WO2001004256A1 - Shaped detergent bodies, especially 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

 "Detergent tablets, in particular for machine dishwashing"

The present invention relates to detergent tablets which contain builders and bleaches. In particular, the invention relates to detergent tablets for automatic dishwashing which are wholly or partially accelerated to dissolve.

Detergent tablets are widely described in the prior art and are becoming increasingly popular with consumers because of the simple dosage. Tableted detergents have a number of advantages over powdered detergents: they are easier to dose and handle and, due to their compact structure, have advantages for storage and transport. Detergent tablets are consequently also comprehensively described in the patent literature. A problem that occurs again and again when using cleaning-active shaped articles is the too slow disintegration and dissolving speed of the shaped articles under application conditions. Since sufficiently stable, i.e. Shaped and unbreakable moldings can only be produced by relatively high compression pressures, there is a strong compression of the molded body components and a consequent delayed disintegration of the molded body in the aqueous liquor and thus to a slow release of the active substances in the cleaning process.

In the field of detergents or cleaning agents, according to the teaching of the European patent EP-B-0 523 099, it is also possible to use the disintegrants which are known from the manufacture of pharmaceuticals. Swellable ones are mentioned as disintegrants Layered silicates such as bentonites, natural substances and natural substance derivatives based on starch and cellulose, alginates and the like, potato starch, methyl cellulose and / or hydroxypropyl cellulose. These disintegrants can be mixed with the granules to be compressed, but can also be incorporated into the granules to be compressed.

International patent application WO-A-96/06156 also states that the incorporation of disintegrants in detergent or cleaning agent tablets can be advantageous. Again, microcrystalline cellulose, sugars such as sorbitol, but also sheet silicates, in particular finely divided and swellable sheet silicates of the bentonite and smectite type, are mentioned as typical disintegrants. Substances contributing to gas formation such as citric acid, bisulfate, bicarbonate, carbonate and percarbonate are also listed as possible disintegration aids.

According to EP-A-0 711 827, the use of particles, which predominantly consist of citrate, which has a certain solubility in water, also leads to an accelerated disintegration of the tablets. It is believed that the dissolution of the citrate locally increases the ionic strength during a transition period, which suppresses the gelling of surfactants and, as a result, does not hinder the disintegration of the tablet. According to this patent application, citrate is therefore not a classic explosive, but serves as an anti-gelling agent.

Detergent tablets which contain cellulose-based disintegrants in granular or, if appropriate, cogranulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent applications WO98 / 40462 (Stefan Herzog) and WO98 / 40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants.

The proposed solutions lead to the desired success in the manufacture of pharmaceutical tablets. In the area of detergents and cleaning agents, they do contribute to an improvement in the disintegration properties of tablets that are active in washing or cleaning; however, the improvement achieved is not sufficient in many cases. In addition, the use of the proposed disintegrants in cleaning-active moldings for automatic dishwashing can lead to specific problems which are completely unknown to drugs or detergents.

The object of the invention was to provide a disintegration aid for cleaning-active moldings which on the one hand shortens the disintegration time of the molding or parts of the molding in household dishwashers, but on the other hand can be easily incorporated into the mixtures to be pressed without losing its effective shape. Compared to the explosives described in the prior art, the effectiveness should not be limited to the disintegration effect, rather the aid should, if possible, take on further tasks in the cleaning process.

It has now been found that the addition of small amounts of finely divided, preferably substantially water-insoluble auxiliaries, in particular zeolite, to phosphate-containing detergent tablets accelerates the solubility of individual phases or of the entire tablet.

The invention relates to laundry detergent and cleaning product tablets which contain builders and bleaches and, optionally, other customary ingredients of cleaning agents and in which the phosphate (s) content in the molding is 20 to 95% by weight, the molding also being 0.1 to Contain 9 wt .-% of a finely divided excipient with an average particle size below 100 microns.

The finely divided adjuvants are preferably used in an even finer form, so that preferred detergent tablets are characterized in that the finely divided adjuvant has an average particle size below 40 μm, preferably below 20 μm and in particular below 10 μm. The particle size distribution of the auxiliary used is the essential feature for the success of the present invention, the type of auxiliary used only playing a subordinate role. However, it has been found that substances with lower water solubility surprisingly produce better effects, so that the finely divided excipient is essentially water-insoluble in preferred detergent tablets.

In the context of the present invention, the term “essentially water-insoluble” denotes substances whose solubility in water is negligibly low. A maximum of milligram amounts in one liter of water dissolve from such substances with negligible water solubilities.

In addition to pyrogenic silicas, zeolite in particular has proven to be particularly suitable from the group of finely divided, preferably water-insoluble auxiliaries. Particularly preferred detergent tablets according to the invention contain zeolite as the finely divided auxiliary.

The following is a description of the most important ingredients of the detergent tablets according to the invention.

Phosphates are used in particular in machine dishwashing detergents as builders, but their use is also advantageously possible in detergents, provided that such use should not be avoided for ecological reasons. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have 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 lime 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 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 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 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 ) and is light soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ^ PO ^ 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. Disodium hydrogenphosphate is lost 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 that like a dodecahydrate a density of 1.62 ^"3 and a melting point of 73-76 ° C (decomposition), as a 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 ), a density of 2.536 ^"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 ß, deliquescent, granular powder with a density of 2.56 ^"3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises, for example, when Thomas slag is heated with carbon and potassium sulfate. Despite the higher price, the Detergent industry preferred the more easily soluble, therefore highly effective, potassium phosphates over corresponding sodium compounds.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , 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), 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 ^"3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.

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

The technically important pentasodium triphosphate, Na ₅ P ₃ O _{] 0} (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] that crystallizes with 6 H ₂ O. _n -Na with n = 3. Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 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 manufacture of Pentasodium triphosphate is reacted with sodium hydroxide 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 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.

The detergent tablets according to the invention contain the phosphate (s) in amounts of 20 to 95% by weight, based in each case on the tablet. In preferred detergent tablets, the phosphate (s) content is 30 to 92.5% by weight, preferably 40 to 90% by weight and in particular 50 to 85% by weight, based in each case on the tablet.

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 fine crystalline, synthetic and bound water-containing zeolite used is preferred Zeolite A and / or X, Y or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. Is commercially available and preferred within the scope of the present invention is used, for example, a co-crystallizate of zeolite X and zeolite A (ca. 80 wt .-% zeolite X) which is marketed by CONDEA Augusta SpA under the trade name VEGOBOND AX ^® and through 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 quantities given relate to the anhydrous, i.e. 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, this network being occupied 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 uptake.

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" connect 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 which is referred to as "ß". With these units various different zeolites can be realized. To date, 34 natural zeolite minerals and around 100 synthetic zeolites are known.

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

Zeolites of the faujasite type are preferably used according to the invention. Together with the zeolites X and Y, the mineral faujasite belongs to the faujasite types within the zeolite structure group 4, which is 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). In addition to the faujasite types mentioned, the zeolite structure group 4 also includes the minerals chabazite and gmelinite as well as the synthetic zeolites R (chabazite type), S (gmelinite type), L and ZK-5. The latter two synthetic zeolites have no mineral analogues.

Faujasite-type zeolites are made up of ß-cages which are tetrahedral linked by D6R subunits, the ß-cages being arranged similar to the carbon atoms in the diamond. The three-dimensional network of the zeolites of the faujasite type 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 approximately 13 Å and can be determined using 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: about 48% o void volume, faujasite: about 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 of the faujasite type” denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4. In addition to the zeolite X, zeolite Y and faujasite and mixtures of these compounds can also be used according to the invention with preference, the pure zeolite X being preferred.

Mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites, which do not necessarily have to belong to the zeolite structural group 4, can also be used according to the invention.

The aluminum silicates which are used according to the invention are commercially available and the methods for their preparation 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 ] x H ₂ O,

K ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] x H ₂ O,

Ca ₄₀ Na ₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] x H ₂ O,

Sr ₂₁ Ba ₂₂ [(AlO ₂ ) ₈₆ (SiO ₂ ) _I06 ] ^■ x H ₂ O,

in which x can have values between 0 and 276 and the pore sizes range 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 ] x H ₂ O, K ₅₆ [(AlO ₂ ) ₅₆ (SiO ₂ ) ₁₃₆ ] x H ₂ O,

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

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

In addition to phosphate (s) and zeolite in the amounts mentioned, the detergent tablets according to the invention can contain further builders, some of which can also serve as alkali carriers. Silicates, carbonates, carboxylates, in particular citrates and polymers, which are described below, should be mentioned here in particular.

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 is sodium and x is 2 or 3. In particular Both β- and δ-sodium disilicate Na ^ Os' 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 Na ^: SiO ₂ modulus 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 / compression or by overdrying. In the context of this invention is under the term "amorphous" also understood as "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 as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. 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. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

Particularly suitable carbonates are alkali metal carbonates and bicarbonates, the sodium salts and among them the anhydrous sodium carbonate (“calcined soda”) being of particular importance. Sodium carbonate decahydrate, sodium hydrogen carbonate, potassium carbonate, potassium carbonate 1,5-water (“potash hydrate”), potassium hydrogen carbonate and mixtures thereof can also be used.

Polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphates can be used as organic cobuilders in the laundry detergent tablets according to the invention. These classes of substances are described below.

Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which 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, ammocarboxylic acids, nitrilotriacetic acid (NTA), provided such use is not objectionable for ecological reasons, and mixtures from 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, 50 to Contain 90% by weight> acrylic acid and 50 to 10% by weight maleic acid. 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 made from dialde hyden such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained from 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, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 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 action of a polysaccharide compared to dextrose, which has a DE of 100 owns. 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 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 as well as 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. An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

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

In addition to the builders, substances from the groups of surfactants, bleaching agents, bleach activators, corrosion inhibitors and dyes and fragrances are particularly important ingredients of cleaning agents. Important representatives from the substance classes mentioned are described below. Preferred detergent tablets furthermore contain one or more surfactant (s). Anionic, nonionic, cationic and / or amphoteric surfactants or mixtures of these can be used in the detergent tablets according to the invention. Mixtures of anionic and nonionic surfactants are preferred from an application point of view. The total surfactant content of the moldings is 5 to 60% by weight, based on the weight of the moldings, surfactant contents above 15% by weight being preferred in the case of detergent tablets and detergent tablets for machine dishwashing usually containing less than 3% by weight> 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, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from C ₁₂ . ₁₈ -monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products into consideration. Alkanesulfonates derived from C _{) 2} are also suitable. ₁₈ -alkanes can be obtained, 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 sulfonated fatty acid glycerol esters are the sulfonation 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. Alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half-esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or 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 which is produced 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 ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C, ₄ -C ₁₅ alkyl sulfates are preferred for reasons of washing technology. 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 straight-chain or branched C ₇ ethoxylated with 1 to 6 mol of ethylene oxide. ₂₁ alcohols, such as 2-methyl-branched C ₉ . _n -Alcohols with an average of 3.5 moles 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 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 soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.

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.

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. 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 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. The preferred ethoxylated alcohols include, for example, C _ι2 . ₁₄ - alcohols with 3 EO or 4 EO, C ₉ . _n - 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 of these, such as mixtures of C ₁₂ . ₁₄ -alcohol with 3 EO and C _I2 .ι ₈ -alcohol with 5 EO. The degrees of ethoxylation indicated are statistical Mean values that 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 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, C 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 ^J

R-CO-N-rZ] (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 (I)

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 ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical is or an oxyalkyl group having 1 to 8 carbon atoms, where C, _ ₄ - alkyl or phenyl groups being preferred, and [Z] is a linear polyhydroxyalkyl residue, whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this rest.

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

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

Detergent tablets preferred in the context of the present invention have total surfactant contents below 5% by weight, preferably below 4% by weight, particularly preferably below 3% by weight and in particular below 2% by weight. 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 supply H ₂ O ₂ in water. Further bleaching agents that can be used 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 bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and 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 monoperphate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimoxyhexoxy acid [ PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocyseboxyacidoxy acid, diperoxyacid, Decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Substances which release chlorine or bromine can also be used as bleaching agents in detergent tablets according to the invention for machine dishwashing. Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric 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 bleaching agents are usually used in machine dishwashing detergents in amounts of 1 to 30% by weight, preferably 2.5 to 20% by weight and in particular 5 to 15% by weight, based in each case on the detergent , Detergent tablets preferred in the context of the present invention contain bleaches from the group of oxygen or halogen bleaches, in particular chlorine bleaches, with particular preference for sodium perborate and sodium percarbonate, in amounts of 2 to 25% by weight, preferably of 5 up to 20 wt .-% and in particular from 10 to 15 wt .-% each based on the molded body.

Bleach activators that support the action of the bleaching agents can also be part of the detergent tablets according to the invention. Known bleach activators are compounds which contain one or more N- or O-acyl groups, such as substances from the class of the anhydrides, the esters, the imides and the acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-l, 3,5-triazine DADHT and isatoic acid

Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid become. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetyloxy, 2,5-acetiacetyl, ethylene glycol 2,5-dihydrofuran, n-methyl-Mo holinium-acetonitrile-methyl sulfate (MMA), and the enol esters known from German patent applications DE 196 16 693 and DE 196 16 767, as well as acetylated sorbitol and mannitol or their mixtures (SORMAN), acylated Sugar derivatives, in particular pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose as well as acetylated, optionally N-alkylated gluc amine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam. Hydrophilically substituted acylacetals and acyllactams are also preferably used. Combinations of conventional bleach activators can also be used. The bleach activators are usually used in machine dishwashing detergents in amounts of 0.1 to 20% by weight, preferably 0.25 to 15% by weight> and in particular 1 to 10% by weight>, in each case based on the detergent, used. In the context of the present invention, the proportions mentioned relate to the weight of the base molding.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be incorporated into the base tablets. 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. Bleach activators from the group of multiply acylated alkylenediamines, in particular tetraacetylethylene diamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (N-) or iso-NOBs iso , n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), preferably in amounts up to 10% by weight>, in particular 0.1% by weight> to 8% by weight o, especially 2 to 8% by weight and particularly preferably 2 to 6 wt .-%> based on the total agent used.

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

Preferred detergent tablets contain bleach activators from the groups of the multiple acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), the N-acylimides, in particular N-nonanoylsuccinimide (NOSI), the acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxy-n-benzene sulfonate or iso-NOBS) and n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), in amounts of 0.25 to 15% by weight>, preferably 0.5 to 10% by weight> and in particular 1 to 5 % By weight>, in each case based on the shaped body.

The detergent tablets according to the invention can contain corrosion inhibitors to protect the wash ware or the machine, silver protection agents in particular being of particular importance in the field of automatic dishwashing. The known substances of the prior art can be used. In general, silver protection agents in particular can be selected from the group consisting of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or Complexes are used. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. In addition, active chlorine-containing agents are often found in cleaner formulations, which can significantly reduce the corroding of the silver surface. In chlorine-free cleaners, especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preferred here are the transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of 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 alkylaminotriazoles and the transition metal salts or complexes, particularly preferably benzotriazole and / or alkylaminotriazole, in amounts of 0.01 to 5% by weight .-%>, preferably from 0.05 to 4 wt .-% and in particular from 0.5 to 3 wt .-%>, each based on the molded body.

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

Particularly suitable enzymes are those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as stains containing protein, fat or starch. Oxidoreductases can also be used for bleaching. Bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyceus are particularly suitable 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. Here are enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytically active enzymes or of protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes, but especially 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.

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. Preferred detergent tablets in the context of the present invention are characterized in that they contain protease and / or amylase.

Dyes and fragrances can be added to the detergent tablets according to the invention in order to improve the aesthetic impression of the resulting products and to provide the consumer with a visually and sensorially "typical and unmistakable" product in addition to performance. 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 isobutylate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl benzyl propylate and styl. The ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and Bourgeonal, the ketones such as the jonones, α-isomethylionone and methyl cedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are 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, lentil flower oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

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.

In order to improve the aesthetic impression of the agents according to the invention, it (or parts thereof) 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 to the substrates to be treated with the compositions, such as glass, ceramics or plastic dishes, so as not to stain them.

Preferred detergent tablets in the context of the present invention further comprise one or more substances from the groups of enzymes, corrosion inhibitors, scale inhibitors, cobuilders, colorants and / or fragrances in total amounts of 6 to 30% by weight, preferably of 7, 5 to 25 wt .-%> and in particular from 10 to 20 wt .-%>, each based on the weight of the molding.

The above information was based on a shaped body, the present invention being not restricted to the fact that only single-phase shaped bodies are provided. Rather, it is also possible for only individual phases, preferably layers, to have a composition according to the invention and thereby achieve the advantages mentioned. be enough. In this way it is possible, for example, to produce a two-layer tablet, one layer of which - based on the layer - contains 0.1 to 9% by weight of zeolite and 20 to 95% by weight of phosphate (s), while the other layer can be free of zeolite and / or phosphate. In this way, the dissolution of one layer compared to another layer can be accelerated in time. Of course, the portion of the molded body which has the composition according to the invention is not bound to the layer shape. 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), also the form of rings, cores, jackets, Have pearls, etc. In this way, ring-core tablets, coated tablets, tablet tablets, etc. can be produced in which all phases or only some of the phases have the composition according to the invention and consequently dissolve more quickly.

Accordingly, in the production of the detergent tablets according to the invention, one is not restricted to the fact that only a particulate premix is pressed into a tablet. Rather, the molded body can also be designed in such a way that multilayer molded bodies are produced in a manner known per se by preparing two or more premixes which are pressed onto one another. In this case, the premix which has been filled in first is not or only slightly pre-pressed in order to obtain a smooth top surface which runs parallel to the mold body bottom, and after the second premix is filled in, the end mold is pressed to the finished mold body. In the case of three-layer or multi-layer molded bodies, a further preliminary molding is optionally carried out after each premix addition, before the molded body is finally pressed after adding the last premix.

Due to the increasing technical complexity, a maximum of two-layer molded articles are preferred in practice, that is to say detergent molded articles are preferred in which the molded article is a two-layer tablet. Already in this intermediate step in the method according to the invention, advantages can be achieved from the division of certain ingredients into the individual layers. For example, detergent tablets are preferred in which one layer contains one or more bleaches and the other layer contains one or more enzymes. Not only this separation of bleaching agents and enzymes can bring advantages, the separation of bleaching agents and optional bleach activators can also be advantageous, so that detergent tablets according to the invention are preferred in which one layer contains one or more bleaching agents and the other one or more bleach activators contains.

In the following information on the further subject matter of the present invention, the manufacture of a partial area of the molded body with a corresponding composition is also included, even if this is not explicitly mentioned in each case.

Another object of the present invention is a process for the production of detergent tablets by pressing a particulate premix in a manner known per se, in which the premix contains phosphate (s) in amounts of 20 to 95% by weight and a finely divided auxiliary with an average particle size below 100 μm, preferably below 40 μm, particularly preferably below 20 μm and in particular below 10 μm in quantities of 0.1 to 9% by weight.

The above information on preferred properties of the auxiliaries used according to the invention (water solubility, amount, type, etc.) apply to the process according to the invention in a completely analogous manner. Again, the use of zeolite is particularly preferred, so that preferred processes are characterized in that the premix contains zeolite in amounts of 0.1 to 9% by weight.

Analogous to the information given above regarding the shaped bodies according to the invention, the preferred embodiments mentioned there (amounts of further ingredients, substances used, physical parameters etc.) are also preferred in the method according to the invention. The premix can, as described above in the description of the molded body, be composed of a wide variety of substances. Regardless of the composition of the premixes to be milled, physical parameters of the premixes can be selected so that advantageous molded-body properties result.

Thus, in preferred variants of the first method according to the invention, the particulate premix has a bulk density above 600 g / 1, preferably above 700 g / 1 and in particular above 800 g / 1.

The particle size in the premixes to be measured can also be adjusted in order to obtain advantageous shaped body properties. In preferred variants for the process according to the invention, 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 are larger than 1600 μm or smaller than 200 μm. Narrower particle size distributions are further preferred here. Particularly 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 have between 600 and 1000 μm.

When carrying out the method according to the invention, one is not restricted to the fact that only a particulate premix is pressed into a molded body. Rather, the method can also be expanded to the effect that multilayer molded bodies are produced in a manner known per se by preparing two or more premixes which are pressed onto one another. In this case, the premix which has been filled in first is lightly pre-pressed in order to obtain a smooth upper surface which runs parallel to the mold body bottom, and after the second premix is filled in the finished mold body is finally pressed. In the case of three- or multi-layer molded bodies, a further preliminary molding is optionally carried out after each premix addition, before the molded body is finally pressed after adding the last premix. Analogous to the above statements, methods are also preferred in this process variant in which two-layer molded bodies are produced by pressing two different particulate premixes onto one another, one of which contains one or more bleaching agents and the other one or more enzymes. Again analogously, processes are also preferred in which two-layer moldings are produced by pressing two different particulate premixes onto one another, one of which contains one or more bleaching agents and the other one or more bleach activators. Here too, methods are preferred which are characterized in that the molded body produced contains protease and / or amylase.

The moldings according to the invention are produced as described in principle above, first by dry mixing the constituents, which can be wholly or partly pregranulated, and then providing information, in particular pressing them into tablets, whereby conventional methods can be used. To produce the shaped bodies according to the invention, the premix (or, in the case of multi-phase shaped bodies, the premixes) is compressed into a solid compact in a so-called die between two punches. 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 resulting molded body 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, at which the particles flow together and the formation of the molded body occurs. 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 stamp or stamps are attached 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 disk, the number of die holes being increased 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 matrix table and the Stamps move around a common vertical axis, whereby the stems are brought into the positions for filling, compression, plastic deformation and ejection with the help of rail-like curved tracks during circulation. At locations where a particularly serious lifting or lowering of the punches is required (Beftillen, compression, ejection), 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. Through suitable process management, 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 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, IMA 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). For example, the hydraulic double pressure press HPF 630 from LAEIS, D. Tablettierwerkzeuge are, for example, from the companies Adams Tablettierwerkzeuge, Dresden, Wilhelm Fett 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 rod 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 covers the presentation form from the tablet to compact cylinder pieces with a ratio of height to diameter above 1.

The portioned compacts can each be designed as separate individual elements that correspond to the predetermined dosage of the detergents and / or cleaning agents. It is also possible, however, to form compacts which connect a plurality of such mass units in one compact, the portioned smaller units being easy to separate, in particular by predetermined predetermined breaking points. For the use of laundry detergents in machines of the type customary in Europe with horizontally arranged mechanics, the portioned compacts as tablets, in cylinder or cuboid form can be expedient, with a diameter / height ratio in the range from about 0.5: 2 to 2: 0.5 is preferred. Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for the production of such pressed articles.

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" shaped body detergent can also be used in other geometric Shapes, for example vertically standing triangles, which are connected to one another only on one of their sides, are realized.

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 moldings that mutually influence one another 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, 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).

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, with at least one peroxy bleaching agent being contained in at least one of the inner layers, 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.

Similar effects can also be achieved by coating individual constituents of the detergent and cleaning agent composition to be treated or the entire molded article. For this purpose, the bodies to be coated can be coated with, for example aqueous solutions or emulsions are sprayed, or else a coating is obtained via the process of melt coating.

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 πDt

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.

Another object of the present invention is the use of preferably water-insoluble substances with average particle sizes below 100 microns, preferably below 40 microns, particularly preferably below 20 microns and in particular below 10 microns as disintegration aids in phosphate-containing detergent tablets

In the use according to the invention, the embodiments characterized above as preferred for the detergent tablets according to the invention and the method according to the invention are preferred. Another preferred object of the present invention is therefore the use of zeolite as disintegration aid in phosphate-containing detergent tablets. This use of zeolite according to the invention leads to molded articles with advantageous properties, as the examples below show. With regard to preferred embodiments of the use according to the invention (particle sizes, further ingredients, composition of the premix, etc.), what has been said above for the method according to the invention applies analogously. The use provides a particularly preferred embodiment of zeolites in amounts of 1 to 9% by weight as disintegration aids in detergent tablets which have phosphate contents between 10 and 95% by weight.

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 outer phase was designed once according to the invention (molded body E), in the comparison molded body V the use of zeolite was dispensed with and instead only phosphate was used. The composition of the bottom phase was identical for both molded 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 shaped bodies:

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

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

The table shows that the molded body E according to the invention, in which the outer phase has a composition according to the invention, disintegrate faster and dissolve better. While the shaped body E according to the invention fell completely through the basket after 20 minutes (= disintegrated) and dissolved, the comparison tablets required 25 minutes to disintegrate and only completely dissolved after 30 minutes.

Claims

claims:

1. washing and cleaning agent shaped body, containing builders and bleaching agents and optionally further conventional ingredients of cleaning agents, characterized in that the content of the shaped body of phosphate (s) is 20 to 95% by weight> and the shaped body continues to be 0.1 to 9 % By weight> of a finely divided excipient with an average particle size below 100 μm.

2. Detergent and molded article according to claim 1, characterized in that the finely divided auxiliary has an average particle size below 40 microns, preferably below 20 microns and in particular below 10 microns.

3. Detergent and shaped body according to one of claims 1 or 2, characterized in that the finely divided auxiliary is essentially water-insoluble.

4. washing or cleaning agent shaped body according to one of claims 1 to 3, characterized in that the shaped body contain zeolite as a finely divided auxiliary.

5. Detergent and molded article according to one of claims 1 to 4, characterized in that, based in each case on the molded article, 0.25 to 7.5% by weight>, preferably 0.5 to 5% by weight> and in particular 1 to 3 wt .-% zeolite, preferably zeolite X, Y and / or P contain.

6. Detergent form according to one of claims 1 to 5, characterized in that the content of phosphate (s) 30 to 92.5 wt .-%>, preferably 40 to 90 wt .-%> and in particular 50 to 85 % By weight, based in each case on the shaped body, is.

7. Detergent and molded article according to one of claims 1 to 6, characterized in that it preferably has total surfactant contents below 5% by weight> below 4% by weight>, particularly preferably below 3% by weight and in particular below 2% by weight>, in each case based on the molded article.

8. Detergent form according to one of claims 1 to 7, characterized in that they contain bleaches from the group of oxygen or halogen bleaches, in particular chlorine bleaches, with particular preference for sodium perborate and sodium percarbonate, in amounts of 2 to 25% by weight .-%>, preferably from 5 to 20 wt .-%> and in particular from 10 to 15 wt .-%, each based on the molded body.

9. washing and cleaning agent form according to one of claims 1 to 8, characterized in that they bleach activators from the groups of polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), N-acylimides, especially N-nonanoylsuccinimide (NOSI), the acylated phenolsulfonates , in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS) and n-methyl-Moφholinium-acetonitrile-methyl sulfate (MMA), in amounts of 0.25 to 15 wt .-%>, preferably of 0.5 up to 10 wt .-%> and in particular from 1 to 5 wt .-%>, each based on the molded body.

10. Detergent form according to one of claims 1 to 9, characterized in that it contains silver protection agents from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes, particularly preferably benzotriazole and / or alkylaminotriazole, in amounts of from 0.01 to 5% by weight, preferably from 0.05 to 4% by weight> and in particular from 0.5 to 3% by weight>, in each case based on the molded article ,

11. Detergent form according to one of claims 1 to 10, characterized in that it further comprises one or more substances from the groups of enzymes, corrosion inhibitors, scale inhibitors, cobuilders, dyes and / or fragrances in total amounts from 6 to 30% by weight, preferably from 7.5 to 25% by weight> and in particular from 10 to 20% by weight>, in each case based on the molded body weight.

12. A process for the production of detergent tablets by pressing a particulate premix in a manner known per se, characterized in that the premix contains phosphate (s) in amounts of 20 to 95% by weight and a finely divided auxiliary with a average particle size below 100 μm, preferably below 40 μm, particularly preferably below 20 μm and in particular below 10 μm in amounts of 0.1 to 9% by weight.

13. The method according to claim 12, characterized in that the premix contains zeolite in 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 has a bulk density above 600 g / 1, preferably above 700 g / 1 and in particular above 800 g / 1.

15. The method according to any one of claims 12 to 14, characterized in that the particulate premix has a particle size distribution in which less than 10 wt .-%>, preferably less than 7.5 wt .-%> and in particular less than 5 wt .-%) of the particles are larger than 1600 μm or smaller than 200 μm.

16. The method according to claim 15, characterized in that the particulate premix has a particle size distribution in which more than 30 wt .-%, preferably more than 40 wt .-%> and in particular more than 50 wt .-%> of the particles Have particle size between 600 and 1000 microns.

17. Use of preferably water-insoluble substances with average particle sizes below 100 μm, preferably below 40 μm, particularly preferably below 20 μm and in particular below 10 μm as disintegration aids in phosphate-containing detergent tablets

18. Use of zeolite as disintegrant in phosphate-containing detergent tablets

19. Use of zeolites in amounts of 1 to 9% by weight as disintegration aids in detergent tablets which have phosphate contents between 10 and 95% by weight.