EP1188820A1 - Shaped detergent bodies with a polyurethane coating - Google Patents

Abstract

Detergent tablets with a polyurethane coating based on di-isocyanates and diols which consist at least partly of polyethylene glycols and/or polypropylene glycols with 5-20000 alkylene oxide units. Washing or cleaning (detergent) tablets comprising compressed detergent particles containing builders and optionally other components are provided with a coating containing polyurethanes derived from diisocyanates of formula (I) and diols of formula (II) which consist at least partly of polyethylene glycols (IIa) and/or polypropylene glycols (IIb). R<1>,R<2> = optionally substituted, linear or branched 1-24C alkyl(ene), aryl(ene) or alkylaryl(ene); and n = 5-2000. An Independent claim is also included for a method for the production of these tablets by compressing particles of a detergent composition and then coating the tablets by immersion in or spraying with a melt, solution or dispersion of polyurethane(s) as described above.

Description

The present invention is in the field of compact molded articles which are washable. and have cleaning-active properties. Such detergent tablets include, for example, detergent tablets for washing textiles, Detergent tablets for automatic dishwashing or cleaning hard surfaces, bleach tablets for use in washing machines or dishwashers, Water softening tablets or stain tablets. In particular concerns the invention detergent tablets, for washing textiles in used in a household washing machine and briefly referred to as detergent tablets and detergent tablets for machine dishwashing.

Detergent tablets are widely described in the prior art are becoming increasingly popular with consumers because of the simple dosage. Tableted detergents and cleaning agents have a powdery one A number of advantages: They are easier to dose and handle and have due to its compact structure offers advantages for storage and transport. Also in the Patent literature, detergent tablets are therefore comprehensively described. A problem that occurs when using washing and cleaning active moldings occurs again and again, is the slow decay and dissolving speed of the molded body under application conditions. Since sufficiently stable, i.e. shape and break resistant Shaped bodies can only be produced by relatively high pressure, there is a strong compression of the molded parts and a consequent delayed disintegration of the shaped body in the aqueous liquor and thus too slow a release of the active substances in the washing or cleaning process. The delayed disintegration of the moldings has the further disadvantage that that conventional detergent tablets do not have the induction chamber Have it washed in by household washing machines as the tablets are not sufficient disintegrate faster into secondary particles that are small enough to get out of the induction chamber to be washed into the washing drum. Another problem, particularly with Detergent tablets occur, the friability of the tablets or their often insufficient stability against abrasion. Sufficient break-resistant, i.e. hard detergent tablets are often produced but this is the burden of packaging, transport and handling, i.e. Case and Rubbing stresses, not sufficiently grown, so that edge breakage and signs of abrasion affect the appearance of the molded body or even to one lead to complete destruction of the molded body structure.

To overcome the dichotomy between hardness, i.e. Transport and handling stability, and easy disintegration of the moldings are many solutions in the prior art has been developed. A well known in particular from pharmacy and in the field the detergent tablets form an extensive approach is incorporation certain disintegration aids that facilitate the access of water or upon access swell from water or develop gas or disintegrate in another form. Other proposed solutions from the patent literature describe the pressing of Premixing certain particle sizes, separating individual ingredients from certain other ingredients as well as the coating of individual ingredients or the entire molded body with binders.

The coating of detergent tablets, also in German Language usage is increasingly referred to as "coating" is the subject of some patent applications.

The European patent applications EP 846 754, EP 846 755 and EP 846 756 (Procter & Gamble) describe coated detergent tablets which comprise a "core" of compressed, particulate detergent and cleaning agent and a "coating", the coating materials being dicarboxylic acids, in particular Adipic acid may be used, which may contain other ingredients such as disintegration aids.

Coated detergent tablets are also the subject of European patent application EP 716 144 (Unilever). According to the information in this document, the hardness of the tablets can be increased by a "coating" without the disintegration and dissolving times being impaired. Film-forming substances, in particular copolymers of acrylic acid and maleic acid or sugar, and polyethylene glycols are mentioned as coating agents.

The proposed solutions disclosed in the prior art use coating materials, some of which are only hesitant in the later washing or cleaning process are solvable and in part only by adding disintegration aids must be made disintegrable. This way either stands at the beginning of the Cleaning cycle no or insufficient active substance available in the liquor, or a dosing over induction chambers of household washing machines is not given at no additional cost.

The present invention was based on the object, coated detergent tablets provide where the beneficial properties of higher hardness without impairing the short disintegration times with small amounts Coating agents can be achieved, such as coating materials Substances should be provided in addition to the mechanical protection of the molded body are readily soluble and / or disintegrable even without the addition of other auxiliaries. The Resistance of the molded body against falling and rubbing loads should be against the known moldings are achieved or further improved. Ideally, they should coated moldings with minimized packaging, i.e. with a cheaper one Individual packaging or even completely without individual packaging to the trade can be delivered without the storage stability of the molded article suffering as a result. An easy to carry out and universally applicable process for the production of such Providing coated moldings was a further object of the present Invention.

It has now been found that certain polyurethanes, at least as the diol component partly contain polyethylene or polypropylene glycols, also for coating of detergent tablets and these are advantageous Give properties.

und R¹ sowie R² unabhängig voneinander für einen substituierten oder unsubstituierten, geradkettigen oder verzweigten Alkyl-, Aryl- oder Alkylarylrest mit 1 bis 24 Kohlenstoffatomen und n jeweils für Zahlen von 5 bis 2000 stehen.The present invention relates to detergent tablets made from compressed particulate detergent and detergent, containing builders (e) and optionally further detergent and detergent components, the tablets being provided with a coating which comprises polyurethanes made from diisocyanates (I) and diols (II ) contains O = C = NR ¹ -N = C = O HOR ² -OH the diols being selected at least in part from polyethylene glycols (II a) and / or polypropylene glycols (II b) H- (O-CH ₂ -CH ₂ ) _n -OH

and R ¹ and R ² independently of one another represent a substituted or unsubstituted, straight-chain or branched alkyl, aryl or alkylaryl radical having 1 to 24 carbon atoms and n each number from 5 to 2000.

The detergent tablets according to the invention have a coating provided that contains certain polyurethanes. These polymers are as follows described in more detail.

• einem Di- oder Polyisocyanat (A) und
• einer Verbindung (B) mit mindestens 2 aktiven Wasserstoffatomen pro Molekül

Polyurethanes are polyadducts of at least two different types of monomers,

• a di- or polyisocyanate (A) and
• a compound (B) with at least 2 active hydrogen atoms per molecule

The polyurethanes contained in the coating of the moldings according to the invention are obtained from reaction mixtures in which at least one diisocyanate Formula (I) and at least one polyethylene glycol of the formula (II a) and / or at least a polypropylene glycol of formula (II b) are included.

The reaction mixtures can additionally contain further polyisocyanates. Also a Content of the reaction mixtures - and thus the polyurethanes - in other diols, triplets, Diamines, triamines, polyetherols and polyesterols are possible. The Compounds with more than 2 active hydrogen atoms usually only in small Amounts in combination with a large excess of 2 active compounds Hydrogen atoms used.

If additional diols etc. are added, certain proportions to those according to the invention are present mandatory polyethylene and / or polypropylene glycol units present in the polyurethane to consider. Detergent tablets are preferred here, in which at least 10% by weight, preferably at least 25% by weight, is particularly preferred at least 50% by weight and in particular at least 75% by weight of that in the polyurethane reacted diols are selected from polyethylene glycols (II a) and / or Polypropylene glycols (II b).

In addition to the special polyurethanes, the coating can contain other ingredients like others Coating materials or ingredients of washing and cleaning agents, in particular Dyes and / or fragrances or disintegrants. Prefers According to the invention, however, are detergent tablets in which the coating at least 10% by weight, preferably at least 25% by weight, particularly preferably at least 50% by weight and in particular at least 75% by weight of polyurethanes contains, with detergent tablets according to the invention particularly are preferred in which the coating consists entirely of polyurethane.

The polyurethanes used according to the invention as coating material contain diisocyanates of the formula (I) as the monomer unit. The diisocyanates used are predominantly hexamethylene diisocyanate, 2,4- and 2,6-toluenediisocyanate, 4,4'-methylene di (phenyl isocyanate) and in particular isophorone diisocyanate. These compounds can be described by the formula I listed above, in which R ^{1 represents} a connecting group of carbon atoms, for example a methylene-ethylene-propylene, butylene, pentylene, hexylene, etc. group. In the above-mentioned, most widely used hexamethylene diisocyanate (HMDI), R ¹ = (CH ₂ ) ₆ , in 2,4- or 2,6-toluenediisocyanate (TDI) R ^{1 is} C ₆ H ₃ -CH ₃ ) , in 4,4'-methylenedi (phenyl isocyanate) (MDI) for C ₆ H ₄ -CH ₂ -C ₆ H ₄ ), and in isophorone diisocyanate R ^{1 is} the isophorone residue (3,5,5-trimethyl-2-cyclohexenone ).

The polyurethanes used according to the invention as the coating material further contain diols of the formula (II) as a monomer unit, these diols at least partly originating from the group of polyethylene glycols (II a) and / or polypropylene glycols (II b). Polyethylene glycols are polymers of ethylene glycol that have the general formula (II a) H- (O-CH ₂ -CH ₂ ) _n -OH are sufficient, where n can have values between 5 and 2000. There are various nomenclatures for polyethylene glycols that can lead to confusion. The specification of the average relative molecular weight after the specification "PEG" is customary in technical terms, so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210. A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and directly after the hyphen is followed by a number which corresponds to the number n in the above-mentioned formula (II a). According to this nomenclature (known as INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997), for example, PEG-6, PEG-8, PEG-9, PEG-10 , PEG-12, PEG-14 and PEG-16 can be used as a monomer module. Polyethylene glycols are commercially available, for example, under the trade names Carbowax® PEG (Union Carbide), Emkapol® (ICI Americas), Lipoxol® MED (HÜLS America), Polyglycol® E (Dow Chemical), Alkapol® PEG (Rhone-Poulenc), Lutrol® E (BASF).

genügen, wobei n Werte zwischen 5 und 2000 annehmen kann. Polypropylene glycols (abbreviation PPG) are polymers of propylene glycol that have the general formula (II b)

are sufficient, where n can have values between 5 and 2000.

Both in the case of compounds of the formula (II a) and in the case of compounds of the formula (II b), such representatives are preferred monomer units in which the number n is a number between 6 and 1500, preferably between 7 and 1200, particularly preferred between 8 and 1000, more preferably between 9 and 500 and in particular between 10 and 200 stands. For certain applications, polyethylene and polypropylene glycols can be used of formulas (II a) and / or (II b) may be preferred, in which n is a number between 15 and 150, preferably between 20 and 100, particularly preferably between 25 and 75 and in particular between 30 and 60.

Examples of optional further in the reaction mixtures for the production of the polyurethanes contained compounds are ethylene glycol, 1,2- and 1,3-propylene glycol, butylene glycols, Ethylenediamine, propylenediamine, 1,4-diaminobutane, hexamethylenediamine and α, ω-diamines based on long-chain alkanes or polyalkylene oxides. invention Detergent tablets, in which the polyurethanes in the coating additional diamines, preferably hexamethylenediamine and / or hydroxycarboxylic acids, preferably dimethylolpropionic acid, are preferred.

To summarize these statements, particularly preferred detergent tablets are characterized in the context of the present invention in that the coating contains polyurethanes of diisocyanates (I) and diols (II) O = C = NR ¹ -N = C = O HOR ² -OH where R ¹ for a methylene-ethylene-propylene, butylene, pentylene group or for - (CH ₂ ) ₆ - or for 2,4- or 2,6-C ₆ H ₃ -CH ₃ , or for C ₆ H ₄ -CH ₂ -C ₆ H ₄ or isophorone (3,5,5-trimethyl-2-cyclohexenone) and R ^{2 is} selected from -CH2-CH2- (O-CH ₂ -CH ₂ ) _n - or -CH ₂ -CH ₂ - (O-CH (CH ₃ ) -CH ₂ ) _n - with n = 4 to 1999.

Depending on which reactants are reacted with each other to form the polyurethanes, the result is polymers with different structural units. Here, detergent tablets according to the invention are preferred, in which the polyurethanes in the coating have structural units of the formula (III) - [OC (O) -NH-R ¹ -NH-C (O) -OR ² ] _k - in which R ^{1 is} - (CH2) 6- or for 2,4- or 2,6-C ₆ H ₃ -CH ₃ , or for C ₆ H ₄ -CH ₂ -C ₆ H ₄ and R ^{2 is} selected is from -CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n - or - CH (CH ₃ ) -CH ₂ - (O-CH (CH ₃ ) -CH ₂ ) _n -, where n is a number from 5 to 199 and k is a number from 1 to 2000.

The diisocyanates described as preferred can be reacted with all the diols described as preferred to give polyurethanes, so that preferred detergent tablets according to the invention have a polyurethane coating which has one or more of the structural units (III a) to (III h): - [OC (O) -NH- (CH ₂ ) ₆ -NH-C (O) -O-CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n ] _k - - [OC (O) -NH- (2,4-C ₆ H ₃ -CH ₃ ) -NH-C (O) -O-CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n ] _k - - [OC (O) -NH- (2,6-C ₆ H ₃ -CH ₃ ) -NH-C (O) -O-CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n ] _k - - [OC (O) -NH- (C ₆ H ₄ -CH ₂ -C ₆ H ₄ ) -NH-C (O) -O-CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n ] _k - - [OC (O) -NH- (CH ₂ ) ₆ -NH-C (O) -O- CH (CH ₃ ) -CH ₂ - (O-CH (CH ₃ ) -CH ₂ ) _n ] _k - - [OC (O) -NH- (2,4-C ₆ H ₃ -CH ₃ ) -NH-C (O) -O-CH (CH ₃ ) -CH ₂ - (O-CH (CH ₃ ) - CH ₂ ) _n ] _k - - [OC (O) -NH- (2,6-C ₆ H ₃ -CH ₃ ) -NH-C (O) -O-CH (CH ₃ ) -CH ₂ - (O-CH (CH ₃ ) - CH ₂ ) _n ] _k - - [OC (O) -NH- (C ₆ H ₄ -CH ₂ -C ₆ H ₄ ) -NH-C (O) -O-CH (CH ₃ ) -CH ₂ - (O-CH (CH ₃ ) -CH ₂ ) _n ] _k - where n is a number from 5 to 199 and k is a number from 1 to 2000.

As already mentioned above, the reaction mixtures can be used in addition to diisocyanates (I) and diols (II) also other compounds from the group of polyisocyanates (in particular Triisocyanates and tetraisocyanates) and from the group of polyols and / or Di- or Polymaine included. In particular triols, tetrols, pentols and hexols as well as di- and triamines can be included in the reaction mixtures. A content of compounds with more than two "active" H atoms (all classes of substances mentioned above with the exception of the diamines) leads to a partial crosslinking of the polyurethane reaction products and can have advantageous properties such as controlling the Dissolving behavior, abrasion stability or flexibility of the coating, process advantages effect when applying the coating etc. The content is usually such Compounds with more than two "active" H atoms on the reaction mixture less than 20% by weight of the total reactants used for the diisocyanates, preferably less than 15% by weight and in particular less than 5% by weight.

In addition to the polyurethanes, the coating can include other coating materials such as for example other polymers or ingredients of washing or cleaning agents, such as dyes, fragrances, etc., but this is preferred only in some cases is (see above).

In preferred embodiments of the present invention, the polyurethanes in the coating have molar masses from 5000 to 150,000 gmol ^-1 , preferably from 10,000 to 100,000 gmol ^-1 and in particular from 20,000 to 50,000 gmol ^-1 . Corresponding detergent tablets are preferred according to the invention.

The detergent tablets coated according to the invention have Properties are significantly improved even with small amounts of coating material on. It is preferred in the context of the present invention that the amount of Coating material less than 5 wt .-%, preferably less than 2.5 wt .-% and in particular less than 1% by weight of the total weight of the coated shaped body accounts. Detergent tablets in which the weight ratio from uncoated molded article to coating larger than 10 to 1, preferably larger than 25 to 1 and in particular greater than 50 to 1 are therefore preferred embodiments of the present invention.

Due to the small amounts in which the above-mentioned polymers are already a highly resilient and advantageous coating of the previously pressed detergent tablets cause coating thicknesses that can be realized in comparison to the dimensions of the moldings are small. In preferred detergent tablets the thickness of the coating on the molded body is 0.1 to 500 µm, preferably 0.5 to 250 µm and in particular 5 to 100 µm.

In addition to the polyurethanes, the coated moldings according to the invention can the coating also contain other ingredients, in particular other ingredients Detergent and cleaning agent ingredients have proven their worth. These substances will generally described in detail below are washing or Preferred detergent tablets, in which the coating additionally one or several substances from the groups of disintegration aids, dyes, optical Brighteners, fragrances, enzymes, bleaching agents, bleach activators, silver protection agents, complexing agents, Surfactants, graying inhibitors and their mixtures in amounts of 0.5 up to 30% by weight, preferably from 1 to 20% by weight and in particular from 2.5 to 10 % By weight, based in each case on the weight of the coating.

According to the invention, it is particularly advantageously possible to incorporate easily soluble substances, so-called solubilizers, into the coating. Particularly preferred solubilizers have solubilities above 200 grams of solubilizer in one liter of deionized water at 20 ° C. As such preferred solubilizers for incorporation into the coating, a whole series of compounds are suitable in the context of the present invention which can originate both from the group of covalent compounds and from the group of salts. It is preferred if the solubilizers have even higher solubilities, so that solubilizers are preferred as an additive to the coating which have a solubility of more than 250 g per liter of water at 20 ° C., preferably of more than 300 g per liter of water at 20 ° C and in particular of more than 350 g per liter of water at 20 ° C. The following list provides an overview of the solubilities of solubilizers suitable in the context of the present invention. Unless other temperatures are explicitly mentioned, the solubility values given in this table refer to the solubility at 20 ° C. Sodium carbonate monohydrate 210 g / l Sodium carbonate decahydrate 210 g / l Lactose monohydrate (25 ° C) 216 g / l disodium hydrogen phosphate dodecahydrate 218 g / l potassium 222 g / l potassium 224 g / l Sodium Dithionite 224 g / l Fumaric acid disodium salt (25 ° C) 228 g / l Calciumlävulinat 250 g / l Glycine (25 ° C) 250 g / l potassium monopersulfate 256 g / l trisodium phosphate dodecahydrate 258 g / l Ammonium iron (II) sulfate hexahydrate 269 g / l magnesium sulfate 269 g / l Potassium hexacyanoferrate (II) trihydrate (12 ° C) 270 g / l di-sodium tartrate dihydrate 290 g / l Calcium acetate hydrate 300 g / l Potassium hexacyanoferrate (III) 315 g / l potassium nitrate 320 g / l Manganese (II) acetate tetrahydrate 330 g / l L (+) - ascorbic acid 333 g / l potassium chloride 340 g / l Lithium sulfate monohydrate 340 g / l Zinc sulphate monohydrate 350 g / l di-potassium oxalate monohydrate 360 g / l sodium chloride 360 g / l L - (-) - malic acid 363 g / l sodium bromate 364 g / l ammonium chloride 370 g / l ammonium 370 g / l Iron (II) sulfate heptahydrate 400 g / l Sodium azide (17 ° C) 417 g / l L-lysine monohydrochloride 420 g / l Magnesium nitrate hexahydrate 420 g / l Zinc acetate dihydrate 430 g / l Potassium bisulfate 490 g / l sodium 490 g / l Sodium sulfite (40 ° C) 495 g / l Magnesium perchlorate hydrate (25 ° C) 500 g / l lithium nitrate 522 g / l β-alanine (25 ° C) 545 g / l L (-) - Sorbose (17 ° C) 550 g / l sodium 556 g / l sodium 570 g / l ammonium 582 g / l Gluconic acid sodium salt (25 ° C) 590 g / l ammonium 598 g / l Aluminum sulfate 18-hydrate 600 g / l Aluminum sulfate hydrate (16-18 H ₂ O) 600 g / l Potassium sodium tartrate tetrahydrate 630 g / l potassium 650 g / l Sodium hydrogen sulfate monohydrate 670 g / l D (+) - galactose (25 ° C) 680 g / l Sodium thiosulfate pentahydrate 680 g / l di-ammonium hydrogen phosphate 690 g / l Magnesium sulfate heptahydrate 710 g / l calcium chloride 740 g / l tri-lithium citrate tetrahydrate (25 ° C) 745 g / l ammonium sulfate 760 g / l Manganese (II) sulphate monohydrate 762 g / l Maleic acid (25 ° C) 788 g / l ammonium carbamate 790 g / l sodium 790 g / l D (+) - glucose monohydrate (25 ° C) 820 g / l lithium chloride 820 g / l sodium 820 g / l Saccharin sodium salt hydrate 830 g / l sodium nitrate 880 g / l tri-potassium phosphate heptahydrate 900 g / l Sodium sulfate decahydrate 900 g / l Iron (III) chloride 920 g / l Iron (III) chloride hexahydrate 920 g / l tri sodium citrate 5,5 hydrate (25 ° C) 920 g / l Zinc sulfate heptahydrate 960 g / l ammonium carbonate 1000 g / l Calcium chloride dihydrate 1000 g / l sodium chlorate 1000 g / l sodium polyphosphate 1000 g / l sodium salicylate 1000 g / l Resorchin 1000 g / l urea 1080 g / l sodium hydroxide 1090 g / l Sodium hydroxide monohydrate 1103 g / l potassium hydroxide 1120 g / l ammonium nitrate 1183 g / l Sodium acetate trihydrate 1190 g / l Ammonium iron (III) citrate 1200 g / l Manganese (II) chloride dihydrate 1200 g / l Ammonium iron (III) sulfate dodecahydrate (25 ° C) 1240 g / l potassium iodide 1270 g / l malonic 1390 g / l Manganese (II) chloride 1400 g / l DL-malic acid (26 ° C) 1440 g / l ammonium acetate 1480 g / l Iron (II) chloride tetrahydrate (10 ° C) 1600 g / l di-potassium hydrogen phosphate 1600 g / l Citric acid monohydrate 1630 g / l Ammonium thiocyanate (19 ° C) 1650 g / l tri-potassium citrate monohydrate (25 ° C) 1670 g / l Magnesium chloride hexahydrate 1670 g / l ammonium iodide 1700 g / l cesium sulfate 1790 g / l sodium iodide 1790 g / l cesium chloride 1800 g / l Zinc nitrate hexahydrate 1800 g / l Zinc nitrate tetrahydrate 1800 g / l Ammoniumamidosulfonat 1950 g / l Sucrose (15 ° C) 1970 g / l Manganese (II) chloride tetrahydrate 1980 g / l di-Kalimtartrat hemihydrate 2000 g / l Sodium perchlorate monohydrate (15 ° C) 2090 g / l potassium thiocyanate 2170 g / l D (+) - Mannose (17 ° C) 2480 g / l Melibiosis monohydrate (25 ° C) 2500 g / l potassium acetate 2530 g / l cesium carbonate 2615 g / l zinc chloride 3680 g / l D (-) - Fructose 3750 g / l Manganese (II) nitrate tetrahydrate 3800 g / l zinc iodide 4500 g / l Calcium chloride hexahydrate 5360 g / l

The amount in which the substances mentioned in the coating according to the invention can be incorporated, are advantageously in the range mentioned above, i.e. in amounts of 0.5 to 30% by weight, preferably 1 to 20% by weight and in particular from 2.5 to 10% by weight, in each case based on the weight of the coating.

The following substances are preferred solubilizers in the context of the present invention: Lactose monohydrate (25 ° C) 216 g / l Sodium Dithionite 224 g / l Fumaric acid disodium salt (25 ° C) 228 g / l Calciumlävulinat 250 g / l Glycine (25 ° C) 250 g / l potassium monopersulfate 256 g / l Ammonium iron (II) sulfate hexahydrate 269 g / l magnesium sulfate 269 g / l Potassium hexacyanoferrate (II) trihydrate (12 ° C) 270 g / l di-sodium tartrate dihydrate 290 g / l Calcium acetate hydrate 300 g / l Potassium hexacyanoferrate (III) 315 g / l potassium nitrate 320 g / l Manganese (II) acetate tetrahydrate 330 g / l L (+) - ascorbic acid 333 g / l potassium chloride 340 g / l Lithium sulfate monohydrate 340 g / l Zinc sulphate monohydrate 350 g / l di-potassium oxalate monohydrate 360 g / l sodium chloride 360 g / l L - (-) - malic acid 363 g / l sodium bromate 364 g / l ammonium chloride 370 g / l ammonium 370 g / l Iron (II) sulfate heptahydrate 400 g / l Sodium azide (17 ° C) 417 g / l L-lysine monohydrochloride 420 g / l Magnesium nitrate hexahydrate 420 g / l Zinc acetate dihydrate 430 g / l Potassium bisulfate 490 g / l sodium 490 g / l Sodium sulfite (40 ° C) 495 g / l Magnesium perchlorate hydrate (25 ° C) 500 g / l lithium nitrate 522 g / l β-alanine (25 ° C) 545 g / l L (-) - Sorbose (17 ° C) 550 g / l sodium 556 g / l sodium 570 g / l ammonium 582 g / l Gluconic acid sodium salt (25 ° C) 590 g / l ammonium 598 g / l Aluminum sulfate 18-hydrate 600 g / l Aluminum sulfate hydrate (16-18 H ₂ O) 600 g / l Potassium sodium tartrate tetrahydrate 630 g / l potassium 650 g / l Sodium hydrogen sulfate monohydrate 670 g / l D (+) - galactose (25 ° C) 680 g / l Sodium thiosulfate pentahydrate 680 g / l di-ammonium hydrogen phosphate 690 g / l Magnesium sulfate heptahydrate 710 g / l calcium chloride 740 g / l tri-lithium citrate tetrahydrate (25 ° C) 745 g / l ammonium sulfate 760 g / l Manganese (II) sulphate monohydrate 762 g / l Maleic acid (25 ° C) 788 g / l ammonium carbamate 790 g / l sodium 790 g / l D (+) - glucose monohydrate (25 ° C) 820 g / l lithium chloride 820 g / l sodium 820 g / l Saccharin sodium salt hydrate 830 g / l sodium nitrate 880 g / l Iron (III) chloride 920 g / l Iron (III) chloride hexahydrate 920 g / l Zinc sulfate heptahydrate 960 g / l ammonium carbonate 1000 g / l Calcium chloride dihydrate 1000 g / l sodium chlorate 1000 g / l sodium salicylate 1000 g / l Resorchin 1000 g / l urea 1080 g / l sodium hydroxide 1090 g / l potassium hydroxide 1120 g / l ammonium nitrate 1183 g / l Sodium acetate trihydrate 1190 g / l Ammonium iron (III) citrate 1200 g / l Manganese (II) chloride dihydrate 1200 g / l Ammonium iron (III) sulfate dodecahydrate (25 ° C) 1240 g / l potassium iodide 1270 g / l malonic 1390 g / l Manganese (II) chloride 1400 g / l DL-malic acid (26 ° C) 1440 g / l ammonium acetate 1480 g / l Iron (II) chloride tetrahydrate (10 ° C) 1600 g / l Ammonium thiocyanate (19 ° C) 1650 g / l Magnesium chloride hexahydrate 1670 g / l ammonium iodide 1700 g / l cesium sulfate 1790 g / l sodium iodide 1790 g / l cesium chloride 1800 g / l Zinc nitrate hexahydrate 1800 g / l Zinc nitrate tetrahydrate 1800 g / l Ammoniumamidosulfonat 1950 g / l Sucrose (15 ° C) 1970 g / l Manganese (II) chloride tetrahydrate 1980 g / l di-Kalimtartrat hemihydrate 2000 g / l Sodium perchlorate monohydrate (15 ° C) 2090 g / l potassium thiocyanate 2170 g / l D (+) - Mannose (17 ° C) 2480 g / l Melibiosis monohydrate (25 ° C) 2500 g / l potassium acetate 2530 g / l cesium carbonate 2615 g / l zinc chloride 3680 g / l D (-) - Fructose 3750 g / l Manganese (II) nitrate tetrahydrate 3800 g / l zinc iodide 4500 g / l Calcium chloride hexahydrate 5360 g / l

The components of the coating of the moldings according to the invention were described above described in more detail. In the following, the components of the moldings themselves, i.e. the uncoated molded body. These moldings are shown below Partly referred to as the "basic molded article", in order to distinguish verbally from the The term "molded article" or "tablet" for the washing and coated according to the invention Achieving detergent tablets, but sometimes also the general term "Shaped body" used. Since the subject of the present invention with a coating provided basic moldings, the following apply to the basic moldings information given, of course, for washing and Detergent tablets that meet the relevant conditions, and vice versa.

The basic moldings contain builders (e) as essential components. In the invention Base moldings can all usually be used in detergents and cleaning agents builders used, in particular thus zeolites, silicates, Carbonates, organic cobuilders and -where no ecological prejudices against their use there are also the phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / 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 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 also have a delay in dissolution compared to conventional water glasses. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (approx ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula n Na ₂ O (1-n) K ₂ O Al ₂ O ₃ (2 - 2.5) SiO ₂ (3.5 - 5.5) H ₂ O can be described. The zeolite can be used both as a builder in a granular compound and can also be used for a kind of "powdering" of the entire mixture to be compressed, usually using both ways of incorporating the zeolite into the premix. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It goes without saying that the generally known phosphates are also used as builder substances possible if such use is not avoided for ecological reasons should be. Have among the variety of commercially available phosphates the alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (Sodium or potassium tripolyphosphate) in the detergent and cleaning agent industry the greatest importance.

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

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 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 a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt with a density of 2.33 gcm ^-3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is light soluble in water.

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

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

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

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

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

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

Polycarboxylates in particular can be used as organic cobuilders in the base moldings / Polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and phosphonates can be used. This Substance classes are described below.

Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such polycarboxylic acids being among polycarboxylic acids can be understood that carry more than one acid function. For example, these are Citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, Fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if provided 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, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures from these.

The acids themselves can also be used. The acids have besides theirs Builder effect typically also the property of an acidifying component and thus also serve to set 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.

For the purposes 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), using a UV detector. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight have from 2000 to 20,000 g / mol. Because of their superior solubility, can 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 special copolymers of acrylic acid with maleic acid, the 50th contain up to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative Molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

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

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

Further preferred copolymers are those which preferably contain acrolein as monomers 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. Polyaspartic acids are particularly preferred or their salts and derivatives, in addition to cobuilder properties also have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which are obtained by converting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups can be obtained. Preferred polyacetals are made from Dialdehydes 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 obtained by partial hydrolysis of starches can be. The hydrolysis can be carried out according to customary methods, for example acid-catalyzed or enzyme-catalyzed Procedures are carried out. They are preferably hydrolysis products with average molecular weights in the range of 400 to 500000 g / mol. There is one Polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30 preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups can be used 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. An oxidized oligosaccharide is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

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

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

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) 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). Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of neutral reactions Sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt the DTPMP. As a builder, the class of phosphonates preferably HEDP used. The aminoalkanephosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it can, especially if the agents also contain bleach, preferably aminoalkane phosphonates, in particular DTPMP to use, or to use mixtures of the aforementioned phosphonates.

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

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

Preferred base tablets furthermore contain one or more surfactant (s). In the basic moldings can be anionic, nonionic, cationic and / or amphoteric surfactants or mixtures of these are used. Are preferred from application technology View mixtures of anionic and nonionic surfactants. The total surfactant content of the moldings is 5 to 60% by weight, based on the Molded body weight, with surfactant contents above 15% by weight being preferred.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C _12-18 monoolefins with an end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. 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. Among fatty acid glycerol esters the mono-, di- and triesters and their mixtures are to be understood as they 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. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated Fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, Capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C 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 especially 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. 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. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

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

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and 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 fat 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 _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 containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ - ₁₄ alcohol with 3 EO and _C12-18 alcohol containing 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, 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 preferred nonionic surfactants, either as the sole nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated Fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.

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

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Other suitable surfactants are polyhydroxy fatty acid amides of the formula (II),

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

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula (III)

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or 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 reacted with fatty acid methyl esters in the presence of an alkoxide as catalyst in the desired Polyhydroxy fatty acid amides are transferred.

In the context of the present invention, preference is given to base moldings which contain anionic (s) and contain nonionic surfactant (s), with application advantages from certain Proportions in which the individual surfactant classes are used, can result.

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

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

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

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

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

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

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

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred base moldings such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight .-% contain. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, formally speaking, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.

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

As another disintegrant based on cellulose or as a component of this component microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions that only attack the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses and dissolve completely, but leave the crystalline areas (approx. 70%) undamaged.

A subsequent disaggregation of the microfine particles resulting from the hydrolysis Celluloses provide the microcrystalline celluloses, the primary particle sizes of approx. 5 µm and for example to granules with an average particle size of 200 µm are compactible.

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

In addition to the ingredients mentioned, builders, surfactants and disintegration aids can the detergent tablets according to the invention further in detergent and cleaning agents usual ingredients from the group of bleaching agents, bleach activators, Dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, Anti-redeposition agents, graying inhibitors, color transfer inhibitors and corrosion inhibitors contain.

The detergent tablets can be used to develop the desired bleaching performance of the present invention contain bleach. Here in particular the usual bleaching agents from the group sodium perborate monohydrate, Sodium perborate tetrahydrate and sodium percarbonate have proven themselves, the latter clearly is preferred.

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

Sodium carbonate peroxohydrate was first made in 1899 by precipitation with ethanol from a Obtained solution of sodium carbonate in hydrogen peroxide, but mistakenly as peroxy carbonate considered. It was not until 1909 that the compound was used as a hydrogen peroxide addition compound recognized, nevertheless the historical name "sodium percarbonate" prevailed in practice.

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

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

In addition to the bleaching agents used, the washing and Detergent tablets contain bleach activator (s), which is within the scope of the present Invention is preferred. Bleach activators are used in detergents and cleaning agents incorporated to improve when washing at temperatures of 60 ° C and below To achieve bleaching effect. As bleach activators, 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 result, are used. Substances containing O- and / or N-acyl groups are suitable the number of carbon atoms mentioned and / or optionally substituted benzoyl groups wear. Multi-acylated alkylenediamines, in particular tetraacetylethylenediamine, are preferred (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-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 and 2,5-diacetoxy-2,5-dihydrofuran.

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

If the moldings according to the invention contain bleach activators, they contain, in each case based on the entire molded body, between 0.5 and 30 wt .-%, preferably between 1 and 20% by weight and in particular between 2 and 15% by weight of one or several bleach activators or bleach catalysts. Depending on the purpose of the Molded articles produced, these amounts can vary. So are in typical universal detergent tablets Bleach activator contents between 0.5 and 10 wt .-%, preferably between 2 and 8% by weight and in particular between 4 and 6% by weight, while bleach tablets are quite high, for example between 5 and 30% by weight, preferably between 7.5 and 25% by weight and in particular between 10 and can have 20 wt .-%. The expert is free in his formulation not restricted and can be more or less bleaching in this way Manufacture detergent tablets, detergent tablets or bleach tablets by he varied the levels of bleach activator and bleach.

A particularly preferred bleach activator is N, N, N ', N'-tetraacetylethylenediamine, which is widely used in washing and cleaning agents. Accordingly, preferred detergent tablets are characterized in that that as a bleach activator tetraacetylethylenediamine in the above Amounts are used.

In addition to the ingredients mentioned, bleach, bleach activator, builder, surfactant and Disintegration aids can be the detergent tablets according to the invention other ingredients from the group that are common in washing and cleaning agents of dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, Anti-redeposition agents, graying inhibitors, color transfer inhibitors and corrosion inhibitors contain.

The aesthetic impression of the detergent tablets according to the invention To improve, they can be colored with suitable dyes. preferred Dyes, the selection of which is not difficult for the person skilled in the art high storage stability and insensitivity to the other ingredients the means and against light and no pronounced substantivity towards textile fibers, so as not to stain them.

Preferred for use in the detergent tablets according to the invention are all colorants that can be oxidatively destroyed in the washing process as well Mixtures of these with suitable blue dyes, so-called blue tones. It has proven to be advantageous to use colorants in water or at room temperature are soluble in liquid organic substances. For example, anionic ones are suitable Colorants, e.g. anionic nitroso dyes. A possible colorant is, for example Naphthol green (Color Index (Cl) Part 1: Acid Green 1; Part 2: 10020), which as Commercial product, for example as Basacid® Green 970 from BASF, Ludwigshafen, is available, as well as mixtures of these with suitable blue dyes. As another Colorants come Pigmosol® Blue 6900 (Cl 74160), Pigmosol® Green 8730 (Cl 74260), Basonyl® Red 545 FL (Cl 45170), Sandolan® Rhodamine EB400 (Cl 45100), Basacid® Yellow 094 (Cl 47005), Sicovit® Patent Blue 85 E 131 (Cl 42051), Acid Blue 183 (CAS 12217-220, Cl Acidblue 183), Pigment Blue 15 (Cl 74160), Supranol® Blau GLW (CAS 12219-32-8, Cl Acidblue 221)), Nylosan® Yellow N-7GL SGR (CAS 61814-57-1, Cl Acidyellow 218) and / or Sandolan® Blue (Cl Acid Blue 182, CAS 12219-26-0).

When choosing the colorant, care must be taken to ensure that the colorants do not have too strong an affinity for the textile surfaces and especially for synthetic fibers. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stabilities against oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the washing or cleaning agents varies. In the case of colorants which are readily water-soluble, for example the above-mentioned Basacid® green or the above-mentioned Sandolan® blue, colorant concentrations are typically selected in the range from a few 10 ^-2 to 10 ^-3 % by weight. In contrast, in the case of the pigment dyes which are particularly preferred on account of their brilliance but are less readily water-soluble, for example the Pigmosol® dyes mentioned above, the suitable concentration of the colorant in washing or cleaning agents is typically a few 10 ^-3 to 10 ^-4 % by weight. ,

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

Fragrances are added to the agents according to the invention to give the aesthetic impression improve the product and the consumer in addition to the performance of the product a visually and sensorially "typical and distinctive" product is available put. As perfume oils or fragrances, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type be used. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. To the Ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g. the Jonone, ∝-isomethylionon and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, belong to the hydrocarbons mainly the terpenes like limes and pinene. However, mixtures are preferred different fragrances are used, which together make an appealing Generate fragrance. Such perfume oils can also contain natural fragrance mixtures, as they are accessible from plant sources, e.g. Pine, citrus, jasmine, patchouly, Rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, Clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, Vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, Orange peel oil and sandalwood oil.

The content of the detergent tablets according to the invention is usually in the range of fragrances up to 2% by weight of the total formulation. The fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances on carriers that affect the adhesion of the perfume reinforce the laundry and through a slower fragrance release for long-lasting The scent of the textiles Cyclodextrins, for example, have become such carrier materials proven, the cyclodextrin-perfume complexes additionally with others Auxiliaries can be coated.

Enzymes include, in particular, those from the classes of hydrolases such as proteases, Esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned in question. All these Hydrolases contribute to the removal of stains such as protein-, fat- or starchy stains and graying. Cellulases and other glycosyl hydrolases can also remove pilling and microfibrils contribute to color retention and increase the softness of the textile. To bleach or to inhibit color transfer, oxidoreductases can also be used. From bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants. Proteases of the subtilisin type and in particular proteases are preferably which are obtained from Bacillus lentus. Here are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic Enzymes or protease and cellulase or from cellulase and lipase or lipolytic acting enzymes or from protease, amylase and lipase or lipolytically acting Enzymes or protease, lipase or lipolytic enzymes and cellulase, in particular, however, protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic acting enzymes are the well-known cutinases. Also peroxidases or oxidases have proven to be suitable in some cases. To the suitable amylases count in particular alpha-amylases, iso-amylases, pullulanases and pectinases. As Cellulases are preferably cellobiohydrolases, endoglucanases and Glucosidases, which are also called cellobiases, or mixtures of these are used. Because different cellulase types distinguish themselves through their CMCase and Avicelase activities can differentiate, the desired by specific mixtures of the cellulases Activities can be discontinued.

The enzymes can be adsorbed on carriers or embedded in coating substances, 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 up to about 4.5% by weight.

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

Of these, particular preference is given to the sulfonated derivatives of phthalic acid and Terephthalic acid polymers.

The moldings according to the invention are produced in two steps. In the first Step are carried out in a manner known per se detergent tablets Pressing of particulate detergent and cleaning agent compositions, the second steps are provided with the coating.

und R¹ sowie R² unabhängig voneinander für einen substituierten oder unsubstituierten, geradkettigen oder verzweigten Alkyl-, Aryl- oder Alkylarylrest mit 1 bis 24 Kohlenstoffatomen und n jeweils für Zahlen von 5 bis 2000 stehen.Another object of the present invention is therefore a process for the production of coated detergent tablets by pressing a particulate detergent composition known per se and subsequent immersion in or spraying with a melt, solution or dispersion of one or more polyurethanes Diisocyanates (I) and Diols (II) O = C = NR ¹ -N = C = O HOR ² -OH the diols being selected at least in part from polyethylene glycols (II a) and / or polypropylene glycols (II b) H- (O-CH ₂ -CH ₂ ) _n -OH

and R ¹ and R ² independently of one another represent a substituted or unsubstituted, straight-chain or branched alkyl, aryl or alkylaryl radical having 1 to 24 carbon atoms and n each number from 5 to 2000.

Analogous to the explanations for the detergent tablets according to the invention the polymers mentioned are also preferred in the process according to the invention, so that reference can be made to the above statements.

A description of the two major process steps follows.

The moldings to be coated later according to the invention are first produced by dry blending the ingredients, all or part of which are pre-granulated and subsequent information, in particular compression into tablets, whereby conventional methods can be used. For the production the shaped body becomes the premix in a so-called die between two stamps compacted into a solid compressed. This process, briefly referred to below as Tabletting is divided into four sections: dosage, compression (elastic deformation), plastic deformation and ejection.

First of all, the premix is introduced into the die, the filling quantity and thus the weight and the shape of the molding being formed being determined by the position of the lower punch and the shape of the pressing tool. The constant metering, even at high molding throughputs, is preferably achieved by volumetric metering of the premix. As the tableting continues, the upper punch touches the premix and lowers further in the direction of the lower punch. With this compression, the particles of the premix are pressed closer together,
the void volume within the filling between the punches continuously decreasing. From a certain position of the upper punch (and thus from a certain pressure on the premix) the plastic deformation begins, in which the particles flow together and the molded body is formed. Depending on the physical properties of the premix, some of the premix particles are also crushed and sintering of the premix occurs at even higher pressures. With increasing pressing speed, that is to say high throughput quantities, the phase of elastic deformation is shortened further and further, so that the resulting shaped bodies can have more or less large cavities. In the last step of tableting, the finished molded body is pressed out of the die by the lower punch and transported away by subsequent transport devices. At this point in time, only the weight of the molded body is finally determined, since the compacts can still change their shape and size due to physical processes (stretching, crystallographic effects, cooling, etc.).

Tableting takes place in commercially available tablet presses, which are basically or double stamps can be equipped. In the latter case, not only Upper stamp used to build up pressure, the lower stamp also moves during of the pressing process towards the upper punch, while the upper punch presses down. Eccentric tablet presses are preferably used for small production quantities, 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 this ram is comparable to the operation of a conventional four-stroke engine. The pressing can be done with an upper and lower stamp, but it can also several stamps can be attached to an eccentric disc, the number of Die holes are 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, on which a so-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 an upper and lower stamp assigned, with the pressing pressure again being active only through the upper or lower stamp, but can also be built using both stamps. The matrix table and the stamps move about a common vertical axis, whereby the stamps with the help of rail-like cam tracks during the circulation in the positions for filling, compression, plastic deformation and ejection. On the places where a particularly serious increase or decrease in the stamp is necessary (filling, compacting, ejecting), these cam tracks are additional low-pressure pieces, low-tension rails and lifting tracks supported. The The die is filled via a rigidly arranged feed device, the so-called Filling shoe, which is connected to a reservoir for the premix. The Press pressure on the premix is individual via the press paths for upper and lower punches adjustable, the pressure build-up by rolling the punch shaft heads happens on adjustable pressure rollers.

Rotary presses can also be equipped with two filling shoes to increase throughput be, with only a semicircle to produce a tablet must become. Several are used to produce two-layer and multi-layer moldings Filling shoes arranged one behind the other without the slightly pressed first layer in front the further filling is ejected. Appropriate litigation is based on this In this way, coated and dot tablets can also be produced, which have an onion-shell-like structure have, whereby in the case of the point tablets the top of the core or the core layers is not covered and therefore remains visible. Also rotary tablet presses can be equipped with single or multiple tools so that, for example, an external one Circle with 50 and an inner circle with 35 holes simultaneously used for pressing become. The throughputs of modern rotary tablet presses are over one Million moldings per hour.

• Verwendung von Kunststoffeinlagen mit geringen Dickentoleranzen
• Geringe Umdrehungszahl des Rotors
• Große Füllschuhe
• Abstimmung des Füllschuhflügeldrehzahl auf die Drehzahl des Rotors
• Füllschuh mit konstanter Pulverhöhe
• Entkopplung von Füllschuh und Pulvervorlage

When tableting with rotary 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 supply

All known from the art can be used to reduce stamp caking Non-stick coatings. Plastic coatings are particularly advantageous, Plastic inlays or plastic stamps. Rotating stamps have also proven to be advantageous proven, where possible, upper and lower stamps rotated should be. 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. This can be done with pressure rails, several pressure rollers or low rotor speeds can be set. There the fluctuations in hardness of the tablet are caused by the fluctuations in the pressing forces systems should be used that limit the pressing force. Here you can elastic stamps, pneumatic compensators or spring elements in the force path be used. 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, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy N.V., Halle (BE / LU) and Mediopharm Kamnik (SI). The hydraulic double-pressure press, for example, is particularly suitable HPF 630 from LAEIS, D. Tableting tools are, for example, from Companies Adams tableting tools, 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. the senses AG, Reinach (CH) and Medicopharm, Kamnik (Sl).

The moldings can be made in a predetermined spatial shape and a predetermined size become. Practically all sensibly manageable designs come as a spatial form into consideration, for example the formation as a board, the shape of bars or bars, Cubes, cuboids and corresponding room elements with flat side surfaces as well in particular cylindrical configurations with a circular or oval cross section. 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 detergents and / or cleaning agents equivalent. However, it is also possible to form compacts that have a plurality connect such mass units in a compact, in particular by predetermined breaking points make it easy to separate portioned smaller units is provided. For the use of laundry detergents in machines common in Europe Types with horizontally arranged mechanics can design the portioned Compacts as tablets, in the shape of a cylinder or cuboid, are expedient, one Diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred. commercial Hydraulic presses, eccentric presses or rotary presses are suitable Devices in particular for the production of such compacts.

The spatial shape of another embodiment of the shaped body is in its dimensions the induction chamber of commercial household washing machines adapted so that the moldings can be dosed directly into the induction chamber without a dosing aid, where it dissolves during the induction process. Of course, there is also a Use of the detergent tablets with a dosing aid is easily possible and Preferred within the scope of the present invention.

Another preferred shaped body that can be produced has a plate or panel-like structure with alternating thick long and thin short segments, see above that individual segments of this "bolt" at the predetermined breaking points that make up the short 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 geometrical Shapes, for example vertical triangles, only on one their sides 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 shaped bodies are obtained, which several Have layers, that is, at least two layers. It is also possible that these different layers have different dissolving speeds. From this This may result in advantageous performance properties of the molded articles. If, for example, components are contained in the moldings, which are mutually dependent affect negatively, so it is possible to find a component in the faster integrate soluble layer and the other component into a slower soluble Incorporate layer so that the first component has already reacted when the second goes into solution. The layer structure of the shaped bodies can be both stack-like take place, a dissolution process of the inner layer (s) at the edges of the molded body already takes place when the outer layers have not yet been completely dissolved , but it can also completely encase the inner layer (s) by the each layer (s) lying further out can be reached, which leads to a prevention the early 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, ie two outer and at least one inner layer, wherein at least one of the inner layers contains a peroxy bleach, while in the case of the stacked shaped body, the two outer layers and in the case of the shell-shaped one Shaped bodies, however, the outermost layers are free of peroxy bleach. Farther it is also possible to use peroxy bleach and any bleach activators present and / or to separate enzymes spatially from one another in a shaped body. such Multi-layer moldings have the advantage that they do not have only one induction chamber or via a metering device which is added to the wash liquor can be; rather, it is also possible in such cases, the molded body into the machine in direct contact with the textiles without staining would be feared by bleach and the like.

In addition to the layer structure, multi-phase shaped bodies can also be produced in the form of toroidal core tablets, core jacket tablets or so-called "bulleye" tablets. An overview of such embodiments of multi-phase tablets is described in EP 055 100 (Jeyes Group). This document discloses toilet block detergents which comprise a molded body of a slowly soluble detergent composition in which a bleach tablet is embedded. At the same time, this document discloses the most varied designs of multi-phase tablets, from simple multi-phase tablets to complicated multi-layer systems with inlays.

After pressing, the detergent tablets have a high stability. The breaking strength of cylindrical shaped bodies can be determined via the measured variable of the diametrical breaking load. This can be determined according to σ = 2 P π dt

Here □ 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 moldings.

Preferred manufacturing processes for detergent tablets are based on one Granules containing surfactants, which combine with other processing components to form one is prepared for compression of the particulate premix. Completely analogous to the The above statements about preferred ingredients of the invention Detergent tablets are also based on the use of other ingredients to transfer their manufacture. In preferred methods, this contains particulate Premix additionally granules (s) containing surfactant and has a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l on.

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

The other ingredients of the detergent tablets according to the invention also can be introduced into the process according to the invention, for which purpose the above is referred to. Preferred methods are characterized in that that the particulate premix additionally contains one or more substances from the group of bleaching agents, bleach activators, disintegration aids, enzymes, pH adjusting agents, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, Silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, Contains color transfer inhibitors and corrosion inhibitors.

The second step of the method according to the invention comprises the application of the coating. Common methods of coating bodies can be used for this purpose become, especially immersing the body in or spraying of the body with a melt, solution or dispersion of the polyurethanes mentioned.

Since the immersion of detergent tablets in melts or solutions or dispersions to the desired only with great technical effort thin coatings, it is preferred in the context of the present invention Spraying polymer solutions or dispersions onto the shaped bodies, the solution or dispersant evaporates and leaves a coating on the molding. In preferred processes according to the invention, an aqueous solution of a or several polyurethanes are sprayed onto the moldings, the aqueous solution, each based on the solution, 1 to 20 wt .-%, preferably 2 to 15 wt .-% and in particular 4 to 10% by weight of polyurethane (s), optionally up to 20% by weight, preferably up to 10% by weight and in particular less than 5% by weight of one or more with water miscible solvent and the rest water.

To shorten the drying time, the aqueous solution can be further with water miscible volatile solvents are added. These come in particular from the group of alcohols, ethanol, n-propanol and iso-propanol being preferred are. For cost reasons, ethanol and isopropanol are particularly recommended.

The spraying of such aqueous solutions or dispersions can vary Types occur that are familiar to the expert. For example, the solution or Dispersion are fed to a nozzle by means of a pump system, where the solution or Dispersion is atomized by the high shear forces. The resulting spray mist can then be directed to the shaped body to be coated, which follows optionally with the help of suitable measures (e.g. blowing with heated Air). However, it is also possible to use a multi-component nozzle and the aqueous solutions or dispersions with the aid of a gas stream to atomize the nozzle. In the simplest case, a two-substance nozzle is used and as Carrier gas compressed air used. To the dispersion, if necessary, before oxidation or To protect other interactions with the carrier gas, other carrier gases can also be used such as nitrogen, noble gases, lower alkanes or ethers become.

It is also possible to reduce the water content of the dispersion or solution, which shortens drying times, interactions with moisture-sensitive Ingredients on the molded body surface minimized and the production costs lowers. The lower alcohols mentioned above are also suitable as solvents here at, completely anhydrous solvent mixtures are less preferred because certain amounts of water favor the formation of a uniform coating layer. In preferred methods according to the invention, a solution or dispersion is used one or more polyurethanes in a solvent or solvent mixture from the group of water, ethanol, propanol, isopropanol, n-heptane and their mixtures with the help of inert blowing agents from the group nitrogen, nitrous oxide, Propane, butane, dimethyl ether and mixtures thereof are sprayed onto the moldings.

i) 30 bis 99 Gew.-%, vorzugsweise 40 bis 90 Gew.-% und insbesondere 50 bis 85 Gew.-% Ethanol, Propanol, iso-Propanol, n-Heptan oder deren Mischungen,

ii) 0 bis 20, vorzugsweise 1 bis 15 und insbesondere 2 bis 10 Gew.-% Wasser,

iii) 1 bis 50, vorzugsweise 2 bis 25 und insbesondere 3 bis 10 Gew.-% eines oder mehrerer Polyurethane.

In such preferred process variants according to the invention, the solutions or dispersions advantageously have the following composition, the details relating in each case to the dispersion to be sprayed on:

i) 30 to 99% by weight, preferably 40 to 90% by weight and in particular 50 to 85% by weight of ethanol, propanol, isopropanol, n-heptane or mixtures thereof,

ii) 0 to 20, preferably 1 to 15 and in particular 2 to 10% by weight of water,

iii) 1 to 50, preferably 2 to 25 and in particular 3 to 10% by weight of one or more polyurethanes.

Other ingredients of the dispersions to be sprayed on can, for example, color or be fragrances or pigments. Such additives improve the visual, for example or olfactory impression of the molded articles coated according to the invention. color and fragrances have been described in detail above. Pigments come for example White pigments such as titanium dioxide or zinc sulfide, pearlescent pigments or color pigments into consideration, the latter in inorganic pigments and organic pigments can be divided. All of the pigments mentioned are preferred if they are used finely divided, i.e. with average particle sizes of 100 µm and well below, used.

In order to achieve the formation of a uniform and as thin a coating as possible, it is preferred to use the solution or dispersion of the coating materials as far as possible to be finely atomized before it hits the molded body. Methods according to the invention, in which the relevant solution and / or dispersion via a nozzle on the molded body is applied, the mean droplet size in the spray less than 100 µm, preferably less than 50 µm and in particular less than 35 µm, are preferred in this way, the above-mentioned preferred thickness easily realize the coating.

Since the polymers used according to the invention as a coating meltable without decomposition are, it is advantageously possible to dispense with the use of solutions or dispersions and instead of applying a melt of the coating to the moldings. Processes according to the invention, in which a melt consists of one or more Polyurethanes, which may contain further constituents, are applied to the moldings are therefore preferred according to the invention.

und R¹ sowie R² unabhängig voneinander für einen substituierten oder unsubstituierten, geradkettigen oder verzweigten Alkyl-, Aryl- oder Alkylarylrest mit 1 bis 24 Kohlenstoffatomen und n jeweils für Zahlen von 5 bis 2000 stehen.Another object of the present invention is the use of polymers or polymer mixtures for coating detergent tablets, the polymer or at least 50% by weight of the polymer mixture being selected from the group of polyurethanes from diisocyanates (I) and diols (II ) O = C = NR ¹ -N = C = O HOR ² -OH the diols being selected at least in part from polyethylene glycols (II a) and / or polypropylene glycols (II b) H- (O-CH ₂ -CH ₂ ) _n -OH

and R ¹ and R ² independently of one another represent a substituted or unsubstituted, straight-chain or branched alkyl, aryl or alkylaryl radical having 1 to 24 carbon atoms and n each number from 5 to 2000.

With regard to preferred embodiments of the use according to the invention (ingredients, Composition of the premix, preferred polymers etc.) applies analogously what has been said above for the method according to the invention.

Claims (20)

Detergent tablets made of compressed particulate laundry detergent and cleaning agent, containing builders (e) and optionally further detergent and cleaning agent components, characterized in that the tablets are provided with a coating which contains polyurethanes from diisocyanates (I) and diols (II) O = C = NR ¹ -N = C = O HOR ² -OH the diols being selected at least in part from polyethylene glycols (II a) and / or polypropylene glycols (II b) H- (O-CH ₂ -CH ₂ ) _n -OH

and R ¹ and R ² independently of one another represent a substituted or unsubstituted, straight-chain or branched alkyl, aryl or alkylaryl radical having 1 to 24 carbon atoms and n each number from 5 to 2000. Detergent tablets according to Claim 1, characterized in that they are provided with a coating in which at least 10% by weight, preferably at least 25% by weight, particularly preferably at least 50% by weight and in particular at least 75% by weight. -% of the diols reacted in the polyurethane are selected from polyethylene glycols (II a) and / or polypropylene glycols (II b). Detergent tablets according to one of claims 1 or 2, characterized in that the coating comprises at least 10% by weight, preferably at least 25% by weight, particularly preferably at least 50% by weight and in particular at least 75% by weight of polyurethane contains. Detergent tablets according to claim 3, characterized in that the coating consists entirely of polyurethane. Detergent tablets according to one of claims 1 to 4, characterized in that the coating contains polyurethanes made from diisocyanates (I) and diols (II) O = C = NR ¹ -N = C = O HOR ² -OH where R ¹ for a methylene-ethylene-propylene, butylene, pentylene group or for - (CH ₂ ) ₆ - or for 2,4- or 2,6-C ₆ H ₃ -CH ₃ , or for C ₆ H ₄ -CH ₂ -C ₆ H ₄ or isophorone (3,5,5-trimethyl-2-cyclohexenone) and R ^{2 is} selected from -CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n - or -CH ₂ -CH ₂ - (O-CH (CH ₃ ) -CH ₂ ) _n - with n = 4 to 1999. Detergent tablets according to one of claims 1 to 5, characterized in that the polyurethanes have structural units of the formula (III) in the coating - [OC (O) -NH-R ¹ -NH-C (O) -OR ² ] _k - in which R ^{1 stands} for - (CH ₂ ) ₆ - or for 2,4- or 2,6-C ₆ H ₃ -CH ₃ , or for C ₆ H ₄ -CH ₂ -C ₆ H ₄ and R ² is selected from -CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n - or -CH (CH ₃ ) -CH ₂ - (O-CH (CH ₃ ) -CH ₂ ) _n -, where n is a Number from 5 to 199 and k is a number from 1 to 2000. Detergent tablets according to one of claims 1 to 6, characterized in that the polyurethanes in the coating contain additional diamines, preferably hexamethylene diamine and / or hydroxycarboxylic acids, preferably dimethylol propionic acid. Detergent tablets according to one of claims 1 to 7, characterized in that the polyurethanes in the coating have molar masses from 5000 to 150,000 gmol ^-1 , preferably from 10,000 to 100,000 gmol ^-1 and in particular from 20,000 to 50,000 gmol ^-1 . Detergent tablets according to one of claims 1 to 8, characterized in that the weight ratio of uncoated tablet to coating is greater than 10 to 1, preferably greater than 25 to 1 and in particular greater than 50 to 1. Detergent tablets according to one of Claims 1 to 9, characterized in that the thickness of the coating on the tablet is 0.1 to 500 µm, preferably 0.5 to 250 µm and in particular 5 to 100 µm. Detergent tablets according to one of claims 1 to 3 or 5 to 10, characterized in that the coating additionally comprises one or more substances from the groups of disintegration aids, dyes, optical brighteners, fragrances, enzymes, bleaching agents, bleach activators, silver preservatives, complexing agents, Contains surfactants, graying inhibitors and mixtures thereof in amounts of 0.5 to 30% by weight, preferably 1 to 20% by weight and in particular 2.5 to 10% by weight, in each case based on the weight of the coating. Process for the production of coated detergent tablets by pressing a particulate detergent composition in a manner known per se and subsequent immersion in or spraying with a melt, solution or dispersion of one or more polyurethanes from diisocyanates (I) and diols (II) O = C = NR ¹ -N = C = O HOR ² -OH the diols being selected at least in part from polyethylene glycols (II a) and / or polypropylene glycols (II b) H- (O-CH ₂ -CH ₂ ) _n -OH

and R ¹ and R ² independently of one another represent a substituted or unsubstituted, straight-chain or branched alkyl, aryl or alkylaryl radical having 1 to 24 carbon atoms and n each number from 5 to 2000. A method according to claim 12, characterized in that an aqueous solution of one or more polyurethanes is sprayed onto the moldings, the aqueous solution, in each case based on the solution, 1 to 20 wt .-%, preferably 2 to 15 wt .-% and in particular 4 to 10% by weight of polyurethane (s), optionally up to 20% by weight, preferably up to 10% by weight and in particular below 5% by weight of one or more water-miscible solvents and the remainder water, contains. A method according to claim 13, characterized in that a solution or dispersion of one or more polyurethanes in a solvent or solvent mixture from the group water, ethanol, propanol, isopropanol, n-heptane and mixtures thereof with the aid of inert blowing agents from the group Nitrogen, nitrous oxide, propane, butane, dimethyl ether and mixtures thereof are sprayed onto the moldings. A method according to claim 14, characterized in that the solution or dispersion has the following composition: iv) 30 to 99% by weight, preferably 40 to 90% by weight and in particular 50 to 85% by weight of ethanol, propanol, isopropanol, n-heptane or mixtures thereof, v) 0 to 20, preferably 1 to 15 and in particular 2 to 10% by weight of water, vi) 1 to 50, preferably 2 to 25 and in particular 3 to 10% by weight of one or more polyurethanes. A method according to claim 12, characterized in that a melt of one or more polyurethanes, which may contain further constituents, is applied to the moldings. Method according to one of claims 12 to 16, characterized in that the molded body to be coated is obtained by pressing a particulate premix containing the surfactant-containing granulate (s) and a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular has at least 700 g / l. A method according to claim 17, characterized in that the surfactant-containing granules have particle sizes between 100 and 2000 µm, preferably between 200 and 1800 µm, particularly preferably between 400 and 1600 µm and in particular between 600 and 1400 µm. Method according to one of claims 17 or 18, characterized in that the particulate premix additionally contains one or more substances from the group of bleaching agents, bleach activators, disintegration aids, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-reposition agents , optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors. Use of polymers or polymer mixtures for coating detergent tablets, the polymer or at least 50% by weight of the polymer mixture being selected from the group of polyurethanes from diisocyanates (I) and diols (II) O = C = NR ¹ -N = C = O HOR ² -OH the diols being selected at least in part from polyethylene glycols (II a) and / or polypropylene glycols (II b) H- (O-CH ₂ -CH ₂ ) _n -OH

and R ¹ and R ² independently of one another represent a substituted or unsubstituted, straight-chain or branched alkyl, aryl or alkylaryl radical having 1 to 24 carbon atoms and n each number from 5 to 2000.