between 10 and 2000. Preferred PPGs have molar masses between 1000 and 10,000, corresponding to values of n between 17 and approximately 170.

Polyethylene glycols (abbreviation PEG) which can preferably be used according to the invention are polymers of ethylene glycol which have the general formula II


are sufficient, where n can have values between 20 and approx. 1000. The preferred molecular weight ranges mentioned above correspond to preferred ranges of the value n in formula IV from approximately 30 to approximately 820 (exactly: from 34 to 818), particularly preferably from approximately 40 to approximately 150 (precisely: from 45 to 136) and in particular from about 70 to about 120 (exactly: from 68 to 113).

In a further preferred embodiment, they contain according to the invention processing masses in the majority of paraffin wax. That is, at least 50% by weight of the total meltable or softenable substances contained, preferably more, consist of paraffin wax. Paraffin wax contents (based on the Total amount of meltable or softenable substances) of about 60% by weight, about 70% by weight or about 80% by weight, with even higher proportions of, for example, more than 90% by weight are particularly preferred. In a particular embodiment of the invention Total amount of meltable or softenable substances used at least one mass made exclusively from paraffin wax.

Paraffin waxes show the other natural waxes mentioned within the scope of the Present invention has the advantage that in an alkaline detergent environment there is no hydrolysis of the waxes (as expected, for example, in the wax esters is), since paraffin wax contains no hydrolyzable groups.

Paraffin waxes consist mainly of alkanes, as well as low levels of iso- and Cycloalkanes. The paraffin to be used according to the invention preferably has essentially no constituents with a melting point of more than 70 ° C., particularly preferably more than 60 ° C. Shares of high-melting alkanes in the paraffin can fall below this Melting temperature in the detergent fleet undesirable wax residues on the cleaning surfaces or the goods to be cleaned. Such wax residue usually lead to an unsightly appearance of the cleaned surface and should therefore be avoided.

Masses to be processed preferably contain as meltable or softenable substances at least one paraffin wax with a melting range of 50 ° C to 60 ° C, wherein preferred methods are characterized in that the deformable mass (es) Paraffin wax with a melting range of 50 ° C to 55 ° C contains.

The content of the paraffin wax used is preferably at ambient temperature (in generally about 10 to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes as high as possible. The more solid wax components in a wax at room temperature, the more it is more useful in the context of the present invention. With increasing proportion of fixed Wax components increase the resilience of the process end products to impacts or Friction on other surfaces, which leads to longer-lasting protection. Height Portions of oils or liquid wax components can weaken the moldings or lead body areas, whereby pores are opened and the active ingredients exposed to the environmental influences mentioned at the beginning.

In addition to paraffin, the meltable or softenable substances can also be the main constituent contain one or more of the waxes or wax-like substances mentioned above. In a Another preferred embodiment of the present invention should be the melt or softenable substances forming mixture must be such that the mass and the resulting formed shaped bodies or shaped body constituents are at least largely water-insoluble. The solubility in water should not be about 10 mg / l at a temperature of about 30 ° C exceed and are preferably below 5 mg / l.

In such cases, however, the meltable or softenable substances should, if possible have low water solubility, even in water at an elevated temperature, in order to Avoid temperature-independent release of the active substances as much as possible.

Preferred masses to be processed according to the invention are characterized in that they as meltable or softenable substances one or more substances with a melting range from 40 ° C to 75 ° C in amounts of 6 to 30% by weight, preferably from 7.5 to 25% by weight and in particular from 10 to 20% by weight, in each case based on the weight of the mass, contain.

A further preferred embodiment of the method according to the invention is thereby characterized in that at least one, but preferably all of the deformable masses one Zeolite content below 10 wt .-%, preferably below 5 wt .-%, particularly preferred below 2% by weight and in particular below 0.5% by weight. After all, it can According to the invention, it should also be preferred that none of the deformable masses contain zeolite. Such detergent compositions have because of their low zeolite content a comparatively low water absorption capacity, which means that during a Extrusion process, in the course of which water is usually used as an extrusion aid problems can arise. For this reason and with the aim of a To make drying of the extrudate unnecessary, for example by hot air, or at least shortening are preferred in the context of the present invention over-dried starting materials used, that is, starting materials that a Have water content below their theoretical water binding capacity.

The theoretical water binding capacity of a raw material can be determined using the following procedure be determined. Some substances form at an assumed storage temperature hydrates stable between 15 and 45 ° C, on the other hand it is known that from they have stable anhydrous modifications at these temperatures. All Ingredients that are stable at the temperatures mentioned anhydrous modifications own and are also used in their anhydrous form, also go into the Calculation water-free; all the rest go with them to their water content Temperatures stable water-containing modification in the calculation. Components like Sodium sulfate, sodium carbonate and polymeric polycarboxylates, however, are considered anhydrous substances, although it is known that these are usually in extrudates are in hydrated form. So is the best known crystal modification of the Sodium sulfate and sodium carbonate each the decahydrate. Of citric acid or citrate an anhydrous and an aqueous stable modification (dihydrate) are also known. In contrast, silicates are only stable in hydrated form. The water content can, however vary widely depending on the module used. Here it is recommended - as with all stable raw materials, the exact water content of which is not known - the water content to determine the stable modification present, for example by annealing. The latter also applies to surfactants, especially anionic surfactants, whereas non-ionic surfactants are usually calculated as anhydrous.

In the process according to the invention it is therefore preferred that the (the) by shear forces compacted, particulate, free-flowing premix (s) a water content have below their calculated water binding capacity, the water content preferably 55 to 95%, preferably 60 to 90% and in particular 65 to 85% of the calculated water binding capacity of this phase (s).

By processing the ingredients of the two-phase or multi-phase washing and Detergent tablets in at least two separate deformable masses can be separate incompatible components from each other. Examples of such incompatible combinations of substances are combinations of bleach activators and / or Bleaching agents on the one hand and compounds sensitive to oxidation such as enzymes, dyes, Fragrances and / or corrosion inhibitors on the other hand.

Accordingly, it is within the framework of one of the present application Process for the preparation of two-phase or multi-phase washing and Detergent tablets preferred that one of the deformable masses of bleach and / or bleach activator, while another deformable mass contains one or more Substances from the group of enzymes, dyes, fragrances, optical brighteners and / or Contains anti-corrosion agents.

But also the joint processing of bleach activator and bleach Impairment of the properties of the process product lead, so that it The present method can be advantageous in that one of the deformable masses of bleach contains, while another deformable mass contains bleach activator.

To the different mixtures of the starting substances in suitable for extrusion to transfer deformable masses, these elevated temperatures (temperatures above 20 ° C) and / or increased pressures (pressures above 1 bar) and / or shear forces get abandoned. Depending on the composition of the starting mixtures and their sensitivity to temperature, pressure and / or shear forces can affect them Parameters can be varied in such a way that as gentle as possible Processing of the ingredients is guaranteed. Within the scope of the present invention preferred temperatures of the deformable masses are before entering the head tool between 20 and 100 ° C, preferably between 30 and 90 ° C and in particular between 40 and 80 ° C, while transferring particulate, free-flowing premixes into a deformable mass preferably pressures of 2 and 150 bar, preferably from 4 to 90 bar and in particular from 6 to 60 bar can be used.

For example, temperature-sensitive substances or substance mixtures can be used Temperatures between 20 and 50 ° C are processed, while pressure sensitive Compounds or mixtures containing such compounds, preferably at Pressures between 2 and 30 bar can be processed and extruded. In a preferred one Embodiment of the method according to the invention, it is finally possible Insert the melt into an extruded body.

The deformable properties of the masses can advantageously by adding Plasticizing aids such as polyethylene glycols, polypropylene glycols, fatty alcohols, Starch derivatives, waxes, paraffins, nonionic surfactants, talc and / or Magnesium stearate to at least one of the phases of the two-phase or multi-phase washing and Detergent tablets are affected.

The particulate, free-flowing premix / premixes are transferred to one / more deformable mass (s) however (among other things) by the action of Shear forces, it is preferred if this process in the compression space of an extruder, preferably a twin-screw extruder. It has proven to be beneficial proved that the ratio of the length of the compression space of the extruder to its Diameters in a range between 32: 1 and 8: 1, preferably between 26: 1 and 10: 1 and in particular between 20: 1 and 12: 1.

For optimal throughput rates with constant product properties and trouble-free To achieve production, it is preferred in the context of the present invention that the Strands of material at a speed of 0.2 m / min to 30 m / min, preferably between 0.25 m / min to 20 m / min, particularly preferably from 0.5 m / min to 15 m / min and in particular from 1 m / min to 10 m / min are discharged from the outlet opening, wherein the head tool has 2 to 10, preferably 3 to 6, outlet openings. to To improve the extrudability of the material strands, it is preferred that at least one this strands of material a lubricant and / or a substance and / or a mixture of substances with a melting point below 40 ° C.

In principle, the method according to the invention is not limited with regard to the shape and size of the outlet openings. With regard to the products to be manufactured and their size or mass, which for such products is usually in the range from 5 to 500 g, preferably from 10 to 250 g, particularly preferably from 15 to 100 g and in particular between 20 and 50 g, Methods are preferred in which the outlet openings have opening areas of from 50 mm ² to 2500 mm ² , preferably from 100 mm ² to 200 mm ² , particularly preferably from 200 mm ² to 1500 mm ² and in particular from 300 mm ² to 1000 mm ² Preferences from 350 mm ² to 750 mm ² .

The material strands emerging from the outlet openings can be cut to length according to the known methods of the prior art, for example by rotating Knives, countersinkable cutters or wires etc. The mass of the finished molded body is based on on the one hand according to the size of the outlet openings, on the other hand according to the length of the Sections. Should be conventional detergent tablets for common ones Purposes such as detergent tablets or detergent tablets for machine dishwashing are provided, methods in which are preferred the material strands emerging from the outlet openings to a length of 5 to 100 mm, preferably from 7.5 to 75 mm, particularly preferably from 10 to 60 mm and in particular from 15 to 50 mm.

Depending on the composition or the intended use However, the limits mentioned can also be exceeded or fallen below. That's the way it is For example, it is possible to process poorly soluble masses after curing and these to lengths from 100 to 1000 mm, preferably from 120 to 750 mm and in particular from Cut off 150 to 500 mm. The cured "rods" obtained in this way can then be placed as depot blocks in washing machines or dishwashers, where a defined part of the block loosens for each wash or rinse cycle, while the rest for the next cleaning cycle remains in the machine or its dosing system.

As already mentioned above, the temperature control during the plasticizing and Extrusion process decisive influence on the deformability of the used Mixtures of substances and the stability of individual ingredients. For phase liability and Product properties within the two or multi-phase extrudate are within the scope of the The inventive method is also advantageous if the temperature difference deformable masses before the assembly in the head tool a value of 30 ° C, preferably does not exceed 20 ° C and in particular 10 ° C.

In the production of multi-phase molded articles, the ratio of the phases to one another can can be chosen freely, it being advantageous from a production point of view can, no deformable mass a volume fraction of the total volume of all deformable Process masses below 5% by volume. Such phases are suitable in principle For example, for the assembly of small components, but are difficult feasible and usually hardly perceptible to the consumer in the end product. It is therefore preferred for aesthetic reasons that the volume fraction of each individual deformable mass of the total volume of all deformable masses above 5 vol .-% is preferably above 10% by volume, the volume data relating to the Draw total volume of all deformable masses after extrusion.

In order to achieve improved phase adhesion of the individual phases after extrusion, it is advantageous if the individual phases of the two-phase or multi-phase strand are not planar Have phase interfaces or the individual phases of the two or more phases Strands have planar phase interfaces, but not parallel to the surface of the two-phase or multi-phase strand.

The general description of the method according to the invention includes one detailed description of those still to be used in the masses to be processed Ingredients.

Preferred end products of the process according to the invention, as preferred washing and Detergent tablets further contain in at least one of the phases of the two- or multi-phase detergent tablets one or more substances the group of builders, cobuilders, surfactants, bleaches, bleach activators, disintegrants Enzymes, dyes, fragrances, anti-corrosion agents, optical brighteners, polymers, or another common ingredient of detergents and cleaning agents.

Builder

According to the present invention, detergents and cleaning agents can all be used builders usually used in detergents and cleaning agents, especially zeolites, silicates, carbonates, organic cobuilders and also Phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. 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.

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

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

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

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

Both the monoalkali metal salts and the dialkali metal salts of the Carbonic acid as well as sesquicarbonates can be included in the funds. preferred Alkali metal ions represent sodium and / or potassium ions. In one embodiment, it can be preferred, the carbonate and / or bicarbonate at least partially as further Mix component separately or subsequently. Also compounds from, for example Carbonate, silicate and optionally other auxiliaries such as anionic surfactants or other, in particular organic builder substances, can be used as a separate component in the finished funds.

In the context of the present invention, a method is preferred in which at least a phase of the two-phase or multi-phase detergent tablets Sodium carbonate, in amounts of 5 to 60% by weight, preferably 10 to 50% by weight contains.

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

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

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

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

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

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

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

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

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

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

As already mentioned in the introduction, the separate processing / extrusion is justified different deformable masses increased flexibility in terms of design the basic formulations of detergents and cleaning agents. For example Mixtures of substances with a high phosphate content after separation of water Ingredients are extruded much better. A preferred embodiment of the The present invention is therefore characterized in that at least one phase of the two-phase or multi-phase detergent tablets phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or Pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of 20 to 80% by weight, preferably from 25 to 75% by weight and in particular from 30 to 70% by weight, each based on the corresponding mass.

builders

As organic cobuilders in the detergents within the scope of the present Invention in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, Aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and Phosphonates are used. These classes of substances are described below.

Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such polycarboxylic acids being among polycarboxylic acids can be understood that carry more than one acid function. For example, these are Citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, Maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and Mixtures of these. Preferred salts are the salts of polycarboxylic acids such as Citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and Mixtures of these.

The acids themselves can also be used. The acids have besides theirs Builder effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or Detergents. In particular, citric acid, succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.

Polymeric polycarboxylates are also suitable as builders, for example those Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a 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 molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2000 to 20,000 g / mol. Because of their superior solubility, this can Group in turn the short-chain polyacrylates, the molar masses from 2000 to 10,000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may be preferred.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As special copolymers of acrylic acid with maleic acid which have 50 to 90% by weight have proven suitable Contain acrylic acid and 50 to 10 wt .-% maleic acid. Your relative Molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can either be as a powder or as an aqueous solution be used. The content of the agents in (co) polymeric polycarboxylates is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

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

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

Further preferred copolymers preferably have acrolein and Acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Likewise, other preferred builder substances are polymeric aminodicarboxylic acids, their To name salts or their precursors. Are particularly preferred Polyaspartic acids or their salts and derivatives, of which in the German Patent application DE-A-195 40 086 discloses that in addition to cobuilder properties also have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which are obtained by converting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 Have hydroxyl groups can be obtained. Preferred polyacetals are made from Dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from Obtained polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be. The hydrolysis can be carried out according to conventional methods, for example acid or enzyme-catalyzed processes are carried out. It is preferably Hydrolysis products with average molecular weights in the range from 400 to 500,000 g / mol. There is one Polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30 preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Useful are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins higher molar masses in the range from 2000 to 30,000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

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

Other useful organic cobuilders are, for example, acetylated Hydroxycarboxylic acids or their salts, which may also be in lactone form can and which have at least 4 carbon atoms and at least one hydroxy group as well as a maximum of two acid groups.

Another class of substances with cobuilder properties are the phosphonates it is especially hydroxyalkane or aminoalkanephosphonates. Among the Hydroxyalkanephosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) from of particular importance as a cobuilder. It is preferably used as the sodium salt, where the disodium salt is neutral and the tetrasodium salt is alkaline (pH 9). As Aminoalkane phosphonates preferably come from ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher Homologues in question. They are preferably in the form of neutral sodium salts, z. B. as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP, used. HEDP is preferred as the builder from the phosphonate class used. The aminoalkanephosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it can, especially if the means too Contain bleach, be preferred aminoalkane phosphonates, in particular DTPMP, to use, or to use mixtures of the phosphonates mentioned.

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

surfactants

Preferred cleaning agents contain one or several surfactant (s) from the groups of anionic, nonionic, cationic and / or amphoteric surfactants.

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 sulfonating 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. Likewise, the esters of α-sulfofatty acids (ester sulfonates), e.g. B. the α-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures, as in the preparation by esterification of a monoglycerol with 1 to 3 moles Obtained fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, Caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or Behenic acid.

As alk (en) yl sulfates are the alkali and especially 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 for reasons of washing technology. 2,3-Alkyl sulfates, which can be obtained as commercial products from Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 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 radicals 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. B. coconut, palm kernel or tallow fatty acids, derived soap mixtures.

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

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

Another class of preferred nonionic surfactants, either as the sole nonionic surfactant or used in combination with other nonionic surfactants 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.

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Alkypolyglycosides that can be used 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 Is 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, which consist of a glucose residue and an n-alkyl chain, are preferably used.

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

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

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

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


in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated Derivatives of this remainder.

[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 be reacted with Fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are transferred.

In the case of detergents and cleaning agents for automatic dishwashing, all surfactants are generally suitable as surfactants. However, the nonionic surfactants described above, and above all the low-foaming nonionic surfactants, are preferred for this purpose. The alkoxylated alcohols are particularly preferred, especially the ethoxylated and / or propoxylated alcohols. The person skilled in the art generally understands alkoxylated alcohols to mean the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the context of the present invention the longer-chain alcohols (C ₁₀ to C ₁₈ , preferably between C ₁₂ and C ₁₆ , such as C ₁₁ -, C ₁₂ -, C ₁₃ -, C ₁₄ -, C ₁₅ -, C ₁₆ -, C ₁₇ - and C ₁₈ -alcohols). As a rule, a complex mixture of addition products of different degrees of ethoxylation is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions. A further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. If desired, final etherification with short-chain alkyl groups, such as preferably the butyl group, can also give the class of "closed" alcohol ethoxylates, which can also be used for the purposes of the invention. For the purposes of the present invention, very particularly preferred are highly ethoxylated fatty alcohols or their mixtures with end-capped fatty alcohol ethoxylates.

bleach

Bleaching agents and bleach activators are important components of detergents and cleaning agents, and a detergent and cleaning agent can contain one or more substances from the groups mentioned within the scope of the present invention. Sodium percarbonate is of particular importance among the compounds which serve as bleaching agents and produce H ₂ O ₂ in water. Further bleaching agents which can be used are, for example, sodium perborate tetrahydrate and the sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.

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

Sodium carbonate peroxohydrate was first made in 1899 by precipitation with ethanol from a Obtained solution of sodium carbonate in hydrogen peroxide, but mistakenly as Peroxycarbonate viewed. It was not until 1909 that the compound was Attachment connection recognized, nevertheless has the historical designation "Sodium percarbonate" has become established in practice.

The industrial production of sodium percarbonate is predominantly produced by precipitation from an aqueous solution (so-called wet process). Here, aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium percarbonate is precipitated by salting-out agents (predominantly sodium chloride), crystallization aids (for example polyphosphates, polyacrylates) and stabilizers (for example Mg ²⁺ ions). The precipitated salt, which still contains 5 to 12% by weight of mother liquor, is then centrifuged off and dried in fluidized bed dryers at 90.degree. The bulk density of the finished product can vary between 800 and 1200 g / l depending on the manufacturing process. As a rule, the percarbonate is stabilized by an additional coating. Coating processes and materials used for coating are widely described in the patent literature. In principle, according to the invention, all commercially available percarbonate types can be used, such as those offered by the companies Solvay Interox, Degussa, Kemira or Akzo.

Detergents for automatic dishwashing can also use bleach from the Group of organic bleaches included. Typical organic bleaches used as Ingredients can be used in the present invention are Diacyl peroxides, such as. B. dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples being especially the alkylperoxyacids and Arylperoxyacids are called. Preferred representatives are (a) peroxybenzoic acid and their ring-substituted derivatives, such as alkyl peroxybenzoic acids, but also peroxy-α- Naphtoic 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, diperocysebacic acid, Diperoxybrassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N- Terephthaloyl-di (6-aminopercapronic acid) can be used.

As a bleaching agent for automatic dishwashing, according to the present invention chlorine or bromine-releasing substances can also be used. Among the appropriate chlorine or bromine-releasing materials come, for example, heterocyclic N-bromine 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.

Bleach activators

To improve the bleaching effect when cleaning at temperatures of 60 ° C and below To achieve cleaning agents within the scope of the present invention Bleach activators included. As bleach activators, compounds that are under Perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 C- Atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted Perbenzoic acid result are used. Suitable substances are O- and / or N- Acyl groups of the number of carbon atoms mentioned and / or optionally substituted Wear benzoyl groups. Multi-acylated alkylenediamines are preferred, in particular 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, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso-NOBS), carboxylic anhydrides, especially 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, according to the The present invention also includes so-called bleaching catalysts in the cleaning agents be incorporated. 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 as well as Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.

explosives

To facilitate the disintegration of highly compressed masses, it is possible to Disintegration aids, so-called tablet disintegrants, to be incorporated into them in order to Shorten disintegration times. Under tablet disintegrants or disintegrators according to Römpp (9th edition, Vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology "(6th edition, 1987, pp. 182-184) understood auxiliaries for the rapid disintegration of tablets in water or gastric juice and for the release of the Provide pharmaceuticals in an absorbable 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 also be generated via the release of gases, which breaks the tablet into smaller particles. Well-known disintegration aids are for example carbonate / citric acid systems, with other organic acids can be used. Swelling 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. All of the disintegration aids mentioned can be used according to the invention.

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

The cellulose derivatives mentioned are preferably not used alone as disintegrants used on cellulose basis, but used in a mixture with cellulose. The salary these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the disintegrant Cellulose. Pure cellulose-based disintegrant is particularly preferred Cellulose used, which is free of cellulose derivatives.

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 German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and the international patent application WO 98/40463 (Henkel). These writings are also details on Production of granulated, compacted or cogranulated cellulose disintegrants remove. 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 to at least 90% by weight between 400 and 1200 µm. The above and in the writings cited described coarser disintegration aids based on cellulose are preferred as disintegration aids in the context of the present invention used and commercially, for example under the name Arbocel® TF-30-HG by available from Rettenmaier.

As another disintegrant based on cellulose or as a component of this component microcrystalline cellulose can be used. This microcrystalline cellulose will obtained by partial hydrolysis of celluloses under such conditions that only the attack amorphous areas (approx. 30% of the total cellulose mass) of the celluloses and dissolve completely, but leave the crystalline areas (approx. 70%) undamaged. A subsequent disaggregation of the microfine celluloses resulting from the hydrolysis delivers the microcrystalline celluloses, which have primary particle sizes of approx. 5 µm and for example compactible to granules with an average particle size of 200 microns are.

In a method according to the present invention, it is preferred that at least one the deformable mass contains a water-soluble disintegrant.

enzymes

Enzymes include, in particular, those from the classes of hydrolases such as proteases, Esterases, lipases or lipolytic enzymes, amylases, cellulases or others Glycosyl hydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases wear in the laundry to remove stains such as protein, fat or starchy stains and graying. Cellulases and others Glycosyl hydrolases can also be removed by removing pilling and Microfibrils help maintain color and increase the softness of the textile. to Bleaching or to inhibit color transfer can also use oxidoreductases become. From bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants. Proteases of the subtilisin type and in particular proteases which are preferred Bacillus lentus are used. There are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic Enzymes or from protease, amylase and lipase or lipolytically active enzymes or Protease, lipase or lipolytic enzymes and cellulase, but especially Protease and / or lipase-containing mixtures or mixtures with lipolytically active Enzymes of particular interest. Examples of such lipolytic enzymes are the well-known cutinases.

Peroxidases or oxidases have also proven to be suitable in some cases. To the suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and Pectinases. Cellobiohydrolases, endoglucanases and - are preferably used as cellulases. Glucosidases, which are also called cellobiases, or mixtures of these are used. Because different cellulase types distinguish themselves through their CMCase and Avicelase activities can differentiate, the desired by specific mixtures of the cellulases Activities can be discontinued.

The enzymes can be adsorbed on carriers or embedded in coating substances in order to protect them against premature decomposition.

dyes

In order to improve the aesthetic impression of the detergent tablets, they can be colored with suitable dyes. As part of the present Invention preferred dyes, the selection of which no difficulty for the expert prepares, have a high storage stability and insensitivity to the rest Ingredients of the agents and against light as well as no pronounced substantivity Textile fibers so as not to stain them.

All are preferred for use in the washing and cleaning agents according to the invention Colorants that can be oxidatively destroyed in the washing process, as well as mixtures the same with suitable blue dyes, so-called blue tones. It has proven to be beneficial proven to use colorants in water or at room temperature in liquid organic substances are soluble. For example, anionic colorants are suitable, z. B. anionic nitroso dyes. A possible colorant is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020), which is a commercial product for example as Basacid® Green 970 from BASF, Ludwigshafen, and Mixtures of these with suitable blue dyes. Coming as additional colorants Pigmosol® Blue 6900 (CI 74160), Pigmosol® Green 8730 (CI 74260), Basonyl® Red 545 FL (CI 45170), Sandolan® Rhodamine EB400 (CI 45100), Basacid® Yellow 094 (CI 47005), Sicovit® Patent Blue 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), Pigment Blue 15 (CI 74160), Supranol® Blue GLW (CAS 12219-32-8, CI Acidblue 221)), Nylosan® Yellow N-7GL SGR (CAS 61814-57-1, CI Acidyellow 218) and / or Sandolan® Blue (CI Acid Blue 182, CAS 12219-26-0) is used.

When choosing the colorant, it must be ensured that the colorants do not have too strong an affinity for the textile surfaces and especially for synthetic fibers. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stabilities against oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the washing or cleaning agents varies. In the case of readily water-soluble colorants, e.g. B. the above-mentioned Basacid® green or the above-mentioned Sandolan® blue, colorant concentrations are typically selected in the range of a few 10 to 10 ^-3 wt .-%. In the preferred because of their brilliance, but less water-soluble pigment dyes, for. B. the above-mentioned Pigmosol® dyes, the suitable concentration of the colorant in washing or cleaning agents, however, is typically a few 10 ^-3 to 10 ^-4 wt .-%.

fragrances

Fragrances are added to the agents in the context of the present invention in order to improve aesthetic impression of the products and the consumer in addition to performance of the product a visually and sensory "typical and distinctive" product for To make available.

Individual perfume oils or fragrances can be used in the context of the present invention Fragrance compounds, e.g. B. the synthetic products of the ester, ether, Aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are e.g. B. benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. Count among the ethers for example benzyl ethyl ether, to the aldehydes z. B. the linear alkanals with 8-18 C- Atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. B. the Jonone, α- Isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, belong to the hydrocarbons mainly the terpenes like limes and pinene.

However, preference is given to using mixtures of different fragrances that work together create an appealing fragrance. Such perfume oils can also be natural Fragrance mixtures contain, as they are accessible from plant sources, for. B. Pine, Citrus, jasmine, patchouly, rose or ylang-ylang oil. Are also suitable Muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, Linden flower 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.

Corrosion inhibitors

Detergents, for machine dishwashing, can protect the dishes or the machine contain corrosion inhibitors, silver protection agents in particular Machine dishwashing have a special meaning. Can be used the known substances of the prior art. Generally, above all Silver protection agents selected from the group of triazoles, benzotriazoles, Bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes are used. Benzotriazole are particularly preferred and / or alkylaminotriazole. You will also often find it in detergent formulations agents containing active chlorine, which significantly reduce the corrosion of the silver surface can. Chlorine-free cleaners especially contain oxygen and nitrogenous ones organic redox-active compounds, such as di- and trihydric phenols, e.g. B. Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, 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 often found Use. The transition metal salts which are 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. You can also Zinc compounds are used to prevent corrosion on the wash ware.

Optical brighteners

In the context of the present invention, the agents can furthermore have optical brighteners Type of derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. Are suitable for. B. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene 2,2'-disulfonic acid or compounds of a similar structure which instead of the morpholino Group a diethanolamino group, a methylamino group, anilino group or one Wear 2-methoxyethylamino group. Brighteners of the substituted type can also be used Diphenylstyryle be present, e.g. B. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.

foam inhibitors

When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, e.g. B. from silicone, paraffins or waxes. The foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance.

In particular, mixtures of paraffins and bisstearylethylenediamides prefers.

graying

Graying inhibitors have the task of removing the dirt detached from the fiber in the Keep the liquor suspended and thus prevent the dirt from re-opening. For this are water-soluble colloids mostly organic in nature, for example water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acid Sulfuric acid esters of cellulose or starch. Also water-soluble containing acidic groups Polyamides are suitable for this purpose. Soluble starch preparations and use starch products other than the above, e.g. B. degraded starch, Aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, are preferred Cellulose ethers, such as carboxymethyl cellulose (sodium salt), methyl cellulose, Hydroxyalkyl cellulose and mixed ethers, such as methylhydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures, and also polyvinyl pyrrolidone for example in amounts of 0.1 to 5 wt .-%, based on the agent used.

Soil repellents

In addition, the detergent tablets can also contain components which have a positive influence on the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled previously several times with a detergent according to the invention, the oil and contains fat-dissolving component, was washed. Among the preferred oil and fat dissolvers Components include, for example, nonionic cellulose ethers such as methyl cellulose and Methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight % and of hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ether, and the polymers known from the prior art Phthalic acid and / or terephthalic acid or their derivatives, in particular polymers from ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionically modified derivatives of these. Of these, those are particularly preferred sulfonated derivatives of phthalic acid and terephthalic acid polymers.

Crease agents

Because textile fabrics, especially from rayon, rayon, cotton and their Mixtures that can be creased because the individual fibers prevent bending, kinking. Pressing and squeezing transverse to the direction of the fibers are sensitive, according to the invention manufactured agents contain synthetic anti-crease. These include, for example synthetic products based on fatty acids, fatty acid esters. fatty acid amides, alkyl esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

Antimicrobial agents

The agents prepared according to the invention can be used to control microorganisms contain antimicrobial agents. A distinction is made here depending on the antimicrobial Spectrum and mechanism of action between bacteriostatics and bactericides, Fungiostatics and fungicides etc. Important substances from these groups are for example Benzalkoniumchloride, Alkylarlylsulfonate, Halogenphenole and Phenolmercuriacetat, whereby these connections can also be dispensed with entirely.

Antioxidants

To unwanted, caused by oxygen and other oxidative processes Preventing changes to the agents and / or the treated textiles can Contain antioxidants. This connection class includes, for example substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

antistatic agents

Increased comfort can result from the additional use of antistatic agents, which are additionally added to the agents produced according to the invention. antistatic agents increase the surface conductivity and thus enable an improved drainage formed charges. External antistatic agents are usually substances with at least one hydrophilic molecular ligands and give a more or less on the surfaces hygroscopic film. These mostly surface-active antistatic agents can be nitrogenous (amines, amides, quaternary ammonium compounds), phosphorus (Phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents divide. The lauryl (or stearyl) dimethylbenzylammonium chlorides disclosed here are suitable as antistatic agents for textiles or as an additive to detergents a finishing effect is achieved.

ironing aids

To improve the water absorption capacity, the rewettability of the treated textiles and to facilitate ironing of the treated textiles can in For example, silicone derivatives are used in the agents produced according to the invention. These also improve the rinsing behavior of the agents through their foam-inhibiting Characteristics. Preferred silicone derivatives are, for example, polydialkyl or Alkylarylsiloxanes, in which the alkyl groups have one to five carbon atoms and all or are partially fluorinated. Preferred silicones are polydimethylsiloxanes, which are optionally can be derivatized and then amino-functional or quaternized or Si-OH-, Si-H- and / or have Si-Cl bonds. The viscosities of the preferred silicones are included 25 ° C in the range between 100 and 100,000 centistokes, the silicones in quantities between 0.2 and 5 wt .-%, based on the total agent can be used.

UV absorbers

Finally, the agents produced according to the invention can also contain UV absorbers, that apply to the treated textiles and improve the lightfastness of the fibers. Compounds which have these desired properties are, for example, those by radiation-free deactivation effective compounds and derivatives of benzophenone with Substituents in the 2- and / or 4-position. Substituted benzotriazoles in 3- Position phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid.

The present invention further relates to two-phase or multi-phase washing and Detergent tablets, produced by, as previously explained, at least two differently composed deformable masses are produced, this one Head tool fed and in this to a two or multi-phase strand are merged and this strand after exiting the outlet opening of the Head tool by means of a cutting device to a predetermined length is cut, characterized in that at least one of the deformable masses through the action of shear and compaction forces, such as in Extruders, is provided from a particulate, free-flowing premix, wherein in a preferred embodiment of the present invention at least one further phase of the molded body is not compacted by shear and compression forces has been.

As stated above, preferred ones are within the scope of the present invention Detergent tablets, or their phases, by a temperature-dependent Solubility profile and there are consequently two or multi-phase washing and Preferred detergent tablets whose phase (s) are not compacted by shear forces a melting or softening point between 30 and 90 ° C, preferably between 40 and 80 ° C, which phase (s) preferably one or more Substances from the group of waxes, paraffins and / or polyalkylene glycols in quantities from 25 to 80% by weight, preferably from 35 to 70% by weight and in particular from 45 to 60% by weight, in each case based on the weight of the phase.

Another preferred embodiment is characterized in that the not by Shear forces compacted phase (s) of the molded body continue one or more surfactant (s) in Amounts of 20 to 75 wt .-%, preferably between 30 and 65 wt .-%, particularly preferably between 40 and 55% by weight, based in each case on the weight of the phase, and optional further components of detergents and cleaning agents, especially dyes and / or perfumes.

Contains the phase (s) of the molded body that are not compacted by shear forces Both wax (e), paraffin (e) and / or polyalkylene glycol (e) and surfactant (e) are so preferred that the ratio of waxes, paraffins and / or polyalkylene glycols to the Surfactants between 3: 1 and 1: 2, preferably between 2: 1 and 1: 1.5 and especially is preferably between 1.5: 1 and 1: 1.25.

Regardless of the nature of the ingredients listed above, the end products of the Methods according to the invention provided in a wide variety of geometric shapes be, this flexibility one of the many advantages of the method according to the invention is. However, it is also possible to produce moldings according to the invention which in their Appearance are based on conventional moldings. For example, the in predetermined spatial shape and predetermined size are made, with the spatial shape practically all sensibly manageable configurations come into consideration, For example, the training as a blackboard, the shape of bars or bars, cubes, cuboids and corresponding room elements with flat side surfaces and in particular cylindrical ones Designs with circular or oval cross-section. This last embodiment captures the presentation form from the tablet to compact cylinder pieces a ratio of height to diameter above 1.

The end products of the process according to the invention can each be different from one another separate individual elements can be formed which correspond to the predetermined dosing amount of the washing and / or detergent. But it is also possible to cut the length Form strands so that a plurality of such mass units in one compact connect, the ease of separation in particular by predetermined breaking points portioned smaller units is provided. For the use of textile detergents in Machines of the type common in Europe with horizontally arranged mechanics can Training as tablets, in a cylindrical or cuboid shape may be appropriate, with a Diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred.

The spatial shape of another embodiment of the shaped body is in its dimensions Detergent dispenser of commercial household washing machines adapted so that the Shaped bodies can be metered directly into the induction bowl without a metering aid, where they are dissolves during the induction process. It goes without saying that the Detergent tablets easily possible via a dosing aid and within the present invention preferred.

Another preferred molded body that can be produced has a plate or panel-like structure with alternating thick long and thin short segments, so that individual segments of this "bar" at the predetermined breaking points, the short thin Display segments, can be canceled and entered into the machine. This The principle of the "bar-shaped" shaped body detergent can also be used in other geometric Shapes, for example vertical triangles, only on one of their sides are connected alongside each other, can be realized.

Such "bar-shaped" strand sections can be made by a post-treatment step after cutting to length, which consists of a second knife or a second Pressing the knife set into the cut strand sections without cutting them up. Also a superficial design or creation of positive or negative lettering done according to the invention. Accordingly, preferred methods are characterized in that the cut moldings are subjected to an aftertreatment step become.

In addition to embossing lettering, the post-treatment step can also emboss of patterns, shapes, etc. In this way, for example universal detergent produced according to the invention by a T-shirt symbol, Color detergent produced according to the invention by a wool symbol, according to the invention Manufactured detergent tablets for machine dishwashing by symbols such as glasses, plates, pots, pans, etc. The creativity of There are no limits to product managers. Preferred according to the invention Methods therefore include an additional post-treatment step Shaping step, especially the embossing.

In a special embodiment of the present invention, it is preferred that the embossing has the shape of a trough or cavity which follows the Embossing process with another extruded or tableted molded body can. According to the invention, such a shaped body is advantageously in its spatial shape adapted to the shape of the trough / cavity and is used in this, for example, by use held by suitable adhesives, the selection of which none of the expert Creates difficulties. Regarding its preferred ingredients, this is an afterthought moldings used compared to the extrudate in the context of the present invention no restrictions are imposed and what has been said for the extrudate applies. In particular So such an insert can contain one or more substances from the group of builders, Cobuilders, surfactants, bleaches, bleach activators, disintegrants, enzymes, dyes, Fragrances, anti-corrosion agents, optical brighteners, polymers, or another contain the usual component of detergents and cleaning agents.

Incorporation of a further, extruded or tableted phase into the previous one described trough / cavity of the original extrudate enables, for example Extension of the principle of time-delayed release explained above selected ingredients (controlled release) on a three-stage release process. The Release of the active substances can depend, among other things, on the pH and / or the temperature of the aqueous liquor. To carry out a through the Ambient temperature controlled release has been the use of melting or softenable substances such as waxes, paraffins, polyalkylene glycols, etc. have been proven (for more details, see above). By processing different types of these and softenable substances, for example, deformable masses can be produced themselves at different temperatures and therefore preferably in different ones Dissolve wash cycles. Finally, it is also possible that one of the deformable Contains a disintegrant, preferably a water-soluble disintegrant, whereby the Components of this phase of the cleaning process shortly after the contact of the Detergent with the aqueous phase are available.

A particularly preferred embodiment of the present invention is accordingly a two-phase or multi-phase, preferably a three-phase shaped body, thereby characterized in that the individual phases have a different dissolution rate have an aqueous phase, it being preferred that one of the phases is a contains water-soluble disintegrant, while at least one further phase contains paraffins, Contains waxes or polyalkylene glycols. Such a shaped body can for example consist of there are two extruded phases and a tableted insert, with it continuing It may be advantageous that the extrudate or parts of the extrudate and / or the in a Embossed tray inserted tablet are provided with a coating.

Under the concept of different dissolution rates within the present invention in particular summarized such temporal differences that in Regarding a machine cleaning program are relevant, for example with the chronological sequence of individual cleaning cycles (e.g. pre-treatment, main treatment, Post-treatment) correlate or the simultaneous release of incompatible ingredients avoid (e.g. release of enzyme before the release of bleach and / or Bleach activators). Consequently, differences in the dissolution rates of the Phases of a shaped body according to the invention preferred, which are in a range from 2 to 120 Minutes.

The coating of the cut extrudates or of the extruded or tableted moldings used in the troughs or cavities of these extrudates represents a further preferred possibility of the dissolving behavior, if the application of an additional coating should be desired. Methods are then preferred in which the aftertreatment step comprises coating the extrudate with a pourable material, preferably a pourable material with a viscosity <5000 mPa.s. According to the invention, both the embossing and the coating of the extrudate can take place before, simultaneously with or after the cutting or cutting of the extrudate in the manner described above. The embossing and coating can also be carried out in any conceivable chronological order. Regardless of the number of phases and the type of aftertreatment, methods are generally preferred which are characterized in that the moldings have a density above 800 kg / dm ^-3 , preferably above 900 kg / dm ^-3 , particularly preferably above 1000 kg / dm ^-3 and in particular above 1100 kg / dm ^-3 . The advantages of the offer form of a compact washing or cleaning agent become particularly clear in such shaped articles.

Claims (28)

1. A process for the production of two-phase or multi-phase detergent tablets, wherein at least two differently shaped deformable masses are produced, these are fed to a head tool and brought together in a two-phase or multi-phase strand and this strand by means of after exiting from the outlet opening of the head tool a cutting device is cut to a predetermined length, characterized in that at least one of the deformable masses is provided by the action of shear and compression forces from a particulate, free-flowing premix. 2. The method according to claim 1, characterized in that at least one, but preferably all of the deformable masses have a zeolite content below 10% by weight, preferably below 5% by weight, particularly preferably below 2% by weight and in particular have less than 0.5% by weight. 3. The method according to any one of claims 1 or 2, characterized in that the deformable masses before entering the head tool temperatures between 20 and 100 ° C, preferably between 30 and 90 ° C and in particular between 40 and Have 80 ° C. 4. The method according to any one of claims 1 to 3, characterized in that the Particulate, free-flowing premix for transfer into a deformable mass Pressures from 2 and 150 bar, preferably from 4 to 90 bar and in particular from 6 to 60 bar is exposed. 5. The method according to any one of claims 1 to 4, characterized in that the Conversion of the particulate, free-flowing premix / premixes into one / more deformable mass (es) in the compression space of an extruder, preferably a twin-screw extruder. 6. The method according to any one of claims 1 to 5, characterized in that the Ratio of the length of the compression space of the extruder to its diameter in a range between 32: 1 and 8: 1, preferably between 26: 1 and 10: 1 and is in particular between 20: 1 and 12: 1. 7. The method according to any one of claims 1 to 6, characterized in that the Strands of material at a speed of 0.2 m / min to 30 m / min, preferably between 0.25 m / min to 20 m / min, particularly preferably from 0.5 m / min to 15 m / min and in particular discharged from 1 m / min to 10 m / min from the outlet opening become. 8. The method according to any one of claims 1 to 7, characterized in that the Head tool 1 to 16, preferably 2 to 10 outlet openings. 9. The method according to any one of claims 1 to 8, characterized in that the outlet openings have an opening area of 50 mm ² to 2500 mm ² , preferably from 100 mm ² to 200 mm ² , particularly preferably from 200 mm ² to 1500 mm ² and in particular from 300 mm ² to 1000 mm ^2, with particular preference from 350 mm ² to 750 mm ² . 10. The method according to any one of claims 1 to 9, characterized in that the Temperature difference of the deformable masses before merging in Head tool a value of 30 ° C, preferably of 20 ° C and in particular of Does not exceed 10 ° C. 11. The method according to any one of claims 1 to 10, characterized in that the Volume share of each individual deformable mass in the total volume of all deformable masses is above 5% by volume, preferably above 10% by volume, where the volume information relates to the total volume of all deformable masses after extrusion. 12. The method according to any one of claims 1 to 11, characterized in that at least one of the deformable masses is a lubricant and / or a substance and / or contains a mixture of substances with a melting point below 40 ° C. 13. The method according to any one of claims 1 to 12, characterized in that at least one of the deformable masses one or more plasticizers from the group of polyethylene glycols, polypropylene glycols, fatty alcohols, Starch derivatives, waxes, paraffins, non-ionic surfactants, talc and / or Contains magnesium tartar. 14. The method according to any one of claims 1 to 13, characterized in that one of the deformable masses containing bleach, while another deformable mass Contains bleach activator. 15. The method according to any one of claims 1 to 14, characterized in that a deformable masses containing bleach and / or bleach activator, while a other deformable mass one or more substances from the group of enzymes, Contains dyes, fragrances, optical brighteners and / or anti-corrosion agents. 16. The method according to any one of claims 1 to 15, characterized in that at least one of the deformable masses phosphate (s), preferably Alkali metal phosphate (s), particularly preferably pentasodium or Pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of 20 up to 80% by weight, preferably from 25 to 75% by weight and in particular from 30 to 70% by weight, each based on the corresponding mass. 17. The method according to any one of claims 1 to 16, characterized in that at least one of the deformable masses of sodium carbonate, in amounts of 5 to 60% by weight, preferably contains from 10 to 50% by weight. 18. The method according to any one of claims 1 to 17, characterized in that at least one of the deformable masses contains a water-soluble disintegrant. 19. The method according to any one of claims 1 to 18, characterized in that the material strands emerging from the outlet opening to a length of 5 to 100 mm, preferably from 7.5 to 75 mm, particularly preferably from 10 to 60 mm and in particular from 15 to 50 mm. 20. The method according to any one of claims 1 to 19, characterized in that the the strands of material emerging before, simultaneously with or after the Tailoring a post-treatment, preferably in the form of a coating and / or embossed. 21. The method according to any one of claims 1 to 20, characterized in that by the Embossing a trough or cavity arises, which follows after the embossing process another extruded or tableted molded body is provided. 22. Two-phase or multi-phase detergent tablets manufactured according to one of claims 1-21, wherein at least two differently composed deformable masses are produced, these are fed to a head tool and in this be brought together into a two or multi-phase strand and this strand after exiting from the outlet opening of the head tool by means of a Cutting device is cut to a predetermined length, thereby characterized in that at least one of the deformable masses by the action of shear and compaction forces from a particulate, free-flowing Premix is provided. 23. Two-phase or multi-phase detergent tablets according to claim 22, characterized in that at least one further phase of the shaped body is not was compacted by shear and compression forces. 24. Two- or multi-phase detergent tablets according to claim 23, characterized in that the phase (s) of the. not compacted by shear forces Molded body has a melting or softening point between 30 and 90 ° C, preferably between 40 and 80 ° C. 25. Two-phase or multi-phase detergent tablets according to one of the Claims 23 or 24, characterized in that they are not caused by shear forces compacted phase (s) of the shaped body one or more substances from the group the waxes, paraffins and / or polyalkylene glycols in amounts of 25 to 80% by weight, preferably from 35 to 70% by weight and in particular from 45 to 60% by weight, in each case based on the weight of the phase, contains. 26. Two-phase or multi-phase detergent tablets according to one of the Claims 23 to 25, characterized in that they are not caused by shear forces compacted phase (s) of the shaped body further one or more surfactant (s) in Amounts of 20 to 75 wt .-%, preferably between 30 and 65 wt .-%, particularly preferably between 40 and 55% by weight, based in each case on the weight of the phase, and optionally further components of detergents and cleaning agents, in particular Dyes and / or perfumes, contains. 27. Two- the multi-phase detergent tablets according to one of the Claims 25 or 26, characterized in that the weight ratio of the Waxes, paraffins and / or polyalkylene glycols do not pass through to the surfactant Shear forces compact phase (s) of the molded body between 3: 1 and 1: 2, preferably between 2: 1 and 1: 1.5 and particularly preferably between 1.5: 1 and 1: 1.25. 28. Two or multi-phase, preferably three-phase washing and Detergent tablets according to one of claims 22 to 27, characterized characterized in that the individual phases are different Have dissolution rate in an aqueous phase, it being preferred that one of the phases contains a water-soluble disintegrant, while at least another phase contains paraffins, waxes or polyalkylene glycols.