DE19940548A1 - Detergent tablets - Google Patents

Abstract

The invention relates to washing or cleaning agent shaped bodies that have an advantageous characteristics profile and contain oxidised derivatives of starch and/or dextrines in amounts of 0.1 to 10 wt. % in relation to the weight of the shaped bodies.

Description

The present invention relates to moldings which are washable and cleaning-active possess and processes for their production. In particular, concerns the Erfin dung Detergent tablets for textile washing in a household washing machine, which are briefly referred to as detergent tablets.

Detergent tablets are widely described in the prior art are becoming increasingly popular with consumers because of the simple dosage. Tableted detergents and cleaning agents have a number of powdered detergents Advantages: They are easier to dose and handle and because of their compact structure Advantages in storage and transport. Even in the Patentlite As a result, laundry detergent and cleaning product tablets are comprehensively described. On Problem that always occurs when using washing and cleaning active moldings occurs again, the too slow disintegration and dissolving speed of the shaped body is below Conditions of use. Because sufficiently stable, d. H. shape and break resistant shape body can only be produced by relatively high pressure, it comes to a strong compression of the molded parts and to a consequent delayed disintegration of the shaped body in the aqueous liquor and thus to one slow release of the active substances in the washing or cleaning process. The ver hesitated disintegration of the moldings has the disadvantage that usual Detergent tablets not over the induction chamber of household Have the washing machine rinsed in as the tablets will not wash in quickly enough Secondary particles disintegrate that are small enough to go from the induction chamber into the wash drum to be washed in.  

A variety of approaches exist in the prior art to solve this problem. Next the use of special ingredients that are intended to promote disintegration Coating of individual ingredients as well as sieving the premix to be pressed proposed.

For example, EP-A-0 466 484 (Unilever) discloses detergent tablets in which the ver pressing premix has particle sizes between 200 and 1200 microns, with upper and the lower limit of the particle sizes do not differ by more than 700 µm. The pressing This document does not suggest the use of significantly coarser particles to form tablets.

EP-A-0 522 766 (Unilever) also relates to moldings made from a compact, partially Chen-shaped detergent composition containing surfactants, builders and disinte Grationshilfsmittel (for example based on cellulose), with at least a part of the parti is coated with the disintegrant, which is both binder and disintegra tion effect when dissolving the moldings in water. This font also shows the general difficulty, molded articles with adequate stability and good at the same time To produce solubility. The particle size in the mixture to be compressed should be above are half of 200 µm, the upper and lower limits of the individual particle sizes being around should not differ from each other by more than 700 µm. This document also becomes explicit stated that the particles should not be coarser than 1200 µm.

In the case of the proposed solutions to achieve better disintegration times, these are to be preferred that are based on the additional use of substances that are not ingredients of washing or cleaning agents are largely avoided. To make the recipe as compact as possible to develop without "ballast", there is still a need for proposed solutions conditions that are based on the selection and / or packaging of substances that are also available in the Washing or cleaning cycle have beneficial effects.

The present invention was therefore based on the task of washing and cleaning Provide moldings that are characterized by a high hardness and have excellent decay properties. These detergents and cleaners  Shaped bodies should also be able to be metered through the induction chamber without the consumer thereby disadvantages and residues in the induction chamber little detergent in the soapy water. In addition to these moldings-specific The washing and cleaning performance of the invention should also have properties Shaped body to be exemplary. The advantageous properties of the bait should be not by additives that only serve to improve the properties of the molded body, be achieved, but through the targeted use of fabrics, which are also used in washing and Cleaning process have an effect.

It has now been found that the use of special cobuilders in defined amounts Property profile of detergent tablets improved.

The invention relates to detergent tablets made of compacts particulate detergent or cleaning agent, the oxidized derivatives of starch and / or dextrins in amounts of 0.1 to 10 wt .-%, based on the shaped body important, included.

Oxidized derivatives of starch are also referred to as "oxidized starches", oxidized Derivatives of dextrins are oxidized starch breakdown products. Representatives from both sub Punching classes are often summarized under the generic term "oxidized starch".

The starch is a homoglycan, more precisely a glucan. Different from cellulose, however In the polysaccharide starch, the glucose units are linked α-glycosidically. Furthermore Starch is made up of two components of different molecular weights: approx. 20-30% by weight straight-chain amylose (molecular weight approx. 50000-150000) and 70-80 wt .-% ver branched chain amylopectin (molar mass approx. 300000-2000000), besides are still small Contain quantities of lipids, phosphoric acid and cations. While amylose as a result of Binding in 1,4-position long, helical, intertwined chains with about 300-1200 When glucose molecules form, the chain branches through in amylopectin an average of 25 glucose building blocks through 1,6 binding to form a knot-like structure about 1500-12000 molecules of glucose.  

Strengths can be achieved by treating with different oxidizing agents under parti degradation in carbonyl and carboxy group-containing derivatives, the so-called oxi strengths. The most technically important oxidizing agent is sodium hypochlo rit, which acts on starch suspended in water in an alkaline medium. The resulting low-viscosity dispersions can be dried, with free-flowing powder products result.

Dextrins are degradation products of starch with the general formula (C ₆ H ₁₀ O ₅ ) _n .xH ₂ O, which are formed when hydrolysis is incomplete with dilute acids (acid dextrins) or due to heat (roasted dextrins) and consist of glucose chains. In enzymatic degradation with amylases, the so-called border dextrins are formed, in which the 1,6-glycosidic bonds of amylopectin that are not accessible to the attack of β-amylase are enriched, while cyclodextrins are formed when Bacillus macerans acts on starch solution.

Dextrins form colorless or yellow, amorphous powders that are very easy in water, in alcohol are almost insoluble. In the US, dextrins are made from corn, in the Federal Republic mainly made from potatoes. The corn dextrins are odorless, that of potatoes Dextrin obtained from starch smells like cucumber. The highest molecular weight dextrins give (like Starch) another blue color with iodine solution, the next degradation color with iodine red or brown, and the low molecular weight dextrins no longer give iodine staining. Each the molecular weights of the dextrins are between 2000 and 500000. It is preferably hydrolysis products with medium molecular weights in the range of 400 to 300,000 g / mol. A polysaccharide with a dextrose Equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, preferably DE is a common measure of the reducing effect of a polysaccharide in ver is equal to dextrose, which has a DE of 100. Both Maltodex can be used trine with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in Range from 2000 to 30000 g / mol.

The oxidized derivatives of 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. A preferred dextrin is described in European patent application EP 0 703 292. Oxidized dextrins obtainable from these dextrins and processes for their preparation are known, for example, from European patent applications EP 427 349, EP 472 042 and EP 542 496 as well as international patent applications WO 93/08251, WO 93/16110, WO 95/07303 and WO 95/12619 known. A product oxidized at C _{6 of} the saccharide ring is preferably used, as can be obtained by the process according to one of the international patent applications WO 93/16110, WO 94/28030, WO 95/20608 and WO 96/03439. In addition, however, preference is also given to the use of dextrins which have been modified oxidatively at their originally reducing end, possibly with the loss of a carbon atom. If the originally reducing end of the oligosaccharide was an anhydroglucose unit, there is an arabinonic acid unit after modification:

(Glucose) _n → (Glucose) _n-1 arabinonic acid.

The average degree of oligomerization n lies with these, which is to be determined analytically Size can also take fractional numerical values, preferably in the range from 2 to 20, in particular 2 to 10. This latter oxidative modification can, for example with the help of Fe, Cu, Ag, Co or Ni catalysts, as in the international patent Application WO 92/18542 described with the help of Pd, Pt, Rh or Os catalysts, as described in European patent EP 0 232 202, or by means of a Quinone / hydroquinone system in alkaline with the addition of oxygen and given if treatment with hydrogen peroxide is carried out.

Detergent tablets according to the invention which contain oxidized derivatives of Starch and / or dextrins with average molecular weights in the range of 440 to 500,000 in Amounts from 0.25 to 7.5% by weight, preferably from 0.5 to 5% by weight, especially before added from 0.75 to 3.5 wt .-% and in particular from 1 to 2 wt .-%, based on the Molded body weights are also preferred, as are washing or cleaning agents molded articles in which the oxidized derivatives of starch and / or contained therein  Dextrins dextrose equivalents (DE) from 0.1 to 50, preferably from 0.5 to 40 and in particular from 2 to 30.

As already mentioned, detergent tablets are particularly preferred in which the oxidized derivatives of starch and / or dextrins contained therein are products oxidized at C _{6 of} the saccharide ring.

The incorporation of the oxidized derivatives of starch and / or dextrins into the invention According to the detergent tablets can be in the delivery form or after prior assembly. The oxidized derivatives of Starch and / or dextrins the premix to be compressed, for example as particles shaped solid added or sprayed onto the premix as an aqueous solution become. Inclusion of the oxidized derivatives of starch and / or dextrins in individual components of the particulate premix, for example in compounds such as builder compounds or in surfactant granules, is possible.

A preferred route of incorporation is the oxidized derivatives of starch and / or to mix dextrins into the premix to be compressed in finely divided form. Preferred detergent tablets are therefore characterized in that that they are the oxidized derivatives of starch and / or dextrins in the form of compounds contain an average particle size below 500 microns, preferably below Have 450 microns and especially below 400 microns.

These compounds can, for example, by spray drying commercially available solutions of oxidized derivatives of starch and / or dextrins can be obtained, or by Auf spray such solutions on carrier materials such as sodium carbonate, sodium sulfate or Silicates or zeolites. Of course, the commercially available particulate gene oxidized derivatives of starch and / or dextrins are used, the ge then called compounds made entirely of oxidized. Starch and / or dextrin derivatives consist. The advantage results from the particle size range mentioned. It is fine in the form of the addition of the oxidized derivatives of starch and / or dextrins Partial compounds preferred that the compounds as high levels of active substance  have punch. Accordingly, preferred forms of washing or cleaning agents are body characterized in that the compounds are the oxidized derivatives of starch and / or dextrins in amounts of more than 10% by weight, preferably more than 20% by weight and in particular of more than 30 wt .-%, each based on the weight of the Compounds included.

An incorporation alternative for the oxidized derivatives of starch and / or dextrins consists in dividing these into individual components of the premix before mixing Incorporate premix. Surfactant granules are particularly suitable for this their manufacture aqueous solutions of oxidized derivatives of starch and / or dex trines can be used as granulation aids. Of course it is possible Lich, several incorporation routes for the oxidized derivatives of starch and / or dextri NEN to combine with each other and both use a surfactant granules that this contains, as well as the oxidized derivatives of starch and / or dextrins the premix for example, in finely divided form. However, it is preferred if a surfactant granule lat is used that contains the oxidized derivatives of starch and / or dextrins that this is the total amount of all oxidized derivatives contained in the moldings Contains starch and / or dextrins. So are detergent tablets that the oxidized derivatives of starch and / or dextrins in the form of a surfactant granulate hold that the total amount of the oxidized derivatives contained in the moldings Contains starch and / or dextrins, preferred embodiments of the present Er finding.

Surfactant granules, their ingredients, and methods of making them are described below described. Regarding the content of oxidized derivatives of starch and / or dextrins Detergent tablets are preferred in which the content of ten Sidgranulats of oxidized derivatives of starch and / or dextrins 0.5 to 20 wt .-%, preferably 0.75 to 15% by weight, particularly preferably 1 to 10% by weight and in particular 1.5 to 5 wt .-%, based in each case on the weight of the surfactant granules.

More generally, detergent tablets are made from compressed, partially Chen-shaped detergents or cleaning agents are preferred, which are characterized in  that they contain a surfactant granulate, which oxidized derivatives of starch and / or Dex contains trines.

The detergent tablets according to the invention contain, in addition to the oxidized derivatives of starch and / or dextrins further ingredients of washing or Detergents. Among these, builders and surfactants in particular come from outstanding role. In the detergent tablets according to the invention All builders commonly used in washing and cleaning agents can be used be contained, in particular thus zeolites, silicates, carbonates, organic cobuilders and where there are no ecological prejudices against their use - including phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium: and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in the international patent application WO-A-91/08171 .

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed 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, compaction / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted in such a way that the products have microcrystalline ranges of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a release delay compared to the conventional water glass glasses, are described, for example, in German patent application DE-A-44 00 024. 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 (approx. 80% by weight zeolite X), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula

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

can be described. The zeolite can be used both as a builder in a granule Ren compound used, as well as a kind of "powdering" of the whole to be pressed Send mixture are used, usually both ways to mis-corporation of the zeolite can be used in the premix. Suitable zeolites have a medium one Particle size of less than 10 µm (volume distribution; measurement method: Coulter Coun ter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight bound water.

It goes without saying that the generally known phosphates are also used as buildersub punching possible, provided that such use is not avoided for ecological reasons should be. Among the large number of commercially available phosphates, the Alka limetal phosphates with particular preference for pentasodium or pentapotassium tri  phosphate (sodium or potassium tripolyphosphate) in detergents and cleaning agents Industry the most important.

Alkali metal phosphates is the general term for the alkali metal (in particular 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 or lime incrustations in tissues and also contribute to cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white, water-soluble powders, which 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 occurs when phosphoric acid is adjusted to pH 4.5 with caustic soda 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 easily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 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 the diphosphate Na ₄ P ₂ O ₇ when heated to a greater extent. Disodium hydrogen phosphate is produced 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 ) have 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 alkaline reaction. It arises e.g. B. when He's 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 dehydrating 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 distinguish 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 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O ] _n -Na with n = 3. In 100 g of water about 17 g dissolve at room temperature, at 20 ° approx. 20 g, at 100 ° around 32 g of the crystal water-free salt; after heating the solution to 100 ° for two hours, Hydrolysis about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with soda 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 (also lime soaps etc.) Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), comes for example in the form of a 50% by weight solution (<23% P ₂ O ₅ , 25% K ₂ O) in the trade. 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 tripolyphos phate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and Sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tri Polyphosphate and sodium potassium tripolyphosphate can be used according to the invention.

Polycarboxylates / Po in particular can be used as organic cobuilders in the moldings lycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, other organi Sche Cobuilder (see below) and phosphonates are used. These substance classes are described below.

Usable organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, with such carboxylic acids under polycarboxylic acids  can be understood that carry more than one acid function. For example, these are Citro Nenoic acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, Fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if one such use is not objectionable for ecological reasons, as well as mixtures from these. Preferred salts are the salts of polycarboxylic acids such as citric acid, Adi Pinic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of the sen.

The acids themselves can also be used. The acids have besides their buil the 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 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 respective acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the investigated polymers. 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, the This group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, preferably his.  

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As a special copolymers of acrylic acid with maleic acid, 50 to Contain 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative mole Cooling mass, based on free acids, is generally from 2000 to 70,000 g / mol preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

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

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

Biodegradable polymers of more than two ver. Are also particularly preferred different monomer units, for example those that act as monomers salts of 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 are those which are described in German patent applications DE- A-43 03 320 and DE-A-44 17 734 are described and preferably as monomers Have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Likewise, further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors. Polyas are particularly preferred paraginic acids or their salts and derivatives, of which in the German patent application dung DE-A-195 40 086 discloses that, in addition to cobuilder properties, it also has a have a bleach-stabilizing effect.  

Other suitable builder substances are polyacetals, which are produced by the implementation of DiaI dehyden with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl have groups that can be obtained. Preferred polyacetals are from Dialde hyden such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from Obtained polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Also oxydisuccinates and other derivatives of disuccinates, preferably ethylenedia mindisuccinate are other suitable cobuilders. Here, ethylenediamine-N, N'- disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and Gly are also preferred in this context cerintrisuccinate. Suitable amounts are in zeolite and / or silicate salts gene formulations at 3 to 15 wt .-%.

Other useful organic cobuilders are, for example, acetylated hydroxycarbon acids or their salts, which may optionally also be in lactone form, and which have at least 4 carbon atoms and at least one hydroxyl group and maxi contain two acid groups. Such cobuilders are used, for example, in the inter national patent application WO 95/20029.

Another class of substances with cobuilder properties are the phosphonates it is in particular hydroxyalkane or aminoalkanephosphonates. Under the hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) from of particular importance as a cobuilder. It is preferably used as the sodium salt the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). As Aminoalkane phosphonates preferably come from ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher Ho mologist in question. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP, used. HEDP is preferred as a builder from the phosphonate class turns. The aminoalkanephosphonates also have a pronounced heavy metal bin de assets. Accordingly, it can, especially if the agent also ent bleach hold, be preferred to use aminoalkane phosphonates, in particular DTPMP, or To use mixtures of the phosphonates mentioned.  

In addition, all compounds that are capable of complexing with alkaline earth train ions as cobuilders.

The amount of builder is usually between 10 and 70 wt .-%, preferably as between 15 and 60 wt .-% and in particular between 20 and 50 wt .-%. The The amount of builders used depends on the intended use, so that bleaching medium tablets and tablets for machine dishwashing May have builders (for example between 20 and 70% by weight, preferably as between 25 and 65 wt .-% and in particular between 30 and 55 wt .-%), as for example detergent tablets (usually 10 to 50% by weight, preferably 12.5 up to 45% by weight and in particular between 17.5 and 37.5% by weight).

Preferred detergent tablets according to the invention further contain towards one or more surfactant (s). Anionic, nonionic, cationic and / or amphoteric surfactants or mixtures of these be set. From an application point of view, mixtures of anioni are preferred and non-ionic surfactants. The total surfactant content of the moldings is 5 to 60% by weight, based on the weight of the shaped body, surfactant contents above 15% by weight are preferred.

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

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under fatty acid glyce The mono-, di- and triesters as well as their mixtures are to be understood as Rinestern, as in the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or obtained in the transesterification of triglycerides with 0.3 to 2 mol of glycerol. Before pulled sulfated fatty acid glycerol esters are the sulfonation products of saturated fat acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, Ca. pric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

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

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

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

Soaps are particularly suitable as further anionic surfactants. Are suitable saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural Fatty acids, e.g. B. coconut, palm kernel or tallow fatty acids, derived soap mixtures.

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

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

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

Another class of preferred nonionic surfactants, which are used either as allei some nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and pro poxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as described, for example, in Japanese Pa tentanmeldung JP 58/217598 are described or which are preferably according to the in the international patent application WO-A-90/13533 become.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N- dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alka nolamides may be suitable. The amount of these nonionic surfactants is before 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 the RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for water, 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 the R for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ¹ for a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R ² for a linear, branched or cyclic alkyl radical or is an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue.

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

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

For example, moldings in which the ratio of Anionic surfactant (s) to nonionic surfactant (s) between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2. Washing and washing are also preferred Detergent tablets which contain anionic (s) and / or nonionic (s) surfactant (s) hold and total surfactant contents above 2.5 wt .-%, preferably above 5 wt .-% and in particular above 10% by weight, in each case based on the shaped body weight. Detergent tablets are particularly preferred, the surfactant (s), preferably anionic (s) and / or nonionic (s) surfactant (s), in quantities from 5 to 40% by weight, preferably from 7.5 to 35% by weight, particularly preferably from 10 up to 30 wt .-% and in particular from 12.5 to 25 wt .-%, each based on the shape body weight, included.

From an application point of view, it can be advantageous if certain classes of surfactants in some phases of the molded article or in the entire molded article, i. H. in all phases, are not included. Another important embodiment of the present invention therefore provides that at least one phase of the moldings is free of nonionic tensi that is.

Conversely, the content of individual phases or the entire form can also be used body, d. H. all phases, certain surfactants have a positive effect. The The introduction of the alkyl polyglycosides described above has been found to be advantageous pointed, so that moldings are preferred in which at least one phase of the moldings contains per alkyl polyglycosides.

Similar to the nonionic surfactants can also be left out of anioni tensides result from individual or all phases of shaped bodies which are suitable for certain areas of application are better suited. It is therefore within the scope of the present  Invention detergent tablets also conceivable in which at least a phase of the moldings is free from anionic surfactants.

As already mentioned, the use of surfactants in cleaning detergents for machine dishwashing is preferably limited to the use of nonionic surfactants in small amounts. In the context of the present invention, detergent tablets preferably to be used as detergent tablets are characterized in that the tablet total surfactant contents are below 5% by weight, preferably below 4% by weight, particularly preferably below 3% by weight and in particular below 2% by weight, based in each case on the weight of the shaped body. Only weakly foaming nonionic surfactants are usually used as surfactants in automatic dishwashing detergents. By contrast, representatives from the groups of anionic, cationic or amphoteric surfactants are of lesser importance. The detergent tablets according to the invention for machine dishwashing particularly preferably contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical branches linearly or preferably in the 2-position methyl may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, Alko holethoxylate with linear residues from alcohols of native origin with 12 to 18 C-Ato men, z. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In particular with detergent tablets or cleaning agents according to the invention Shaped articles for automatic dishwashing, it is preferred that the washing and cleaning Detergent tablets contain a nonionic surfactant that has a melting point above room temperature. Accordingly, the washing agents according to the invention contain or detergent tablets preferably a nonionic surfactant with a melt point above 20 ° C. Non-ionic surfactants to be used preferably Melting points above 25 ° C, particularly preferred nonionic Surfactants have melting points between 25 and 60 ° C, especially between 26.6 and 43.3 ° C.

Suitable nonionic surfactants, the melting or softening points in the above Temperature range are, for example, low-foaming nonionic ten side, which can be solid or highly viscous at room temperature. Will be at room temperature rature highly viscous nonionic surfactants used, it is preferred that these have a viscosity above half of 20 Pas, preferably above 35 Pas and in particular above 40 Pas exhibit. Also non-ionic surfactants, which have a waxy consistency at room temperature, are preferred.

Preferred nonionic surfactants to be used as solid at room temperature originate from the group pen of the alkoxylated nonionic surfactants, especially the ethoxylated primary alcohols and Mixtures of these surfactants with structurally more complex surfactants such as Po lyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

In a preferred embodiment of the present invention, this is nonionic Surfactants with a melting point above room temperature an ethoxylated nonionic surfactant, that from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 C- Atoms with preferably at least 12 mol, particularly preferably at least 15 mol,  especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has gone.

A particularly preferred nonionic surfactant which is solid at room temperature is made from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol, of ethylene oxide won. Among these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

The nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule. Such PO units preferably make up to 25% by weight, in particular more preferably up to 20% by weight and in particular up to 15% by weight of the total moles mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally contain polyoxyethylene Have polyoxypropylene block copolymer units. The alcohol or alkylphenol part such nonionic surfactant molecules preferably make up more than 30% by weight, especially be preferably more than 50% by weight and in particular more than 70% by weight of the total molma such nonionic surfactants.

Other nonionic surfactants to be used with particular preference with melting points above Room temperature contain 40 to 70% of a polyoxypropy len / polyoxyethylene / polyoxypropylene block polymer blends, the 75 wt .-% of a vice returned block copolymers of polyoxyethylene and polyoxypropylene with 17 moles of ethyl lenoxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of Po lyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles Ethylene oxide and 99 moles of propylene oxide per mole of trimethylol propane.

Nonionic surfactants, which can be used with particular preference, are from for example under the name Poly Tergent® SLF-18 from Olin Chemicals true.  

A further preferred surfactant can be represented by the formula I.

R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ]

describe in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1 , 5 and y stands for a value of at least 15.

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x = ≧ 2, each R ³ in the above formula can be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred for the radical R ³ . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula can be different if x ≧ 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, when x is 3, the R ³ group can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which can be joined together in any order, for example (EO ) (PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO ) (PO) (PO). The value 3 for x has been chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa.

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula can be used

R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²

simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particular preference is given to surfactants in which the radicals R ¹ and R ^{2 have} 9 to 14 C atoms, R ³ stands for H and x assumes values from 6 to 15.

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

These substances, which are also referred to as "explosives" due to their effect, ver increase their volume when water enters, and on the one hand increases their own volume (Swelling), on the other hand, a pressure can be generated via the release of gases which can break the tablet into smaller particles. Well-known disintegration aid medium are, for example, carbonate / citric acid systems, but also other organic ones Acids can be used. Swelling disintegration aids are, for example synthetic polymers such as polyvinyl pyrrolidone (PVP) or natural polymers or mo  differentiated natural substances such as cellulose and starch and their derivatives, alginates or casein Derivatives.

Preferred detergent tablets contain 0.5 to 10% by weight preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disinfectants Gration aids, each based on the weight of the molded body.

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred moldings such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6 % By weight. 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 disintegrators 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 cellulose, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocellulose. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The cellulose derivative content of these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. It is particularly preferred to use cellulose-based disintegrant which is cellulose-free and free of cellulose derivatives.

The cellulose used as disintegration aid is preferably not finely divided form, but before mixing into the premixes to be pressed  converted into a coarser form, for example granulated or compacted. Washing and Detergent tablets, the disintegrant in granular or optionally cogranu Contained form, are in the German patent applications DE 197 09 991 (Ste fan Herzog) and DE 197 10 254 (Henkel) and the international patent application WO98 / 40463 (Henkel). These writings are also more detailed information on the Her position of granulated, compacted or cogranulated cellulose disintegrants men. 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 on cellulose In the context of the present invention, bases are preferred as disintegration aids used and commercially, for example under the name Arbocel® TF-30-HG by available from Rettenmaier.

As a further disintegrant based on cellulose or as part of this compo microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions that only attack the 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 cellulo produced by the hydrolysis sen supplies the microcrystalline celluloses, which have primary particle sizes of approx. 5 µm sen and, for example, to granules with an average particle size of 200 microns are pactable.

Preferred detergent and cleaning agent form in the context of the present invention Bodies additionally contain a disintegration aid, preferably a disintegration agent cellulose-based auxiliary agents, preferably in granular, cogranulated or compact tated form, in amounts of 0.5 to 10 wt .-%, preferably from 3 to 7 wt .-% and in particular from 4 to 6% by weight, in each case based on the weight of the shaped body, where preferred disintegration aids average particle sizes above 300 microns preferably have above 400 microns and in particular above 500 microns.  

The detergent tablets according to the invention can moreover contain a gas-developing shower system. The gas-developing shower system can consist of a single substance that releases a gas when in contact with water. Under These compounds should be mentioned in particular the magnesium peroxide, which is in contact releases oxygen with water. The gas-releasing bubble system usually exists however, in turn, from at least two constituents, which together form gas react. While here a variety of systems is conceivable and executable, the at release nitrogen, oxygen or hydrogen, for example, that will be invented bubble system used according to the detergent tablets according to the invention read probably based on economic as well as ecological considerations sen. Preferred shower systems consist of alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable from the alkali Release tall salts in aqueous solution carbon dioxide.

In the case of the alkali metal carbonates or bicarbonates, the sodium and potassium are salts are clearly preferred over the other salts for cost reasons. Self ver the pure alkali metal carbonates or -hydrogen carbonates are used; rather, mixtures of different car bonates and hydrogen carbonates may be preferred for washing technology reasons.

In preferred detergent tablets, 2 to 20% by weight, preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or bicarbonate and 1 to 15, preferably 2 to 12 and in particular special 3 to 10 wt .-% of an acidifying agent, based in each case on the total Shaped body, used.

As an acidifying agent that releases carbon dioxide from the alkali salts in aqueous solution are, for example, boric acid and alkali metal bisulfates, alkali metal dihy drug phosphates and other inorganic salts can be used. However, are preferred organic acidifiers are used, with citric acid being particularly preferred added acidifier. However, the other fixed ones can also be used in particular Mono-, oligo- and polycarboxylic acids. Wine is preferred from this group  acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid like polyacrylic acid. Organic sulfonic acids such as amidosulfonic acid are also a settable. Commercially available and as an acidifying agent within the scope of the present Sokalan® DCS (trademark of BASF) is also preferably used according to the invention Mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adi pinic acid (max. 33% by weight).

In addition to the ingredients mentioned builder, surfactant and disintegration aid, The detergent tablets according to the invention are further used in detergents. and cleaning agents usual ingredients on the group of bleaching agents, bleaching agents gates, dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, Anti-redeposition agents, graying inhibitors, color transfer inhibitors and corro ion inhibitors included.

The detergents and cleaning agents can be used to develop the desired bleaching performance Shaped body of the present invention contain bleach. Here in particular in particular the usual bleaching agents from the group sodium perborate monohydrate, Sodium perborate tetrahydrate and sodium percarbonate have proven their worth.

"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 peroxy viewed carbonate. It was not until 1909 that the compound was Addition compound recognized, nevertheless the historical designation "sodium per carbonate "prevailed in practice.  

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

In the bleaching agents used, the content of the moldings in these substances is from Depending on the intended use of the molded body. While common universal detergents in Ta in sheet form between 5 and 30% by weight, preferably between 7.5 and 25% by weight and contain in particular between 12.5 and 22.5% by weight of bleach, the contents are for bleach or bleach booster tablets between 15 and 50 wt .-%, preferably between 22.5 and 45% by weight and in particular between 30 and 40% by weight.

In addition to the bleaching agents used, the washing and Detergent tablets contain bleach activator (s), which is within the scope of the invention is preferred. Bleach activators are used in detergents and cleaning agents incorporated to improve cleaning when washing at temperatures of 60 ° C and below achieve bleaching effect. 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 perbenzo result acid, are used. Suitable substances are O- and / or N- Acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl carry groups. Multi-acylated alkylenediamines, in particular tetraa, are preferred cetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-  dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetyl glycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated more term alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5- dihydrofuran.

In addition to the conventional bleach activators or in their place, too so-called bleaching catalysts can be incorporated into the moldings. With this stuff fen are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo salt complexes or -carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N- containing tripod ligands and Co, Fe, Cu and Ru amine complexes are bleached catalysts can be used.

If the moldings according to the invention contain bleach activators, they each contain Weil based on the entire molded body, between 0.5 and 30 wt .-%, preferably between 1 and 20% by weight and in particular between 2 and 15% by weight of one or more other bleach activators or bleach catalysts. Depending on the intended use of the herge The shaped bodies may vary. So are in typical universal detergent tablets bleach activator contents between 0.5 and 10 wt .-%, preferably between 2 and 8 wt .-% and in particular between 4 and 6 wt .-% usual, while Bleach tablets definitely higher contents, for example between 5 and 30 wt .-%, preferably between 7.5 and 25% by weight and in particular between 10 and 20% by weight can have. The expert is not limited in his freedom of formulation restricts and can make stronger or weaker bleaching detergent tablets , detergent tablets or bleach tablets by changing the contents of bleach activator and bleaching agent varied.

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

In addition to the ingredients mentioned, bleach, bleach activator, builder, surfactant and Disintegration aids, the washing and cleaning agents according to the invention molded body further ingredients from the group that are common in washing and cleaning agents of dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, Anti-redeposition agents, graying inhibitors, color transfer inhibitors and corro ion inhibitors included.

For the aesthetic impression of the detergent and cleaning agent form according to the invention to improve the body, they can be colored with suitable dyes. Before drawn dyes, the selection of which is not difficult for the person skilled in the art a high storage stability and insensitivity to the other ingredients of the Medium and against light and no pronounced substantivity towards textile fibers in order not to stain them.

Preferred for use in the detergent and cleaning agent form according to the invention bodies are all colorants that can be oxidatively destroyed in the washing process as well Mixtures of these with suitable blue dyes, so-called blue tones. It turned out to be proven to use colorants that are in water or at room temperature liquid organic substances are soluble. For example, anionic ones are suitable Colorants, e.g. B. anionic nitroso dyes. A possible colorant is, for example se Naphtholgrün (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020), which as a trade product, for example, available as Basacid® Green 970 from BASF, Ludwigshafen is, and mixtures of these with suitable blue dyes. As another colorant come 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® Blau 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).  

When choosing the colorant, care must be taken to ensure that the colorants do not have too strong an affinity for the textile surfaces and especially for synthetic fibers. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stabilities against oxidation. Generally speaking, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaning agents varies. In the case of readily water-soluble colorants, e.g. B. the above-mentioned Basacid® green or the above-mentioned Samdolan® blue, dyeing medium concentrations in the range of a few 10 ^-2 to 10 ^-3 wt .-% are typically selected. 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 detergents or cleaning agents, however, is typically some 10 ^-3 to 10 ^-4 wt .-%.

The moldings can be optical brighteners of the derivative type of the diaminostilbene contain sulfonic acid or its alkali metal salts. Are suitable for. B. salts of 4,4'- Bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or the same well-structured compounds that a diethanolamino instead of the morpholino group group, a methylamino group, an anilino group or a 2-methoxyethylamino wear group. Brighteners of the substituted diphenylstyryl type can also be used be essential, 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 too the aforementioned brighteners can be used. The optical brighteners are in the detergent tablets according to the invention in concentrations between between 0.01 and 1% by weight, preferably between 0.05 and 0.5% by weight and in particular between 0.1 and 0.25% by weight, based in each case on the entire shaped body puts.

Fragrances are added to the agents according to the invention in order to maintain an aesthetic appearance to improve product pressure and consumer in addition to product performance  a visually and sensorially "typical and distinctive" product is available put. As perfume oils or fragrances, individual fragrance compounds, e.g. B. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and Koh type Hydrogen oils are used. Fragrance compounds of the ester type are e.g. B. Benzyl acetate, phenoxyethyl isobutyrate, p-tert.-butylcyclohexyl acetate, linalyl acetate, dime thylbenzyl-carbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. To the Ethers include, for example, benzyl ethyl ether, the aldehydes e.g. B. the linear Alka nale with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. B. the Jonone, ∝- Isomethylionon and methyl-cedryllcetone, to the alcohols anethole, citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, are hydrocarbons mainly the terpenes such as limes and pinene. However, Wed are preferred uses different fragrances, which together make an appealing Generate fragrance. Such perfume oils can also contain natural fragrance mixtures ten, as they are accessible from plant sources, e.g. B. Pine, Citrus, Jasmine, Pat chouly, rose or ylang-ylang oil. Muscatel, sage oil, Ka. Are also suitable millen oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, Vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, Orange peel oil and sandalwood oil.

The content of the detergent and cleaning agent formulations according to the invention is usually body of fragrances up to 2% by weight of the total formulation. The fragrances can can be incorporated directly into the agents according to the invention, but it can also be advantageous be to apply the fragrances to carriers that will adhere the perfume to the laundry intensify and through a slower fragrance release for long-lasting fragrance of the texti lien worry. Cyclodextrins, for example, have proven to be such carrier materials lasts, the cyclodextrin-perfume complexes additionally with other auxiliary substances fen can be coated.

Enzymes in particular come from the hydrolase classes such as the protea sen, esterases, lipases or lipolytically active enzymes, amylases, cellulases or  other glycosyl hydrolases and mixtures of the enzymes mentioned in question. All this hy drolasen wear in the laundry to remove stains such as protein, fat or starchy stains and graying. Cellulases and other glycosyl hy drolasen can also be removed by removing pilling and microfibrils Color preservation and increase the softness of the textile. For bleaching or Inhibition of color transfer can also be used oxidoreductases. Especially are particularly suitable from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well their genetically modified variants obtained enzymatic active ingredients. Before Proteases of the subtilisin type and in particular proteases derived from Ba cillus 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 lipolytically acting enes zymmen or from protease, amylase and lipase or lipolytic enzymes or Protease, lipase or lipolytically active enzymes and cellulase, but especially Protease and / or lipase-containing mixtures. or mixtures with lipolytically active Enzymes of special interest. Examples of such lipolytic enzymes are the well-known cutinases. Peroxidases or oxidases have also been found in some Cases proved to be suitable. Suitable amylases include in particular alpha- Amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferred as cellobiohydrolases, endoglucanases and glucosidases, which also cellobiases ge are called, or mixtures of these are used. Since different cellulase Distinguishing types by their CMCase and Avicelase activities can by ge targeted mixtures of the cellulases the desired activities can be set.

The enzymes can be adsorbed on carriers or embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5% by weight.

In addition, the detergent tablets can also ent components hold, which positively influence the oil and fat washability from textiles (so-called  called soil repellents). This effect is particularly evident when a textile is dirty is already several times with a detergent according to the invention, this Contains oil and fat-dissolving component, was washed. Among the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methylhydroxy-propyl cellulose with a proportion of methoxyl groups from 15 to 30 wt .-% and of hydroxypropoxyl groups from 1 to 15 wt .-%, each bezo gene on the nonionic cellulose ether, as well as those known from the prior art Polymers of phthalic acid and / or terephthalic acid or their derivatives, in particular special polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Especially be of these, the sulfonated derivatives of phthalic and terephthalic acids are preferred re-polymers.

Another object of the present invention is a method for producing Detergent tablets by molding a particle shaped premix in which the premix oxidized derivatives of starch and / or Dextrins in amounts of 0.1 to 10 wt .-%, based on the premix.

With regard to preferred oxidized derivatives of starch and / or dextrins, here too reference is made to the preceding explanations as in relation to further In Ingredients of the premix to be pressed or incorporation options for the oxidized derivatives of starch and / or dextrins.

The moldings according to the invention are first produced by dry means Mixing of the components, which can be partially or completely pre-granulated, and on concluding information, in particular pressing into tablets, with conventional che procedures can be used. This is used to manufacture the molded articles Premix in a so-called die between two stamps to form a solid grain primed compacted. This process, hereinafter referred to as tableting is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection.  

First, the premix is introduced into the die, the filling quantity and thus the weight and shape of the resulting molded body through the position of the lower one Stamp and the shape of the press tool can be determined. The constant dose tion even at high molding throughputs is preferably a volumetric Dosage of the premix reached. In the further course of tabletting, the Upper stamp the premix and continues to lower towards the lower stamp. At this compression, the particles of the premix are pressed closer together where at the void volume within the filling between the punches continuously decreases. From a certain position of the upper stamp (and thus from a certain pressure on the premix) begins the plastic deformation, in which the particles flow together and the molded body is formed. Depending on the physi properties of the premix, some of the premix particles are also broken down presses and the premix is sintered at even higher pressures. At increasing press speed, i.e. high throughput, the phase of elasti 's deformation is continuously shortened, so that the resulting molded body more or may have smaller cavities. In the last step of tableting the Finished molded articles are pressed out of the die by the lower punch and through subsequent transport devices transported away. At this point, it's just that Weight of the molded body finally determined, because the compacts due to physical Processes (stretching, crystallographic effects, cooling etc.) their shape and size can still change.

Tableting takes place in commercially available tablet presses, which are basically or double stamps can be equipped. In the latter case, not only the waiter stamp used to build up pressure, also the lower stamp moves during the Pressing process towards the upper punch, while the upper punch presses down. For Small production quantities are preferably used with eccentric tablet presses which the one or more stamps are attached to an eccentric, which in turn on one Axis is mounted with a certain rotational speed. The movement of this Press ram is comparable to the way a conventional four-stroke engine works. The Ver pressing can be done with one upper and one lower stamp, but several can also be used re stamp on an eccentric disk, the number of die holes  gen is expanded accordingly. The throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs, rotary tablet presses are selected, in which on a so-called called matrix table a larger number of matrices is arranged in a circle. The The number of matrices varies between 6 and 55, depending on the model, with larger matrices also are commercially available. Each die on the die table is a top and bottom stamp assigned, again the pressing pressure active only by the upper or lower stamp, but can also be built up by both stamps. The matrix table and the Stamps move around a common vertical axis, the stamp with the help of rail-like cam tracks during the circulation in the positions for Be filling, compression, plastic deformation and discharge. On the stel len, where a particularly serious raising or lowering the stamp is necessary (filling, compacting, ejecting), these cam tracks are replaced by additional che low-pressure pieces, pull-down rails and lifting tracks supported. The filling The matrix is developed via a rigidly arranged feed device, the so-called Filling shoe, which is connected to a reservoir for the premix. The press pressure on the premix is individual via the press paths for upper and lower punches adjustable, the pressure build-up by rolling the stamp shaft heads past ver adjustable pressure rollers happens.

Rotary presses can also use two filling shoes to increase throughput hen be, with only one semicircle to manufacture a tablet that must. Several fillers are used to produce two- and multi-layer moldings shoes arranged one behind the other without the slightly pressed first layer in front of the further filling is ejected. Appropriate litigation leads to this se also coated and dot tablets can be produced, which have an onion-shell-like structure have, whereby in the case of the point tablets the top of the core or the core layers is not covered and therefore remains visible. Rotary tablet presses are also included Single or multiple tools can be equipped, so that, for example, an outer circle with 50 and an inner circle with 35 holes simultaneously used for pressing  the. The throughputs of modern rotary tablet presses are over a million forms body per hour.

When tableting with rotary presses, it has proven to be advantageous to carry out the tablet 25475 00070 552 001000280000000200012000285912536400040 0002019940548 00004 25356ttierung with the lowest possible weight fluctuations of the tablet. The fluctuations in hardness of the tablet can also be reduced in this way. Small fluctuations in weight can be achieved in the following ways:

• - Use of plastic inserts with small thickness tolerances
• - Low number of revolutions of the rotor
• - Big filling shoes
• - Matching the filler paddle speed to the speed of the rotor
• - Filling shoe with constant powder height
• - Decoupling of filling shoe and powder feed

To reduce the build-up of stamps, all of them can be used in technology known non-stick coatings. Plastic coatings are particularly advantageous, Plastic inlays or plastic stamps. Rotating stamps also have an advantage proven, whereby the upper and lower stamps are rotatable if possible should. In the case of rotating stamps, a plastic insert is generally not required become. The stamp surfaces should be electropolished here.

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

Tableting machines suitable for the purposes of the present invention are, for example available from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMA  Verpackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms. Other providers are, for example Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Li verpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy N.V., Halle (BE / LU) and Me diopharm Kamnik (SI). The hydraulic double is particularly suitable HPF 630 printing press from LAEIS, D. Tableting tools are, for example, from the company Adams Tablettierwerkzeuge, Dresden, Wilhelm Fette GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber & Söhne GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharmatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Werkzeugbau, Tamm available. Other providers are e.g. B. the Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).

The moldings can ge in a predetermined spatial shape and a predetermined size be manufactured. Practically all sensibly manageable designs come as a spatial form tations, for example the training as a blackboard, the bars or bars shape, cubes, cuboids and corresponding room elements with flat side surfaces as well in particular cylindrical configurations with a circular or oval cross cut. This last embodiment covers the presentation form from the tablet to to compact cylinder pieces with a ratio of height to diameter above 1. The shaped bodies according to the invention can take on any geometric shape, whereby in particular concave, convex, biconcave, biconvex, cubic, tetragonal, or Thorhombic, cylindrical, spherical, segment-like, disc-shaped, tetrahedral drale, dodecahedral, octahedral, conical, pyramidal, ellipsoid, five-, seven- and octagonal-prismatic and rhombohedral shapes are preferred. Also completely crazy Gular base areas such as arrow or animal shapes, trees, clouds, etc. can be realized become. If the shaped bodies according to the invention have corners and edges, they are preferably rounded. As an additional optical differentiation is an execution shape with rounded corners and chamfered ("chamfered") edges preferred.

The laundry detergent or cleaning product tablets can each be ge separate individual elements can be formed which correspond to the predetermined dosage of the washing and / or detergent. However, it is also possible to form compacts,  which connect a plurality of such mass units in one compact, in particular the predetermined separations make it easier to separate smaller portions Units is provided. For the use of textile detergents in machines of the Europe usual type with horizontally arranged mechanics can the training of the portioned compacts as tablets, in cylindrical or cuboid form where appropriate at a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred. Commercial hydraulic presses, eccentric presses or rotary presses are suitable Devices in particular for the production of such compacts.

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

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

But it is also possible that the various components do not become one Tablet are pressed, but that molded bodies are obtained that have several layers ten, i.e. at least two layers. It is also possible that these ver different layers have different dissolving speeds. From this you can advantageous application properties of the molded articles result. If at for example, components are contained in the moldings, which are mutually nega tiv influence, so it is possible to find a component in the more rapidly soluble layer to integrate and incorporate the other component in a slower soluble layer  ten, so that the first component has already reacted when the second goes into solution. The layer structure of the moldings can be stacked, with one solder process of the inner layers) at the edges of the molded body, if the outer layers are not yet completely detached, it can also be one complete coating of the inner layer (s) by the outer layer (s) Layer (s) can be reached, which prevents the premature dissolution of Be components of the inner layer (s).

Another object of the present invention is therefore a method of manufacture multi-phase detergent tablets by Ver known per se pressing several particulate premixes in which at least one of the premixes oxidized derivatives of starch and / or dextrins in amounts of 0.1 to 10% by weight, based on the premix.

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

In addition to the layer structure, multi-phase moldings can also be in the form of a toroidal core Tablets, core coated tablets or so-called "bulleye" tablets are produced. An overview of such embodiments of multi-phase tablets is in EP 055 100 (Jeyes Group). This document discloses blocks of toilet detergent, which composes a molded body from a slowly soluble detergent  tion in which a bleach tablet is embedded. This document reveals at the same time the most diverse designs of multiphase molded bodies from from simple multi-phase tablets to complicated multi-layer systems Insoles.

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

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

Preferred manufacturing processes for detergent tablets are based on a surfactant-containing one Granulate from that with other processing components to one to be pressed particulate premix is prepared. Completely analogous to the above stungen about preferred ingredients of the washing and cleaning agent according to the invention The use of further ingredients in their manufacture is also to be transferred to the molded article In preferred processes contains at least one particulate premix additionally granules (s) containing tenside and a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l.

In preferred processes according to the invention, the surfactant-containing granules have particles sizes between 100 and 2000 microns, preferably between 200 and 1800 microns, particularly preferably between 400 and 1600 μm and in particular between 600 and 1400 μm.

The other ingredients of the washing and cleaning agents according to the invention Shaped bodies can be introduced into the process according to the invention, for which purpose the  above is referred to. Preferred methods are thereby indicates that at least one particulate premix additionally one or more other substances from the group of bleaching agents, bleach activators, disintegration aids, Enzymes, pH adjusting agents, fragrances, perfume carriers, fluorescent agents, dyes, Foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying Contains inhibitors, color transfer inhibitors and corrosion inhibitors.

As already mentioned above, a preferred embodiment of the present invention provides that at least a part, preferably the total amount, of the oxidized derivatives of starch and / or dextrins contained in the moldings is introduced into the moldings according to the invention via a surfactant-containing granulate. Another Ge object of the present invention is therefore a process for the production of detergent tablets by the steps

• a) Production of a surfactant-containing granulate, the oxidized derivatives of starch and / or Contains dextrins,
• b) mixing the granules from step a) with further ingredients of washing or Detergents,
• c) pressing the premix formed in step b) into shaped bodies or shaped bodies areas

is marked.

Regarding the most important ingredients of the Ten produced in step a) Sidgranulate - surfactants and builders, which in the present case also include oxidized derivatives of starch and / or dextrins can count on the above Explanations are referred. Other optional ingredients of the surfactant granules, the can also be part of the premix are described below. It follows Information on the preparation of the surfactant granules in step a) of the invention Procedure.

When selecting the suitable machines and process parameters for the process Step a) can be carried out by the specialist on machines and apparatuses known from the literature as well as technical operations such as those described in W. Pietsch, "Size En  largement by agglomeration ", Verlag Wiley, 1991, and the literature cited there are written. The following explanations represent only a small part of the possibilities represent the specialist for the implementation of this step of the fiction procedure.

As already mentioned, the production of surfactant granules {according to step a) the method of the invention} in a variety of conventional mixing and granulating perform devices. For carrying out the method according to the invention step a) suitable mixers are, for example, Eirich® mixers of the R or RV series (Trademark of the machine factory Gustav Eirich, Hardheim), the Schugi® Flexomix, the Fukae® FS-G mixer (trademark of Fukae Powtech, Kogyo Co., Japan), the Lödige® FM, KM and CB mixers (trademark of Lödige Maschinenbau GmbH, Paderborn) or the Drais® series T or K-T (trademark of Drais-Werke GmbH, Mannheim). Some preferred embodiments of process step a) according to the invention are described below.

For example, it is possible and preferred that process step a) in a low step Mixer / granulator at peripheral speeds of the tools from 2 m / s to 7 m / s is carried out. Alternatively, in preferred process variants, the process Step a) in a high-speed mixer / granulator at peripheral speeds of 8 m / s up to 35 m / s.

Regardless of whether fast or slow-running mixers to perform the Ver step a) are used, the granulation in step a) is preferably carried out by Build-up granulation with granulating liquids. Here are methods according to the invention preferred, in which in step a) particulate solids with the addition of one or more granulating fluids.

The oxidized derivatives of starch and / or dextrins can both be a component the granulated bed to be granulated as well as ingredient of one or more granulating be liquids. Processes according to the invention in which the solid to be granulated Bed oxidized derivatives of starch and / or dextrins are therefore also preferred  such as procedures characterized in that at least one of the on the feast Granulated liquids fed into the bed of material oxidized derivatives of starch and / or Contains dextrins.

While the two process variants described above use each describe a mixer, it is also possible according to the invention to combine two mixers to combine. For example, processes are preferred in which in process step a) a liquid granulation aid in a first, low-speed Mi shear / granulator is placed on a moving solid bed, 40 to 100 wt .-%, based on the total amount of components used, the solid and liquid loading pre-granulated parts and the pre in a second, high-speed mixer / granulator Granules from the first stage of the process, optionally with the remaining solid and / or liquid constituents are mixed and converted into granules. With this procedure A granulation aid is used in the first mixer / granulator for a party Given bed of fabric and the mixture pre-granulated. The composition of the granules tion aid and the solid bed placed in the first mixer are so ge selects that 40 to 100 wt .-%, preferably 50 to 90 wt .-% and in particular 60 to 80 wt .-%, of the solid and liquid components, based on the total amount of one set components, are in the "pre-granules". This "pre-granulate" is now in the second mixer mixed with other solids and with the addition of further liquid components granulated to the finished surfactant granulate.

According to the invention, the sequence of low-speed, high-speed mixers mentioned can can also be reversed, so that a method according to the invention results in which the liquid granulation aids in a first, high-speed mixer / granulator Moving solid bed is given, 40 to 100 wt .-%, based on the total amount of the components used, the solid and liquid components pre-granulated and in a second, low-speed mixer / granulator, the pre-granulate from the first Process stage with the remaining solid and / or liquid components if necessary is mixed and transferred into granules.  

All of the above-described design variants of the Ver driving can be carried out batchwise or continuously. In the above Design variants of method step a) according to the invention described some high-speed mixers / granulators are used. It is within the scope the present invention particularly preferred that a Mi shear is used, both a mixing and a shredding device has, the mixing shaft at speeds of 50 to 150 revolutions gen / minute, preferably from 60 to 80 revolutions / minute and the shaft of the comminution tion device at speeds of 500 to 5000 revolutions gen / minute, preferably from 1000 to 3000 revolutions / minute, is operated.

Preferred granulation processes for the production of mixer granules are described in Mi shear granulators performed where some mixer parts or the entire mixer are heated to temperatures that are at least 20 ° C above the temperature that have the substances to be granulated at the beginning of the granulation process. So will Granulated solids that were stored at 20 ° C and with this temperature in the Mi shear, it is preferred that some or all mixer parts at least one Have a temperature of 40 ° C. Overall, however, a temperature of 120 ° C for the Mixer parts or the entire mixer must not be exceeded. Are only parts of the Heated to the temperatures mentioned, these are preferably the mixers walls or the mixer tools. The former can be heated by a jacket, the latter can be brought to the desired temperature by built-in heating elements.

It is further preferred in the production of granules containing surfactants in whole or in part heated mixers the use of non-aqueous granulation aids, esp special nonionic surfactants with a melting point in the range of 20 to 50 ° C exhibit. The bulk can be carried out by the described preferred granulation process Increase the weight of the surfactant granules, while at the same time undesirable caking on the wall on the mixer walls can be significantly reduced. The use of such herge provided surfactant granules in tablettable premixes leads to washing and cleaning moldings which differ from mixtures which are conventionally used provided granules contain, characterized by a further reduced disintegration time.  

In step b) of the process described last, the surfactant granules are mixed with others Ingredients of detergents or cleaning agents mixed, all of which continue ingredients described above can be used. In the last step it will Premix to shaped bodies or shaped body areas, for example layers more layered molded body, pressed.

The use of oxidized derivatives of starch and / or dextrins with the aim of physi To improve the properties of detergent tablets is until long not disclosed in the prior art. Another subject of the present Er The invention is therefore the use of oxidized derivatives of starch and / or Dex trine to improve the physical properties of washing or cleaning medium shaped bodies.

In addition to improving the abrasion resistance and increasing the edge break resistance who which in particular increases hardness and minimizes disintegration times. The use of oxidized derivatives of starch and / or dextrins to increase hardness and verrin Reducing the disintegration time of detergent tablets is therefore a long way off rer object of the present invention.

I can also achieve the mentioned advantageous properties with surfactant granules, which contain oxidized derivatives of starch and / or dextrins. Another aspect The present invention is therefore the use of surfactant granules which oxi dated derivatives of starch and / or dextrins contain, to improve the physi the properties of detergent tablets, in particular for Increase hardness and decrease disintegration time.  

Examples

A tower powder containing surfactants was produced by spray drying and used as the basis for Granules containing surfactant was used. The tower powder was made with another compo nents (zeolite, NaOH, anionic surfactant acid, nonionic surfactant) in a 130 liter Ploughshare mixer granulated by Lödige. For granulation of the invention Surfactant granules E a 40% solution of oxidized starch in water was used, in the case of the granulation of the comparison granulate V, only the Zu was carried out in the same place giving water. The amounts of solids and liquids used as well as the The order of addition to the mixer is given in Table 2.

Following the granulation, the granules were in a fluidized bed apparatus The company Glatt at a supply air temperature of 60 ° C over a period of 30 minutes dries. After drying, fine particles <0.6 mm and coarse particles <1.6 mm sieved.

The surfactant granules E and V were then pressed together with other components prepared premix, after which the pressing in a Korsch eccentric press Tablets (diameter: 44 mm, height: 22 mm, weight: 37.5 g) took place. It was the pressure was adjusted so that three series of moldings were obtained (E1, E2, E3 or V1, V2, V3), which differed in their hardness. The assembly The spray-dried tower powder shows Table 1 the composition of the Compressing premixes (and thus the shaped body) are shown in Table 3.

Table 1

Composition of the spray-dried tower powder [% by weight]

Table 2

Granulation approach

Table 3

Composition of the premixes [% by weight]

The hardness of the tablets became after two days of storage by deforming the tablet measured to break, the force acting on the side surfaces of the tablet and the maximum force that the tablet withstood was determined.

To determine tablet disintegration, the tablet was placed in a beaker with water placed (600 ml of water, temperature 30 ° C) and the time until the tablet is completely case measured. The experimental data are shown in Table 4:

Table 4

Detergent tablets [physical data]

By using oxidized starch according to the invention, the disintegration time of the Detergent tablets reduced, which is particularly evident in the case of higher tablet hardness has a positive effect.

Claims (23)

1. Detergent tablets made of compressed, particulate detergents or cleaning agents, characterized in that they contain oxidized derivatives of starches and / or dextrins in amounts of 0.1 to 10% by weight, based on the weight of the molded article. 2. shaped detergent or cleaning product according to claim 1, characterized in that they oxidized derivatives of starch and / or dextrins with average molecular weights in Range from 440 to 500,000 in amounts from 0.25 to 7.5% by weight, preferably from 0.5 to 5% by weight, particularly preferably from 0.75 to 3.5% by weight and in particular from 1 to 2 wt .-%, based on the weight of the molded body. 3. shaped detergent or cleaning product according to one of claims 1 or 2, characterized characterized in that the oxidized derivatives of starch and / or contained therein Dextrins dextrose equivalents (DE) from 0.1 to 50, preferably from 0.5 to 40 and in particular from 2 to 30. 4. Detergent tablets according to one of claims 1 to 3, characterized in that the oxidized derivatives of starch and / or dextrins contained in them at C _{6 of} the saccharide ring are oxidized products. 5. shaped detergent or cleaning product according to one of claims 1 to 4, characterized characterized in that they are the oxidized derivatives of starch and / or dextrins in the form of compounds containing an average particle size below 500 microns preferably have below 450 microns and in particular below 400 microns. 6. Detergent tablets according to claim 5, characterized in that the compounds contain the oxidized derivatives of starch and / or dextrins in quantities of more than 10% by weight, preferably of more than 20% by weight and in particular of contain more than 30% by weight, in each case based on the weight of the compound.   7. Detergent tablets 1 to 4, characterized in that they have the oxidized derivatives of starch and / or dextrins in the form of a surfactant granulate keep that the total amount of the oxidized derivatives contained in the moldings of starch and / or dextrins. 8. shaped detergent or cleaning product according to claim 7, characterized in that the content of the surfactant granules of oxidized derivatives of starch and / or Dex 0.5 to 20% by weight, preferably 0.75 to 15% by weight, particularly preferably 1 up to 10 wt .-% and in particular 1.5 to 5 wt .-%, each based on the weight of the surfactant granules. 9. Detergent tablets made from compressed, particulate detergent or cleaning agents, characterized in that they contain a surfactant granulate ten, which contains oxidized derivatives of starch and / or dextrins. 10. shaped detergent or cleaning product according to one of claims 1 to 9, characterized characterized in that they additionally contain a disintegration aid, preferably a Disintegration aid based on cellulose, preferably in granular, cogranulated ter or compact form, in amounts of 0.5 to 10 wt .-%, preferably of 3 up to 7 wt .-% and in particular from 4 to 6 wt .-%, each based on the shape body weight, included. 11. shaped detergent or cleaning product according to one of claims 1 to 10, characterized characterized in that they are surfactant (s), preferably anionic (s) and / or non-ionic chemical surfactant (s), in amounts from 5 to 40% by weight, preferably from 7.5 to 35% by weight, particularly preferably from 10 to 30% by weight and in particular from 12.5 to 25% by weight, each based on the weight of the molded article. 12. Process for the production of detergent tablets by form giving a particulate premix, characterized in that that the premixed oxidized derivatives of starch and / or dextrins in amounts of 0.1 to 10 wt .-%, based on the premix.   13. Process for the production of multiphase detergent tablets by pressing several particulate premixes known per se, thereby characterized in that at least one of the premixes oxidized derivatives of starch and / or dextrins in amounts of 0.1 to 10% by weight, based on the premix, contains. 14. The method according to any one of claims 12 or 13, characterized in that mind at least one particulate premix additionally contains granulate (s) containing surfactant and a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular has at least 700 g / l. 15. The method according to claim 14, characterized in that the surfactant-containing granules Particle sizes between 100 and 2000 μm, preferably between 200 and 1800 μm, particularly preferably between 400 and 1600 μm and in particular between 600 and 1400 µm. 16. The method according to any one of claims 12 to 15, characterized in that mind least a particulate premix additionally one or more substances from the Group of bleaching agents, bleach activators, disintegration aids, enzymes, pH Setting agents, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors ren, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, Contains color transfer inhibitors and corrosion inhibitors. 17. Process for the production of detergent tablets, characterized by the steps

• a) preparation of a surfactant-containing granulate which contains oxidized derivatives of starch and / or dextrins,
• b) mixing the granules from step a) with further ingredients of washing or cleaning agents,
• c) pressing the premix formed in step b) into shaped bodies or shaped body regions.

18. The method according to claim 17, characterized in that in step a) particulate solids with the addition of one or more granulating liquids the. 19. The method according to claim 18, characterized in that the solid to be granulated Contains bed oxidized derivatives of starch and / or dextrins. 20. The method according to claim 18, characterized in that at least one of the on Granulated liquids added to the solid bed oxidized derivatives of starch and / or dextrins. 21. Use of oxidized derivatives of starch and / or dextrins for improvement tion of the physical properties of detergent tablets. 22. Use of oxidized derivatives of starch and / or of the dextrins for increasing the hardness and reduction of the disintegration time of detergent and cleaning agent form bodies. 23. Use of surfactant granules, which oxidized derivatives of starch and / or Contain dextrins to improve the physical properties of laundry or detergent tablets, in particular to increase hardness and reduction reduction in decay time.