DE19932569A1 - Detergent tablets, in particular for machine dishwashing - Google Patents

Abstract

The invention relates to an auxiliary disintegration agent for shaped bodies with a detergent action. Said auxiliary disintegration agent reduces the decomposition time of the shaped body or of parts of the shaped body in usual domestic dishwashers and can be easily incorporated into the mixtures for compacting without the effective shape of the body being lost. According to the invention, said auxiliary disintegration agents are auxiliary agents that have a fine-particle consistency with formulations containing phosphates, especially zeolites. The decomposition time of the shaped detergent bodies is improved when they contain 20 to 95 wt. % phosphate(s) and 0.1 to 9 wt. % zeolite(s).

Description

The present invention relates to detergent tablets, the framework contain substances and bleach. In particular, the invention relates to cleaning agents Shaped body for automatic dishwashing, which accelerates dissolution completely or partially are.

Detergent tablets are widely described in the prior art and enjoy popular with consumers because of the simple dosage. Tableted Detergents have a number of advantages over powdered ones: They are one easier to dose and to handle and, due to their compact structure, have plans parts during storage and transport. Cleaning is also in the patent literature consequently, the moldings described in detail. A problem with the application of cleaning-active moldings, however, occurs again and again, is too low Decay and dissolution rate of the shaped bodies under conditions of use. There sufficiently stable, d. H. shape and break resistant molded articles only by proportion high pressures can be produced, there is a strong compression of the Molded parts and a resulting delayed disintegration of the Shaped body in the aqueous liquor and thus to a slow release of the Ak active substances in the cleaning process.  

In the field of detergents or cleaning agents, according to the teaching of the European the patent EP-B-0 523 099, the disintegrants used by the Arz Neimittelfertigung ago are known. Swellable ones are mentioned as disintegrants Layered silicates such as bentonites, natural substances and natural substance derivatives on starch and cellulo se base, alginates and the like, potato starch, methyl cellulose and / or hydroxy propyl cellulose. These disintegrants can ver with the granules to be compressed mixes, but can also be incorporated into the granules to be pressed.

International patent application WO-A-96/06156 also states that the installation of explosives in detergent or cleaning agent tablets can be advantageous. How that is why microcrystalline cellulose, sugars such as sorbitol, but also layered silicates, especially finely divided and swellable layered silicates from the Type of bentonite and smectite called. Also substances contributing to gas formation such as Citric acid, bisulfate, bicarbonate, carbonate and percarbonate are considered as possible Zer case aids listed.

According to EP-A-0 711 827 the use of particles leads to the predominant Part consist of citrate, which has a certain solubility in water, in the second Line also to accelerate tablet disintegration. It is believed that through the Dissolution of the citrate increases the ionic strength locally where during a transition period suppressed by the gelation of surfactants and as a result the disintegration of Ta blette is not hindered. According to this patent application, citrate is therefore not a classic explosive, but serves as an anti-gelling agent.

Detergent tablets, the disintegrants based on cellulose in granular or optionally contain cogranulated form, are in the German patent applications dungen DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) as well as the interna tional patent applications WO 98/40462 (Stefan Herzog) and WO 98/40463 (Henkel) described. These documents also contain more information on the production of granulated, compacted or cogranulated cellulose disintegrant.  

The proposed solutions lead to the manufacture of medicinal tablets to the desired success. In the area of detergents and cleaning agents, they contribute to one Improving the disintegration properties of washing or cleaning tablets; however, the improvement achieved is not sufficient in many cases. In addition can the use of the proposed disintegrants in cleaning active moldings for automatic dishwashing leads to specific problems, medicines or Detergents are completely unknown.

The object of the invention was to provide a disintegration aid for cleaning To provide tive moldings, on the one hand, the disintegration time of the molded body or of Parts of the molded body in household dishwashers shortened, but on the other hand, can be easily incorporated into the mixtures to be pressed, without losing his losing effective form. Compared to the explosive described in the prior art effectiveness should not be limited to the disintegration effect, rather, the tool should, if possible, perform other tasks in the cleaning process take.

It has now been found that the addition of small amounts of finely divided, preferably in essential water-insoluble auxiliaries, in particular zeolite, to phosphate-containing Detergent tablets the solubility of individual phases or the ge entire molded body accelerated.

The invention relates to detergent tablets, the builders and bleach and optionally other common ingredients of cleaning agents hold and in which the content of the molded body of phosphate (s) 20 to 95 wt .-% be carries, wherein the molded body with 0.1 to 9 wt .-% of a finely divided auxiliary contain an average particle size below 100 microns.

The finely divided auxiliaries are preferably used in an even finer form, so that preferred detergent tablets are characterized in that the  finely divided excipient an average particle size below 40 microns, preferably un has below 20 microns and in particular below 10 microns.

The particle size distribution of the auxiliary used is essential for the success of the present the invention the essential feature, the type of auxiliary used only plays a subordinate role. However, it has been shown that substances with less Solubility in water Surprisingly bring better effects, so that the fine Auxiliary in preferred detergent tablets essentially what is insoluble in serum.

The term "essentially water-insoluble" in the context of the present Invention substances whose solubility in water is negligible. Of such substances with negligible water solubilities dissolve to a maximum Milligram amounts in one liter of water.

Ne has emerged from the group of finely divided, preferably water-insoluble auxiliaries ben pyrogenic silicas, in particular zeolite, have proven to be particularly suitable. Be contain particularly preferred detergent tablets according to the invention as a finely divided auxiliary zeolite.

The most important ingredients of the laundry detergents according to the invention are described below. or detergent tablets.

Phosphates are used in particular in machine dishwashing detergents as builders used, but their use is also advantageously possible in detergents, provided that a derar use should not be avoided for ecological reasons. Among the multitude of the commercially available phosphates, the alkali metal phosphates have in particular Preference for pentasodium or pentapotassium triphosphate (sodium or potassium tri polyphosphate) 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 or lime incrustations in tissues and also contribute to cleaning performance.

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

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

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

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

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

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

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

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

The detergent tablets according to the invention contain this or the Phosphate (s) in amounts of 20 to 95 wt .-%, each based on the molded body. In preferred laundry detergent and cleaning product tablets is the content of phosphate (s) 30 to 92.5% by weight, preferably 40 to 90% by weight and in particular 50 to 85% by weight, each based on the molded body.

In a particularly preferred embodiment, the detergent tablets according to the invention contain zeolite as a second constituent from the group of builders. The use of the zeolite in the amounts mentioned and with the particle size distribution mentioned leads to an accelerated dissolution of the shaped body or of the phases of the shaped body which have the stated composition. The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or X, Y or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X), which is available from CONDEA Augusta SpA under the brand name VEGOBOND AX® is distributed and by the formula

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

can be described. The quantities given relate to the anhydrous, d. H. non-hydrated zeolite. Suitable zeolites preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Zeolite has the general formula M _{2 / n} O.Al ₂ O ₃ .x SiO ₂ .y H ₂ O, in which M is a cation of valence n, x represents values which are greater than or equal to 2 and y values can be between 0 and 20. The zeolite structures are formed by linking AlO ₄ tetrahedra with SiO ₄ tetrahedra, whereby this network is cooled by cations and water molecules. The cations in these structures are relatively mobile and can be exchanged for other cations in different degrees. Depending on the type of zeolite, the intercrystalline "zeolitic" water can be released continuously and reversibly, while for some types of zeolite structural changes are also associated with the water release or absorption.

In the structural subunits, the "primary binding units" (AlO ₄ tetrahedra and SiO ₄ tetrahedra) form so-called "secondary binding units", which have the form of one or more rings. For example, 4-, 6- and 8-membered rings appear in different zeolites (referred to as S4R, S6R and S8R), other types are connected via four- and six-membered double ring prisms (most common types: D4R as a square prism or D6R as a hexagonal prism ). These "secondary subunits" combine different polyhedra, which are denoted by Greek letters. The most common is a polyhedron, which is made up of six squares and eight equilateral hexagons and is referred to as "β". A variety of different zeolites can be realized with these units. To date, 34 natural zeolite minerals and around 100 synthetic zeolites are known.

The best known zeolite, zeolite 4A, is a cubic assembly of β-cages linked by D4R subunits. It belongs to the zeolite structure group 3 and its three-dimensional network has pores of 2.2 Å and 4.2 Å in size, the formula unit in the unit cell can be expressed with Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ]. Describe 27 H ₂ O.

Zeolites of the faujasite type are preferably used according to the invention. Along with The mineral faujasite belongs to the faujasite types within the zeolites X and Y. Zeolite structure group 4, characterized by the double six-ring subunit D6R (compare Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, page 92). The zeolite structure group 4 includes ne In addition to the faujasite types mentioned, the minerals chabazite and gmelinite as well as the synthetic zeolites R (chabazite type), S (gmelinite type), L and ZK-5. The last two synthetic zeolites mentioned have no mineral analogues.

Faujasite-type zeolites are composed of β-cages, which are linked tetrahedrally via D6R subunits, the β-cages being arranged similarly to the carbon atoms in the diamond. The three-dimensional network of the faujasite-type zeolites used in the process according to the invention has pores of 2.2 and 7.4 Å, the unit cell also contains 8 cavities with a diameter of approx. 13 Å and can be determined by the formula Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .264 H ₂ O. The network of zeolite X contains a void volume of approximately 50%, based on the dehydrated crystal, which represents the largest empty space of all known zeolites (zeolite Y: approx. 48% void volume, faujasite: approx. 47% void volume). (All data from: Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, pages 145, 176, 177).

In the context of the present invention, the term "zeolite from faujasite Type "all three zeolites that form the faujasite subgroup of zeolite structure group 4. In addition to zeolite X, zeolite Y and faujasite and Mi are also according to the invention mixtures of these compounds can be used according to the invention with preference, the pure Zeolite X is preferred.

Mixtures or cocrystallizates of zeolites of the faujasite type with other Zeo Lithen that do not necessarily have to belong to zeolite structure group 4 are invented usable according to the invention.

The aluminum silicates which are used according to the invention have been obtained commercially Lich, and the methods for their presentation are described in standard monographs.

Examples of commercially available X-type zeolites can be described by the following formulas:

Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .xH ₂ O,
K ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .xH ₂ O,
Ca ₄₀ Na ₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .xH ₂ O,
Sr ₂₁ Ba ₂₂ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .xH ₂ O,

in which x can take values between 0 and 276 and the pore sizes from 8.0 to 8.4 Å.  

Y-type zeolites are also commercially available and can be expressed, for example, by the formulas

Na ₅₆ [(AlO ₂ ) ₅₆ (SiO ₂ ) ₁₃₆ ] .xH ₂ O,
K ₅₆ [(AlO ₂ ) ₅₆ (SiO ₂ ) ₁₃₆ ] .xH ₂ O,

in which x stands for numbers between 0 and 276 and have a pore size of 8.0 Å, describe.

Preferred detergent tablets contain, each based on the Molded articles, 0.25 to 7.5% by weight, preferably 0.5 to 5% by weight and in particular 1 to 3% by weight of zeolite, preferably zeolite X, Y and / or P.

In addition to phosphate (s) and zeolite in the amounts mentioned, the inventive Detergent tablets contain additional builders, some of which also can serve as an alkali carrier. Here are in particular silicates, carbonates, carboxylates, in particular to mention citrates and polymers, which are described below.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-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, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171 .

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

Alkali carbonates and bicarbonates in particular come as carbonates traditional, the sodium salts and among them the anhydrous sodium carbonate ("calci nated soda ") are particularly important. Sodium carbonate Decahydrate, sodium hydrogen carbonate, potassium carbonate, potassium carbonate 1,5-water ("Potash hydrate"), potassium hydrogen carbonate and mixtures of these.

As organic cobuilders in the washing and cleaning agents according to the invention telformkörper polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, Aspa Ragic acid, polyacetals, dextrins, other organic cobuilders (see below) and Phos phonate can be used. These classes of substances are described below.

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

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

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

In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the respective acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the investigated polymers. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2000 to 20,000 g / mol. Because of their superior solubility, the This group in turn the short-chain polyacrylates, the molecular weights from 2000 to  10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, preferably his.

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

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

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

Biodegradable polymers of more than two ver. Are also particularly preferred different monomer units, for example those that act as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives contain.

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

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

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

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be. The hydrolysis can be carried out according to conventional methods, for example acid or enzyme lysed procedures are carried out. It is preferably hydrolysis pro Products with average molecular weights in the range of 400 to 500,000 g / mol. There is a poly saccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30 preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and dry glu can be used cosesirupe 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.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 and international patent applications WO 92/18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608 are known. An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

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

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

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

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

In addition to the builders, there are in particular substances from the groups of surfactants Bleach, bleach activators, corrosion inhibitors and color and fragrance important ingredients of detergents. Important representatives from the above Substance classes are described below.

Preferred detergent tablets furthermore contain one or more Surfactant (s). Can in the detergent tablets according to the invention anionic, nonionic, cationic and / or amphoteric surfactants or Mi can be used from these. Are preferred from an application point of view Mixtures of anionic and nonionic surfactants. The total surfactant content of the Shaped body is 5 to 60 wt .-%, based on the weight of the shaped body, in which In the case of detergent tablets, surfactant contents above 15% by weight are preferred and Reini Detergent tablets for machine dishwashing usually less than Contain 3% by weight of surfactant.

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

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

As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ -Oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis and have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which are produced for example according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

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

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

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

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

Usually only surfactants are used in automatic dishwashing detergents low-foaming nonionic surfactants are used. Representatives from the groups of In contrast, anionic, cationic or amphoteric surfactants have a lower level Importance. Particularly preferably contain inventive Detergent tablets for machine dishwashing nonionic surfactants.

In particularly preferred embodiments of the present invention, the detergent tablets according to the invention contain nonionic surfactants, in particular special nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols, preferably having 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. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred eth oxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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

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

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

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

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

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

in the R for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ¹ for a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R ² for a linear, branched or cyclic alkyl radical or is an aryl radical or an oxyalkyl radical with 1 to 8 carbon atoms, C _1-4 alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue.

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

In addition to the pure nonionic surfactants, other substances can of course also be used from the group of ionic surfactants, for example anionic or cationic surfactants the detergent tablets according to the invention may be included.

Preferred detergent and cleaning agent form in the context of the present invention Bodies have total surfactant contents below 5% by weight, preferably below 4% by weight, particularly preferably below 3% by weight and in particular below 2 wt .-%, each based on the molded body.

Sodium percarbonate and sodium perborate monohydrate are of particular importance among the compounds which serve as bleaching agents and produce H ₂ O ₂ in water. Other useful bleaching agents are, for example, sodium perborate tetrahydrate, peroxypyrophosphate, citrate perhydrates and H ₂ O ₂ -supplying acidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Cleaning agents according to the invention can also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaches are the Diacylperoxi de, such as. B. dibenzoyl peroxide. Other typical organic bleaching agents are the peroxy acids, the examples being in particular the alkyl peroxy acids and the aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, ε-phthalimoxyhexanoic acid [p-phthalimidhexanoic acid (ε-phthalimidoxythanoic acid) (ε-phthalimoxyhexanoic acid) )], o-Carboxybenzamidoperoxycapronsäure, N- nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-Diperoxyazelain acid, Diperocysebacinsäure, diperoxybrassylic acid, diperoxyphthalic acids which, 2- decyldiperoxybutane-1 , 4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

As a bleach in detergent tablets according to the invention for the machine Dishwashing can also use chlorine or bromine-releasing substances. Suitable chlorine or bromine releasing materials include, for example heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, Tribromo isocyanuric acid, dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

The bleaches are usually used in machine dishwashing detergents in amounts of 1 up to 30% by weight, preferably from 2.5 to 20% by weight and in particular from 5 to 15% by weight, each based on the agent used. Within the scope of the present invention preferred detergent tablets contain bleaches from the group the oxygen or halogen bleach, in particular the chlorine bleach, below particular preference for sodium perborate and sodium percarbonate, in amounts of 2 up to 25% by weight, preferably from 5 to 20% by weight and in particular from 10 to 15% by weight, each based on the molded body.

Bleach activators that support the action of the bleach can also be be part of the detergent tablets according to the invention. Known Bleach activators are compounds that contain one or more N or O acyl groups hold, such as substances from the class of anhydrides, esters, imides and acylier ten imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetyl methylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglu  cose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic acid drid ISA.

As bleach activators can be compounds that are under perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms and / or optionally substituted perbenzoic acid are used become. Substances which contain O- and / or N-acyl groups of the C- Bear atomic number and / or optionally substituted benzoyl groups. Are preferred multiple acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydra-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), Carboxylic anhydrides, especially phthalic anhydride, acylated polyvalent Alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), and those from the German Patent applications DE 196 16 693 and DE 196 16 767 known enol esters as well acetylated sorbitol and mannitol or their mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetyl glucose (PAG), pentaacetyl fructose, Tetraacetylxylose and Octaacetyllactose as well as acetylated, optionally N-alkylated Glucamine and gluconolactone, and / or N-acylated lactams, for example N- Benzoylcaprolactam. Hydrophilically substituted acylacetals and acyllactams also preferably used. Combinations of conventional bleach activators can be used. The bleach activators are made in machine Dishwashing agents usually in amounts of 0.1 to 20 wt .-%, preferably 0.25 up to 15% by weight and in particular from 1 to 10% by weight, in each case based on the composition, used. In the context of the present invention, the aforementioned relate Quantities based on the weight of the base molding.

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

Bleach activators from the group of multi-acylated alkylene are preferred diamines, especially tetraacetylethylenediamine (TAED), N-acylimides, especially N- Nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile- Methyl sulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0.1% by weight up to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight on the entire medium.

Bleach-enhancing transition metal complexes, especially with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably cobalt (ammin) - Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate in usual amounts, preferably in an amount up to 5 wt .-%, in particular from 0.0025 wt .-% to 1 wt .-% and be particularly preferably from 0.01% by weight to 0.25% by weight, in each case based on the total Means used. But in special cases, more bleach activator can be used the.

Preferred detergent tablets contain bleach activators from the Groups of polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), the N-acylimides, especially N-nonanoylsuccinimide (NOSI), the acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS and n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), in amounts of 0.25 to 15% by weight, preferably from 0.5 to 10% by weight and in particular from 1 to 5 wt .-%, each based on the molded body.  

The detergent tablets according to the invention can protect the items to be washed or the machine contain corrosion inhibitors, silver protection agents in particular Machine dishwashing have a special meaning. Can be used are the known substances of the prior art. In general, Sil Protective agents selected from the group of triazoles, benzotriazoles and bisbene zotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or Complexes are used. Benzotriazole are particularly preferred and / or alkylaminotriazole. You will also often find it in detergent formulations Agents containing active chlorine, which significantly reduce the corrosion of the silver surface can. In chlorine-free cleaners, especially oxygen and nitrogenous org African redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, Pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds. Also salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Prefers are the transition metal salts that are selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably cobalt (ammin) - Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides cobalt or manganese and manganese sulfate. Zinc compounds can also be used to prevent corrosion on the wash ware.

Preferred detergent tablets contain silver protective agents from the Group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the Al kylaminotriazole and the transition metal salts or complex, particularly preferred Benzotriazole and / or alkylaminotriazole, in amounts of 0.01 to 5 wt .-%, preferably se from 0.05 to 4% by weight and in particular from 0.5 to 3% by weight, in each case based on the molded body.

The moldings according to the invention can of course contain enzymes. In the enzymes to be used optionally in the detergent tablets according to the invention are preferably commercially available solid enzyme preparations.  

Enzymes in particular come from the hydrolase classes such as the protea sen, esterases, lipases or lipolytically acting enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal stains such as protein, fat or starchy stains. For Bleach can also be used with oxidoreductases. Are particularly well suited Bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and from their genetically modified adorned variants obtained enzymatic agents. Proteases are preferred of the subtilisin type and in particular proteases obtained from Bacillus lentus, used. Enzyme mixtures, for example of protease and amylase or Protease and lipase or lipolytic enzymes or from protease, amylase and Lipase or lipolytic enzymes or protease, lipase or lipolytic we enzymes, but especially protease and / or lipase-containing mixtures or Mixtures with lipolytically active enzymes of particular interest. examples for Such lipolytic enzymes are the well-known cutinases. Peroxidases too or oxidases have been found to be suitable in some cases. To the appropriate ones Amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectina sen.

The enzymes can be adsorbed on carriers or embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5% by weight. Reini preferred in the context of the present invention Means shaped tablets are characterized in that they protease and / or amylase contain.

Dyes and fragrances can be the detergent and cleaning agent form according to the invention body can be added to ver the aesthetic impression of the resulting products improve and give the consumer a visual and sensory "typical and to provide a distinctive "product. As perfume oils or fragrances individual fragrance compounds, e.g. B. the synthetic products of the type Esters, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used.  

Fragrance compounds of the ester type are e.g. B. benzyl acetate, phenoxyethyl isobuty rat, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenyls thylacetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example Benzyl ethyl ether, to the aldehydes z. B. the linear alkanals with 8-18 C atoms, citral, Citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. B. the Jonone, α-isomethylionone and methylcedryl ketone the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and Terpineol, the hydrocarbons mainly include terpenes such as limonene and pinene. However, mixtures of different fragrances are preferably used, which together create an appealing fragrance. Such perfume oils can also na contain natural fragrance mixtures as they are accessible from plant sources, e.g. B. 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, lin flower oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil such as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the cleaning agents according to the invention , but it can also be advantageous to apply the fragrances to carriers.

To improve the aesthetic impression of the agents according to the invention, it can (or Parts of it) can be colored with suitable dyes. Preferred dyes whose Selection is not difficult for the expert, has a high storage stability and insensitivity to the other ingredients of the agents and to light as well as no pronounced substantivity towards those to be treated with the agents Substrates such as glass, ceramics or plastic dishes so as not to stain them.

Preferred detergent tablets in the context of the present invention per also contain one or more substances from the groups of enzymes, Korrosi onsinhibitors, deposit inhibitors, cobuilders, colors and / or fragrances in total  from 6 to 30% by weight, preferably from 7.5 to 25% by weight and in particular from 10 to 20 wt .-%, each based on the weight of the molded body.

The above information was based on a shaped body, the present Invention is not limited to the fact that only single-phase molded body is provided the. Rather, it is also possible for only individual phases, preferably layers, to have one have composition according to the invention and thereby he advantages be enough. In this way it is possible, for example, a two-layer tablet produce a layer - based on the layer - 0.1 to 9 wt .-% zeolite and Contains 20 to 95 wt .-% of phosphate (s), while the other layer free of zeolite and / or can be phosphate. In this way the dissolution of a layer can be counteracted be accelerated over another shift. Of course, the Teilbe rich of the molded body, which has the composition according to the invention, not to the Layer form bound. Rather, the phase of the molded body, which - based on the Phase - contains 0.1 to 9% by weight of zeolite and 20 to 95% by weight of phosphate (s), including that Have the shape of rings, cores, coats, pearls, etc. That way are ring core tablets, coated tablets, tablet tablets, etc., in which all phases or only some of the phases have the composition according to the invention and accordingly follow resolve faster.

In the manufacture of the detergent tablets according to the invention accordingly, it is not limited to the fact that only a particulate Vorge mix is pressed into a shaped body. Rather, the molded body can also be so design that one produces in a manner known per se multilayered articles by two or more premixes are prepared which are pressed together. Here If the premix is filled first, it is not or only slightly pre-pressed to give a smooth and get parallel to the top of the molded body, and after Ein fill the second premix to the finished molded article. At three or multilayered moldings optionally another after each premix addition Pre-compression before the molded body is finally compressed after adding the last premix becomes.  

Due to the increasing technical complexity, there are a maximum of two in practice layered molded articles preferred, d. H. they are detergent tablets preferred, in which the shaped body is a two-layer tablet. Already at this intermediate Step in the method according to the invention can from the division of certain In Benefits on the individual layers can be achieved.

For example, detergent tablets are preferred, in which one Layer one or more bleaches and the other layer one or more enzymes contains. Not only this separation of bleach and enzymes can bring benefits, separation of bleaching agents and optional bleach activators can also be carried out be advantageous, so that detergent tablets according to the invention before are added, in which one layer one or more bleaching agents and the other one or contains several bleach activators.

In the following information on the further subject of the present invention analogous to the production of a partial area of the molded body with a corresponding combination setting includes, even if this is not explicitly mentioned.

Another object of the present invention is a method for producing Detergent tablets by pressing a particulate pre mixed in a manner known per se, in which the premix phosphate (s) in amounts of 20 to 95 wt .-% and a finely divided excipient with an average particle size un below 100 microns, preferably below 40 microns, particularly preferably below of 20 microns and especially below 10 microns in amounts of 0.1 to 9 wt .-% ent holds.

The above information on preferred properties of the invention th auxiliaries (water solubility, amount, type, etc.) apply to the inventive Ver drive completely analog. Again, the use of zeolite is particularly preferred, so that  preferred methods are characterized in that the premix zeolite in Men contains gene from 0.1 to 9 wt .-%.

Analogous to the information given above regarding the shape according to the invention bodies are the preferred embodiments mentioned there (amounts of further content substances, substances used, physical parameters, etc.) also in the invention Process preferred.

The premix can, as described above in the comments on the shaped body ben, be composed of different substances. Independent of The composition of the premixes to be compressed can include physical parameters of the Premixes are selected so that advantageous molded body properties result.

In preferred variants of the first method according to the invention, this shows the particle shaped premix a bulk density above 600 g / l, preferably above 700 g / l and especially above 800 g / l.

The particle size in the premixes to be pressed can also be obtained partial shape properties can be set. In preferred variants for the According to the inventive method, the particulate premix has a particle size distribution in which less than 10% by weight, preferably less than 7.5% by weight and in particular less than 5% by weight of the particles larger than 1600 μm or smaller than Are 200 µm. Narrower particle size distributions are further preferred here. Especially Advantageous process variants are characterized in that the particulate premix has a particle size distribution in which more than 30% by weight, preferably more than 40% by weight and in particular more than 50% by weight of the particles have a particle size between 600 and 1000 microns.

When carrying out the method according to the invention, one is not restricted to that only a particulate premix is pressed into a shaped body. A lot the process can also be expanded to the extent that it is known per se  How to produce multilayered molded articles by using two or more premixes prepares that are pressed together. This is the premix that is filled in first slightly pre-pressed to create a smooth upper that runs parallel to the molded body bottom side and after filling in the second premix to the finished molded body finally pressed. In the case of three-layer or multi-layer moldings, Optionally add another pre-compression before adding the last premix the molded body is finally pressed.

Analogous to the above explanations, Ver preferably drive in which two-layer molded articles are produced by two different particulate premixes are pressed together, one of which one contains one or more bleaches and the other contains one or more enzymes. Again, analog processes are also preferred in which two-layer moldings are made by mixing two different particulate premixes others are pressed, one of which contains one or more bleaches and the other one or contains several bleach activators. Here, too, methods that are preferred are characterized in that the molded body produced protease and / or amylase contains.

The moldings according to the invention are produced in principle as above described, first by dry mixing the ingredients, all or part may be pre-granulated, and subsequent information, especially Ver compress to tablets, whereby conventional methods can be used. To produce the moldings according to the invention, the premix (or more phase moldings the premixes) in a so-called matrix between two Stamping compressed to a solid compressed. This process, briefly below called tableting is divided into four sections: dosage, compression (elastic deformation), plastic deformation and ejection.

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

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

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

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

The throughputs of modern rotary tablet presses are over a million tablets per hour.

When tableting with rotary presses, it has proven to be advantageous to carry out tableting 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. Slight weight fluctuations can be achieved in the following ways:

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

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

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

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

The moldings can ge in a predetermined spatial shape and a predetermined size be manufactured. Practically all sensibly manageable designs come as a spatial form tations, for example the training as a blackboard, the bars or bars shape, cubes, cuboids and corresponding room elements with flat side surfaces as well in particular cylindrical configurations with a circular or oval cross cut. This last embodiment covers the presentation form from the tablet to to compact cylinder pieces with a ratio of height to diameter above 1.

The portioned compacts can each be separate individual elements be formed, the predetermined dosage of washing and / or cleaning medium corresponds. However, it is also possible to form compacts that have a plurality connect such mass units in a compact, in particular by vorege bene predetermined breaking points the easy separability of portioned smaller units hen is. For the use of textile detergents in machines of the type common in Europe with horizontally arranged mechanics, the formation of the portioned compacts as Tablets, in the shape of a cylinder or cuboid, with a diameter / height Ratio in the range of about 0.5: 2 to 2: 0.5 is preferred. Commercial hydrau  Lik presses, eccentric presses or rotary presses are suitable devices in particular especially for the production of such compacts.

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

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

In a further preferred embodiment of the invention, a molded body consists of at least three layers, ie two outer and at least one inner layer, wherein at least one of the inner layers contains a peroxy bleach, while in the case of the stacked shaped body, the two outer layers and in the case of the shell-shaped one  Shaped bodies, however, the outermost layers are free of peroxy bleach. Farther it is also possible to use peroxy bleach and any bleach activators present and / or to separate enzymes spatially from one another in a shaped body.

Similar effects can also be achieved by coating individual components of the detergent and cleaning agent composition to be pressed, or all of them Reach shaped body. For this purpose, the bodies to be coated can be coated with, for example aqueous solutions or emulsions are sprayed, or via the process of Get a coating on the melt coating.

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

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

Another object of the present invention is the use of vorweiswei se water-insoluble substances with average particle sizes below 100 µm preferably below 40 µm, particularly preferably below 20 µm and in particular those below 10 µm as disintegration aids in phosphate-containing washing and Detergent tablets.

Also in the use according to the invention, the above for the fiction moderate detergent tablets and the inventive method as preferred marked embodiments preferred. Another preferred Ge  The object of the present invention is therefore the use of zeolite as disinte Gration aids in phosphate-containing detergent tablets. This Use of zeolite according to the invention leads to moldings with advantageous properties as shown in the examples below. Regarding preferred execution Form the use according to the invention (particle sizes, other ingredients, zu composition of the premix etc.) applies analogously to the above for the invention procedure said. The use provides a particularly preferred embodiment of zeolites in amounts of 1 to 9 wt .-% as disintegration aid in washing and Detergent tablets, the phosphate contents between 10 and 95 wt .-% sen, before.  

Examples

By pressing two different premixes, two-layer rectangular shaped bodies were produced, which consisted of 68% by weight of lower and 32% by weight of upper phase. The composition of the upper phase was designed once according to the invention (molded body E), in the comparative molded bodies V the use of zeolite was dispensed with and instead only phosphate was used. The composition of the lower phase was identical for both shaped bodies E and V. The following table shows the composition (in% by weight, based on the respective premix) of the three premixes and thus of the two different two-phase moldings:

The disintegration rate and the solubility of the shaped bodies were measured in a beaker glass equipment determined. A 20 g tablet was balanced in a Basket held in a beaker with a liter of water at 50 ° C, in which a pro The electric stirrer rotated at 800 revolutions per minute. Since the basket is balanced, the decay rate results from the loss of mass. The solubility was  determined by conductivity measurement, the conductivity value after 40 minutes as 100% was defined and the determined values were hereby standardized.

The results of these tests are shown in the table below, in which the solubility data in% (the final conductivity) and the decay data in g (quantity already decayed) are summarized.

The table shows that the shaped bodies E according to the invention in which the upper phase is a has composition according to the invention, disintegrate faster and dissolve better. While the molded body E according to the invention after 20 minutes completely by Baskets have fallen (= disintegrated) and are dissolved, the comparison tablets need to be broken fall 25 minutes and only fully dissolved after 30 minutes.

Claims (19)

1. laundry detergent and cleaning product tablets , containing builders and bleaches and optionally further conventional ingredients of cleaning products, characterized in that the phosphate (s) content in the tablets is 20 to 95% by weight and the tablets further 0.1 to 9 % By weight of a finely divided excipient with an average particle size below 100 microns. 2. Detergent tablets according to claim 1, characterized in that the finely divided excipient has an average particle size below 40 microns preferably has less than 20 microns and in particular less than 10 microns. 3. Detergent tablets according to one of claims 1 or 2, characterized characterized in that the finely divided excipient is essentially water-insoluble. 4. Detergent or cleaning product tablet according to one of claims 1 to 3, characterized characterized in that the moldings contain zeolite as a finely divided auxiliary. 5. Detergent tablets according to one of claims 1 to 4, characterized characterized in that, based in each case on the shaped body, 0.25 to 7.5% by weight, preferably 0.5 to 5% by weight and in particular 1 to 3% by weight of zeolite, preferably two Se zeolite X, Y and / or P contain. 6. Detergent tablets according to one of claims 1 to 5, characterized characterized in that the phosphate (s) content is 30 to 92.5% by weight, preferably 40 up to 90 wt .-% and in particular 50 to 85 wt .-%, each based on the molding per, is. 7. Detergent tablets according to one of claims 1 to 6, characterized characterized in that they have total surfactant contents below 5% by weight, preferably  below 4% by weight, particularly preferably below 3% by weight and in particular which have less than 2% by weight, based in each case on the shaped body. 8. Detergent tablets according to one of claims 1 to 7, characterized characterized in that they contain bleaches from the group of oxygen or halogen Bleaching agents, in particular chlorine bleaching agents, with particular preference for Sodium perborate and sodium percarbonate, in amounts of 2 to 25% by weight, preferably as from 5 to 20 wt .-% and in particular from 10 to 15 wt .-%, each based on the molded body. 9. Detergent tablets according to one of claims 1 to 8, characterized characterized in that they bleach activators from the groups of multiple acylated Alkylenediamines, in particular tetraacetylethylenediamine (TAED), the N-acylimides, in particular N-nonanoylsuccinimide (NOSI), the acylated phenol sulfonates, in particular special n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) and n- Methyl morpholinium acetonitrile methyl sulfate (MMA), in amounts from 0.25 to 15% by weight, preferably from 0.5 to 10% by weight and in particular from 1 to 5% by weight, each based on the molded article. 10. Detergent tablets according to one of claims 1 to 9, characterized characterized in that they contain silver protection agents from the group of the triazoles, the benzotria zoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and over gear metal salts or complex, particularly preferably benzotriazole and / or alky laminotriazole, in amounts of 0.01 to 5% by weight, preferably 0.05 to 4% by weight and in particular from 0.5 to 3% by weight, based in each case on the shaped body ten. 11. Detergent tablets according to one of claims 1 to 10, characterized characterized in that they continue to contain one or more substances from the groups of En enzymes, corrosion inhibitors, scale inhibitors, cobuilders, colors and / or fragrances  in total amounts from 6 to 30 wt .-%, preferably from 7.5 to 25 wt .-% and ins contains in particular from 10 to 20% by weight, in each case based on the weight of the shaped body. 12. Process for the production of detergent tablets by Ver pressing a particulate premix in a manner known per se, thereby ge indicates that the premix phosphate (s) in amounts of 20 to 95 wt .-% and a finely divided excipient with an average particle size below 100 μm, preferably below 40 µm, particularly preferably below 20 µm and ins particularly contained below 10 microns in amounts of 0.1 to 9 wt .-%. 13. The method according to claim 12, characterized in that the premix zeolite in Contains amounts of 0.1 to 9 wt .-%. 14. The method according to any one of claims 12 or 13, characterized in that the Particulate premix a bulk density above 600 g / l, preferably has above 700 g / l and in particular above 800 g / l. 15. The method according to any one of claims 12 to 14, characterized in that the part Chen-shaped premix has a particle size distribution in which less than 10% by weight, preferably less than 7.5% by weight and in particular less than 5 wt .-% of the particles are larger than 1600 microns or smaller than 200 microns. 16. The method according to claim 15, characterized in that the particulate pre mixture has a particle size distribution in which more than 30% by weight preferably more than 40% by weight and in particular more than 50% by weight of the particles ne particle size between 600 and 1000 microns. 17. Use of preferably water-insoluble substances with medium particle size ß below 100 microns, preferably below 40 microns, particularly preferred below 20 µm and in particular below 10 µm as disintegration aid medium in phosphate-containing detergent tablets.   18. Use of zeolite as disintegration aid in phosphate-containing washing and detergent tablets. 19. Use of zeolites in amounts of 1 to 9 wt .-% as disintegration aid medium in detergent tablets, the phosphate content between 10 and 95% by weight.