WO2000015753A1 - Moulded detergent and cleaning agent compositions containing alkyl benzene sulfonate - Google Patents

Abstract

The invention relates to moulded detergent and cleaning agent compositions having technically advantageous and improved properties. Such compositions are obtained by virtue of the fact that they contain alkyl benzene sulfonate compounds containing more than 40 % by weight alkyl benzene sulfonate in relation to the compound.

Description

 , ABS-containing detergent tablets "

The present invention is in the field of compact moldings which have washing and cleaning properties. Such washing and cleaning agent shaped articles include, for example, detergent shaped articles for washing textiles, cleaning agent shaped articles for machine dishwashing or cleaning hard surfaces, bleaching agent shaped articles for use in washing machines or dishwashers, water softening shaped articles or stain tablets. In particular, the invention relates to detergent tablets which are used for washing textiles in a household washing machine and are referred to briefly as detergent tablets.

Detergent tablets are widely described in the prior art and are becoming increasingly popular with consumers because of the simple dosage. Tableted detergents and cleaning agents have a number of advantages over powder-form ones: They are easier to dose and handle and, thanks to their compact structure, have advantages in terms of storage and transport. Consequently, detergent tablets are also described comprehensively in the patent literature. A problem that occurs again and again when using washing and cleaning active molded articles is the too slow disintegration and dissolving speed of the molded articles under application conditions. Since sufficiently stable, ie shape and break-resistant molded bodies can only be produced by relatively high pressure, there is a strong compression of the molded body components and a consequent delayed disintegration of the molded body in the aqueous liquor and thus to a slow release of the active substances in the washing or cleaning process. The delayed disintegration of the molded article also has the disadvantage that conventional detergent and molded article articles cannot be washed in via the washing-in chamber of household washing machines, since the tablets do not disintegrate into secondary articles that are small enough to pass from the washing-in chamber into the washing drum to be washed in.

To overcome the dichotomy between hardness, i.e. Transport and handling stability, and easy disintegration of the molded body, many approaches have been developed in the prior art. A particularly well-known approach from pharmacy and extended to the field of detergent tablets is the incorporation of certain disintegration aids which facilitate the access of water or which swell or develop gas or other forms upon access of water. Other proposed solutions from the patent literature describe the cessation of premixes of certain particle sizes, the separation of individual ingredients from certain other ingredients and the coating of individual ingredients or the entire molded article with binders. However, since the addition of substances which are only intended to accelerate the disintegration of the molded articles, at the same time reduces the amount of active substances for a given molded article weight, there is still the task of producing detergent molded articles in which detergents and cleaning agents or other detergents Ingredients are available in such a way that the addition of disintegrating substances is not necessary.

The washing performance of washable and cleaning-active molded articles is guaranteed by the use of surfactants, alkylbenzenesulfonates occupying an important position due to their high cleaning performance and large-scale availability. One of the objects of the present invention was therefore to provide a detergent molded article in which the preparation of a surfactant alone causes it to disintegrate more quickly at a predetermined hardness. Another object of the present invention was to make the incorporation form of the alkylbenzenesulfonate variable to such an extent that the form usually used in the production of detergent and cleaning agent cores of surfactant granules used can be used in varying amounts and a resulting quantity of surfactant can easily be compensated for via the premix to be tabletted, without adversely affecting the physical properties of the detergent tablets, in particular the hardness and disintegration time. In addition, the incorporation form to be found should be so flexibly manageable that it can be introduced into the detergent tablets not only via the premix, but also via the surfactant granules, without resulting in negative properties of the molded articles during incorporation in this way.

In extensive experiments, the applicant has now been able to determine concentrated alkylbenzenesulfonate compounds with alkylbenzenesulfonate contents above 40% by weight as surfactant carriers which can be used universally in the production of detergent tablets and which impart improved physical properties to the tablets.

The present invention relates to detergent tablets made of compressed, particulate detergents and cleaning agents which contain alkylbenzenesulfonate compounds with alkylbenzenesulfonate contents above 40% by weight, based on the compound.

Alkylbenzenesulfonates as powerful anionic surfactants have been known since the 1930s. At that time, alkylbenzenes were produced by monochlorination of kogasin fractions and subsequent Friedel-Crafts alkylation, which were sulfonated with oleum and neutralized with sodium hydroxide solution. In the early 1950s, to produce alkylbenzenesulfonates, propylene was tetramerized to branched α-dodecylene and the product was converted to tetrapropylene benzene via a Friedel-Crafts reaction using aluminum trichloride or hydrogen fluoride, which was subsequently sulfonated and neutralized. This economical possibility of producing tetrapropylene benzene sulfonates (TPS) led to the breakthrough of this class of surfactants, which subsequently displaced the soaps as the main surfactant in washing and cleaning agents. Due to the lack of biodegradability of TPS, there was a need to prepare new alkylbenzenesulfonates that are characterized by improved ecological behavior. These requirements are met by linear alkyl benzene sulfonates fills, which today are almost exclusively manufactured alkylbenzenesulfonates and are given the abbreviation ABS.

Linear alkylbenzenesulfonates are made from linear alkylbenzenes, which in turn are accessible from linear olefms. For this purpose, petroleum fractions with molecular sieves are separated on an industrial scale into the n-paraffins of the desired purity and dehydrogenated to the n-olefins, resulting in both α- and i-olefins. The resulting olefins are then reacted with benzene in the presence of acidic catalysts to give the alkylbenzenes, the choice of Friedel-Crafts catalyst having an influence on the isomer distribution of the linear alkylbenzenes formed: when using aluminum trichloride, the content of the 2-phenyl isomers is in the mixture with the 3, 4, 5 and other isomers at approx. 30% by weight, however, if hydrogen fluoride is used as a catalyst, the 2-phenyl isomer content can be reduced to approx. 20% by weight . Finally, the sulfonation of linear alkylbenzenes is now possible on a large industrial scale with oleum, sulfuric acid or gaseous sulfur trioxide, the latter being by far the most important. For the sulfonation, special film or tube bundle reactors are used, which deliver as a product a 97% by weight alkylbenzenesulfonic acid (ABSS) which is marketed in this way or neutralized with NaOH to form aqueous ABS pastes with active substance contents of around 60% by weight, which then go on sale.

It is preferred in the context of the present invention that the alkylbenzenesulfonate compounds have alkylbenzenesulfonate contents above 50% by weight, preferably above 60% by weight and in particular above 70% by weight, based on the compound.

By choosing the neutralizing agent, a wide variety of salts, ie alkylbenzenesulfonates, can be obtained from the ABSS. For reasons of economy, it is preferred to prepare and use the alkali metal salts and, among them, the sodium salts of the ABSS. These can be described by the general formula I: H ₃ C— (CH ₂ )

in which the sum of x and y is usually between 5 and 13. It is preferred in the context of the present invention if the alkylbenzenesulfonate compounds contain the alkali metal, preferably sodium salts of C ₈ -i6-, preferably C ₉ -ι ₃ - alkybenzenesulfonic acids which are derived from alkylbenzenes which have a tetralin content of less than 5% by weight .-%, based on the alkylbenzene.

It is further preferred to use alkylbenzenesulfonates whose alkylbenzenes have been prepared by the HF process, so that detergent tablets are preferred in which the alkylbenzenesulfonate compounds contain the alkali metal, preferably sodium, salts of C ₈ -i ₆ -, preferably C _{9 3} alkybenzenesulfonic acids containing 2-phenyl isomer content below 22% by weight, based on the alkylbenzenesulfonic acid.

The detergent tablets according to the invention preferably contain the alkylbenzenesulfonate compounds in amounts of from 0.5 to 20% by weight, preferably from 1 to 15% by weight, particularly preferably from 2 to 10% by weight and in particular from 3 to 8 wt .-%, each based on the molded body weight.

Regardless of the form of incorporation of the alkylbenzenesulfonates, detergent tablets are preferred, the alkylbenzenesulfonate contents of 1 to 30% by weight, preferably 5 to 25% by weight and in particular 10 to 15% by weight, based in each case the molded body weight.

The total amount of alkylbenzenesulfonates can be introduced via ABS compounds, but it is also possible and within the scope of the present invention preferred that the washing and cleaning agent molded articles contain, in addition to the alkylbenzenesulfonate compounds, an alkylbenzenesulfonate-containing surfactant granulate.

If the total amount of ABS is not introduced into the detergent tablets according to the invention via ABS compounds, but if other ways of incorporation - for example via an ABS-containing surfactant granulate - are selected, it is preferred that at least 20% by weight, preferably at least 30% by weight and in particular at least 40% by weight of the total alkyl benzene sulfonate contained in the molded bodies is introduced into the molded bodies via the alkyl benzene sulfonate compounds. For the evaluation of the amount introduced into the detergent tablets through the ABS compounds, it is completely irrelevant whether these ABS compounds are only mixed when the individual components are mixed, i.e. in the preparation of the premix, or whether they are already used in the production of other granules, in particular surfactant granules. If the ABS compounds are added during the production of the surfactant granules, it is also irrelevant whether the surfactant granules contain other, for example nonionic, surfactants or only ABS as further surfactants. In this way, according to the invention, a surfactant granulate can be produced which, on the one hand, contains ABS compounds according to the invention, but on the other hand can also have a further ABS content which results, for example, from ABSS added during the granulation.

In addition to the ABS compounds used according to the invention, the washing and cleaning agent foils contain customary ingredients of washing and cleaning agents, in particular from the groups of surfactants and / or builders. Further ingredients that can be used in the detergent tablets according to the invention are, for example, disintegration aids, bleaching agents, bleach activators, enzymes, dyes and fragrances, optical brighteners, polymers, foam inhibitors, etc.

To develop the washing performance, the detergent tablets according to the invention can, in addition to the ABS, contain further surface-active substances from the group of anionic, nonionic, zwitterionic or cationic surfactants. hold, anionic surfactants are clearly preferred for economic reasons and because of their range of services.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Surfactants of the sulfonate type are, for example, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from C ₂ -ι ₈ -Monoolefmen with terminal or internal double bond by kidney sulphonated with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates, which are for example obtained from C ₂ -ι ₈ alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become. Preferred sulfated fatty acid glycerol esters are the sulfate products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

As alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid semiesters of the Ci ₂ -C ₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 1 -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 ₂ -C ₆ alkyl sulfates and C ₁₂ - cis alkyl sulfates and C ₄ -Ci ₅ alkyl sulfates are preferred for washing technology reasons. Also 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 Shell Oil Company under the name DAN ^® are suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C ₇ ethoxylated with 1 to 6 mol of ethylene oxide. ₂₁ alcohols, such as 2-methyl-branched C ₉ _n alcohols with an average of 3.5 moles of ethylene oxide (EO) or C ₂ -ιs 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 _{8-0 8} fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

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

The anionic surfactants, including the soaps, can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts. In the context of the present invention, detergent tablets are preferred which contain 5 to 50% by weight, preferably 7.5 to 40% by weight and in particular 10 to 20% by weight of anionic surfactant (s), based in each case on the Molded body weight, included.

When selecting the anionic surfactants that are used in the detergent tablets according to the invention, there are no general conditions to be observed that prevent freedom of formulation. However, preferred detergent tablets have a soap content which exceeds 0.2% by weight, based on the total weight of the tablet. Anionic surfactants to be used with preference are the alkylbenzenesulfonates and fatty alcohol sulfates, with preferred detergent tablets 2 to 20% by weight, preferably 2.5 to 15% by weight and in particular 3 to 8% by weight of fatty alcohol sulfate (s) in each case based on the molded body weight

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical has a methyl or linear branching in the 2-position may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. Preferred ethoxylated alcohols include, for example _C12 - ₁₄ - alcohols with 3 EO or 4 EO, C n-alcohol with 7 EO, Cι ₃ .ι ₅ alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ - ι ₈ - alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₁ 2. ι ₄ - alcohol with 3 EO and Cι ₂ -ι alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Usable alkyl polyglycosides satisfy the general formula RO (G) _z , in which R is a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is Is a symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.

Linear alkyl polyglucosides, ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.

The detergent tablets according to the invention can preferably contain alkyl polyglycosides, with APG contents in the tablet of more than 0.2% by weight, based on the total tablet, being preferred. Particularly preferred detergent tablets contain APG in amounts of 0.2 to 10% by weight, preferably 0.2 to 5% by weight and in particular 0.5 to 3% by weight.

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

R ¹

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

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

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

R ^ OR ²

I.

R-CO-N- [Z] (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 oxy-alkyl radical having 1 to 8 carbon atoms, C ₄ alkyl or phenyl radicals are preferred and [Z] stands for a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives thereof 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, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

In addition to the wash-active substances, builders are the most important ingredients in detergents and cleaning agents. In the detergent tablets according to the invention, all builders commonly used in detergents and cleaning agents can be present, in particular thus zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - also the phosphates.

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

Amorphous sodium silicates with a module Na2θ: Siθ 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, which are delayed in dissolution, can also be used 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 "amoφh" is also understood to mean "roentgenamoφh". This means that the silicates at 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 integrated in such a way that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Particularly preferred are compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray silicates.

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

nNa ₂ 0 ^• (ln) K ₂ 0 'A1 ₂ 0 ₃ ' (2 - 2.5) Si0 ₂ ^• (3.5 - 5.5) H ₂ 0

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 used, usually both ways of incohering 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 is of course also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the detergent and cleaning agent industry.

Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HP0) _n and orthophosphoric acid H P0 _{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 P0 ₄ , exists as a dihydrate (density 1.91 like ^"3 , melting point 60 °) and as a monohydrate (density 2.04 like ^{" 3} ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ 0) at 200 ° C, and at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ 0) and Maddrell's salt (see below). NaH ₂ P0 _{4 is} acidic; it occurs when phosphoric acid is adjusted to pH 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH2PO ₄ , is a white salt with a density of 2.33 gcm ^" , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KP0) _x ] and is easily soluble in Water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gladly ^"3 , water loss at 95 °), 7 mol. (Density 1.68 gladly ^{" 3} , melting point 48 ° with loss of 5 H ₂ 0) and 12 mol. Water ( Density 1.52 ^"3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to diphosphate Na ₄ P 0 ₇ when heated more. Disodium hydrogenphosphate is used by neutralizing phosphoric acid with soda solution of phenolphthalein as an indicator posed. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HP0, is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na P0 ₄ , are colorless crystals that like a dodecahydrate a density of 1.62 ^"3 and a melting point of 73-76 ° C (decomposition), as a decahydrate (corresponding to 19-20% P2O ₅ ) Melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P2O5) a density of 2.536 like ^"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 three-base potassium phosphate), K ₃ P0 ₄ , is a white, deliquescent, granular powder with a density of 2.56 ^"3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction Heating of 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 θ7, exists in anhydrous form (density 2.534 like ^"3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 like ^{" 3} , melting point 94 ° with loss of water). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na P ₂ 0 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), K4P2O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 ^"3 , which is soluble in water, the pH of the 1% solution at 25 ° Is 10.4.

Condensation of NaH ₂ P0 ₄ or KH2P0 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, NasP ₃ Oιo (sodium tripolyphosphate), is an anhydrous or 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (0) (ONa) -0] _n -Na 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 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ Oιo (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% by weight solution (> 23% P ₂ O ₅ , 25% K ₂ 0). 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:

(NaP0 ₃ ) ₃ + 2 KOH - »Na ₃ K ₂ P ₃ 0, o + H ₂ O

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

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

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

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

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

In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the investigated polymers. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document. Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

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

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

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

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

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Polyas- Paraginic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A-195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, methods. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 owns. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427349, EP-A-0 472 042 and EP-A-0 542 496 and international patent applications WO 92 / 18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608 are known. An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous. Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediaminisisuccinate, are further suitable cobuilders. Ethylene diamine N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are 3 to 15% by weight in formulations containing zeolite and / or silicate.

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

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, l-hydroxyethane-l, l-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9). Preferred aminoalkane phosphonates are ethylenediaminetetrarethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition, all compounds that are able to form complexes with alkaline earth metal ions can be used as cobuilders.

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

The production of washable and cleaning-active molded articles takes place by applying pressure to a mixture to be veφressing, which is located in the cavity of a press. In the simplest case of molded body production, which is hereinafter simply called tableting, the mixture to be tabletted is made directly, i.e. without previous granulation. The advantages of this so-called direct tableting are its simple and inexpensive application, since no further process steps and consequently no further plants are required. However, these advantages are offset by disadvantages. For example, a powder mixture that is to be tabletted directly must have sufficient plastic deformability and have good flow properties; furthermore, it must not show any tendency to segregate during storage, transport and filling of the die. These three requirements are extremely difficult to master with many substance mixtures, so that direct tableting is not often used, particularly in the manufacture of detergent tablets. The usual way of producing detergent tablets is therefore based on powdery components (“primary particles”) which are agglomerated or granulated by suitable processes to form secondary particles with a larger particle diameter. These granules or mixtures of different granules are then mixed with individual powdery additives and fed to the tableting.

The present invention therefore also relates to a process for the production of detergent tablets, characterized by the steps a) production of alkylbenzenesulfonate compounds with alkylbenzenesulfonate contents above 40% by weight, based on the compound, b) mixing with other processing components to form a compressible premix, c) compressing to shaped bodies.

It is also preferred in the process according to the invention that the alkylbenzenesulfonate compounds prepared in step a) have alkylbenzenesulfonate contents above 50% by weight, preferably above 60% by weight and in particular above 70% by weight, based on the compound .

The ABS compounds in step a) are produced using customary methods, the production by granulation, preferably fluidized bed granulation, being preferred. The raw materials for the production of the ABS compounds can be both the ABS pastes and the free ABSS. For reasons of process economy, it is preferred to neutralize the ABSS only when the ABS compounds are being produced, since this reduces the amount of water to be dried out later. For neutralization, for example, alkaline solids, onto which the ABSS is sprayed, or aqueous alkalis can be used. In the latter case, ABSS and alkali are sprayed onto moving solid beds made of carrier material. However, it is also possible to mix acid and alkali with compressed air in a hollow chamber nozzle and at the same time to neutralize and atomize.

Preferred detergent tablets in the context of the present invention are obtained by squeezing a particulate premix comprising at least one surfactant-containing granulate and at least one subsequently admixed powdery component. The granules containing surfactant can be produced by conventional industrial granulation processes such as compacting, extrusion, mixer granulation, pelletization or fluidized bed granulation. It is advantageous for the later detergent tablets if the premix to be veφresses has a bulk density that comes close to the usual compact detergent. In particular, it is preferred that in step b) one or more surfactant granules are treated as processing components in the premix and the particulate Premix has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g / 1.

When using the preferred production process, it is a particularly preferred variant if the or at least one of the surfactant granules (e) contains alkylbenzenesulfonates. In preferred process variants, the surfactant-containing granules also meet certain particle size criteria. Methods according to the invention are preferred in which 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.

In addition to the active substances (ABS and possibly further anionic and / or nonionic and / or cationic and / or amphoteric surfactants), the surfactant granules preferably also contain carriers which particularly preferably come from the group of builders. Particularly advantageous processes are characterized in that the surfactant-containing granules contain anionic and / or nonionic surfactants and builders and total surfactant contents of at least 10% by weight, preferably at least 20% by weight and in particular at least 25% by weight, having.

As already mentioned above, it is irrelevant for the implementation of the present invention whether the ABS compounds are mixed with the surfactant granules and other processing components, ie added to the premix, or whether they are already used completely in the preparation of the surfactant granules. Preferred processes according to the invention are characterized in that the surfactant-containing granules were prepared with the addition of all or part of the alkylbenzenesulfonate compounds produced in step a) with alkylbenzenesulfonate contents above 40% by weight, based on the compound. Here, too, it is again preferred if at least 20% by weight, preferably at least 30% by weight and in particular at least 40% by weight of the total of the alkylbenzenesulfonate contained in the moldings in the form of the alkylbenzenesulfonate compounds prepared in step a) is incorporated into the Shaped body is introduced. In this way it is possible, for example, to produce surfactant granules which contain part of the ABS contained in them in the form of ABS compounds, while the other part of the ABS reaches the surfactant granules in a different form, for example by spraying on ABSS. If such surfactant granules are produced, it is no longer necessary to add further amounts of ABS compound when producing the premix. Of course, the total amount of ABS in the surfactant granules can also come from ABS compounds or the surfactant granules can be completely free of ABS compounds. The only thing essential to the invention is that the premix to be veφress and thus the washing and cleaning agent moldings contain ABS compound with ABS contents above 40% by weight, based on the compound.

Before the particulate premix is pressed into detergent tablets, the premix can be "powdered" with finely divided surface treatment agents. This can be of advantage for the quality and physical properties of both the premix (storage, molding) as well as the finished detergent tablets. Finely divided powdering agents are well known in the art, mostly zeolites, silicates or other inorganic salts being used. However, the premix is preferably “powdered” with finely divided zeolite, zeolites of the faujasite type being preferred. In the context of the present invention, the term “faujasite-type zeolite” denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4 (compare Donald W. Breck: “Zeolite Molecular Sieves”, John Wiley & Sons, New York , London, Sydney, Toronto, 1974, page 92). In addition to the zeolite X, zeolite Y and faujasite and mixtures of these compounds can also be used, the pure zeolite X being preferred. Mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites which do not necessarily have to belong to the zeolite structural group 4 can also be used as powdering agents, it being advantageous if at least 50% by weight of the powdering agent is used a zeolite of the faujasite type.

In the context of the present invention, detergent tablets are preferred which consist of a particulate premix which contains granular components and subsequently admixed powdery substances, the or one of the subsequently mixed powdered components is a zeolite of the faujasite type with particle sizes below 100 μm, preferably below 100 μm and in particular below 5 μm and is at least 0.2% by weight, preferably at least 0.5% by weight and in particular more than 1% by weight %> of the premix to be consumed.

In addition to the constituents mentioned, surfactant, builder and disintegration aid, or in their place the premixes to be treated and thus the detergent tablets according to the invention can contain further ingredients from the group of bleaching agents, bleach activators, disintegration aids, enzymes, pH regulators which are customary in detergents and cleaning agents , Fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.

Among the compounds which serve as bleaching agents and produce H2O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other usable bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H2O2-providing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced. If such bleach tablets are to be used for textile washing, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, regardless of which other ingredients are contained in the molded articles. If cleaning tablets or bleach tablets for machine dishwashing are manufactured, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monophthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidopercapid [Phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocyseboxyacid, diperoxyacid acid, diperoxyacid acid, diperoxy acid, Decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Chlorine or bromine-releasing substances can also be used as bleaching agents in molded articles for automatic dishwashing. Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid,

Dibromo isocyanuric acid and or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

In order to achieve an improved bleaching effect when washing or cleaning at temperatures of 60 ° C. and below, bleach activators can be incorporated into the detergent tablets according to the invention. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoyl-succinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or iso-nonanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetyl acetate, ethylene 2,5-diacetoxy-2,5-dihydrofuran.

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

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

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

Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 8% by weight and in particular 4 to 6% by weight of a disintegration aid, in each case based on the molded article weight.

Disintegration agents based on cellulose are used as preferred disintegration agents in the context of the present invention, so that preferred detergent tablets form such a disintegration agent based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 8% by weight and in particular 4 up to 6% by weight contain. Pure cellulose has the formal gross composition (C _ό HioOs, and formally considered a ß-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molar masses 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 to which hydroxy hydrogen atoms have been substituted, but celluloses in which the hydroxyl groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives, for example alkali celluloses belong to the group of cellulose derivatives , Carboxymethylc ellulose (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.

Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged. A subsequent disaggregation of the microfine celluloses resulting from the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 μm and can be compacted, for example, to granules with an average particle size of 200 μm. Particularly suitable enzymes are those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxidoreductases can also be used for bleaching or for inhibiting color transfer. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

The enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.5 to about 4.5% by weight. In addition, the detergent tablets can also contain components that positively influence the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component. The preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

The shaped bodies can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-moφholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which, instead of the Moφholino group, have a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group. In addition, brighteners of the substituted diphenylstyryl type may be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2- sulfostyryl) diphenyls. Mixtures of the aforementioned brighteners can also be used.

Dyes and fragrances are added to the detergent tablets according to the invention in order to improve the aesthetic impression of the products and to provide the consumer with a visually and sensorially "typical and unmistakable" product. Individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert.- Butylcyclohexyl acetate, lmalyl acetate, dimethylbenzyl carbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzylethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones, for example, the jonones, oc -Isomethylionon and methyl-cedrylketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include tephenols such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, 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 dye content of the agents according to the invention is usually less than 0.01% by weight, while fragrances can make up up to 2% by weight of the total formulation.

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

In order to improve the aesthetic impression of the agents according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity to textile fibers, in order not to dye them. The molded articles according to the invention are first produced by dry mixing the constituents, which can be wholly or partially pregranulated, and then providing information, in particular feeding them into tablets, whereby conventional methods can be used. To produce the shaped bodies according to the invention, the premix is compacted in a so-called die between two punches to form a solid compact. This process, which is briefly referred to below as tabletting, is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection.

First, the premix is introduced into the die, the filling quantity and thus the weight and the shape of the molded body being formed being determined by the position of the lower punch and the shape of the pressing tool. The constant dosing, even at high mold throughputs, is preferably achieved by volumetric dosing of the premix. As the tabletting continues, the upper punch touches the premix and lowers further towards the lower punch. With this compression, the particles of the premix are pressed closer together, the cavity 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 the tabletting process, the finished molded article is pressed out of the die by the lower punch and transported away by subsequent transport devices. At this point in time, only the weight of the molded body is finally determined, since the compacts can still change their shape and size due to physical processes (stretching, crystallographic effects, cooling, etc.). Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches. In the latter case, not only is the upper stamp used to build up pressure, the lower stamp also moves towards the upper stamp during the pressing process, while the upper stamp presses down. For small production quantities, eccentric tablet presses are preferably used, in which the punch or stamps are fastened to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed. The movement of these rams is comparable to that of a conventional four-stroke engine. The pressing can take place with one upper and one lower punch, but several punches can also be attached to one eccentric disk, the number of die holes being increased accordingly. The throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs, rotary tablet presses are selected in which a larger number of dies is arranged in a circle on a so-called die table. The number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available. Each die on the die table is assigned an upper and lower punch, whereby the pressure can only be built up actively by the upper or lower punch, but also by both punches. The die table and the stamps move about a common vertical axis, the stamps being brought into the positions for filling, compaction, plastic deformation and ejection by means of rail-like cam tracks during the rotation. At locations where a particularly serious lifting or lowering of the punches is required (filling, compacting, ejecting), these cam tracks are supported by additional low-pressure pieces, low-pressure rails and lifting tracks. The die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix. The pressing pressure on the premix can be individually adjusted via the pressing paths for the upper and lower punches, the pressure being built up by rolling the punch shaft heads past adjustable pressure rollers. Rotary presses can also be provided with two filling shoes to increase the throughput, with only a semicircle having to be run through to produce a tablet. For the production of two-layer and multi-layer molded bodies, several filling shoes are arranged one behind the other without the slightly pressed first layer being ejected before further filling. With suitable process control, jacket and dot tablets can also be produced in this way, which have an onion-shell-like structure, the top side of the core or core layers not being covered in the case of the dot tablets and thus remaining visible. Rotary tablet presses can also be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used simultaneously for pressing. The throughputs of modern rotary tablet presses are over one million molded articles per hour.

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

- Use of plastic inserts with small thickness tolerances

- Low number of revolutions of the rotor

- Big filling shoes

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

- Filling shoe with constant powder height

- Decoupling of filling shoe and powder feed

All non-stick coatings known from the art are suitable for reducing stamp caking. Plastic coatings, plastic inserts or plastic stamps are particularly advantageous. Rotating punches have also proven to be advantageous, with the upper and lower punches being designed to be rotatable if possible. In the case of rotating stamps, a plastic insert can generally be dispensed with. The stamp surfaces should be electropolished here. It was also shown that long pressing times are advantageous. These can be set with pressure rails, several pressure rollers or low rotor speeds. Since the fluctuations in the hardness of the tablet are caused by the fluctuations in the pressing forces, systems should be used which limit the pressing force. Here elastic stamps, pneumatic compensators or resilient elements can be used in the force path. The pressure roller can also be designed to be resilient.

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

The molded body can be manufactured in a predetermined spatial shape and a predetermined size. Practically all practical configurations can be considered as the spatial shape, for example, the design as a board, the bar or bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross section. This last embodiment covers the presentation form from the tablet to compact cylinder pieces with a ratio of height to diameter above 1. The portioned compacts can each be designed as separate individual elements that correspond to the predetermined dosage of detergents or cleaning agents. It is also possible, however, to form compacts which connect a plurality of such mass units in one compact, the portioned smaller units being easy to separate, in particular by predetermined predetermined breaking points. For the use of laundry detergents in machines of the type customary in Europe with horizontally arranged mechanics, the portioned compacts as tablets, in cylinder or cuboid form can be expedient, with a diameter / height ratio in the range from about 0.5: 2 to 2: 0.5 is preferred. Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for the production of such pressed articles.

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

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

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

In a further preferred embodiment of the invention, a molded body consists of at least three layers, i.e. two outer and at least one inner layer, at least one peroxy bleaching agent being contained in one of the inner layers, while in the case of the stacked molded body the two outer layers and in the shell-shaped molded body the outermost layers, however, are free of peroxy bleach. Furthermore, it is also possible to spatially separate peroxy bleaching agents and any bleach activators and / or enzymes that may be present in a molded body. Such multilayer molded bodies have the advantage that they can be used not only via a dispensing chamber or via a metering device which is added to the washing liquor; rather, in such cases it is also possible to put the molded body into direct contact with the textiles in the machine without the risk of bleaching from bleaching agents and the like.

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

In addition to the shape and a multilayer structure, colored particles, so-called speckles, can also be incorporated into the molded body as optical differentiation respectively. Here, for example, a white molded body can be colored homogeneously with colored, for example blue, red, green, yellow, etc., speckles. In order to provide a homogeneous distribution of the colored speckles over the entire tablet and thus a visually attractive shaped body, the amount of colored speckles and their particle size should be adapted to the rest of the premix which forms the shaped body matrix from which the speckles emerge optically. For example, if a tableting mixture has a particle size of 200 to 1800 μm, speckles that move in the same or coarser particle size will only achieve a homogeneous distribution above a threshold value of> 6% by weight, based on the tablet composition. Smaller quantities then lead to an optically unattractive accumulation of speckles in some shaped body areas, while other areas remain almost unspotted. In order to achieve a homogeneous impression even at lower use concentrations of colored particles, it is advisable to reduce the particle size of the colored speckle particles. In the above example of the tabletting mixture in the range from 200 to 1800 μm, a homogeneous distribution of the speckles is already achieved with 2 to 3% by weight> color speckle particles if these particle sizes have between 200 and 800 μm.

A homogeneous speckling, which can be achieved in the manner described above by adapting the speckle particle size and quantity to the premix, also makes it possible to visualize a layer structure of the shaped bodies. In this way, two- or multi-layer molded bodies can be produced, one layer of which is undyed, while a second layer is highlighted by sprinkles. This concept can also be applied, for example, to three-layer tablets in which one layer is undyed, the second is speckled and the third is colored through. In addition to the coloring of layers, cores or other sub-areas in core-coated tablets, ring-core tablets or point tablets can also be colored or sprinkled, for example. The person skilled in the art has hardly any limits when varying these implementation options for optical differentiation.

After pressing, the detergent tablets have a high stability. The impact strength of cylindrical shaped bodies can be determined via the measured variable of the diametrical fracture stress. This can be determined according to 2P πDt

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

Another object of the present invention is the use of alkylbenzenesulfonate compounds with alkylbenzenesulfonate contents above 40% by weight, based on the compound, to improve the hardness and the rate of disintegration of detergent tablets. By using the ABS compounds in detergent moldings, the physical properties of the moldings can be improved, as the following examples show:

Examples:

A polymer compound was produced by spray drying and served as the basis for a granulate containing tenside. Next sodium C ₉ was .ι ₃ by spray neutralization of 97% - 50% alkyl benzene sulfonic acid _with> NaOH in a fluidized bed a 75%> prepared sodium ABS compound. The compositions of the two compounds are shown in Table 1. The spray-dried polymer compound was granulated with other components (zeolite, fatty alcohol sulfate, NaOH, alkylbenzenesulfonic acid, nonionic surfactant, soda, silicate) in a 50 liter ploughshare mixer from Lödige. The amounts of the substances used and the order of addition to the mixer are given in Table 2. In Comparative Example V, the entire amount of alkylbenzenesulfonate was added in the form of the alkylbenzenesulfonic acid, in the process El according to the invention only a part of the total amount of alkylbenzenesulfonate in the form of the alkylbenzenesulfonic acid was added during the granulation, the rest of the total amount of alkylbenzenesulfonate was added directly to the premix Form of the ABS compound added. Finally, in example E2 according to the invention, only part of the total of the alkylbenzenesulfonate in the form of the alkylbenzenesulfonic acid contained in the moldings was added during the granulation, the rest of the total amount of alkylbenzenesulfonate was added in the form of the ABS compound; However, compound added to the granulation batch.

Table 1:

Composition of the spray-dried or spray-neutralized compounds [% by weight>]

Acrylic acid-maleic acid copolymer (BASF)

Table 2: Composition of the granulation batches [g]

** Composition: 92% by weight C 12-1 g fatty alcohol sulfate 3% by weight sodium carbonate 5% by weight water, salts

Following the granulation, the granules were in a fluidized bed apparatus from Glatt at a supply air temperature of 60 ° C. over a period of 30 minutes to a water content of 8.0 ± 0.2% by weight. dried. After drying, fine particles <0.6 mm and coarse particles> 1.6 mm were screened off. To determine the water content of the granules, 2 g of the granules were heated for 10 minutes at 130 ° C. on a type MA 30 device from Sartorius and the drying loss was determined gravimetrically.

The surfactant granules E1 and E2 or V were then processed with further components to form a compressible premix, after which the Veφres- in a Korsch eccentric press solution to tablets (diameter: 44 mm, height: 22 mm, weight: 37.5 g). The pressure was set so that two series of molded bodies were obtained (El, E2 and V or El ', E2' and V), which differ in their hardness. Table 3 shows the composition of the premixes to be fed (and thus the shaped body).

Table 3: Composition of the detergent tablets [wt .-%>]

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

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

Table 4: Physical data of the detergent tablets

Table 4 shows that the disintegration times of detergent tablets are significantly reduced by the use of the ABS compounds according to the invention, it being irrelevant whether the ABS compounds are added to the compressible premix or are added during the manufacture of the surfactant granules.

Claims

Claims:

1. washing and cleaning agent molded body made of compressed, particulate washing and cleaning agent, characterized in that they contain alkylbenzenesulfonate compounds with alkylbenzenesulfonate contents above 40% by weight>, based on the compound.

2. Detergent form according to claim 1, characterized in that the alkylbenzenesulfonate compounds have alkylbenzenesulfonate contents above 50% by weight, preferably above 60% by weight and in particular above 70% by weight, based on the compound .

3. Detergent form according to one of claims 1 or 2, characterized in that the alkylbenzenesulfonate compounds contain the alkali metal, preferably sodium salts of C ₈ .i ₆ -, preferably C _- ₃ -alkybenzenesulfonic acids, which are derived from alkylbenzenes which have a tetralin content of less than 5% by weight, based on the alkylbenzene.

4. Detergent form according to one of claims 1 to 3, characterized in that the alkylbenzenesulfonate compounds contain the alkali metal, preferably sodium salts of C ₈ .ι ₆ -, preferably C -ι ₃ -alkybenzenesulfonic acids, which contain a content of 2-phenyl isomer below 22% by weight, based on the alkylbenzenesulfonic acid.

5. Detergent and molded article according to one of claims 1 to 4, characterized in that it contains alkylbenzenesulfonate compounds in amounts of 0.5 to 20% by weight, preferably 1 to 15% by weight o, particularly preferably 2 up to 10% by weight and in particular from 3 to 8% by weight, in each case based on the molded body weight.

6. Detergent and molded article according to one of claims 1 to 5, characterized in that it contains alkylbenzenesulfonate contents of 1 to 30% by weight>, preferred example, from 5 to 25 wt .-% and in particular from 10 to 15 wt .-%, each based on the molded body weight.

7. Detergent form according to one of claims 1 to 6, characterized in that they contain, in addition to the alkylbenzenesulfonate compounds, an alkylbenzenesulfonate-containing surfactant granulate.

8. Detergent and molded article according to one of claims 1 to 7, characterized in that at least 20% by weight>, preferably at least 30% by weight> and in particular at least 40% by weight of the total alkylbenzenesulfonate contained in the molded articles the alkylbenzenesulfonate compounds are introduced into the moldings.

9. A process for the production of washing and cleaning agent shaped articles, characterized by the steps

a) Production of alkylbenzenesulfonate compounds with alkylbenzenesulfonate contents above 40% by weight, based on the compound, b) Mixing with further preparation components to form a compressible premix, c) molding to shaped bodies.

10. The method according to Anspmch 9, characterized in that the alkylbenzenesulfonate compounds prepared in step a) alkylbenzenesulfonate contents above 50% by weight, preferably above 60% by weight and in particular above 70% by weight, based on the Compound.

11. The method according to any one of claims 9 or 10, characterized in that the alkylbenzenesulfonate compounds in step a) are produced by granulation, preferably fluidized bed granulation.

12. The method according to any one of claims 9 to 11, characterized in that in step b) one or more surfactant granules as conditioning components are inkoφoriert in the premix and the particulate premix has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular has at least 700 g / 1.

13. The method according to Anspmch 12, characterized in that the or at least one of the surfactant granules (e) contains alkylbenzenesulfonates.

14. The method according to any one of claims 12 or 13, characterized in that the surfactant-containing granules have particle sizes between 100 and 2000 microns, preferably between 200 and 1800 microns, particularly preferably between 400 and 1600 microns and in particular between 600 and 1400 microns.

15. The method according to any one of claims 12 to 14, characterized in that the surfactant-containing granules contains anionic and / or nonionic surfactants and builders and total surfactant contents of at least 10 wt .-% _, preferably at least 20 wt .-% and in particular at least 25% by weight.

16. The method according to any one of claims 13 to 15, characterized in that the surfactant-containing granules with the addition of all or part of the alkylbenzenesulfonate compounds produced in step a) with alkylbenzenesulfonate contents above 40 wt .-%, based on the compound, was produced .

17. The method according to Anspmch 16, characterized in that at least 20% by weight, preferably at least 30% by weight and in particular at least 40% by weight of the total alkylbenzenesulfonate present in the moldings in the form of that prepared in step a) Alkylbenzenesulfonate compounds is introduced into the molded body.

18. The method according to any one of claims 9 to 17, characterized in that the particulate premix additionally one or more substances from the group of bleaching agents, bleach activators, disintegration aids, enzymes, pH adjusting agents, Contains fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.

19. Use of alkylbenzenesulfonate compounds with alkylbenzenesulfonate contents above 40% by weight, based on the compound, to improve the hardness and the rate of disintegration of detergent tablets.