WO2001014512A1 - Washing or cleaning agent shaped bodies - 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

 , ash or detergent tablets "

The present invention relates to moldings which have washing and cleaning properties and methods for their production. In particular, the invention relates to 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 and are becoming increasingly popular with consumers because of the simple dosage. Tableted detergents and cleaning agents have a number of advantages over powdered detergents: They are easier to dose and handle and, thanks to their compact structure, have advantages in terms of storage and transport. Detergent and cleaning agent bodies are consequently also comprehensively described in the patent literature. A problem that occurs again and again when using shaped articles which are active in washing and cleaning is the insufficient rate of disintegration and dissolution of the shaped articles under conditions of use. Since sufficiently stable, that is to say shape and break-resistant molded articles can only be produced by relatively high compression pressures, there is a strong compression of the molded article components and consequent delayed disintegration of the molded article in the aqueous liquor and thus to a slow release of the active substances in the Washing or cleaning process. The delayed disintegration of the moldings has the further disadvantage that conventional detergent and cleaning agent bodies cannot be washed in via the washing-in chamber of household washing machines, since the tablets do not disintegrate into secondary particles in a sufficiently rapid time, which are small enough to be washed into the washing drum from the washing-in chamber to become. A variety of approaches exist in the prior art to solve this problem. In addition to the use of special ingredients that are intended to promote disintegration, the coating of individual ingredients and the screening of the premixes to be pressed are also proposed.

For example, EP-A-0 466 484 (Unilever) discloses detergent tablets in which the premix to be compressed has particle sizes between 200 and 1200 μm, the upper and lower limits of the particle sizes not differing by more than 700 μm. The pressing of significantly coarser particles into tablets is not suggested in this document.

EP-A-0 522 766 (Unilever) also relates to moldings made from a compact, particulate detergent composition containing surfactants, builders and disintegration aids (for example based on cellulose), at least some of the particles being coated with the disintegration agent, which is both binder - As well as disintegration effect when dissolving the moldings in water. This document also indicates the general difficulty of producing moldings with adequate stability and good solubility at the same time. The particle size in the mixture to be pressed should be above 200 μm, the upper and lower limits of the individual particle sizes should not differ from one another by more than 700 μm. This document also explicitly states that the particles should not be coarser than 1200 μm.

In the proposed solutions to achieve better disintegration times, preference should be given to those that largely dispense with the additional use of substances that are not ingredients of detergents or cleaning agents. In order to develop recipes that are as compact as possible without "ballast", there is still a need for proposed solutions based on the selection and / or packaging of substances which also have advantageous effects in the washing or cleaning cycle.

The present invention was therefore based on the object of providing detergent tablets which are distinguished by high hardness and have excellent disintegration properties. These detergents and cleaning agents Shaped bodies should also be able to be metered through the induction chamber without the consumer suffering disadvantages due to residues in the induction chamber and too little detergent in the wash liquor. In addition to these molded body-specific properties, the washing and cleaning performance of the molded body according to the invention should also be exemplary. The advantageous properties of the molded article should not be achieved by additives which only serve to improve the molded article properties, but by the targeted use of substances which also have an effect in the washing and cleaning process.

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

The invention relates to detergent tablets made of compressed, particulate laundry detergent or cleaning agent which contain oxidized derivatives of starch and / or dextrins in amounts of 0.1 to 10% by weight, based on the weight of the tablet.

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

The starch is a homoglycan, more precisely a glucan. In contrast to cellulose, the glucose units in the polysaccharide starch are linked α-glycosidically. In addition, starch is made up of two components of different molecular weights: approx. 20-30% by weight of straight-chain amylose (molecular weight, approx. 50000-150000) and 70-80% by weight of branched-chain amylopectin (molecular weight approx. 300000- 2000000), it also contains small amounts of lipids, phosphoric acid and cations. While the amylose forms long, helical, intertwined chains with about 300-1200 glucose molecules as a result of the binding in the 1,4-position, the chain in the amylopectin branches after an average of 25 glucose units through 1,6-binding to form a knot-like structure with about 1500-12000 molecules of glucose. Starches can be converted into carbonyl- and carboxy group-containing derivatives, the so-called oxidized starches, by treatment with different oxidizing agents with partial degradation. The technically most important oxidizing agent is sodium hypochlorite, which acts on starch suspended in water in an alkaline environment. The resulting low-viscosity dispersions can be dried, resulting in free-flowing powder products.

Dextrins are degradation products of starch with the general formula (C ₆ Hι ₀ θ ₅ ) _n xH ₂ O, which are formed in the case of incomplete hydrolysis with dilute acids (acid dextrins) or by the action of heat (roasted dextrins) and consist of glucose chains. Enzymatic degradation with amylases produces the so-called border dextrins, in which the 1,6-glycosidic bonds of amylopectin that are not accessible to the attack of the β-amylase are enriched, while cyclodextrins are formed when Bacillus macerans acts on the starch solution.

Dextrins form colorless or yellow, amorphous powders, which are very easily soluble in water, almost insoluble in alcohol. In the USA, dextrins are made from corn, in the Federal Republic mainly from potatoes. The corn dextrins are odorless, the dextrin obtained from potato starch smells like cucumber. The high molecular weight dextrins (like starch) give a blue color with iodine solution, the next degradation level turns red or brown with iodine, and the low molecular weight dextrins no longer give iodine color. Depending on the production process, the molar masses of the dextrins are between 2000 and 500000. They are preferably hydrolysis products with average molar masses in the range from 400 to 300000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used.

The oxidized derivatives of dextrins are their reaction products with oxidizing agents which are able to oxidize 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 427349, EP 472 042 and EP 542 496 and 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, 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 .ι-arabinonic acid.

In these, the average degree of oligomerization n, which can also take fractional numerical values as the quantity to be determined analytically, is preferably in the range from 2 to 20, in particular 2 to 10. This latter oxidative modification can be carried out, for example, with the aid of Fe, Cu or Ag. , Co or Ni catalysts, as described in international patent application WO 92/18542, using Pd, Pt, Rh or Os catalysts, as described in European patent EP 0232 202, or using a quinone / Hydroquinone system in alkaline with the addition of oxygen and optionally aftertreatment with hydrogen peroxide.

Detergent tablets according to the invention, the oxidized derivatives of starch and or dextrins with average molecular weights in the range from 440 to 500,000 in amounts of 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% by weight, based on the weight of the molded article, are also preferred, such as detergent or cleaning article tablets in which the oxidized substances contained therein are present Derivatives of starch and / or 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 in them are products oxidized at C _{6 of} the saccharide ring.

The incorporation of the oxidized derivatives of starch and / or dextrins into the laundry detergent or cleaning product tablets according to the invention can take place directly in the delivery form or after prior packaging. For example, the oxidized derivatives of starch and / or dextrins can be added to the premix to be treated, for example as a particulate solid, or sprayed onto the premix as an aqueous solution. It is also possible to incorporate the oxidized derivatives of starch and / or dextrins into individual constituents of the particulate premix, for example in compounds such as builder compounds or in surfactant granules.

A preferred way of incorporation is to mix the oxidized starch and / or dextrin derivatives into the premix to be treated in finely divided form. Preferred shaped detergents or cleaning agents are therefore characterized in that they contain the oxidized derivatives of starch and / or dextrins in the form of compounds which have an average particle size below 500 μm, preferably below 450 μm and in particular below 400 μm.

These compounds can be obtained, for example, by spray drying commercially available solutions of oxidized derivatives of starch and / or dextrins, or by spraying such solutions onto carrier materials such as sodium carbonate, sodium sulfate or silicates or zeolites. Of course, the commercially available particulate oxidized derivatives of starch and or dextrins can also be used, the compounds mentioned then consisting entirely of oxidized derivatives of starch and / or dextrins. The advantage results from the particle size range mentioned. When adding the oxidized derivatives of starch and / or dextrins in the form of finely divided compounds, it is preferred that the compounds contain as much active substance as possible. have punch. Accordingly, preferred shaped detergents or cleaning agents are characterized in that the compounds contain 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 more than 30% by weight. -%, each based on the weight of the compound.

An incorporation alternative for the oxidized derivatives of starch and / or dextrins is to inkoφorieren these into individual components of the premix before the premix is mixed. Surfactant granules are particularly suitable for this purpose, in the production of which aqueous solutions of oxidized derivatives of starch and / or dextrins can be used as granulation aids. It is of course possible to combine several incorporation routes for the oxidized derivatives of starch and / or dextrins and to use both a surfactant granulate that contains them and to add the oxidized derivatives of starch and / or dextrins to the premix, for example in finely divided form. However, if a surfactant granulate is used which contains the oxidized derivatives of starch and / or dextrins, it is preferred that it contains the total amount of all oxidized derivatives of starch and / or dextrins contained in the molded articles. Thus, detergent tablets which contain the oxidized derivatives of starch and / or dextrins in the form of a surfactant granulate which contains the total amount of the oxidized derivatives of starch and / or dextrins contained in the tablets are preferred embodiments of the present invention.

Surfactant granules, their ingredients and processes for their preparation are described below. Regarding the content of oxidized derivatives of starch and / or dextrins, detergent tablets are preferred in which the content of the surfactant granules of oxidized derivatives of starch and / or dextrins is 0.5 to 20% by weight, preferably 0.75 to 15 % By weight, particularly preferably 1 to 10% by weight and in particular 1.5 to 5% by weight, in each case based on the weight of the surfactant granules.

More generally, detergent tablets made of compressed, particulate detergent or cleaning agent are also preferred, which are characterized in that that they contain a surfactant granulate which contains oxidized derivatives of starch and / or dextrins.

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

Suitable crystalline layered sodium silicates have the general formula NaMSiχO _2x + ι ^'H ₂ O wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, preferred values for x being 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ 'yH ₂ O are preferred, with β-sodium disilicate being able to be obtained, for example, by the method described in international patent application WO-A-91/08171.

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

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

nNa ₂ O ^• (ln) K ₂ O 'Al ₂ O ₃ ^" (2 - 2.5) SiO ₂ ^■ (3.5 - 5.5) H ₂ O

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

It is of course also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. Among the large number of commercially available phosphates, the alkali metal phosphates have particular preference for pentasodium or pentapotassium tri- phosphate (sodium or potassium tripolyphosphate) is of the greatest importance in the detergent and cleaning agent industry.

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

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 like ^"3 , melting point 60 °) and as a monohydrate (density 2.04 like ^{" 3} ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O) at 200 ° C, and 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 sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt with a density of 2.33 ^"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 gladly ^{* 3} , water loss at 95 °), 7 mol. (Density 1.68 gladly ^"3 , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 ^"3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to diphosphate Na ₄ P ₂ O ₇ when heated more strongly. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water. Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm ^'3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ) have a melting point of 100 ° C. and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) a density of 2.536 ^"3. Trisodium phosphate is readily soluble in water with an alkaline reaction and is evaporated from a solution of exactly 1 mol Disodium phosphate and 1 mole 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 ^"3 , has a melting point of 1340 ° and is in water with an alkaline reaction easily soluble. It arises, for example, when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

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

exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^" , which is soluble in water, the pH of the 1% solution at 25 ° being 10.4.

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates. The technically important pentasodium triphosphate, Na ₅ P ₃ Oιo (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O - Well with n = 3. About 17 g of the crystal water-free salt dissolve in 100 g of water at room temperature, about 20 g at 60 ° and around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ Oιo (potassium tripolyphosphate), for example in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) on the market. 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 KP ₃ O _{] 0} + H ₂ O

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

Organic cobuilders which can be used in the moldings are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.

Usable organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, with such carboxylic acids being among polycarboxylic acids can be understood that carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

The acids themselves can also be used. In addition to their builder effect, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

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

In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship 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 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group. Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content 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 contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.

Also particularly preferred are biodegradable polymers composed of more than two different monomer units, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers ,

Further preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A-195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect. Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

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

Further usable organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such cobuilders are described, for example, in international patent application WO 95/20029.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, l-hydroxyethane-l, l-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9). Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. 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. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned. In addition, all compounds that are able to form complexes with alkaline earth metal ions can be used as cobuilders.

The amount of builder is usually between 10 and 70% by weight, preferably between 15 and 60% by weight and in particular between 20 and 50% by weight. The amount of builders used depends on the intended use, so that bleach tablets and molded articles for machine dishwashing can have higher amounts of builders (for example between 20 and 70% by weight, preferably between 25 and 65% by weight and in particular between 30 and 55% by weight), for example detergent tablets (usually 10 to 50% by weight, preferably 12.5 to 45% by weight and in particular between 17.5 and 37.5% by weight).

Preferred detergent tablets according to the invention furthermore contain one or more surfactant (s). Anionic, nonionic, cationic and or amphoteric surfactants or mixtures of these can be used in the moldings. Mixtures of anionic and nonionic surfactants are preferred from an application point of view. The total surfactant content of the molded article is from 5 to 60% by weight, based on the weight of the molded article, with surfactant contents above 15% by weight being preferred.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Suitable surfactants of the sulfonate type are preferably C ₉ -ι ₃ - alkylbenzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from _2- Cι ι ₈ monoolefins with an internal or terminal double bond by Sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfomerization products is considered. Also suitable are alkanesulfonates which are obtained from C _2-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable. Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become. Preferred sulfated fatty acid glycerol esters are the sulfate products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C ₂ -C ₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₀ -C ₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₆ alkyl sulfates and Cj ₂ - cis alkyl sulfates and C ₄ -C [alkyl sulfates are preferred from a washing-technical point of view. In addition, 2,3-alkyl sulfates, which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-2 ι alcohols ethoxylated with 1 to 6 mol ethylene oxide, such as 2-methyl-branched C ₉ n alcohols with an average of 3.5 mol ethylene oxide (EO) or C ₁₂ . ₁₈ fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ι _{8- 8} 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 whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

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

The anionic surfactants, including the soaps, can be in the form of their sodium, potassium or ammonium salts and also 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, in particular in the form of the sodium salts.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical has a linear or preferably 2-methyl branching may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. ₁₄ - - The preferred ethoxylated alcohols include, for example, ₁₂ C, alcohols containing 3 EO or 4 EO, C ₉ .n alcohol containing 7 EO, C13-15- alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C _{12 -} ι ₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-14 alcohol with 3 EO and C12-18 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 ranks ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are 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 preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

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

R ^]

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

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

R ^! -OR ²

R-CO-N- [Z] (II)

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R represents a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C - 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 thereof 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, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst. For the purposes of the present invention, detergent tablets are preferred which contain anionic (s) and nonionic (s) surfactant (s), with application technology advantages being able to result from certain quantitative ratios in which the individual classes of surfactants are used.

For example, shaped bodies are particularly preferred in which the ratio of anionic surfactant (s) to nonionic surfactant (s) is between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2 is. Also preferred are detergent tablets which contain anionic and / or nonionic surfactant (s) and total surfactant contents above 2.5% by weight, preferably above 5% by weight and in particular above of 10% by weight, based in each case on the molded body weight. Particularly preferred are detergent tablets, the surfactant (s), preferably anionic (s) and / or nonionic (s) surfactant (s), in amounts of 5 to 40% by weight, preferably 7.5 to 35% by weight .-%, particularly preferably from 10 to 30 wt .-% and in particular from 12.5 to 25 wt .-%, each based on the molded body weight.

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

Conversely, the content of individual phases or the entire molded body, i.e. all phases, a positive effect can be achieved on certain surfactants. The introduction of the alkyl polyglycosides described above has proven to be advantageous, so that moldings are preferred in which at least one phase of the moldings contains alkyl polyglycosides.

Similar to the non-ionic surfactants, the omission of anionic surfactants from individual or all phases can result in moldings which are more suitable for certain fields of application. It is therefore within the scope of the present The invention also conceives of detergent molded articles in which at least one phase of the molded article is free from anionic surfactants.

As already mentioned, the use of surfactants in detergent tablets 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 of 2 wt .-%, based in each case on the weight of the molded 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 can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. ₁₄ - - The preferred ethoxylated alcohols include, for example, ₁₂ C, alcohols containing 3 EO or 4 EO, C _9- π-alcohol with 7 EO, Cι _3- i ₅ alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C _{] 2-} ι ₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12- ι ₄ alcohol with 3 EO and C _12- ι ₈ - 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 can also be used more than 12 EO can be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In particular in the case of detergent tablets or detergent tablets for machine dishwashing, it is preferred that the detergent tablets contain a nonionic surfactant which has a melting point above room temperature. Accordingly, the detergent tablets according to the invention preferably contain a nonionic surfactant with a melting point above 20 ° C. Nonionic surfactants to be used preferably have melting points above 25 ° C., particularly preferred nonionic surfactants have melting points between 25 and 60 ° C., in particular between 26.6 and 43.3 ° C.

Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming mechanical surfactants which can be solid or highly viscous at room temperature. If nonionic surfactants which are highly viscous at room temperature are used, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.

Preferred nonionic surfactants to be used at room temperature originate from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols, and mixtures of these surfactants with structurally more complicated surfactants such as polyoxypropylene / 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, the nonionic surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has resulted.

A particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C _6-20 - alcohol), preferably a C ₁₈ - alcohol and at least 12 moles, preferably at least 15 mol and recovered in particular at least 20 moles of ethylene oxide , Among these, the so-called "narrow ranks ethoxylates" (see above) are particularly preferred.

The nonionic surfactant, which is solid at room temperature, preferably has additional propylene oxide units in the molecule. Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol portion of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.

Further nonionic surfactants with melting points above room temperature which are to be used with particular preference contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which comprises 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol of propylene oxide and 25 % By weight of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ^® SLF-18 from Olin Chemicals. Another preferred surfactant can be represented by the formula

R ^, 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 having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x denotes values between 0.5 and 1, 5 and y represents 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, ahphatic 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, ahphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH 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, if x is 3, the radical R ³ 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 is has been chosen as an example here and can certainly be larger, the range of variation increasing with increasing x values and for example including 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'θ [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

1 ") preferred are surfactants in which the radicals R and R have 9 to 14 carbon atoms, R ^{3 is} H and x assumes values from 6 to 15.

In order to facilitate the disintegration of highly compressed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, in order to shorten the disintegration times. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, p. 182-184), tablet disintegrants or accelerators of decay are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in absorbable form.

These substances, which are also referred to as "explosives" due to their effect, increase their volume when water enters, whereby on the one hand the intrinsic volume increases (swelling) and on the other hand a pressure can be generated by the release of gases, which breaks the tablet into smaller particles disintegrates. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modern 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 disintegration auxiliaries, in each case based on the molded article weight.

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred molded bodies 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 .-% contain. Pure cellulose has the formal gross composition (C ₆ Hιoθ ₅ ) _n and is formally considered a ß-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The cellulose derivative content of these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free from cellulose derivatives is particularly preferably used as the disintegrant based on cellulose.

The cellulose used as disintegration aid is preferably not used in finely divided form, but rather before being added to the premixes to be treated converted into a coarser form, for example granulated or compacted. Detergent tablets, which contain disintegrants in granular or optionally granulated form, are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO98 / 40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 μm and in particular at least 90% by weight between 400 and 1200 μm. The above and described in more detail in the documents cited coarser disintegration aids, are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ^® TF-30-HG from Rettenmaier available in the present invention.

Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged. A subsequent disaggregation of the microfine celluloses resulting from the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 μm and can be compacted, for example, to granules with an average particle size of 200 μm.

Detergent tablets preferred in the context of the present invention additionally contain a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight. % and in particular from 4 to 6% by weight, in each case based on the molded body weight, preferred disintegration aids having average particle sizes above 300 μm, preferably above 400 μm and in particular above 500 μm. The detergent tablets according to the invention can also contain a gas-developing shower system. The gas-developing shower system can consist of a single substance that releases a gas when it comes into contact with water. Among these compounds, magnesium peroxide should be mentioned in particular, which releases oxygen on contact with water. Usually, however, the gas-releasing bubble system itself consists of at least two components that react with one another to form gas. While a large number of systems are conceivable and executable here, which release nitrogen, oxygen or hydrogen, for example, the bubbling system used in the detergent tablets according to the invention can be selected on the basis of both economic and ecological considerations. Preferred effervescent systems consist of alkali metal carbonate and / or hydrogen carbonate and an acidifying agent which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.

In the case of the alkali metal carbonates or bicarbonates, the sodium and potassium salts are clearly preferred over the other salts for reasons of cost. Of course, the pure alkali metal carbonates or bicarbonates in question do not have to be used; rather, mixtures of different carbonates and bicarbonates may be preferred for reasons of washing technology.

In preferred detergent tablets, the shower system is 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 3 to 10% by weight of an acidifying agent, based in each case on the entire molded body.

Acidifying agents which release carbon dioxide from the alkali salts in aqueous solution are, for example, boric acid and alkali metal bisulfates, alkali metal dihydrogen phosphates and other inorganic salts. However, organic acidifying agents are preferably used, citric acid being a particularly preferred acidifying agent. However, the other solid mono-, oligo- and polycarboxylic acids can also be used in particular. From this group are preferred wine acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight).

In addition to the constituents mentioned, builders, surfactants and disintegration aids, the detergent tablets according to the invention can contain further ingredients customary in detergents and cleaning agents from the group of bleaching agents, bleach activators, dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, antiredeposition agents, graying inhibitors, Color transfer inhibitors and corrosion inhibitors included.

To develop the desired bleaching performance, the detergent tablets of the present invention can contain bleaches. The usual bleaching agents from the group of sodium perborate monohydrate, sodium perborate tetrahydrate and sodium percarbonate have proven particularly useful here.

“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 H ₂ O ₂ and is therefore not peroxy carbonate. Sodium percarbonate often forms a white, water-soluble powder with a density of 2.14 ^"3 , which easily disintegrates into sodium carbonate and bleaching or oxidizing oxygen.

Sodium carbonate peroxohydrate was first obtained in 1899 by ethanol precipitation from a solution of sodium carbonate in hydrogen peroxide, but was mistakenly regarded as peroxy carbonate. It was not until 1909 that the compound was recognized as a hydrogen peroxide addition compound, but the historical name "sodium percarbonate" has become established in practice. The industrial production of sodium percarbonate is mainly produced by precipitation from an aqueous solution (so-called wet process). Here, aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium percarbonate is precipitated by salting-out agents (predominantly sodium chloride), crystallization aids (for example polyphosphates, polyacrylates) and stabilizers (for example Mg ions). The precipitated salt, which still contains 5 to 12% by weight of mother liquor, is then filtered off and dried in fluidized bed dryers at 90.degree. The bulk density of the finished product can vary between 800 and 1200 g / 1 depending on the manufacturing process. As a rule, the percarbonate is stabilized by an additional coating. Coating processes and materials used for coating are widely described in the patent literature. In principle, according to the invention, all commercially available percarbonate types can be used, such as those offered by the companies Solvay Interox, Degussa, Kemira or Akzo.

In the bleaching agents used, the content of these substances in the shaped bodies depends on the intended use of the shaped bodies. While conventional universal detergents in tablet form contain between 5 and 30% by weight, preferably between 7.5 and 25% by weight and in particular between 12.5 and 22.5% by weight of bleaching agent, the contents of bleaching agent or bleach booster tablets are between 15 and 50% by weight, 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 detergent tablets according to the invention can contain bleach activator (s), which is preferred in the context of the present invention. Bleach activators are incorporated into detergents and cleaning agents in order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give ahphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and or optionally substituted benzoyl groups are suitable. Multi-acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4- dioxohexahydro-l, 3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanulfonoyloxybenzonoyloxybenzonoyloxybenzonoyloxybenzonoyloxybenzonoyloxybenzoyloxybenzonoyloxybenzoyloxybenzoyloxybenzoyloxybenzoyloxybenzoyloxybenzoyloxybenzoyloxybenzoyloxybenzoyloxybenzoyloxybenzoyloxybenzonoyloxybenzoyloxybenzoyloxybenzoyloxybenzoyloxybenzoyloxybenzoyloxybenzoyloxybenzoyloxybenzoyloxy iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be incorporated into the moldings. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.

If the molded articles according to the invention contain bleach activators, they each contain, based on the total molded article, between 0.5 and 30% by weight, preferably between 1 and 20% by weight and in particular between 2 and 15% by weight, of one or more Bleach activators or bleach catalysts. These quantities can vary depending on the intended use of the molded articles produced. For example, bleach activator contents of between 0.5 and 10% by weight, preferably between 2 and 8% by weight and in particular between 4 and 6% by weight, are common in typical universal detergent tablets, while bleach tablets contain quite high contents, for example between 5 and 30% by weight, preferably between 7.5 and 25% by weight and in particular between 10 and 20% by weight. The person skilled in the art is not restricted in its freedom of formulation and can thus produce more or less bleaching detergent tablets, detergent tablets or bleach tablets by varying the bleach activator and bleach content.

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

In addition to the constituents mentioned, bleaching agent, bleach activator, builder, surfactant and disintegration aid, the detergent tablets according to the invention can contain further ingredients from the group of dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, antiredeposition agents, graying inhibitors, which are customary in detergents and cleaning agents. Color transfer inhibitors and corrosion inhibitors included.

In order to improve the aesthetic impression of the detergent tablets according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity towards textile fibers in order not to dye them.

Preferred for use in the detergent tablets according to the invention are all colorants which can be oxidatively destroyed in the washing process, and also mixtures thereof with suitable blue dyes, so-called blue toners. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. For example, anionic colorants, for example anionic nitroso dyes, are suitable. One possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020). Which as a commercial product ^® for example as Basacid Green 970 from BASF, Ludwigshafen, and mixtures thereof with suitable blue dyes. Other colorants include 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 ^® Patentblau 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. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the washing or cleaning agents varies. For highly soluble dyes, for example, the above-mentioned Basacid ^® Green or the above-mentioned Sandolan Blue ^®, are typically selected dye concentrations in the range of some 10 ^"2 to ^{10" 3} wt .-%. In the due to their brilliance, particularly preferred, but are less readily water-soluble pigment dyes, for example the above-mentioned Pigmosol ^® ATTO-dyes, the appropriate concentration of the colorant is in washing or cleaning agents, however, typically a few 10 ^"3 to ^{10" 4} wt .-% ,

The moldings can contain optical brighteners of the type of derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-moφholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which, instead of the Moφholino group, contain a diethanolamino - carry a group, a methylamino group, an anilino group or a 2-methoxyethylamino group. In addition, brighteners of the substituted diphenylstyryl type may be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2- sulfostyryl). Mixtures of the aforementioned brighteners can also be used. The optical brighteners are in the detergent tablets according to the invention in concentrations between 0.01 and 1% by weight, preferably between 0.05 and 0.5% by weight and in particular between 0.1 and 0.25% by weight. %, each based on the entire molded body, used.

Fragrances are added to the agents according to the invention in order to improve the aesthetic impression of the products and to the consumer in addition to the performance of the product to provide a visually and sensorially "typical and distinctive" product. Individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert.-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethylmethylphenylglycineate, allyl cycloproxylhexylateyl pylylateyl pylylateyl pylylateyl pylylateyl pylylateyl pylylatepylate. The ethers include, for example, benzylethyl ether, the aldehydes include, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, and the ketones include, for example, the jonones, cc-isomethylionone and methyl cedryl ketone , the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and teφineol, the hydrocarbons mainly include the teφenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures, such as those obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrance content of the detergent tablets according to the invention is usually up to 2% by weight of the total formulation. The fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.

Enzymes include in particular those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned in question. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxidoreductases can also be used to bleach or inhibit color transfer. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

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

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

Another object of the present invention is a process for the production of detergent tablets by molding a particulate premix, in which the premix is based on oxidized derivatives of starch and or dextrins in amounts of 0.1 to 10% by weight on the premix.

With regard to preferred oxidized derivatives of starch and / or dextrins, reference can also be made here to the preceding explanations, as well as with regard to further ingredients of the premix to be treated or incorporation options for the oxidized derivatives of starch and / or dextrins.

The molded articles according to the invention are first produced by dry mixing the constituents, which can be wholly or partially pregranulated, and then providing information, in particular feeding them into tablets, whereby conventional methods can be used. To produce the molded body, the premix is compressed in a so-called die between two punches to form a solid concentrate. This process, which is briefly referred to as tableting in the following, 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 the shape of the molded body being formed being determined by the position of the lower punch and the shape of the pressing tool. The constant dosing, even at high mold throughputs, is preferably achieved by volumetric dosing of the premix. As the tableting continues, the upper punch touches the premix and lowers further in the direction of the lower punch. During this compression, the particles of the premix are pressed closer together, the void volume within the filling between the punches continuously decreasing. From a certain position of the upper punch (and thus from a certain pressure on the premix), the plastic deformation begins, in which the particles flow together and the molded body is formed. Depending on the physical properties of the premix, some of the premix particles are also crushed and sintering of the premix occurs at even higher pressures. With increasing pressing speed, that is to say high throughput quantities, the phase of elastic deformation is shortened further and further, so that the resulting shaped bodies can have more or less large cavities. In the last step of tableting, the finished molded body is pressed out of the die by the lower punch and transported away by subsequent transport devices. At this point in time, only the weight of the molded body is finally determined, since the compacts can still change their shape and size due to physical processes (stretching, crystallographic effects, cooling, etc.).

Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches. In the latter case, not only is the upper stamp used to build up pressure, the lower stamp also moves towards the upper stamp during the pressing process, while the upper stamp presses down. For small production quantities, eccentric tablet presses are preferably used, in which the punch or stamps are fastened to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed. The movement of these rams is comparable to that of a conventional four-stroke engine. The pressing can take place with one upper and one lower punch, but several punches can also be attached to one eccentric disc, the number of die bores 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 a larger number of dies is arranged in a circle on a so-called die table. The number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available. Each die on the die table is assigned an upper and lower punch, and again the pressure can be built up actively only by the upper or lower punch, but also by both stamps. The die table and the stamps move about a common vertical axis, the stamps being brought into the positions for filling, compaction, plastic deformation and ejection by means of rail-like cam tracks during the rotation. Wherever a particularly serious lifting or lowering of the punches is required (filling, compacting, ejecting), these cam tracks are supported by additional low-pressure pieces, low-tension rails and lifting tracks. The die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix. The pressing pressure on the premix can be individually adjusted via the pressing paths for the upper and lower punches, the pressure being built up by rolling the punch shaft heads past adjustable pressure rollers.

Rotary presses can also be provided with two filling shoes to increase the throughput, with only a semicircle having to be run through to produce a tablet. For the production of two-layer and multi-layer molded bodies, several filling shoes are arranged one behind the other without the slightly pressed first layer being ejected before further filling. With suitable process control, jacket and dot tablets can also be produced in this way, which have an onion-shell-like structure, the top side of the core or the core layers not being covered in the case of the dot tablets and thus remaining visible. Rotary tablet presses can also be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used simultaneously for pressing. the. The throughputs of modern rotary tablet presses are over one million molded articles per hour.

When tableting with concentricity presses, it has proven to be advantageous to carry out the tabletting with the smallest possible fluctuations in the weight of the tablet. The fluctuations in hardness of the tablet can also be reduced in this way. Small fluctuations in weight can be achieved in the following ways:

- Use of plastic inserts with small thickness tolerances

- Low number of revolutions of the rotor

- Big filling shoes

- Matching the filler paddle speed to the speed of the rotor

- Filling shoe with constant powder height

- Decoupling of filling shoe and powder feed

To reduce stamp caking, all non-stick coatings known from the art are available. Plastic coatings, plastic inserts or plastic stamps are particularly advantageous. Rotating punches have also proven to be advantageous, with the upper and lower punches being designed to be rotatable if possible. In the case of rotating stamps, a plastic insert can generally be dispensed with. The stamp surfaces should be electropolished here.

It was also shown that long pressing times are advantageous. These can be set with pressure 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 which limit the pressing force. Here elastic stamps, pneumatic compensators or resilient elements can be used in the force path. The pressure roller can also be designed to be resilient.

Tableting machines suitable within the scope of the present invention are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Hörn & Noack Pharmatechnik GmbH, Worms, EVLA Veφackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms. Other providers include Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Liveeool (GB), I. Holand Ltd., Nottingham (GB), Courtoy NV, Halle (BE / LU) and Me- diopharm Kamnik (SI). The hydraulic double pressure press HPF 630 from LAEIS, for example, is particularly suitable. Tableting tools are, for example, from Adams Tablettierwerkzeuge, Dresden, Wilhelm Fette GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Söhne GmbH, Hamburg, Hofer GmbH, Weil, Hörn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Werkzeugbau, Tamm available. Other providers include Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).

The molded body can be manufactured in a predetermined spatial shape and a predetermined size. Practically all practical configurations can be considered as the spatial shape, for example, the design as a board, the bar or bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross section. This last embodiment encompasses the presentation form from the tablet 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, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthophombic , cylindrical, spherical, segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, seven-sided and octagonal-prismatic and rhombohedral shapes are preferred. Completely irregular base areas such as arrow or animal shapes, trees, clouds, etc. can also be realized. If the shaped bodies according to the invention have corners and edges, they are preferably rounded. As an additional optical differentiation, an embodiment with rounded corners and beveled (“chamfered”) edges is preferred.

The washing or cleaning agent shaped bodies can each be designed as separate individual elements which correspond to the predetermined metered amount of the washing and / or cleaning agents. However, it is also possible to form compacts, which connect a plurality of such mass units in a compact, the portioned smaller units being easy to separate, in particular by predetermined predetermined breaking points. For the use of textile detergents in machines of the type customary in Europe with horizontally arranged mechanics, the portioned compacts can be designed as tablets, in cylindrical or cuboid form, with a diameter / height ratio in the range from approximately 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 pressed articles.

The spatial shape of another embodiment of the molded body is adapted in its dimensions to the detergent dispenser of commercially available household washing machines, so that the molded body can be metered directly into the dispenser without metering aid, where it dissolves during the dispensing process. However, it is of course also possible to use the detergent tablets without problems using a metering aid and is preferred in the context of the present invention.

Another preferred molded body that can be produced has a plate-like or plate-like structure with alternating thick long and thin short segments, so that individual segments of this "bolt" at the predetermined breaking points, which represent the short thin segments, broken off and into the Machine can be entered. This principle of the "bar-shaped" molded article washing agent can also be implemented in other geometric shapes, for example vertically standing triangles, which are connected to one another only on one of their sides along the side.

However, it is also possible that the various components are not pressed into a uniform tablet, but that shaped bodies are obtained which have several layers, that is to say at least two layers. It is also possible that these different layers have different dissolving speeds. This can result in advantageous application properties of the molded body. If, for example, components are contained in the molded body that mutually influence each other negatively, it is possible to integrate one component in the more rapidly soluble layer and to incorporate the other component in a more slowly soluble layer. ten, so that the first component has already reacted when the second goes into solution. The layer structure of the molded body can take place in a stack-like manner, with the inner layer (s) already loosening at the edges of the molded body when the outer layers have not yet been completely removed, but it is also possible for the inner layer (s) to be completely encased ) can be achieved by the layer (s) lying further outwards, which leads to the premature dissolution of components of the inner layer (s).

Another object of the present invention is therefore a process for the production of multi-phase detergent tablets by pressing a plurality of particulate premixes known per se, 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, i.e. two outer and at least one inner layer, at least one of the inner layers containing a peroxy bleach, while in the stacked molded body the two outer layers and in the case of the molded body the outermost layers, however, are free of peroxy bleach. Furthermore, it is also possible to spatially separate peroxy bleaching agents and any bleach activators and / or enzymes that may be present in a molded body. Such multilayer molded bodies have the advantage that they can be used not only via a dispensing chamber or via a metering device which is added to the washing liquor; rather, in such cases it is also possible to put the molded body into direct contact with the textiles in the machine without the risk of bleaching from bleaching agents and the like.

In addition to the layer structure, multi-phase molded bodies can also be produced in the form of toroidal core tablets, core-coated tablets or so-called “bulleye” tablets. An overview of such embodiments of multi-phase tablets is described in EP 055 100 (Jeyes Group). This document discloses toilet cleaning agent blocks which have a shaped shape Body made from a slowly soluble detergent composition tion in which a bleach tablet is embedded. At the same time, this document discloses the most varied forms of configuration of multi-phase shaped bodies, from simple multi-phase tablets to complicated multi-layer systems with inlays.

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

2P σ =

7lDt

Herein σ stands for diametral fracture stress (DFS) in Pa, P is the force in N that leads to the pressure exerted on the molded body that causes the molded body to break, D is the molded body diameter in meters and t the height of the molded body.

Preferred manufacturing processes for detergent tablets are based on a surfactant-containing granulate which is processed with further processing components to give a particulate premix to be treated. Completely analogous to the above statements about preferred ingredients of the detergent tablets according to the invention, the use of further ingredients can also be transferred to their production. In preferred processes, at least one particulate premix additionally contains granulate (s) containing surfactant and has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g / 1.

In preferred methods according to the invention, the surfactant-containing granulate has 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.

The further ingredients of the detergent tablets according to the invention can also be introduced into the method according to the invention, for which purpose the above is referred to. Preferred processes are characterized in that at least one particulate premix additionally contains one or more substances from the group of bleaching agents, bleach activators, disintegration aids, enzymes, pH regulators, 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 further 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 shaped bodies is introduced into the shaped bodies according to the invention via a surfactant-containing granulate. Another object of the present invention is therefore a process for the production of detergent tablets which, through the steps a) production of a surfactant-containing granulate which contains oxidized derivatives of starch and / or dextrins, b) mixing the granulate from step a) with further ingredients of detergents or cleaning agents, c) pressing the premix formed in step b) into shaped bodies or shaped body areas.

With regard to the quantitative most important ingredients of the surfactant granulate produced in step a) - the surfactants and the builders, which in the present case also include the oxidized derivatives of starch and / or dextrins - reference can be made to the above statements. Further optional ingredients of the surfactant granules, which can also be part of the premix, are described below. The following is information on the preparation of the surfactant granules in step a)) of the process according to the invention.

When selecting the suitable machines and process parameters for process step a), the person skilled in the art can fall back on machines and apparatuses known from the literature as well as process engineering operations, as described, for example, in W. Pietsch, "Size largement by agglomeration ", Verlag Wiley, 1991, and the literature cited therein. The following explanations represent only a small part of the possibilities which the person skilled in the art has for carrying out this step of the method according to the invention.

As already mentioned, the production of surfactant granules {corresponding to step a) of the process according to the invention} can be carried out in a large number of conventional mixing and granulating devices. Eirich ^® mixer Series R or RV (trademark of Maschinenfabrik Gustav Eirich, Hardheim), the Schugi ^® Flexomix, the Fukae ^® FS-G mixers include for example (trademark of Fukae Powtech for carrying out the process step according to the invention a) suitable mixer, Kogyo Co., Japan), the Lödige ^® FM, KM and CB mixers (trademarks of Lödige Maschinenbau GmbH, Paderborn) or the Drais ^® series T or KT (trademarks 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) is carried out in a medium-speed mixer / granulator at peripheral speeds of the tools from 2 m / s to 7 m / s. Alternatively, in preferred process variants, process step a) can be carried out in a high-speed mixer / granulator at peripheral speeds of 8 m / s to 35 m / s.

Regardless of whether high-speed or slow-speed mixers are used to carry out process step a), the granulation in step a) is preferably carried out by build-up granulation with granulating liquids. Processes according to the invention are preferred in which, in step a), particulate solids are granulated with the addition of one or more granulating liquids.

The oxidized derivatives of starch and / or dextrins can be part of the solid bed to be granulated as well as an ingredient of one or more granulating liquids. Processes according to the invention in which the solid bed to be granulated contains oxidized derivatives of starch and / or dextrins are therefore also preferred such as processes which are characterized in that at least one of the granulating liquids applied to the solid bed contains oxidized derivatives of starch and / or dextrins.

While the two process variants described above each describe the use of one mixer, it is also possible according to the invention to combine two mixers with one another. For example, processes are preferred in which, in process step a), a liquid granulation aid is added to a moving solid bed in a first, low-speed mixer / granulator, 40 to 100% by weight, based on the total amount of the constituents used, of the solid and pre-granulated liquid constituents and, in a second, high-speed mixer / granulator, the pre-granules from the first process stage are optionally mixed with the remaining solid and / or liquid constituents and converted into granules. In this variant of the method, a granulation aid is placed on a solid bed in the first mixer / granulator and the mixture is pregranulated. The composition of the granulation aid and the solid bed placed in the first mixer are chosen so that 40 to 100% by weight, preferably 50 to 90% by weight and in particular 60 to 80% by weight, of the solid and liquid constituents are obtained on the total amount of the constituents used, are in the "pre-granules". These "pre-granules" are now mixed with other solids in the second mixer and granulated with the addition of further liquid components to the finished surfactant granules.

The sequence of low-speed, high-speed mixers mentioned can also be reversed according to the invention, so that a process according to the invention results in which the liquid granulation aid is added to a moving solid bed in a first, high-speed mixer / granulator, 40 to 100% by weight, based on to the total amount of the constituents used, the solid and liquid constituents are pregranulated and, in a second, low-speed mixer / granulator, the pregranules from the first process stage are optionally mixed with the remaining solid and / or liquid constituents and converted into a granulate. All of the design variants of the method according to the invention described above can be carried out batchwise or continuously. In the embodiment variants of process step a) according to the invention described above, high-speed mixers / granulators are used in some cases. It is particularly preferred in the context of the present invention that a mixer is used as a high-speed mixer, which has both a mixing and a comminution device, the mixing shaft at speeds of 50 to 150 revolutions / minute, preferably 60 to 80 revolutions / Minute and the shaft of the comminution device is operated at speeds of 500 to 5000 revolutions / minute, preferably from 1000 to 3000 revolutions / minute.

Preferred granulation processes for producing mixer granules are carried out in mixer granulators in which some mixer parts or the entire mixer are heated to temperatures which are at least 20 ° C. above the temperature which the substances to be granulated have at the beginning of the granulation process. Thus, if solids are granulated that have been stored at 20 ° C. and enter the mixer at this temperature, it is preferred that some or all of the mixer parts have a temperature of at least 40 ° C. Overall, however, a temperature of 120 ° C for the mixer parts or the entire mixer should not be exceeded. If only parts of the mixer are heated to the temperatures mentioned, these are preferably the mixer walls or the mixer tools. The former can be brought to the desired temperature by a heatable jacket, the latter by built-in heating elements.

It is further preferred in the production of surfactant-containing granules in wholly or partially heated mixers to use non-aqueous granulation aids, in particular nonionic surfactants, which have a melting point in the range from 20 to 50 ° C. The described preferred granulation process allows the bulk density of the surfactant granules to be increased, while at the same time undesirable caking on the walls of the mixer is significantly reduced. The use of the surfactant granules produced in this way in tablettable premixes leads to detergent tablets which are characterized by a further reduced disintegration time compared to mixtures which contain conventionally produced granules. In step b) of the process described last, the surfactant granules are mixed with further ingredients of detergents or cleaning agents, it being possible for all of the ingredients described above to be used. In the last step, the premix is pressed into molded bodies or molded body areas, for example layers of multi-layer molded bodies.

The use of oxidized derivatives of starch and / or dextrins with the aim of improving the physical properties of detergent tablets has not hitherto been disclosed in the prior art. Another object of the present invention is therefore the use of oxidized derivatives of starch and / or the dextrins to improve the physical properties of detergent tablets.

In addition to improving the abrasion resistance and increasing the edge break resistance, the hardness in particular is increased and the decay times are minimized. The use of oxidized derivatives of starch and / or dextrins to increase the hardness and reduce the disintegration time of detergent tablets is therefore a further subject of the present invention.

I can also achieve the aforementioned advantageous properties by means of surfactant granules which contain oxidized derivatives of starch and / or dextrins. Another aspect of the present invention is therefore the use of surfactant granules, which contain oxidized derivatives of starch and / or dextrins, to improve the physical properties of detergent tablets, in particular to increase the hardness and reduce the disintegration time. Examples:

A tower powder containing surfactant was produced by spray drying and was used as the basis for granules containing surfactant. The tower powder was granulated with other components (zeolite, NaOH, anionic surfactant acid, nonionic surfactant) in a 130 liter ploughshare mixer from Lödige. A 40% solution of oxidized starch in water was used to granulate the surfactant granules E according to the invention; when the comparison granules V were granulated, only water was added at the same point. The amounts of the solids and liquids used and the order of addition to the mixer are given in Table 2. Following the granulation, the granules were dried in a fluidized bed apparatus from Glatt at a supply air temperature of 60 ° C. over a period of 30 minutes. After drying, fine particles <0.6 mm and coarse particles> 1.6 mm were screened off.

The surfactant granules E and V were then prepared with further components to form a press-capable premix, after which the pressing into tablets (diameter: 44 mm, height: 22 mm, weight: 37.5 g) was carried out in a Korsch eccentric press. The pressure was adjusted so that three series of molded bodies were obtained (El, E2, E3 and VI, V2, V3), which differed in their hardness. Table 1 shows the composition of the spray-dried tower powder; Table 3 shows the composition of the premixes to be treated (and thus the shaped body).

Table 1: Composition of the spray-dried tower powder [% by weight]

Table 2: Granulation approach

EMOX TSD from Emsland-Starch

Table 3: Composition of the premixes [% by weight]:

After two days of storage, the hardness of the tablets was measured by deforming the tablet until it broke, the force acting on the side surfaces of the tablet and the maximum force which the tablet withstood being determined.

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

Table 4: Detergent tablets [physical data]

Through the use of oxidized starch according to the invention, the disintegration time of the detergent tablets is reduced, which has a clearly positive effect, particularly with higher tablet hardness.

Claims

claims:

1. washing or cleaning agent molded body made of compressed, particulate washing or cleaning agent, characterized in that they contain oxidized derivatives of starch and / or dextrins in amounts of 0.1 to 10 wt .-%, based on the weight of the shaped body.

2. washing or cleaning agent shaped body according to claim 1, characterized in that it oxidized derivatives of starch and / or dextrins with average molecular weights in the range from 440 to 500,000 in amounts of 0.25 to 7.5 wt .-%, preferably of 0.5 to 5 wt .-%, particularly preferably from 0.75 to 3.5 wt .-% and in particular from 1 to 2 wt .-%, based on the molded body weight.

3. washing or cleaning agent shaped body according to one of claims 1 or 2, characterized in that the oxidized derivatives of starch and / or dextrins contained therein dextrose equivalents (DE) from 0.1 to 50, preferably from 0.5 to 40 and in particular from 2 to 30.

4. washing or cleaning agent shaped body 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. Washing or cleaning agent molded article according to one of claims 1 to 4, characterized in that it contains the oxidized derivatives of starch and / or dextrins in the form of compounds which have an average particle size below 500 μm, preferably below 450 μm and in particular below 400 µm.

6. washing or cleaning agent molded article according to claim 5, characterized in that the compounds the oxidized derivatives of starch and / or dextrins in amounts of more than 10 wt .-%, preferably of more than 20 wt .-% and in particular of more than 30 wt .-%, each based on the weight of the compound.

7. washing or cleaning agent molded bodies 1 to 4, characterized in that they contain the oxidized derivatives of starch and / or dextrins in the form of a surfactant granulate which contains the total amount of the oxidized derivatives of starch and / or dextrins contained in the molded bodies.

8. washing or cleaning agent molded article according to claim 7, characterized in that the content of the surfactant granules of oxidized derivatives of starch and / or dextrins 0.5 to 20 wt .-%, preferably 0.75 to 15 wt .-%, particularly preferred 1 to 10% by weight and in particular 1.5 to 5% by weight, in each case based on the weight of the surfactant granules.

9. washing or cleaning agent shaped body made of compressed, particulate washing or cleaning agent, characterized in that they contain a surfactant granulate which contains oxidized derivatives of starch and / or dextrins.

10. Detergent or molded article according to one of claims 1 to 9, characterized in that it additionally contains a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight. , preferably from 3 to 7 wt .-% and in particular from 4 to 6 wt .-%, each based on the molded body weight.

11. Detergent or shaped article according to one of claims 1 to 10, characterized in that it contains surfactant (s), preferably anionic (s) and / or nonionic (s) surfactant (s), in amounts of 5 to 40% by weight .-%, preferably from 7.5 to 35% by weight, particularly preferably from 10 to 30% by weight and in particular from 12.5 to 25% by weight, in each case based on the molded body weight.

12. A process for the preparation of washing or cleaning agent foams by shaping a particulate premix, characterized in that the premix contains oxidized derivatives of starch and / or dextrins in amounts of 0.1 to 10% by weight, based on the premix ,

13. A process for the production of multi-phase detergent or cleaning product by known compression of several particulate premixes, characterized in that at least one of the premixes contains oxidized derivatives of starch and / or dextrins in amounts of 0.1 to 10% by weight, based on the premix.

14. The method according to any one of claims 12 or 13, characterized in that at least one particulate premix additionally contains surfactant-containing granules (s) and a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g / 1.

15. The method according to claim 14, characterized in that the surfactant-containing granules have particle sizes between 100 and 2000 microns, preferably between 200 and 1800 microns, particularly preferably between 400 and 1600 microns and in particular between 600 and 1400 microns.

16. The method according to any one of claims 12 to 15, characterized in that at least one particulate premix additionally one or more substances from the group of bleaching agents, bleach activators, disintegration aids, enzymes, pH adjusting agents, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, Contains silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.

17. Process for the production of detergent tablets, characterized by the steps a) Production of a surfactant-containing granulate which contains oxidized derivatives of starch and / or dextrins, b) Mixing the granulate from step a) with further ingredients of detergents or cleaning agents, c ) Pressing the premix formed in step b) into shaped bodies or shaped body areas.

18. The method according to claim 17, characterized in that in step a) particulate solids are granulated with the addition of one or more granulating liquids.

19. The method according to claim 18, characterized in that the solid bed to be granulated contains oxidized derivatives of starch and / or dextrins.

20. The method according to claim 18, characterized in that at least one of the granulation liquids added to the solid bed contains oxidized derivatives of starch and / or dextrins.

21. Use of oxidized derivatives of starch and / or of the dextrins to improve the physical properties of detergent tablets.

22. Use of oxidized derivatives of starch and / or dextrins to increase the hardness and reduce the disintegration time of detergent tablets.

23. Use of surfactant granules which contain oxidized derivatives of starch and / or dextrins to improve the physical properties of detergent tablets, in particular to increase the hardness and reduce the disintegration time.